FACULTY OF CHEMISTRY
Maria Curie-Skłodowska University
ANNUAL ANNUAL ANNUAL ANNUAL REPORTREPORTREPORTREPORT
2009
Faculty of Chemistry, Maria Curie-Skłodowska University
Maria Curie-Skłodowska Sq. 3, 20-031 Lublin, Poland
No responsibility is assumed by the editors for content and
English language.
Editor: Anna Deryło-Marczewska
Technical Assistance: Wojciech Stefaniak
F.Ch. UMCS Report 2009 – 3 –
CONTENTS PART 1
BS REPORTS .................................................................................. 15 Department of General and Coordination Chemistry
Zofia Rzączyńska and Justyna Sienkiewicz-Gromiuk
The Hydrothermal Synthesis of Lanthanide(III) Coordination Polymers
with 2,2’- And 4,4’-Biphenyldicarboxylic Acids ......................................................17
Wiesława Ferenc and Katarzyna Czapla
Complexes of Chosen D-Block Elements with 2-Amino-4,6-Dimethylo-
pyrimidine.................................................................................................................19
Wiesława Ferenc and Agnieszka Dziewulska-Kułaczkowska
Synthesis and Properties of New Ligands (Schiff Bases) Containing
3-Formylchromone...................................................................................................21
Wiesława Ferenc and Beata Cristóvão
Synthesis and Magnetic Studies of D-F Heteronuclear Compounds
with Schiff Bases.......................................................................................................23
Renata Łyszczek
Construction and Investigations of Coordination Polymers of Ln(III)
Ions with Pyridine-3,5-Dicarboxylic Acid................................................................25
Liliana Mazur
Synthesis and Structural Investigations of Complexes of Selected
Bioelements with Ferulic and Caffeic Acids ............................................................27
Department of Inorganic Chemistry
Zbigniew Hubicki and Grzegorz Wroński
Investigation of Sorption Mechanism of Ga(Iii) and In(III) Ions
on Polymeric Sorbent Impregnated by D2EHPA Acid.............................................29
Dorota Kołodyńska and Zbigniew Hubicki
Agent of the New Generation Baypure CX 100 in the Sorption of the Heavy
Metal Ions on Ion Exchangers of the Different Type ...............................................31
Monika Wawrzkiewicz and Zbigniew Hubicki
Application of Gel and Macroporous Strongly Basic Anion Exchangers
in Acid Blue 29 Removal from Aqueous Solutions ...................................................33
Contents – 4 –
Zbigniew Hubicki and Grzegorz Wójcik
Investigation of Arsenic(III and V) Sorption on Liquid Ion Exchangers
Impregnated Resins ..................................................................................................35
Marek Majdan, Magdalena Makarska-Białokoz
and Agnieszka Gładysz-Płaska
Synthesis and Properties of Transparent Silica Gels Dotted
with Octaethylporphyrine.........................................................................................37
Marek Majdan, Agnieszka Gładysz-Płaska
and Magdalena Makarska-Białokoz
The Influence of the Complexation on the Lanthanides Adsorption
on the Zeolite A and Y....................................................................................................39
Department of Analytical Chemistry and Instrumental Analysis
Dorota Gugała-Fekner, Dorota Sieńko, Jolanta Nieszporek
and Jadwiga Saba
Influence of Tertbutanol and Base Electrolyte Concentration
on the Kinetics and Mechanism of Zn2+
Ions Electroreduction................................41
Ryszard Dobrowolski
Elimination of Interferences In Slurry Sampling Gfaas Measurements ..................43
Ryszard Dobrowolski
Trace Metals Enrichment from Environmental Samples by Application
of Modified Activated Carbons.................................................................................45
Mieczysław Korolczuk, Katarzyna Tyszczuk
and Małgorzata Grabarczyk
Determination of Trace of Cobalt(II) in Complex Matrices
by Adsorptive Stripping Voltammetry.......................................................................47
Cecylia Wardak
The Construction and Research of Properties of Cadmium Ion-Selective
Electrodes with Solid Contact ..................................................................................49
Grażyna Dalmata and Agnieszka Nosal-Wiercińska
The Influence of Water Activity on the Electroreduction Proces of Bi(III)
Ions in Chlorates (VII)..............................................................................................51
Zygmunt Fekner
Digital Simulation of Cyclic Reciprocal Derivative Chronopotentiometry
with Programmed Current of Adsorption Systems with Slow Charge
Transfer ....................................................................................................................53
Barbara Marczewska, andrzej Persona and Tomasz Gęca
Influence of Chosen Antibiotics on Electrophoretic Determination
of Human Albumin....................................................................................................55
F.Ch. UMCS Report 2009 – 5 –
Department of Interfacial Phenomena
Katarzyna Szymczyk and Bronisław Jańczuk
Investigations of the Adsorption and Volumetric Properties of Anionic
and Nonionic Surfactants Mixtures..........................................................................59
Katarzyna Szymczyk and Bronisław Jańczuk
Investigation of the Wettability of Polymeric Solids by Aqueous Solution
of Binary Mixtures of Anionic and Nonionic Surfactants ........................................61
Tomasz Białopiotrowicz
Theoretical Analysis of the Influence of the Error in the Work of Adhesion
Data on Real Values of the Surface Free Energy and Its Components
– Is It Possible To Improve the Accuracy of a Solution? .........................................63
Aleksandra Szcześ, Emil Chibowski and Lucyna Hołysz
Effects of Static Magnetic Field on Water and Electrolyte Solutions
Properties .................................................................................................................65
Aleksandra Szcześ Phospholipid Influence on Calcium Carbonate Precipitation .................................67
Department of Adsorption
Agnieszka Kierys, Waldemar Buda and Jacek Goworek
The Porosity and Morphology of Mesoporous Silica Agglomerates........................69
Department of Planar Chromatography
Irena Malinowska, Barbara Ościk-Mendyk, Małgorzata Janicka
and Marek Studziński
The Influence of the Magnetic Field on Separation and Resolution
of Chosen Chromatographic Systems.......................................................................71
Irena Malinowska, Barbara Ościk-Mendyk, Małgorzata Janicka
and Ludomir Kwietniewski
A New Method for the Determination of Retention of Substance
in Ternary Mobile Phases ........................................................................................73
Irena Malinowska, Barbara Ościk-Mendyk, Małgorzata Janicka
and Ludomir Kwietniewski
The Application of Linear Form of Ościk’s Equation for Determination
of Hydrophobicity Index...........................................................................................75
Department of Physicochemistry of Solid Surface
Anna Deryło-Marczewska, Adam W. Marczewski,
Szymon Winter, Dariusz Sternik and Grzegorz Żukociński
Synthesis and Investigations of Properties of Siliceous and Carbonaceous
Mesoporous Materiale .............................................................................................77
Contents – 6 –
Anna Deryło-Marczewska, Magdalena Błachnio,
Adam W. Marczewski and Bogdan Tarasiuk
Studies of the Processes of Herbicides Removing from Aqueous
Solutions on Microporous Activated Carbons..........................................................79
Department of Chromatographic Methods
Andrzej L. Dawidowicz and Ewelina Rado
MSPD as Sample Preparation Method for GC Analysis of Essential Oils
in Herbs ....................................................................................................................81
Jadwiga Skubiszewska-Zięba, Roman Leboda
and Barbara Charmas
Application of Mechanocal, Hydrotheral and Microwave Treatment
for Preparation of Catalysts and Adsorbents ...........................................................83
Department of Theoretical Chemistry
Andrzej Dąbrowski and Mariusz Barczak
Synthesis and Structural-Adsorption Properties of Bridged
Polysilsesquioxanes Functionalized with Different Groups.....................................85
Andrzej Dąbrowski, Mariusz Barczak and Stanisław Pikus
Synthesis, Structure and Adsorption Properties of Nanoporous SBA-15
Materials with Framework and Surface Functionalities..........................................87
Władysław Rudziński
Theoretical Description of the Adsorption Kinetics Based on the Statistical
Rate Theory of Interfacial Transport (SRT) .............................................................89
Paweł Szabelski and Władysław Rudziński
Theoretical Studies of Adsorption on Chemically and Structurally
Modified Solid Surfaces............................................................................................91
Krzysztof Woliński
Solvent Effect in the NMR Spectroscopy of Selected Nuclei.....................................92
Mateusz Drach, Jolanta Narkiewicz-Michałek, Marta Szymula
and Jerzy Jabłoński
Solubilisation of Organic Substances in the Bulk and Surface Micelles
– Theory and Experiment .........................................................................................93
Department for Modeling of Physico-Chemical Processes
Tomasz Zientarski
Theory and Simulations of Nonuniform Molecular Fluids. Molecular
Dynamics Study of Adatom Size Effect on Stress Evolution
in Lennard-Jones Thin Films....................................................................................95
F.Ch. UMCS Report 2009 – 7 –
Department of Chemical Technology
Janusz Ryczkowski, Agnieszka Dębczak and
Sylwia Pasieczna-Patkowska
Adsorption of New Generation Chelates on Alumina Support.................................97
Andrzej Machocki, George Avgouropoulos and Theophilos Ioannides
Determination of Surface Properties of Palladium Catalyst
for the Reaction of Complete Oxidation of Methane................................................99
Marek Rotko and Andrzej Machocki
Investigation of Isotopic Disturbances of Oxygen un the Reaction
of Methane Oxidation Over Palladium and Platinum Catalysts............................101
Beata Stasińska
Optimization of Active Phase Palladium Catalysts................................................103
Beata Stasińska
Study of Activity Palladium Catalysts on Commercial Support
Produced By Fertilizers Research Institute in Puławy...........................................107
Adam Lesiuk
The Influence of the Projected Transport System in the Lubelskie
Voivodeship on the Quality of the Atmospheric Air ...............................................107
Tadeusz Borowiecki, Andrzej Denis, Monika Pańczyk
and Czesława Sikorska
Promoted Nickel Catalysts in the Hydrocarbon Reactions....................................109
Department of Radiochemistry and Colloid Chemistry
Stanisław Chibowski, Małgorzata Wiśniewska and Teresa Urban
Influences of Polyacrylic Acid Adsorption and Solution pH on Alumina
Suspension Stability................................................................................................113
Jacek Patkowski
Influence of Magnetic Field of Various Strength on Zeta Potential
of Magnetite/Ionic Polymers Interface...................................................................114
Stanisław Chibowski, Marek Reszka, Radosław Dobrowolski
and Dorota Skórniewska
Radiocarbon Dating of the Biogenic Sediments, Peat-Soil Profile
(0-6m) from the Spławy Lake Site (Dorohucza Lowland) ......................................115
Department of Crystallography
Anna E. Kozioł, Barbara Mirosław, Marta Struga
and Jerzy Kossakowski
Structure of Unsymmetrically Disubstituted Derivatives of Thiourea
and Their Cyclization Products..............................................................................117
Contents – 8 –
Stanisław Pikus, Małgorzata Zienkiewicz, Elżbieta Olszewska
and Maciej Kozak
Organosilicas Containing Zr And Ti Ions ..............................................................119
Department of Organic Chemistry
K. Michał Pietrusiewicz, Anna Flis, Nikolai Vinokurov,
I. Baumgart and Holger Butenschoen
Synthesis of New Chiral Organophosphorus Systems for Asymmetric
Catalysis .................................................................................................................121
K. Michał Pietrusiewicz, Anna Szmigielska, Anna Flis,
Nikolai Vinokurov and Holger Butenschoen
Synthesis and Applications of Cyclic and Macrocyclic
Organophosphorus Compounds.............................................................................123
Department of Polymer Chemistry
Barbara Gawdzik, Marta Grochowicz and Beata Podkościelna
The Influence of the Chemical Structure of Monomers on the Properties
of Porous Methacrylate Copolymers......................................................................125
Department of Optical Fibres Technology
Jan Rayss, Wiesław Podkościelny, Andrzej Gorgol
and Jan Widomski
Studies on Photocurable Hybrid Material..............................................................127
Paweł Mergo, Jan Wójcik, Krzysztof Skorupski,
Krzysztof Poturaj and Mariusz Makara
Large Mode Area Fibers with Dedicated Mode Field Diameters
– Theory, Fabrication and Characterization .........................................................129
Department of Environmental Chemistry
Bożena Czech
V-TiO2/Al2O3 and Co-TiO2/Al2O3 V – The Catalysts of Photooxidation
of Organic Pollutants in Water ..............................................................................131
Marcin Kuśmierz and Dobiesław Nazimek
Research on Kinetics of Reaction Between CH4 and O2 on Metals
of the VIII Group ....................................................................................................133
F.Ch. UMCS Report 2009 – 9 –
Department of Chemical Education
Ryszard M. Janiuk, Jarosław Dymara, Zofia Kloc
and Agnieszka Kamińska-Ostęp
Studies on Factors Affecting Course and Results of Chemical
Education ...............................................................................................................135
PART 2
BW REPORTS ............................................................................... 137
Department of Analytical Chemistry and Instrumental Analysis
Jolanta Nieszporek, Dorota Sieńko, Dorota Gugała-Fekner
and Jadwiga Saba
Properties of Mixed Adsorption Layers: Tetramethylthiourea
and Tertbutanol in 4M NaClO4 at Mercury Electrode...........................................139
Department of Radiochemistry and Colloid Chemistry
Władysław Janusz and Anita Sędłak
Specific Adsorption of Carbonate Ions at the Yttrium Oxide/Electrolyte
Solution Interface ...................................................................................................141
Andrzej Komosa, Magdalena Piekarz and Jolanta Orzeł
Optimization of Plutonium Extraction with Methyltrioctylammonium
Chloride Preceding its Determination by Liquid Scintillation
Spektrometry...........................................................................................................143
Andrzej Komosa, Katarzyna Ślepecka and Jolanta Orzeł
Effect of Liquid Scintillation Cocktail Volume on 3H and
14C
Measurement Parameters Using the Quantulus Spectrometer ..............................144
Department of Organic Chemistry
K. Michał Pietrusiewicz, Zbigniew Drzazga, Anna Flis,
Renata Parcheta and Elżbieta Łastawiecka
Reactions of Cyclic Organophosphorus Compounds with Nucleophiles ...............145
Contents – 10 –
Department of Optical Fibres Technology
Jan Rayss, Małgorzata Gil, Wiesław Podkościelny,
Andrzej Gorgol and Jan Widomski
Studies on Photopolymerization Kinetics ...............................................................147
Jan Wójcik, Janusz Pędzisz, Krzysztof Poturaj,
Aleksandr Walewski, Lidia Czyżewska, Jacek Klimek,
Jarosław Kopeć, Krzysztof Skorupski, Paweł Mergo
and Mariusz Makara
Technology of Microstructured Plastic Optical Fibers by Stacking
Method....................................................................................................................149
PART 3
GRANTS.........................................................................................151 Department of Analytical Chemistry and Instrumental Analysis
Mieczysław Korolczuk and Katarzyna Tyszczuk
Stripping Analysis of Biologically Active Compounds with Application
of a Lead Film Electrode........................................................................................153
Department of Interfacial Phenomena
Katarzyna Szymczyk and Bronisław Jańczuk
A Study of Interactions of Ternary Surfactant Systems
at Water-Air Interface ............................................................................................155
Agnieszka Ewa Wiącek, Lucyna Hołysz and Emil Chibowski
Electrokinetic Properties of N-Tetradecane/Ethanol Emulsions
With DPPC and Enzyme Lipase or Phospholipase A2 ...........................................157
Emil Chibowski and Konrad Terpiłowski
Surface Free Energy of Polypropylene and Polycarbonate Solidifying
at Different Solid Surfaces......................................................................................159
Department of Theoretical Chemistry
Andrzej Dąbrowski, Mariusz Barczak, Władysław Janusz
and Ewa Skwarek
Functionalized SBA-15 Organosilicas as Sorbents of Zinc(II) Ions ......................161
F.Ch. UMCS Report 2009 – 11 –
Paweł Szabelski, Tomasz Pańczyk, Mateusz Drach
and Tomasz P. Warzocha
Theoretical Studies of the Adsorption of Chiral Molecules
on Solid Surfaces....................................................................................................163
Department for Modeling of Physico-Chemical Processes
Małgorzata Borówko, Stefan Sokołowski
and Tomasz Staszewski
Theory and Computer Simulations of Adsorption of Fluids
on Surfaces Modified with Chain Molecules..........................................................165
Leszek Sałamacha, Andrzej Patrykiejew and Stefan Sokołowski
Computer Simulations of Binary Mixtures in External Field.................................167
Department of Chemical Technology
Andrzej Machocki, Andrzej Denis, Wiesław Grzegorczyk
and Wojciech Gac
Hydrogen From Bio-Alcohols. An Efficient Route for Hydrogen
Production Via Novel Reforming Catalysts ...........................................................169
Andrzej Machocki, Andrzej Denis, Wiesław Grzegorczyk
and Wojciech Gac
A High-Selective Catalyst for Conversion of Ethanol to Hydrogen.......................171
Marek Rotko and Andrzej Machocki
Determination of Kinetic-Mechanistic Parameters of the Reaction
of Complete Oxidation of Methane by Means of Reagents
Labeled with Stable Isotopes..................................................................................173
Janusz Ryczkowski, Tadeusz Borowiecki, Monika Pańczyk
Kazimierz Stołecki and Andrzej Gołębiowski
Catalysts for Multicomponent Gas Reforming in Gas Heated
Reformer.................................................................................................................175
Sylwia Pasieczna-Patkowska, Bożena Czech,
Janusz Ryczkowski and Jacek Patkowski**
New Oxidation and Photooxidation Catalysts for the Removal
of Organic Pollutants from Water and Wastewater ...............................................177
Wojciech Gac, Witold Zawadzki and Zbigniew Surowiec
Synthesis and Characterisation of Physico-Chemical, Catalytic
and Magnetic Properties of High-Surface Area Oxide Materials..........................179
Contents – 12 –
Beata Stasińska, Agnieszka Marcewicz-Kuba, Monika Pańczyk,
Marcin Kuśmierz, Wojciech Gac, Marek Rotko,
Witold Zawadzki and Dobiesław Nazimek
Proekological Technology Utilization Coal Mine Methane...................................181
Department of Radiochemistry and Colloid Chemistry
Stanisław Chibowski, Małgorzata Wiśniewska
and Teresa Urban
Studies of Temperature Influence on Adsorption Behaviour
of Nonionic Polymers at the Zirconia-Solution Interface.......................................183
Department of Crystallography
Elżbieta Olszewska, Stanisław Pikus, Marek Majdan
and Bogdan Tarasiuk
X-Ray Powder Diffraction – New Inorganic and Organic
Compounds IV ........................................................................................................185
Stanisław Pikus, Elżbieta Olszewska, Marek Majdan
and Bogdan Tarasiuk
X-Ray Powder Diffraction – New Inorganic and Organic
Compounds XII.......................................................................................................186
Department of Organic Chemistry
Sylwia Sowa, Marek Stankevič and K. Michał Pietrusiewicz
Boran Jako Nowy Selektywny Odczynnik Redukujący
w Chemii Funkcjonalizowanych Fosfonianów, Fosfinianów
I Tlenków Fosfin .....................................................................................................189
Marek Stankevič, K. Michał Pietrusiewicz, Oleh M. Demchuk,
Sylwia Sowa and Anna Szmigielska
Selective Functionalisation of Tertiary Phosphines Possessing Aryl
Substituents with Alkali Metals as a Method of the Synthesis
of Organophosphorus Compounds Possessing Useful Properties .........................191
Oleg M. Demchuk, Katarzyna Kielar and K. Michał Pietrusiewicz
Novel Bulky and Electronically Rich Atropoisomeric Phosphorus
Ligands: Synthesis and Application .......................................................................193
K. Michał Pietrusiewicz, Oleg Demchuk, Katarzyna Szwaczko,
Anna Flis and Elżbieta Łastawiecka
Opracowanie Nowych Efektywnych Procesów Katalizowanych
Kompleksami Metali I Związkami Metaloorganicznymi: Związków
Metaloorganicznych Jako Odczynników w Stereoselektywnej Syntezie
Organicznej, Polimerów w Roli Prekursorów Nowych Materiałów,
Chiralnych Związków Organicznych......................................................................196
F.Ch. UMCS Report 2009 – 13 –
Department of Environmental Chemistry
Adam Lesiuk, Marcin Kuśmierz, Joanna Strusińska
and Bożena Czech
From Student To Expert – Environmental Protection In Practice.........................199
PART 4
PUBLICATIONS............................................................................. 201
PART 5
CONFERENCE CONTRIBUTIONS................................................ 227
PART 6
VISITORS AT FACULTY OF CHEMISTRY IN 2009 ...................... 267
PART 7
AWARDS ....................................................................................... 271
PART 1
BS REPORTS
F.Ch. UMCS Report 2009 (BS) – 17 –
THE HYDROTHERMAL SYNTHESIS OF LANTHANIDE(III) COORDINATION POLYMERS WITH 2,2’-
AND 4,4’-BIPHENYLDICARBOXYLIC ACIDS
Zofia RZĄCZYŃSKA and Justyna SIENKIEWICZ-GROMIUK DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
The design and synthesis of metal−carboxylate complexes has became a flourishing research area because of their interesting topologies and crystal packing modes, alongside their potential applications in many areas including gas storage, magnetism, catalysis, optics, as well as conductivity [1]. Among the large family of carboxylate ligands, the flexible biphenyl carboxylate derivatives, such as 2,2’- and 4,4’-biphenyldicarboxylate have attracted considerable interest. 2,2’- and 4,4’-biphenyldicarboxylic ligands have four potential donor carboxylate oxygen atoms which can coordinate to metal ions with different connection modes and display strong reactivity with f block metal ions [2].
The two series of lanthanide(III) complexes with 2,2’-biphenyldicarboxylic [3] and 4,4’-biphenyldicaroxylic acids were prepared by classical precipitation method to study their structural (elemental analysis, XRD technique), thermal (thermogravimetric analysis) and spectroscopic properties (FT-IR, FT-Raman).
In view of luminescent properties of some lanthanide(III) compounds, we also carried europium(III) biphenyldicarboxylates out by hydrothermal synthesis. The stechiometric amounts of aqueous slime or ethanol solution of 2,2’- or 4,4’-biphenyldicarboxylic acids (15 ml) and aqueous slime of europium(III) hydroxide (15 ml) were filled in Teflon-lined autoclave at 150°C under autogenous pressure. After 96 hours (for ethanol solution of acids) or 72 hours (for water slime of acids) autoclaves were cooled and the crystalline solid products were separated by filtration.
Solid complexes of europium(III) biphenyldicarboxylates were obtained as hydrated compounds with the metal:ligand ratio 2:3. The complexes acquired by hydrothermal reaction contain fewer molecules of water than appropriate compounds obtained by classical precipitation method. The europium(III) 2,2’-biphenyldicarboxylate obtained from ethanol solution involves 2.5 molecules of water whereas alike compound received from water slim holds 2 water molecules. The complex with 2.5 water molecules is crystalline and crystallizes in triclinic crystal system with the elemental cell parameters: a = 13.54; b = 15.21; c = 13.97Å and α = 58.72; β = 65.82; γ = 48.88°, the volume of elemental cell is equal to 1843 Å3.
Department of General and Coordination Chemistry – 18 –
Fig.1. X-ray diffraction pattern and TG and DSC curves in air atmosphere (β = 10°C/min) of Eu2L3·2.5H2O, L = (C14H8O4
2–). Europium(III) complexes were analyzed by FT-IR spectroscopy. The lack of
stretching and deformation vibrations of –COOH groups, in the IR spectra of europium(III) compounds, indicates that all carboxylate groups are deprotonated and committed to coordination of metal ions . The intensive bands corresponding to the stretching asymmetric vibrations νas(COO–) in the IR spectra of complexes are observed at 1554ethanol, 1553 cm–1
aq (1556 cm–1classical) and 1406 cm–1
(1409 cm–1 classical) for the symmetric stretching vibrations νs(COO–) of carboxylate anions. The differences between the position of the νas(COO–) and νs(COO–) modes (∆ν(COO–)) in the complexes of europium(III) diphenate (obtained by hydrothermal and classical method) is similar (∆ν(COO–)) = 148ethanol –147 cm–1
aq and 147 cm–1
classical, so carboxylate groups may be chelated in these complexes irrespective of synthesis method. References:
[1] X.-X. Xu, X.-X. Liu, X. Zhang and T. Sun, Transition Met. Chem. [2] X.-X. Xu, X.-X. Liu, X. Zhang and T. Sun, Polyhedron, 28 (2009) 2997. [3] Z. Rzączyńska, J. Sienkiewicz-Gromiuk and H. Głuchowska, J. Therm. Anal.
Calorim., DOI 10.1007/s10973-009-0326-7.
F.Ch. UMCS Report 2009 (BS) – 19 –
COMPLEXES OF CHOSEN d-BLOCK ELEMENTS WITH 2-AMINO-4,6-DIMETHYLOPYRIMIDINE
Wiesława FERENC and Katarzyna CZAPLA DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
The complexes of 2-amino-4,6-dimethylopyrimidine with Co(II), Cu(II) and Mn(II) ions were synthesized in the solid state as hydrated and anhydrous salts with the following colours: dark blue for Cu(II) complex, blue for Co(II) and pale pink for that of Mn(II). Their formulae are as follows: Cu4(admp)2Cl4, Co3(admp)4Cl6 · 2H2O and Mn3(admp)2Cl6, where admp = 2-amino-4,6-dimethylopyrimidine. In the spectrum of 2-amino-4,6-dimethylopyrimidine the clear bands of asymmetric and symmetric vibrations of NH2 group are observed at 3405 cm-–1 and 3312 cm–1, while those in the spectra of complexes are at: 3471 cm–1 and 3383 cm–1(νas) and 3293 cm–1(νs) for Cu(II) complex; 3410 cm–1(νas) and 3314 cm-1(νs) for Co(II) complex and 3407 cm–1(νas) and 3350 cm-1(νs) for Mn(II) In the IR spectrum of ligand the band at 1630 cm–1 is assigned to the NH2 deformation vibrations. This band in the spectra of Co(II) and Cu(II) complexes occurs at 1640 cm–1 and 1622 cm–1, respectively, while in that of Mn(II) it is significantly shifted to 1680 cm–1. In the spectrum of Co(II) complex the band at 3554 cm–1 confirms the presence of crystallization water molecules. The thermal stability of compounds of 2-amino-4,6-dimethylopyrimidine with Cu(II), Co(II) and Mn(II) ions was investigated in air and argon atmosphere in the range of 293-1273K. The TG, DTG and DTA curves were recorded. From the obtained results it appears that only Co(II) complex is hydrated whereas the rest of them are anhydrous compounds. The complexes are decomposed in the various ways. Dihydrate of Co(II) loses, at first, two water molecules and forms anhydrous compound, that next it is decomposed to Co3O4. The dehydration process is accompanied by endothermic effect seen on DTA curve. The mixture containing Cu and carbon is the final product of decomposition of Cu(II). The Mn(II) complex decomposed in two stages. In the first step the MnCl2, as intermediate product, is formed that in the second step is decomposed to Mn3O4.The FTIR spectra of gaseous products evolved during thermal decomposition of complexes in the range of 293-1173K in argon atmosphere were recorded in the TG/FTIR system. Their interpretation reveals them to be molecules of NH3 (3320 cm–1, 960 cm-1, 920 cm-1), HCl (3100-2600 cm–1), HCN (2380-220 cm–1, 780-770 cm–1), hydrocarbons and chlorocarbon derivatives (3100-2700 cm-1, 1700-1640 cm-1,1500-1300 cm1) and pyridine (3080 cm-1, 1900 cm-1, 1600 cm-1, 1400 cm-1, 780 cm-1). The gaseous products of pyrimidine thermal decomposition in argon are: C2H2, HCN, H2, acrylonitrile, cyanoacetylene.
The NMR spectra of ligand and analysed complexes were recorded. In the spectrum of ligand the three singlet signals were recorded with the shifts: 2.27; 4.86 and 6.46 ppm, which are attributed to the following groups: CH3, NH2 and CHar,
Department of General and Coordination Chemistry – 20 –
respectively. In the spectrum of Co(II) complex the singlet at 2.15 ppm corresponds to CH3 group shift. The singlet at 3.89 ppm is attributed to the NH2 group displacement. The signal of singlet of CHar group appears at 6.42 ppm. In the spectra of Cu(II) and Mn(II) complexes two signals of the shifts at 2.50; 2.17; and 6.17; 6.40 ppm, as singlets, are attributed to the shifts of CH3 and CHar groups, respectively. The signal of NH2 group was being probably diluted at the measurement temperature. From the obtained results it appears that in the analysed complexes the coordination took place but it is not possible to state univocally through which nitrogens it occurs. IR spectra reveal its through pyrimidine nitrogen atom while those of NMR through that of amino group, because there are clear interactions around it. We can know the details concerning the ways of coordination from the single crystal determinations. However, the structures of complexes have not been determinated since their monocrystals have not been obtained so far.
The magnetic susceptibility of complexes were measured and the magnetic moments calculated. In the case of Cu(II) complex the values of magnetic moments calculated for the temperature range of 76-303K change from 0.59µB (76K) to 0.43µB (303K). The magnetic susceptibility values in that range decrease with the increase of temperature and the course of curve χM = f(T) is not regular. The low values of magnetic moments and the untypical course of the curve χM = f(T) indicate the ferromagnetic and paramagnetic interactions in this compound. In the complexes of Mn(II) and Co(II) the magnetic susceptibility values decrease with rising temperatures which indicates them to obey the Curie –Weiss law [1-9].
References:
[1] L.A. Kazicyna, N.B. Kupletska, Spectrometric Identifications of Organic
Compound Structures, Polish Scientific Publisher, Warsaw 1976. [2] R.N. Silverstein, and G.C. Bassler, Spectrometric Identifications of Organic
Compounds , Polish Scientific Publisher, Warsaw, 1970. [3] A.D. Cross, and R.A. Jones, An Introduction to Practical Infra-Red
Spectroscopy , Butterworths, London, 1969. [4] K. Nakamoto, Infrared and Ramana Spectra of Inorganic and Coordination
Compounds, John-Wiley and Sons, New York, 1997. [5] M. Sikorska-Iwan, and R. Mrozek-Łyszczek, J. Therm. Anal. Cal., 78 (2004)
487. [6] M. Ban, J. Madarasz, P. Bombicz, G. Pokol and S Gal, J. Therm. Anal. Cal., 78
(2004) 545. [7] A.K. Bridson, Inorganic Spectroscopic Methods, Oxford University Press, New
York, 1998 [8] L.M. Harwood and T.D. Claridge, Introduction to Organic Spectroscopy,
Oxford University Press, New York, 1999. [9] J. Pielichowski, and K. Pielichowski, Conference Papers, Thermal Analysis
School, Zakopane, 1996.
F.Ch. UMCS Report 2009 (BS) – 21 –
SYNTHESIS AND PROPERTIES OF NEW LIGANDS (SCHIFF BASES) CONTAINING 3-FORMYLCHROMONE
Wiesława FERENC and Agnieszka DZIEWULSKA-KUŁACZKOWSKA DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
Schiff bases derived from an amine and an aldehyde are an important class of ligand. These ligands coordinate to metal ions via azomethine nitrogen atom and have been studied extensively. The transition metal complexes having oxygen and nitrogen donor Schiff bases possess unusual configuration, structural lability and are sensitive to molecular environment. Schiff bases and their metal complexes are becoming increasingly important as biochemical, analytical, industrial reagents and redox catalysts as well as pigment dyes [1].
3-Formylchromone (4-oxo-4H-1-benzopyran-3-carboxaldehyde, C10H6O3) (Fig. 1) is the derivative of the parent chromone compounds especially occurring in the plants, which are heterocyclic compounds containing oxygen [2-4]. Chromones are compounds, which contain γ-pyrone nucleus fused to benzene ring at the 5- and 6-position. Molecules, contain in their structure chromone ring, have attracted attention because of their interesting biological properties. Many of them show antifungal, antiallergic, antiviral, antihypertensive and anticancer activities [5-8]. Additionally, chromone derivatives are essential, for the synthesis of many important oxygen heterocyclics, pyrazoles and xantones [7].
Fig. 1 Structure of 3-formylchromone
Three new Schiff bases containing 3-formylchromone have been obtained. The first of them were synthesized from 1,4-benzodioxan-6-amine, the second from 1,3-cyclohexanebis(methylamine) and the third from 1,2-diaminobenzene. The used amines have been shown in Fig. 2
The synthesized Schiff bases have been characterized by elemental analysis, FTIR spectroscopy, thermogravimetric and X-ray studies.
Fig. 2 Structure of used amines
Department of General and Coordination Chemistry – 22 –
The analysis of the diffractograms suggests that the ligands are polycrystalline compounds [9]. The structures of the compounds were not determined because their single crystals were not obtained yet. References:
[1] K. El-Baradie, Monatshefte fur Chemie, 136 (2005) 1139. [2] T. Youssef , M. Ramadan and A. Khalifa, Phytochemistry, 8, 49 (1988) 2579. [3] H. Gao, L. Wu, and M. Kuroyanagi, Chinese Chem Letters, 14, 3 (2003) 274. [4] H. Tanaka, M. Hirata, H. Etoh, H. Shimizu, M. Sako, J. Murata, H. Murata,
D. Darnaedi and T. Fukai, Phytochemistry, 62 (2003) 1243. [5] T. Walenzyk, Ch. Carola, H. Buchholz and B. König, Tetrahedron, 61 (2005)
7366. [6] O. Sherif, H. El-Fattah and M. El-Ajily, J Therm Anal Calorim., 74 (2003) 181. [7] V. Arjunan, S. Subramanian and S. Mohan, Spectr Acta, A60 (2004) 995. [8] E. Budzisz, M. Małecka, M. Woźniczka and A. Kufelnicki, J. Mol. Struct. 753
(2005) 113. [9] Z. Bojarski and E. Łągiewka, Rentgenowska analiza strukturalna, PWN,
Warszawa, 1988.
F.Ch. UMCS Report 2009 (BS) – 23 –
SYNTHESIS AND MAGNETIC STUDIES OF d-f HETERONUCLEAR COMPOUNDS WITH SCHIFF BASES
Wiesława FERENC and Beata CRISTÓVÃO DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
The heterometallic copper(II) and lanthanide(III) complexes of 5-bromosalicylideneglycylglycine – H3L (L = C11H8N2O4Br) were synthesized. The formulation of these complexes as:
PrCu3(C11H8N2O4Br)3·13H2O, EuCu3(C11H8N2O4Br)3·13H2O, GdCu3(C11H8N2O4Br)3·13H2O, TbCu3(C11H8N2O4Br)3·13H2O ErCu3(C11H8N2O4Br)3·13H2O YbCu3(C11H8N2O4Br)3·13H2O
follows from elemental and thermal analysis, spectroscopic data (IR) and literature data concerning these type of compounds.
The magnetic behaviour of the title compounds was studied in the temperature range of 76-303 K. For GdCu3(C11H8N2O4Br)3·13H2O complex the magnetic susceptibility changes with temperature according to the Curie-Weiss law and the observed effective moment at 76 K is 9.84µB, while at room temperature it is 9.90µ. This value is higher than the spin only value calculated that the spin–spin interaction is absent between Cu(II) (S = 1/2) and Gd(III) (S = 7/2). A survey of the literature shows that for Cu2Gd compound the spin-only value expected for isolated two Cu(II) and one Gd(III) ions is equal to 8.30µB . Here it should be noted that
Gd(III) is a 4f7 ion with a 8S7/2 ground state with the first excited states very high in energy. As the zero-field splittings of the ground states are fairly small, the spin-only formalism may be applied to the magnetic study of the (Cu–Gd) and (Cu–Gd–Cu) clusters. According to Bencini et al. (in the case of compounds having one gadolinium(III) and two copper(II) ions) if the three spins SGd = 7/2 and SCu1 = SCu1
= 1/2 are allowed to interact, the resulting total spin states are one S = 9/2, one S = 5/2, and two S = 7/2. The calculated spin-only value for S = 9/2 resulting from the ferromagnetic interaction between Cu(II) and Gd(III) ions is 9.95µB. On the basis of literature and obtained values of effective magnetic moment which are in the range 9.58-9.90µB we can suppose that coupling between gadolinium(III) and copper(II) in analysed Cu-Gd compound is ferromagnetic.
One plausible mechanism that cause a ferromagnetic coupling between gadolinium(III) and copper(II) as proposed by C. Benelli et al. and O. Kahn et al. is the spin-polarization, that occurs when the magnetic orbital of copper(II) overlaps with the empty 5d orbital of gadolinium through a filled bridging orbital. The
Department of General and Coordination Chemistry – 24 –
fraction of unpaired electron, thus polarized from copper(II) to gadolinium(III) is parallel to the f electrons due to Hund’s rule, affording a ferromagnetic coupling between copper(II) and gadolinium(III). The fact that 4f orbital is shielded by the outer filled 5s and 5p orbitals, and lanthanoid ions generally form complexes using 6s, and/or 5d orbitals, further supports the spin-polarization mechanism. Indeed, ferromagnetic coupling between gadolinium(III) and copper(II) is possible only through a superexchange interaction mediated by the bridging oxygen ligands. In other words, the magnetic orbitals centered on Gd(III) and Cu(II) must have a fairly large overlap density on the oxygen atom, which can be obtained only through a fairly substantial covalency of the Gd–O bond.
Owing to the difficultes in analysing the magnetic properties of (Cu, Ln) pairs involving a Ln(III) ions, which possesses a first-order orbital moment, we restricted ourselves to consider only (Cu, Gd) complex. Acorrding to J.-P. Costes et al. and O. Kahn et al. for the 4f1–4f6 configurations of Ln3+, angluar and spin moment are antiparallel in 2S+1LJ free-ion ground state (J = L – S) ( where S, L and J, are the spin, orbital and total quantum numbers, respectively). A parallel alignment of the Cu2+ and Ln3+ spin momenta would lead to an antiparallel alignment of the angular momenta, that is to an overall antiferromagnetic interaction. Conversely, for the 4f8–4f13 configurations (J = L + S), a parallel alignment of the Cu2+ and Ln3+ spin momenta would result in an overall ferromagnetic interaction.
References:
[1] A. Bencini, C. Benelli, A. Caneschi, R. L. Carlin, A. Dei, D. Gatteschi, J. Am.
Chem. Soc., 107 (1985) 8128. [2] G. Novitchi, S. Shova, A. Caneschi, J. P Costes, M. Gdaniec, N. Stanica,
Dalton Trans., (2004) 1194. [3] M. Andruh, I. Ramade, E. Codjovi, O. Guillou, O. Kahn, J. C. Trombe, J. Am.
Chem. Soc., 115 (1993) 1822. [4] J.-P. Costes, F. Dahan, A. Dupuis, J. P. Laurent, Chem. Eur. J., 4 (1998) 1616. [5] A. Bencini, C. Benelli, A. Caneschi, A. Dei, D. Gatteschi, Inorg. Chem., 25
(1986) 572. [6] O. Kahn, M. F. Charlot, Nouv. J. Chem., 4 (1980) 567. [7] Y.-T. Li, D. -Z. Liao, Z.-H. Jiang, G.-L. Wang, Polyhedron, 14 (15) (1995)
2209. [8] Y.-T. Li, C.-W. Yan, X.-C. Zeng , Transition Met. Chem., 26 (2001) 110. [9] T. Shiga, M. Ohba, H. Okawa, Inorg. Chem. Comm., 6 (2003) 15.
[10] O. Kahn, Molecular Magnetism, New York, Verlag-Chemie, 1993.
F.Ch. UMCS Report 2009 (BS) – 25 –
CONSTRUCTION AND INVESTIGATIONS OF COORDINATION POLYMERS OF Ln(III) IONS
WITH PYRIDINE-3,5-DICARBOXYLIC ACID
Renata ŁYSZCZEK DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
Metal-organic frameworks (MOFs) have attracted huge attention as a new class of hybrid porous solids. They are promising materials in various industrial fields like: selective gas adsorption (hydrogen, carbon dioxide, methane) and gas separation (notably greenhouse gases), medicine, magnetism and heterogeneous catalysis [1, 2]. Metal-organic frameworks are well characterized crystalline architectures with open-framework structures, which can be self-assembled by the coordination of metal ions with bridging linkers (O or/and N donors). Recently, porous lanthanide-organic frameworks have been constructed because of their light-emitting properties that make them particularly suitable for the devolvement of optical devices and tunable luminescent sensors for chemical species [3, 4].
The aim of this work was to synthesize and investigate the lanthanide pyridine-3,5-dicarboxylate series as novel metal-organic frameworks having interesting structures along with the special luminescence properties. Elementary analysis, TG/DSC, IR, X-ray diffraction methods and luminescence spectra verified the physiochemical properties of the investigated compounds.
The compounds of general formula [Ln2pdc3(dmf)2]⋅nH2O, where Ln = La(III)-Lu(III); pdc- C5H3N(COO)2
2- and n = 3-7 have been prepared by a solvothermal method (140°C, 5 days).
Isostructural character of the studied complexes have been confirmed by the single crystal X-ray diffraction measurements as well as their powder diffraction patterns. The investigated compounds crystallize in the orthorhombic system and Pnma space group. The complexes form a three-dimensional framework built up from pyridine-3,5-dicarboxylate linkers and Ln(III) ions. Additionally, central atom is coordinated by monodentate dmf molecule. The structures possess 1-D channels occupied by delocated water molecules (Fig.1). Fig.1. The 3-D crystal structure of the [Er2(pdc)2(dmf)2]⋅4H2O complex. (The water molecules included in the channels were omitted for clarity).
Department of General and Coordination Chemistry – 26 –
Thermal decomposition of the isostructural series of complexes takes place in the two main steps. The first one is connected with departure of weakly bonded water molecules included in the channels of the frameworks (30-190°C) and coordinated dmf molecules (190-260°C). The complexes of light lanthanides from La(III) to Sm(III) (except neodymium complex) form unstable Ln2pdc3 compounds, remaining complexes form stable in the range 260-450°C desolvated compounds. The second mass loss is connected with the degradation and burning of the desolvated form of complexes. The way of thermal decomposition of the complexes has been confirmed by TG-FTIR spectra of gaseous products released during decomposition. The FTIR spectra show in the temperature range 30-200°C only absorption bands in the wavenumeber range 4000-3500cm–1 and 1800-1300cm–1 attributed to the stretching and deformation vibrations of water molecules. Upon this temperature characteristic bands derived from gaseous dimethylformaide molecules appear. Further heating up to about 450°C leads to carbon dioxide CO2 (2359, 2343cm–1), CO (2177, 2113 cm–1) and some hydrocarbons release. As the final solid products of thermal decomposition of the complexes in the air atmosphere, suitable oxides are formed.
Microporous properties were investigated for selected complexes of heavy lanthanides due to their higher thermal stability. The specific surface area of the complexes [Er2pdc3(dmf)2]·4H2O and [Tm2pdc3(dmf)2]·7H2O were obtained from nitrogen sorption experiments carried out at 77 K using an Autosorb 1CMS Quantachrome analyzer. They show BET surface of 302 and 101 m2/g, respectively.
The luminescence properties of Eu(III) and Tb(III) pyridine-3,5-dicarboxylates have been investigated due to their strong light emission in red and green regions, respectively. The emission spectrum of Eu(III) complex exicted at 339 nm reveals well-resolved magnified luminescence of the f-f transition at 590 nm, 615 nm and 685nm ascribed to the 5Do→
7F1, 5Do→
7F2 and 5Do→7F4 transitions, respectively.
The emission intensities depend on the excitation wavelength. The strong dependence of the luminescent intensity on the excitation wavelength also indicates an energy transfer from the pdc2- to Eu(III) ion. The emission spectrum of Tb(III) complex exited at 372nm shows strong four bands in the region 400-700 nm assigned to the terbium 5D4 →
7F6, 5D4 →
7F5, 5D4 →
7F4 and 5D4 →7F3 transitions.
The broad emission bands in the range 240-400nm would be assigned to the emission of ligand to metal charge transfer (LMCT).
The investigated complexes due to their luminescence properties can be potential used as chemical sensors [4, 5]
References:
[1] J.-R. Li, R.J. Kuppler and H.-C Zhou, Chem. Soc. Rev., 38 (2009) 1477. [2] H. Furukawa and O.M. Yaghi, J. Am. Chem. Soc., 131 (2009) 8875. [3] M.D. Allendorf, C.A. Bauer, R.K. Bhakta and R.J. Houk, Chem. Soc. Rev., 38
(2009) 1330. [4] G. J. McManus, J.J. Perry, M. Perry, B. D. Wagner and M.J. Zaworotko, J.
Chem. Soc., 129 (2007) 9094.
F.Ch. UMCS Report 2009 (BS) – 27 –
SYNTHESIS AND STRUCTURAL INVESTIGATIONS OF COMPLEXES OF SELECTED BIOELEMENTS WITH FERULIC
AND CAFFEIC ACIDS
Liliana MAZUR DEPARTMENT OF GENERAL AND COORDINATION CHEMISTRY
Ferulic acid [3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid] and caffeic acid [3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid) belong to the natural phenolic acids, which we found in many plants i.e. brown rice, wheat, oat, as well as in many fruit. These acids are biologically active substances of low toxicity, which can be absorbed and readily metabolized in human body. They have influence on many physiological functions as antioxidants and as substances which reduce blood pressure.
This study focused on synthesis and structural investigations of new complexes of alkali metals with phenolic acids. The complexes prepared from aqueous solution have general formula Na(K)fer(caf)⋅nH2O. The compounds are stable at room temperature. During heating they loss the water molecules and next decompose to the mixture of sodium carbonate, oxide and peroxide as well as carbon. The IR spectra of complexes point to the coordination through all function groups. Unfortunately, not all crystals obtained during synthesis were suitable for single crystal X-ray analysis. Potassium ions form with ferulic acid complex of the formula [K(fer)2(H2O)]n which crystallizes in the orthorhombic Pna21 space group. This compound form three-dimensional polymer where potassium atoms are coordinated by oxygen atoms of carboxylate, hydroxyl and methoxy group from 3-(4-hydroxy-3-methoxyphenyl)-2-propenoate ligands as well as water molecule. The crystal structure of the complex is stabilized by a network of strong O−H...O and weak C−H...O hydrogen bonds.
Fig. 1. The 3-D structure of [K(fer)2(H2O)]n. Hydrogen atoms were omitted for clarity.
F.Ch. UMCS Report 2009 (BS)
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INVESTIGATION OF SORPTION MECHANISM OF Ga(III) AND In(III) IONS ON POLYMERIC SORBENT IMPREGNATED
BY D2EHPA ACID
Zbigniew HUBICKI and Grzegorz WROŃSKI DEPARTMENT OF INORGANIC CHEMISTRY
The impregnation process of Amberlite XAD-7 and XAD-16 by using D2EHPA acid was carried out. 1 g of Amberlite XAD-7 or XAD-16 was impregnated by using D2EHPA solution in acetone (prepared by disolving 0.3 g D2EHPA – concentration of the solution was 4%). The commercial sorbent was contacted with D2EHPA solution for 6 hours.
The impregnation process was controlled by potentiometeric titration of the solution obtained after the impregnation process by using NaOH titered solution. It was found that the concentration of D2EHPA in Amberlite XAD-7 was 0.2198 g/g and Amberlite XAD-16 – 0.1411 g/g. The surface area (BET), average pore size and average volume of pore for commercial and impregnated sorbents were determined.
For both investigated sorbents, the surface area decreases due to pores plugging by D2EHPA acid in the sorbent. The average size pore after the impregnation process increases which can be interpreted by disappearend micropores plugged by D2EHPA acid. (Fig. 1)
47,48
108,44
0 20 40 60 80 100 120
Amberlite XAD 7
Amberlite XAD 7+ D2EHPA
Å
Fig. 1. Comparison of average pores size for Amberlite XAD-7 and Amberlite XAD-7 impregnated by D2EHPA acid.
The photoacoustic spectra FT-IR/PAS were recorded for the commercial and impregnated by D2EHPA sorbents. No differences are observed before and after the impregnation process which can be related with the fact that characteristic stretching and deformity vibrations in impregnated Amberlite XAD-7 spectum for P=O, P-O-C i P-O-H groups occur at 1234 cm–1, 1043 cm–1, 1610 cm–1 wavelengths. This may be due to the fact that the peaks originating from the
Department of Inorganic Chemistry
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vibration of the skeleton XAD-7 (polyester skeleton) overlap with those originating from D2EHPA [1]. The characteristic stretching and deformity vibrations in the impregnated Amberlite XAD-16 spectrum for P=O, P-O-C groups occur at 1238 cm–1, 1037 cm–1 wavelengths and are well visible. Other characteristic vibrations for D2EHPA cover those of polystyrene skeleton.
The kinetic studies and influence of pH on the soprtion process were carried out on the impregnated polymeric sorbent. After 15 min the equilibrium between the water solution and the solid phase was achieved.
The largest value of the recovery factor – 49.48 % for Ga(III) ion was observed at pH 1.5. The largest value of the recovery factor – 71.2 % for In(III) ion was observed at pH 1.83. The isotherms of Ga(III) and In(III) sorption were obtained. The sorption capacities were:
– for Amberlit XAD-7 – Ga(III) 20 mg/g(Fig. 2); – for Amberlit XAD-7 impregnated by D2EHPA – Ga(III) 180 mg/g(Fig. 2); – for Amberlit XAD-16 – Ga(III) 10,4 mg/g; – for Amberlit XAD-16 impregnated by D2EHPA – Ga(III) 21.5 mg/g; – for Amberlit XAD-7 – In(III) 81 mg/g; – for Amberlit XAD-7 impregnated by D2EHPA – In(III) 236 mg/g; – for Amberlit XAD-16 – In(III) 38 mg/g; – for Amberlit XAD-16 impregnated by D2EHPA – In(III) 49.7 mg/g.
Fig. 2. The isotherms of Ga(III) sorption: Amberlite XAD-7 and Amberlite XAD-7 by impregnated D2EHPA.
It was stated that it is not possible to determine the mechanism of Ga(III) i In(III) sorption on the investigated polymeric sorbents, based on the investigations. As follows from literature to the equation process of In(III) ion sorption in the similar model is according In3+
w. + 3(HR)2org. → InR3org. · 3HR + 3H+w. where:
w. – water phase, a org. – the organic phase[2].
References:
[1] D. Darvishi et al., Hydrometallurgy, 77 (2005). [2] Казанбаев Л. А. и др., „Индий Тєхнологии Получэния”, Руда и Металли, Москва 2004.
F.Ch. UMCS Report 2009 (BS)
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AGENT OF THE NEW GENERATION BAYPURE CX 100 IN THE SORPTION OF THE HEAVY METAL IONS ON ION
EXCHANGERS OF THE DIFFERENT TYPE
Dorota KOŁODYŃSKA and Zbigniew HUBICKI DEPARTMENT OF INORGANIC CHEMISTRY
Industrial development has lead to a drastic increase of heavy metal concentrations in the environment. Except for heavy metal ions, synthetic organic metal-sequestering ligands such as aminopolycarboxylic acids (mainly ethylenediaminetetraacetic acid, EDTA and nitrilotriacetic acid, NTA) are also present in various wastewaters. Their presence is associated, among others, with their application in pulp and paper, textile, metalurgical, food, cosmetics, pharmaceutical and agricultural industries. EDTA and DTPA have proven to be practically non-biodegradable in standard tests. The available data suggest that EDTA and its salts are not generally removed during wastewater treatment [1-3]. Increasing concern about the direct or indirect potential effects of the presence of the above mentioned complexones in the environment that is: mobilization of contaminant metal ions adsorbed in sediments; solubilization of radioactive metal ions and increase of their environmental mobility; contribution to eutrophication water processes (e.g. the EDTA molecule contains approximately 10% of nitrogen that could eventually be available to the aquatic microbiota and redissolves calcium and ferrium phosphates, releasing phosphorous); the ligand-metal complexes may significantly increase the bioavailability of extremely dangerous heavy metals, for example Cu(II)-EDTA and Cd(II)-EDTA complexes which are more toxic than their respective free metals cause, that these complexons are nowadays replaced by modern agents sufficiently biodegradable or eliminable.
Therefore, the aim of this study was to explain the influence of chemical conditions on the ion exchange capacity and on the kinetics of copper(II), cobalt(II) nickel(II) and iron(III) in the presence of the complexing agent of a new generation that is sodium salt of N-(1,2-dicarboxyethyl)-D,L-aspartic, which has the commercial name Baypure CX 100. Its chemical structure is presented in Fig.1
In the studies there was applied the ion exchange which is a method used in water treatment and wastewater purification. This method is suitable for removal of all contaminants in the ionic form also including heavy metal ions in the presence of complexing agents from different systems. The following medium and weakly
HOOC
HOOC
COOH
COOHNH
IDSFig. 1. The chemical structure of IDS.
Department of Inorganic Chemistry
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basic anion exchangers Lewatit MonoPlus MP 64, Lewatit MP 62 as well as strongly basic anion exchanger Amberlite IRA 402 were used in the investigations.
A series of experiments was conducted to optimise the method for the their removal from industrial effluents. It was found that the sorption efficiency of strongly, medium as well as weakly basic anion exchangers varied depending on metal ions concentration, pH, contact time, agitation, temperature and properties of anion exchangers such as their form. From the determined breakthrough curves the distribution coefficients (Dg) and (Dv), the ion exchange capacities (Cw, Ct) and the time required for the moving the exchange zone (tz) as well as the total time required for the formation of exchange zone (tT) were calculated. The exemplary results obtained for Lewatit MonoPlus MP 64, Lewatit MP 62 are presented in Figs. 2 and 3.
The largest percentages of heavy metal complexes with IDS removal were found for the strongly basic anion exchanger (up to 98 % for Cu(II), 82 % for Fe(III), 67 % for Ni(II) and 55 % for Co(II)). Satisfactory results were also obtained for medium and weakly basic anion exchangers. Besides, a kinetic procedure was developed to study the kinetics of anion exchange. Two different kinetic behaviours were tested for the investigated systems.
References:
[1] O. Gyliene, T. Vengris, A. Stončius, O. Nivinskiene, J. Hazard. Mater., 159 (2008) 446.
[2] M. Sillanpää, J. Rämö, Chemosphere, 45 (2001) 881. [3] D. Kołodyńska, H. Hubicka, Z. Hubicki, Desalination, 239 (2009) 216.
0 2 4 6 8 10 12 140
20
40
60
80
100
pH
Rec
ov
ery
fa
ctor
(%)
IRA 402 MP 64 MP 62
Fig. 2. The effect of pH on the Cu(II) complexes with IDA sorption on Amberlit IRA 402, Lewatit MonoPlus MP 64 and Lewatit MP 62 (c0 1·10–3 mol/L, anion exchan-ger concentration of 10 g/dm3, t = 2h, agitation speed 180 rpm).
0 50 100 1500
20
40
60
80
100
Rec
ov
ery f
act
or
(%)
Cu(II) Fe(III) Co(II) Ni(II)
t [min]
Fig. 3. Comparison of the recovery factor (% R) values for Cu(II), Co(II), Ni(II) and Fe(III) complexes with IDS on Amberlite IRA 402 depending on the phase contact time (0.5 g of the anion exchanger, initial concentration 1·10–3 M).
F.Ch. UMCS Report 2009 (BS)
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APPLICATION OF GEL AND MACROPOROUS STRONGLY BASIC
ANION EXCHANGERS IN ACID BLUE 29 REMOVAL FROM AQUEOUS SOLUTIONS
Monika WAWRZKIEWICZ and Zbigniew HUBICKI
DEPARTMENT OF INORGANIC CHEMISTRY Introduction
Since the environmental pollutions are increasing day-by-day, the need to reduce the impurities particularly in wastewaters of textile industry is important. The textile sewages contain not only dyes but also detergents, grease, oils, solvents and inorganic salts. Of them colour removal is of significant importance. Literature about removal of dyes using such sorbents as ion exchange resins is very scare.
The aim of this paper was, therefore, to study the applicability of the commercially available gel (Purolite A-850) and macroporous (Purolite A-520E) strongly basic anion exchangers for removal of Acid Blue 29 (AB29) from aqueous solution. The structure of Acid Blue 29 is presented in Fig. 1.
NO2N
N
SO3Na
N
NH2
OH
NaO3S
N
Fig. 1. Acid Blue 29 (C22H14N6O9S2Na2) structure.
The sorption capacities of the anion exchangers for Acid Blue 29 were investigated by determining the equilibrium isotherms. Kinetic studies were carried out taking the initial dye concentration in the range 100-500 mg/L into account. The experimental data were analyzed using the pseudo-first and second order kinetic models as well as the intraparticle diffusion equation. The effects of phase contact time, temperature and solution pH on the dye adsorption were examined, too.
Results and discussion
Purolite A-520E of the quaternary ammonium functional groups showed high sorption capacities (qt) towards Acid Blue 29, ranging from 9.9 to 48.2 mg/g when the initial concentration of dye changed from 100 to 500 mg/dm3. It was found that qt values determined for the gel anion exchanger were lower compared with those obtained for the macroporous anion exchanger. The equilibrium was reached after 60 min and 40 min of phase contact time for Purolite A-520E and A-850, respectively.
The fitting of sorption of Acid Blue 29 on the strongly basic anion exchangers was investigated by three common isotherm models, namely, the Langmuir,
Department of Inorganic Chemistry
– 34 –
Freundlich, as well as Temkin model. The applicability of isotherm equations was compared by estimation of the correlation coefficients. It was found that Acid Blue 29 sorption on Purolite A-520E and AC-20G was well described by Langmuir isotherm (Table 1).
Table 1. Values of isotherm parameters for removal of Acid Blue 29 from aqueous solution using the strongly basic anion exchangers.
Parameters Isotherm model
Purolite A-850 Purolite A-520E
Langmuir Q0 [mg/g] b [ L/mh]
RL
R2
83.3 0.921 0.047 0.999
321.5 0.003 0.065 0.889
Freundlich KF [mg/g]
n
R2
46.3 10.4 0.611
21.4 4.4
0.835
The rate constants k1 were calculated according to Langergren pseudo-first order rate expression from the slopes of the log(qe-qt) vs. t plots taking into account AB29 initial concentration. It was noticed that k1 decreased with the increase in the initial dye concentration, some deviations were observed for the solution containing 500 mg/dm3 of AB29. The correlation coefficients were high, ranging from 0.937 to 0.996 and from 0.983 to 0.999 for the anion exchangers of polystyrene and polyacrylic matrix, respectively. However, the calculated equilibrium capacities qe,cal were in good agreement with the values of experimental capacities qe,exp for solutions of the initial concentrations: 100-500 mg/dm3, the better results were obtained using the pseudo-second order equations. The high values of r2 (≈ 0.999) confirm that the sorption process follows a pseudo-second order mechanism. It is generally assumed that a sorption process that fits the pseudo second-order kinetic model is the one controlled by chemisorption.
The influence of temperature on Acid Blue 29 sorption by Purolite A-520E and A-850 was studied with the constant initial concentration of 200 mg/dm3. The equilibrium sorption capacity increased when the temperature of dye solution increased from 20 to 50°C for both anion exchangers. Decrease in sorption capacity of Purolite A-520E with the increasing initial solution pH was observed. The same effects of temperature and solution pH were observed for Purolite A-850. Conclusion
The studied anion exchangers can be presented in the following series:
Purolite A-520E > Purolite A-850
as far as their application is concerned in the removal of this dye from wastewaters.
F.Ch. UMCS Report 2009 (BS)
– 35 –
INVESTIGATION OF ARSENIC(III AND V) SORPTION ON LIQUID
ION EXCHANGERS IMPREGNATED RESINS
Zbigniew HUBICKI and Grzegorz WÓJCIK
DEPARTMENT OF INORGANIC CHEMISTRY
Arsenic is mobilized by natural weathering reactions, biological activity, geochemical reactions, volcanic emissions and other anthropogenic activities. Soil erosion and leaching contribute to 612×108 and 2380×108 g/year of arsenic, respectively, in dissolved and suspended forms in the oceans. Arsenic exists in the −3, 0, +3 and +5 oxidation states. Two forms are common in natural waters: arsenite (AsO3
3−) and arsenate (AsO43−), referred to as arsenic(III) and arsenic(V).
Pentavalent (+5) or arsenate species are AsO43− , HAsO4
2− , H2AsO4− whereas
trivalent (+3) arsenites include As(OH)3, As(OH)4 −, AsO2OH2
− and AsO33− .
Pentavalent species predominate and are stable in oxygen rich aerobic environments. Trivalent arsenites predominate in moderately reducing anaerobic environments such as groundwater. Long term drinking water exposure causes skin, lung, bladder, and kidney cancer as well as pigmentation changes, skin thickening (hyperkeratosis) neurological disorders, muscular weakness, loss of appetite, and nausea.
The aim of these studies was to prepare the solvent impregnated resin and then sorption of arsenic(V) ions from water solution in the pH range from 1 to 14.
Impregnation of an organic extractant into a polymeric support offers several advantages over common extraction systems, eg.:
– impregnated resins combine solvent extraction and ion exchange technologies, providing the selectivity characteristics of dissolved extractants with the operational simplicity of solid ion exchange equipment such as fixed bed columns and fluidised beds,
– the ease of phase separation due to the elimination of problems dealing with the formation of stable emulsions,
– the ease of solvent impregnated resin preparation, – the wide choice of reagents of desired selectivity, – the support resins are ideally macroporous organic polymers with a high
surface area and good mechanical stability, flow characteristics and have solvent swelling during the impregnation process [1].
The resin Amberlite XAD-7 HP and the liquid ion exchanger Aliquate 336 have been used in the impregnation processes. Aliquate 336 is an extractant which contains nitrogen donor atoms. Aliquat 336 is a trioctylmethylammonium chloride (Sigma-Aldrich) with the molecular formula shown in Figure 2. Amberlite XAD-7 HP is a commercial resin (Rohm & Haas Co., France) with a macroporous structure (Fig. 1).
Department of Inorganic Chemistry
– 36 –
H2C CCH2C
CH3H2C C
H2C
CH3 CH3
C C CO
O O
O
O
O
R1 R R1
O
C
C
OH2C
H2C
CH3
CH2CC
H2C
CH3
C C
CH3
O O
O O
R1 R1
Fig. 1. The parts of skeleton of Amberlite XAD-7 HP.
Fig. 2. The molecular formula of Aliquat 336.
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400
Time [min]
%R
pH1
pH4
pH8
pH12
Fig. 3. Effect of contact time on recovery factors of arsenic(V) ions in the pH range 1-14 on Amberlite XAD 7 HP impregnated using Aliquat 336.
Amberlite XAD-7 HP impregnated using Aliquat 336 is suitable for sorption of arsenic (V) ions. Sorption depends on the pH value. With the increasing pH sorption of arsenic ions increases. In the pH range 8-14 values of recovery factors are near 100%. Moreover the kinetics of sorption is very fast, it is a very important factor during purification of water in the column process. There is no sorption in the pH range 1-4, it can be related with the fact that arsenic ions exist in the H3AsO3 form.
References:
[1] B. Saha, R.J. Gill, D.G. Bailey, N. Kabay, M. Arda, Reac. and Func. Polym., 60 (2004) 224.
NH2C
H2C
CH2
(CH2)5
(H2C)5
CH2
H2C CH3
H3C
(H2C)5H2CH3C
CH3
+
Cl-
F.Ch. UMCS Report 2009 (BS)
– 37 –
SYNTHESIS AND PROPERTIES OF TRANSPARENT SILICA GELS
DOTTED WITH OCTAETHYLPORPHYRINE
Marek MAJDAN, Magdalena MAKARSKA-BIAŁOKOZ and Agnieszka GŁADYSZ-PŁASKA
DEPARTMENT OF INORGANIC CHEMISTRY
2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine (H2OEP) was encapsulated
in transparent monolithic silica gels by sol-gel polymerization of tetraethylortosilicate [1]. TEOS was polymerized through hudrolysis and condensation. Hydrochloric acid and ammonia were used as hydrolysis and condensation catalysts respectively. Five parallel series of the sols were prepared with the concentrations of porphyrine ranging from 0.000001 to 0.00002 M. The plastic cells were sealed with a parafilm and the gelation was achieved after 3 days. After one month the parafilm was treated with needle to enable slow evaporation of the solvent during monolith drying. The obtained alcogels have a structure penetrated by EtOH and water. In the first perion wet gels were dried in a desiccator over a water at 400C during 3-4 weeks. Then the parafilm was removed and drying was continued until the shrinking of monoliths.
Fig. 1. UV-VIS spectrum of octaethylporphyrine encapsulated in silica gel (period of condensation: 4 months)
A
λ nm
Department of Inorganic Chemistry
– 38 –
The typical spectrum of porphyrine encapsulated in silica gel is shown on Fig.1. There is remarkable decrease of the Soret band intensity with the increase of porphyrine concentration, which is the result of porphyrine aggregation. The Q band has four components and its evolution in this range of concentrations and after the period of 4 months condensation is typical for free unprotonated porphyrine form. For longer periods of condensations (Fig.2), i.e. for 6 months, the Q band was dramatically changed and merely 2 components were observed, which fact is in our opinion the evidence for the protonation of porphyrine and formation of so-called dications. Apart from that the Soret band is broadened as a result of the different forms of polymerized dications formed in gel.
Fig. 2. The UV-VIS spectrum of octaethylporphyrine (concentration 0.00002 M.) after 6 months of condensation .
References:
[1] M. Trytek, J. Fiedurek, A. Lipke, S. Radzki, J. Sol-Gel Sci Technol., 51 (2009) 272.
λ nm
A
F.Ch. UMCS Report 2009 (BS)
– 39 –
THE INFLUENCE OF THE COMPLEXATION ON THE LANTHANIDES ADSORPTION ON THE ZEOLITE A AND Y
Marek MAJDAN, Agnieszka GŁADYSZ-PŁASKA
and Magdalena MAKARSKA-BIAŁOKOZ DEPARTMENT OF INORGANIC CHEMISTRY
The tetrad effect in the lantahnide chemistry discovered by Fidelis and Siekierski on the one side [1] and by Peppard on the other side [2] is based on the periodical changes of the physical and chemical properties of the lanthanide compounds with the division of the lanthanide family into four subgroups: La-Nd, Pm-Gd, Gd-Ho, Er-Lu. The effect was explained from the viewpoint of the bonding energy changes in lanthanide ions-ligands interaction, i.e. taking into account of ligand field theory and the change of Racah parameters of interelectronic repulsions in the lanthanide ions. In the recent papers we have shown the periodicity in lanthanides adsorption on the mordenite [3] and zeolite Y [4]. The experiments were conducted from nitrate media and we have concluded that the Ln-O bond for the lanthanide complexes existing in the aqueous phase is more covalent in character than those one for the complexes in the zeolite phase.
The aim of this paper is to compare the lanthanides adsorption behaviour in chloride and nitrate media, i.e. its influence of the shape of tetrad effect.
The Fig.1. reveals the change of the lanthanide distribution constants logKd to the zeolite A phase from chloride and nitrate media. For adsorption conducted from chloride media the tetrad effect is convex in nature contrary to the nitrate media case [5], where the change from convex to concave effect is observed in La-Nd and Er-Lu tetrads. For the adsorption of the lanthanides on the zeolite Y the tetrad effect is convex for 2M NaCl and concave for its lower concentrations.
One can conclude that there is essential difference between the lanthanides complexation by Cl- and NO3
- ions. The covalency of Ln-O bond in nitrato complexes is stronger than those one in of Ln-Cl bond in chloride complexes and as a result we can observe exlusively convex tetrad effect in the lanthanides adsorption from chloride media for the zeolite A. Our result is the first one showing the real difference between the lanthanide nitrato and chloride complexes, which up to date were recognized as weak outer sphere complexes with similar stability constants change in the lanthanide series. References:
[1] S. Siekierski, Pol. J. Chem., 66 (1992) 215. [2] D.F. Peppard, G.W. Mason, S. Lewey, J. Inorg. Nucl. Chem., 31 (1969) 2271. [3] A. Gładysz-Plaska, M. Majdan, S. Pikus, J. Colloid Interf. Sci., 317 2 (2008)
409.
Department of Inorganic Chemistry
– 40 –
z e o l i te A - N a C l
L a C e P r N d P m S m E u G d T b D y H o E r T m Y b L u
log
Kd
-1 ,0
-0 ,5
0 ,0
0 ,5
1 ,0
1 ,5
2 ,0
0 ,0 0 1 M N a C l
0 ,0 1 M N a C l
0 ,1 M N a C l
1 ,0 M N a C l
2 ,0 M N a C l
z e o li te A - N a N O3
L a C e P r N d P m S m E u G d T b D y H o E r T m Y b L u
log
Kd
- 1 ,0
-0 ,5
0 ,0
0 ,5
1 ,0
1 ,5
0 ,0 0 1 M N a N O 3
0 ,0 1 M N a N O 3
0 ,1 M N a N O 3
1 ,0 M N a N O 3
2 ,0 M N a N O 3
Z e o li te Y - N a C l
L a C e P r N d P m S m E u G d T b D y H o E r T m Y b L u
log
Kd
- 1 ,5
-1 ,0
-0 ,5
0 ,0
0 ,5
1 ,0
1 ,5
2 ,0
2 ,5
0 ,0 0 1 M N a C l
0 ,0 1 M N a C l
0 ,1 M N a C l
1 ,0 M N a C l
2 ,0 M N a C l
Z e o lite Y - N a N O3
L a C e P r N d P m S m E u G d T b D y H o E r T m Y b L u
log
Kd
- 2 ,0
-1 ,5
-1 ,0
-0 ,5
0 ,0
0 ,5
1 ,0
0 ,0 0 1 M N a N O 3
0 ,0 1 M N a N O 3
0 ,1 M N a N O 3
1 ,0 M N a N O 3
2 ,0 M N a N O 3
[4] A. Gładysz-Płaska, M. Majdan, S. Pikus, W. Lewandowski, J. Colloid Interf.
Sci., 313, 1, (2007), 97. [5] M. Majdan, A. Gładysz-Płaska, S. Pikus, D. Sternik, O. Maryuk, E. Zięba, P.
Sadowski, J. Mol. Struct., 702 (2004) 95.
Fig. 1. The change of the lanthanide distribution constants in Ln(NO3)3, LnCl3- zeolite Y, zeolite A systems (0.1 g zeolite, 100 ml aqueous phase, temperature 23°C).
F.Ch. UMCS Report 2009 (BS) – 41 –
INFLUENCE OF TERTBUTANOL AND BASE ELECTROLYTE CONCENTRATION ON THE KINETICS AND MECHANISM OF Zn2+
IONS ELECTROREDUCTION
Dorota GUGAŁA-FEKNER, Dorota SIEŃKO, Jolanta NIESZPOREK and Jadwiga SABA
DEPARTMENT OF ANALYTICAL CHEMISTRY AND INSTRUMENTAL ANALYSIS
A study on the influence of mixed adsorption layers which were composed of two organic substances on Zn2+ ions reduction at mercury electrolyte was conducted. The first one i. e. tetramethylthiourea (TMTU) underwent chemical adsorption [1] and the other i.e. tertbutanol (TB) a physical adsorption [2]. A study on the kinetics and mechanism of Zn2+ ion electroreduction enabled to observe the equilibrium of the adsorption-desorption processes at potentials beyond the area of maximum adsorption. The mentioned above studies were carried out in 0.1M, 0.5M and 1.0M NaClO4.
Fig. 1 presents the cyclic voltammetric curves for Zn2+ electroreduction in 1.0M NaClO4 in the presence of 5.10–4M TMTU and TB.
Fig. 1. The dependence of I = f(E) in cyclic voltammetry for systems: 1.0M NaClO4 + 5.10–3M Zn2+ + 5.10–4M TMTU + TB.
Department of Analytical Chemistry and Instrumental Analysis – 42 –
An introduction of 5.10–4M TMTU into a solution containing 1.0M NaClO4 + Zn2+ caused an increase of anodic and cathodic peaks height and simultaneously led to their gathering closer. However the addition of TB lowered the heights of these peaks and caused their extension along the potentials axis. The differences between anodic and cathodic peaks, ∆E are presented in Table 1. Table 1. The difference between anodic and cathodic peaks ∆E/V for systems NaClO4 + 5.10–3M Zn2+ + 5.10–4M TMTU + TB.
∆E/V cTB/M
0.1M NaClO4 0.5M NaClO4 1.0M NaClO4 0 0.067 0.069 0.083
0+TMTU 0.065 0.058 0.058 0.05 0.065 0.058 0.058 0.10 0.069 0.058 0.056 0.20 0.069 0.069 0.056 0.30 0.071 0.077 0.083 0.40 0.083 0.115 0.115 0.50 0.107 0.147 0.145
Results presented in Table 1 indicate the strongest TMTU and TB adsorption
at Zn2+ reduction potentials in 1.0M NaClO4. It may therefore be concluded that the adsorptions size calculated for maximal potentials adsorption may be extrapolated for more distant potentials.
References:
[1] D. Gugała, Z. Fekner, D. Sieńko, J. Nieszporek, J. Saba, Elektrochim. Acta, 49 (2004) 2227
[2] D. Gugała, J. Nieszporek, Z. Fekner, D. Sieńko, J. Saba, Ann. Pol. Chem.
Soc., 3 (2004) 896.
F.Ch. UMCS Report 2009 (BS) – 43 –
ELIMINATION OF INTERFERENCES IN SLURRY SAMPLING GFAAS MEASUREMENTS
Ryszard DOBROWOLSKI
DEPARTAMENT OF ANALYTICAL CHEMISTRY AND INSTRUMENTAL ANALYSIS
The slurry sampling technique is today a well-established methodology for direct determination of trace metals in solid samples using electrothermal atomic absorption spectrometry. This methodology simplifies sample pretreatment, reduces sample preparation time and minimizes the risk of contamination and analyte losses caused by an incomplete release of the analyte from the solid. Moreover, this method enables study of the micro-heterogeneity of solid material.
With the introduction of the concept of the stabilized temperature platform furnace (STPF), the use of modifiers has become an essential part of electrothermal atomic absorption spectrometry. The main purpose of chemical modifiers is either to stabilize the analyte thermally or increase the volatility of the matrix. Hence, the bulk of the matrix may be removed, by volatilization or decomposition, during the pyrolysis step, prior to atomization of the analyte. Permanent modifiers have been successfully applied to the analysis of real samples in ETAAS in recent years, leading to several benefits in comparison to conventional modifiers. The main observed advantages are: lowering modifier blanks due to elimination of volatile impurities during graphite treatment, better detection limits, longer signal term stability and faster heating programs. A procedure of permanent chemical modification consist of the introduction of several aliquots of the chemical modifier solution into the graphite tube, followed by stepwise drying-pyrolysis, obtaining a coating of the chemical modifier thermally deposited on the graphite surface [1,2]. During this treatment, the volatile impurities such as chlorides are eliminated. However interferences caused by sulfates, silica, alumina, iron oxides are difficult to eliminate. Application of permanent modifiers can simplify species during atomization step and remove partly interferences.
The aim of this study was the elimination of the interferences during the investigation of atomization mechanism of strontium and barium in marine sediment, soil and biological samples by slurry sampling GFAAS technique with the application of niobium and iridium as permanent modifiers. At the first step in this investigation the optimum masses of niobium and iridium modifiers for Sr and Ba determination were established. In case of barium determination, the use of iridium as a permanent modifier didn’t ensure reproducible results. For this reason iridium isn’t recommended as a modifier for barium determination. The optimal amounts of niobium for Sr and Ba determination were 8 µg and 20 µg, respectively. Although covering the tube with niobium didn’t enhance significantly the signals of Sr and Ba but it prevented from the corrosion of the tube, which was connected with the hydrolysis of barium and strontium carbides. Strontium and barium
Department of Analytical Chemistry and Instrumental Analysis – 44 –
atomization mechanisms have been studied by examination of pyrolysis and atomization curves. In the Fig. 1 and 2 pyrolysis and atomization curves for strontium in biological material (slurry of rat’s bones powdered) are shown. The optimal temperatures of pyrolysis and atomization for strontium are: 1400°C and 2600°C, respectively. In the Fig. 3 and 4 pyrolysis and atomization curves for barium in soil NCS DC 73398 are shown. The optimal temperatures of pyrolysis and atomization for barium are: 1200°C and 2500°C, respectively. The practical application of niobium permanent modifiers for Sr and Ba determination in marine sediment, soil and biological samples using slurry sampling GFAAS technique were particularly studied. Certified reference materials: soil NCS DC 73398 (NCS) and sediment PACS-1 (IAEA) were used for validation of analytical procedures. The good agreement for Sr and Ba determination were achieved between the results obtained by slurry sampling GFAAS technique and certified values for studied CRMs. The developed methodology was used to determine Sr and Ba in ‘real’ samples prepared from BSS Baltic sediment collected by National Institute of Geology (Warsaw, Poland) and for biological material (bones of rat).
0
0.1
0.2
0.3
0.4
0.5
400 800 1200 1600 2000Temperature [°C]
Ab
so
rban
ce
integrated absorbance maximum absorbance
0
0,2
0,4
0,6
0,8
1500 1700 1900 2100 2300 2500 2700
Temperature [°C]
Ab
so
rba
nc
e
integrated absorbance maximum absorbance
Fig. 1. Ashing curves for 0.20 ng of strontium in biological material for graphite tube modified with optimal amount of niobium.
Fig. 2. Atomization curves for 0.20 ng of strontium in biological material for graphite tube modified with optimal amount of niobium
0
0,1
0,2
0,3
200 600 1000 1400 1800
Temperature [°C]
Ab
so
rba
nc
e
integrated absorbance maximum absorbance
0
0,1
0,2
0,3
0,4
0,5
1800 2000 2200 2400 2600
Temperature [°C]
Ab
so
rba
nc
e
integrated absorbance maximum absorbance
Fig. 3. Ashing curves for 0.28 ng of barium in CRM NCS DC 73398 for graphite tube modified with optimal amount of niobium.
Fig. 4. Atomization curves for 0.28 ng of barium in CRM NCS DC 73398 for graphite tube modified with optimal amount of niobium
References:
[1] A.B. Volynsky, Spectrochim. Acta part B, 55 (2000) 103. [2] A.B. Volynsky, Spectrochim. Acta part B, 53 (1998) 1607.
F.Ch. UMCS Report 2009 (BS) – 45 –
TRACE METALS ENRICHMENT FROM ENVIRONMENTAL SAMPLES BY APPLICATION OF MODIFIED ACTIVATED
CARBONS
Ryszard DOBROWOLSKI DEPARTAMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
Chromium occurs in natural and industrial water as a result of electroplating, leather tanning, textile industries, sanitary landfill leaching and water-cooling towers in two oxidation states: trivalent Cr(III) and hexavalent Cr(VI). Cr(III) is considered as a essential trace nutrient for human, which has an imported role in the glucose, lipid, protein and cholesterol metabolism, while Cr(VI), in turn, is highly toxic. It can damage the human physiological, neurological and biological systems, being also a source of various cancer diseases [1]. Owing to the different toxicities of Cr(VI) and Cr(III), there is a great interest in the speciation and determination of chromium species in environmental matrices. The concentration of chromium in natural waters is very low, about a few µg l-1and thus preconcentration and separation steps are frequently required to improve the detection limits of many analytical techniques.
Several procedures have been used for the preconcentration and separation of Cr(VI) from Cr(III) species, e.g. ion exchange, precipitation and co-precipitation, chelation, extraction, electrolysis and activated carbon adsorption [2]. Adsorption of heavy metals onto activated carbons is found to be the most effective for separation and enrichment of trace metals from aqueous solutions because of their extended surface area, microporous structure, high adsorption capacity and high degree of surface reactivity. However, the chemical nature of activated carbons determined by the amount and nature of surface functional groups is more important. The surface of activated carbons can be easily modified in various ways, e.g. by treatment with solutions of acids and alkalis resulting in increasing the amount of alkaline and acidic groups of carbon’s surface, impregnation with metal salts or outgassing treatment at high temperature (above 1100ºC), resulting in the removal of surface functional groups and the change in anions-exchange capacity [3].
The aim of this study was the evaluation of possibilities of application of modified activated carbons for separation and enrichment of Cr(VI) from aqueous solutions. For this purpose modifications of medical activated carbon (C*) by treatment with concentrated HNO3 solution (OC*) and outgassing treatment at high temperature (OGC*) were proposed. The basic parameters affecting the adsorption capacity of chromium on modified activated carbons were studied (Fig. 1). The influence of some interferent ions and kinetics study are shown in Fig. 2 and Fig. 3, respectively. The effect of modifications of activated carbons has been determined by setting the initial runs of adsorption isotherms (Fig. 4). The mechanism of adsorption of chromium on modified activated carbons was studied. It was stated
Department of Analytical Chemistry and Instrumental Analysis – 46 –
that reduction Cr(VI) to Cr(III) and further surface precipitation to Cr(OH)3 on OC* and ion exchange in case of OGC* are the main adsorption mechanisms of chromium onto these modified activated carbons. The desorption studies showed that the adsorption of chromium on these adsorbents is irreversible and the best way of determination of Cr(VI) after its preconcentration would be the application of slurry sampling graphite furnace atomic absorption spectrometry technique.
Fig. 1. pH influence on Cr(VI) adsorption onto modified activated carbons, m = 0.2 g, V =50 cm3, CCr(C*) = 0.26 mg/dm3, CCr(OC*) = 2.60 mg/dm3, CCr(OGC*) = 1.20 mg/dm3, t = 3h, T = 25°C.
Fig. 2. The influence of NO3– on Cr(VI)
adsorption onto modified activated carbons, m = 0.2 g, V = 50 dm3, pH optimal, CCr(C*) = 2.60 mg/dm3, CCr(OC*) = 14.50 mg/dm3, CCr(OGC*) = 5.20 mg/dm3, t = 3h, T = 25ºC.
Fig. 3. Adsorption kinetics of Cr(VI) onto modified activated carbons, m = 0.2 g, V = 50 dm3, pH optimal, CCr(C*) = 0.26 mg/dm3, CCr(OC*) = 2.60 mg/dm3, CCr(OGC*) = 1.20 mg/dm3, t = 3h, T = 25ºC.
Fig. 4. Initial runs of adsorption isotherms of Cr(VI) onto modified activated carbons, m = 0.2 g, V = 50 cm3, pH optimal, t = 3h, T = 25ºC.
References:
[1] J.O. Nriagu, E. Niebeor (Eds.), Chromium in Natural and Human Environment,
Wiley, New York, 1988. [2] S. Latva, J. Jokiniemi, S. Peraniemi, M. Ahlgren, J. Anal. At. Spectrom.,18
(2003) 84. [3] R. Dobrowolski, chapter: Application of Activated Carbons for the Enrichment
of Toxic Metals and their Determination by Atomic Spectroscopy. in: Adsorption and its Application in Industry and Environmental Protection. Dąbrowski A. (Ed.), Elsevier, Amsterdam (1998) 777-806.
F.Ch. UMCS Report 2009 (BS) – 47 –
DETERMINATION OF TRACE OF COBALT(II) IN COMPLEX MATRICES BY ADSORPTIVE STRIPPING VOLTAMMETRY
Mieczysław KOROLCZUK, Katarzyna TYSZCZUK and Małgorzata GRABARCZYK
DEPARTMENT OF ANALYTICAL CHEMISTRY AND INSTRUMENTAL ANALYSIS
Electrochemical methods, especially, adsorptive stripping voltammetry (AdSV) are known as simple, sensitive and inexpensive. For determinations of Co(II) in complex matrices by AdSV usually mercury electrodes were used. The disadvantage of mercury electrodes is the toxicity of mercury, so bismuth film [1] and thick film graphite electrodes were also applied recently to Co(II) determination in complex matrices. In this communication a lead film electrode was used for Co(II) determination by AdSV in complex matrices. The procedure proposed exploits the enhancement effect of a cobalt peak observed in the system Co(II) – nioxime – PIPES – CTAB. Due to the fact that at a lead film electrode Ni(II) and Co(II) signals are better separated than at other electrodes [2], the interference of Ni(II) present in the samples was eliminated. The interference of surfactants was also minimised because the presence of cationic surfactant CTAB was necessary to observe the enhancement effect of a Co(II) peak. To obtain a low detection limit of Co(II) determinations an optimisation of parameters influencing film formation and accumulation of Co(II) complexes with nioxime was performed.
In the standard procedure of measurement an aliquot of the analysed sample was pippeted into the electrochemical cell and triply distilled water was added to the volume 9.44 cm3. Then 0.5 ml 0.5 mol/dm3 PIPES buffer, 20 mm3 0.1 mol/dm3 nioxime and 25 mm3 0.01 mol/dm3 Pb(NO3)2 were added. The solution was deaerated for 5 min and 15 mm3 1.0 % CTAB was added. CTAB was added after the deaeration step to avoid the foaming of the solution containing a high concentration of the surfactant. In the course of Co(II) determination the potential of the electrode was changed in the following sequence: –1.05 V for 10 s; 0.2 V for 10 s; –1.05 V for 30 s and –0.65 V for 120 s. The first two steps were applied to clean the electrode after the preceding measurement. The film was reduced to the metallic state and then was stripped from the electrode. During the third and fourth step a lead film was plated and Co(II) complexes with nioxime were accumulated on the electrode, respectively. During all these steps the solution was stirred using a magnetic stirring bar. Then after a rest period of 5 s a square wave voltammogram was recorded. The selected parameters were: stripping potential ramp from –0.65 to –1.05 V, frequency 100 Hz, step height 5 mV, square wave amplitude 50 mV.
The calibration graph for the accumulation time of 600 s was linear in the range from 1·10–10 to 1·10–9 mol/dm3 and obeyed the equation y = 582 x + 5; the correlation coefficient r = 0.9996. The relative standard deviation from five
Department of Analytical Chemistry and Instrumental Analysis – 48 –
determinations of Co(II) at concentration 2·10–9 mol/dm3 following accumulation time of 600 s was 3.8 %. The detection limit estimated from 3 times the standard deviation of the blank signal was 1.1·10–11 mol/dm3. The voltammograms obtained for the low determined Co(II) concentrations are presented in Fig. 1.
Special attention was paid to the interference of Zn(II) and Ni(II) as these ions are usually reduced at a potential close to that of the reduction of the Co(II) – nioxime complex. In proposed procedure determinations of Co(II) can be carried out in the presence of a 108 fold excess of Zn(II) and a 2·104 fold excess of Ni(II). To study the influence of surface active substances on the analytical signal in the proposed procedure two types of surfactants, anionic – sodium dodecylsulfate (SDS), and nonionic - Triton X-100 were used. It was observed that the addition of SDS at a concentration 50 mg/dm3 caused a decrease of the Co(II) peak to 24 % of its original value. The addition of Triton X-100 at a concentration 50 mg/dm3 caused a decrease of the Co(II) peak to 26 % of its original value. The above results show that the method can be used for determination of Co(II) without serious interference of surface active substances.
a
b
c
d
e
-1.050-0.850-0.650
-5-0.170x10
-5-0.123x10
-5-0.075x10
E / V
i /
A
Fig. 1. Square wave voltammograms obtained for low determined Co(II) concentrations: (a) blank; (b) as (a) + 1·10–10; (c) as (a) + 2·10–10; (d) as (a) + 5·10–10 and (e) as (a) + 1·10–9 mol/dm3. Accumulation time 600 s.
References:
[1] M. Korolczuk, M. Grabarczyk and A. Moroziewicz, Electroanalysis, 19 (2007) 2155.
[2] M. Korolczuk, K. Tyszczuk and M. Grabarczyk, Electrochem. Commun., 7
(2005) 1185.
F.Ch. UMCS Report 2009 (BS) – 49 –
THE CONSTRUCTION AND RESEARCH OF PROPERTIES OF CADMIUM ION-SELECTIVE ELECTRODES WITH SOLID
CONTACT
Cecylia WARDAK DEPARTAMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
The use of ion-selective electrodes in the analysis and monitoring of environmental, clinical, and industrial ions and gases has been continuously expanding [1-3]. Solid internal contact electrodes refer to a type of ISEs in which the internal reference electrode is in direct contact with the electroactive membrane and contains no internal solution. These electrodes will have certain advantages such as their small size, lower cost of production and ability to operate in high pressure environments where conventional ISEs might be damaged. Furthermore such electrode has allowed for low detection limit, which has been attributed to the absence of transmembrane ion fluxes [4].
The mechanism of the potential formation of ion selective electrodes (ISEs) with a liquid or pseudoliquid (polymeric) membrane depends strongly on extraction and ion-exchange processes between the aqueous and organic phases [5, 6]. It is known that the nature and amount of the lipophilic additive strongly influence the response of the membrane ion-selective sensors, such as reducing the membrane resistance, improving the response behavior and selectivity and in some cases, where the extraction capability is poor, increase the sensitivity of the membrane sensors. Therefore, I have decided to use ILs as components of the polymeric membrane of ISE selective to cadmium ions, and it was with great joy that I obtained an electrode better characterizing the analytical parameters.
The aim of this research was to create ion-selective electrodes sensitive to cadmium ions (ISE-s) with solid contact based on a PVC membrane phase containing a ionic liquid as an additional component. It seems that ILs can replace commonly used lipophilic ionic additives (phenyl borates) in the membrane phase, which are introduced to the membrane to reduce the anion interference and to lower the membrane resistance. Additionally chloride ILs keep constant concentration of chloride ions in the membrane phase what guarantee potential stability of internal Ag/AgCl electrode.
In this work I have investigated membranes containing three ionic liquid: 1-ethyl-3-methylimidazolium chloride(EMImCl), 1-butyl-3-methylimidazolium chloride (BMImCl) and 1-hexyl-3-methylimidazolium chloride (HMImCl). These ionic liquid are known to be immiscible in water but soluble in majority plasticizers. Their concentration in the membrane phase was 204.6 mmol/kg for EMImCl, 171.8 mmol/kg for BMImCl, 146.6 mmol/kg for HMImCl and 5 mmol /kg for KTpClPB. Two plasticizers: 2-nitrophenyl octyl ether (NPOE)and
Department of Analytical Chemistry and Instrumental Analysis – 50 –
bis(1-butylpenthyl) adipate (BBPA), were used for membrane preparation. The concentration of ionophore is 1% (9.5 mmol/kg).
In order to evaluate the effect of the addition of ILs to the electrode membrane phase, basic analytical parameters of electrodes containing them in the membrane phase were determined
The research has found that the properties of the Cd2+ion-selective electrode can be significantly improved by the addition of 3 %wt, of ILs to the membrane phase. This effect was found to depend both on the kind of plasticizer used for the preparation of the membranes as well as on the kind of IL.
The comparison of the structure of ILs used for membrane preparation shows that the effect of ILs on electrode properties also depends on the kind of substituent in position R1 of the imidazole ring. The IL with R1 = butyl cause a more positive change in the properties of electrodes containing them in the membrane phase than the ILs having as R1 = ethyl or hexyl.
The best analytical parameters are exhibited by electrode containing 1-butyl-3-methylimidazolium chloride in the membrane phase based on plasticizer NPOE. The characteristic slope of this electrode is 31.4 mV/decade, the limit of detection is 7.1·10–7 mol/dm3, the linearity range 1.0·10–6 – 1.0·10–1 mol/dm3 and values of selectivity coefficients are beneficial log Kpot
Cd/M ≤ –5.5. ILs act as very promising solid contact of ISE with polymeric membrane
because they connect two functions in one membrane component. On the one hand ILs keep constant concentration of chloride ions in the membrane phase what guarantee the stability of potential of internal Ag/AgCl reference electrode. On the other hand they lower the membrane resistance and reduce anion interference, altogether improving the analytical parameters of the electrode such as detection limit, measuring range, working pH range and selectivity.
The obtained results confirm an important role of extraction in the process of the formation of membrane potential and can be useful in the preparation of an ion-selective membrane sensitive to other ions, but in order to recognize the role of ILs in the ion-selective membrane further research is required concerning a wider group of ILs, ionophores and plasticizers.
References:
[1] E. Bakker and E. Pretsch, Anal. Chem., 72 (2002) 420A. [2] E. Bakker and E. Pretsch, Trends. Anal. Chem., 20 (2001) 11. [3] R. De Marco, G. Clarke, B. Pejcic, Electroanal., 19 (2007) 1987. [4] J. Sutter, A. Radu, S. Peper, E. Bakker and E. Pretsch, Anal. Chim. Acta, 523
(2004) 53. [5] Y. Yoshida, M. Matsui, K. Maeda and S. Kihara, Anal. Chim. Acta, 374 (1998)
269. [6] R. Dumkiewicz, K. Sykut and C. Wardak, Chem. Anal., 45 (2000) 383.
F.Ch. UMCS Report 2009 (BS) – 51 –
THE INFLUENCE OF WATER ACTIVITY ON THE ELECTROREDUCTION PROCES OF Bi(III) IONS
IN CHLORATES (VII)
Grażyna DALMATA and Agnieszka NOSAL-WIERCIŃSKA DEPARTMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
Water is a particular solvent for the sake of many strange physical and
physicochemical properties, which are responsible for its role in biological life of Earth and versatility as environment. The complex studies of elements properties in aqueous environment allow to appoint the conditions of chemical and electrochemical processes equilibrium and indicate the areas of thermodynamic stability of the different forms of an element.
The influence of water activity on the electroreduction of Bi (III) ions on mercury from chlorates (VII) solutions at pH = 0 was studied [1, 2].
At dc polarograms of Bi (III) electroreduction in 0.5-8 M chlorates (VII) (what corresponds to the water activity from 0.989 to 0.543) it is visible clearly that with the decrease of water activity the dc waves decrease and shift towards the positive potentials. These changes are considerably bigger in concentrated solutions of chlorates (VII). With the increase of chlorates (VII) concentration from 0.5 to 4 M the slight decrease of swv peak current of Bi (III) electroreduction and the shift of the peak towards the positive potentials are observed (Fig. 1).
Fig. 1. SWV peaks of 10–3M Bi(III) electroreduction in chlorates (VII) pH = 0. Concentration of chlorates (VII) indicated at each curve. Dependence of the swv peak current (—) and peak potential (---) on concentration of chlorates (VII).
Department of Analytical Chemistry and Instrumental Analysis – 52 –
As the chlorates (VII) concentration increases from 4 M to 8 M the swv peak current of Bi (III) electroreduction considerably increases and shifts towards the positive potentials. At cyclic voltammetric curves the anodic peaks are considerably higher and better defined than the cathodic peaks. The potentials difference of anodic and cathodic peak in the function of polarization rate decreases with the increase of chlorates (VII) concentration what indicates that it is just the dehydration rate which decides on the rate of Bi (III) electroreduction process in the solutions with the low water activity. The kinetic parameters of Bi (III) electroreduction were determined from the chronovoltammetric and the faraday impedance measurements. For the low chlorates (VII) concentrations with the increase of supporting electrolyte concentration the values of formal potentials, cathodic transfer coefficients and standard rate constants decreases. For the higher concentrations the increase of these parameters values are observed. The values of rate constants determined from the faraday impedance measurements are compatible with these ones determined from chronovoltammetric measurements. The course of potential dependence of rate constants of Bi (III) electroreduction in chlorates (VII) points at the multistage process of Bi (III) electroreduction and confirms the regularity observed earlier, that in the solutions with the low water activity the mechanism of Bi (III) electroreduction differs from this one in the solutions with the high water activity. References:
[1] Š. Komorsky-Lovrić, M. Lovrić and M. Branica, J. Electrochem. Soc., 140 7
(1993) 1850. [2] M. Lovrić and M. Branica, Indian J. Chem., 29A (1990) 435.
F.Ch. UMCS Report 2009 (BS) – 53 –
DIGITAL SIMULATION OF CYCLIC RECIPROCAL DERIVATIVE CHRONOPOTENTIOMETRY WITH PROGRAMMED CURRENT
OF ADSORPTION SYSTEMS WITH SLOW CHARGE TRANSFER
Zygmunt FEKNER DEPARTMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
The behavior of electrode processes is often affected by adsorption of electroactive species. In this paper, we continue our investigation on digital simulation and analyzing quasi-irreversible and irreversible electrode reactions coupled with non-linear adsorption of reactant and/or product of electrode reaction using cyclic reciprocal derivative chronopotentiometry (CRDCP) with programmed current. In the case of non-linear adsorption the analytical expressions of (dt/dE)-E curves are derived for “diffusionless” systems only, i.e. when large adsorption constants Ki are assumed and diffusion of electroactive species during chrono-potentiometric cycles is negligible and when totally reversible or totally irreversible
charge transfer is assumed ( ∞→<<− 010 or1 ksk ). In the cases with medium
adsorption constants and for quasi-irreversible charge transfer analytical expressions of CRDCP curves do not exists and digital simulations are required especially when programmed current is applied. The simulations were carried out using the point method, which is based on finite-difference approximation of derivatives in Fick’s second diffusion equation with exponentially expanding space grid.
To illustrate the influence of adsorption constants on parameters of the chronopotentiometric and CRDCP curves some simulation results are presented in Table 1. Table 1. Simulation dimensionless values of cathodic and anodic transition times (τc and τa), ratio of peak heights (Ry) and distance between peak-poten- tials (∆Ep) of the simulated CRDCP curves for irreversible electrode processes (dimensionless K0 = 0.171015) at various adsorption constants of ox and red with two successive exponentially programmed currents
applied of the form ( ) ( ) ( )ttI exp2π±= .
redox KK = cτ aτ yR pE∆
5.010 2.1475 2.0133 1.1185 6.9718 0.110− 2.0769 1.9361 1.1310 6.9760 5.210− 1.2343 0.9978 1.3576 7.3323 0.410− 0.5496 0.2526 2.4869 9.1322
0 0.5015 0.2034 2.8278 9.4312
Department of Analytical Chemistry and Instrumental Analysis – 54 –
In Fig. 1 are presented the dimensionless chronopotentiometric (Fig. 1A) and CRDCP curves (Fig. 1B) (the first cycle i.e. the first cathodic and anodic current steps) for system from Table 1 with Kox = Kred = 10–25.
The influence of electron transfer coefficient α on parameters of the chronopo-
tentiometric and CRDCP curves is presented in Table 2. Table 2. Influence of electron transfer coefficient α on parameters of the chronopo tentiometric and CRDCP curves for system Kox = Kred = 10–25 from Table 1. Other conditions as in Table 1.
α cτ aτ yR pE∆
0.3 1.2343 0.9978 0.5973 8.5576 0.4 1.2343 0.9978 0.9172 7.5708 0.5 1.2343 0.9978 1.3576 7.3323 0.6 1.2343 0.9978 2.0112 7.6906 0.7 1.2343 0.9978 3.0938 8.8454
F.Ch. UMCS Report 2009 (BS) – 55 –
INFLUENCE OF CHOSEN ANTIBIOTICS ON ELECTROPHORETIC DETERMINATION OF HUMAN ALBUMIN
Barbara MARCZEWSKA, Andrzej PERSONA and Tomasz GĘCA
DEPARTAMENT OF ANALYTICAL CHEMISTRY AND INSTRUMENTAL ANALYSIS
Electrophoresis in one of the methods used for determination of albumin which is the marker of kidney diseases [1]. The change of electrophoretic picture of albumins due to exterior factors caused diagnostic errors which may indicate pathological state of healthy human organism and the other side masks presence of the disease. Therefore an essential problem is not only quantitative determination of albumin but also the effect of various factors influenced on the measurement reliability. The measurements can be disturbed by the drug containing biologically active substances which forming compounds with proteins [2-4].These pharmaceutical preparations are taken by the ill people due to kidney disease and accompanying ailments.
The aim of the paper was to study the effect of some antibiotics: ampicillin, gentamicin, cefuroxime, most commonly applied for kidney diseases, on the electrophoresis of human albumin under native conditions on polyacrylamide gel. Materials and methods
The subject of investigation was determination of the influence of antibiotics: ampicillin, gentamicin, cefuroxime in therapeutic doses on the determined albumin level in urine.
The experiments were carried out in model samples containing human albumin at the concentration 50 mg/dm3 in phosphate buffer solutions (in physiological urine pH = 6.5) in the presence of therapeutic level of drugs and in biological fluid in the presence of drugs.
Commassie blue assay was performed on polyacrylamide gel electrophoresis by the use of Kucharczyk set. After separation, gels were dyed with Commassie Brillant Blue R 250 solution. Stained gels were scanned and the obtained data were processed using BioDocAnalyse software. Statistical data analysis was carried out by Statistica. Results
The obtained results are presented in Tables 1 and 2. In model solutions the maximal and minimal doses of antibiotics in relation to the amounts detected in urine as a free form were used and in natural samples - the maximal dose. The studied antibiotics dissolved in the phosphate buffer did not give electrophoretic bands. The calibration curve of human albumin was made for seven concentrations
Department of Analytical Chemistry and Instrumental Analysis – 56 –
of model solutions (20-80 mg/dm3). At least 10 repetitions were made for each concentration.
Table 1. Parameters characterizing the electrophoretic bands of the model samples containing 50 mg/dm3 of albumin in phosphate buffer of pH = 6.5 in the absence and presence of antibiotics.
Solution
Area of the band[j.u.]
Density volume of the band [j.u.]
Value from the calibration
curve[mg/dm3]
Albumin 1559 ± 5% 102865 ± 8 50
Albumin+ampicillin 2,97g/dm3 1535 ± 5% 119359 ± 10% 51
Albumin+ampicillin 5,97g/dm3 1502 ± 10% 112593 ± 8% 49
Albumin +gentamicin 0,36g/dm3 1577 ± 8% 106771 ± 8% 52
Albumin+getamycin 0,84g/dm3 1565 ± 8% 113529 ± 10% 52
Albumin +cefuroxime 2,86g/dm3 1534 ± 9% 102508 ± 5% 50
Albumin +cefuroxime 5,72g/dm3 1558 ± 6% 122138 ± 5% 51
Table 2. Parameters characterizing the electrophoretic bands of urine samples pH = 6.8 in the absence and presence of antibiotics.
Solution
Area of the band[j.u.]
Density volume 0f the band [j.u.]
Value from the calibration
curve[mg/dm3]
urine 1064 ± 10 37842 ± 10 35
urine + ampicillin 5,97g/dm3 1106 ± 7 43397 ± 9 36
urine +getamicin 0,84g/dm3 1115 ± 5 39904 ± 6 37
urine +cefuroxime 5,72g/dm3 1104 ± 9 22478 ± 10 38
Conclusions
The studies carried out for both model and natural solutions exhibit lack of effect of antibiotics, used in therapeutic doses, for analytical determination of human albumin by slab gel electrophoresis.Similar dependence for bovine albumin in the presence of ampicillin was also fund by Marshall and Williams [5] applying colorimetric assay with the use of the dye Coomassie Brilliant Blue .
Albumin has some hydrophobic binding sites and binds diverse drugs first of all negatively charged hydrophobic compounds. For drug compounds there have been proposed two affinity binding sites in subdomains IIA and IIIA with charged lysine199 and arginine 222, 257, 410, 485.
Anion of the Coomassie blue D-250 in the acidic media binds with unprotonated groups of aminoacids by means of electrostatic bonds. The strongest aminoacid binding with the dye is arginine, weakly bonded are histidine, lysine, tyrosine and tryptofane. Van der Waals forces and hydrophobic interactions also tace part in interaction mechanisms. A lack of interference of the studied antibiotics can be caused by:
F.Ch. UMCS Report 2009 (BS) – 57 –
1. Binding of the compounds by albumin serum to a small extent (18-22% for ampicillin, 20-30% for gentamicin and 32 % for cefuroxime)
2. Formation of the drug-albumin complexes not blocking active sites with which the dye used for dyeing of slabs combines
3. The drug-albumin complex is not as stable as complex of albumin and dye A lack of effect of chosen antibiotics seems to be essentials information from point of view of medical diagnosis References:
[1] A. Umbreit and G. Wiedemann, Clin. Chim. Acta, 259 (2000) 163. [2] J. Oravcowa, B. Böhs and W. Linder, J.Chromatogr.B, 677(1996) 1. [3] D.S. Hageand,and S.A. Tweed, J. Chromatogr.B, 699 (1997) 499. [4] X.X. Yang, Z.P. Hu, S.Y. Chan and S,F. Zhou, Clin. Chim. Acta, 365 (2006) 9. [5] T. Marshall and K.M. Williams, Anal. Biochem., 322 (2003) 275-278.
F.Ch. UMCS Report 2009 (BS) – 59 –
INVESTIGATIONS OF THE ADSORPTION AND VOLUMETRIC
PROPERTIES OF ANIONIC AND NONIONIC SURFACTANTS
MIXTURES
Katarzyna SZYMCZYK and Bronisław JAŃCZUK
DEPARTMENT OF INTERFACIAL PHENOMENA
The tendency of surfactants to adsorb at interfaces in an oriented fashion and
micelle formation are their two fundamental properties However, these phenomena
are still not well recognized.
With regard to surfactants adsorption and micelle formation, both the
composition and structure of the adsorbed layer and micelle are of interest as they
are directly relevant to practical applications such as detergency and flotation [1, 2].
Because the behavior of surfactants mixtures in the monolayer and micelle
formation is different than of individual surfactants, and in some cases synergetic
effects are observed, it is therefore more appropriate to investigate multi-component
systems with two or more species interacting in an equilibrated system [1]. This
synergism can be attributed to nonideal mixing effects in aggregates, and it results
in critical micelle concentrations (CMC) and interfacial tensions that are
substantially lower than it could be expected on the basis of the properties of
unmixed surfactants alone. In most cases the molecular interaction parameters,
which have been derived from the application of a nonideal model to the
thermodynamics of the system [2] are used to measure the nature and extent of the
interactions between two different surfactant molecules in a mixed monolayer at
this interface and mixed micelle and to prove synergism. Moreover, micelles
formed from a solution of mixed surfactants generally have a different surfactant
composition than in the bulk phase [1, 2]. Because aggregation of the surface active
agents into micelles is related to changes of their apparent molal and partial molal
volumes [3, 4] it is interesting how the changes of mole fractions of surfactants in
micelles influence the synergetic effects in mixed micelle formation and their
volumetric properties. Thus, the purpose of our studies was to determine the
influence of the concentration and composition of aqueous solutions of binary
mixtures of anionic, sodium decylsulfate (SDS) and nonionic p-(1,1,3,3-
tetramethylbutyl) phenoxypoly(ethyleneglycol), Triton X-100 (TX100) surfactants
on the interactions between surfactants in mixed layers and micelles as well as on
the values of CMC and volume change upon micelle formation on the basis of
surface tension and density measurements.
From the measured values of the surface tension, LVγ , of aqueous solutions of
SDS, TX100 and their mixtures and calculations based on the equation derived by
Rubingh and Rosen [1, 2] it results that the mole fractions of surfactants in the
mixed monolayer are different from those in the bulk phase for a given value of
Department of Interfacial Phenomena – 60 –
LVγ corresponding to the saturated monolayer of surfactants at water-air interface
[5]. Moreover, negative values of molecular interaction parameters in mixed
monolayers together with the existing condition of synergism indicate that there is a
negative synergism in surface tension reduction for values of the surface tension
corresponding to the mixed saturated monolayer at water-air interface equal 60, 55
mN/m for surfactant mixture at α = 0.2 (α is a mole fraction of TX100) and at
LVγ = 60, 55, 52,8 mN/m forα = 0.8 [5].
From the surface tension isotherms it also results that the values of critical
micelle concentration strongly depend on the composition of the mixture of anionic
and nonionic surfactants and there is a small minimum between the values of CMC
and monomer mole fraction of TX100 in the bulk phase. The values of the
molecular interaction parameter, activity coefficients as well as the excess Gibbs
energy of mixed micelle formation calculated on the basis of the Rosen approach
[1, 2] proved that there is synergism in mixed micelle formation of aqueous
solutions of TX100 and SDS at α TX100 = 0.2 [5].
The calculations of the apparent molar volume of surfactants, vφ , indicate that
for both pure surfactants and each mixture studied at specific concentrations, lower
than CMC, the values of vφ are the same. This leveling of the vφ values below
CMC indicates that at these concentrations dimers or thrimers are begining to form.
Knowing the values of the density of aqueous solutions of individual surfactants the
partial molal volumes in micellized and dispersed state and volume, V∆ , changes,
upon micelle formation can also be determined. From this calculation it results that
there is a deviation from the linear relationship between V∆ at CMC and monomer
mole fraction of TX100 in the mixture. The V∆ values as well as the standard free
energy of micelization process of TX100 and SDS surfactant mixtures, can also be
determined on the basis of the values of the composition of the mixed micelle
calculated from the Rubingh and Rosen approach [1, 2].
References:
[1] J. M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New
York, 2004.
[2] D. N. Rubingh in: K. Mittal (Ed.), Solution Chemistry of Surfactants, Plenum
Press, New York, 1979, 337.
[3] K. M. Kale and R. Zana, J. Colloid Interface Sci., 61 (1977) 312.
[4] S. Kato, S. Harada, H. Nakashima and H. Nomura J. Colloid Interface Sci., 150
(1992) 305.
[5] K. Szymczyk and B. Jańczuk, Journal of Surfactants and Detergents, in press.
F.Ch. UMCS Report 2009 (BS) – 61 –
INVESTIGATION OF THE WETTABILITY OF POLYMERIC SOLIDS
BY AQUEOUS SOLUTION OF BINARY MIXTURES OF ANIONIC
AND NONIONIC SURFACTANTS
Katarzyna SZYMCZYK and Bronisław JAŃCZUK
DEPARTMENT OF INTERFACIAL PHENOMENA
The characteristic phenomenon for surfactant mixtures, is mixed monolayer
formation at the water-air interface. In most cases the molecular interaction
parameters, which have been derived from the application of a nonideal model to
the thermodynamics of the system [1], are used to measure the nature and extent of
the interaction between two different surfactant molecules in a mixed monolayer at
this interface. However, regardless of the fact that surfactants are the main wetting
regulators, studies only of the surface and bulk properties of surfactant solutions are
not sufficient. Systematic studies of the effect of surfactants mixtures on wetting of
solid surfaces, including calculations of molecular interaction parameters of
surfactants in mixture at solid-water interface and thereby the monomer mole
fractions of surfactants in mixture at this interface have not been carried out, so far.
Thus, the purpose of our studies was to determine the influence of the concentration
and composition of aqueous solutions of binary mixtures of anionic and nonionic
surfactants, sodium decyl sulfate (SDS) and p-(1,1,3,3-tetramethylbutyl)
phenoxypoly(ethylene glycol), Triton X 100 (TX100) on the wettability of
poly(tetrafluoroethylene) (PTFE) and polymethyl methacrylate (PMMA) [2]. The
correlation between the adsorption of the surfactants at water-air and solid-water
interface and the advancing contact angle was also investigated.
The obtained results indicate that the values of the surface tension and the
contact angle on PTFE and PMMA surface depend on the concentration and
composition of the surfactants mixture. On the curves presenting the relationship
between the surface tension, contact angle and monomer mole fraction of TX100
(α) in the mixture of TX100 and SDS at the concentration corresponding to that of
the saturated monolayer at water-air interface there is a deviation from the linear
relationship which suggests that the composition of the saturated monolayer at
water-air, PTFE-water and PMMA-water interface should be different than that in
the bulk phase. This suggestion is confirmed by the values of the mole fraction of
surfactants in the mixed monolayers for eachα calculated from the equation
derived by Rubingh and Rosen [1]. At all values of α and θ or LVγ the mole
fraction of TX100 in the mixed monolayers ( 1X θ1X ) is bigger than in the bulk
phase. For PTFE the values of θ1X are almost the same as 1X for a given LVγ and
θ that is, for example, for 55 mN/m and 95°, where the decrease of the surface
Department of Interfacial Phenomena – 62 –
tension of water and contact angle for PTFE is equal 17 in contrast to PMMA,
where the values of θ1X are smaller than 1X .
Nearly the same values of the mole fraction of surfactants in the mixed
monolayer at water-air and PTFE-water interface suggest that adsorption of the
surfactants at water-air and PTFE-water interface is the same and the orientation of
TX100, SDS molecules at both interfaces in saturated monolayer should also be the
same (the hydrocarbon chain directed towards air and PTFE, respectively).
A direct method to investigate a relative adsorption at interfaces in wetting
studies was developed by Lucassen-Reynders [3]. By combining the Young and
Gibbs equations we obtain a relationship on the basis of which, assuming that SVΓ
≈ 0, it is possible to establish the ratio of SLΓ to LVΓ by plotting the adhesional
tension ( θγ cosLV ) vs surface tension ( LVγ ). From this relationship it results that
in the case of PTFE for all investigated mixtures a linear relationship exists between
the adhesional and surface tension. For single surfactants and their mixtures nearly
the same constants in the linear relationships were found. Therefore, it was possible
to establish a general expression to describe the changes of the adhesional tension
as a function of the surface tension for all surfactants, which
is: 90.46cos +−= LVLV γθγ (1). The constant –1 in Eq. (1) indicates that in the
case of PTFE for a single surfactants and their mixtures at a given concentration in
the bulk phase the surface excess concentration of surfactants at water-air interface
is the same as that at PTFE-water interface. So, it confirms our conclusion
mentioned above that adsorption of the surfactants at water- air and PTFE-water
interfaces and the orientation of their molecules is the same. In the case of PMMA
we obtain the following relationships: 42,3217,0cos +−= LVLV γθγ for aqueous
solutions of TX100 and all mixtures and 30,7271,0cos +−= LVLV γθγ for SDS. It
is interesting firstly that for this solid we cannot describe the relationship
between θγ cosLV and LVγ by one function, and the secondly that the constants
equal -0,17 and -0,71 indicate that in the case of the mixtures of TX100 and SDS
adsorption at PMMA-water interface is about five times smaller than at water-air
interface. This conclusion is confirmed by the values of molecular interaction
parameters calculated for water-air and PMMA-water interface [2].
References:
[1] J.M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New
York, 2004.
[2] K. Szymczyk and B. Jańczuk, Journal of Surfactants and Detergents, in press.
[3] [3] F. H. Lucassen-Reynders; J. Phys. Chem., 67 (1963) 969.
F.Ch. UMCS Report 2009 (BS) – 63 –
THEORETICAL ANALYSIS OF THE INFLUENCE OF THE ERROR
IN THE WORK OF ADHESION DATA ON REAL VALUES
OF THE SURFACE FREE ENERGY AND ITS COMPONENTS
–IS IT POSSIBLE TO IMPROVE THE ACCURACY
OF A SOLUTION?
Tomasz BIAŁOPIOTROWICZ
DEPARTMENT OF INTERFACIAL PHENOMENA
The usefulness of the van Oss-Chaudhury-Good theory (vOCGT) [1-3] was
shown in the previous papers [4,5] of this series by analyzing the influence of the
error in the solution of the equations resulting from this theory. The main objective
of this series of papers was to present an extended analysis of the influence of the
error on the calculated values of Lifshitz-van der Waals (LW) component and acid
and base (A and B) parameters of the surface free energy based on artificially
created work of adhesion input data. vOCGT is potentially very useful in obtaining
specific information about the state of a solid surface that cannot be obtained by any
other method, for example, X-ray photoelectron spectroscopy (XPS) or Time-of-
Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Information on the acid and base
properties of a given solid surface could help us understand many processes.
vOCGT was checked for a large artificial set of the work of adhesion input
data calculated for 15 solids and 300 liquids. Numerical values of LW component
and acid (A) and base (B) parameters were assigned to 15 solids. These 15 solids
were grouped in 5 sets of 3 solids in each. Also the numerical values of LW
component and A and B parameters were assigned to 300 liquids (three sets of 100
liquids in each). Data for these solids and liquids were especially selected to
represent real types of materials encountered in practice. For all 15 solids and 300
liquids the values of the work of adhesion were calculated and these values were
assumed to be error-free. Next, new values of the work of adhesion were obtained
by adding a random homoscedastic error (of the same standard deviation) of normal
distribution, belonging to 8 distributions of a mean value equal to the value of the
error-free work of adhesion and standard deviations of 0.5, 1, 2, 5, 7, 10, 15 and 20
mJ/m2. The LW components and A and B parameters for these solids were back-
calculated for each error level. Basing on these results it was found that there
existed a linear correlation between the root mean square error (RMSE) of the
solution and the standard deviation of the work of the adhesion data [4,5]. This
correlation gives the possibility to determine what should have been the maximal
standard deviation of the work of adhesion when the calculated value of the given
LW component or A or B parameter differed no more than 1 mJ/m2
from the error-
free (true) value in the case when the condition number (CN) of the 3-equation or
overdetermined set was below 5. Such a value was defined as σCR1CN5.
Department of Interfacial Phenomena – 64 –
The main goal of the presented analysis [6,7] was to show how to find the best,
only moderately biased solution having a set of contact angle data for a given set of
liquids. For this reason a comparison between the minimal, maximal and mean
σCR1CN5 values for 3-equation and overdetermined sets with CN < 5 was made. In
Fig. 1 this comparison is presented.
Fig. 1. Comparison of the minimal, maximal and mean σCR1CN5 values for 3-equation
and overdetermined sets with CN < 5.
Conclusions
1. It was also found that overdetermined sets with condition numbers below 5
were less susceptible to an error in the work of adhesion data than those with
higher condition numbers.
2. The solution of an overdetermined set of equations has always advantage over
the solution of separate 3-equation sets, therefore the best way to improve a
solution quality is to use the overdetermined set of equations.
References:
[1] C.J.van Oss, L. Ju, M.K.Chaudhury, R.J.Good, J. Colloid Interface Sci.,
128 (1989) 313.
[2] C. J. van Oss, Interfacial Forces in Aqueous Media, Dekker, New York,
1994, p.12.
[3] R.J Good, C.J. van Oss, in “Modern Approaches to Wettability”, Eds.
M.E.Schrader, G.I. Loeb, Plenum Press, New York, 1992, p. 1.
[4] T. Białopiotrowicz, J. Adhesion Sci. Technology, 21 (2007) 1539.
[5] T. Białopiotrowicz, J. Adhesion Sci. Technology, 21 (2007) 1557.
[6] T. Białopiotrowicz, J. Adhesion Sci. Technology, 23 (2009) 799.
[7] T. Białopiotrowicz, J. Adhesion Sci. Technology, 23 (2009) 815.
F.Ch. UMCS Report 2009 (BS) – 65 –
EFFECTS OF STATIC MAGNETIC FIELD ON WATER
AND ELECTROLYTE SOLUTIONS PROPERTIES
Aleksandra SZCZEŚ, Emil CHIBOWSKI and Lucyna HOŁYSZ
DEPARTMENT OF INTERFACIAL PHENOMENA
Although changes caused by magnetic field depend on many factors and are
still somewhat controversial, the influence of static or alternating magnetic (MF)
and electromagnetic fields (EMF) on the physicochemical properties of water or
aqueous solutions and suspensions has attracted much interest [1–8].The changes
caused by MF depend on many factors such as: the field strength [2], direction of
the applied field [3], time of the magnetic exposure [4], flow rate of the solutions
[5], additives present in the system [6], pH [7], etc. The effects lasted even up to
many hours since the removal of MF and this phenomenon is called ‘memory
effect’[8].
The aim of our study was to examine the changes in the conductivity (κ) of
water and electrolyte solutions due to MF exposure. Also the changes in the
amounts of evaporated water from pure water and the electrolyte aqueous solutions
caused by MF treatment were evaluated. For this purpose flowing water and
electrolytes solutions were exposed for 5 or 20 min to a weak static magnetic field
and then their conductivity and amount of evaporated water were measured as a
function of time. Simultaneously these quantities were determined also for
magnetically untreated samples which were the reference systems.
It was found that the magnetic field increases the amounts of evaporated water
and influence the conductivity of the examined solutions. However, these effects
depend on the time of magnetic treatment, magnetic field induction, nature of the
ions present in the solutions and flow rate of the examinated liquids.
For the electrolyte solutions containing water structure-disordering ions these
effects depend on the thermodynamic functions of the ions hydration. Roughly,
linear changes in the conductivity versus ‘scaled’ these functions were obtained.
The best liner fit of κ∆ vs. *hydH∆ ,
*hydG∆ ,*hydS∆ , r and rr∆ was found if
MF was applied for 5 min during the solutions circulation and the best linear fit
occurred for κ∆ vs. *
phydC∆ if MF was applied for 20 min during the solutions
circulation.
Department of Interfacial Phenomena – 66 –
A) B)
-270 -260 -250 -240 -230 -220 -210-0.04
-0.03
-0.02
-0.01
0.00
0.01
0.02
0.03
0.04
KI
KBr
KCl
1
3
5
10
15
20
25
30
1440 min
after MF treatment
∆κ=
κM
F-κ
o [m
S/c
m]
Σ(∆r/r)∆hyd
H [kJ/mol]
-146 -144 -142 -140 -138 -136-0.10
-0.08
-0.06
-0.04
-0.02
0.00
0.02
0.04
KI
KCl
KBr 1
3
5
10
15
20
25
30
1440 min
after MF treatment
∆κ=
κM
F-κ
o [m
S/c
m]
Σ∆hyd
Cp [J/(K mol)]
Fig. 1. Changes in conductivity after: A) 5 min and B) 20 min of magnetic treatment
versus the thermodynamic functions of the ions hydration.
On this basis it can be concluded that magnetic field causes changes in the
hydration shell of the ions.
References:
[1] E.J.L Toledo, T.C. Ramalho, Z.M. Magriotis, J. Mol. Structure, 888 (2008)
409–415.
[2] K. Higashitani, A. Kage, S. Katamura, K. Imai, S. Hatade, S. J. Colloid
Interface Sci., 156 (1993) 90–95
[3] J.S. Backer, S.J. Judd, Wat. Res., 30 (1996) 247–260.
[4] K. Higashitani, K. Okuhara, S. Hatade, J. Colloid Interface Sci., 152 (1992)
125–131.
[5] C. Gabrielli, R. Jaouhari, G. Maurin, M. Keddam, Wat. Res., 35 (2001) 3249–
3259.
[6] E. Chibowski, L. Hołysz, A. Szcześ, M. Chibowski, Wat. Sci. Technology., 49
(2004) 169–176.
[7] S.A. Parsons, B.L. Wang, S.J. Judd, T. Stephenson, Wat. Res., 31 (1997) 339–
550.
[8] J.M.D. Coey, S. Cass, J. Magn. Magn. Mater., 209 (2000) 71–74.
F.Ch. UMCS Report 2009 (BS) – 67 –
PHOSPHOLIPID INFLUENCE ON CALCIUM CARBONATE
PRECIPITATION
Aleksandra SZCZEŚ
DEPARTMENT OF INTERFACIAL PHENOMENA
Calcium phosphate and calcium carbonate are principal inorganic crystals
produced in biomineralization processes in biological systems. The formation of
these minerals is an important process occurring at the interface between living
organisms and mineral phases such as macromolecular frameworks, lipid
membranes or cell walls. Ordered deposition of calcium phosphate on an
extracellular organic matrix is the first stage of hard tissue mineralization in
vertebrates. Calcium carbonate is also one of the most important biomineral present
in mollusk shells or corals. A lot of works focused on the process of
biomineralization at interfaces were done, especially at air-water interface [1, 2] and
at solid substrates surface in the aqueous phase [3]. Organic templates such as
insoluble Langmuir films of lipids or fatty acids at air-water interface are
considered as a good model system for biomineralization study of the processes
taking place in living organism. The interfacial interactions associated with
template-directed crystallization is important for understanding the natural
processes, e.g. bone, tooth and shells formation. Such knowledge is also needed for
applying the biomimetic strategies to develop advanced technologies for the
production of novel materials, e.g. advanced composites and coatings for medical,
chemical, optical and electronic applications. Moreover, the presence of organic
substrates not only induces mineral nucleation and its growth, but they also make
the mineral surface more hydrophobic.
In this study calcium carbonate was precipitated from CaCl2 and Na2CO3
equimolar solutions in the presence of phospholipid – dipalmitoylphospha-
tidylcholine (DPPC). It was found that DPPC modifies the surface of calcium
carbonate from hydrophilic to more hydrophobic. Water droplet settled on pure
CaCO3 compressed powder samples as a thin pellet does not form what means that
unmodified calcium carbonate is easily wetted by water. However, for CaCO3
precipitated in the presence of the phospholipid the contact angle of water is about
23°.
In other experiments, plates of mica with deposited DPPC, mono- or bilayers
on their surface by Langmuir–Blodgett technique were placed at room temperature
in a simulated body fluid (SBF) of ion concentration nearly equal to that of human
blood plasma. Such solution is often used to predict in vivo bone bioactivity and
ability of apatite to form on the surface of different materials used as bone
substitutes [4]. Among others things, SBF contains Ca2+
, −
3HCO and −2
4HPO ions.
The phospholipid present on the mica surface was found to enhance a mineral
Department of Interfacial Phenomena – 68 –
deposition. Moreover, the mineral deposit structure obtained in the presence of
DPPC was better organized.
References:
[1] L-J. Zhang, H-G. Liu, X-S. Feng, D-J. Qian, L. Hang, X-L. Yu, Q-L. Feng,
Thin Solid Films, 458 (2004) 287–291.
[2] S. Hacke, D. Möbius, V-T.Lieu, Appl. Surface Sci. 246 (2005) 362–366.
[3] A.W. Xu, Y. Ma, H. Cöflen, J. Mater. Chem., 17 (2006) 415–449.
[4] T. Koubo, H. Takadama, Biomateriale, 27 (2006) 2907–2915.
F.Ch. UMCS Report 2009 (BS) – 69 –
THE POROSITY AND MORPHOLOGY OF MESOPOROUS SILICA
AGGLOMERATES
Agnieszka KIERYS, Waldemar BUDA and Jacek GOWOREK
DEPARTMENT OF ADSORPTION
Following the discovery of ordered mesoporous silica materials [1, 2] many
papers on synthesis of mesoporous MCM-41 have been published. Mesoporous
silicas have been widely used as catalysts, adsorbents, host materials for
biologically active substances, chemisensors. Therefore, for many of their
applications silica samples need to be specially synthesized tailoring the pore
dimensions and morphology of the particles. The porosity and morphology of
MCM-41 are determined by various factors.
The aim of present investigations was to test how the concentration of the
reacting components influences the morphology, texture and inter-particle
agglomeration of the final product The formation of silica agglomerates on the
micrometer scale and pore ordering on the nanometre scale was studied by nitrogen
adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM) and
atomic force microscopy (AFM).
Siliceous MCM-41 mesoporous molecular sieves were prepared following the
synthesis procedure reported in ref [2]. Four different samples were prepared at
different water contamination and at a constant molar ratio of the remaining
components. The starting molar composition of the reacting mixture was CTAB
(0.1375) : TEOS (1) : NH3 (2.8) : H2O (n) – where n = 141.2; 77.7; 55.0; 36.5 for
MCM-41-1, -2, -3 and -4 sample, respectively. The specific surface areas SBET , the
total pore volumes Vp,t and volumes of regular pores Vp,m derived from αs – plots are
listed in Table 1.
Table 1. Parameters characterizing porosity of the investigated samples obtained
from nitrogen adsorption and XRD data.
Sample name SBET
(m2/g)
Vp,t
(cm3/g)
Vp,m
(cm3/g)
d100
(nm)
WD
(nm)
bD
(nm)
MCM-41-1 1137 1.31 0.75 3.68 3.52 0.73
MCM-41-2 1075 0.98 0.76 4.51 4.33 0.70
MCM-41-3 1146 0.98 0.83 4.46 4.35 0.69
MCM-41-4 1153 0.95 0.82 4.42 4.30 0.68
SBET – specific surface area, Vp,t – total pore volume, Vp,m – primary mesopore volume,
d(100) – interplanar spacing, WD – primary mesopore diameter derived from d(100) spacing,
bD – pore wall thickness.
Department of Adsorption – 70 –
Atomic force microscopy was used to determine the particle size and surface
organization of the synthesized materials. Fig 1. shows the surface images for
MCM-41 sample composed of large crystalites.
Fig. 1. Surface morphology of MCM-41-4 particles as determined by AFM. Parts a and
c – high mode 2D and 3D images, respectively, part b – magnification of the
crystallite surface of indicated location and part d – profilometric cross-section of
the indicated location.
Although the dimensions of “grain-like” entities on the surface of MCM-41-4
crystallite are relatively large, their hexagonal arrangement may suggest that the
AFM image (part b, c, d in Figure 1) represents the plane of pore openings. The
distance of the neighbour species registered by AFM is larger than the dimensions
of the unit cell (~ 5 nm for studied sample) calculated from XRD experiment, which
might be reflected by the tip artefacts in AFM images [3]. The AFM images are a
convolution of the tip shape and the surface topography. Thus, the surface features
smaller than the tip diameter will appear larger than they are themselves. However,
it is reasonable to assume that a high regularity of the surface objects demonstrated
in Fig. 1 reflects real surface organization characteristic of MCM-41 silica.
References:
[1] J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D.
Schmitt, C. T. W. Chu, D. H. Olson, E. W. Sheppard, S. B. McCullen, J. B.
Higgins and J. L. Schlenker, J. Am. Chem. Soc., 114 (1992) 10834.
[2] M. Grün, K. K. Unger, A. Matsumoto and K. Tsutsumi, in Characterization of
Porous Solids IV, ed. By B. McEnaney, J.T. Mays, J. Rouquerol, F. Rodriguez-
Reinoso, K.S.W. Sing, K.K. Unger, The Royal Society of Chemistry, London,
1997, p. 81.
[3] T. Miwa, M. Yamaki, H. Yoshimura, S. Ebina and K. Nagayama, Langmuir, 11
(1995) 171.
F.Ch. UMCS Report 2009 (BS) – 71 –
THE INFLUENCE OF THE MAGNETIC FIELD ON SEPARATION
AND RESOLUTION OF CHOSEN CHROMATOGRAPHIC
SYSTEMS
Irena MALINOWSKA, Barbara OŚCIK-MENDYK, Małgorzata JANICKA
and Marek STUDZIŃSKI
DEPARTMENT OF PLANAR CHROMATOGRAPHY
Magnetic field plays a great role in the life on the Earth. Magnetic field protects
our planet from cosmic radiation. It is known that magnetic field can influence some
process in nature. The influence concern reaction – in live organisms and outside them
[1, 2]. Magnetic field has been used in different therapies , in present times magnetic
field is claimed to be one of the method for burn therapy [9].
There is a lot of evidences of influence of magnetic field on some processes
existing in nature – both in animate and non-animate. In many cases the influence
of magnetic field is observed, but there is no explanation of nature of the influence.
In order to explain how magnetic field influences some process existing in nature,
some chromatographic experiments has been realized.
Chromatography is one of the method for separation of the components of the
mixture. The process in every chromatographic method and technique proceeds on
the phase boundary – similarly to a lot of vital processes in live organism,
particularly the metabolism of each single cell. Therefore explanation how magnetic
field influences the process can also give some explanation why magnetic field
influences some process in live organisms. In these cases chromatographic methods
may be a proper methods for realization of the idea. Thin layer chromatography is
one of the least complicated chromatographic method. The use of the magnetic field
in the chromatographic systems may be very complicated. Planar chromatography
systems enable to use the magnetic field quite easily. For this reason we decided to
carry out our investigations in the TLC systems.
In presented investigations thin-layer chromatographic process were carried in
magnetic field generated between two neodymium magnets. The inductivity of the
magnetic field was 0.48 T. In the experiment lines of the magnetic field were
perpendicular to direction of the mobile phase and the sorbent layer. In presented
paper the mixtures of Datura innoxia Mill. alkaloids (obtained in Medical Academy
of Lublin, Department of Analytical and Physical Chemistry) were separated by use
planar elctrochromatography method in magnetic field and without it on dry SiO2
plates. The retention data, obtained in magnetic field have been compared with the
data obtained without external magnetic field. For tertiary alkaloids the changes of
the resolution between neighboring solutes in magnetic field and without it in
different chromatographic development obtained in SiO2 layer in toluene/ethyl
acetate/methanol 70/15/15 (v/v/v) mobile phase are presented in Table 1.
Department of Planar Chromatography – 72 –
Table 1. RS values obtained in magnetic field and without it for tertiary alkaloids
from Chelidonmiu Majus L, on SiO2 layer in different TLC and HPTLC
plates.
The influence of the magnetic field are observed for quaternary alkaloids too.
Fig. 2 a, b presented densytogram obtained for quaternary alkaloids extract obtained
in magnetic field and without it.
a)
b)
Fig. 1. Chromatograms of quaternary alkaloids obtained in magnetic field (a) and without it
(b) on the same chromatographic system as tertiary alkaloids.
References:
[1] R.J. Reiter, B.A. Richardson., The FASEB Journal, 6 (1992) 2282-2287.
[2] O. Toshiki, Papers of Joint Technical Meeting in Medical and Biological
Engineering, 2 (1998) 131-133.
[3] V.I. Gaiduk, T.V. Sisiura, A.M. Boiarskaja, Klin. Khir., 3 (1987) 8-10.
8,5 TLC 4.5 TLC 4.5 HPTLC Solute pair
MF MF MF
allocryptopine/protopine 2.79 2.29 1.21 0.91 1.78 1.15
protopine/homochelidonine 3.18 4.57 2.81 3.36 3.50 3.22
homochelidonine/chelidonine 0.84 0.95 0.83 0.52 0.91 1.74
F.Ch. UMCS Report 2009 (BS) – 73 –
A NEW METHOD FOR THE DETERMINATION OF RETENTION
OF SUBSTANCE IN TERNARY MOBILE PHASES
Irena MALINOWSKA, Barbara OŚCIK-MENDYK, Małgorzata JANICKA
and Ludomir KWIETNIEWSKI
DEPARTMENT OF PLANAR CHROMATOGRAPHY
Adsorption liquid chromatography is one of most widely used techniques
available for analysis of complex organic mixtures. Significant progress has been
made during the last twenty years in the theory of adsorption liquid chromatography
with a mixed mobile phase. The quasi-chemical theory of the retention process is
widely known. This treatment, starting from the original displacement model,
incorporates various factors characterizing the adsorption equilibria for
multicomponent eluents. Because of their relative simplicity, binary mobile phases
are generally favored over more complex solvent mixtures. However, it frequently
happens that ternary mobile phases have to be used for a given separation. The
general equations derived for multicomponent mobile phases are complicated and
they involve parameters which are difficult to extract from experimental
measurements. That is why simple methods for calculating of the capacity ratio in
ternary mixed solvent are much desired.
Borówko and Ościk-Mendyk [1] proposed a fast method for predicting the
capacity ratio in ternary mobile phase on the basis of experiments estimated for two
binary solvents. The ratio of mole fractions of two less polar solvents, r = x2/x3, was
constant. The capacity ratio in the ternary mobile phase, (logk), was calculated by
means of capacity ratios in the binary solvents, (1+2) and (1+3), containing the
same mole fractions of the most polar solvent (x1 = const). The equation used in
study was as follows:
)31()21( log1
1log
1log
+++
+
+
= kr
kr
rk (1)
The aim of the report is continuation of study on relationship between values
of retention parameters and mobile phase composition. The fast method for
predicting the capacity ratio in ternary mobile phase on the basis of experiments
estimated for two binary solvents was analyzed. The three polar, specific negative
stationary phases were tested – aminopropyl-, cyanopropyl- and diol-silica.
The chromatographic measurements were made using thin-layer adsorption
chromatography. The components of mobile phase were: n-heptane, toluene, ethylene
chloride, chloroform and tetrafydrofuran. A ternary mobile phase can be considered as a
mixture of the polar solvent 1 and binary mixed solvent 2+3. In the preparation of the
ternary mobile phases the concentration of the binary phase (2+3) was first defined
i.e. their molar ratio (r = x2/x3) was equal to 1/3, 1 and 3. Then the most polar solvent
was added in concentrations equalling to 0.3, 0.4, 0.5, 0.6 and 0.7 of the molar fraction
value. The measurements were made for binary and ternary mobile phases. Then logk
Department of Planar Chromatography – 74 –
values for ternary mobile phases were calculated according to above equation and
compared to those obtained in experimental measurements. The measurements were
made twice and average values were analyzed.
Table 1. The values of logk calculated according to eq. (1) and obtained from
experimental data in different chromatographic systems.
Conclusions
– the proposed equation may be used for fast predicting the capacity ratio in the
ternary mobile phases on the basis of experimental data obtained for two
binary solutions,
– the tested equation shows good conformability with experimental data.
References:
[1] M. Borówko and B. Ościk-Mendyk, Chromatographia, 60 (2004) 51.
r = 1/3 r = 1 r = 3 Substance x1
exp. th. exp. th. exp. th.
Heptane + Toluene + Tetrahydrofuran
0.3 –0.008 –0.009 –0.069 –0.073 –0.140 –0.136
0.4 –0.100 –0.102 –0.145 –0.150 –0.189 –0.197
0.5 –0.155 –0.162 –0.200 –0.203 –0.250 –0.243 acridine
NH2 0.6 –0.213 –0.215 –0.251 –0.247 –0.281 –0.279
0.3 0.200 0.195 0.120 0.114 0.040 0.035
0.4 0.110 0.109 0.040 0.039 –0.030 –0.031
0.5 0.030 0.040 –0.027 –0.021 –0.078 –0.081
indole
NH2
0.6 –0.025 –0.020 –0.068 –0.071 –0.120 –0.122
Heptane + Toluene + Chloroform
0.3 0.722 0.704 0.555 0.544 0.401 0.383
0.4 0.569 0.559 0.432 0.421 0.272 0.281
0.5 0.428 0.431 0.313 0.317 0.200 0.203
0.6 0.300 0.307 0.228 0.222 0.131 0.135
2-nitroaniline
CN
0.7 0.200 0.209 0.141 0.149 0.080 0.083
0.3 0.400 0.411 0.232 0.228 0.083 0.079
0.4 0.252 0.248 0.131 0.125 0.006 0.003
0.5 0.141 0.137 0.032 0.041 –0.070 –0.056
0.6 0.050 0.044 –0.040 –0.032 –0.110 –0.107
NH C CCl3
O
CN 0.7 –0.010 –0.020 –0.090 –0.081 –0.135 –0.142
Heptane + Toluene + Chloroform
0.3 0.788 0.777 0.567 0.554 0.343 0.311
0.4 0.525 0.514 0.321 0.333 0.144 0.151
0.5 0.292 0.297 0.154 0.161 0.020 0.026
0.6 0.138 0.142 0.040 0.044 –0.060 –0.054
F NH C CCl3
O
Diol 0.7 0.020 0.016 –0.060 –0.054 –0.110 –0.123
F.Ch. UMCS Report 2009 (BS) – 75 –
THE APPLICATION OF LINEAR FORM OF OŚCIK’S EQUATION
FOR DETERMINATION OF HYDROPHOBICITY INDEX
Irena MALINOWSKA, Barbara OŚCIK-MENDYK, Małgorzata JANICKA
and Ludomir KWIETNIEWSKI
DEPARTMENT OF PLANAR CHROMATOGRAPHY
In the studies Ościk’s equation assuming partition-displacement model for
chromatographic process is proposed for description of solute retention in reversed-
phase liquid chromatography. Moreover, a numerical method of calculation of
solutes retention factors in water, derived from the linear form of this equation is
presented. Experimental RP HPLC results were obtained for alkyl benzene
homologues using chemically bonded stationary phases: RP-8 (octylsilyl-silica),
ODS (octadecylsilyl-silica) and PLRP-S (polystyrene-divinylbenzene polymer, PS-
DVB) and water-methanol and/or water-acetonitrile mixtures as effluents.
Calculated chromatographic parameters, log kw, were analyzed as hydrophobicity
indices and related to nominal retention index and experimental and calculated
log P values.
The results obtained in the studies enable to formulate the following
conclusions:
– Ościk’s equation describes well solute retention in RP LC because very
good accordance between theoretical and experimental retention
factors for all solutes tested was obtained, independently of stationary
and mobile phase properties (Figure 1); – chromatographic log kw parameters calculated by numerical method basing
on linear form of Ościk’s equation are very good hydrophobicity indices
which is demonstrated by linear relationships between log kw values and
nominal retention indices (Figure 2) and experimental and calculated log P
partition parameters (Figure 3).
0 0.2 0.4 0.6 0.8
-2
0
2
4
log k
s(1
2)
x1l
Fig. 1. Theoretical (lines) and experimental
(points) log ks(12) values obtained for propyl
benzene in different chromatographic
systems: () RP-8/water-methanol and (∆)
RP-8/water-acetonitrile.
Department of Planar Chromatography – 76 –
0.00 2.00 4.00 6.00
0.00
2.00
4.00
6.00
References:
[1] M.M. Sanagi, U.K. Ahmad, K. Hassan and G. Musa, J. Chromatogr. A, 722
(1996) 59.
[2] M. Janicka, J. Liq. Chromatogr. Rel. Technol., 32 (2009) 2779.
0.00 2.00 4.00 6.00
0.00
400.00
800.00
1200.00
Ret
enti
on i
ndex
, I
log P
exp
log kw
log kw
Fig. 2. I vs. log kw relationships obtained for
() RP-8/water-acetonitrile; () RP-8/water-
methanol; (∆) ODS/water-acetonitrile and
() PLRP-S/water-acetonitrile.
Fig. 3. log Pexpvs. log kw relationships
obtained for () RP-8/water-acetonitrile;
() RP-8/water-methanol; (∆) ODS/water-
acetonitrile and () PLRP-S/water-
acetonitrile
F.Ch. UMCS Report 2009 (BS) – 77 –
SYNTHESIS AND INVESTIGATIONS OF PROPERTIES OF SILICEOUS AND CARBONACEOUS MESOPOROUS
MATERIALS
Anna DERYŁO-MARCZEWSKA, Adam W. MARCZEWSKI*,
Szymon WINTER, Dariusz STERNIK and Grzegorz ŻUKOCIŃSKI
DEPARTMENT OF PHYSICOCHEMISTRY OF SOLID SURFACE
*DEPARTMENTNT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
The problem of dye removal from waters and wastewaters is important and
extensively investigated [1]. Regarding the dye stability to light and oxidizing
agents and resistance to biodegradation the usefulness of some traditional methods
for treatment of dye-containing sewage is limited. As an alternative method the
adsorption process can be used as an effective technique in the treatment of dye
containing wastewaters [2]. Among various adsorbents the activated carbons seem
to be very popular because of their high affinity towards different solutes resulting
in their effectiveness in purification of waters and wastewaters from inorganic and
organic substances of differentiated properties. Commonly used granular activated
carbons are microporous materials with certain share of mesopores serving as
transport routes. The equilibrium of adsorption process in pore system of
microporous carbon granules establishes slowly as a result of slow solute diffusion
in the internal adsorbent space, even though the adsorption is usually very strong.
With regard to small micropore sizes the effective usage of activated carbons is
limited to low-molecular substances.
In the present paper the adsorption properties of two mesoporous carbons of
divergent porosity towards methylene blue and methyl orange were studied [3]. The
carbons were synthesized by the method of impregnation of mesoporous silicas
with carbon precursor. The adsorption isotherms from aqueous solutions of
methylene blue and methyl orange and the kinetic profiles were measured. The
solute interactions with carbon surface were investigated by the thermal analysis.
The parameters characterizing the structural properties of two synthesized
carbonaceous materials are compared in Table 1.
Table 1. The values of parameters characterizing porous structure of synthesized
carbons calculated from nitrogen adsorption/desorption isotherms [3].
Carbon SBET
[m2/g]
Vt
[cm3/g]
Vp
[cm3/g]
Sext
[m2/g]
D
[nm]
W-1 255 0.14 0.13 7 1.8
W-2 705 0.72 0.54 100 4.1
Department of Physicochemistry of Solid Surface – 78 –
The differences in structural properties of the synthesized adsorbents influence
the adsorption of studied dyes from aqueous solutions. For both adsorbates much
stronger adsorption is observed on the carbon W-2 characterized by higher specific
surface area and wider pores. Lower adsorption on W-1 is a result of its low surface
area and small pore sizes. Clearly, some of the smallest pores are not accessible for
large dye molecules additionally reducing the amount of adsorbed dyes.
Kinetics of adsorption process may be a critical factor while regarding the
usefulness of the adsorption technique on a large scale in technological or
environmental applications. Thus, for all adsorption systems the solute
concentration-time profiles were measured.
For analysis of the kinetics data of adsorption of methylene blue (MB) and
methyl orange (MO) on W-1 and W-2 carbons the multi-exponential equation was
used:
∑=
−−=
n
i
iieqeq tkfaaa1
)exp( where 11
=∑=
n
i
if
The data and fitted curves are shown in Fig. 1 (left panel). Moreover, in Fig. 1
(right panel) the parameter spectra of fitted equation are shown. One can easily find
the similarities between MB and MO adsorption kinetics on the same carbon – for
carbon W-1 (solid lines) having small pores, slow processes (low ki) prevail (high
share fi), however, for carbon W-2 (dotted lines) with bigger pores, the kinetic terms
corresponding to various kinetic rate constants have similar magnitudes fi.
0
0,2
0,4
0,6
0,8
1
0 1000 2000 3000 4000t [min]
c/co
0,00
0,05
0,10
a [m
mo
l/g
]
MB / W-1
MO / W-1
MO (2) / W-1
MB / W-2
MO / W-2C/Co (m-exp fit)
a (m-exp fit)
0,0
0,2
0,4
0,6
-5 -4 -3 -2 -1 0
log ki
fi
MB / W-1MO / W-1MO (2) / W-1MB / W-2MO / W-2
Fig. 1. Adsorption kinetics of methylene blue (MB) and methyl orange (MO) on
mesoporous carbons W-1 and W-2 (lines – optimized multi-exponential equation)
(left) and parameter spectrum of fitted lines (right).
References:
[1] R.C. Bansal, M. Goyal, Activated Carbon Adsorption, CRC Press, Boca Raton
2005.
[2] Y. Al Degs, M. Khraisheh, Water Res. 34 (2000) 927.
[3] A. Derylo-Marczewska, A.W. Marczewski, Sz. Winter, and D. Sternik, Appl.
Surf. Sci., (2010), doi:10.1016/j.apsusc.2009.12.085.
F.Ch. UMCS Report 2009 (BS) – 79 –
STUDIES OF THE PROCESSES OF HERBICIDES REMOVING FROM AQUEOUS SOLUTIONS ON MICROPOROUS ACTIVATED
CARBONS
Anna DERYŁO-MARCZEWSKA, Magdalena BŁACHNIO,
Adam W. MARCZEWSKI* and Bogdan TARASIUK
**
DEPARTMENT OF PHYSICOCHEMISTRY OF SOLID SURFACE
*DEPARTMENTNT OF RADIOCHEMISTRY AND COLLOID
CHEMISTRY
**DEPARTMENT OF ORGANIC CHEMISTRY
The contamination of surface and ground waters by pesticides is an important
problem investigated over the years. Pesticides are group of inorganic and organic
compounds that may pollute water due to their extensive application in agriculture.
The harmful effect of these types of compounds results from their generally high
mobility and persistence in the aqueous media and to their toxicity. MCPA (4-
chloro-2-methyphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) are
examples of widely used herbicides which belong to the group of synthetic
herbicides, the chlorophenoxy herbicides. They are commonly preferred because of
their low cost and good selectivity. They may be used also in combination with
other herbicides for the post-emergence control of broad-leaved weeds [1]. Mobility
of MCPA and 2,4-D in natural environment may be attributed to their anionic form.
Since anionic pesticides are very weakly retained by most of the soil components
because of their structural negative charge, they remain dissolved in the soil
solution and can rapidly move around leading subsequent contamination of surface
and ground waters.
Regarding a wide variety of herbicides of different physical and chemical
properties, it is difficult to apply a single method for their removal from water.
Conventional water treatment processes such as filtration, disinfection, coagulation,
and sedimentation have been reported to be more effective in removing less water
soluble and easily degradable pesticides [2]. Another potential method for the
removal of herbicides from water is adsorption. In order to find good adsorbents for
the removal of pesticides from contaminated aqueous solutions many studies were
conducted on various materials.
In the present study, the process of removal of the popular herbicides MCPA
and 2,4-D from aqueous solutions by adsorption on granular activated carbon F-
300 (Chemviron Carbon, Feluy, Belgium) was investigated. The adsorption
isotherms and the kinetic curves were measured experimentally and studied by
applying conventional theoretical models [3]. The data of thermal decomposition
of pure activated carbon and carbon samples with adsorbed herbicides were also
analyzed [3].
Department of Physicochemistry of Solid Surface – 80 –
In Fig. 1 the adsorption isotherms of 2,4-D and MCPA measured at 288, 298,
308 and 318 K are compared. In the case of both systems slight temperature effect
is observed – adsorption of MCPA ad 2,4-D increase slightly with increasing
temperature. Such a behavior of adsorption systems may be a result of superposition
of various effects. The increase of adsorption with temperature indicates
endothermic character of adsorption, it could also be due to the enhanced mobility
of 2,4-D and MCPA ions from the bulk solution towards the adsorbent surface and
extent of penetration within adsorbent structure overcoming the activation energy
barrier and enhancing the rate of intraparticle diffusion. This trend may be also
attributed to creation of some new active sites on the adsorbent surface due to bond
rupture. The opposite trend of adsorption decreasing with temperature increase may
be interpreted by exothermic character of adsorption process, increase of solubility
resulting in adsorption decrease, and increase of oscillation energy of herbicide
molecules resulting in desorption from surface phase to bulk phase.
The results of kinetic experiments are also shown in Fig. 1 as the relative
adsorption progress (a/aeq) data for MCPA and 2,4-D. The kinetic processes for
MCPA (smaller and easier soluble) are clearly faster than in the case of 2,4-D. This
effect may result in apparently higher adsorption of MCPA in applications where
the granular F-300 is used with limited contact time. The data were fitted by using
the standard PFO (pseudo-first order) and PSO (pseudo-second order) equations.
The results of fitting to the PFOE were not satisfactory, whereas the results for
PSOE were quite good.
0
1
2
0 0,1 0,2 0,3 0,4
ceq [mmol/l]
aeq [m
mo
l/g
]
MCPA(15oC)
MCPA(25oC)
MCPA(35oC)
MCPA(45oC)
0
0,01
0,02
0,03
0,04
0,05
0,06
0,07
0 5000 10000 15000t [min]
a(t
) [m
mo
l/g
]
MCPA / F-300
2,4-D / F-300
Fig. 1. Comparison of isotherms of MCPA adsorption from aqueous solutions on the
activated carbon F-300 at different temperatures and comparison of kinetic
adsorption curves for MCPA and 2,4-D at 293 K.
References:
[1] C. Tomlin, The pesticide manual, 10th Edition, Crop Protection Publications,
UK, 1994.
[2] A. Kouras, A. Zouboulis, C. Samara, T. Kouimtzis, Environ. Pollut., 10 (1998)
193.
[3] A. Deryło-Marczewska, M. Błachnio, A.W. Marczewski, A. Świątkowski, 52
Zjazd PTChem i SITPChem, Łódź 2009, OC-08-09, p. 24.
F.Ch. UMCS Report 2009 (BS) – 81 –
MSPD AS SAMPLE PREPARATION METHOD
FOR GC ANALYSIS OF ESSENTIAL OILS IN HERBS
Andrzej L. DAWIDOWICZ and Ewelina RADO
DEPARTAMENT OF CHROMATOGRAPHIC METHODS
Sample preparation is the crucial step in procedures of chemical analysis of
plant material. Recently, some interest has been focused on those sample
preparation methods which allow for the reduction of organic solvent consumption,
exclusion of sample component degradation, elimination of additional sample
clean-up and pre-concentration step before chromatographic analysis, improvement
of extraction efficiency and selectivity, and/or kinetics.
Matrix solid-phase dispersion (MSPD) is a simple and cheap sample
preparation procedure involving simultaneous disruption and extraction of various
solid and semi-solid materials. MSPD involves the direct mechanical blending of
sample with a SPE sorbent (mainly octadecyl modified silica). In this process, the
sorbent acts as both an abrasive material disrupting sample architecture and as a
‘bound’ solvent that assists in accomplishing sample disruption. After the
homogenisation step blended mixture is transferred into a SPE barrel and subjected
to elution step with an appropriate eluent. The obtained eluate is analysed in the
final step of the analytical procedure.
MSPD has been used for performing the extraction of a variety of matrices for
a number of compounds. However, there is a little knowledge about the MSPD
application as a sample preparation method for the analysis of essential oil
components in herbs.
The presented paper discusses the possibility of MSPD application for the
analysis of essential oil components in the following herbs: thyme (Thymus vulgaris
L.), mint (Mentha piperita), sage (Salvia officinalis L.), chamomile (Chamomilla
recutita L.), lemon balm (Melissa Officinalis L.), marjoram (Origanum majorana
L.), savory (Satureja hortensis L.), oregano (Origanum vulgare). The results
obtained using MSPD are related to analogous ones gained applying two other
sample preparation methods - steam distillation, recognized as the standard essential
oil preparation method, and pressurized liquid extraction (PLE), regarded as one of
the most effective extraction techniques
Results and Discussion
Table 1 contains the total amounts of essential oil components estimated in the
examined herbs using steam distillation, PLE and MSPD. The presented values
were calculated in relation to the known amount of hexadecane added to the herb
extracts as a quantity standard.
The consideration of the collected data leads to the conclusion that the greatest
total amounts of essential oil components are estimated when PLE or MSPD is used
Department of Chromatographic Methods – 82 –
for sample preparation in herb analysis procedure. According to the literature, PLE
is one of the most effective sample preparation methods. High extraction power of
PLE results from the application of high pressure during the extraction process,
allowing to use an extrahent at a temperature above its normal boiling point and in
consequence to remove the analytes efficiently and quickly from various matrices.
Hence, PLE results presented in Table 1 can only be treated as a confirmation of
high extracting ability of PLE in relation to essential oil components from herb.
More interesting seem to be, however, the MSPD results as they indicate that the
extraction efficacy of this very simple and cheap sample preparation procedure is
equivalent to that for PLE which, in contrary to MSPD, is technically advanced and
developed method. High yield of essential oil components in MSPD process results
both from the chemical character of the compounds and the capacity of bonded C-
18 layer which plays the role of a reservoir for the isolated components.
Table 1. Total amounts of essentials oils components estimated in herbs using
steam distillation, PLE and MSPD. Mean values ± sd, n = 3.
Sample preparation method Type of herb
Steam distillation PLE MSPD
Chamomile 1.85 ± 0.08 2.19 ± 0.09 2.07 ± 0.15
Thyme 9.48 ± 0.44 9.99 ± 0.41 9.91 ± 0.65
Lemon balm 0.63 ± 0.05 0.85 ± 0.05 0.88 ± 0.06
Mint 8.72 ± 0.35 9.60 ± 0.30 9.87 ± 0.66
Sage 7.84 ± 0.36 8.54 ± 0.27 8.36 ± 0.55
Marjoram 3.35 ± 0.15 4.68 ± 0.17 5.06 ± 0.37
Savory 17.68 ± 0.63 17.32 ± 0.68 17.86 ± 0.95
Oregano 2.16 ± 0.08 3.04 ± 0.12 3.17 ± 0.26
As results from Table 1 the standard essential oil separation method - steam
distillation - is generally less effective isolation process of essential oil components
than MSPD and PLE. Isolation efficiency of steam distillation is equivalent to PLE
and MSPD only in the case of essential oil components from savory.
Conclusions
MSPD has been demonstrated to be a suitable preparation technique for the
isolation of essential oil components from herbs. The results presented in the paper
prove that the total amount of essential oil obtained by MSPD is equivalent to that
gained by one of the most effective extraction technique, PLE. In contrary to PLE,
MSPD is performed using a very simple and cheep equipment, what strongly
emphasizes its usefulness in analytical procedure. Moreover, the method requires a
small sample size and offers considerable savings in terms of solvent consumption,
cost of materials, sample manipulation and time involved. In consequence, MSPD
can be regarded as GRAS (generally recognized as save) method.
F.Ch. UMCS Report 2009 (BS) – 83 –
APPLICATION OF MECHANOCAL, HYDROTHERAL
AND MICROWAVE TREATMENT FOR PREPARATION
OF CATALYSTS AND ADSORBENTS
Jadwiga SKUBISZEWSKA-ZIĘBA, Roman LEBODA
and Barbara CHARMAS
DEPARTMENT OF CHROMATOGRAPHIC METHODS
I. Investigation of physicochemical transformation at mechanochemical,
hydrothermal and microwave treatment of barium titanyloxalate.
Barium metatitanate BaTiO3 (BMT) is one of the most prevalent and popular
electroceramic materials. It is applied for preparation of multilayer capacitors,
thermistors, sensitive elements of gas and water vapor sensors, catalyst supports,
photocatalyst and for other purposes. Recent possibilities of temperature decrease at
BMT synthesis as well as the preparation of this substance in the nanocrystalline
powder form, which should improve servicing characteristics of the products,
arouse of great interest.
The effect of mechanochemical (in air and water) as well as hydrothermal and
microwave treatments on physicochemical transformations of barium titanyloxalate
BaTiO(C2O4)2·4H2O (BTO) as precursor of BaTiO3 was studied. The obtained
samples were examined using XRD and thermal analysis, FTIR spectroscopy, argon
thermodesorption and granulometry.
It was stated that mechanochemical treatment (MChT) of barium titanyloxalate
in air for 5 h leads to formation of barium metatitanate with structural defects and
next it is transformed into well-crystallized cubic modification of barium
metatitanate at calcination in air already at 550°C. Whereas without preliminary
MChT this phase is formed during the thermal decomposition only at 800°C. The
product of barium titanyloxalate MChT in the aqueous medium is transformed into
barium metatitanate after its next calcination at 700°C. All samples of barium
metatitanate synthesized by means of MChT were characterized by much larger
specific surface area compared with ones prepared by means of usual calcination of
barium titanyloxalate. Preliminary hydrothermal and microwave treatments of
barium titanyloxalate promote formation of barium orthotitanate (Ba2TiO4) and
carbonate (BaCO3) mixture. The results obtained in presented work can be useful
for synthesis of BMT which can be applied for different purposes
II. Deposition of tungsten heteropolycompounds on activated silica surface
Heteropolycompounds (HPC) owing to their remarkable properties are widely
applied in many processes important from the practical point of view. They are very
strong Broensted acids both in the form of dissolved and solid states, what favours
their application in homo– and heterogeneous acid–base catalysis and in ion
Department of Chromatographic Methods – 84 –
exchange processes and as solid electrolytes. On the other hand, HPC contain such
transition metals as molybdenum, tungsten, vanadium and others which results in
their red-ox properties and the possibility of their using in catalytic oxidation of
organic compounds. Thus HPC are bi-functional catalysts. There are also numerous
examples of their application in adsorption, membrane and other processes.
The aim of the studies was the investigation of the possibilities of
phosphorotungstic heteropolyacid H3PW12O40 (PTA, Fluka) chemical grafting to the
surface of silica previously activated by various functional groups and next
determination of some physicochemical characteristics of the obtained materials.
Model mesoporous silica–aerosilogel in the form of cylindrical granules was used
as initial support. Aerosilogel granules were prepared by extrusion of aqueous
dispersion of aerosil A-300 (Kalush, Ukraine) with the solid/liquid phase ratio equal
0.25, and then dried at 20°C for 48 h. The silica granules obtained in such way were
preliminarily activated by two methods:
– by the reaction of surface silanol groups with 3- aminopropyltrietoxysilane;
– the interactions of surface silanol groups with polyhydroxy alcohols–butanediol
and glycerine.
Then phosphorus–tungstic heteropolyacid H3PW12O40 (PTA) was deposited on
the activated supports from aqueous or acetone solutions (20%, w/w):
– at room temperature (20°C);
– in the laboratory stainless autoclave at 150–250°C;
– in microwave reactor at 150°C (NANO-2000, Plazmotronika, Poland);
– in planetary ball mill at 600 rpm (Pulverisette-6, Fritsch).
On the basis of obtained results it was stated that the samples prepared as a
result of interaction of PTA with aminogroups immobilized on silica surface were
characterized by the following properties:
– Keggin structure of heteropolyanion.
– Presence on their surface both the organic and inorganic groups, which allow to
include them into functional hybrid materials.
– Developed mesoporous structure.
– Not very high acidity, however variable in a sufficiently wide range.
– Stability (resistance to dissolution) in aqueous and organic media.
– Sufficiently high thermostability up to 500°C.
Deposited samples can be use for extraction of small amounts of ammonia
from gaseous mixtures. The above mentioned characteristics indicate the
possibilities of applying such materials as adsorbents, ion exchangers and also in
liquid- and gaseous phase catalysis (with some limitations).
References:
[1] V.V. Sydorchuk, V.A. Zazhigalov, S.V. Khalameida, K. Wieczorek-Ciurowa,
J. Skubiszewska-Zięba, R. Leboda, Investigation of physicochemical transformation at
mechanochemical, hydrothermal and microwave treatment of barium titanyloxalate,
Journal of Alloys and Compounds, 482 (2009) 229–234
[2] V.V. Sydorchuk, V. Zazhigalov, S. Khalameida, J. Skubiszewska-Zięba, B. Charmas,
R. Leboda, Deposition of tungsten heteropolycompounds on activated silica surface,
Coll. Surf. A., 341 (2009) 53-59
F.Ch. UMCS Report 2009 (BS) – 85 –
SYNTHESIS AND STRUCTURAL-ADSORPTION PROPERTIES OF BRIDGED POLYSILSESQUIOXANES FUNCTIONALIZED
WITH DIFFERENT GROUPS
Andrzej DĄBROWSKI and Mariusz BARCZAK DEPARTMENT OF THEORETICAL CHEMISTRY
Bridged polysilsesquioxanes (BPs) are a class of hybrid organic-inorganic materials, formed by molecular building blocks [1-3]. Such building units include a bridge of organic origin that links two or more Si atoms by hydrolytically stable Si–C bonds. BP xerogels can be presented as bis(trialkoxysilanes) structures (RO)3Si–R′–Si(OR)3, where R is the alkyl group, and R′ is the organic bridge (spacer). By co-condensation of two or more monomers it is possible to design on a molecular level the surface chemical composition of final materials keeping control over their chemical and physical properties, including structure-adsorption characteristics. Schema of such cocondensation is depicted on Fig. 1.
Fig. 1. Schema of the co-condensation of tetraethoxysilane or bridged bis(trialkoxy- silane) with functionalized trialkoxysilane (on the bottom – numeration of the samples).
Amino-, thiol-, urea-, acethoxy-, cyano-, isocyanato-, chloro-, vinyl-, and
phenyl- functionalized polysilsesquioxane and polysiloxane xerogels have been obtained by co-condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) or tetraethoxysilane (TEOS) with appropriate trifunctional silanes (FOSs). In the Table 1 the structural-adsorption characteristics of the obtained samples are given.
Department of Theoretical Chemistry – 86 –
Тable 1. Structure-adsorption characteristics of the obtained xerogels [4].
adsorption parameters adsorption parameters BPs serie
SBET [m2/g
]
Vp [cm3]
dBJH [nm]
content of functional
groups [mmol/g]
POs serie
SBET [m2/g
]
Vp [cm3]
dBJH [nm]
content of functional
groups [mmol/g]
A1 593 1.25 8.1 2.4
(2.8) B1 406
(329) 0.70
(0.72) 5.1
(5.8) 3.8
(4.2)
A2 614 0.52 3.3 2.3
(2.5) B2 499
(151) 1.07
(0.35) 10.9 (9.6)
3.5 (3.6)
A3 738 0.62 3.3 2.1
(2.5) B3
346 (136)
0.71 (0.27)
9.0 (7.7)
3.9 (3.6)
A4 0 --- --- 3.1
(2.6) B4 132
(117) 0.72
(0.60) 16.8
(16.2) 3.9
(3.8)
A5 1027 1.52 6.1 2.0
(2.7) B5 611
(378) 1.18
(0.60) 7.4
(5.6) 3.4
(3.9)
A6 792 0.53 2.8 2.7
(2.7) B6
486 (432)
0.37 (0.29)
3.0 (2.9)
4.0 (3.9)
A7 494 0.41 3.2 2.6
(2.7) B7 505
(342) 0.39
(0.21) 2.9
(2.9) 3.9
(3.9)
A8 849 0.72 3.2 ---
(2.7) B8 517
(391) 0.31
(0.22) 2.5
(2.5) ---
(3.9)
A9 451 0.30 2.9 ---
(4.6) B9 15 (4)
0.1 (0.0)
--- (---)
--- (6.2)
A10 1182 1.15 3.4 ---
(3.1) B10 876
(849) 0.79
(0.60) 3.2
(2.8) ---
(4.8)
A11 606 0.34 2.6 ---
(2.5) B11 295 (4)
0.17 (0)
2.5 (---)
--- (3.6)
A12 826 0.61 2.9 ---
(2.7) B12 603
(527) 0.39
(0.30) 2.6
(2.7) ---
(3.9)
Ethylene-bridged polysilsesquioxane xerogels have better structure-adsorption
characteristics (SBET: 450-1200 m2/g, Vp: 0.35-1.5 cm3) than corresponding polysiloxanes (SBET: 15-900 m2/g, Vp: 0.1-1.2 cm3) confirming that the presence of ethylene bridges in the framework has a big impact on the final properties. Both series of materials have high loadings of functional groups (2.1-2.6 mmol/g in the case of BPs and 3.4-4.0 mmol/g in the case of POs). The principal factors influencing structure-adsorption characteristics of investigated hybrid materials are: the presence of organic bridges in the crosslinked structure and the nature of the functional groups. Thus it is possible to adjust the porosity by choosing appropriate monomers, providing that way in situ conditions necessary to develop desired type of porous structure.
References:
[1] K.J. Shea, D.A. Loy, O. Webster, J. Am. Chem. Soc., 114 (1992) 6700. [2] H.W. Oviatt, K.J. Shea, J.H. Small, Chem. Mater., 5 (1993) 943. [3] K.J. Shea, J. Moreau, D.A. Loy, R.J.P. Corriu, B. Boury [in:]Functional Hybrid
Materials, P.Gomez-Romero, C.Sanchez (Eds.), pp. 50-85, Wiley-VCH, Weinheim, 2004.
[4] M. Barczak, P. Borowski, A. Dąbrowski, Colloids and Surfaces A Physico-
chemical Aspects, 347 (2009) 114.
F.Ch. UMCS Report 2009 (BS) – 87 –
SYNTHESIS, STRUCTURE AND ADSORPTION PROPERTIES OF NANOPOROUS SBA-15 MATERIALS WITH FRAMEWORK
AND SURFACE FUNCTIONALITIES
Andrzej DĄBROWSKI, Mariusz BARCZAK and Stanisław PIKUS* DEPARTMENT OF THEORETICAL CHEMISTRY *DEPARTMENT OF CRYSTALLOGRAPHY
Ordered mesoporous silicas (OMOs) are attractive materials due to their high surface areas, large pore volumes, large, uniform and adjustable pore sizes, and diverse morphology what makes them potential catalysts and adsorbents [1]. The first successful attempt in these field was done by researchers from Mobil when a family ordered mesoporous aluminosilicates, denoted as M41S materials, was obtained by supramolecular templating approach [2, 3]
Very important advantage connected with the sol-gel synthesis of silica materials is the possibility of introduction of the organic groups into the ordered structure during one-pot synthesis. In this way new organic-inorganic hybrids with desired optical, mechanical and electrical properties can be created, what make such materials attractive in adsorption, catalysis or sensing [4]. Functionalized materials are called ordered mesoporous organosilicas (OMOs) or periodic mesoporous organosilicas (PMOs) depending on the type of moieties incorporated (side-end groups sticking inside the pores in the case of the former or bridging groups incorporated in the mesopores walls in the case of the latter). Such a surface functionalization leads to materials differing in the reactivity, pore accessibility and distribution of organic groups. These groups can be attached to the internal and external surfaces of mesopores as well as incorporated in the framework as integrated bridges.
Herein, we report the synthesis channel-like mesoporous organosilicas synthesized by co-condensation of tetraethoxysilane (TEOS) with bridged polysilsesquioxane monomers bearing ethylene and phenylene bridges and alkoxysilanes bearing aminopropyl, mercaptopropyl, vinyl and phenyl groups which can form surface species. Obtained materials were characterized by powder X-ray diffraction (XRD), nitrogen sorption measurements, elemental analysis and atomic force microscopy (AFM).
Syntheses of all channel-like mesoporous SBA-15 silicas were performed in the presence of P123 triblock copolymer by co-condensation of TEOS and organotrialkoxysilane (APTES, MPTES, VTES or PTES) or/and bridged silsesquioxane (BTESE or BTESB) to introduce the desired surface and framework functional groups. All functionalized SBA-15 materials were synthesized by one-pot route using by the similar synthesis procedure reported elsewhere [4].
Isotherms of the all samples have a sharp capillary condensation step, reflecting capillary condensation of adsorbate in the uniform mesopores channels, and evaporation step related to the evacuation of adsorbate from the pores. Thus, it
Department of Theoretical Chemistry – 88 –
can be concluded that a framework of materials has an uniform array of mesopores with the same diameter. All materials exhibit high values of surface area (SBET) ranging from 700 to 1063 m2/g. Other structural-adsorption parameters are presented in the Table 1.
Table 1. Structure-adsorption characteristics of the materials studied.
No. molar ratio of
monomers SBET [m2/g]
Vp [cm3/g]
dBJH [nm]
dKJS [nm]
dXRD [nm]
1 TEOS 700 0.95 5.6 9.3 8.1
2 TEOS/BTESE/APTES
18:1:1 842 2.31 11.4 --- ---
3 TEOS/BTESE/MPTES
18:1:1 777 1.02 4.6 7.7 7.8
4 TEOS/BTESB/APTES
18:1:1 836 1.26 5.7 9.2 8.6
5 TEOS/BTESB/MPTES
18:1:1 820 0.93 4.3 7.7 6.5
6 TEOS/PTES
18:2 1063 1.28 4.8 8.2 7.1
7 TEOS/VTES
18:2 973 1.35 5.4 7.9 ---
8 TEOS/PTES/VTES
18:1:1 976 1.13 4.6 8.0 ---
Both, structural parameters (SBET, Vp, d) and degree of ordering are dependent upon the type of functionalized silane used in the synthesis. It was shown that simultaneous addition of certain amount of amine groups leads to ordered structure if the phenylene bridge monomer is also present in the initial mixture. However, the higher concentrations of amine groups make the final sample less ordered or even unordered, which is reflected by disappearance of the diffraction peaks on XRD patterns. In the case of vinyl and vinyl/phenyl functionalized SBA-15 organosilicas the type of ordering is rather tetragonal than hexagonal testifying to the fact that even relatively small amount of co-monomer added during the synthesis can affect the final structure and type of ordering.
Two methods of determining the average mesopores size, KJS method [5] and method based only on the XRD measurements [6], has been tested showing a good convergence between these two. References:
[1] E. B. Celer, M. Jaroniec, J. Am. Chem. Soc. 128 (2006) 14408. [2] C. T. Kresge et al., Nature 359 (1992) 710. [3] J. S. Beck et al., J. Am. Chem. Soc. 114 (1992) 10834. [4] R. M. Grudzien, B. E. Grabicka, M. Jaroniec, Adsorption 12 (2006) 293. [5] M. Kruk, M. Jaroniec, A. Sayari, Langmuir 13 (1997) 6267. [6] S. Pikus, L.A. Solovyov, M. Kozak, M. Jaroniec, Appl. Surf. Sci., 253 (2007)
5682.
F.Ch. UMCS Report 2009 (BS) – 89 –
THEORETICAL DESCRIPTION OF THE ADSORPTION KINETICS BASED ON THE STATISTICAL RATE THEORY
OF INTERFACIAL TRANSPORT (SRT)
Władysław RUDZIŃSKI DEPARTMENT OF THEORETICAL CHEMISTRY
Adsorption at a solid/solution interface is one of the most commonly used physical processes applied in the purification of waste waters. Understanding mechanisms of the kinetics of this process is crucial for designing sorption processes effectively. The main results can be summarized as follows:
1. The utility of the Weber-Morris and the Lagergren linear representations has been studied. The effects of different sorbent particle sizes, non-linear adsorption isotherm equations (including the non-linearity caused by the surface energetic heterogeneity) and the changing sorbate concentration in the bulk phase have been taken into account [1].
2. A novel two-resistance model for description of the sorption kinetics by porous particles has been proposed. The model takes into account two kinetic steps of different kinds which are involved in the overall sorption process rate: (i) the rate of solute diffusion in pores of the sorbent particles having uniform sizes and characterized by the homogeneous intraparticle diffusion coefficient and (ii) the rate of a direct adsorption/desorption process on the surface, described by applying the statistical rate theory (SRT) approach [2].
3. The connection between the most commonly applied mathematical expressions, such as the pseudo-second and the pseudo-first order equations and different models of sorption kinetics was investigated. These formulae do not correspond to any specific physical model but they approximate well the behaviours predicted by many different theoretical approaches [3].
4. The heavy metal ions biosorption processes were modeled. The origin of the commonly observed, so-called “heterogeneity effects” has been explained. Two most popular models were considered for that purpose: the adsorption model and the ion exchange model. The Condensation Approximation method has been used in order to develop the model describing the influence of surface heterogeneity on biosorption equilibria. As this model has been derived by accepting the ion exchange processes on the biosorbent surface, the obtained expressions are able to take into account also the pH effect [4].
5. Two stoichiometric assumptions (MX2 and M1/2X) have been compared for describing the divalent metal ions binding by the protonated sorbent/biosorbent. Mathematical expressions corresponding to these both models have been developed by applying the ion exchange model and methods of statistical thermodynamics. The M1/2X model appears to be unphysical because it does not
Department of Theoretical Chemistry – 90 –
take into account the basic fact that two sites binding one metal ion must be neighbouring.
6. The possible explanation for the applicability of NCAMs (Non-Competitive Adsorption Models, i.e. the models corresponding to the Langmuir model in which the maximum uptake value is pH-dependent) for biosorption systems is proposed. Both the metal ion speciation in the bulk solution and the formation of multidentate surface complexes are taken into account.
References:
[1] W. Plaziński and W. Rudziński, J. Phys. Chem. C, 113 (2009) 12495. [2] W. Plazinski and W. Rudzinski, Langmuir, in press, DOI: 10.1021/la902211c. [3] W. Plaziński, W. Rudziński and A. Plazińska, Adv. Colloid Interface Sci., 152
(2009) 2. [4] W. Plaziński and W. Rudziński, Environmental Science and Technology, 43
(2009) 7465.
F.Ch. UMCS Report 2009 (BS) – 91 –
THEORETICAL STUDIES OF ADSORPTION ON CHEMICALLY AND STRUCTURALLY MODIFIED SOLID SURFACES
Paweł SZABELSKI* and Władysław RUDZIŃSKI*,**
*DEPARTMENT OF THEORETICAL CHEMISTRY, **INSTITUTE OF CATALYSIS AND SURFACE CHEMISTRY, POLISH ACADEMY OF SCIENCES, KRAKÓW, POLAND
The main purpose of our theoretical studies was to determine the optimal distribution of active sites on a solid surface leading to the preferential adsorption of molecules with predefined conformation. To that purpose we considered adsorption of linear and bent molecular chains of different length on a heterogeneous surface represented by a square lattice. It was assumed that the molecules are rigid and consist of spherical segments each of which occupies one lattice site. The active sites were distributed on the surface according to different test hypotheses. The energy of interaction between a single segment and an active site was characterized by aε while the energy of the segment-inert site interaction was equal to iε . Using different distributions of the active sites within the unit cell of the surface we were able to construct model adsorbents with markedly different selectivity towards the selected molecular conformation. To quantify these surfaces we calculated the corresponding Henry constants for each type of molecule and thus the associated selectivity (ratio of the Henry constants). The derived analytical expressions for the selectivity enabled detailed analysis of the influence of the energy difference
a iε ε− on the preference of the surface for adsorption of the selected molecule. For example, for certain patterns of active sites it was shown that manipulating the energy difference can result in the preferential adsorption of linear molecules over bent molecules. Comparison of the obtained results allowed us to chose the optimal pattern of active sites which provides the most effective separation of linear and bent molecules from their mixture under low pressures.
Department of Theoretical Chemistry – 92 –
SOLVENT EFFECT IN THE NMR SPECTROSCOPY OF SELECTED NUCLEI
Krzysztof WOLIŃSKI DEPARTMENT OF THEORETICAL CHEMISTRY
The studies on solvent effect in the NMR spectrum have been continued. The presence of a solvent has been included in the calculations via the so called Conductor like Solvent Model (COSMO) [1]. In the COSMO method interactions of a molecule with an environment are described in terms of interactions of electron density and nuclei charges of a molecule with screening charges on the cavity due to the polarization effect. The COSMO method have been used in calculations of the nitrogen NMR spectrum for series of five oxa- and oxadiazoles in the presence of twelve solvents with different dielectric constant. Additionally, in order to take into account the hydrogen bonding, especially in water solutions, the ESM model (Explicit
Solvation Model) and its combination with the COSMO approach were used. In order to obtain the best agreement with the experimental data [2] twenty six popular DFT potentials and the Hartree–Fock method have been examined. The highest accuracy has been obtained using the DFT/O3LYP method which had an average error of about 2 ppm. The following results of this work should be emphasized:
1. The theoretical results obtained within the COSMO approach reproduce correctly the experimental tendency of the solvent effects on the nitrogen chemical shifts in the oxa- and oxadiazoles series.
2. The best COSMO results was obtained in the case of aprotic solvent even with the not high dielectric constants. It shows that the COSMO model does not take into account the specific solute-solvent interaction like hydrogen bonding. Even though these interactions were not considered the computed solvent-induced changes of the nitrogen chemical shifts are in fair agreement with the experimental values.
3. The presence of possible hydrogen bonds in water solutions was simulated by the ESM model and its combination with the COSMO approach. The use of the ESM+COSMO models significantly improves the reproduction of the experimental data. For the completely saturated first solvation sphere of the considered molecular models the best results were achieved.
4. The direct and indirect contributions to the total solvent effect for the considered molecules were investigated. Their dependence on the dielectric constant of the solvent was observed.
References:
[1] A. Klamt, G. Schuurmann, J. Chem. Soc. Perkin Trans., 2 (1993) 799 [2] M. Witanowski, Z. Biedrzycka, W. Scinska, Z. Grabowski, G.A. Weeb, J. Mag. Reson. Ser. A, 120 (2) (1996) 148
F.Ch. UMCS Report 2009 (BS) – 93 –
SOLUBILISATION OF ORGANIC SUBSTANCES IN THE BULK AND SURFACE MICELLES – THEORY AND EXPERIMENT
Mateusz DRACH, Jolanta NARKIEWICZ-MICHAŁEK,
Marta SZYMULA* and Jerzy JABŁOŃSKI*
DEPARTMENT OF THEORETICAL CHEMISTRY *DEPARTMENT OF RADIOCHEMISTRY
AND COLLOID CHEMISTRY
In 2009 we continued the investigations of the propyl gallate (PG) adsolubilisation in the SDS (anionic), CTAB (cationic) and TX100 (nonionic) surfactant micelles formed at the solid/solution interface [1]. We also investigated the α-tocopherol (α-T) adsolubilisatian in the microemulsion water/pentanol stabilised by anionic SDS [2]. Both PG and α-T are very popular and the most frequently investigated antioxidants owing to their slow oxidation kinetics. PG is of moderate hydrophilic character whereas α-T is strongly hydrophobic. PG solubility in water is small (<0.002 mol dm-3) and α-T is completely insoluble. Their solubility can be enhanced significantly in the presence of surfactant micelles.
In Figs. 1-4 some of the obtained results are presented.
0 0.0002 0.0004 0.0006 0.0008
CGP (mol/dm3)
0
0.2
0.4
0.6
0.8
1
Γ (
µm
ol/m
2)
GP/CTAB/NaBr/SiO2
CTAB/GP/NaBr/SiO2
GP/NaBr/SiO2
0 0.0004 0.0008 0.0012 0.0016
CGP (mol/dm3)
0
0.4
0.8
1.2
1.6
Γ (
µm
ol/m
2)
GP/SDS/NaCl/Al2O3
GP/NaCl/Al2O3
Fig. 1 Adsorption isotherms of PG on silica from aqueous solution in the presence of 0.01 M NaBr and from the same solution containing 0.001 M CTAB. The decrease of CTAB adsorption with the increasing GP adsorption is also shown. The lines are drawn to guide the eye.
Fig. 2 Adsorption isotherms of PG on Al2O3 from 0.01 M NaCl at pH=6.5 and from the same solution containing 0.01 M SDS. The lines are drawn to guide the eye.
Department of Theoretical Chemistry – 94 –
0 0.0001 0.0002 0.0003 0.0004 0.0005
CTX (mol/dm3)
0
0.2
0.4
0.6
0.8
Γ (
µm
ol/m
2)
TX 100/GP/NaCl/Al2O3
TX 100/NaCl/Al2O3
Fig. 3 Adsorption isotherms of TX-100 on Al2O3 from 0.01 M NaCl at pH=6.5 and from the same solution containing 0.001 M PG. The lines are drawn to guide the eye.
Fig. 4 Dependence of the aggregate diameter in the SDS/water/pentanol/ vita-min E system on the pentanol concentra-tion.
These results can be summarized as follows:
1. In the absence of surfactant, propyl gallate does not adsorb on the silica surface from aqueous solution. However, in the presence of CTAB, its uptake by silica significantly increases. Alumina is quite an effective adsorbent for SDS and propyl gallate and does not adsorb nonionic TX-100. The addition of PG promotes adsorption of SDS and TX-100.
2. α-T solubilises to a high extent in the water/SDS/pentanol microemulsion but does not influence the microemulsion droplet size. It suggests that α-T solubilises in the interfacial layer of a microemulsion droplet.
References:
[1] M. Drach, J. Jabłoński, J. Narkiewicz-Michałek, M. Szymula, “Co-Adsorption of Surfactants and Propyl Gallate on The Hydrophilic Oxide Surfaces”, Applied Surface Sci., accepted for publication.
[2] J. Cieśla, J. Narkiewicz-Michalek, M. Szymula, A. Bieganowski, “Characterization of SDS/Water/Pentanol/Vitamin E Systems by the Use of Photon Correlation Spectroscopy Method”, J.Colloid Interface Sci., submitted for publication.
F.Ch. UMCS Report 2009 (BS) – 95 –
THEORY AND SIMULATIONS OF NONUNIFORM
MOLECULAR FLUIDS
MOLECULAR DYNAMICS STUDY OF ADATOM SIZE EFFECT
ON STRESS EVOLUTION IN LENNARD-JONES THIN FILMS
Tomasz ZIENTARSKI
DEPARTMENT FOR THE MODELING OF PHYSICO-CHEMICAL
PROCESSES
The stress are usually generated during the process of deposition of thin films,
irrespective of the deposition technique applied, and one can influence the
reliability of evaluation of the properties of the deposited system by applying
appropriate techniques [1]. The stress often leads to unfavourable consequences for
defective functioning or even to breakdowns of thin-film elements. Therefore,
recognition of phenomena that are mainly responsible for the stress in thin metal
films is of significance. The computer simulations have an enormous potential to
provide better understanding of the growth and stress generation of thin films as
well as to mimic their real deposition processes.
The aim of this work is to investigate general aspects of stress evolution during
the deposition of thin films. In contrast to the previous investigation [2], we
consider here different size of substrate and film atoms. Molecular dynamics used
in this work is based on the method described earlier [2]. According to this
approach the trajectories of individual atoms are evaluated by integrating Newton's
equation of motion. The interactions between atoms in the film and between atoms
in the film and in the surface atoms are assumed to be pairwise additive and the pair
potential is represented by a truncated (12,6) Lennard-Jones function:
( ) ( )[ ]
max
max
612
0
,//4)(
rr
rrrrrU
>
≤−=
σσε (1)
where r is the distance between the atoms, ε and σ are the strength and size
parameters, respectively, and maxr is the cut-off distance.
Moreover, we used the following definition of stress for atomic systems:
∑ ∑= ≠=
∂⊗+⊗
Ω=
N
i
N
ijji ij
ij
ijiiir
rUrvvmS
1 ,1,
)(
2
11 (2)
where im is the mass of the atom i , iv is its velocity, jiij rrr −= is the vector
between the atoms i and j , N is the total number of atoms in the domain of the
volume Ω and ⊗ denotes the tensor product of two vectors.
Department for the Modeling of Physico-Chemical Processes – 96 –
The stress is a 33× tensor, where xxS , yyS and zzS are stresses in the x , y
and z directions. The sign convention adopted here for the stress is positive for
expansion and negative for compression.
The relative size of deposited atoms, measured with respect to the size of the
atoms forming the solid, changes in the range from 7.0 to 0.1 . During simulation
the films grow according the Volmer-Weber mode. Simulations show that
depending on the number of deposited atoms a mismatch of the lattice constant in
film and substrate leads to various evolution of mean biaxial stress. Films with only
tensile stress and evolution with transition from compressive to tensile stress were
obtained. When the film becomes continuous, the stress during the growth attains a
maximum value, but later new grain boundaries are formed.
During deposition of thin films the contribution of geometrical stress (tensile)
is greater than the compressive contribution, caused by creation of new grains. The
tensile stress plays a dominant role with increasing σ .
For systems with different size of adsorbed atoms, apart from the first layers,
higher monolayers have also significant contribution to the total stress. For
92.0>σ the monolayers result in a tensile stress. However for σ close to 0.1 the
first layer plays a dominant role.
Fig. 1. Mean biaxial stress evolution (Sxy) in selected layers during simulation versus the
number of deposited atoms for different size of atoms. Sxy = (Sxx + Syy)/2.
References:
[1] See, for instance, MRS Bulletin, 27 (2002).
[2] T. Zientarski, D. Chocyk, Molecular Physics, 105 (2007) 3099.
F.Ch. UMCS Report 2009 (BS) – 97 –
ADSORPTION OF NEW GENERATION CHELATES
ON ALUMINA SUPPORT
Janusz RYCZKOWSKI, Agnieszka DĘBCZAK and Sylwia PASIECZNA-PATKOWSKA
DEPARTMENT OF CHEMICAL TECHNOLOGY
Chelating compounds (EDTA-type reagents) are broadly applied in many
chemical processes. Recently, new generation of chelates was introduced. Those
new chelating compounds are characterized by high biodegradability in the
environment in the comparison to the traditional EDTA-type compounds used.
The commercially available support (γ-Al2O3 from Engelhard), was pre-
shaped to the particles of 0.063-0.13 mm. BET surface area (SBET) and point zero
charge (pHPZC) values were obtained experimentally: SBET = 83 m2/g, pHPZC = 8.6.
The impregnating sodium salts of aminopolycarboxylates were purchased from
commercial suppliers: Fluka (EDDS - ethylenediaminedisuccinic acid) and BASF
(DTPA – diethylenetriaminepentaacetic acid, HEDTA - N-(hydroxyethyl)ethylene-
diaminetriacetic acid, MGDA – methylglycinediacetic acid), and used in the form
of 0.1 M aqueous solutions. Samples were examined by FT-IR/PAS in a solid state.
This can be generaly described as a “frozen” body with impregnant-adsorbent
interactions created in the stage of sample preparation (Fig. 1).
FT-IR/PAS measurements were performed using a Bio-Rad (Excalibur
3000MX) spectrometer and helium purged MTEC300 photoacoustic detector, over
the 4000-400 cm-1
range. The spectra were obtained at room temperature (RT) at 4
cm-1
resolution and normalized by computing the ratio of a sample spectrum to the
spectrum of a MTEC carbon black as a refererence material. A stainless steel cup
was filled with samples (thickness < 6 mm). Each step of data collection was
preceded by the PA cell purging with dry helium for 5 minutes. Interferograms of
512 scans were average for each spectrum.
Fig. 1. Scheme of samples preparation for FT-IR/PAS measurements.
Department of Chemical Technology – 98 –
Spectral characteristic of sodium salts of studied chelates adsorbed on alumina
confirms its chemical interaction with the support surface. The carboxyl group is
known to give a strong band in the range 1735–1550 cm–1
associated with the C=O
stretching vibration [1, 2]. Distinguishable for the series of chelates adsorbed onto
alumina (Fig. 2) is the region of asymmetric stretching vibration with distinctly
separated bands originating from νC=O stretching vibration (~1650-1675 cm–1
) and
νasCOO- (~1580 cm
–1). The asymmetric stretching is most intensive for EDDS
(Fig. 2d). For almost all chelates the maximum of the νsCOO- is within the same
range.
1800 1600 1400 1200
Wavenumber (cm-1)
PA
sig
na
l (a
.u.)
(a)
(c)
(b)
1594
--
-13
39
165
2-
165
0-
15
79--
1304
-
-14
01
1357
--
-1401
-1433
165
0-
14
46
--
14
01-
14
00-
-16
41
-13
96
(d)
(e)
15
81--
157
8-
1341
-133
6--
----
16
75
-12
66
Fig. 6. FT-IR/PA spectra of (a) alumina and chelates adsorbed on its surface:
(b) MGDA, (c) HEDTA, (d) EDDS, (e) DTPA.
FT-IR/PA spectroscopic technique enables to study the interaction between
adsorbate and inorganic support. The observed changes in the recorded spectra of
the supported complexones are mainly due to interactions of the chelate carboxyl’s
with inorganic hydroxyl groups (chemical nature of the interaction). The pHPZC of
the support has a strong influence on the band position of the adsorbed species.
Moreover, the molecular structure of the impregnate used has an influence on the
observed interactions, too.
References:
[1] L.J. Bellamy, The Infrared Spectra of Complex Molecules, Wiley, New York,
1958, p. 162.
[2] G. Socrates, Infrared, Infrared and Raman Characteristic Group Frequencies,
Tables and Charts, 3rd
ed., Wiley, Chichester, 2001, pp 125–130.
[3] A. Dębczak, J. Ryczkowski, J. Patkowski, Appl. Surf. Sci., accepted for
publishing.
F.Ch. UMCS Report 2009 (BS) – 99 –
DETERMINATION OF SURFACE PROPERTIES OF PALLADIUM CATALYST FOR THE REACTION OF COMPLETE OXIDATION
OF METHANE
Andrzej MACHOCKI, George AVGOUROPOULOS*
and Theophilos IOANNIDES*
DEPARTMENT OF CHEMICAL TECHNOLOGY
*INSTITUTE OF CHEMICAL ENGINEERING AND HIGH
TEMPERATURE CHEMICAL PROCESSES, PATRAS, GREECE
Nickel oxide as the support of the palladium phase improves its catalytic
activity in the complete oxidation of methane. Some NiO-Al2O3 supported
palladium catalysts with various NiO/Al2O3 ratios were prepared by sol-gel method
with (C2H6)4NOH as a precipitant, dried conventionally (CD) or with supercritical
carbon dioxide (SD) and calcined. Prior to the XPS measurements the palladium
oxide phase was reduced with hydrogen at 110°C, without reduction of the support.
X-ray photoelectron spectra of samples were taken in an ultrahigh vacuum
system. Unmonochromatized AlKα line at 1486.6 eV was used in all XPS
measurements. The XPS core level spectra were analyzed with a fitting routine
which decomposes each spectrum into individual, mixed Gaussian-Lorentzian
peaks using a Shirley background subtraction. The binding energies were calculated
by reference to the energy of C1s peak of contaminant carbon at 285 eV.
The surface composition of catalysts is shown in Table 1 and the XPS spectra
for Pd 3d and O 1s – in Fig.1. Depending on the composition of the catalyst support
and the method of support preparation the relative amounts of metallic palladium
and palladium oxide are different. Over the surface of catalysts with nickel oxide-
containing supports the palladium phase is highly oxidized than that on the surface
of alumina-supported catalysts. It forms even PdO2 oxide beside PdO. The
palladium oxide phase in the catalysts dried with supercritical carbon dioxide
(samples Pd/N2 and Pd/N6) is more difficult to reduction. On the surface of the
samples with the highest amounts of nickel oxide in the bulk support (Pd/N5 and
Pd/N6) the excess of oxygen was even found.
Table 1. Surface composition of catalysts in terms of atomic ratios
Sample Pd (% at) Ni (% at) Al (% at) O (% at)
Pd/Al2O3-SD-A 0.7 0 31.5 67.8
Pd/Al2O3-CD-B 0.8 0 28.6 70.6
Pd/N1 0.5 40.7 16.4 42.4
Pd/N2 1.3 38.2 21.5 39.0
Pd/N5 0.7 36.2 12.9 50.2
Pd/N6 0.4 47.8 13.5 38.3
Department of Chemical Technology – 100 –
348 344 340 336 332 328
337.7 : PdO2
336.8 : PdO
335.2 : Pd0 Pd 3d
Pd-Al-Ni-O Pd/N6 (x1.7)
Pd-Al-Ni-O Pd/N5
Pd-Al-Ni-O Pd/N2 (x0.45)
Pd-Al-Ni-O Pd/N1 (x1.4)
Pd-Al-O CD B
Pd-Al-O SD A
Inte
nsity (
a.u
.)
Binding Energy (eV)
540 538 536 534 532 530 528 526 524
527.4-528 : isolated O2- ?
529.7-530.3 : Palladium oxide
Nickel oxide531.8-532.7 : Al
2O
3
Ni2O
3
Ni(OH)2
H2O
531.3 : Al2O
3533.3-533.9 : H
2O
Pd-Al-O SD A
Pd-Al-O CD B
Pd-Al-Ni-O Pd/N1 (x1.4)
Pd-Al-Ni-O Pd/N2
Pd-Al-Ni-O Pd/N5
Pd-Al-Ni-O Pd/N6O 1s
Inte
nsity (
a.u
.)
Binding Energy (eV)
Fig. 1. XPS spectra for Pd 3d and O 1s of supported palladium catalysts.
F.Ch. UMCS Report 2009 (BS) – 101 –
INVESTIGATION OF ISOTOPIC DISTURBANCES OF OXYGEN IN THE REACTION OF METHANE OXIDATION
OVER PALLADIUM AND PLATINUM CATALYSTS
Marek ROTKO and Andrzej MACHOCKI
DEPARTMENT OF CHEMICAL TECHNOLOGY
The complete oxidation of methane (flameless combustion) has been studied
due to wide industrial applications, mainly in the production of energy and in
several processes, which allow to protect the environment, by the decreasing of the
emission of nitrogen oxide, carbon monoxide and unburned hydrocarbons.
The one from many proposed catalytic materials for the complete methane
oxidation are palladium-platinum catalysts. In contradiction to palladium catalysts,
which are considered as the most active catalysts for this process, palladium-
platinum catalysts demonstrate lower activity but within a longer time frame their
activity is stable, and does not change. The methane oxidation on palladium
catalysts is known as a very complex process and there are still many questions and
contradictions, especially when the
mechanism of this reaction and the changes
which undergo on the catalyst surface under
various reaction conditions are debated.
However, when we start to consider the
oxidation of methane over palladium-
platinum catalysts we get a huge load of
new additional questions and contradictions.
This paper presents the results of the
steady state isotopic transient kinetic
analysis (SSITKA) of the isotopic switching
between two different isotopes of oxygen in
the steady state of the methane oxidation.
The palladium-platinum catalysts
employed in these studies were prepared by the incipient wetness impregnation of
the commercial Al2O3 support with an aqueous solutions of Pd(NH3)4(NO3)2 and
Pt(NH3)4(NO3)2. The precursors were dried at 110°C (2 h), calcined at 500°C (1 h)
and, prior to the measurements, the catalysts were reduced at 300°C (1 h). The
content of palladium and platinum is about 0.4 wt.% and the molar ratio of Pd:Pt is
1:1 and 1:4 for Pd-Pt-IWI_1-1 and Pd-Pt-IWI_1-4, respectively.
The activity of palladium-platinum catalysts in the complete oxidation of
methane was determined in a quartz reactor filled with 0.1 g of the catalyst sample.
The flow rate of the reaction mixture including 2 vol% of CH4, 6 vol% of O2, 10
vol% of Ar and 82 vol% of He was 100 cm3/min. The linear temperature increase
was 10°C/min.
250 350 450 550 650 750
Temperature (oC)
0
0.2
0.4
0.6
0.8
1
Me
than
e c
on
ve
rsio
n
Pd-Pt_1-4
Pd-Pt_1-1
Fig. 1. Activity of the Pd-Pt catalysts
Department of Chemical Technology – 102 –
0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
18O
2
16O
18O
16O
2
Kr
No
rma
lize
d c
on
ce
ntr
ati
on
Time (s)
Ar
0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
No
rma
lized
co
ncen
tra
tio
n
Time (s)
C18
O2
C16
O18
O
C16
O2
Kr
Ar
Fig. 1. SSITKA results for the Pd-Pt_1-1 catalyst at 615oC
The SSITKA measurements were performed on 0.1 g of the catalyst by
switching from 16
O2/Ar/CH4/He to 18
O2/Kr/CH4/He at various temperatures
ensuring the low, middle and high conversion of methane. The flow rate of the
reaction mixture including 2 vol% of CH4, 6 vol% of 16
O2 (or 18
O2), 10 vol% of Ar
(or Kr) and 82 vol% of He was 100 cm3/min.
The activity of palladium-platinum catalysts (Fig. 1) is very similar and for both
catalysts the distinct decrease of their activity is observed at about 550°C, which
probably is connected with the decomposition of PdO and/or PtO2.
The SSITKA results (Fig. 1) demonstrate the adsorption of oxygen (delays
between Ar and 16
O2) and intermediates leading to the formation of carbon dioxide
(delays between Ar and C16
O2) on palladium-platinum catalysts. Moreover, the 16
O18
O and C16
O18
O molecules appear after the isotopic switching. The average
surface life-time of 16
O2 (t16O2) and 16
O18
O (t16O18O) increases with temperature while
the average surface life-time of C16
O2 (tC16O2) and C16
O18
O (tC16O18O) in the most
cases decreases (Table 1). The surface concentration of 16
O2 (N16O2) and 16
O18
O
(N16O18O) increases with temperature while the surface concentration of C16
O2
(NC16O2) and C16
O18
O (NC16O18O) also generally increases. The presence of 16
O18
O
suggests that oxygen from the catalyst lattice undergoes the exchange with oxygen
from the gas phase, while the presence of C16
O18
O suggests that oxygen from the
catalyst lattice takes part in the methane oxidation. This fact is said for the oxidation
of methane according to the Mars-van Krevelen reaction mechanism.
Table 1. Kinetic parameters for the complete methane oxidation.
Pd-Pt_1-1 Pd-Pt_1-4
Temperature, oC 408 615 697 415 535 665
Methane conversion % 4.3 32.8 73.6 7.0 14.0 77.9
t16O2, s 6.4 37.2 56.2 5.1 24.3 50.5
t16O18O, s 0 190.4 246.0 0 130.5 218.5
tC16O2, s 1261.7 284.2 260.1 1051.5 386.8 269.9
tC16O18O, s 655.8 431.8 438.5 802.6 504.0 446.0
N16O2, µmol/g 277.3 1296.6 1276.9 216.9 982.8 1082.8
N16O18O, µmol/g 0 6636.4 5589.4 0 5278.2 4685.2
NC16O2, µmol/g 808.4 1388.9 2852.4 1096.7 806.9 3132.7
NC16O18O, µmol/g 420.2 2110.3 4808.8 837.1 1051.3 5176.8
F.Ch. UMCS Report 2009 (BS) – 103 –
OPTIMIZATION OF ACTIVE PHASE PALLADIUM CATALYSTS
Beata STASIŃSKA
DEPARTMENT OF CHEMICAL TECHNOLOGY
Although catalysts for methane utilization are well known, the low
concentration of methane and the costs of its utilization cause that only few
technologies of the catalytic oxidation of methane in coal mine ventilation air were
developed on the world market [1]. This paper proposes the catalytic oxidation of
methane as the solution for the problem of methane utilization when its
concentration in air is insufficient for flame combustion [2].
The catalytic activity and palladium surface area are strongly dependent on the
support nature and its properties as well as on its interactions with the active phase.
The aims of the presented paper were to characterize alumina-supported palladium
catalysts with various amount of palladium active phase on pure alumina support
and commercial support.
Experimental
Palladium was deposited on the supports by their impregnation with an
aqueous solution of palladium nitrate Pd(NO3)2. After each impregnation step the
catalyst precursors were dried at 115°C. Finally they were calcined at 500°C in air.
Prior to the use the catalysts were reduced with hydrogen at 110°C for 1 hour. The
data regarding basic characterization of the supports and palladium catalysts are
presented in Table 1.).
Table 1. Catalyst characterization results.
Catalyst BET surface area
m2/g
Pd content
wt.%
Palladium
dispersion, %
Pd crystallite
size, nm
0,4%Pd/Al2O3 242,0 0,43 11,92)
94,02)
1,0%Pd/Al2O3 242,6 1,04 9,72)
115,82)
1,5%Pd/Al2O3 229,5 1,55 16,72)
67,02)
2,5%Pd/Al2O3 225,5 2,61 11,12)
100,82)
0,23%Pd/Al2O3 2,7 0,23 – –
0,57%Pd/Al2O3 2,3 0,57 1,6 7,2
1) – according to XRF 2) – according to total chemisorption of H2 at 110oC by static-volumetric method
The complete oxidation of methane was carried out over catalysts (0.2 g)
mixed with the pieces of quartz of 0.75-1.2 mm in diameter at the ratio of 1:10, in
the air-methane (2 vol%) reaction mixture which the space velocity was equal to
90000 Ncm3/(gcat⋅h).
Department of Chemical Technology – 104 –
Discussion and conclusions
The results of the catalytic activity tests over palladium catalysts with different
amount of palladium are shown in Figure 1 A and B.
A B Fig. 1. Catalytic oxidation of methane over palladium catalysts: A – on pure alumina support
(–2.5 % Pd/Al2O3, – 1.5 % Pd/Al2O3, –1. 0 % Pd/Al2O3, – 0.4 % Pd/Al2O3)
and B – on commercial alumina support ( – 0.57 % Pd/Al2O3, – 0.23 % Pd/Al2O3)
(reaction mixture: 2% CH4+20% O2+78% N2,)
The experiments on Pd/Al2O3 catalysts on pure alumina support with different
amount of palladium loading show that increase of the palladium concentration
phase in catalysts increases their activity in oxidation reaction. Catalyst with 0.4
and 1% Pd on pure alumina support have good activity in methane oxidation
reaction. For these catalysts the total oxidation temperature was observed at 550
(0.4 % Pd) and 500°C (1.0 % Pd). Studies of the palladium catalysts obtained on
commercial support show their lower activity in oxidation reaction than palladium
catalysts on pure alumina support. For these catalysts oxidation process started at
350 (0.57 % Pd) and 400oC (0.23 %wt. Pd).
The general conclusions is that the Pd/Al2O3 catalysts on commercial support
are lower activity then palladium catalysts on pure alumina support. Additions
included in commercial alumina support decreases activity palladium catalysts.
References:
[1] Assessment of Worldwide Market Potential for Oxidizing Coal Mine Ventilation
Air Methane, US Environmental Protection Agency, EPA 430 - R -03-002, 2003
[2] B. Stasińska, A. Machocki, K. Antoniak, M. Rotko, J.L. Figueiredo,
F. Goncalves, Catal. Today, 137 (2008) 329.
0
10
20
30
40
50
60
70
80
90
100
200 300 400 500 600 700 800 900
Time [min.]
Meth
ane c
on
vers
ion
[%
] .
0
10
20
30
40
50
60
70
80
90
100
200 300 400 500 600 700 800 900
Time [min.]
Me
tha
ne
co
nve
rsio
n [%
] .
F.Ch. UMCS Report 2009 (BS) – 105 –
STUDY OF ACTIVITY PALLADIUM CATALYSTS ON COMMERCIAL SUPPORT PRODUCED BY FERTILIZERS
RESEARCH INSTITUTE IN PUŁAWY
Beata STASIŃSKA
DEPARTMENT OF CHEMICAL TECHNOLOGY
Ventilation air is a difficult methane source to use as an energy carrier, as air
volume is large, methane is very diluted as well as variable in its concentration
(0.1–1.0 vol.%) and flow rate. The catalytic oxidation of methane may be
considered as a promising solution of methane-poor gas mixtures utilization. The
successful possibility of utilization of methane-poor mixtures, such as ventilation
air from coal mines depends on engineering solution, catalyst used and methane
concentration in mixture with air [1, 2]
The aims of the presented paper were to characterize alumina-supported
palladium catalysts with various space velocity and various methane concentration.
Experimental
Studied catalyst was prepared on commercial support produced by Fertilizers
Research Institute in Puławy. The alumina support (Table 1) prepared at very high
temperatures provides the catalysts with high catalytic activity, thermal stability,
and mechanical strength. The support are produced in a form of 7-hole cylinders
with flat (G-0117).
Table 1. Physicochemical properties of support.
Support G-0117
chemical composition, wt. % Al2O3 with SiO2 (max. 0.1)
dimensions, mm:
D
H
n · dh
16.5
16.5
7 · 3.4
bulk density, kg/dm3 0.9 ± 0.1
radial mechanical strength, daN/ring 60
axial mechanical strength, daN/ring 800
abrasion, wt. % 2
The experiments were carried out on Pd/Al2O3 catalysts with palladium
loading by impregnation method.
Department of Chemical Technology – 106 –
The flameless combustion of methane was carried out in the mixture
with different methane concentration: (2-x)CH4 + 20%O2 + (78+x) %N2 and
different space velocity 6000-12000 (h–1
).
Discussion and conclusions
Study in reactions with different methane concentration shows that methane
concentrations and space velocity reaction mixture effected on temperatures total
oxidation of methane and do not effected on temperatures at which oxidation
process got started.
Table 2. Temperature of the start point and total oxidation of methane in different
mixtures
Temperature start/total oxidation methane in different mixture
[°C]
Methane concentrations
[vol.%]
0.5 1,0 1,0 1,0 2,0
Space velocity
[h–1
]
Catalysts
6000 6000 9000 12000 6000
0.073% Pd/Al2O3 250/500 255/510 255/520 260/580 260/540
0.079% Pd/Al2O3 255/480 255/490 – – 260/500
0,148% Pd/Al2O3 – 250/480 – – –
0,240% Pd/Al2O3 – 240/450 – – –
When concentrations of methane in reaction mixture is increasing the
temperature of total oxidation of methane is growing up. Palladium catalysts
obtained on commercial support are highly active. The increase of palladium
content (0,073-0,240 wt.%) in the catalysts decreases the temperatures at which
oxidation process started and the total oxidation was observed.
This studies show that catalysts obtained on the commercial support may be
successfully used in industry conditions.
References:
[1] Su Shi, A. Beath, H. Guo, C. Mallett, An assessment of mine methane
migration and utilisation technologies, Prog. Energy Combst. Sci., 31 (2005)
123.
[2] B. Stasińska, S. Napieraj, Zagospodarowanie metanu z powietrza
wentylacyjnego kopalń węglowych, Przem. Chem., 88 (2009) 1121.
[3] B. Stasinska, A. Machocki, K. Antoniak, M. Rotko, J.L. Figueiredo,
F. Goncalves, Importance of palladium dispersion in Pd/Al2O3 catalysts for
complete oxidation of humid low-methane–air mixtures, Catal. Today, 137
(2008) 329.
F.Ch. UMCS Report 2009 (BS) – 107 –
THE INFLUENCE OF THE PROJECTED TRANSPORT SYSTEM IN THE LUBELSKIE VOIVODESHIP ON THE QUALITY
OF THE ATMOSPHERIC AIR
Adam LESIUK
DEPARTMENT OF CHEMICAL TECHNOLOGY
Transport is a major source of air pollution in urban areas. Its negative
influence on the quality of the air could be decreased by the ring roads building. In
Lubelskie Voivodeship the ring roads buildings are planned in 2010-2013 [1]:
– Tomaszów Lubelski ring road – 9,4 km long,
– Chełm ring road – 18,4 km long,
– Lublin ring road – 34 km long,
The influence on the quality of the air of every new transport investment
should be measured. The aim of the conducted investigations was to determine the
influence of the planned road from Lublin to the ring road (Jakubowice) on the
quality of the air during its exploitation.
Planned Lublin ring road is presented on the Map 1.
Map 1. Planned Lublin ring road
Department of Chemical Technology – 108 –
The intensity of car movement on the projected road and NOx emissions factor
used for the measurement (prof. Chłopek method) is presented in Table 1.
Table 1. The prognosis of the intensity of car movement on the projected road
in 2015 and NOx emissions factor used for the measurement.
Type of vehicle The traffic density
(vehicle per day)
NOx emissions factor
(g/km)
car 11704 0.660
van 1110 1.022
trucks 322 5.298
bus 39 6.897
Measurements of nitrogen dioxide (NOx) spreading were conducted by
measure program OPERAT 2000 made by PROEKO company from Kalisz. The
conducted investigations of NOx emissions have shown that the NO2 acceptable
concentration in the road surrondings will not be exceeded for 1 hour (200 µg/m3)
and for year 40 µg/m3 [2].
References:
[1] www.gddkia.gov.pl
[2] Rozporządzenie Ministra Środowiska z dnia 3 marca 2008 r. w sprawie
poziomów niektórych substancji w powietrzu (Dz. U z 2008 r., Nr 47, poz.
281).
F.Ch. UMCS Report 2009 (BS) – 109 –
PROMOTED NICKEL CATALYSTS IN THE HYDROCARBON REACTIONS
Tadeusz BOROWIECKI, Andrzej DENIS, Monika PAŃCZYK
and Czesława SIKORSKA
DEPARTMENT OF CHEMICAL TECHNOLOGY
Steam reforming of hydrocarbons carried out on the nickel catalysts is one of
the most important processes of syngas and hydrogen production. In the process
conditions beside desirable reactions are also side reactions in which carbon
deposits are formed, deactivating the catalyst and destructing its structure. Under
reaction conditions (temperature 800-900°C and high partial pressure of water
vapour) the following processes can take place: sintering of the catalysts, reactions
between catalyst components, textural changes, and changes in the mechanical
strength. It is well known that noble metals and transition metals (Ni and Co) show
high catalytic activity in the steam reforming. Though noble metal catalysts are less
sensitive to carbon deposition, supported Ni catalyst is popularly used because of
the big differences in price. Simple and the cheapest way of the catalysts quality
improvement is an introduction of promoters [1]. It turns out, that the small amount
of additives introduced into the catalysts’ formula have a great influence on their
textural properties, activity, selectivity and lifetime.
As follows from literature data the best promoters of nickel catalysts to
improve resistance to coking are K and Mo. Promoters enhancing resistance to
coking, as a rule, decrease activity in the steam reforming reaction.
Wang et al., [2] pointed to interesting properties of the 2 wt. % Re promoted
nickel catalyst on the commercial support in the hydrocarbon steam reforming.
Borowiecki et al. [3] for the Ni-Re catalyst on the α-Al2O3 support with the various
amounts of promoter shown, that rhenium is a very good additive to nickel catalysts
of the steam reforming of hydrocarbons. The addition of rhenium up to 4 wt. %
causes increase in the amount of chemisorbed hydrogen, increase in dispersion of
active phase, increase in resistance to coking and increase in activity.
In the literature one did not find the information on promoting with the
rhenium of nickel-catalysts on other supports than α-Al2O3. The aim of this work
was the preparation of nickel-rhenium catalysts on common supports (α-Al2O3,
γ-Al2O3, MgO, SiO2, ZrO2 i TiO2) and the estimation of the influence of rhenium
addition on the course of coking phenomena in the reaction of the steam reforming
of methane.
Experimental
Catalysts were received with the method so called „dry impregnation” on the
supports with the grain 0.3-0.6 mm which prior to the impregnation were dried at
Department of Chemical Technology – 110 –
60°C. The support was impregnated with nickel from the aqueous solution of nickel
nitrate, and in the following step (after calcination at 400°C by 6 hours) with
rhenium from the aqueous solution of the ammonium perrhenate. After drying of
the samples the nickel-rhenium catalyst precursors were calcined at 500°C by 6
hours. For examined catalysts there was determined contents of metals, general and
active surface areas and the resistance on coking by the estimation the course of
temperature programmed surface reaction TPSR (methane steam reforming). The
nickel content in the catalysts was as follows: 13.7 ± 0.5 wt.%, while rhenium
within the range 1.67 to 2.23 wt.%. In the table 1 was summarized results for the
most interesting pairs of studied catalysts.
Table 1. Physicochemical characteristic of examined catalysts.
Textural properties
Catalyst Total surface
area [m2/g]
Pores diameter
[Ǻ]
Active surface
area [m
2/g]
dH*
[nm]
Ni/α-Al2O3 8.7 81 1.18 114.6
Ni-Re/α-Al2O3 9.4 71 1.18 114.6
Ni/γ-Al2O3 182.2 149 5.92 22.8
Ni-Re/γ-Al2O3 185.7 143 8.42 16.0
Ni/SiO2 – – 1.16 116.1
Ni-Re/SiO2 210.4 151 1.27 106.2
Ni/ZrO2 45.7 184 1.05 128.9
Ni-Re/ZrO2 45.8 173 1.47 91.9
* – mean size of nickel crystallites from hydrogen chemisorption
Conclusion
The kind of the support has a huge influence on the results of the introduction
of rhenium to nickel catalysts.
1. Rhenium in a different manner influences the quantity of chemisorbed
hydrogen. For system supported on α-Al2O3 there was not noticed any change
in nickel surface area, while on the supports SiO2, ZrO2 and γ-Al2O3 the
increase in this value was: 10, 40 and 47%, respectively.
2. The results of coking by the TPSR method are dependent on two variables
(temperature and time) and they are quick however, they can serve as the initial
method of the data estimation connected with the rhenium presence in
examined catalysts. On their base one can ascertain that the addition of Re
causes not large changes in the temperature of the coking initiation of studied
catalysts pairs.
F.Ch. UMCS Report 2009 (BS) – 111 –
3. Passed also isothermal studies showed that the presence of Re limited the
quantity of formed deposit. The size of the effect is strongly dependent on the
kind of the support and the temperature of the conducted experiment.
4. For the full estimation of the results connected with the Re presence in
investigated catalysts there are necessary activity studies of examined catalysts.
References:
[1] T. Borowiecki, M. Czubryt-Idzik, A. Denis, W. Gac, A. Gołębiowski,
Cz. Sikorska, K. Stołecki, Przem. Chem., 82 (2003) 671.
[2] L. Wang, K. Murata, M. Inaba, Appl. Catal. A: Gen., 257 (2004) 43.
[3] T. Borowiecki, A. Denis, M. Pańczyk, W. Gac, K. Stołecki, Pol. J. Chem., 82
(2008) 1733.
F.Ch. UMCS Report 2009 (BS) – 113 –
INFLUENCES OF POLYACRYLIC ACID ADSORPTION AND SOLUTION pH ON ALUMINA SUSPENSION STABILITY
Stanisław CHIBOWSKI, Małgorzata WIŚNIEWSKA and Teresa URBAN
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
Metal oxide – polymer solution systems exist in many industrial and ecological processes. The presence of macromolecular substances in the colloidal suspension of solid particles influences the stabilization-flocculation properties of such system. These conditions depend on conformation of polymer chains both adsorbed on the solid surface and in the bulk solution.
Thus, the aim of the experiments was determination of the solution pH influence on the conformation of the polyacrylic acid (PAA) chains adsorbed on the Al2O3 surface and stabilization properties of such systems. The changes in the suspension stability were observed using Turbiscan LabExpert with the cooling module TLAb Cooler and with a spectrophotometer Specord M52 (Carl Zeiss Jena) at pH = 3, 6 and 9. The Turbiscan Stability Index (TSI) is a parameter, which can be used for estimation of the suspension stability (Table 1). Table 1. The Turbiscan Stability Indexes (TSI) for the alumina suspensions without and with adsorbed PAA; CPAA= 100ppm, CNaCl=1·10–2 mol/dm3.
TSI System
pH = 3 pH = 6 pH = 9
Al2O3 13.64 13.77 68.03 Al2O3 – PAA 2000 52.81 10.65 15.41
Al2O3 – PAA 240000 74.96 10.01 14.17
Analysis of the data in Table 1 leads to the conclusion that the addition of PAA causes lowering of the alumina suspension stability at pH 3, whereas at pH = 9 polymer improves it considerably. On the other hand, at pH = 6 the polymer adsorption causes insignificant increase of Al2O3 suspension stability. The conformational changes of polymer chains with the increasing pH are responsible for such behavior of investigated systems. The bridging flocculation probably takes place at pH=3 and the steric stabilization occurs at pH = 6. The interesting behavior show the systems at pH=9, at which the Al2O3 suspension without PAA was unstable and polymer addition distinctly improves its stabilization properties (electrosterical stabilization).
The spectrophotometric data acquired for the investigated systems are in good agreement with those obtained with Turbiscan LabExpert.
Department of Radiochemistry and Colloid Chemistry – 114 –
INFLUENCE OF MAGNETIC FIELD OF VARIOUS STRENGTH ON ZETA POTENTIAL OF MAGNETITE/IONIC POLYMERS
INTERFACE
Jacek PATKOWSKI DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
A study on influence of external magnetic field on zeta potential of magnetite/ionic polymers interface was conducted. Magnetite (Fe3O4) was chosen because of its known magnetic properties. Polymers analysed are: PEI (poly-ethyleneimine) and PAA (polyacrylic acid). The former is a cationic polymer and the latter – anionic polymer. The charge on both polymers varies with changing pH.
There are three factors under consideration, when changes in zeta potential are observed:
– an influence on the adsorbent (magnetite), – an influence on adsorbing polymer molecules (both cationic and anionic), – an influence on water molecules in solution.
Influence of magnetic field on zeta potential of
Fe3O4/NaCl 10-2/PEI
0
10
20
30
40
50
60
70
0 2 4 6 8 10 12
pH
zeta
[mV
]
Fe3O4+NaCl 10-2+PEI
Fe3O4+NaCl+PEI+mm
Fe304+NaCl+PEI+ms
The results are that:
1. There is a significant influence of magnetic field on zeta potential (a decrease) of Fe3O4/H2O interface, especially in case of stronger magnetic field applied.
2. After addition of NaCl as a carrying electrolyte, the situation is very similar (the greatest decrease is observed for stronger magnetic field).
3. For a system Fe3O4/NaCl/PEI, magnetic field causes an increase of zeta potential.
4. A zeta potential of a system Fe3O4/NaCl/PAA seems inert to applied external magnetic field.
F.Ch. UMCS Report 2009 (BS) – 115 –
RADIOCARBON DATING OF THE BIOGENIC SEDIMENTS, PEAT-SOIL PROFILE (0-6m) FROM THE SPŁAWY LAKE SITE
(DOROHUCZA LOWLAND)
Stanisław CHIBOWSKI, Marek RESZKA, Radosław DOBROWOLSKI* and Dorota SKÓRNIEWSKA*
DEPARTMENT OF RADICHEMISTRY AND COLLOID CHEMISTRY *DEPARTMENT OF PHYSICALGEOGRAPHY
AND PALEOGEOGRAPHY
Age of organic origin samples, determined with use of radiocarbon 14C ranges as far as 50 000 years back. The method is very useful in geographical and archeological research. A lot of information concerning history, soil formation and climate of studied area may be obtained from organic compounds known as humic substances. Extraction of organic matter from soil is complicated and labor-consuming process. It must by done carefully to avoid contamination of the sample by contemporary carbon. Some elements must be removed to enable synthesis and measurements final compounds by scintillation counting.
In cooperation with Department of Paleogeography UMCS a soil profile 6m deep and 5cm diameter was researched. It was divided in 5cm slices and these of a big concentration of organic matter were chosen. Such selected samples were processed using alkali-acid extraction. The applied process was supplemented with purification of precipitated humic acid with HF solution that removes silicate, phosphorous and carbonates residues. Extracted humic substances were converted to form suitable to radiocarbon dating.
To calculate radiocarbon age the Easy View software (Wallac-Perkin-Elmer) was used and to calibrated age of the samples the OxCal 3.10 (Bronk Ramsey 2005) program. In agreement with assumptions age of the layer located at the bottom of the profile was much older than these ones above. Applied method of organic matter extraction demands greater than used amount of soil to ensure proper accuracy of radiocarbon dating. Obtained data allowed to distinguish four main periods in the history of studied area. The first one dated 14156-13396BC denotes the earliest accumulation of organic matter, then degradation connected with climate changes and accumulation of algae 9668-9266BC. After these an existence of water basin period succeed between 52-621AD that was followed by peat formation 1665-1915AD. Considering slow accumulation of organic particles in environment it produces greater time range and obtained results are averaged.
Department of Radiochemistry and Colloid Chemistry – 116 –
References:
[1] A. Walanus, T. Goslar, Wyznaczanie wieku metodą 14C, Wydawnictwo Uniwersytetu Rzeszowskiego, 2004.
[2] A. Walanus, Drawing the Optimal Depth-age Curve on the Basis of Calibrated Radiocarbon Dates, Geochronometr., 31 (2008) 1.
F.Ch. UMCS Report 2009 (BS) – 117 –
ANTIOXIDANTS ACTIVITY IN EMULSIONS STABILIZED BY IONIC SURFACTANTS
Marta SZYMULA, Adam GALL and Jolanta NARKIEWICZ-MICHAŁEK*
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY *DEPARTMENT OF THEORETICAL CHEMISTRY
In 2009 we studied the action of antioxidants in various microemulsions, which is often different from that observed in homogeneous systems. In our investigations we used cyclic voltammetry to assess quantitatively the electron-donating capability of antioxidants in microemulsions. On the basis of the obtained electrochemical characteristics we were able to better understand of the antioxidant’s action in the systems of practical use.
We used the cyclic voltammetry with the glassy carbon electrode to investigate the behaviour of the two antioxidants: ascorbic acid (AA) and α-tocopherol (α-T) in the microemulsions stabilized by anionic (SDS/pentanol/water) and cationic (CTAB/octane/butanol/water) surfactants. These antioxidants have completely different hydrophilic/hydrophobic character. Some of the obtained results are shown in Figs. 1-4.
0 40 80H O (%)
200
300
400
500
600
700
0
20
40
60
80
100
Pe
ak c
urr
en
t (µ
A)
AA in CTAB/octane/butanol/water
Peak current
Peak potential
0 20 40 60 80 100H O (%)
480
520
560
600
640
680
0
10
20
30
40
50
Pea
k c
urr
en
t (µ
A)
Vitamin E in CTAB/octane/butanol/water
Peak current
Peak potential
Fig. 1 Variation of AA oxidation peak potential Epa and peak current Ipa at the GC electrode with water content in the CTAB/octane/butanol/water system.
Fig. 2 Variation of α-T oxidation peak potential Epa and peak current Ipa at the GC electrode with water content in the CTAB/octane/butanol/water system.
From the obtained results it follows that in the microemulsions the oxidation process of AA is more difficult than in water solutions. In both microemulsions the oxidation potential is much higher and the peak current much lower than in the buffer solution. For water insoluble α-T the peak potential increases gradually when the microemulsion changes from the oil-in-water (o/w) to water-in-oil (w/o)
Department of Radiochemistry and Colloid Chemistry – 118 –
whereas the peak current first increases (o/w) and then decreases (w/o) with the increasing butanol content. Our results confirm the view that the redox parameters of antioxidants depend on which part of the microemulsion phase the antioxidant molecules are located in. The influence of the microemulsion properties (charge and size) on the apparent diffusion coefficient of antioxidants and thus their transport to the electrode surface was analyzed.
0 20 40 60 80 100H O (%)
200
300
400
500
600
700
0
20
40
60
80
100
Pe
ak c
urr
en
t (µ
A)
AA in SDS/pentanol/water
Peak current
Peak potential
0 20 40 60 80 100H O (%)
400
450
500
550
600
650
700
0
10
20
30
40
50
Pe
ak c
urr
en
t (µ
A)
Vitamin E in SDS/pentanol/water
Peak current
Peak potential
Fig. 3 Variation of AA oxidation peak potential Epa and peak current Ipa at the GC electrode with water content in the SDS/pentanol/water system.
Fig. 4 Variation of α-T oxidation peak potential Epa and peak current Ipa at the GC electrode with water content in the SDS/pentanol/water system.
F.Ch. UMCS Report 2009 (BS) – 117 –
STRUCTURE OF UNSYMMETRICALLY DISUBSTITUTED
DERIVATIVES OF THIOUREA AND THEIR CYCLIZATION
PRODUCTS
Anna E. KOZIOŁ, Barbara MIROSŁAW, Marta STRUGA*
and Jerzy KOSSAKOWSKI*
DEPARTMENT OF CRYSTALLOGRAPHY
*MEDICAL UNIVERSITY, WARSAW, POLAND
A series of new thiourea derivatives had been synthesized. The substituents of
the thiourea moiety were polycyclic imide R1 and hydrophobic group R2 (Scheme
1). Next, linear compounds were used for preparation of the 1,3-thiazepine system
in the condensation reaction with 1,4-dibromobutane (Scheme 2) [1-3]. Because
both derivatives of thiourea and 1,3-thiazepine are biologically active compounds,
selected antiviral and pharmacological properties had been studied.
cyclic imide ––– thiourea ––– alkyl/aryl
R1
A N
O
O
CH2 CH CH2
R2
1
B N
O
O
CH3
2
C N
O
O
OCH3
3
Scheme 1. Molecular structure of selected compounds.
R1NH
R2NH
S
+ Br–(CH2)4–Br
→ NS
N
R1
R2
Scheme 2. Synthesis of 1,3- thiazepine derivatives.
Department of Crystallography – 118 –
The molecular structure of parent compounds A1, B2 and thiazepines B2 and C3 have been studied by the X-ray crystallography. This analysis indicated that of
three possible conformers of disubstituted thiourea moiety (Scheme 3), two are
observed in the solid state, viz. trans-trans and trans-cis.
N
S
N
HH
RR
N
S
N
H
R
R
H
N
S
N
R
H
R
H
trans-trans trans-cis cis-cis
Scheme 3. Conformations od disubstituted thiourea.
Thus, each conformer is able to form quite different pattern of hydrogen bonds
in intermolecular contacts (Fig. 1). The molecular flexibility explains also the
mechanizm of the cyclization reaction.
a
b
Fig. 1. Hydrogen bonds involving thiourea fragments: a) conformer tt forms the N-H...S
bonds; b) conformer tc forms the N-H...O bonds.
References:
[1] M. Struga, J. Kossakowski, A.E. Koziol, T. Lis, E. Kedzierska, S. Fidecka,
Synthesis and pharmacological activity of thiourea derivatives of 1,7,8,9-tetra-
methyl-4-azatricyclo [5.2.1.02,6
]dec-8-ene-3,5-dione, Lett. Drug Design
Discov., 6 (2009) 445.
[2] M. Struga, J. Kossakowski, B. Miroslaw, A.E. Koziol, A. Zimniak, Synthesis of
new 1,3-thiazepine derivatives, J. Heterocyclic Chem., 46 (2009) 298.
[3] M. Struga, J. Kossakowski, A.E. Koziol, E. Kedzierska, S. Fidecka, P. La
Colla, C. Ibba, G. Collu, G. Sanna, B. Secci, R. Loddo, Synthesis,
pharmacological and antiviral activity of 1,3-thiazepine derivatives, Eur. J.
Med. Chem., 44 (2009) 4960.
F.Ch. UMCS Report 2009 (BS) – 119 –
PMO-Zr
PMO-Ti
PMO-Zr-Ti
ηΝ♦ηΝ♦ηΝ♦ηΝ♦ηηηηηηηη0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Inte
nsit
y[a
rbit
rary
un
its,im
p/s
ec]
Fig. 1. Comparison of the XRD
patterns for PMO-Zr-Ti, PMO-Ti and
PMO-Zr.
ORGANOSILICAS CONTAINING Zr AND Ti IONS
Stanisław PIKUS, Małgorzata ZIENKIEWICZ, Elżbieta OLSZEWSKA
and Maciej KOZAK*
DEPARTMENT OF CRYSTALLOGRAPHY
*DEPARTMENT OF MACROMOLECULAR PHYSICS,
A. MICKIEWICZ UNIVERSITY, POZNAŃ, POLAND
Periodic mesoporous organosilicas (PMO) are a new class of organic-
inorganic materials which were first synthesized in 1999. The integration of organic
groups with inorganic constituents (silicon atoms) in one material gives many
advantages and provides an excellent opportunity for organosilicon chemistry. They
are characterized by the presence of organic bridging groups directly links two Si
atoms, incorporated into the channel walls and by possibility of controlling types of
organic groups in the bridged organosilane precursors. In the few last years the
doped PMO materials with zirconium, chromium , vanadium and titanium have
attracted much attention for obtaining catalytic materials.
The PMO materials containing Zr (PMO-Zr), Ti (PMO-Ti) or containing Zr
and Ti species in one material (PMO-Zr,Ti) were prepared (details synthesis see
paper [1]).
The PMO powders were characterized
by using powder X-ray diffraction (DRON3-
SEIFERT, Cu tube), X-ray photoelectron
spectroscopy (UHV, PREVAC),
transmission electron microscope (JEOL
JEM 1200 EXII, Tokyo, Japan).
The powder X-ray diffraction data
shows for PMO-Zr and PMO-Zr-Ti materials
prominent peak at 2θ = 0.8-1o
and for PMO-
Ti prominent peak at 2θ = 2o
(see Fig.1),
thus confirming that the materials have a 2D
hexagonal ordering of pore channels (p6mm
symmetry group)
A TEM images of chosen PMO
containing Zr and Ti are shown in Figure 2.
The TEM images confirm the ordered
structure of these materials, and show the
cylindrical pores are arranged in an ordered
hexagonal array.
Department of Crystallography – 120 –
Fig. 2. TEM images of chosen PMO materials containig Zr and Ti.
Fig. 3 shows XPS spectra
of samples PMO-Zr-Ti and
SBA-15. X-ray Photoelectron
Spectroscopy is bases on the
foundation that changing unit
components in structure causes
change of binding energy. The
binding energy of O 1s for
sample PMO-Zr-Ti was 530.95
eV. Therefore this value is less
about 0.43 eV than pure
comparison sample SBA-15
(531.38eV). Moreover binding
energy of Si2p (100.68 eV for
PMO-Zr-Ti is lower than that
in SiO2 (103.2-103.9 eV). It suggest that the heteroatoms are present in the hybrid
frameworks. Similar relationship for PMO-Zr and PMO-Ti was observed.
Conclusions
PMO materials were obtained using one-pot synthesis. The XRD patterns
indicate the hexagonal symmetry (p6mm symmetry group) and influence nature of
surfactant on the structure type (SBA-15 or MCM-41). The TEM images confirm
the hexagonal structure. The addition of organic phase improves the quality of the
material in grounds of the same structure directing agent. XPS data prove the
successful incorporation of heteroatom’s (Zr and Ti) in PMOs. The best structural
parameters show samples containing Zr and Ti species (content ratio Zr:Ti was 1:1)
in one material.
References:
[1] M. Zienkiewicz, S. Pikus, E. Olszewska, M. Barczak, Solid State Phenomena,
in Press.
O1s
SBA-15
PMO-Zr-Ti
500510520530540550
Binding energy [eV]
0
300
600
900
1200
Inte
nsit
y[a
rbit
rary
un
its]
530.95 eV
531.38 eV
Fig. 3. X-ray photoelectron spectrum comparison of
binding energy for PMO-Zr-Ti and pure SBA-15.
F.Ch. UMCS Report 2009 (BS) – 121 –
SYNTHESIS OF NEW CHIRAL ORGANOPHOSPHORUS
SYSTEMS FOR ASYMMETRIC CATALYSIS
K. Michał PIETRUSIEWICZ, Anna FLIS, Nikolai VINOKUROV,*
I. BAUMGART* and Holger BUTENSCHOEN
*
DEPARTMENT OF ORGANIC CHEMISTRY
*LEIBNIZ UNIVERSITAT HANNOVER, GERMANY
Optically active P-stereogenic 1,2-diphosphinoethanes constitute an important
class of chiral bidentate ligands of great practical utility in the field of asymmetric
catalysis. The corresponding P-stereogenic diphosphine oxides, which are the most
direct precursors to such ligands, have recently been shown to be easily accessible
through a simple conjugate addition of secondary phosphine oxides to
enantiomerically pure (SP)-(-)-methylphenylvinylphosphine oxide. More recently,
we reported on the synthesis of trans-(SP,SP)-(-)-1,2-bis(methylphenylpnosphi-
nyl)ethene (1) by efficient metathetic dimerization of (SP)-(-)-methyl-
phenylvinylphosphine oxide and then studied the reactivity of 1 in 1,3-dipolar
cycloadditions to achieve new bidentate P-stereogenic ligands. Although we have
postulated the di-s-cis conformation of 1 as the reactive conformation in its thermal
1,3-dipolar cycloadditions, no experimental evidence with regard to the conformatio
of 1 has yet been available. With the prospect of a planned use of 1 also in another
cycloaddition reaction, namely Diels-Alder cycloaddition, we have decided to
study, within this project, the solid state structure of trans-(SP,SP)-(-)-1,2-
bis(methylphenylpnosphinyl)ethene (1) by a single-crystal X-ray structure analysis.
1
Fig. 1. Ortep view of 1 showing 50% probability elipsoid
Department of Organic Chemistry – 122 –
The molecular structure of 1 is displayed in Figure 1. It reveals indeed the di-s-
cis conformation of the O=P-C=C-P=O fragment. As typically observed for type
R3P=O compounds deformations of the tetrahedral environment of the P atoms
caused an increase of the O-P-C and the simultaneous decrease of teh C-P-C
valency angles. The values observed fall in the range of 110.28(15) – 115.80(17)°
and 101.69(17) = 107.26(15)° for P1 and, 110.87(15) – 114.73(15)° and 102.42(17)
– 107.94(14)° for P2, respectively. The deviations from the syn-coplanarity of the
two phosphoryl P=O bonds and the ethene plane are only minute and amount to
6.21 (37) and –1.83 (36).
In addition, DFT calculations showed the observed di-s-cis conformation of 1
to be more stable than the corresponding di-s-trans conformation by 16.54 kJ/mol
(TURBOMOLE 5.7 Method BP86/SV(P).
It is also important to add that the identification of the preferred conformation
of 1 has enabled us to distinguish between the two possible stereochemical
approaches of 1 and cyclopentadiene in the subsequently studied Diels-Alder
cycloaddition. The two possible approaches of the reaction components are
displayed below.
P
PH
HO
O
Me
Me
Ph
Ph
P
PH
HO
O
Me
Me
Ph
Ph
P
P
O
OH
HPh Ph
Me
Me
P
P
O
OH
HPh Ph
Me
Me
PP
PP
di-s-cis di-s-trans
(SP,SP,R,R)-2
major
(SP,SP,S,S)-3
minor Scheme 1. Stereochemistry of the Diels-Alder cycloaddition of cyclopentadiene with di-s-
cis-(SP,SP)-1 (left) and with di-s-trans-(SP,SP)-1 (right). P Substituents in the
cycloadducts are omitted for clarity.
It could then be concluded that the dominating stereocourse of the studied
Diels-Alder cycloaddition would be the one shown in the left part of the above
figure.
F.Ch. UMCS Report 2009 (BS) – 123 –
SYNTHESIS AND APPLICATIONS OF CYCLIC
AND MACROCYCLIC ORGANOPHOSPHORUS COMPOUNDS
K. Michał PIETRUSIEWICZ, Anna SZMIGIELSKA, Anna FLIS,
Nikolai VINOKUROV* and Holger BUTENSCHOEN
*
DEPARTMENT OF ORGANIC CHEMISTRY
*LEIBNIZ UNIVERSITAT HANNOVER, GERMANY
Asymmetric hydrogenation plays a vital role in fundamental research as well
as in pharmaceutical and chemical industries in providing enantiomerically pure
compounds. Chiral diphosphines, which constitute the main family of ligands for
catalysis, have chirality normally resident in the carbon backbone or, less
commonly, at the phosphorus atoms. Although optically active diphosphines such
as CHIRAPHOS, DIOP and NORPHOS are very efficient ligands for asymmetric
catalysis, ligand scaffolds, in which stereogenic phosphorus atoms are bound to a
rigid 1,2-ethane backbone remain rare. Recently, we demonstrated that the homo-
metathesis of (SP)-methylphenylvinylphosphine oxide in the presence of modern
olefin metathesis precatalysts allows the efficient synthesis of P-homochiral (SP,SP)-
1. We have now shown that the stereoselective Diels-Alder cycloaddition of (SP,SP)-
1 to cyclopentadiene can be used as a convenient route to a new P-stereogenic
diphosphine ligand.
PMe
Ph
PMe
Ph
O
O
(SP,SP)-1
CH2Cl2, 25 °C, 21 h
92 %
1.3 : 1
(SP,SP,2R,3R)-2 (SP,SP,2S,3S)-3
P P
P PO O
Me Ph
Ph Me
+
O MePh
OMe
Ph
Scheme 1. Asymmetric Diels-Alder reaction of (SP,SP)-1 with cyclopentadiene
The cycloaddition proceeded smoothly at 25 ºC in CH2Cl2 to give two
diastereomeric products (SP,SP,2R,3R)-2 and (SP,SP,2S,3S)-3 in a ratio of 1.3 : 1 (31
P
NMR, 1H NMR) in 92% yield. To increase the diastereoselectivity of the studied
Diels-Alder cycloaddition, we tested several Lewis acids such as AlCl3, Sc(OTf)3,
SnCl4, TiCl4 were tested. After some screening it was found that TiCl4 can be
successfully used to improve the diastereomeric ratio of the cycloadducts
(SP,SP,2R,3R)-2 and (SP,SP,2S,3S)-3 (Table 1). Best results were obtained by
addition of only 0.5 equivalents of TiCl4, which resulted in a significant increase of
the ratio of diastereoisomers to 9:1 whereas the addition of larger amounts of Lewis
acid resulted in lower diastereoselectivities.
Department of Organic Chemistry – 124 –
Unfortunately we did not succeed in a separation of the diastereomers by
column chromatography. To separate (SP,SP,2R,3R)-2 and (SP,SP,2S,3S)-3 a method
developed by Brunner for separation of enantiomers of NORPHOS was applied. By
means of (–)-O,O-dibenzoyltartaric acid monohydrate [(–)-DBTA] in boiling
methanol the diastereomeric cycloadducts were separated affording (SP,SP,2R,3R)-2
in 96% de and (SP,SP,2S,3S)-3 in 90% de after hydrolysis with 2N NaOH (Scheme
2). This separation based on the difference in solubilty of the complexed
diastereomeric cycloadducts relies on the formation of hydrogen bridges between
the carboxyl group of (–)-DBTA and the P=O groups.
Table 1. The asymmetric Diels-Alder cycloaddition of (SP,SP)-1 with cyclopentadiene.
TiCl4
[equiv] solvent/ T [°C] t [h]
(SP,SP,2R,3R)-2 : (SP,SP,2S,3S)-3
a yield [%]
– Toluene /110 18 1.3:1 95
– CH2Cl2 / 20 21 1.3:1 90
0.5 CH2Cl2 / 20 17 9:1 87
1.0 CH2Cl2 / 20 19 7:1 85
1.5 CH2Cl2 / 20 24 5:1 82
2.0 CH2Cl2 / 20 48 3:1 70 a The diastereomeric ratio was determined by
31P NMR
1. (–)-DBTA, MeOH, 5 h, reflux
3. 2 N NaOH
2. fract. crystallization
31 %, 96 % de 41 %, 90 % de1.3 : 1
(SP,SP,2R,3R)-2 (SP,SP,2S,3S)-3
P P
P PO O
Me Ph
Ph Me
+
O MePh
OMe
Ph P P
P PO O
Me Ph
Ph Me
+
O MePh
OMe
Ph
(SP,SP,2R,3R)-2 (SP,SP,2S,3S)-3
Scheme 2. Separation of diastereoisomeric cycloadducts by means of (–)-DBTA
The absolute configuration of the major cycloadduct was established by
crystallographic method (Figure 1).
Fig. 1. Structure of (SP,SP,2R,3R)-2 in the crystal.
In conclusion, we
have developed a pro-
ductive approach to no-
vel C,P-stereogenic di-
phosphines by asym-
metric Diels-Alder cyc-
loaddition. Asymmetric
catalysis based on these
novel C,P-chiral li-
gands is underway in
our laboratories.
F.Ch. UMCS Report 2009 (BS) – 125 –
THE INFLUENCE OF THE CHEMICAL STRUCTURE
OF MONOMERS ON THE PROPERTIES OF POROUS
METHACRYLATE COPOLYMERS
Barbara GAWDZIK, Marta GROCHOWICZ and Beata PODKOŚCIELNA DEPARTMENT OF POLYMER CHEMISTRY
Porous polymer beads have been prepared by copolymerization of vinyl monomers and cross-linking agents such as divinylbenzene (DVB), ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TRIM) in the presence of inert diluents (porogens) by different methods of polymerizations: suspension, emulsion, dispersion, emulsion-suspension, etc. The various factors e.g. temperature, amount of cross-linking monomer and initiator, the type of vinyl monomers, composition of the porogenic solvents influenced on porous structure, mechanical strength, thermal stability, and resistance to solvent absorption of beads. The most popular macroporous copolymers based on styrene/divinylbenzene are hydrophobic materials and they are characterized by insufficient exchange rates in aqueous media. For application in aqueous systems, less hydrophobic polymeric materials are desirable. Hydroxyacrylate or meth(acrylate) monomers are an important group of less hydrophobic materials. These monomers are produced by esterification of epoxide compounds or resins with acrylate or methacrylate acid in the presence of a acidic or basic type catalyst or transition metal complexes [1-3]. In this paper we report synthesis of new porous methacrylate copolymers in the form of porous microspheres. They were prepared by suspension-emulsion copolymerization of 2-hydroxy-3-methacryloyloxypropoxybenzene (MPH), 1,3-di(2-hydroxy-3-methacryloyloxypropoxy)benzene (1,3DMH) and 1,4-di(2-hydroxy-3-methacryloyloxypropoxy)benzene (1,4DMH) with TRIM [3,4]. The new methacrylate monomers used in these polymerization reactions were synthesized by us. Their chemical structures are shown in Fig. 1. The mixtures of toluene and n-dodecane (in the case of MPH-TRIM material) or chlorobenzene and decan-1-ol (in the case of 1,3DMH-TRIM and 1,4DMH-TRIM materials) were used as a pore forming diluents. Toluene and chlorobenzene are thermodynamically good solvents for forming copolymers whereas n-dodecane and decan-1-ol are non-solvents.
Fig. 1. Chemical structures of MPH (a), 1,3DMH (b) and 1,4DMH (c) monomers.
O
O H
O
O
O
O H
O
O
OO
O H
O
OO
O H
OO
O H
O
O
a c
b
Department of Polymer Chemistry – 126 –
Porous structures of obtained MPH-TRIM, 1,3DMH-TRIM and 1,4DMH-TRIM copolymers were characterized by nitrogen adsorption-desorption measurements in a dry state, and by inverse size exclusion chromatography (ISEC) in a swollen state. Porous structure parameters listed in Table 1 indicate that pore forming diluent mixtures influenced the porous structure of studied copolymers. In the case of MPH-TRIM and 1,3DMH-TRIM materials the most developed specific surface area and the highest pore volume were obtained in the presence of 85% (v/v) good solvent. 1,4DMH-TRIM materials behave in insignificantly different way. Generally one can conclude that chemical structure of monomers have influence on copolymers porous structure. MPH-TRIM materials, obtained from difunctional monomer MPH, possess smaller specific surface areas than those obtained from tetrafunctional 1,4DMH and 1,3DMH monomers. Additionally, their physical properties such as swelling behavior, general selectivity, thermal and mechanical resistances are also different.
Table 1. Porous structure parameters of the obtained copolymers.
Copolymer
Concentration of solvent in the
mixture with non-solvent (%)
Specific surface area
(m2/g)
Pore volume (cm3/g)
Most probable
pore diameter (Å)
MPH-TRIM 100 85 50
74 166 10
0.15 0.69 0.02
35 300 –
1,3DMH-TRIM 100 85 50
93 340 187
0.18 0.85 0.65
40 337 380
1,4DMH-TRIM 100 85 50
88 135 210
0.28 0.58 0.73
390 250 300
References:
[1] B. Podkościelna, A. Bartnicki and B. Gawdzik, J. Appl. Polym. Sci., 111 (2009) 1257.
[2] B. Podkościelna and B. Gawdzik, Appl. Surf. Sci., in press. [3] M. Grochowicz, B. Gawdzik and A. Bartnicki; J. Polym. Sci. Part A, 47 (2009)
3190. [4] M. Grochowicz, B. Gawdzik and A. Bartnicki; J. Appl. Polym. Sci., 107 (2008)
3718.
F.Ch. UMCS Report 2009 (BS) – 127 –
STUDIES ON PHOTOCURABLE HYBRID MATERIAL
Jan RAYSS, Wiesław PODKOŚCIELNY, Andrzej GORGOL and Jan WIDOMSKI
DEPARTMENT OF OPTICAL FIBRES TECHNOLOGY
The aim of this work was investigation of europium and terbium fluorescence complexes compounds with orto-methylobenzoic acid and dimethyl 2,6-naphthalenedicarboxylate. In this research photopolymerization influence on the complexes compounds was investigated. Also intramolecular energy transfer mechanism between ligand and central atom was studied, so-called antenna effect. Complexes, which show this effect will be, in the next part of investigation, used to build optical UV-VIS sensor. All studies was made using spectrophotometer.
Solutions were transferred by syringe into capillary tubes made of quartz glass, which allows permeability of UV-VIS. Next, the capillaries were placed into metal cuvet, which keeps the capillary in vertical position. Thus prepared samples were placed into spectrophotometer. In order to establish the optimal wavelength, at which maximum luminescence appears, the experiments were performed using different excitation wavelengths. Studies show that this wavelength equal to 370nm.
The next step of the investigations was the photopolymerization of the mixtures containing europium complex, Ebecryl 575 and butyl acrylate. In this complex antenna effect appears. It is crucial that the fluorescence spectrum of central atom and ligand do not overlap, because it could quench the luminescence. In order to chose the optimal concentration of luminophores in the solutions, in which they show maximum of luminescence, the series of the solutions were prepared. Figure 1 shows the dependence between intensity and wavelength. It can be observed that then the concentration of the luminophore increases, the intensity of luminophores also increases.
Fig. 1. Intensity vs wavelength.
Department of Optical Fibres Technology – 128 –
It can also be observed that luminescence phenomenon is not block by photopolymerization process, which can be seen in the Fig. 2.
Fig. 2. Intensity vs wavelength before and after photopolymerization
The Fig. 2 shows the dependence between intensity and wavelength. The
measurement was made by wavelength of 350 nm for the composition of the highest complex concentration.
References:
[1] E. DeOliveira, C.R. Neri, Osvaldo A. Serra, and A.G.S. Prado "Chemistry of Materials", 09 October 2007.
[2] A.M. Konkowski, S. Lis, M. Pietraszkiewicz, Z. Hnatejko, K. Czarnobaj, and M. Elbanowski "Chemistry of Materials", 08 January 2003.
F.Ch. UMCS Report 2009 (BS) – 129 –
LARGE MODE AREA FIBERS WITH DEDICATED MODE
FIELD DIAMETERS – THEORY, FABRICATION
AND CHARACTERIZATION
Paweł MERGO, Jan WÓJCIK, Krzysztof SKORUPSKI, Krzysztof POTURAJ and Mariusz MAKARA
DEPARTMENT OF OPTICAL FIBRES TECHNOLOGY
In recent years, low and high birefringent photonic crystal fibers PCF found multiple applications. Most interesting are: supercontinuum generation, sensing properties inaccessible for classical fibers and liquid crystal fibers LC PCF [1]. In the present state of technology, PCFs are connected to sources and detectors with classical optical fibers, mostly single mode. Their mode field diameter is usually larger than for typical photonic fibers. This results in big power losses when connecting with classical fibers and consequently, with light sources and detectors [2].
The aim of this work is elaborating low birefringent PCF production technology. Their mode field diameter will be close to that of classical single mode fibers in second and third transmission window. Such photonic crystal fibers are commercially available. However those are ordinary PCFs, and in many cases special properties, like high pressure sensitivity, will be required. This leads to reverse situation – what parameters classical single mode fibers should have to match the parameters of special photonic fibers.
This work is an experimental confirmation of the modeling of PCFs with dedicated mode field diameter versus wavelength. Results of large mode area LMA fibers modeling with the finite element and multipole methods, technology of LMA fibers production, and measurements of mode field diameter by transverse offset method are presented.
Fabrication by stacking method of series of LMA fibers with type IV and II silica glass lead to obtain fibers presented on the Fig. 1.
a) b) c)
Fig. 1 Cross sections of fabricated LMA fibers: 081120(a),1090327 (b) 090329 (c). Commercial program COMSOL exploit the finite elements method for obtain the radial field distribution and the power profile versus fiber radius we have
Department of Optical Fibres Technology – 130 –
used. Additionally free CUDOS program exploit multiple method we used in order to comparison results obtained with COMSOL. Exemplary results are presented on the Fig. 2.
Fig. 2. Field and power radial distributions obtained by COMSOL for fiber no.081120.
Mode field diameters were calculated as 1/e for field and 1/e2 for power profiles. Dependence of mode field diameter distributions versus wavelengths are presented on the figure 3a. Measurements of mode field diameters we obtain by transverse offset method for 081120 and SMF28 telecommunication fiber – see Fig. 3b.
Fig. 3. Spectral variable of mode field diameters of investigated fibers obtained by COMSOL program (a) and results of mode field diameter measurements by transverse offset method for 081120 and SMF 28 fiber (3b).
In conclusion: mode field diameter for fiber no 081120 is close to SMF 28 telecommunication fiber. We can do modeling and produce fibers with mode field diameter adapted for any photonic and classical fibers up to 10 micrometers. References:
[1] F. Poli A. Cucinotta S. Selleri, Photonic Crystal Fibers – Properties and Applications, Springer, 2007
[2] Y. Wang,,* H. Bartelt, S. Brueckner, J. Kobelke, M. Rothhardt, K. Mörl, W. Ecke, R. Willsch, Splicing Ge-doped photonic crystal fibers using commercial fusion splicer with default discharge, Optics Express, (2008) 7258.
[3] NKT Photonics, Catalog pages of LMA fibers, www.nktphotonics.com.
400 600 800 1000 1200 1400 1600 1800 2000wavelength [nm]
6.5
7
7.5
8
8.5
9
9.5
MDF [µm
]
081120
1090327
090329
Mode field diameter fo LMA
800 1000 1200 1400 1600wavelength [nm]
7.5
8
8.5
9
9.5
10
10.5
11
11.5
12
MD
F [µm
] 081120
SMF-28
Mode field diameter of LMA fibers
F.Ch. UMCS Report 2009 (BS) – 131 –
V-TiO2/Al2O3 AND Co-TiO2/Al2O3 V – THE CATALYSTS
OF PHOTOOXIDATION OF ORGANIC POLLUTANTS IN WATER
Bożena CZECH DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
In respect of common presence of phenol in water and wastewater the methods for its removal are widely tested [1]. Various organic and some inorganic compounds can be rendered harmless by using Advanced Oxidation Processes (AOPs) that base on the generation of highly reactive OH*. *OH can be generated in different ways depending on the pollutant and treatment conditions: chemically (H2O2/O3, O3/OH-, Fe2+ or Fe3+/H2O2), photochemically (H2O2/UV, O3/UV) and photocatalytically (mainly TiO2/UV) [1-2].
Photoreactions were conducted in the band reactor of our construction [2]. In case to prevent the problems with filtration after the experiments as the catalysts were typed γ–Al2O3 supported TiO2 catalysts modified with V addition prepared according to [3] by Double Impregnation Method or Classical Impregnation Method. As the model contaminants were used solutions of phenol prepared to have the COD value ca. 3000 mg O2/dm3 that is typical for real wastewater and simultaneously is exceeding the norms what may indicate highly concentrated (according to COD) wastewater. As the oxidizing agents were typed oxygen (from air) and H2O2, the effectiveness was measured in the few configurations: TiO2/UV/O2/H2O2, TiO2/O2/H2O2, TiO2/UV/O2, TiO2/O2.
The catalysts were examined in Analytical Laboratory of Faculty of Chemistry UMCS in Lublin to determine the total surface area – BET method, TiO2 content – XRF method and V by AAS method (Table 1). All XRD spectra of studied catalysts are similar and TiO2 is present in a form of anatase.
Table 1. Physicochemical properties of studied catalysts.
Catalyst Ti content
[wt.%] V content
[wt.%] total surface area
[m2/g] impregnation
method
Ti1 6.69 – 75.37
Ti2 3.34 – 93.96
Vc 6.82 0.54 91.96 CIM – 10 min.
Vd 5.34 4.40 71.30 DIM – 8 min.
All studied catalysts (Fig. 1 and Fig. 2) enable a significant removal of phenol,
at least in 50%. The effect of H2O2 addition to photooxidation over V-TiO2/Al2O3 is not obvious and depends on the type of compounds. Generally mineralization is
Department of Environmental Chemistry – 132 –
increased in the presence of H2O2. Phenol oxidation is proceeded directly by h+ or by *OH (mainly). Illias et al.[4] indicate that H2O2 addition during aeration of phenolic wastes do not cause the significant changes in phenol removal.
Fig. 1. COD changes during phenol removal O2 - aeration, UV – UV irradiation, H2O2 – H2O2 addition, H2O2/UV - addition of H2O2 during UV irradiation.
Fig. 2. The COD changes in time during photocatalytic oxidation of phenol with H2O2.
According to obtained results of photocatalytic oxidation of phenol in water it
may be concluded that:
1. The most efficient method for removal of phenol is photocatalytic oxidation with H2O2 over V-TiO2/Al2O3, but the effect of treatment was better than over unmodified catalysts only at about 10-15%
2. It is economically unjustified to introduce any modifier agents into catalysts during photooxidation of phenol over TiO2/Al2O3.
3. It is economically unjustified to use additionally any oxidizing agents such as H2O2,during photoxidation of phenolic waste using TiO2/Al2O3 because it may even retard oxidation.
4. The H2O2 addition is important and deepens the photooxidation of phenol but only over V modified catalysts.
References:
[1] A. Dobosz and A. Sobczynski, Wat. Res., 37 (2003) 1489. [2] B. Czech and W. Cwikła-Bundyra, Pol. J. Chem. Technol., 9 (2007) 18. [3] B. Czech and D. Nazimek, Pol. J. Environ. Stud., 13 (2004) 5. [4] I. Ilisz and A. Dombi, Appl. Catal. A, 180 (1999) 35.
F.Ch. UMCS Report 2009 (BS) – 133 –
RESEARCH ON KINETICS OF REACTION BETWEEN
CH4 AND O2 ON METALS OF THE VIII GROUP
Marcin KUŚMIERZ and Dobiesław NAZIMEK
DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
Selective oxidation of methane is one of the most challenging tasks in catalysis nowadays. Activation of methane is the major problem: bonds between carbon and hydrogen atoms are very strong, molecule is small, non-polar and symmetric. Simultaneously, intermediates leading to valuable products of reaction (such as methanol, formaldehyde) are highly unstable in temperature range, in which activation of methane occurs. Several attempts concerning hetero- and homogenous catalytic reactions are described in literature [1, 2].
Catalysts based on copper are known for their activty in oxidation of hydrocarbons [3-5]. Copper oxide is also a component of the commercial catalyst for methanol synthesis. The aim of this research was to test the activity of copper catalysts supported on natural zeolite – clinoptilolite.
A set of six copper catalysts was prepared by the ion exchange method utlizing copper nitrate as a precursor. Clinoptilolite Na-K form was supplied by Erem S. C. Its total surface area was 34.15 ± 0.22 m2/g, volume of macropores was 0.00089cm3/g and mean pore size 78.4Å. Copper loadings were measured by the X-ray Fluorescence method and ranges from 1.15 wt. % to 3.36 wt. %. This parameter is linearly correlated with concentration of Cu+2 solution.
It can be tested by means of IR spectroscopy whether metal ions are introduced into zeolite structure. According authors of paper [7] intensity of band at c. a. 680cm-1 and, especially, band at c. a. 670 cm–1, changes when ion exchange occurs. However quantitavie interpretation is difficult, decreasing intensity of these bands indicates that lighter ions are replaced by heavier ones. Transmission spectra presented in Figure 1 clearly show that such a phenomenon occures.
Oxidation of methane (O2/CH4 = 3) was studied using a gradientless reactor described in paper [6]. A Chrompack CP9001 chromatograph with PC computer as an integrator was used to analyse the products.
Measured turnover frequencies and activation energies are summarized in Table 1. The activity measured across the catalysts series were very low within temperature range 300-450°C. This low activity can be attributed to presence of iron in clinoptililite (1.6 wt. %) which is known to decrese the activity of methane oxidation catalyst.
The most desired product of the reaction – methanol was not detected. The only products of the reaction across the examined temperature range were carbon dioxide and water. The results clearly indicates, that Cu/clinoptilolite catalysts perform very poor in reaction of selectie methane oxidation.
Department of Environmental Chemistry – 134 –
Fig. 1. Transmission spectra of clinoptilolite and selected catalysts (CuCL05, CuCL11).
Table 1. Turnover frequencies at 450°C (s–1) and activation energies Ea (kJ/mol).
catalyst TOF Ea
CuCL01 0.00565 117.4 ± 14.5
CuCL03 0.00836 120.1 ± 4.4
CuCL05 0.00754 104.2 ± 12.1
CuCL07 0.00482 131.1 ± 10.2
CuCL09 0.01422 164.6 ± 18.7
CuCL11 0.00382 126.3 ± 10.7
References:
[1] K. Otsuka, Y. Wang, Applied Catalysis A: General, 222 (2001) 145. [2] C. E. Taylor, R. P. Noceti, Catalysis Today, 55 (2000) 259. [3] P. Y. Silvert, V. Vijayakrishanan, P. Vibret, R. Herrera-Urbina, K. T. Elhissen,
Nanostructures Materiale, 7 (1999) 611. [4] I. Tachard, A. B. C. da Silva, F. Argolo, S. M. O. Borito, H. O. Pastore, H. M.
C. Adrade, Natural Gas Conversion VIII, 167 (2007) 195. [5] K. O. Xavier, J. Chacko, K. K. Mohammed Yusuff, Applied Catalysis A
General, 258 (2004) 251. [6] D. Nazimek, M. Kuśmierz, P. Kirszensztejn, Polish Journal of Applied
Chemistry, L (1-2) (2006) 41. [7] W. Mozgawa, T. Bajda, Journal of Molecular Structure, 170 (2006) 792.
F.Ch. UMCS Report 2009 (BS) – 135 –
STUDIES ON FACTORS AFFECTING COURSE AND RESULTS
OF CHEMICAL EDUCATION
Ryszard M. JANIUK, Jarosław DYMARA, Zofia KLOC
and Agnieszka KAMIŃSKA-OSTĘP
DEPARTMENT OF CHEMICAL EDUCATION
Didactic of Chemistry is the field of science whose fast development and
establishment of position among related science have taken place during the last
several scores of years. Equally its dynamic development, particularly in some
scientific centers, is also observed in Poland [1]. At the same time chemical
education undergoes some changes. The causes inducing these changes as well as
the conditions favoring or making their introduction into Polish educational system
difficult have been analyzed [2]. The survey which aim was to get to know the
opinions of members of the Polish Scientific Societies about state of science
education in Poland and necessity of undertaking mutual activities concerning the
issues of science education in Polish schools, has been conducted. [3]. It showed
that most people questioned are of negative opinions about state of science
education in Poland schools. Current changes in the Polish educational system
concerning science education were evaluated in a similar way. Almost 82% of those
questioned consider that it is necessary for all Societies to get engaged jointly in
improving of state of science education in Polish schools.
At present much attention is devoted to including some elements of knowledge
about science into chemical education. This covers a wide range of problems,
including among others: history and science methodology, influence of science on
development of our civilization and its role in contemporary society, ways of
communication as well ethical problems in science. Chemistry lessons provide
many opportunities for including these issues. However, it depends on teachers’
qualifications and whether these elements of knowledge about science are found in
curricula and textbooks [4]. Another problem more often perceived in chemical
education is application of suitable methods and teaching aids for dyslexic pupils
[5] making use of quickly developing information technology [6]. Here also of
significant importance is teachers’ knowledge concerning learning difficulties of
dyslexic pupils [7] and whether the teachers are able to apply suitable teaching
methods for such pupils [8].
Extramural activities are very important tool in the development of pupils’
interests in science subjects including chemistry. There are many possibilities in
such domain which can be successfully applied [9]. The element of chemical
education largely deciding about its effects is pupils’ homework. As follows from
the studies it is not sufficiently exploited and pupils exhibit unwilling attitude
towards it [10].
Department of Chemical Education – 136 –
The investigations curried out for the first year chemistry students show that
their knowledge in general chemistry is unsatisfactory. As it affects negatively the
further course of their studies, some measures must be undertaken to make up for
their deficiencies [11]. Application of pre-laboratory testing using information
technology techniques, for instance concerning the analytical calibration methods
[12] can be helpful during the classes in analytical chemistry [13].
References:
[1] R.M. Janiuk, H. Gulińska. ”Rozwój dydaktyki chemii w Polsce”, Materiały 52 Zjazdu
PTChem i SiTPChem, Łódź 2009, S13-SL-13-01, p. 307.
[2] R.M. Janiuk. „Refleksje nad kształceniem chemicznym – co, w jaki sposób i w jakim
celu należy w nim zmienić?”, Materiały IX Konferencji: Nowe wyzwania dydaktyki
chemii, 25-27.04. 2008, Ciążeń k. Poznania, pp. 226-235.
[3] R.M. Janiuk. „Edukacja przyrodnicza w opinii członków polskich towarzystw
naukowych”, Materiały 52 Zjazdu PTChem i SiTPChem, Łódź 2009, S13-OC-13-07,
p. 309.
[4] R.M. Janiuk. „Wiedza o nauce w kształceniu chemicznym”, Proceedings of the 19th
International Conference on Chemistry Education, Vol. 1, Hradec Kralove, IX. 2009,
pp. 50-63.
[5] A. Kamińska-Ostęp, H. Gulińska. „Teaching methods and aids assisting dyslexic
pupils in learning chemistry”, Journal of Baltic Science Education, Vol. 7, No 3, 2008,
pp. 147 – 154.
[6] A. Kamińska-Ostęp, H. Gulińska. „The use of information technologies in teaching
chemistry to dyslexic students”, Research, Reflections and Innovations in Integrating
ICT in Education. Lizbona, Portugalia 20-26.04.2009. Vol. 2, pp. 1184 – 1188.
[7] A. Kamińska-Ostęp. „Wyniki badań nauczycieli chemii na temat kształcenia uczniów z
dysleksją”, Materiały III Międzynarodowej konferencji: Badania w dydaktyce
przedmiotów przyrodniczych. Uniwersytet Pedagogiczny im. KEN, Kraków 26-28.06.
2008, pp. 182-185.
[8] A. Kamińska-Ostęp. „Trudności i problemy uczniów dyslektycznych w uczeniu się
chemii w opinii nauczycieli”. Materiały IX Konferencji: Nowe wyzwania dydaktyki
chemii, 25-27.04. 2008, Ciążeń k. Poznania, pp. 82-84.
[9] J.W. Dymara. „Rozwijanie zainteresowań uczniów chemią poprzez zajęcia
pozaszkolne”, Proceedings of the 19th International Conference on Chemistry
Education, Vol. 2, Hradec Kralove, IX. 2009, pp. 80-86.
[10] A. Kamińska-Ostęp. „Teoria i praktyka w świetle badań dotyczących pracy domowej
ucznia”, Chemia bliżej życia. Dydaktyka chemii w dobie reformy edukacji. Poznań 2009, pp. 146-153
[11] Z. Kloc. „Badania poziomu wiedzy z chemii ogólnej studentów I roku”, Materiały IX
Konferencji: Nowe wyzwania dydaktyki chemii, 25-27.04. 2008, Ciążeń k. Poznania,
pp. 236-239.
[12] A. Persona, J.W. Dymara. „Kalibracja analityczna w analizie instrumentalnej”,
Materiały 52 Zjazdu PTChem i SiTPChem, Łódź 2009, S13-PC-13-13, p. 314.
[13] A. Persona, T. Gęca, J.W. Dymara. „Computer-aided classes in analytical chemistry”,
Materiały III Międzynarodowej konferencji: Badania w dydaktyce przedmiotów
przyrodniczych. Uniwersytet Pedagogiczny im. KEN, Kraków 2008, pp. 294-297.
PART 2
BW REPORTS
F.Ch. UMCS Report 2009 (BW) – 139 –
PROPERTIES OF MIXED ADSORPTION LAYERS:
TETRAMETHYLTHIOUREA AND TERTBUTANOL IN 4M NaClO4
AT MERCURY ELECTRODE
Jolanta NIESZPOREK, Dorota SIEŃKO, Dorota GUGAŁA-FEKNER
and Jadwiga SABA
DEPARTMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
The studies of tertbutanol (TB) adsorption were carried in 4M NaClO4 as the
base electrolyte in the presence of a constant tetramethylthiourea (TMTU)
concentration; 0.050M or 0.005M. TB influence on the differential capacity course
is more visible in the presence of 0.005M TMTU. However maximal changes to EZ
zero charge potential, are nearing and are 22mV and 16mV in the presence 0.05M
TMTU and 0.005M TMTU, respectively (Tab.1)
Table 1. The dependence of zero charge potential, –EZ/V v.s.Ag/AgCl electrode in
the system 4M NaClO4 + TMTU + TB.
cTB 0.005M TMTU 0.050M TMTU
0.00 0.656 0.687
0.01 0.656 0.687
0.03 0.652 0.687
0.05 0.650 0.687
0.08 0.649 0.681
0.09 0.649 0.678
0.10 0.645 0.678
0.20 0.589 0.677
0.30 0.580 0.677
0.40 0.562 0.674
0.50 0.540 0.665
The obtained TB relative surface excess Г’ values are higher in the presence of
0.050M TMTU. This effect indicates that TB adsorption is easier at a less hydrated
electrode surface. Tab. 2 presents Frumkin isotherm constants for the studied
system.
Department of Analytical Chemistry and Instrumental Analysis – 140 –
Table 2. The free energy of adsorption, ∆Go and interaction parameters, A obtained
from Frumkin isotherm in the system: 4M NaClO4 + TMTU + TB.
0.005M TMTU 0.05M TMTU –E/V
–∆G0/kJ/
.mol –A –∆G
0/kJ/mol –A
0.75 10.65 0.10 11.99 0.36
0.80 10.75 0.18 12.19 0.32
0.85 11.07 0.14 12.43 0.36
0.90 10.90 0.17 12.39 0.31
1.00 9.73 0.16 11.64 0.30
1.05 10.23 0.19 11.79 0.38
Values presented in Table 2 confirm observations based on the zero charge
values.
The inability to determine parameters characterizing the maximum adsorption
of TB as well as the lack of any maxima on the Γ’ = f(E) curves confirm that the
adsorption of TB [1] loss its physical character in the presence of TMTU.
References:
[1] E. Blomgren, J. O’M. Bockris, C. Jesch, J. Phys. Chem., 65 (2000) 1961.
F.Ch. UMCS Report 2009 (BW) – 141 –
SPECIFIC ADSORPTION OF CARBONATE IONS
AT THE YTTRIUM OXIDE/ELECTROLYTE SOLUTION INTERFACE
Władysław JANUSZ and Anita SĘDŁAK DEPARTMENT RADIOCHEMISTRY AND COLLOID CHEMISTRY
Nanocrystaline yttrium oxide has many high technological applications such
as: material science, inorganic synthesis and laser technology [1]. Synthesis and
processing dispersion of yttrium oxides in aqueous solution may change its surface
properties as a result of adsorption of carbonate ions that are present in environment
of the reaction due to absorption of carbon dioxide or dissolution of carbonaceous
minerals. Carbonate ions have large adsorption affinity to surface of yttrium oxide
and change its surface properties and stability of yttrium oxide dispersion.
All measurements were carried out on commercial (Sigma-Aldrich) yttrium
oxide. The specific surface of the sample, determined by BET method, was
3.7 m2/g. Characteristic values of grain size distributions where: d(0.1) = 1.06 µm,
d(0.5) = 6.51 µm and d(0.9) = 15.75 µm. The crystalline size, determined by means
of Scherrer method, was 33.74 nm. Adsorption measurements of carbonate ions
from the NaClO4 solution were carried out with 14C isotope as the radiotracer.
The adsorption kinetic of carbonate ions at the yttrium oxide/electrolyte
solution interface is depicted in Fig 1. The quality of fitting using pseudo-first-order
and pseudo second-order equations was good.
The initial concentration of carbonate ions was from 3·10–3
M to 1·10–6
M
respectively. The shapes of adsorption of carbonate ions plot vs. pH are
characteristic for anions adsorption onto metal oxides and are called “adsorption
envelope” eg. Fig 2. One can observe increase of adsorption and decrease of
concentration of carbonate ions with a decrease of pH of the electrolyte.
Specific adsorption of carbonate anions at the yttrium oxide/electrolyte
interface leads to decrease of pHiep due to the increase of its concentration,
complexed by anions, positively charged groups at the Y2O3/electrolyte interface
and simultaneous decrease of concentration of ionized positively charged forms like
≡YO2+ Because the diffuse layer charge is proportional to algebraic sum of
negatively and positively charged groups, the decrease of concentration of
positively charged groups leads to the majority of negative charged ones, so
decrease of zeta potential and shift of pHiep towards low pH, Fig 3.
References:
[1]. A. S. Kumara, A. R. Duraia, T. Sornakumar, Mat. Lett., 58 (2004) 1808– 1810.
[2]. R.O James, P.J. Stiglich, and T.W. Healy, Disc. Faraday Soc., 59 (1975)142.
Department of Radiochemistry and Colloid Chemistry – 142 –
0 20 40 60 80 100 120
t [min]
0
0.004
0.008
0.012
0.016
Adsorp
tio
n [
µmol/m
2]
8
8.2
8.4
8.6
8.8
9
pH
Exp.
Pseudo I st. order
Pseudo II nd
7 8 9 10
pH
0
0.01
0.02
0.03
0.04
0.05
Carb
onate
ions a
dsorp
tion [
µm
ol/m
2]
0
2E-007
4E-007
6E-007
8E-007
1E-006
1.2E-006
1.4E-006
1.6E-006
1.8E-006
2E-006
2.2E-006
2.4E-006
2.6E-006
2.8E-006
3E-006
Carb
ona
te io
ns c
oncentr
ation [m
ol/dm
3]
Concentration
Adsorption
Fit
Fig. 1. Fitting the kinetics of adsorption
of carbonate ions form initial con-
centration 1·10–5
M on the yttrium oxi-
de/electrolyte interface, pseudo-se-
cond-order equation (long dashed li-
nes), pseudo-first-order equation (short
dashed lines) and symbols – experi-
mental data .
Fig. 2. Adsorption density and concentration of
carbonate ions as a function of pH solution in the
Y2O3/0.001M NaClO4 + 0.000003 M HCO3– sys-
tem. Solid line – fit using non-stoichiometric mo-
del of ion exchange for pK = 1.059 and nOH =
0.74 [2].
6 7 8 9 10
pH
-40
-35
-30
-25
-20
-15
-10
-5
0
5
10
15
20
ζ p
ote
nti
al
[mV
]
Carbonate ion concentration
[mol/dm3]
0,001
0,0001
0,00001
0,000001
Fig. 3. The ζ potential as a function of pH and carbonate ion concentration
in the Y2O3/0.001M NaClO4 system.
F.Ch. UMCS Report 2009 (BW) – 143 –
OPTIMIZATION OF PLUTONIUM EXTRACTION
WITH METHYLTRIOCTYLAMMONIUM CHLORIDE PRECEDING
ITS DETERMINATION BY LIQUID SCINTILLATION
SPECTROMETRY
Andrzej KOMOSA, Magdalena PIEKARZ and Jolanta ORZEŁ
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
Plutonium is still present in the environment. Long but divers half-lives are a
reason of plutonium isotopic ratio variation with time. In spite of rather small
hazard for human health plutonium isotopes can serve as tracers for environmental
migration of polyvalent ions. The importance of plutonium determination in
environmental samples is connected with existence of nuclear power plants and
terrorist threat all over the world. Therefore, elaboration of rapid method of Pu
isotope determination in environmental samples is highly desirable.
Optimization of selective extraction conditions for separating plutonium from
uranium and thorium standard solutions using methytrioctylammonium chloride
(Aliquat 336) as extracting agent were studied. Influence of such parameters as
concentration of extracting agent and nitric acid, and kind of reducing agent on
efficiency of extraction were tested. The method was developed for standard
solutions of Pu, Th and U. A Quantulus liquid scintillation spectrometer was used
for determination of alpha activity of these isotopes. It was found that using
HDEHP in a first stage of elaborated procedure and Aliquat 336 in the next is
possible to separate Pu from the mixture of U and Th. Optimal values of measuring
parameters such as a PSA value and a scintillation cocktail volume were established
as well.
Methyltrioctylammonium chloride dissolved in xylene reveals a good extracting
power for plutonium, uranium and thorium from wide range of nitric acid
concentration. The optimal extraction condition was obtained using 3M HNO3 and
0.1M Aliquat 336. Concentration of nitric acid was found to influence on both the
extraction efficiency and quench, optimal concentration being 3M HNO3.
Increase in volume of scintillation cocktail caused increase in the SQP
quench parameter value. It was found that optimal PSA value for measuring the
alpha and beta pulses separately was equal to 30. The highest selectivity of
plutonium separation from both uranium and thorium can be achieved using 0.2M
HDEHP in the first step and 5% ascorbic acid in 1M HCl as reducing agent for Pu
stripping, and 0.1M Aliquat 336 for second extraction. In these conditions 96% of
plutonium can be found in organic phase with only traces of thorium and uranium
present.
Department of Radiochemistry and Colloid Chemistry – 144 –
EFFECT OF LIQUID SCINTILLATION COCKTAIL VOLUME
ON 3H AND
14C MEASUREMENT PARAMETERS USING
THE QUANTULUS SPECTROMETER
Andrzej KOMOSA, Katarzyna ŚLEPECKA and Jolanta ORZEŁ
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
Due to a necessity to reduce of radioactive wastes and taking into account high
costs of liquid scintillation cocktails the use of smaller cocktail volume is required.
Therefore, the aim of our study was to investigate an influence of cocktail volume
on measurement parameters of nine various commercial cocktails during tritium
and 14
C standard solutions counting in conditions of variable quench.
Study on the influence of cocktail volume on such measuring parameters as
counting efficiency, Standard Quench Parameter (SQP) and Figure of Merit (FOM)
were performed. Nine commercial cocktails were tested by using the Quantulus
spectrometer. Two kinds of vials (low-diffusion teflon-coated polyethylene and
high-performance glass) and two standard solutions (14
C and 3H) were used.
Measurements were performed at seven quench levels ensured by carbon
tetrachloride addition into the scintillation vials. Various quench sensitivity of
studied cocktails was found. Cocktails based on simple benzene-derived solvents
revealed the best quench resistance. In general, increasing cocktail volume caused
the counting efficiency increased. However, background increased as well, what
resulted in FOM diminishing. Studied cocktails revealed also various responses on
volume changes
It was found that commercial scintillating cocktails reveal various quench
sensitivity. The cocktail volume increase made the counting efficiency and
background increased as well. This causes diminishing the FOM values with
increasing volume. The best cocktails for measuring 14
C and tritium are those based
on benzene-derived solvent (especially butyl-PBD dissolved in pure benzene,
Permablend dissolved in toluene and Insta Fluor). The worst cocktails are those
which have complex chemical composition (as Hionic Fluor) or contain too small
concentration of scintillators (as HiSafe 3).
F.Ch. UMCS Report 2009 (BW) – 145 –
REACTIONS OF CYCLIC ORGANOPHOSPHORUS
COMPOUNDS WITH NUCLEOPHILES
K. Michał PIETRUSIEWICZ, Zbigniew DRZAZGA, Anna FLIS,
Renata PARCHETA and Elżbieta ŁASTAWIECKA
DEPARTMENT OF ORGANIC CHEMISTRY
Phospholanes, five-membered phosphorus compounds constitute an important
structural motif in organophosphorus chemistry due to the stabilizing effects which
five-membered ring brings about into five-coordinate organophosphorus
compounds and five coordinate organophosphorus reaction intermediates. They also
find growing use as vauable ligands for transition metal complexes serving as
catalysts in the field of asymmetric catalysis.
Synthesis of phospholanes is based mainly on the McCormack process which
produces unsaturated phospholanes (phospholenes) from butadiene and
dichlorophosphine in a single cycloaddition step. The double bond in phospholenes
can then be hydrogenated or functionalized to provide the desired phospholane
derivative (Scheme 1). Other syntheses of phospholanes (or phospholenes) are of
rather marginal utility.
PR Cl
Cl
..+
PR O
McCormack
reaction PR O
PR O
or
R'
Scheme 1. Cycloaddition route to phospholenes and phospholanes.
The McCormack synthesis is nowadays carried out almost exclusively with the
dichlorophenylphosphine due to its ready availability which favourably contrasts
that of alkyldichlorophosphines. This is especially true for dichloromethyl-
phosphine which has always been of restricted use due to its hazardous properties
and military provenance (nerve gas production).
P-alkyl substituted phospholanes are important synthetic targets as ligands
which are more electron-rich at phosphorus than their P-aryl counterparts. In order
to work out a feasible route to P-Me (and P-alkyl phospholanes) we looked at a
possibility of using well-behaved dichlorophenylphosphine for synthesis of P-Ph
phospholane first and then possibly substitute the Ph group with the Me group by
means of the nucleophilic substitution at ring P.
Our earlier experiments revealed that attempted substitution of P-Ph with
MeLi directly on phospholenes led to substitution at P but at the same time also
opening of the phospholene ring took place and the formation of dimethyl(ho-
moallyl)phosphine oxide resulted (Scheme 2).
Department of Organic Chemistry – 146 –
Scheme 2. Ring-opening reaction of phospholene
Considering that the observed ring opening was favored by the departure of
vinylic anion as a relatively good leaving group we choose to study similar
substitution on the saturated phenylphopholane ring in which the only leaving group
better than the alkyl anion would be phenyl anion. 3-Phenylphospholane oxide was
thus subjected to a series of reactions with alkyllithium reagents as nucleophiles
(Scheme 3).
Scheme 3. Substitution at P in phenylphospholane oxide.
Methyl lithium proved to be very successful a nucleophile for the desired
transformation to occur. With other alkyllithium reagents the observed conversions
were low and with large t-butyllithium was none. Disappointingly, we were also not
able to substitute P-phenyl with the P-allyl group by this method despite several
trials and our need for the P-allyl functionalized product.
To summarize, as demonstrated in the above example MeLi can be effectively
used to substitute Ph with the Me group in phospholanes. If limited to MeLi the
process might become of more general use with substituted phosphoolane
substrates. At the moment it clearly solves the problem of ready synthesis of the
parent methylphospholane oxide from easily accessible phenylphospholane oxide.
Further studies of nucleophilic substitution at P in five-membered
organophosphorus ring compounds will follow.
P
Ph O
1.2 RLi
rt, 6 h
R
MeLin-BuLis-BuLit-BuLIAllylLi
%
932628 - -
P
R O
P
Ph O
PMe
Me
O2 MeLi
rt, 6 h
70%
F.Ch. UMCS Report 2009 (BW) – 147 –
STUDIES ON PHOTOPOLYMERIZATION KINETICS
Jan RAYSS, Małgorzata GIL, Wiesław PODKOŚCIELNY, Andrzej GORGOL and Jan WIDOMSKI
DEPARTMENT OF OPTICAL FIBRES TECHNOLOGY
The aim of this work was investigation of photopolymerization kinetics of mixtures containing N-vinylpyrrolidone. As the investigation method, photo differential scanning calorimetry was chosen. The investigated compositions were pure Ebecryl 150 and mixtures EB150/NVP 75/25; 50/50; and 25/75 w/w.
In the first period of investigation we have tried to use the mechanistic model of photopolymerization, in order to obtain the kp and kt values. However, because of some troubles arising from the assumptions on which this model is based, we decided to use the slope of dH/dT versus time in the first period of photopolymerization as a measure of the reaction rate. Table 1 presents the results obtained in different temperatures in the period from 0 to 60 s of UV irradiation.
Table 1.
0-60s 25°C 60°C 80°C
100% EB150 0.0458 0.1367 0.2377
75%EB150/ 25%NVP
0.2775 0.2725 0.2458
50%EB150/ 50%NVP
0.3388 0.3685 0.3528
25%EB150/ 75%NVP
0.1655 0.2431 0.2705
The data presented show, as it was possible to predict, that reaction rate of
pure EB150 increases with the temperature rise. This effect is caused by decrease of viscosity of EB150.
More interesting is the observation that NVP addition increases the reaction rate for the EB150/NVP mixtures, but only to 50/50 weight percent ratio, independently on temperature. It is interesting that for composition containing lower amounts of NVP (up to 50/50 ratio) the reaction rates are almost independent on temperature. The distinct influence on reaction rate is observed for 25% EB150/75% NVP mixture. Probably, it is caused by very complicated process of photopolymerization of NVP.
Next, the photo-DSC measurements were performed using NVP and buthyl acrylate as active diluents with bis[4-(2,3-epoxypropoxy)phenyl)]sulfide (BES-EP) and [4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulphide as a thermoset
Department of Optical Fibres Technology – 148 –
compound. The photopolymerization processes were carried out in 25°C for BES-DA and in 40°C for BES-DM. The results (Table 2) show the higher reactivity of both monomers mixed with NVP than those with buthyl acrylate. Also, pure acrylate is more reactive than methacrylate. Table 2.
25°C 40°C
Compositions 50% TK-AS/
50 %NVP 50% TK-AS/
50 %AB 80% TK-AS/
20% AB 50% TK-124/
50% NVP
Reaction rate 0.0356 0.0229 0.0231 0.0031
Also some experiments were carried out using bis[4(2-hydroxy-3-
acryloyloxypropoxy)phenyl]sulfone (BSO-DA) as thermoset and NVP as a reactive diluent.(Fig. 1).
Fig. 1. Polymerization heat vs reaction time.
What can be observed, that for this composition increase of the temperature
increases reaction rate. More interesting is the fact, that this composition react quicker than previous ones.
F.Ch. UMCS Report 2009 (BW) – 149 –
TECHNOLOGY OF MICROSTRUCTURED PLASTIC OPTICAL FIBERS BY STACKING METHOD
Jan WÓJCIK, Janusz PĘDZISZ, Krzysztof POTURAJ,
Aleksandr WALEWSKI, Lidia CZYŻEWSKA, Jacek KLIMEK, Jarosław KOPEĆ, Krzysztof SKORUPSKI, Paweł MERGO
and Mariusz MAKARA DEPARTMENT OF OPTICAL FIBRES TECHNOLOGY
There are known several methods of microstructured plastic optical fibers (mPOF) fabrication: stacking, drilling, extrusion, injection moulding and polymerization in mould.
It is not understood why stacking method well known for silica fibers fabrication is weakly advanced for mPOF fabrication. We have carefully theoretically analysed this problem and in conclusion we found, that stacking method will be useful for mPOF production. According that conclusion we modified stacking method previously elaborated in our laboratory for silica glass for organic glasses, especially for poly methyl methacrylate (PMMA). Commercially available Plexiglas rods and tubes we have used for fibers fabrication. Scheme of fabrication process include several stages:
– drawing of capillaries and thin rods from commercially available PMMA tubes and rods,
– stacking capillaries and thin rods into primary photonic structure, – sintering under pressure in carefully choose temperature, – thinning of preform in order to obtain rod suitable for next process stages, – overcladding into thick wall PMMA tube, – pressurized drawing of fibers.
Following figures illustrated semi-finished products obtained in exemplary fabrication process.
Fig. 1. Raw materials (rod, tubes, capillaries and thon rods) - left; structure after stacking – centre; structure after pressurized sintering – right.
Department of Optical Fibres Technology – 150 –
Fig. 2. mPOF preform after overcladding – left; structural parameters of exemplary low birefringence real fiber –right top; cross-section of high birefringence real fiber – right bottom.
090823 P3
0
2
4
6
8
10
12
14
16
18
20
600 650 700 750 800 850 900
wavelength [nm]
att
en
uati
on
[d
B/m
]
Fig. 3. Spectral attenuation plot of low birefringence mPOF fabricated with commercially available PMMA – it is typical attenuation of the best offered raw materials.
Lowering of attenuation will be possible with PMMA we will made in our laboratory with carefully cleaned monomers, initiators and another agents.
Our technology we have presented on COST 299 meeting on September 2009 and during discussion after presentation it seem that this technology mPOF is the best in Europe.
PART 3
GRANTS
F.Ch. UMCS Report 2009 (Grants) – 153 –
STRIPPING ANALYSIS OF BIOLOGICALLY ACTIVE
COMPOUNDS WITH APPLICATION OF LEAD FILM ELECTRODE
Mieczysław KOROLCZUK and Katarzyna TYSZCZUK
DEPARTMENT OF ANALYTICAL CHEMISTRY
AND INSTRUMENTAL ANALYSIS
In 2005 the lead film electrode was for the first time introduced for adsorptive
stripping voltammetric measurements of inorganic ions such as Co(II) and Ni(II)
[1]. Till now the lead film electrode has been used for the determination of other
inorganic ions such as U(VI), Mo(VI) [2, 3] and organic compounds such as folic
acid, trimethoprim, testosterone, rifampicine, glipizide, rutin and sildenafil citrate
(Viagra) [4, 5]. This kind of electrode can be easily regenerated by stripping the
lead film after the preceding measurement and the formation of a new film before
each measurement. Although lead compounds used for plating a lead film are toxic,
their toxicity and volatility is lower as compared to the mercury and mercury
compounds used for the preparation of mercury electrodes. For example, the
maximum contaminant level in drinking water recommended by EPA for lead is
equal to 15 µg/dm3, while for mercury it is 2 µg/dm
3.
The organic compounds can be accumulated at a lead film electrode and then
an analytical signal corresponding to their reduction or oxidation can be registered
[4, 5]. As an example rutin was accumulated at in situ formed lead film electrode
and in the course of the stripping step lead film and then rutin was oxidised.
A signal corresponding to the oxidation of the organic compound was used for its
quantification [4].
In the course of rutin determination the potential of the electrode was changed
in the following sequence: 0.5 V for 10 s; –1.15 V for 25 s and –0.75 V for 30 s.
The first step was applied to clean the electrode from a lead remaining after the
preceding measurement. During the second and third steps a lead film was plated
on a glassy carbon electrode and rutin was accumulated by adsorption on the
electrode, respectively. During all three steps the solution was stirred using a
magnetic stirring bar. Then after a rest period of 5 s a square-wave voltammogram
was recorded at a frequency of 200 Hz, while the potential was scanned from –0.75
to 1.0 V. The amplitude was 50 mV.
The calibration graph for rutin the accumulation time of 30 s was linear from
5·10–10
to 1·10–8
mol/dm3 and obeyed the equation y = 168 x + 0.0063, where y and
x are the peak current (µA) and rutin concentration (µmol/dm3), respectively. The
correlation coefficient r was 0.999. The relative standard deviation for a rutin
concentration of 5·10–9
mol/dm3 was 3.9 % (n = 5). The detection and quantification
limits for an accumulation time of 30 s estimated from 3 and 10 times the standard
deviation for the lowest determined concentration of rutin were about 2.5·10–10
and
Department of Analytical Chemistry and Instrumental Analysis – 154 –
8.3·10–10
mol/dm3, respectively. The voltammograms obtained for the increasing
concentrations of rutin are presented in Fig. 1.
Fig. 1. Square-wave voltammograms obtained for solutions containing increasing
concentrations of rutin: a) 5·10–10
mol/dm3; b) 1·10
–9 mol/ dm
3; c) 2·10
–9 mol/ dm
3;
d) 5·10–9
mol/ dm3; e) 1·1
-8 mol/ dm
3. Rutin was accumulated for 30 s at –0.75 V.
The lead film was deposited for 25 s at –1.15 V.
The in situ plated lead film electrode was applied to the rutin determination by
adsorptive stripping voltammetry in the tablets (label amount: 25 mg/tablet) without
any matrix effects. The recovery of five independent experiments was 102 % with
relative standard deviation (RSD) of 3.9 %. The quantitative results obtained for the
tablets were in agreement with the data supplied by the manufacturer and with those
obtained by a reported method (the recovery was 101 % with RSD of 2.8 %, n = 5)
[6]. On the basis of these results it can be stated that the proposed procedure can be
applied to rapid and sensitive determination of rutin in its pharmaceutical
formulations.
References:
[1] M. Korolczuk, K. Tyszczuk and M. Grabarczyk, Electrochem. Commun., 7
(2005) 1185.
[2] M. Korolczuk, K. Tyszczuk and M. Grabarczyk, Talanta, 72 (2007) 957.
[3] K. Tyszczuk and M. Korolczuk, Anal. Chim. Acta, 624 (2008) 232.
[4] K. Tyszczuk, J. Pharmaceut. Biomed., 49 (2009) 558.
[5] K. Tyszczuk and M. Korolczuk, Bioelectrochem., DOI:10.1016/
j.bioelectrochem. 2009. 08.005.
[6] A.A. Ensafi and R. Hajian, Electroanal., 18 (2006) 579.
(Grant the Ministry of Science and Higher Education No. N204 1472 33)
F.Ch. UMCS Report 2009 (Grants) – 155 –
A STUDY OF INTERACTIONS OF TERNARY SURFACTANT
SYSTEMS AT WATER-AIR INTERFACE
Katarzyna SZYMCZYK and Bronisław JAŃCZUK
DEPARTMENT OF INTERFACIAL PHENOMENA
Surfactants are usually prepared commercially as mixtures rather than pure
forms due to the fact that it is simply much more efficient and more economically
viable to synthetise mixtures. So, it is important to compare and contrast the
behavior of the mixtures with pure forms to analyse the effects of head groups and
chain length mixing. Mixed systems are often more efficient in the enviroment,
which is called synergism [1, 2]. The fundamentals of synergism in binary systems
have been understood on the basis of nonideal theories, for example, regular
solution approximation [3], especially by means of β parameters. In our ealier
studies we proved that there was synergism in the surface tension reduction and the
mixed micelle formation in binary mixtures of two nonionic and nonionic-cationic
surfactants [4, 5]. In the mixtures of two nonionic we also proved the synergetic
effect in reduction of the contact angle of water on PTFE surface [6].
However, while most experimental and theoretical works on mixtures of
surfactants have focused on binary mixtures, in practice, ternary and other
multicomponent surfactant mixtures are also encounterd. To our knowledge rare
studies on mixed adsorption and surface tension reduction of ternary surfactant
mixtures, taking the properties of binary mixtures into consideration, can be found
in the literature. Thus, the purpose of our studies was to determine the influence of
the concentration of aqueous solution of a third surfactant on the values of the
surface tension of different binary mixtures of the aqueous solution composed of
two nonionic surfactants, p-(1,1,3,3-tetramethylbutyl) phenoxypoly(ethylene-
glycols), Triton X-100 (TX100) and Triton X-165 (TX165) and cationic surfactant,
cetyltrimethylammonium bromide (CTAB) in which synergism was confirmed on
the basis of the values of the molecular interaction parameters. Ternary mixtures
were prepared by adding the third surfactant to the binary mixture of TX100
+ TX165 (α TX100 = 0.2), CTAB + TX100 (α CTAB = 0.2) and CTAB +
TX165T (α CTAB = 0.2). The interactions between surfactants in the surface
layers were also investigated.
From the analysis of the smallest values of the surface tension of ternary
mixture of surfactants, LVγ , that is for the highest values of the concentration of the
third surfactant it results that the ternary mixture (CTAB + TX165,α CTAB
= 0.2, LVγ = 50 mN/m) + TX100 has not only the best efficiency but also the best
effectiveness in the reduction of the surface tension of water. From this point of
view it was interesting if this ternary mixture of surfactants shows the best
synergetic effect in reduction of the surface tension of water among six studied
mixtures, and a better synergetic effect in relation to the binary mixture of CTAB
Department of Interfacial Phenomena – 156 –
+ TX165 (α CTAB = 0.2). However, Rosen’s equations used for calculations of the
monomer mole fraction and molecular interaction parameters at mixed binary
monolayer cannot be applied directly for ternary mixtures. It is possible to
determine of molecular interaction parameter if we assume the binary system as a
one surface active agent. Taking these into account the following interaction
parameters were calculated: (TX100, TX165) – CTAB, 3)12( −β ; (CTAB, TX100)
– TX165 2)13( −β ; (CTAB, TX165) – TX100, 1)23( −β , but not at the same value of the
surface tension for all ternary mixtures because of the limitation of Rosen’s
equation for values of α between 0.2 and 0.8.
From these calculations it results that when we add the nonionic surfactant
TX100 to binary mixtures CTAB + TX165 in these ternary mixtures (CTAB
+ TX165, α CTAB = 0.2, LVγ = 60 and 50 mN/m) + TX100 (C=108
– 10–2
M)
(mixture (1) and (2), respectively) the smallest value of the molecular interaction
parameter exist for mixture (1) at LVγ = 48.0 mN/m where 3)12( −β = –25.599. This
value of 3)12( −β is not only the smallest for these two ternary mixtures, but for all
studied systems, which indicates that in mixture (1) at value LVγ = 48.0 mN/m the
best synergism exists.
If we compare the smallest values of the surface tension (mN/m) obtained for
the individual surfactants studied with their binary and ternary mixtures it results
that among these systems ternary mixtures of surfactants (1) and (2) have the best
synergetic effect in reduction of the surface tension of water.
References:
[1] A. Murphy, G. Taggard, Colloid Surf. A, 205 (2002) 237.
[2] J. M. Rosen, Surfactants and Interfacial Phenomena, Wiley-Interscience, New
York, 2004.
[3] A. Schiloach, D. Blankschtein, Langmuir, 14 (1998) 1618.
[4] K. Szymczyk, B. Jańczuk, Langmuir, 23 (2007) 4972.
[5] K. Szymczyk, B. Jańczuk, Colloids Surf. A, 293 (2007) 39.
[6] K. Szymczyk, B. Jańczuk, Langmuir, 23 (2007) 8740.
[7] K. Szymczyk, B. Jańczuk, Langmuir, DOI: 10.1021/la9027173.
(Grant of Ministry of Science and Higher Education No. N204 130635)
F.Ch. UMCS Report 2009 (Grants) – 157 –
ELECTROKINETIC PROPERTIES
OF N-TETRADECANE/ETHANOL EMULSIONS WITH DPPC
AND ENZYME LIPASE OR PHOSPHOLIPASE A2
Agnieszka Ewa WIĄCEK, Lucyna HOŁYSZ and Emil CHIBOWSKI
DEPARTMENT OF INTERFACIAL PHENOMENA
In biotechnological and pharmaceutical systems the electrokinetic phenomena
present at oil/water interface in the presence of lipids or phospholipids, as well as
effects of lipases or phospholipases are important for the occurring processes. However,
these phenomena are still not well recognized. Generally, in dispersed systems zeta
potential is an important and useful parameter of droplet surface charge, which can be
used to predict and control the stability of colloidal emulsions. Measurement of zeta
potential and droplet size are often the key for understanding the dispersion and
aggregation processes in practical applications. Studies on lipases and phospholipases
shed light on some of their molecular structure properties, conformational changes
occurring in the presence of lipids and phospholipids, behavior of the enzymes existing
at interfaces and the stability of dispersion systems altogether.
The electrokinetic properties via zeta potential and effective diameter of n-
tetradecane/ethanol emulsions in the presence of dipalmitoylphosphatidylcholine
(DPPC) and enzyme lipase (Candida Cylindracea) were determined as a function of pH.
The role of phosphate buffer (pH = 8) and ethanol concentration in enzymatic reactions
with lipase or phospholipase A2 (PLA2) was investigated, too, because ions can
collaborate with lipid and influence the zeta potential values.
The obtained results indicate that the zeta potential of n- tetradecane emulsion
in 1M ethanol aqueous solution is negative and its value decreases with increasing
pH. In the presence of DPPC the negative zeta potential decreases and the
difference is bigger at a lower pH. However, during 2h experiment time the
emulsions were stable, probably because of their steric stabilization.
The influence of enzyme (lipase or PLA2) on the zeta potential and effective
diameter of n- tetradecane /DPPC droplets in 1M ethanol in buffer at pH=8 as a
function of time at several lipase concentrations is shown in Fig. 1. It can be seen that
the maximal effect of lipase action appears after 1h if 1mg of this enzyme is present.
This lag-time is probably due to the fact that the buffer stabilizes DPPC molecules and
hydrolysis is more difficult. The effect of PLA2 (1mg) is comparable with that of lipase
at a higher concentration (2.5mg). The observed influence of the enzymes on n-
tetradecane/DPPC zeta potentials must result from DPPC molecules hydrolysis. The
difference between the two enzymes activity may result from the fact that two palmitic
acid molecules are the products of DPPC molecule hydrolysis by lipase, while only one
molecule of this acid is formed during phospholipase A2 action. Generally, the effective
diameters of the droplets correlate with the changes in zeta potential, i.e. lower zeta
potential corresponds with bigger effective diameter.
Department of Interfacial Phenomena – 158 –
0 20 40 60 80 100 120-30
-25
-20
-15
-10
-5
0
n-tetradecane(0.1 ml)/DPPC(1 mg) + Et(1 M) in buffer
without enzyme
1 mg of lipase
2.5 mg of lipase
1mg of PLA2
Ze
ta p
ote
ntia
l, m
V
Time, min
0 20 40 60 80 100 120
500
1000
1500
2000
2500
3000
3500
n-tetradecane(0.1 ml)/DPPC(1 mg) + Et(1 M) in buffer
without enzyme
1 mg of lipase
2.5 mg of lipase
1mg of PLA2
Eff
ective d
iam
ete
r, n
m
Time, min
Fig. 1. Influence of lipase and PLA2 on the zeta potential and effective diameter
of n- C14H30/DPPC droplets in 1 M ethanol in buffer at pH=8 as a function of time at
different lipase concentration.
It seemed also interesting to investigate the ethanol concentration effect on the
n-alkane/DPPC zeta potential and droplet size during the enzyme action. Some of the
results are presented in Fig. 2, where it can be seen that the effect of the enzyme is
lower in the emulsion with 1M ethanol than in emulsion without alcohol. Accumulation
of ethanol molecules in DPPC layer may hinder the access of the enzymes to active
places of DPPC. The concentration of ethanol (1M) radically changes the measured
emulsion parameters. At higher ethanol concentration the effective diameters are the
most stable which guarantee the emulsion stability.
0 20 40 60 80 100 120
-25
-20
-15
-10
n-tetradecane(0.1 ml)/DPPC(1 mg) + PLA2 in buffer
without ethanol
0.5M ethanol
1M ethanol
Ze
ta p
ote
ntia
l, m
V
Time, min
0 20 40 60 80 100 1200
1000
2000
3000
4000
5000n-tetradecane(0.1 ml)/DPPC(1 mg) + PLA
2 in buffer
Eff
ective
dia
me
ter,
nm
Time, min
without ethanol
0.5M ethanol
1M ethanol
Fig. 2. Influence of PLA2 on the zeta potential and effective diameter of n-tetradecane/DPPC
droplets in buffer at pH=8 as a function of time at different ethanol concentration.
The influence of the enzymes on the effective diameter and the zeta potential
clearly depends on the kind of enzyme and its concentration. Small values of the zeta
potential of n-tetradecane/DPPC (in ethanol) droplets in the presence of both
investigated enzymes suggest different mechanism than that of electrostatic
stabilization.
(Grant of Ministry of Science and Higher Education No. N204 128 32/3188)
F.Ch. UMCS Report 2009 (Grants) – 159 –
50 52 54 56 58 60 62 64 66 68 70 72 74
25
30
35
40
45
orig in .
PTFE
g lass
stee l
γ s
tot ,
mJ/m
2
Surface tens ion of probe liquid , m N/m
PolypropyleneD iiodom ethane
W ater
Form am ide
Glycerol
50 52 54 56 58 60 62 64 66 68 70 72 74
36
38
40
42
44
46
48 orig in.PTFE
glass steel
Surface tension of probe liqu id , m N/m
Polycarbonate
D iiodom ethane
Glycero l
Form am ide
W ater
SURFACE FREE ENERGY OF POLYPROPYLENE
AND POLYCARBONATE SOLIDIFYING AT DIFFERENT SOLID
SURFACES
Emil CHIBOWSKI and Konrad TERPIŁOWSKI
DEPARTMENT OF INTERFACIAL PHENOMENA
The properties of a solid surface reflect to some extent its bulk properties.
Although the structure and chemistry of the top surface layer is determined by the
crystal moieties right below the layer [1], the force field of the contacting phase
may also have a significant effect on the final structure, and consequently on the
properties of the solid surface layer [2]. For example, Schonhorn [3] found that
when polyethylene crystallized in air the contact angle of glycerol was 81°, but if it
was crystallized next to gold or mercury the contact angle amounted 53°, and the
calculated surface free energy amounted 36 and 70 mJ/m2, respectively. This was
the result of changes in the surface structure of the polypropylene from soft low-
density to high- energy faces of polyethylene crystals [2].
In our experiments commercial samples of polypropylene and polycarbonate
manufactured in Poland were used. Plates of these polymers 20 × 25 mm in size
were cleaned before using them for contact angle measurement [4]. The
polypropylene plates were first placed in a desiccator at 120°C until they became
soft; then they were placed on a flat solid surface and the soft top surface of a
polypropylene plate was covered with a flat plate of Teflon, glass or stainless steel
and loaded with a 10 g weight and waited until it became hard. Thus prepared
samples were kept in a desiccator before using them for contact angle
measurements. The polycarbonate plate surfaces of the same size were modified in
a similar way, but instead of keeping them in a desiccator to soften 115 - 135 cm3 of
chloroform was poured onto the surface to dissolve a layer and then the same
procedure as above was applied. Water, formamide, glycerol and diiodomethane
were used as probe liquids for advancing and receding contact angle measurements.
Fig. 1. Apparent surface free energy of PP polypropylene and polycarbonate PC samples
determined from the contact angle hysteresis [4] of diiodomethane, water, formamide
and glycerol.
Department of Interfacial Phenomena – 160 –
The apparent surface free energy was calculated from the contact angle
hysteresis of the probe liquids [4] The results of the energy obtained for
polypropylene PP (crystalline) and polycarbonate PC (amorphous) are presented in
Fig.1. The results show the importance of the chemical nature of the polymers for
their apparent surface free energy subjected to modifications. Moreover, the kind of
the solid matrix surface next to which the polymer solidifies is of significant
importance too. The calculated apparent surface free energy values depend to some
extent also on the kind of the probe liquid, especially when apolar and polar liquids
are used. This can be explained by assuming that the strength of the interactions
originating from the solid surface depends on the strength and kind of interactions
of the probe liquid. In the case of the two polymers the dispersion solid/liquid
interactions are of course of primary importance, which appears here to have the
greatest value for the apparent surface free energy when determined from apolar
diiodomethane contact angles, whose surface tension is practically of dispersive
nature only, and is the biggest, 50,8 mN/m, among the probe liquid used. A very
small induced polar interaction of the surface can be considered, too, which may be
due to the surface modifications, which was found in case of PP samples.
Application of the equation of state for the surface free energy determination
generally gives similar trends of the polymer surface free energy changes as those
obtained from the contact angle hysteresis. However, from both models no straight
correlation can be found between the apparent surface free energy of the polymer
samples and several factors characterizing their surfaces and the properties of the
probe liquids used. The details of these investigations are described in ref. [4].
References:
[1] J.C. Vickerman, in: Surface Analysis – The Principal Technique, (J.C.
Vickerman, I. Glimore, Eds.), 2nd
Edition, Wiley, New York, 2009.
[2] F.M. Fowkes, in: Hydrophobic Surfaces, (F.M. Fowkes Ed.), Academic Press,
New York, 1969.
[3] H. Schonhorn, Macromolecules, 1 (1968) 145.
[4] E. Chibowski, K. Terpilowski, Applied Surface Science, 256 (2009), 1573
(Grant of Ministry of Science and Higher Education No. N204 130435)
F.Ch. UMCS Report 2009 (Grants) – 161 –
FUNCTIONALIZED SBA-15 ORGANOSILICAS AS SORBENTS OF ZINC(II) IONS
Andrzej DĄBROWSKI, Mariusz BARCZAK, Władysław JANUSZ* and Ewa SKWAREK*
DEPARTMENT OF THEORETICAL CHEMISTRY *DEPARTMENT OF RADIOCHEMISTRY
AND COLLOID CHEMISTRY
Ordered nanoporous organosilicas constitute a very exciting field in materials chemistry and have numerous potential applications due to their high surface areas, large pore volumes of ordered mesopores and narrow pore size distributions as well as the possibility of easy functionalization. Among them, the SBA-15 materials have become one of the most popular ordered silica nanomaterials due to large mesopores (up to 15 nm), thicker pore walls, presence of irregular interconnecting micropores and higher thermal and hydrothermal stabilities caused by its thicker mesopores walls. SBA-15 materials are synthesized by hydrolysis and condensation of silica precursor under strong acidic conditions by employing amphiphilic triblock copolymer (usually Pluronic P123) followed by removal of polymeric template by either extraction or calcination at elevated temperatures.
Possibility of introduction of different functional groups into the framework or the surface of OMS, makes these materials very attractive for catalytic and adsorption processes, sensing devices and environmental applications. Such hybrid materials are known as ordered mesoporous organosilicas (OMOs). Such a surface functionalization leads to materials differing in the reactivity, pore accessibility and distribution of organic groups. It is particularly important when adsorption application are considered, especially from the water systems.
One of the important metal ion present in the biosphere, particularly in waters and waste waters is zinc. The presence of zinc in the environment may cause damage to the human body because of their toxicity and carcinogenicity. Zinc is present in the air, soil, water and almost all foods. Acute exposure to Zn(II) cause health problems such as stomach cramps, skin irritations, vomiting, nausea and anemia. Very high levels of zinc can damage the pancreas, disturb the protein metabolism and cause arteriosclerosis. The maximum acceptable concentration of zinc in drinking water recommended by WHO is 5.0 mg/cm3. Beyond the permissible limits, zinc is considered as toxic.
Up to day the sorption of zinc ions on OMOs surface have not been studied in detail yet, despite the fact that these materials seems to be perfectly suited for removal of metal ions.
Mesoporous SBA-15 organosilicas with amine-, thiol-, vinyl-, phenyl- and cyano- groups different surface groups were prepared by co-condensation of TEOS and appropriate monomers. Both, structural-adsorption parameters (SBET, Vp, d) and
Department of Theoretical Chemistry – 162 –
degree of ordering are dependent upon the type of functionalized silane used in the synthesis.
Zinc ions in water solutions form the following complexes with hydroxyl
groups: +ZnOH , 2(aq)Zn(OH) , −
3Zn(OH) , −24Zn(OH) . The corresponding pK
values of these hydroxyl complexes are: pK1 = 4.4, pK2 11.1, pK3 = 13.1, pK4 = 14.6, respectively. Analysis of the concentration of the Zn(II) species as a function of pH shows that up to pH = 8.5 the dominant ion is Zn(II) aqua ion, whereas above pH = 8.5 hydroxycomplexes 2(aq)Zn(OH) predominate. The
percentage of +ZnOH ions is small, reaching a maximum corresponding to a value of several percent at pH = 8.5. At higher concentrations of zinc ions amorphous zinc hydroxide can appear in the studied system, the pIr negative logarithm of the solubility product of which is 15.5.
The exemplary adsorption edge of the zinc ions as a function of pH in system 4/NaCl solution is presented in Fig. 1. It can be seen that the adsorption edge shifts toward higher pH values with increase of the initial concentrations of Zn(II) ions. The position of the adsorption edge characterized by pH50% parameter increases from pH = 6.18 for the lowest initial concentration of zinc (1·10–6M) to pH 8.65 for the highest initial concentration of zinc (1·10–3M). Changes in the adsorption edge slope characterized by the parameter ∆pH10-90% are observed in the whole concentration range from 0.98 to 3.55.
Fig. 1. Adsorption of Zn (II) ions at S63/0.001M NaCl interface as a function of pH. The investigations proved, that it is possible to exchange specificity of
adsorption materials by chemical modification of surface SBA-15 by introduction of desired type of functional groups by co-condensation route.
(Grant the Ministry of Science and Higher Education No. N204 111135)
F.Ch. UMCS Report 2009 (Grants) – 163 –
THEORETICAL STUDIES OF THE ADSORPTION OF CHIRAL MOLECULES ON SOLID SURFACES
Paweł SZABELSKI, Tomasz PAŃCZYK*, Mateusz DRACH
and Tomasz P. WARZOCHA*
DEPARTMENT OF THEORETICAL CHEMISTRY, *INSTITUTE OF CATALYSIS AND SURFACE CHEMISTRY,
POLISH ACADEMY OF SCIENCES, KRAKÓW, POLAND
Temperature programmed desorption of model chiral molecules from a chiral surface with periodic pattern of active sites was studied theoretically using the Monte Carlo method. The simulations were performed for enantiomerically pure and racemic layers adsorbed on the chiral surface with an ordered superstructure of the active sites. It was demonstrated that an efficient separation of the enantiomers on the nanostructured surface can be achieved by suitable manipulating energetic properties of the surface. Moreover, the influence of factors such as lateral interactions in the adsorbed phase and mobility of the adsorbed molecules on the desorption kinetics was examined. The obtained results provided some insights into the mechanism of chiral selection with nanostructured surfaces under ultra high vacuum conditions. In particular, it was demonstrated that effectiveness of the separation decreases with coverage due to reduced chances of diffusion of the enantiomers and occupation of their energetically preferred clusters of adsorption sites.
Fig. 1. Thermal desorption spectra of the racemic mixture of enantiomers S and R from the chiral nanostructured surface, simulated for different total initial coverages indicated in the figure.
Department of Theoretical Chemistry – 164 –
It was found that the extent to which the less retained enantiomer can be removed from the surface was found to be strongly dependent on both coverage and nature of intermolecular interactions in the adsorbed phase. In particular, it was shown that the effectiveness of the separation decreases markedly when density of the adsorbed layer grows as well as when attractive interactions between adsorbed molecules are switched on. These negative factors make it difficult to resolve the enantiomers in a single TPD run but they do not exclude the possibility of a complete separation of the enantiomers in a cyclic TPD process. This demonstrates the great potential of the nanostructured chiral surface for applications in continuous chiral separation processes.
References:
[1] P. Szabelski, T. P. Warzocha and T. Pańczyk, Thermochimica Acta , 427 (2010) 77.
(Grant the Ministry of Science and Higher Education No. 1 T09A 103 30)
F.Ch. UMCS Report 2009 (Grants) – 165 –
THEORY AND COMPUTER SIMULATIONS OF ADSORPTION
OF FLUIDS ON SURFACES MODIFIED WITH CHAIN
MOLECULES
Małgorzata BORÓWKO, Stefan SOKOŁOWSKI
and Tomasz STASZEWSKI DEPARTMENT FOR THE MODELLING OF PHYSICO-CHEMICAL
PROCESSES
In this paper we study the structure of chemically bonded phases in poor solvents. The polymer molecules are modeled as freely jointed spheres with one end pinned to the surface. The polymer segments interact with the wall via the hard-wall potential. However, interactions between segments are described by the Lennard-Jones (12-6) potential. The intermolecular attractions define solvent conditions.
The system is treated in the framework of the density functional theory [1]. The free energy is calculated in a perturbation manner [2]. It is divided into ideal and excess terms. The latter contains contributions due to volume exclusion, due to chain connectivity and due to attractive interactions between spherical components. The hard sphere contribution is calculated according to the fundamental measure theory [3]. The connectivity term follows from the Wertheim’s first order perturbation theory [4]. The free energy resulting from attractive interactions is obtained within the mean field approximation. The thermodynamic potential is minimized with respect to the distribution of the chains the system. All details of the calculations can be found in Refs. [2, 5].
Properties of chemically bonded phases depend on the structure of interface layer. Therefore, the understanding of structural transitions in surface films is of considerable technological importance. The structure of end-grafted chains can be either “mushroom” or “brush” depending on grafting density ρp. In a mushroom-like structure the chains are isolated and assume unperturbed dimension. However, at high grafting densities particular chains can overlap and interchain repulsion causes the chain stretch in a direction perpendicular to the wall.
A focal point of our investigations is to evaluate the variations in structure which occurs with change in grafting density and temperature. The average distance of segments from the surface <z> scaled by its maximum value <z>max is treated as a measure of the brush weight. We have estimated these normalized brush heights for different parameters characterizing the system. We introduce the reduced temperature defined as T* = Tk/ε, where ε is the energy parameter in the Lennard-Jones (12-6) potential. In all calculations we assume that ε is equal to unity (ε = 1). Temperature controls the strength of interactions between segments. A change in temperature causes a change in solvent conditions.
The theoretical dependences log (<z>/<z>max) vs log ρp are presented in Fig. 1. One can distinguish here three regimes. At low ρp <z> is practically unaffected by
Department for the Modeling of Physico-Chemical Processes – 166 –
grafting density. This regime corresponds to the mushroom-like structure. For high grafting densities the brush height increases sharply with ρp. The function log (<z>/<z>max) vs log(ρp) becomes linear. In this regime brush structure dominates. For relatively temperature (T*=5) there are only these two regimes. However, at lower temperatures one can identify the third regime for moderate grafting densities. The brush height decreases with increasing grafting density and achieves a minimum.
Fig. 1. Log-log plot of normalized brush height, <z>/<z>max, vs grafting density for oktamers at different temperatures: T*=5 (the dashed line), T*=2 (the solid line) and T* = 1.3 (the dashed-dotted line).
In this regime the molecular interactions between chains which cause formation of coils are stronger than entropic repulsion of grafted chains from the surface. The properties of such surface films require further studies.
The density functional theory predicts a gradual transition from the mushroom-like to brush structure with increases in grafting density. At low temperatures a new structure is observed for average surface coverage. References:
[1] J.Z. Wu, AIChE J., 52 (2006) 1169. [2] M. Borówko, W. Rżysko, S. Sokołowski, T. Staszewski, J. Chem. Phys., 126
(2007) 214703. [3] Y. Rosenfeld, Phys. Rev. Lett., 63 (1989) 980. [4] M.S. Wertheim, J. Chem. Phys., 87 (1987) 7323. [5] M. Borówko, W. Rżysko, S. Sokołowski, T. Staszewski, J. Phys. Chem. B, 113
(2009) 4763.
(Grant of Ministry of Science and Higher Education, No. N204 151237)
F.Ch. UMCS Report 2009 (Grants) – 167 –
COMPUTER SIMULATIONS OF BINARY MIXTURES
IN EXTERNAL FIELD
Leszek SAŁAMACHA, Andrzej PATRYKIEJEW and Stefan SOKOŁOWSKI
DEPARTMENT FOR THE MODELLING OF PHYSICO-CHEMICAL PROCESSES
The ground state behavior of two-dimensional symmetrical mixtures subjected to the external potential of square symmetry is discussed. It is demonstrated that different commensurate, high-order commensurate as well as incommensurate phases may appear depending on the properties of the mixture as well as on the corrugation of external potential. In particular, it is shown that a finite corrugation of external potential considerably influences the stability of different ordered states. The ground state calculations are confirmed by finite temperature grand canonical Monte Carlo simulations. We consider a simple model of a two-dimensional symmetrical mixture consisting of atoms A and B, and interacting via the truncated (12,6) Lennard-Jones potential:
>
≤−=
max
max
rr
rrrrru
ijijij
ij
0
])/()/[(4)(
612σσε
(1)
where i and j mark the species A and B. Since the mixture is assumed to be symmetrical, σσσ == BBAA and εεε == BBAA . The corresponding potential
parameters for interaction between a pair of unlike atoms are given by σσ sAB =
and εε eAB = (where s and e are adjustable constants). The cut-off distance max
r is
set at iiσ0.3 and we do not use any long-range corrections. Throughout this paper
we use the parameter ε as a unit of energy. Thus, the reduced units of temperature
)/( *εkTT = , chemical potentials ),,/( *
BAirii == µµ and of all other energy-
like quantities are used. The mixture is placed in an external field of square symmetry and modeled using a simple cosine potential: )]/2cos()/2[cos(),( ayaxVyxv b ππ += (2)
where bV measures the corrugation of the potential and a determines its period.
Here, we use a as a unit of length, and express all distances in reduced units. In particular, we define )/( *
aijij
σσ = . Of course, bV is expressed in units of ε . The
energy of any microstate, consisting of AN and BN particles of species A and B, in
the volume V, can be represented by:
∑∑∑ ∑
∑∑
=== =
<<
++
++=
BAA B
BA
N
i i
N
i i
N
i
N
j ijAB
N
ji ijBB
N
ji ijAABA
vvu
UUE
111 1)()()(
)()(),(
rrr
rrRR
(3)
Department for the Modeling of Physico-Chemical Processes – 168 –
where AR and BR are multidimensional vectors representing the positions of all
atoms of the components A and B in the system ),,,,( 21 iNi rrrR K= Ai = or B.
In the grand canonical ensemble, the Hamiltonian of the model reads:
BBAABABA NNEH **),(),( µµ −−= RRRR (4)
Here we shall consider only the situation, when the chemical potentials of both species are the same )( ***
µµµ ==BA
, so that the above equation becomes:
NEH BABA
*),(),( µ−= RRRR (5)
where BA NNN += .
Fig. 1. The ground phase diagrams for the systems characterized by 01.1*
=σ , 0.1=e and dif- ferrent 8.1=
bV ( a), 0.2 (b), 0.4 (c), 0.6 (d), 0.8 (e) and 10 (f).
It has been demonstrated that the surface potential of finite corrugation may lead to the formation of several solid-like mixed phases of different structure, which depends on the properties of the mixture as well as on the height of potential barriers between adjacent potential wells. It was also demonstrated that the stability of the majority of mixed ordered phases strongly depends on the ability of atoms to displace from registry positions. Several of the ordered structures observed in the ground state is expected to be stable only at very low temperatures only. At the temperatures above the disordering transition the atoms are still pinned to surface potential minima, but exhibit a rather random distribution of the components. Similar disordering is expected to occur for other mixed structures.
References: [1] L. Sałamacha, A. Patrykiejew, S. Sokołowski, J. Phys. Chem. B, 113(42) (2009) 13687.
(Grant of Ministry of Science and Higher Education, No. N202 046 137)
F.Ch. UMCS Report 2009 (Grants) – 169 –
HYDROGEN FROM BIO-ALCOHOLS. AN EFFICIENT ROUTE FOR HYDROGEN PRODUCTION
VIA NOVEL REFORMING CATALYSTS
Andrzej MACHOCKI, Andrzej DENIS, Wiesław GRZEGORCZYK
and Wojciech GAC
DEPARTMENT OF CHEMICAL TECHNOLOGY
Production of hydrogen from bio-ethanol for fuel cell applications takes place
via catalytic steam reforming (SRE) C2H5OH + 3H2O → 2CO2 + 6H2. It is very
advantageous process as the sources of hydrogen are both alcohol and water.
Among various catalysts considered for that process cobalt-based catalysts are very
attractive. Very promising results of the SRE over such catalysts were reported.
Cobalt is also far less expensive than noble metals, also used as catalysts of the
SRE.
The present communication reports effects of the modification of supported
cobalt-based catalysts with cerium on their activity and selectivity in the SRE.
The Co/support and Co-Ce/support catalysts were obtained by impregnation of
ZrO2 (47 m2/g, Aldrich) and ZnO (100 m
2/g, home production) with cobalt(II)
(Aldrich) or cobalt(II) and cerium(III) (Fluka) nitrates aqueous solutions. The
relative molar concentrations of cobalt and cerium were 1/1. The solutions
contained also citric acid (CA) in the molar ratios of Co/CA or Co+Ce/CA equal to
1/1. Precursors of catalysts were
dried overnight at 110°C and
calcined at 400°C for 1 h. Prior to the
use in the SRE, the catalysts were
reduced with hydrogen at 500°C for
1h. The basic characterization of the
catalysts is presented in Table 1.
The cobalt and cerium loadings
were determined by the XRF
technique while the surface area of
the cobalt active phase (SCo) and its mean size of crystallites (dCo) were calculated
on the basis of the total hydrogen chemisorption at 35°C. The reducibility of
catalysts was characterized by means of the temperature-programmed reduction
with hydrogen.
The SRE was carried out under atmospheric pressure over catalysts (0.1 g,
0.15-0.3 mm) diluted (1/10 w/w) with 0.15-0.3 mm grains of quartz. The aqueous
solution of ethanol (10.85 wt.%, the molar ratio EtOH/water equal to 1/21),
simulating a fermentation broth, was supplied to an evaporator (150°C) and the
reactant vapours without diluting with any inert gas were fed to the reactor at the
flow rate of 0.268 mol/h.
Table 1. Catalyst characterization results.
Catalyst
Co / Ce
contents
wt.%
SCo
m2/gcat
dCo
nm
Co/ZrO2 8.2 / - 0.20 276
Co-Ce/ZrO2 9.1 / 22.3 1.79 34
Co/ZnO 8.8 / - 0.63 244
Co-Ce/ZnO 9.2 / 22.9 1.02 61
Department of Chemical Technology – 170 –
One of the most evident changes in the
catalyst properties caused by the cerium modifier
is an increase of the cobalt dispersion and its
surface area (Table 1).
The TPR results (Fig. 1) confirmed that most
of cobalt oxides present in the catalysts undergoes
reduction with hydrogen at 500°C. It is also seen
that the amount of cobalt reduced in the Co-
Ce/ZnO is lower than in the case of unmodified
Co/ZnO catalyst.
Even at the relatively low temperature of
420°C, except Co/ZnO, conversion of ethanol in
the SRE is 100% (Table 2).
The activities of both catalysts with the ZrO2 support are higher than those
with ZnO support. Particularly, the conversion of water over Co/ZrO2 and Co-
Ce/ZrO2 is much higher. As a consequence, those catalysts enable to achieve higher
selectivity and the yield of hydrogen formation. ZnO-contained catalysts generate
large amounts of acetaldehyde but much smaller amounts of methane. As it is
shown in Table 2, cerium modifier improves activity and selectivity of the catalysts.
In the case of Co/ZrO2 the changes are very significant and profitable. Presence of
cerium increases conversion of water and selectivities of the SRE towards hydrogen
and carbon dioxide while the selectivities to carbon monoxide and acetone were
decreased. The efficiency of hydrogen formation over Co-Ce/ZrO2 catalyst is very
close to a balanced, thermodynamic yield, which takes into account the
participation of side reactions, estimated to be about 5.5 mole of hydrogen formed
from one mole of ethanol. The modified catalyst with the ZnO support enabled us to
get such yield of hydrogen only at 540°C and higher temperatures.
The positive effects of the modification of the Co/ZrO2 with cerium were
retained also at higher temperatures of the steam reforming of ethanol.
(Grant ERA-NET ACENET No ACE.07.009)
Table 2. Results of the steam reforming of bio-ethanol at 420°C.
Conversion, % Selectivity, % Catalyst
EtOH H2O H2 CO2 CO CH4 CH3CHO (CH3)2CO H2/EtOH
in
Co/ZrO2 100 7.3 85.0 51.6 22.1 13.6 1.6 10.7 3.13
Co-Ce/ZrO2 100 14.3 91.9 80.8 6.4 12.2 0.4 0.3 5.48
Co/ZnO 72 3.1 64.3 12.4 14.8 3.7 69.1 0.0 1.79
Co-Ce/ZnO 100 4.1 73.3 27.0 18.2 3.1 38.2 13.3 2.10
0 200 400 600 800
TEMPERATURE (oC)
HY
DR
OG
EN
UP
TA
KE
(a
.u.)
Co/ZnO
Co/ZrO2
Co-Ce/ZrO2
Co-Ce/ZnO
Fig. 1. TPR profiles of catalysts.
F.Ch. UMCS Report 2009 (Grants) – 171 –
A HIGH-SELECTIVE CATALYST FOR CONVERSION OF ETHANOL TO HYDROGEN
Andrzej MACHOCKI, Andrzej DENIS, Wiesław GRZEGORCZYK
and Wojciech GAC
DEPARTMENT OF CHEMICAL TECHNOLOGY
The catalytic steam reforming of bioethanol (SRE) C2H5OH + 3H2O → 2CO2
+ 6H2 is an attractive option for sustainable production of hydrogen for small scale,
scattered fuel cell applications. There are still no commercial catalysts for the SRE
process. They were not needed by the industry. At present we witness intensive
preparations for an expansion of hydrogen economy. One of such activities has
become the research on a catalyst for the efficient hydrogen production from bio-
ethanol. Promising results of the SRE were obtained over supported cobalt
catalysts. The present communication reports structural, chemisorption and redox
properties of nano- and micro-dispersed zirconia and ceria-supported cobalt
catalysts and their effectiveness in the SRE process, i.e. their activity, selectivity
and hydrogen yield.
The characteristics of the supports and catalysts are shown in Table 1 and in
Figure 1. Supported cobalt (8-9 wt.%) catalysts were obtained by the impregnation
method. The cobalt loading
was measured by the XRF
technique. The structure of
catalysts was determined by
nitrogen adsorption, hydrogen
chemisorptions and X-ray
diffraction. The reducibility
of oxide form of catalysts was
characterized by the H2-TPR.
The SRE was carried out in a
Fig.1. AFM pictures of ceria and zirconia catalyst
supports (a side of the picture is 1 µm).
CeO2-N CeO2-M
ZrO2-N ZrO2-M
Table 1. Characterization results of the supports and catalysts.
Support
Support
crystallite
size
nm
Surface
area
m2/g
Catalyst
Total
surface
area
m2/g
Cobalt
surface
area
m2/g
Cobalt
crystallite
size, nm
CeO2-N 22 72.9 Co/CeO2-N 66.9 3.82 14.0
CeO2-M >100 3.1 Co/CeO2-M 9.8 0.85 68.3
ZrO2-N 33 47.7 Co/ZrO2-N 40.5 0.70 85.2
ZrO2-M >100 5.4 Co/ZrO2-M 12.4 0.20 276.0
Department of Chemical Technology – 172 –
stream of vapours of an aqueous solution of ethanol (10.85 wt.%, the EtOH/water
molar ratio was 1/21).
Ceria supports enable to obtain smaller cobalt crystallites and their higher
surface area. The main different structural features of the nano- and micro-powder
ceria- and zirconia-supported catalysts are the higher cobalt surface area and the
much smaller average size of its crystallites in the case of catalysts with the high-
dispersed supports.
The results of the temperature-programmed reduction (Fig. 2) and the
temperature-programmed desorption of hydrogen showed that small crystallites of
the cobalt phase strongly interact with the high-dispersed supports. They have also a
great influence on the effects of the SRE.
Both ceria and zirconia nano-powder supports enable to achieve a high yield
of hydrogen (Fig. 3). However, for the nano-powder ceria-supported cobalt catalyst
the yield of hydrogen formed from one molecule of ethanol supplied to the SRE
process is the highest; even at the relatively low temperature of 420°C it is close to
the 5.5 mol H2/mol EtOH. At the same time there were achieved: the complete
conversion of ethanol, very close to the maximum conversion of water and 92 %,
84 % and 5 % selectivities towards hydrogen, carbon dioxide and carbon monoxide,
respectively. Therefore, the high-dispersed ceria is the more advantageous
component of the cobalt catalyst designed for the SRE than nano-zirconia and
micro-powders of these oxides.
It is very reasonable that good catalysts for the SRE should have at the same
time small crystallites of the cobalt active phase and the ceria support. On the
surface of the former the activation of ethanol, while on the surface of ceria
activation of water occurs. The intimate contact of both catalyst components and a
short-enough distance from their border to the center of the surface of cobalt
crystallites ensure reagents to interact together to form desirable products of the
SRE, i.e. hydrogen and carbon dioxide.
(Grant the Ministry of Science and Higher Education No. N N204 228534)
0 200 400 600 800TEMPERATURE (oC)
HY
DR
OG
EN
UP
TA
KE
(a
.u.)
Co/CeO2-N
Co/CeO2-M
Co/ZrO2-N
Co/ZrO2-M
350 400 450 500 550 600
TEMPERATURE (oC)
0
1
2
3
4
5
6
HY
DR
OG
EN
YIE
LD
(mo
l H
2 /
mol E
tOH
in)
Co/CeO2-N
Co/CeO2-M
Co/ZrO2-N
Co/ZrO2-M
Fig. 2. H2-TPR profiles of catalysts. Fig. 3. Yield of H2 in the SRE.
F.Ch. UMCS Report 2009 (Grants) – 173 –
DETERMINATION OF KINETIC-MECHANISTIC PARAMETERS OF THE REACTION OF COMPLETE OXIDATION OF METHANE
BY MEANS OF REAGENTS LABELED WITH STABLE ISOTOPES
Marek ROTKO and Andrzej MACHOCKI
DEPARTMENT OF CHEMICAL TECHNOLOGY
The complete methane oxidation (flameless combustion) is known as the
catalytic process which offers an alternative way of the energy production from the
natural gas to the flame combustion. Moreover, this catalytic process can also be
used for oxidation of methane from its low-concentration mixtures, e. g. from coal
mine post-ventilation air. The wide application of the catalytic combustion can limit
the emission of huge amounts of NOX, CO and hydrocarbons into atmosphere.
The most attractive catalytic materials for the methane oxidation are palladium
catalysts, which demonstrate the highest activity and good thermo-stability of the
active phase. However, their activity depends on many various physicochemical
parameters, among others, the dispersion of the active phase. Moreover, it is very
curious that platinum catalysts, which
demonstrate the highest activity for the
combustion of heavier alkanes (ethane, butane)
is less active than palladium in the case of the
methane oxidation, and also that the palladium-
platinum catalysts demonstrate a high and
stable activity within a longer time frame than it
is observed for palladium catalysts. In order to
obtain additional information about this
process, the steady state isotopic transient
kinetic analysis (SSITKA) has been curried out.
This paper presents a small part of the
SSITKA results, which consider the methane oxidation on the palladium-platinum
catalysts. The Pd-Pt-IE and Pd-Pt-IWI catalysts were prepared by ether the ion
exchange (IE) or the incipient wetness impregnation (IWI) of the commercial Al2O3
support with an aqueous solutions of Pd(NH3)4(NO3)2 and Pt(NH3)4(NO3)2. The
precursors were dried at 110°C (2 h) and calcined at 500°C (1 h), and also prior to
the measurements the catalysts were reduced at 300°C (1 h). The palladium and
platinum content in the catalysts was determined by the X-ray fluorescence (XRF)
method (Pd-Pt-IE: Pd = 0.15 wt.% and Pt = 0.09 wt.%; Pd-Pt-IWI: Pd = 0.26 wt.%
and Pt = 0.12 wt.%). The total surface area of catalysts was determined by using
BET method (for both catalysts 101 m2/g).
The activity of palladium-platinum catalysts in the methane oxidation was
determined in a quartz reactor filled with 0.1 g of a catalyst sample. The flow rate
of the reaction mixture (2 vol% of CH4, 6 vol% of O2, 10 vol% of Ar and 82 vol%
of He) was 100 cm3/min. The linear temperature increase was 10°C/min.
250 350 450 550 650 750 850
Temperature (oC)
0
0.2
0.4
0.6
0.8
1
Meth
an
e c
on
vers
ion
Pd-Pt-IE
Pd-Pt-IWI
Fig. 1. Activity of the Pd-Pt catalysts.
Department of Chemical Technology – 174 –
0 10 20 30 40 50 60
0.0
0.2
0.4
0.6
0.8
1.0
No
rma
lize
d c
on
cen
tra
tio
n
Time (s)
13CH
4
12CH
4Kr
Pd-Pt-IE
T=482oC
Ar
0 10 20 30 40 50 60
0.0
0.2
0.4
0.6
0.8
1.0
No
rma
lize
d c
on
cen
tra
tio
n
Time (s)
13CO
2
12CO
2
Kr
Pd-Pt-IE
T=482oC
Ar
Fig. 2. SSITKA results for the methane oxidation on the Pd-Pt-IE catalyst at 482°C.
Table 1. Kinetic parameters for methane oxidation.
Pd-Pt-IE Pd-Pt-IWI
Methane conversion, % 1.6 60.5 64.8 11.4 81.2 85.4
Temperature, oC 365 482 707 398 512 597
t12CH4, s 0.08 0 0 0.28 0 0
N12CH4, µmol/g 1.16 0 0 3.73 0 0
t12CO2, s 11.46 2.13 1.88 4.21 1.14 0.52
N12CO2, µmol/g 2.73 19.21 18.20 7.15 13.76 6.58
The SSITKA measurements were performed on 0.1 g of the catalyst by
switching from 12
CH4/Ar/O2/He to 13
CH4/Kr/CH4/He at various temperatures,
ensuring the low, middle and high conversion of methane. The flow rate of the
reaction mixture (2 vol% of 12
CH4 (or 13
CH4), 6 vol% of O2, 10 vol% of Ar (or Kr)
and 82 vol% of He) was 100 cm3/min.
The activity of palladium-platinum catalysts (Fig. 1) is very similar and for
both catalysts the distinct decrease of their activity is observed at 620°C and 640°C.
This activity decrease can be connected with the decomposition of PdO and/or
PtO2.
The delays between Ar and 12
CH4 as well as between Ar and 12
CO2 are the proof
of adsorption of methane and carbon dioxide on the palladium catalyst (Fig. 2). On
the basis of these delays the average surface life-time and surface concentration of
methane and intermediates leading to the formation of carbon dioxide were calculated
(Table 1). Methane is observed only at the lowest temperature, corresponding to the
starting point of the methane oxidation (see the values of t12CH4 and N12CH4). The
values of the average surface life-time (t12CO2) and the surface concentration (N12CO2)
of intermediates change with temperature. The t12CO2 decreases with temperature
while for the N12CO2, the maximum value is observed. It means that the reaction rate
of methane oxidation increases with temperature – the value of the reaction rate is
equal to the reciprocal of the t12CO2, and also that the number of active centres on the
catalyst surface during the methane oxidation achieves the maximum – the number of
active centres corresponds to the N12CO2. In spite of very similar activity of both
catalysts, the number of active centres and the reaction rate over their surface are
significantly different.
(Grant the Ministry of Science and Higher Education No. N N204 162636)
F.Ch. UMCS Report 2009 (Grants) – 175 –
CATALYSTS FOR MULTICOMPONENT GAS REFORMING IN GAS HEATED REFORMER
Janusz RYCZKOWSKI, Tadeusz BOROWIECKI, Monika PAŃCZYK
Kazimierz STOŁECKI* and Andrzej GOŁĘBIOWSKI
*
DEPARTMENT OF CHEMICAL TECHNOLOGY
*INSTITUTE OF FERTILIZERS, PUŁAWY
The main aim of the project is the elaboration of the catalysts for
multicomponent gas reforming coming from coal gasification in the gas heated
reformer (GHR) [1, 2].
Nickel catalysts samples were prepared in the Institute of Fertilizers (Pulawy)
[1]. The activity of catalysts of the series II (γ-Al2O3 support modified with La) is
greater than catalysts of the series I (α-Al2O3 support). In both series of catalysts
most profitable activity proprieties show samples with the intermediate nickel
content (11/07 and 14/07, respectively) [2]. Further studies were conducted with the
selected catalysts (Table 1).
Table 1. Base characteristic of the examined catalysts.
Catalyst
Base system New marking Ni (wt. %) La (wt. %) Promoter (M)
11/2007* Ni(I) -
Ni(I)+M
14.8±0.4 -
Ru, Rh, Au, Pt, Pd
14/2007** Ni(II)
Ni(II)+M
17.5±0.5 0.87±0.03
Au, Pt, Pd
* – supported on α-Al2O3; ** – supported on γ-Al2O3
Task II.3.4 – Examining of the influence of promoters on the propriety
of chosen catalysts.
Recognized on the ground of previously performed research two nickel
catalysts were chosen for further modifications by noble metals (Ru, Rh, Au, Pd
and Pt).
Received modified catalysts were subjected to the physicochemical and
catalytic characterization (e.g.: total and active surface areas, activity and the
resistance on coking in the steam reforming of methane). Conducted research allow
to conclude that the platinum could be the only potential modifier of the catalysts
intended to GHR type reactors.
Department of Chemical Technology – 176 –
Task II.3.5 – Investigation of the morphology of carbon deposits and their
gasification.
There were conducted studies of the morphology of carbon deposits formed on
the investigated nickel catalysts (Table 1). These research showed besides that aside
from of used support, the formed carbon deposit is mostly as typical carbon
whiskers with the thickness adequate to the size of raised small nickel particle.
In some catalysts (Ni(I) and Ni(I)+Au) another form of carbon deposit is
formed, so-called “shell-carbon” (larger nickel are covered by it). Warming up of
the catalysts does not cause any changes of the morphology of created carbon
deposits. However, there can be observed change of the average diameter of the
formed carbon whiskers. Gasification of carbon deposit (formed both on based and
modified nickel catalysts) in the mixture of the steam, hydrogen and nitrogen
showed that it could become practically completely removed.
References:
[1] J. Ryczkowski, T. Borowiecki, W. Gac, Annual Report, Faculty of Chemistry,
MCSU, Lublin, 2008.
[2] T. Borowiecki, M. Pańczyk, J. Ryczkowski, K. Stołecki, A. Gołębiowski,
Karbo, 1 (2009) 39-44.
(Grant of Ministry of Education and Science No. PBZ-MEiN-2/2/2006)
F.Ch. UMCS Report 2009 (Grants) – 177 –
NEW OXIDATION AND PHOTOOXIDATION CATALYSTS FOR THE REMOVAL OF ORGANIC POLLUTANTS FROM WATER
AND WASTEWATER
Sylwia PASIECZNA-PATKOWSKA, Bożena CZECH*,
Janusz RYCZKOWSKI and Jacek PATKOWSKI**
DEPARTMENT OF CHEMICAL TECHNOLOGY
*DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
**DEPARTMENT OF RADIOCHEMISTRY
AND COLLOID CHEMISTRY
Photocatalytical methods enable the advanced destruction of the majority of
organic pollutants into CO2, water and some inorganic compounds at room
temperature and atmospheric pressure. Many factors exert the influence on
photodegradation: the type of semiconductor and its surface area, the light intensity,
solvent used, temperature, pH and substances present in the solution. Catalysis is
applied for the decomposition of most organic compounds containing halogens,
nitrogen and sulphur [1]. The main aim of our studies was to determine the catalytic
activity of the TiO2/Al2O3 supported catalysts containing Co, V, Ni, Cu, Zn, Mo, Fe
(Table 1) for the removal of the pollutants from wastewater.
Table 1. Studied catalysts.
Ti content
[% wt.]
Me* content
[% wt.]
Ti content
[% wt.]
Me* content
[% wt.]
TiO2/Al2O3 2.69
CIM-Ni 2.79 2.81 DIM-Ni 2.52 2.70
CIM-Mo 2.05 6.30 DIM-Mo 2.36 5.71
CIM- Zn 2.34 2.75 DIM-Zn 2.83 2.71
CIM-Cu 2.62 3.13 DIM-Cu 2.70 3.01
CIM-Co 2.73 2.69 DIM-Co 2.68 2.55
CIM-Fe 2.77 3.20 DIM-Fe 2.35 2.80
Cx100/Al2O3-TiO2/Co 2.70 2.03 DIM-Co 2.68 2.55
DS100/Al2O3-TiO2/Co 2.62 1.79
EDDS/Al2O3-TiO2/Co 3.02 1.83
Cx100/Al2O3-TiO2/Ni 2.74 2.18 DIM-Ni 2.52 2.70
DS100/Al2O3-TiO2/Ni 2.58 1.82
EDDS/Al2O3-TiO2/Ni 2.85 1.94 * Me - metal
The effectiveness of the removal was measured in the following
configurations: TiO2/O2, TiO2/UV/O2, TiO2/O2/H2O2, TiO2/UV/O2/H2O2. The aim
Department of Chemical Technology – 178 –
of the research was also to investigate possible routes of interactions between the
catalyst precursor used and the support surface when using the classical
impregnation method (CIM) [2] and the double impregnation method (DIM) [3].
FT-IR/PAS method has confirmed the adsorption phenomenon of EDTA, EDDS
and IDS on the TiO2/Al2O3 surface as well as the interactions of chelating
molecules with the inorganic support surface.
The pHpzc of TiO2/Al2O3 was 3.57. During the impregnation of TiO2/Al2O3 with
the solution whose pH was higher than pHpzc preferential adsorption of cations
occurs [4], because of the negative charge of the surface. The pH of disodium salt
of the EDTA solution was about 4.71 (first step of the impregnation based on DIM),
so adsorption of EDTA2–
ions is impeded, because –OH and –O- groups dominate
on the support surface (pH>pHpzc). However, adsorption of EDTA occurs and it can
be seen for FT-IR/PAS spectra [5]. EDTA may then bind with titania-alumina
surface or via hydrogen bonds [4] or via electrostatic interactions. The latter is
possible because of a presence of positively charged –OH2+
groups which interact
with negatively charged COO– groups from EDTA. This phenomenon takes place
despite higher concentration of –O– than –OH
2+ groups. The pHpzc of the support
has also an influence on further adsorption of different metal salts both using CIM
and DIM. Obtained catalyst were examined in photocatalytic degradation of
organics in wastewater were conducted in a band reactor of our construction [6].
According to the obtained results it may be concluded that:
– for the removal of non-ionic surfactants, e.g. Triton X-100, from water all
modified TiO2/Al2O3 catalysts can be successfully applied;
– the effect of the treatment is independent from the catalysts impregnation method;
– the effect of H2O2 addition is not clear and depends on the type of modifier
in the catalysts; e.g. using H2O2 during Triton X-100 oxidation over Co-
TiO2/Al2O3 the effects of surfactant removal are visible, but over V-
TiO2/Al2O3 are not observed and oxidation can be even retarded; generally
the addition of H2O2 causes deeper oxidation of Triton X-100,
– it is economically unjustified to conduct the treatment for more than 2 hours,
– analysis of FT-IR/PAS spectra shows that photoacoustic spectroscopy is a very
useful tool for observation of various species formed during the impregnation
process and the outcomes are useful for the interpretation of catalytic results.
References:
[1] G. Centi., P. Ciambelli, S. Perathorner, P. Russo, Catal. Today, 75 (2002) 3.
[2] B.C. Gates, Chem. Rev., 95 (1995) 511.
[3] J. Barcicki, D. Nazimek, W. Grzegorczyk, T. Borowiecki, R. Frąk, M. Pielach, React.
Kinet. Catal. Lett., 17 (1981) 169.
[4] J. Ryczkowski, Vibr. Spectrosc., 43 (2007) 203.
[5] S. Pasieczna-Patkowska, B. Czech, J. Ryczkowski, J. Patkowski, Appl. Surf. Sci. (in
press).
[6] B. Czech, W. Ćwikła–Bundyra, Pol. J. Chem. Technol., 9 (2007) 18.
(Grant of UMCS Deputy Rector)
F.Ch. UMCS Report 2009 (Grants) – 179 –
SYNTHESIS AND CHARACTERISATION OF PHYSICO-CHEMICAL, CATALYTIC AND MAGNETIC
PROPERTIES OF HIGH-SURFACE AREA OXIDE MATERIALS
Wojciech GAC, Witold ZAWADZKI and Zbigniew SUROWIEC*
DEPARTAMENT OF CHEMICAL TECHNOLOGY **
DEPARTAMENT OF NUCLEAR METHODS,
INSTITUTE OF PHYSICS UMCS, LUBLIN, POLAND
Cobalt and iron oxides are interesting materials for different applications,
including catalysis, sorption, separation, sensing, electronics, numerous magnetic
devices. Nanomaterials have recently found wide interests. Their unique physical,
chemical or magnetic properties usually results from the small size of the species or
suitable arrangement of the structural units. Nanomaterials can be prepared by the
set of different methods. The nanocasting technique involves: 1) adsorption or
filling and then decomposition of precursors in the nanometre voids of the soft or
hard templates, 2) removal of the templates, and 3) separation and additional
thermal treatment of obtained replicas. Different surfactant micellar systems,
biological materials, carbon nanofibers, micro- or mesoporous silica and alumina
can be used as 3D matrices. The templates can be removed by the thermal treatment
(e.g. surfactants and carbon materials) or by leaching, e.g. using NaOH or HF
solutions.
The aim of the recent work was preparation and characterization of cobalt and
iron oxides by the nanocasting technique.
Two types of the silica materials of different porosity and surface properties
were used for the synthesis of the oxides. After adsorption and then thermal
decomposition of cobalt and iron nitrates in the commercial wide-pore SiO2 and as-
prepared MCM-48 type silica materials, the templates were leached out in the
NaOH solution.
Samples were investigated by the nitrogen adsorption/desorption method, X-
ray diffraction, FT-IR spectroscopy, scanning electron microscopy, X-ray
photoelectron spectroscopy. Redox and catalytic properties were studied by the
temperature programmed reduction method (TPR) and methanol test oxidation
reaction. Magnetic properties were examined by the application of 57
Fe Mössbauer
spectroscopy and Gouy balance method.
An application of the silica materials led to the development of nanomaterials
composed of the species formed in the pore system of matrices. Strongly dispersed
Co3O4 and Fe2O3 phases were detected. The samples prepared by the application of
the high-surface area templates, containing interconnected mesopores of the size
around 3 nm showed larger surface area and more regular arrangement of the oxide
species than the samples obtained from the macroporous silica. High surface area
mesoporous cobalt oxide was formed after removal of MCM-48 template.
Department of Chemical Technology – 180 –
-12 -8 -4 0 4 8 12
Velocity (mm/s)
99.20
99.40
99.60
99.80
100.00
Tra
nsm
issio
n
98.40
98.80
99.20
99.60
100.00
Tra
nsm
issio
n
-12 -8 -4 0 4 8 12
Velocity (mm/s)
98.4
98.8
99.2
99.6
100.0
98.0
98.4
98.8
99.2
99.6
100.0
F e/SiO2/K/D
Fe/SiO2/K
Fe/MCM48/K/D
Fe/MCM48/K
0 200 400 600 800
Temperature [oC]
0
400
800
1200
1600
Hyd
rog
en
co
nsu
mp
tio
n [
a.u
.]
Co/MCM48/K
Co/MCM48/K/D
Co/SIO2/K
Co/SIO2/K/D
0 200 400 600 800
Temperature [oC]
0
200
400
600
800
Hyd
rog
en
co
nsu
mption
[a
.u]
Fe/MCM48/K
Fe-MCM48/K/D
Fe/SiO2/K
Fe-SiO2/K/D
Microscopic studies indicated similar morphology of the oxides to the original silica
matrices.
It was found that magnetic properties of iron and cobalt oxides were related to
the porous structure of the silica supports (Fig. 1).
Fig. 1. The 57
Fe Mössbauer spectra of the samples before and after silica removal,
Fe/SiO2(MCM48)/K and Fe/SiO2(MCM48)/K/D, respectively.
The detailed studies of the nature of the oxides evidenced differences in the
redox properties of the species located within the silica templates and after their
removal (Fig. 2).
Fig. 2. The TPR curves of the samples before and after silica removal.
Samples showed high activity in the test methanol oxidation reaction.
(Grant of UMCS Deputy Rector)
F.Ch. UMCS Report 2009 (Grants) – 181 –
PROEKOLOGICAL TECHNOLOGY UTILIZATION COAL MINE METHANE
Beata STASIŃSKA, Agnieszka MARCEWICZ-KUBA*,
Monika PAŃCZYK, Marcin KUŚMIERZ, Wojciech GAC,
Marek ROTKO, Witold ZAWADZKI and Dobiesław NAZIMEK*
DEPARTMENT OF CHEMICAL TECHNOLOGY
*DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
In Poland the methane management from ventilation air is an important
ecological problem. In last years in many Polish coal mines the underground
installations for methane utilization have been constructed and the economic usage
of grasped methane in thermal-energetic installations have been developed, but only
when the concentration of methane is higher than 45%. The problem of methane
utilization is very difficult because in each mine the situation is quite different.
Ventilation air is a difficult source of methane to use as an energy carrier, as air
volume is large, methane is very diluted as well as variable in its concentration
(0.1–1.0 vol.%) and flow rate.
The catalytic oxidation of methane may be considered as a promising solution of
methane-poor gas mixtures utilization. The process allows not only for complete
oxidation of methane in its low-concentrated mixtures but it also may be carried out
at moderate (depended on the catalyst used) temperatures. After mixing of post-
ventilation air with methane recovered in the coal seam drainage systems (before
mining and from worked areas of the mine) it is even possible to produce of energy.
Fig. 1. Comparison of temperatures of the starting point and the point of the total oxidation
of methane for oxide and metallic catalytic.
0 200 400 600 800 1000 1200
Temperature, K
Pd
Rh
Ru
Pt
Cu
Cr
Mn
Fe
La
Co
Ni
Al
Meta
l/su
pp
ort
O
xid
e/s
up
po
rt....
.
start of
oxidation
total
oxidation
Department of Chemical Technology – 182 –
Various catalysts (Fig. 1) were investigated in the oxidation of low
concentrated methane–air mixtures and the best performance of supported
palladium catalysts was observed.
The Pd/Al2O3 catalysts allow to initiate flameless combustion of methane from
its low-concentrated air mixtures at the temperature lower than 300 oC and to
achieve its total oxidation at temperatures at which no oxidation of nitrogen to
nitrogen oxide occurs.
The main aim of the project is the elaboration of the palladium catalysts on
industrial support with high activity and possible smallest concentrating active phase.
For palladium catalysts prepared on industrial support was studied their activity:
– in the mixture with different methane concentration:
(2 – x)CH4 + 20%O2 + (78 + x)%N2
– in the mixture with different space velocity 3000-12000 (h–1
)
– during methane oxidation reaction for 800 hours (Fig. 2).
Chosen from these research catalysts will be being studied on Wroclaw
Institute of Technology. Research in Wroclaw will allow to design prototype of
reactor for oxidation methane from coal mine air ventilation.
Fig. 2. Activity palladium catalysts in methane oxidation reaction (500°C, 1% methane
in air, 6000h–1
)
References:
[1] B. Stasińska, A. Machocki, Catalysts for the utilization of methane from the coal
mine ventilation air, Polish Journal of Chemical Technology, 9 3 (2007) 29.
[2] B. Stasińska, S. Napieraj: Zagospodarowanie metanu z powietrza
wentylacyjnego kopalń węglowych, Przemysł Chemiczny, 11 (2009) 1121.
(UDA-POIG Project 01.03.01-00-072/08-00)
Met
han
e co
nv
ersi
on, %
F.Ch. UMCS Report 2009 (Grants) – 183 –
STUDIES OF TEMPERATURE INFLUENCE ON ADSORPTION BEHAVIOUR OF NONIONIC POLYMERS
AT THE ZIRCONIA-SOLUTION INTERFACE
Stanisław CHIBOWSKI, Małgorzata WIŚNIEWSKA and Teresa URBAN
DEPARTMENT OF RADIOCHEMISTRY AND COLLOID CHEMISTRY
Many parameters associated with polymer and solid characteristics as well as
solution conditions influence the macromolecule conformation. Of all these factors,
only temperature effect on adsorption behaviour of polymer is not extensively
discussed in the world literature [1]. The temperature conditions are very important
for the colloidal system stability in the presence of polymer and stabilization or
destabilization effect may be achieved by proper choice of temperature range.
Thus, the aim of the study was determination of the temperature influence
(15-35°C) on the adsorption layer structure of three nonionic polymers:
polyethylene glycol (PEG), polyethylene oxide (PEO) and polyvinyl alcohol (PVA)
on the zirconium dioxide surface. The applied techniques (spectrophotometry,
viscosimetry, potentiometric titration and microelectrophoresis) allowed
characterization of the changes in structure and thickness of polymer adsorption
layers with the increasing temperature.
Table 1. The adsorbed amounts (Γ) and the thickness of PEG (PEO) and PVA
adsorption layers (δ) on the ZrO2 surface, CNaCl = 1·10–2
mole/dm3,
Cpolymer = 100 ppm, pH = 6.
15°C 25°C 35°C
Polymer Γ
[mg/m2]
δ
[nm]
Γ
[mg/m2]
δ
[nm]
Γ
[mg/m2]
δ
[nm]
PEG 2 000 0.25 1.91 0.31 2.82 0.46 3.28
PEO 218 000 0.40 3.88 0.72 5.08 0.94 6.62
PVA 22 000 1.37 2.18 1.67 3.52 2.02 4.77
PVA 38 000 1.62 4.36 1.86 6.34 2.13 8.64
The obtained results (Table 1) indicate that the polyvinyl alcohol (PVA)
adsorption causes greater changes in zirconia surface properties than that of
polyethylene glycol (PEG) and polyethylene oxide (PEO). It is associated with the
presence in the PVA chains of unhydrolysed acetate groups, which undergo
dissociation. Thus, not only hydrogen bridges interactions (as in the case of PEG
and PEO) but also electrostatic forces are responsible for their adsorption on the
solid surface.
The conformation changes of the adsorbed polymer with the rising
temperature from the more coiled structure (at 15°C) to the developed one (at 35°C)
Department of Radiochemistry and Colloid Chemistry – 184 –
result in the increase of the adsorbed amounts and thicknesses of polymer
adsorption layer.
-40
-30
-20
-10
0
10
20
2 3 4 5 6 7 8 9 10 11
σσ σσo
[ µµ µµC
/cm
2]
pH
15o C NaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
-40
-30
-20
-10
0
10
20
2 3 4 5 6 7 8 9 10 11
σσ σσo
[ µµ µµC
/cm
2]
pH
25o C NaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
-40
-30
-20
-10
0
10
20
2 3 4 5 6 7 8 9 10 11
σσ σσo
[ µµ µµC
/cm
2]
pH
35o CNaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
-30
-20
-10
0
10
20
30
2 3 4 5 6 7 8 9 10 11ζζ ζζ[m
V]
pH
15o C
NaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
-30
-20
-10
0
10
20
30
2 3 4 5 6 7 8 9 10 11ζζ ζζ[m
V]
pH
25o C
NaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
-30
-20
-10
0
10
20
30
2 3 4 5 6 7 8 9 10 11ζζ ζζ[m
V]
pH
35o C
NaCl 0.01M
PEG 2 000
PEO 218 000
PVA 22 000
PVA 38 000
a) b) c)
Fig. 1. The surface charge density and zeta potential of ZrO2 in the absence and presence
of PEG (PEO) and PVA at: a)15°C, b) 25°C and c) 35°C; CNaC l= 1·10–2
mole/dm3,
Cpolymer = 100 ppm.
Adsorption of the polymer at 35°C causes the most noticeable changes in the
ZrO2 surface charge density and its zeta potential (Fig. 1). The main reason for such
behaviour is more stretched structure of the adsorbed polymer layers at higher
temperature.
Additionally, the electrokinetic properties of the investigated systems in the
presence of the polymer are the sum of three effects: the blockade of the solid active
sites by the adsorbed polymer chains and electrolyte ions, the shift of slipping plane
caused by the adsorption of polymer chains and the presence of functional groups
undergoing dissociation. The contribution of these mechanisms to the changes of
electrokinetic behaviour of such systems depends on the polymer type, its
molecular weight and temperature conditions.
The effect of blockade of the solid active sites by the adsorbed macromolecules
and electrolyte ions is more probable for lower temperature and low polymer
molecular weight. On the other hand, the effect of the slipping plane shift becomes
dominant for higher temperature and high polymer molecular weight. Additionally, in
the case of polyvinyl alcohol the presence of the dissociated acetate groups in the
adsorbed chains is also responsible for decrease of the zeta potential of zirconia
particles.
References:
[1] L.C. Guo, Y. Zhang, N. Uchida, K. Uematsu, J. Europen Ceram. Soc., 17
(1997) 45.
(Grant of Ministry of Science and Higher Education No. N204 071 32/1869)
F.Ch. UMCS Report 2009 (Grants) – 185 –
X-RAY POWDER DIFFRACTION – NEW INORGANIC
AND ORGANIC COMPOUNDS IV
Elżbieta OLSZEWSKA, Stanisław PIKUS, Marek MAJDAN*
and Bogdan TARASIUK**
DEPARTMENT OF CRYSTALLOGRAPHY
*DEPARTMENT OF INOGRANIC CHEMISTRY
**DEPARTMENT OF ORGANIC CHEMISTRY
The purpose of this grant is to generate new high quality powder patterns for
the PDF-2 computer file collected by International Centre for Diffraction Data
(ICDD-USA). In 2009, the 12 new experimental X-ray powder diffraction patterns
were collected, interpreted and send to ICDD (see Table 1).
Table 1. List of submitted XRD reference patterns.
Number Chemical formula Name
1. Sr2,1 Na2,8Al7Si41O96 ·24H2O SrNa mordenite
2. Ba2.1 Na2.8Al7Si41O96 ·24H2O BaNa mordenite
3. C16H13ClF3NO2 2-(4-chloro-3-methylphenoxy)-N-[3-
(trifluoromethyl)phenyl]acetamide
4. C14H20ClNO3 2-(4-chloro-3-methylphenoxy)-N-[1-
(hydroxymethyl)propyl]propanamide
5. C14H20ClNO4 2-(4-chloro-3-methylphenoxy)-N,N-bis(2-
hydroxyethyl)propanamide
6. C13H17ClN2O2 1-[(4-chlorophenoxy)acetyl]-4-methylpiperazine
7. C17H19BrCl2N2O2 1-butyl-2-[(2,4-dichlorophenoxy)acetyl]
aminopyridinium bromide
8. C23H31BrCl2N2O2 2-[(2,4-dichlorophenoxy)acetyl]amino-1-
decylpyridinium bromide
9. C29H43Cl3N2O2 2-[(2,4-dichlorophenoxy)acetyl]amino-1-
hexadecylpyridinium chloride
10. C15H12BrCl2NO2 N-(4-bromophenyl)-2-(2,5-
dichlorophenoxy)propanamide
11. C15H11Cl4NO2 2-(2,5-dichlorophenoxy)-N-(3,4-
dichlorophenyl)propanamide
12. C16H12Cl2F3NO2 2-(2,5-dichlorophenoxy)-N-[3-
(trifluoromethyl)phenyl]propanamide
All patterns were indexed and all have been approved for publishing in
Powder Diffraction File as the reference patterns.
(Grant from ICDD, USA, N. 04-08)
Department of Crystallography – 186 –
X-RAY POWDER DIFFRACTION – NEW INORGANIC
AND ORGANIC COMPOUNDS XII
Stanisław PIKUS, Elżbieta OLSZEWSKA, Marek MAJDAN
*
and Bogdan TARASIUK**
DEPARTMENT OF CRYSTALLOGRAPHY
*DEPARTMENT OF INORGANIC CHEMISTRY
**DEPARTMENT OF ORGANIC CHEMISTRY
The purpose of this grant is to generate new high quality powder patterns for
the PDF-2 computer file collected by International Centre for Diffraction Data
(ICDD-USA). In 2009, the 20 new experimental X-ray powder diffraction patterns
were collected, interpreted and send to ICDD (see Table 1).
Table 1. List of submitted XRD reference patterns.
Number Chemical formula Name
1. Mg2,3Na2,4Al7Si41O96 ·24H2O MgNa mordenite
2. Ca2,5Na2Al7Si41O96 ·24H2O CaNa mordenite
3. C13H18ClNO3 2-(4-chloro-3,5-dimethylphenoxy)-N-(3-
hydroxypropyl)acetamide
4. C14H20ClNO3 2-(4-chloro-3,5-dimethylphenoxy)-N-(2-
hydroxy-1,1-dimethylethyl)acetamide
5. C15H22ClNO3 2-(4-chloro-3,5-dimethylphenoxy)-N-(2-
hydroxy-1,1-dimethylethyl)propanamide
6. C16H15ClFNO2 2-(4-chloro-3,5-dimethylphenoxy)-N-(4-
fluorophenyl)acetamide
7. C17H17ClFNO2 2-(4-chloro-3,5-dimethylphenoxy)-N-(4-
fluorophenyl)propanamide
8. C16H14Cl2FNO2 2-(4-chloro-3,5-dimethylphenoxy)-N-(3-
chloro-4-fluorophenyl)acetamide
9. C15H10Cl4FNO2 N-(3-chloro-4-fluorophenyl)-2-(2,4,5-
trichlorophenoxy)propanamide
10. C15H10Cl5NO2 N-(3,5-dichlorophenyl)-2-(2,4,6-
trichlorophenoxy)propanamide
11. C14H18Cl3N3O2 N-(2-piperazin-1-ylethyl)-2-(2,4,6-
trichlorophenoxy)acetamide
F.Ch. UMCS Report 2009 (Grants) – 187 –
12 C13H15Cl3N2O2 1-methyl-4-[(2,4,6-
trichlorophenoxy)acetyl]piperazine
13. C14H8Cl5NO2 N-(3,4-dichlorophenyl)-2-(2,4,6-
trichlorophenoxy)acetamide
14. C14H8Cl5NO2 N-(3,5-dichlorophenyl)-2-(2,4,6-
trichlorophenoxy)acetamide
15. C14H7Br3Cl3NO2 N-(2,4,6-tribromophenyl)-2-(2,4,6-
trichlorophenoxy)acetamide
16. C14H12Cl2N2O2 2-(2,5-dichlorophenoxy)-N-(3-methylpyridin-
2-yl)acetamide
17. C15H9Br3Cl3NO2 N-(2,4,6-tribromophenyl)-2-(2,4,6-
trichlorophenoxy)propanamide
18. C15H12Cl3NO2 N-(3-chloro-4-methylphenyl)-2-(2,4-
dichlorophenoxy)acetamide
19. C16H15Cl2NO2 N-(3-chloro-4-methylphenyl)-2-(4-
chlorophenoxy)propanamide
20. C17H17Cl2NO2 2-(4-chloro-3,5-dimethylphenoxy)-N-(3-
chloro-4-methylphenyl)acetamide
All patterns were indexed and all have been approved for publishing in
Powder Diffraction File as the reference patterns.
(Grant from ICDD, USA, N. 97-01)
F.Ch. UMCS Report 2009 (Grants) – 189 –
BORAN JAKO NOWY SELEKTYWNY ODCZYNNIK REDUKUJĄCY W CHEMII FUNKCJONALIZOWANYCH FOSFONIANÓW,
FOSFINIANÓW I TLENKÓW FOSFIN
Sylwia SOWA, Marek STANKEVIČ and K. Michał PIETRUSIEWICZ
DEPARTMENT OF ORGANIC CHEMISTRY
Conversion of phosphine oxides into phosphine-boranes is typically conducted by a
two-step reduction-complexation sequence which involves reduction of P=O bond with a
strong reducing agent such as LiAlH4, HSiCl3 and subsequent complexation of the formed
phosphine with borane complexes (BH3-SMe2 or BH3-THF). The main drawback is a
necessity of separation of the formed phosphine from the reaction mixture, which causes
problems and lowers the attractiveness of this methodology. A solution to this problem
could be use of borane-containing reducing agent which could provide both the reduction of
phosphine oxide and the complexation of the formed phosphine. Recently, we reported the
expedient transformation of secondary phosphine oxides into corresponding phosphine-
boranes by the use of commercially available BH3-SMe2 complex. We have now developed
a new method for the conversion of tertiary phosphine oxides possessing hydroxyalkyl
substituents directly into corresponding phosphine-boranes with BH3 complexes.
R1P
R2
O
OHBH3-THF (3 equiv.)
THF, rt, 4h R1P
R2
OH
BH3
1 2 Substituents
Nr Compound R
1 R
2
Isolated yields of 2
(%)
1 1a Ph o-An 100
2 1b Ph 1-Nphtha
86
3 1c p-MeO-C6H4 p-MeO-C6H4 90
4 1d p-F-C6H4 p-F-C6H4 72
5 1e 3,5-Me2-C6H3 3,5-Me2-C6H3 57
6 1f Ph t-Bu 84
7 1g Ph PhCH2 86
8 1h Ph i-Pr 85
9 1i Ph c-Hex 80
10 1j Ph 2-NphthCH2 81
11 1k c-Hex c-Hex 69
12 1l n-Hex n-Hex 76
a – Nphth = naphthyl
We were pleased to find, that phosphine oxides 1 were readily transformed into the
corresponding tertiary phosphine-boranes without affecting of hydroxymethyl
functionality (Table). In order to check the role of hydroxy substituent in starting
Department of Organic Chemistry – 190 –
hydroxymethylphosphine oxides 1, reduction of t-butylmethylphenylphosphine oxide, a
compound lacking OH functionality, was attempted but turned out unsuccessful.
PhP
Me
t-Bu
OBH3-THF (3 equiv.)
THF, reflux, 24hNo reaction
It was proven therefore, that the presence of OH functionality in the substrate
molecule is essential for the reduction of P=O bond to occur under studied
conditions. Added substituents in the hydroxylated side-chain are well tolerated as
demonstrated below for the Ph substituted cases.
R1P
R2
O
OHBH3-SMe2 (3 equiv.)
THFconditons
R1P
R2
OH
BH3
3 4
Ph Ph
Substituents
Nr Compound R
1 R
2
Conditions Isolated yields
of 4 (%)
1 3a Ph o-An reflux, 24h 81
2 3b Ph 1-Nphtha
reflux, 24h 48
3 3f Ph t-Bu reflux, 24h 91
4 3g Ph PhCH2 reflux, 24h 97
5 3k c-Hex c-Hex rt, 72h 44
6 3k c-Hex c-Hex reflux, 24h 67
Introduction of a hydroxyl functionality to the substrate in a more distant β position showed similar beneficial effect and similarly facilitated the reduction.
R1P
R2
O BH3-SMe2 (3 equiv.)
Toluene, 80oC, 12h R1P
R2
BH3
5 6
OH OH
5a R1 = Ph, R2 = o-An 26%
5b R1 = Ph, R2 = 1-Nphth 55%
5n R1 = Ph, R2 = Ph 84%
In conclusion, an efficient methodology for the reduction of P=O bond in tertiary
phosphine oxides possessing hydroxyalkyl substituent at phosphorus atom was
developed, wherein commercially available BH3 complexes act as both the reducing
and the complexating agents. The presence of proximal hydroxyl group in the substrate
is essential for the reduction to take place. Lenghtening the distance between P=O bond
and –OH group causes diminishing of the substrate propensity for reduction and use of
more forcing conditions is needed to afford effective reduction of P=O bond.
Stereochemical experiments performed on optically active (hydroxymethy)
phosphine oxides revealed that the reduction process occurred with complete
retention of configuration at P atom.
(Grant the Ministry of Science and Higher Education No. N204 1110 35)
F.Ch. UMCS Report 2009 (Grants) – 191 –
SELECTIVE FUNCTIONALISATION OF TERTIARY PHOSPHINES POSSESSING ARYL SUBSTITUENTS WITH ALKALI METALS
AS A METHOD OF THE SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS POSSESSING USEFUL PROPERTIES
Marek STANKEVIČ, K. Michał PIETRUSIEWICZ, Oleh M. DEMCHUK,
Sylwia SOWA and Anna SZMIGIELSKA
DEPARTMENT OF ORGANIC CHEMISTRY
Development of new methodologies of the synthesis of tertiary phosphines is
still of practical value in regard of increasing interest in homogeneous catalysis where
tertiary phosphines have found wide applications as ligands in numerous transition
metal-catalysed transformations [1]. This is especially true for alkylphosphines,
which appeared to be very effective in a series of metal-catalysed coupling reactions
with nonactivated haloarenes as substrates [2]. One of the possible ways of the
synthesis of alkylphosphines, especially those possessing cyclohexyl moieties, is
dearomatisation of arylphosphines, which are readily accessible through variety of
methods. The aim of this project is to develop the methodology of the synthesis of
alkylphosphines from arylphosphines through dearomatisation of aryl substituent.
First experiments were performed on dialkylarylphosphine-boranes, as boranes
are convenient precursors of free phosphines and modification of one aryl ring will
give directly trialkylphosphine-borane. Treatment of a set of four model phosphine-
boranes with a solution of alkali metals in liquid ammonia led to the formation of
one of products (Scheme 1).
Scheme 1.
Under the applied conditions compounds 1a, b and d readily formed Birch
reduction products 3a,b and d. Only 1c yielded a mixture of three compounds
where the main compound was unreacted starting material 1c accompanied with
secondary phosphine-borane Ph(t-Bu)P(BH3)H 2c and Birch reduction product 3c.
Replacement of sodium with other alkali metals (lithium or potassium) in all cases
except one yielded a mixture of compounds 1, 2 and 3 and the level of conversion
lowered remarkably. In the case of 1c, replacement of sodium with magnesium was
beneficial and yielded desired 3c in 63% yield.
R1P
R2
BH3 1. Na (2.5 equiv.)
2. NH4Cl
THF/NH3, -78oC, 5 min R1P
R2
BH3
1 3
R1P
HR2
BH3
2
+R1
P
R2
BH3
1
+
1a R1 = R2 = -(CH2)4-
1b R1 = t-Bu, R2 = Me
1c R1 = t-Bu, R2 = Bn
1d R1 = R2 = Me
84%
85%
19%
83%
-
-
22%
-
-
-
39%
-
Department of Organic Chemistry – 192 –
Another issue was made in order to obtain in situ alkylation of formed
carboanions with reactive alkyl halides which will lead to the formation of tertiary
carbon center (Scheme 2).
Scheme 2.
Indeed, addition of benzyl chloride to reaction mixture afforded in the case of
1a, b and d appropriate α-alkylation products 4a,b and d in good to excellent
yields. Again, 1c was the exception as the formation of 5c was observed which
arises from benzyl group cleavage-alkylation-deprotonation-alkylation sequence.
Other experiments on this topic are currently underway in our laboratory.
References:
[1] For examples see: (a) X.-B. Wang, W. Zeng, Y.-G. Zhou, Tetrahedron Lett., 49
(2008) 4922. (b) T. den Hartog, S.R. Harutyunyan, D. Font, A.J. Minnaard,
B.L. Feringa, Angew. Chem. Int. Ed., 47, 2008, 398. (c) J. Chen, Q. Liu, S.
Spinella, A. Lei, X. Zhang, Org. Lett., 10 (2008) 3033.
[2] For examples see: (a) L. L. Hill, L. R. Moore, R. Huang, R. Craciun, A. J.
Vincent, D.A. Dixon, J. Chou, C. J. Woltermann, K. H. Shaughnessy, J. Org.
Chem., 71 (2006) 5117. (b) R.B. Bedford, M. Betham, J.P.H. Charmant, A.L.
Weeks, Tetrahedron, 64 (2008) 6038. (c) T. Hama, J.F. Hartwig, Org. Lett., 10
(2008) 1545.
(Grant the Ministry of Science and Higher Education No. N204 2328 34)
R1P
R2
BH31. Met (2.5 equiv.)
2. BnCl (2.0 equiv.)
3. NH4Cl
THF/NH3
1. -78oC, 5 min
2. -78oC, 15 min
R1P
R2
BH3
Ph
Ph
1 5
1-phenylphospholane-borane (1a)
Ph(t-Bu)CH3P-BH3 (1b)
Ph(t-Bu)BnP-BH3 (1c)
Ph(CH3)2P-BH3 (1d)
-
-
51%
-
92%
74%
-
55%
Na
K
K
Na
Metal Yields
R1P
R2
BH3
6
R1P
R2
BH3
4
-
-
-
6%
+ +
Ph
Ph
F.Ch. UMCS Report 2009 (Grants) – 193 –
NOVEL BULKY AND ELECTRONICALLY RICH ATROPOISOMERIC PHOSPHORUS LIGANDS: SYNTHESIS
AND APPLICATION
Oleg M. DEMCHUK, Katarzyna KIELAR
and K. Michał PIETRUSIEWICZ
DEPARTMENT OF ORGANIC CHEMISTRY
It is usually assumed that coupling of two aryls bearing more than two ortho-
substituents is a difficult synthetic task [1]. Therefore the asymmetric couplings
promoted by chiral transition metal complexes are really rare mostly because of
lack of the suitable ligands. Actually, popular triaryl phosphines and bis-
phosphines, widely available in optically pure forms, do not form catalysts efficient
enough to couple multiply ortho- substituted aryls in such reactions as Suzuki
Miura, Negishi etc., even in Heck reaction. Electronically rich bulky di-, tri-
alkylphosphines and especially bulky biaryl C,P- ligands form highly active
catalysts for those X-coupling reactions, but only very few of such ligands are
chiral and commercially available. Thus, design of active catalysts which allow to
perform a creation of an atropoisomeric biaryl core indeed to be an intriguing goal.
We decide to use an innateness of properly substituted biaryls to posses a chiral
axis for introducing of an atropoisomeric chirality in to the phosphine structure. A
short and inexpensive approach, optimised for synthesis of highly active scalemic
ligands, has been therefore developed based on previously reported syntheses of
ligand Nap-Phos [2] and recently published protocol of quinones [3] arylation.
O
O
OMe
1) Cy2PHO, Cs2CO3PhMe, DMF, Bu4NBr
2) CH3I, NaH
~80%MeO O
PCy2
MeOOMe
PCy2
OMeO
Me
O
(Me2SiH)2O, Ti(Oi-Pr)4THF, 70 oC, 24h
70%
PCy2
OMeO
Me
20%Ligand-1
HSiCl3, Et3N, PhMe
81% Scheme 1. Synthesis of new C,P-ligand.
Prepared in this way ligand was tested in model Suzuki Miura cross-coupling
and brought results comparable with those observed for the ligand S-Phos [4]
recognised by its highly catalytically active palladium complexes. Even in difficult
cases of sterically hindered couplings, utilisation of the complexes of our ligand
allows to reach high yields of four ortho-substituted products (52-85%, 8
examples), several deactivated aromatic chlorides were also successfully coupled
with substituted arylboronic acids, nevertheless electronically deficient fluorinated
boronic acids did not couple well even in relatively high reaction temperature.
Department of Organic Chemistry – 194 –
Racemic phosphine was converted to a pair of diastereoisomeric palladium
complexes by treatment with [(S)-1-[1-(dimethylamino)ethyl]-2-naphthalenyl-
C,N]palladium(II) chloride. Pure isomers were separated by flash column
chromatography or fractional crystallisation. Recorded X-ray structure of one of
those complexes allows to read an absolute configuration of the ligand in it.
MeO
P
OMe
Cy Cyrac.
Pd
NMe2
Cl
2
flash cromatogaphyor
crysralisation
Cl
OMe
P OMe
CyCy
Pd
NMe Me Me
Cl
1)
2)
Scheme 2. Diastereoseparation and absolute
configuration determination.
Enantiomerically pure phosphines were isolated from the diastereoisomerically
pure complexes to be utilised in an asymmetric synthesis.
Cl
OMe
P OMe
CyCy
Pd
NMe Me Me
Cl MeO
P
OMe
Cy Cy
HCl, Me2CO KCN, DCM/H2O
~50% ~50%MeO
P
OMe
CyCy
PdCl2
A B (R)-Ligand-1 Scheme 3. Synthesis of enantiomerically pure ligand.
As a model asymmetric reaction we choose synthesis of dimethoxybinaphthyl
by Suzuki Miura coupling of 2-methoxynaphthalen-1-ylboronic acid with 1-bromo-
2-methoxynaphthalene. The best asymmetric induction (70% yield, 54% ee) in the
synthesis of dimethoxybinaphthyl realised by X-coupling reaction was observed in
Negishi coupling mediated by 5%-mol of palladium (as Pd2dba3*CHCl3) and 20%-
mol of ligand C [5]. Utilization of 5%-mol of palladium source and 10%-mol of
Buchwald ligand D was effected in 78% yields of racemic product [6]. Utilization
of 5%-mol of racemic palladium complex B of our ligand (palladium to ligand ratio
is one to one) brought 80% yield of the product. Unfortunately yield rapidly
dropped down to 35% when we utilised only 2.5%-mol of enantiopure complex A,
product was formed in 33% ee. We got almost the same results in case of utilisation
palladocyclic complex B. The reaction run with application of 2.5%-mol of
palladium acetate in combination with 7,5%-mol of (R)-Ligand-1 similarly brought
product in 50% yield and 40% ee. Despite of simplicity of this model, the
F.Ch. UMCS Report 2009 (Grants) – 195 –
asymmetric cross-couplings leading to the dimethoxybinaphthyl are turned to be
difficult reactions with apparent internal limitation of the stereochemic outcome.
X = -B(OH)2, -ZnCl
Scheme 4. Model asymmetric synthesis.
In conclusion, we have developed straightforward synthetic approach to biaryl
core based chiral non-racemic atropoisomeric bidentate C,P-chelating electronically
reach and sterically hindered phosphorus ligand. The high efficiency of new ligand
was confirmed in series of difficult coupling reactions also in those stereoselective.
An optimisation of the presented protocols and further development in different
coupling reactions is underway in our laboratories and will be reported in due
course.
References:
[1] (a) I. Cepanec, Synthesis of Biaryls, Elsevier: Amsterdam, 2004. (b) Metal-
Catalyzed Cross-Coupling Reactions, A. Meijere, F. Diederich (Eds.) Wiley-
VCH: Weinheim, 2005.
[2] O. M. Demchuk, T. Blackburn, V. Snieckus, SYNLETT, (2006) 2908.
[3] O. M. Demchuk, K. M. Pietrusiewicz, SYNLETT, (200090 114.
[4] T. Barder, S. walker, J. Martinelli, S. Buchwald, , J. Am.Chem.Soc., 127 (2005)
4685.
[5] M. Genov, B. Fuentes, P. Espinet, B. Pelaz, Tetrahedron; Asym., 17 (2006)
2593.
[6] J. Yin, M. Rainka, X. Zhang, S. Buchwald, J. Am.Chem.Soc., 124 (2002) 1162.
(Grant the Ministry of Science and Higher Education No. N204 3337 33)
PPh2
NMe2
Fe
PCy2
02JACS116206TA2593
DC
Department of Organic Chemistry – 196 –
OPRACOWANIE NOWYCH EFEKTYWNYCH PROCESÓW KATALIZOWANYCH KOMPLEKSAMI METALI I ZWIĄZKAMI
METALOORGANICZNYMI: ZWIĄZKÓW METALOORGANICZNYCH JAKO ODCZYNNIKÓW W STEREOSELEKTYWNEJ SYNTEZIE
ORGANICZNEJ, POLIMERÓW W ROLI PREKURSORÓW NOWYCH MATERIAŁÓW, CHIRALNYCH ZWIĄZKÓW
ORGANICZNYCH
K. Michał PIETRUSIEWICZ, Oleg DEMCHUK, Katarzyna SZWACZKO,
Anna FLIS and Elżbieta ŁASTAWIECKA
DEPARTMENT of ORGANIC CHEMISTRY
Enantiomerically pure P-stereogenic 1,2-diphosphines have gained prominence
among the chiral auxiliary ligands in asymmetric catalysis involving transition
metal complexes. The five-membered ring motif included in the structure of the
most successful ligands of this type led us to develop a new route to such five-
membered ring systems. The route was based on the ring-opening cross-metathesis
of a variety of olefins with readily available enantiopure NORPHOS leading to
substituted divinylcyclopentane-1,2-diphosphine products. Efforts to construct
polymeric ligands of that type by supposedly straightforward ring-opening
metathetic polymerization (ROMP) of parent NORPHOS proved however
unsuccessful. Instead, an alternative approach via ROM reactions of NORPHOS
utilizing ring brominated styrenes as the olefinic cross-partners was developed. The
ROM products, such as 1, could then serve as the monomers in their Suzuki-
Miyaura polymerization with the suitable bis(boronic acid) co-monomers. An
example of such synthesis of polymeric ligands utilizing dibromostyrene ROM
product 1 and 4,4’-biphenylenediboronic acid as substrates in the presence of
palladium catalyst together with the X-ray structure of 1 is shown below.
The absolute stereochemistry of the substarte and, consequently, also the
ligand was established by X-ray single crystal analysis of 1.
PPh2Ph2P
O O
Br
Br DMF, Cs2CO3, 150 oC
S-Phos (7.5 mol-%), Pd(OAc)2 (2.5 mol-%)
(HO)2B B(OH)2
PPh2
PPh2
*
*
n
1)
2) H2, Pd/C3) HSiCl3, Et3N1
F.Ch. UMCS Report 2009 (Grants) – 197 –
P
OPh
The resulting polymeric product of
poly(terphenyl) skeleton (Mn = 12 000, n = 16,
Mn/Mw = 1,3) contained the desired chiral
cyclopentane-1,2-diphosphine chelating units and
had all the features of an excellent chiral ligand.
For realization of another part of the project
related to five-membered phosphine ligands an
unknown 1-phenyl-2-vinylphospholane oxide (3) was
needed as the key substrate in the enantiomerically
pure form.
PPh O
PPh O
2 3
?
In view of the fact that the
corresponding 1-phenyl-2-methylene-
phospholane oxide (2) was already
available in our lab, we decided to
search for a process which could secu-
re conversion of 3 into 2 and, in general, a homologation of a vinyl phosphine oxide
into an allylphosphine oxide.
A two-step process consisting in the first step of treatment of a vinylphosphine
oxide with triphenylphosphine in the presence of tetrafluoroboric acid and of
reacting the resulting phosphonium salt with a strong base and formaldehyde in the
second step was developed. The whole transformation is delineated below.
P
O
R1
R2
P
O
R1
R2
P
O
R1
R2
PPh3
-BF4
+HBF4
EtOH
PPh3 TMPLi
(CH2O)n
The developed process is general and can be applied to almost any
vinylphosphine oxide. When applied to enantiomerically pure vinylphopshine
oxides it produces enantiomerically pure allylphosphine oxides with full retention
of configuration at P.
[α ]D = -21.03 (c 1.3,
MeOH)
Sp
2 : 1 Sp
[α ]D = +87.69 [α ]D = +14.58 [α ]D = -30.37(c 1,08, CHCl3)
(c 0.715, CHCl3) (c 0.72,CHCl3)
Me P
Ph
O PPh3, HBF4, P
Ph
O
MeEtOH
P
Ph
O
PPh3BF4Me
+ _ 1. K2CO3, 2. (CH2O)n
tp. 12h
82% 94%
P
OPh
Department of Organic Chemistry – 198 –
The examples of the synthesized new enantiomerically pure allylphosphine
oxides, acyclic and cyclic, are shown in the scheme above.
Grant PBZ-KBN-118-T09-14 (completed in May 21, 2009)
F.Ch. UMCS Report 2009 (Grants) – 299 –
FROM STUDENT TO EXPERT – ENVIRONMENTAL
PROTECTION IN PRACTICE
Adam LESIUK, Marcin KUŚMIERZ*,
Joanna STRUBIŃSKA**
and Bożena CZECH*
DEPARTMENT OF CHEMICAL TECHNOLOGY
*DEPARTMENT OF ENVIRONMENTAL CHEMISTRY
**DEPARTMENT OF CELL BIOLOGY,
FACLUTY OF BIOLOGY AND EARTH SCIENCES, UMCS, LUBLIN
Educational project From student to expert – environmental protection in
practice is co-financed by European Social Fund within the framework of
Operational Programme Human Capital. The project has been implemented and
realized at the Faculty of Chemistry, University of Maria Curie-Skłodowska in
Lublin since 1st september 2009 and finishes on 30
th september 2015. Three main
objectives of the project are specified below:
1. Increase in number of students of Environmental Protection in University
of Maria Curie-Skłodowska.
2. Increase in number of graduates of Environmental Protection.
3. Increse the chances of graduates on job market.
These goals are realized through the integration of theoretical and practical
knowledge. Nine forms of support are offered to the students:
1. Scholarship programme.
2. Tutorial course in mathematics.
3. Tutorial course in chemistry.
4. Course in mental skills training.
5. Educational trips to industrial plants, mines (etc.) and fairs devoted to
environmental protection.
6. Educational trips devoted to environmental monitoring.
7. Apprenticeships in selected firms and departments of administration in
Lublin.
8. Administrative aspects and tasks in environmental protection (course).
9. Environmental management ISO/EMAS (course).
In the present academic year (fall of december 2009) first forementioned
objective has been accomplished, three support forms (No 2, 3, 5) have been
completed and one (No 1) is still in progress. Sixty six students already benefited
from the project. More detailed information is available in the project web site
(http://osde.umcs.lublin.pl).
PART 4
PUBLICATIONS
F.Ch. UMCS Report 2009 – 203 –
Department of General and Coordination Chemistry 1. R. Łyszczek, Thermal investigation and infrared evolved gas analysis of light
lanthanide(III) complexes with pyridine-3,5-dicarboxylic acid, J. Anal. Appl.
Pyrolysis, 86 (2009) 239.
2. A. Dziadoń, M. Konieczny, M. Gajewski, M. Iwan, Z. Rzączyńska,
Microstructure evolution at the Cu-Ti interface during high temperature
synthesis of copper-intermetallic phases layered composite, Archives of
Metallurgy and Materials, 54 (2009) 455.
3. M. Barczak, A. Dąbrowski, M. Iwan, Z. Rzączyńska, Mesoporous
organosilicas functionalized by alkyl groups: synthesis, structure and adroption
properties, J. Physics: Conference Series, 146 (2009) 012002.
4. A. Dziewulska-Kułaczkowska, W. Ferenc, Thermal and spectra properties of
di- and trimethoxybenzoates of silver(I), Ecl. Quim., 34( 1) (2009) 63.
5. A. Dziewulska-Kułaczkowska, L. Mazur, W. Ferenc, Thermal, spectroscopic
and structural studies of zinc(II) complex with nicotinamide, J. Therm. Anal.
Cal., 96 (2009) 255.
6. B. Cristóvão, W. Ferenc, Synthesis and magnetic studies of copper(II)-
lanthanide(III) 5-bromosalicylideneglycylglycine, Ecl. Quim., 34( 1) (2009) 25.
7. M. Pitucha, Z. Rzączyńska. L. Mazur, Synthesis and structural studies of (R)-
(+)-1-[(1-methylpyrrol-2-yl)acetyl]-4-(1-phenylethyl)semicarbazide, Analytical
Sciences: X-ray Structure Analysis Online, 25(6) (2009) 67.
8. A. Pachuta-Stec, J. Rzymowska L. Mazur E. Mendyk M. Pitucha Z.
Rzączyńska, Synthesis, structure elucidation and antitumour activity of N-
substituted amides of 3-(3-ethylthio-1,2,4-triazol-5-yl)propenoic acid,
European Journal of Medicinal Chemistry 44 (9) (2009) 3788.
9. Z. Rzączyńska, J. Sienkiewicz–Gromiuk, H. Głuchowska, Structural and
thermal properties of rare earth complexes with 2,2’–biphenyldicarboxylic
acid, J. Therm. Anal. Cal., DOI 10.1007/s10973-009-0326-7.
10. M. Kalinowska, R. Świsłocka, Z. Rzączyńska, J. Sienkiewicz, W.
Lewandowski, Spectroscopic (FT-IR, FT-Raman, UV and 1H,
13C NMR) and
theoretical studies of m-anisic acid and lithium, sodium, potassium, rubidium
and ceasium m-anisates, Journal of Physical Organic Chemistry, DOI
10.1002/poc.1581.
11. W. Ferenc, A. Dziewulska-Kułaczkowska, Badania spektroskopowe 3,5-
dimetoksy- oraz 3,4,5-trimetoksybenzoesanów Co(II), Ni(II) i Cu(II),
Materiały: Nauka i przemysł-metody spektroskopowe w praktyce, nowe
wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-
227-2934-2) pp. 377-380.
Publications – 204 –
12. W. Ferenc, B. Cristóvão, Synteza oraz badanie właściwości fizykochemicznych
kompleksów kwasu 5-chloro-2-nitrobenzoesowego z wybranymi pierwiastkami
d-elektronowymi, Materiały: Nauka i przemysł-metody spektroskopowe w
praktyce, nowe wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009,
(ISBN 978-83-227-2934-2), pp. 372-376.
13. W. Ferenc, M. Bernat, Analiza spektroskopowa 4-chlorofenoksyoctanów
Mn(II), Co(II), Ni(II), Cu(II), Nd(III), Gd(III), Ho(III), Materiały: Nauka i
przemysł-metody spektroskopowe w praktyce, nowe wyzwania i możliwości.
UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-2) pp. 381-
385.
14. J. Sienkiewicz-Gromiuk, Z. Rzączyńska, Widma doświadczalne i teoretyczne
(IR, Ramana) kwasu 4,4’-bifenylodikarboksylowego, Materiały: Nauka i
przemysł-metody spektroskopowe w praktyce, nowe wyzwania i możliwości.
UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-2) pp. 446-
449.
15. A. Danczowska-Burdon, I. Rusinek, Z. Rzączyńska, Spektroskopia IR w
badaniu typu wiązań w związkach koordynacyjnych pierwiastków ziem
rzadkich z kwasem 2,4-pirydynodikarboksylowym, Materiały: Nauka i
przemysł-metody spektroskopowe w praktyce, nowe wyzwania i możliwości.
UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-2) pp. 450-
454.
16. M. Kalinowska, R. Świsłocka, W. Lewandowski, W. Ferenc, Wpływ
wybranych jonów metali przejściowych na strukturę i rozkład ładunku
elektronowego kwasu cynamonowego, Materiały: Nauka i przemysł-metody
spektroskopowe w praktyce, nowe wyzwania i możliwości. UMCS, Wydział
Chemii, Lublin 2009, (ISBN 978-83-227-2934-2) pp. 129-135.
Department of Inorganic Chemistry 1. D. Kołodyńska, H. Hubicka, Z. Hubicki, Studies of application of
monodisperse anion exchangers in sorption of heavy metal complexes with
IDS, Desalination, 239 (2009) 216.
2. D. Kołodyńska, Żywice chelatujące w procesie usuwania jonów metali
ciężkich w obecności czynnika kompleksującego z wód i ścieków, Przemysł
Chemiczny, 88 (2009) 182.
3. D. Kołodyńska, H. Hubicka, Polyacrylate anion exchangers in sorption of
heavy metal ions with non-biodegradable complexing agents, Chemical
Engineering Journal, 150 (2009) 308.
4. D. Kołodyńska, Polyacrylate anion exchangers in sorption of heavy metal ions
with the biodegradable complexing agent, Chemical Engineering Journal, 150
(2009) 280.
F.Ch. UMCS Report 2009 – 205 –
5. D. Kołodyńska, E. Skwarek, Z. Hubicki, W. Janusz, The effect of adsorption of
Pb(II) and Cd(II) ions in the presence of EDTA on characteristic of electrical
double layer at the ion exchanger/NaCl electrolyte solution interface, Journal
of Colloid and Interface Science, 333 (2009) 448.
6. D. Kołodyńska, Iminodisuccinic acid as a new complexing agent for removal
of heavy metal ions form industrial effluents, Chemical Engineering Journal,
152 (2009) 277.
7. D. Kołodyńska, Z. Hubicki, S. Pasieczna-Patkowska, FT-IR/PAS studies of
Cu-EDTA complexes sorption on chelating ion exchanger, Acta Physica
Polonica A, 116 (2009) 340.
8. G. Wroński, A. Dębczak, Z. Hubicki, Application of the FT-IR/PAS Method in
Comparison οf Ga(III) and In(III) Sorption on Lewatit OC-1026 and Amberlite
XAD-7 Impregnated D2EHPA, Acta Physica Polonica A, 116 (2009), 435.
9. A. Łodyga, A. Turczyn, Z. Hubicki, Technologia produkcji węglanu guanidyny
o wysokiej czystości, Przemysł Chemiczny, 88 (2009) 1343.
10. Z. Hubicki, E. Zieba, G. Wojcik, J. Ryczkowski, FT-IR/PAS and SEM EDX
Studies on Aluminosilicates Modified by Cs(I), Th(IV) and U(VI), Acta
Physica Polonica A, 116 (2009) 312.
11. P. Rusek, Z. Hubicki, G. Wójcik, A. Debczak, Application of the FT-IR/PAS
and DRS Methods for Studying Heavy Metal Ions Sorption on the Inorganic
Sorbents, Acta Physica Polonica A, 116 (2009) 407.
12. G. Wójcik, Z. Hubicki, J. Ryczkowski Investigations of Chromium(III) and
(VI) Ions Sorption on SIR by using Photoacoustic and DRS Methods, Acta
Physica Polonica A, 116 (2009) 432.
13. P. Rusek, Z. Hubicki, G. Wójcik Zastosowanie metod FT-IR PAS do badań
procesów sorpcji jonów metali ciężkich i amonu na naturalnych sorbentach
nieorganicznych z wód osadowych z komunalnych oczyszczalni ścieków,
Materiały: Nauka i przemysł-metody spektroskopowe w praktyce, nowe
wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-
227-2934-2) 432.
14. B. Czech, S. Pasieczna-Patkowska, G. Wójcik, Usuwanie zanieczyszczeń
organicznych z wód i ścieków w reaktorze wstęgowym, Materiały VI
Kongresu Technologii Chemicznej, 21-25 czerwca 2009 r.,Warszawa, Chemik
6, 2009, Suplement, Tom 2, (PL ISSN 0009-2886) 233.
15. M. Wawrzkiewicz, Z. Hubicki Application of nitroso-R-salt in modification of
strongly basic anion-exchangers Amberlite IRA-402 and Amberlite IRA-958,
Desalination, 249 (2009) 1228.
16. M. Leszczyńska, Z. Hubicki Application of weakly and strongly basic anion
exchangers for the removal of brilliant yellow from aqueous solutions
Desalination and Water Treatment, 2 (2009) 156.
17. M. Wawrzkiewicz, Z. Hubicki Kinetics of adsorption of sulphonated azo dyes
on strong basic anion exchangers, Environmental Technology, 30(10) (2009)
1059.
Publications – 206 –
18. M. Wawrzkiewicz, Z. Hubicki Removal of tartrazine from aqueous solutions
by strongly basic polystyrene anion exchange resins, Journal of Hazardous
Materials, 164 (2009) 502.
19. M. Wawrzkiewicz, Z. Hubicki Equilibrium and kinetic studies on the
adsorption of acidic dye by the gel anion exchanger, Journal of Hazardous
Materials, 172 (2009) 868.
20. M. Wawrzkiewicz, Z. Hubicki Kinetic studies of dyes sorption from aqueous
solutions onto the strongly basic anion-exchanger Lewatit MonoPlus M-600,
Chemical Engineering Journal, 150 (2009) 509.
21. M. Wawrzkiewicz, Z. Hubicki Equilibrium and kinetic studies on the sorption
of acidic dye by macroporous anion exchanger, Chemical Engineering Journal,
(2009), doi:10.1016/j.cej.2009.10.041.
22. Z. Hubicki, A. Wołowicz, M. Wawrzkiewicz Application of commercially
available anion exchange resins for preconcentration of palladium(II)
complexes from chloride–nitrate solutions, Chemical Engineering Journal,
150(1) (2009) 96.
23. A. Wołowicz, Z. Hubicki, Palladium(II) complexes adsorption from the
chloride solutions with macrocomponent addition using strongly basic anion
exchange resins, type 1, Hydrometallurgy, 98 (2009) 206.
24. Z. Hubicki, A.Wołowicz, A comparative study of chelating and cationic ion
exchange resins for the removal of palladium(II) complexes from acidic
chloride media, Journal of Hazardous Materials, 164 (2009) 1414.
25. A.Wołowicz, Z. Hubicki, Sorption of palladium(II) complexes onto the
styrene-divinylbenzene anion exchange resins, Chemical Engineering Journal,
152 (2009) 72.
26. Z. Hubicki, A. Wołowicz, Adsorption of palladium(II) from chloride solutions
on Amberlyst A 29 and Amberlyst A 21 resins, Hydrometallurgy, 96 (2009)
159.
27. M. Greluk, Z. Hubicki, Sorption of SPADNS azo dye on polystyrene anion
exchangers: Equilibrium and kinetic studies, Journal of Hazardous Materials,
172 (2009) 289.
28. Z. Hubicki, M. Wawrzkiewicz, A. Wołowicz, Application of ion exchange
methods in recovery of Pd(II) ions – a review, Chem. Anal., 53 (2008) 759.
29. M. Makarska, G. Pratviel, Long-range charge transport through double-
stranded DNA mediated by manganese- or iron-porphyrins, Journal of
Biological Inorganic Chemistry, 13(6) (2008) 973.
30. M. Majdan, E. Sabah, M. Bujacka, Właściwości adsorpcyjne sepiolitu,
Przemysł Chemiczny, 87/10 (2008) 1022.
31. M. Majdan, M. Bujacka, E. Sabah, A. Gładysz-Płaska , S. Pikus, D. Sternik ,
Z. Komosa, A. Padewski, Unexpected difference in phenol sorption on PTMA-
and BTMA-bentonite, J. Environ. Manage, 91(1) (2009) 195.
32. A. Gajowiak, M. Majdan, K. Drozdzal, Sorption of uranium(VI) on clays and
clay minerals, Przemysł Chemiczny, 88(2) (2009) 190.
33. E. Sabah, M. Majdan, Removal of phosphorus from vegetable oil by acid-
activated sepiolite, J. Food. Eng., 91(3) (2009) 423.
F.Ch. UMCS Report 2009 – 207 –
34. M. Majdan, E. Sabah, M. Bujacka, S. Pikus, A. Gładysz-Płaska, Spectral and
equillibrium properties of phenol–HDTMA- and phenol–BDMHDA-bentonite
as a response to the molecular arrangements of surfactant cations, J. Mol.
Struct., 938 (2009) 29.
Department of Analytical Chemistry and Instrumental Analysis 1. D. Gugała-Fekner, D. Sieńko, J. Nieszporek, M. Klin and J. Saba, Mixed
adsorption layers of 0.1M tert–butanol–tetramethylthiourea at the interface of
Hg/aqueous perchlorate solutions, Journal of Colloid and Interface Science,
332 (2009) 291.
2. D. Sieńko, D. Gugała-Fekner, J. Nieszporek, Zygmunt Fekner and J. Saba,
Adsorption of tetramethylthiourea in concentrated NaClO4 solutions, Collect.
Czech. Chem. Commun., 74 (2009) 1309.
3. A. Nosal–Wiercińska and G. Dalmata, The application of catalytic properties
of N–methylthiourea to the determination of In(III) at low levels by square
wave voltammetry, Monatsh. Chem. 140 (2009) 1421.
4. S. Skrzypek, A. Nosal-Wiercińska and W. Ciesielski, Electrochemical studies
of ganciclovir as the adsorbed catalyst on mercury electrode, Collect. Czech.
Chem. Commun., 74 (2009) 1455.
5. D. Gugała-Fekner, Z. Fekner, J. Nieszporek, D. Sieńko and J. Saba, Adsorption
of tert–butyl alcohol at the Hg/aqueous perchlorate interface in the presence of
tetramethylthiourea, Collect. Czech. Chem. Commun., 74 (2009) 1517.
6. K. Tyszczuk, M. Korolczuk, Application of an in situ plated electrode to the
determination of glipizide in pharmaceutical formulation, Chemical Analysis
(Warsaw), 54 (2009).
7. K. Tyszczuk, M. Korolczuk, New protocol for determination of rifampicine by
adsorptive striping voltammetry, Electroanalysis, 21 (2009) 101.
8. K. Tyszczuk, I. Rutyna, M. Korolczuk, Determination of trace of cobalt in
complex matrixes by catalytic adsorptive stripping voltammetry at a lead film
electrode Electroanalysis, 21 (2009) 779.
9. M. Korolczuk, A. Stępniowska, K. Tyszczuk, Determination of cadmium by
stripping voltammetry at a lead film electrode, International Journal of
Environmental Analytical Chemistry, 89 (2009) 727 .
10. K. Tyszczuk, M. Korolczuk, Voltammetric methods for the determination of
sildenafil citrate (Viagra) in pure form and in pharmaceutical formulations,
Bioelectrochemistry, (2009), doi:10.1016/j.bioelectrochem.2009.08.005.
11. M. Grabarczyk, M. Korolczuk, Development of a simple and fast voltammetric
procedure for determination of trace quantity of Se(IV) in natural lake and river
water samples, J. Hazard. Mater., doi:10.1016/j.jhazmat.2009.10.110.
12. M. Grabarczyk, B. Baś, M. Korolczuk, Application of a renewable silver based
mercury film electrode to the determination of Cr(VI) in soil samples,
Microchim. Acta, 164 (2009) 465.
Publications – 208 –
13. C. Wardak, Ionic liquids as new lipophilic additives to the membrane of lead
ion-selective electrodes with solid contact, International Journal of
Environmental Analytical Chemistry, 89 (2009) 735.
14. K. Tyszczuk, Sensitive voltammetric determination of rutin at an in situ plated
lead film electrode, Journal of Pharmaceutical and Biomedical Analysis, 49
(2009) 558.
15. B. Marczewska, M. Przegaliński, O–Aminofenol właściwości i zastosowanie,
Wiadomości Chemiczne, 63 (2009).
16. I. Malinowska, B. Marczewska, Zastosowanie metod spektroskopowych w
analizie TLC, Materiały: Nauka i przemysł-metody spektroskopowe w
praktyce, nowe wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009,
(ISBN 978-83-227-2934-2), 75.
17. B. Marczewska, A. Persona, T. Gęca, D. Smolarz, Wyznaczanie parametrów
fizykochemicznych kwasów fenolowych w aspekcie ich aktywności
biologicznej, Materiały: Nauka i przemysł-metody spektroskopowe w praktyce,
nowe wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009, (ISBN
978-83-227-2934-2), 87.
18. R. Dobrowolski, M. Otto, A. Adamczyk, Wysokorozdzielcza absorpcyjna
spektrometria atomowa – charakterystyka analityczna metody, Materiały:
Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości. UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-
2) 99.
19. M. Otto, R. Dobrowolski, A. Adamczyk, J. Reszko-Zygmunt, Oznaczanie
selenu po wstępnym wzbogaceniu na węglach aktywnych z wykorzystaniem
techniki dozowania zawiesiny do atomizera elektrotermicznego, Materiały:
Nauka i przemysł-metody spektroskopowe w praktyce, nowe wyzwania i
możliwości. UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-
2) 112.
20. R. Dobrowolski, M. Marzec, Specjacja w środowisku glebowym, w monografii
„Specjacja Chemiczna – Problemy i możliwości”, (D. Barałkiewicz, E. Bulska,
Eds.), Wydawnictwo Malamut, 2009, pp. 81–96.
21. R. Dobrowolski, M. Skowrońska, M. Marzec, Badanie form specjacyjnych
cynku w glebach Parków Narodowych południowo–wschodniej Polski z
zastosowaniem ekstrakcji sekwencyjnej, w monografii „Specjacja Chemiczna
– Problemy i możliwości”, (D. Barałkiewicz, E. Bulska, Eds.), Wydawnictwo
Malamut, 2009, pp. 96–104.
22. A. Kaczor, D. Matosiuk, A. Persona, Teaching protein science with application
of computer – case study of BCL-2 protein family, Problems of Education in
21st Century, 11 (2009) 69.
23. M. Persona, A. Persona, T. Gęca, A. Kaczor, D. Matosiuk, Computers In
medicinal chemistry, molecular modeling and calculation of the structure-
correlated parameters describing skin permeability of theaflavonoids, Problems
of Education in 21st Century, 11 (2009) 139.
F.Ch. UMCS Report 2009 – 209 –
Department of Interfacial Phenomena 1. K. Szymczyk, B. Jańczuk, Thermodynamics of micellization of aqueous
solutions of binary mixtures of two anionic surfactants, Langmuir, 25(8) (2009)
4377.
2. K. Szymczyk, B. Jańczuk, A study of the interaction of ternary surfactant
systems at the water-air interface, Langmuir, doi: 10.1021/la9027173.
3. A. Zdziennicka, Surface behavior of Triton X-165 and short chain alcohol
mixtures, Langmuir, doi: 10,1021/la902618c
4. A. Zdziennicka, The adsorption properties of short chain alcohols and Triton
X-100 mixtures at the wataer-air interface, J. Colloid Interface Sci., 335 (2009)
175.
5. A. Zdziennicka, Adsorption and volumetric properties of Triton X-100 and
propanol mixtures, J. Colloid Interface Sci., 336 (2009) 423.
6. A. Zdziennicka, K. Szymczyk, B. Jańczuk, Correlation between surface free
energy of quartz and its wettability by aqueous solutions of nonionic, anionic
and cationic surfactants, J. Colloid Interface Sci., 340 (2009) 243.
7. A. Zdziennicka, B. Jańczuk, Wettability of quartz in presence of nonionic
surfactants and short chain alcohols mixtures, J. Colloid Interface Sci., doi:
10.1016/j.jcis.2009.11.067.
8. J. Harkot, B. Jańczuk, Surface and volume properties of dodecylethyldimethyl-
ammonium bromide and benzyldimethyldodecylammonium bromide i: surface
properties of dodecylethyldimethylammonium bromide and benzyldimethyl-
dodecylammonium bromide, J. Colloid Interface Sci., 331 (2009) 494.
9. J. Harkot, B. Jańczuk, Surface and volume properties of dodecylethyldimethyl-
ammonium bromide and benzyldimethyldodecylammonium bromide ii:
volumetric properties of dodecylethyldimethylammonium bromide and benzyl-
dimethyldodecylammonium bromide, J. Colloid Interface Sci., 330 (2009) 467.
10. K. Szymczyk, B. Jańczuk, Adsorption of binary mixtures of anionic surfactants
at water-air and poly(tetrafluoroethylene)-water interfaces, J. Surfact. Deterg. doi: 10.1007/s11743-009-1146-2.
11. J. Harkot, B. Jańczuk, The role of adsorption of dodecylethyldimethyl-
ammonium bromide and benzyldimethyldodecylammonium bromide surfac-
tants in wetting of polytetrafluoro-ethylene and poly(methyl methacrylate)
surfaces, Appl. Surface Sci., 255 (2009) 3623.
12. A. Zdziennicka, The wettability of polytetrafluoroethylene and
polymethylmethacrylate by aqueous solutions of Triton X-100 and propanol
mixtures, Appl. Surface Sci., 255 (2009) 3801.
13. A. Zdziennicka, The wettability of polytetrafluoroethylene and polymethyl-
methacrylate by aqueous solutions of Triton X-100 and short chain alcohol
mixtures, Appl. Surface Sci., 255 (2009) 7369.
14. E. Chibowski, K. Terpiłowski, Surface free energy of polypropylene and
polycarbonate solidifying at different solid surfaces, Appl. Surface Sci., 256
(2009) 1573.
Publications – 210 –
15. T. Białopiotrowicz, Influence of erroneous data on results in Acid-Base Surface
Free Energy Theories Calculations. III. Solution of a three-equation set in the
case of homoscedastic error, J. Adhesion Sci. Technol., 23 (2009) 799.
16. T. Białopiotrowicz, Influence of erroneous data on results in Acid-Base Surface
Free Energy Theories Calculations. IV. Solution of an overdetermined set in
the case of homoscedastic error, J. Adhesion Sci. Technol., 23 (2009) 815.
17. M. Jurak, E. Chibowski, Surface free energy and topography of mixed lipid
layers on mica, Colloids and Surfaces B: Biointerfaces (2009),
doi:10.1016/j.colsurfb.2009.08.034
18. A.E. Wiącek, Electrokinetic properties of n-tetradecane/ethanol emulsions with
DPPC and enzyme Lipase or Phospholipase A2, Colloids Surf. A, 332 (2009)
150.
19. E. Chibowski, K. Terpiłowski, Comparison of apparent surfach free energy of
some solids determined by different approaches, Contact Angle, Wettability
and Adhesion (K. L. Mittal Ed.), Vol. 6, Boston, 2009, p. 283.
20. A. Szcześ, Influence of the surfactant nature on the calcium carbonate synthesis
in water-in-oil emulsion, J. Crystal Growth, 311 (2009) 1129.
21. M. Jurak, E. Chibowski, Zeta potential and surface free energy changes of solid
supported phospholipid (DPPC) layers caused by the enzyme phospholipase
A2 (PLA2), Adsorption, 15 (2009) 211.
Department of Adsorption
1. J. Goworek, R. Zaleski, A. Borówka, R. Kusak, A. Kierys, Pore structure and
morphology of mesoporous silicate and aluminosilicate molecular sieves by
nitrogen adsorption, AFM and PALS, in: Characterization of Porous Solids
VIII, (S. Kaskel, P. Llewellyn, F. Rodriguez-Reinoso, Eds.), RSC Publishing,
Special Publications, Vol. 318, London, 2009, p. 303.
2. R. Zaleski, J. Goworek, A. Borówka, A. Kierys, M. Wiśniewski, Positron
Porosimetry Study of Mechanical Stability of Ordered Mesoporous Materials,
in: Characterization of Porous Solids VIII, (S. Kaskel, P. Llewellyn, F.
Rodriguez-Reinoso, Eds.), RSC Publishing, Special Publications, Vol. 318,
London, 2009, p. 400.
3. A. Dąbrowski, E. Robens, E. Mendyk, A. Bischoff, A. Schreiber, W. Gac, M.
Dumanska-Slowik, K. Skrzypiec, J. Goworek, Determination of Surface Area,
Porosity and Surface Properties of Lunar Regolith, in: Characterization of
Porous Solids VIII, (S. Kaskel, P. Llewellyn, F. Rodriguez-Reinoso, Eds.),
RSC Publishing, Special Publications, Vol. 318, London, 2009, p. 362.
4. J. Goworek, A. Kierys, W. Gac, A. Borówka, R. Kusak, Thermal degradation of
CTAB in as-synthesized MCM-41, J. Therm. Anal. Cal., 96 (2009) 375.
5. R. Zaleski, J. Goworek , M. Maciejewska,
Positronium lifetime in porous VP-
DVB copolymer, Physica Status Solidi C, 6 (2009) 2445.
6. R. Zaleski, W. Stefaniak, M. Maciejewska, J. Goworek, Porosity of polymer
materials by various techniques, J. Por. Mater., 16 (2009) 691.
F.Ch. UMCS Report 2009 – 211 –
7. R. Zaleski, J. Goworek, n-Nonadecane embedded in mesopores, Mater. Sci.
Forum, 607 (2009) 180.
8. R. Zaleski, W. Stefaniak, M. Maciejewska, J. Goworek, Porosity evolution of
VP-DVB/MCM-41 nanocomposite, J. Coll. Interf. Sci., (2009) doi:10.1016/
j.jcis.2009.11.019.
9. A. Kierys, W. Buda, J. Goworek, The porosity and morphology of mesoporous
silica agglomerates, J. Por. Mater., (2009), doi:10.1007/s10934-009-9337-9.
Department of Planar Chromatography 1. T. Djaković-Sekulić, A. Smolinski, N. Perisić-Janjić, M. Janicka, Chemometric
characterization of (chromatographic) lipophylicity parameters of newly
synthesized s-triazine derivatives, J. Chemometrics, 22 (2008) 195.*
2. M. Janicka, Application of Ościk’s equation for description of solute retention
in RP HPLC and calculation of retention factor in water, J. Liq. Chromatogr.
Rel. Technol., 32 (2009) 2779.
3. I. Malinowska, B. Marczewska, Zastosowanie metod spektroskopowych w
analizie TLC, Materiały: Nauka i przemysł-metody spektroskopowe w
praktyce, nowe wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009,
(ISBN 978-83-227-2934-2), 75.
4. E.M. Grzelak, I.Malinowska, I. Choma, Determination of Cefacetrile and
Cefuroxime Resitues in Milk by Thin-Layer Chromatography, J. Liquid
Chromatogr & Related Technol., 32 (2009) 2043.
5. M. Krauze-Baranowska, I.Malinowska, D. Głód, M. Majdan, A. Wilczyńska,
UTLC of flavonols from flowers of Sambucus nigra, Journal of Planar
Chromatography, 22 (2009) 385.
*Edited in 2009.
Department of Physicochemistry of Solid Surface
1. A.W. Marczewski, A. Deryło-Marczewska, I. Skrzypek, S. Pikus, M. Kozak,
Study of structure properties of organized silica sorbents synthesized on
polymeric templates, Adsorption, 15 (2009).
2. Derylo-Marczewska, A.W. Marczewski, Sz. Winter, and D. Sternik, Studies of
Adsorption Equilibria and Kinetics in the Systems: Aqueous Solution of Dyes –
Mesoporous Carbons, Appl. Surf. Sci., DOI:10.1016/j.apsusc.2009.12.085.
3. M. Majdan, M. Bujacka, E. Sabah, A. Gładysz-Płaska, S. Pikus, D. Sternik,
Z. Komosa, A. Padewski, Unexpected difference in phenol sorption on PTMA-
and BTMA-bentonite, Journal of Environmental Management, 91 (2009) 195.
Publications – 212 –
Department of Chromatographic Methods 1. A.L. Dawidowicz, E. Rado, D. Wianowska, Static and dynamic superheated
water extraction of essential oil components from Thymus vulgaris L., Journal
of Separation Science, 32(17) (2009) 3034.
2. L. Dawidowicz, D. Wianowska, Application of the MSPD technique for the
HPLC analysis of rutin in Sambucus nigra L. The linear correlation of the
MSPD process, Journal of Chromatographic Science, 47(10) (2009) 914.
3. A.L Dawidowicz, K. Kondzioła, M. Kobielski, Determination of Free
Indomethacin in Human Plasma Using HPLC with UV Detection, Journal
Liquid Chromatogr. and Related Technologies, 32(18) (2009) 2686.
4. D. Wianowska, M.Ł. Hajnos, A.L. Dawidowicz, A. Oniszczuk,
M. Waksmundzka-Hajnos, K. Głowniak, Extraction methods of 10-
deacetylbaccatin III, paclitaxel and cephalomannine from Taxus baccata L.
twigs: A comparison (Comparison of extraction methods), Journal of Liquid
Chromatography and Related Technologies, 32(4) (2009) 589.
5. A. Książek, P. Borowski, K. Woliński, Theoretical analysis of the solvent
effects on the nitrogen NMR chemical shifts in oxazols and oxadiazols, J.
Magn. Res., 197 (2009) 153.
6. M. Barczak, P. Borowski, A. Dąbrowski, Structure-adsorption properties of
ethylene-bridged polysilsesquioxanes and polysiloxanes functionalized with
different groups, Colloids and Surfaces A: Physicochem. Eng. Aspects, 347
(2009) 114.
7. P. Borowski, M. Fernández-Gómez, M. P. Fernández-Liencres, T. P. Ruiz and
M. Q. Rincón, An effective scaling frequency factor method for scaling of
harmonic vibrational frequencies: application to toluene, styrene and its 4-
methylderivative J. Mol. Struct., 924 (2009) 493.
8. M. Pitucha, P. Borowski, Z. Karczmarzyk, A. Fruziński, Synthesis,
experimental and theoretical investigations of some new 4,4’-bis(3-substituted-
4,5-dihydro-1H-1,2,4-triazol-5-one-4-yl)diphenylmethane derivatives J. Mol.
Struct., 919 (2009) 170.
9. M. Kamińska, I. Choma, Influence of Perchlorate Ion on the Retention of
Fluoroquinolones in RP-TLC, Journal of Liquid Chromatography & Related
Technologies, 32 (2009) 1331.
10. E.M. Grzelak, I. Malinowska, I. M. Choma, Determination of Cefacetrile and
Cefuroxime Residues in Milk by Thin-Layer Chromatography, Journal of
Liquid Chromatography & Related Technologies, 32 (2009) 2043.
11. P. Borowski, A. Drzewiecka, M. Fernández-Gómez, M. P. Fernández-Liencres,
T. P. Ruiz, A new, reduced set of scaling factors for both SQM and ESFF
calculations, Vib. Spect., doi:10.1016/j.vibspec.2009.09.004.
12. M. Struga, B. Mirosław, M. Pakosińska-Parys, A. Drzewiecka, P. Borowski, J.
Kossakowski, A.E. Kozioł, Synthesis, characterization and supramolecular
synthons in crystals of new derivatives of 10-oxa-4-azatricyclo[5.2.1.02,6]dec-
8-ene-3,5-dione, J. Mol. Struct., doi: 10.1016/j.molstruc.2009.11.028.
F.Ch. UMCS Report 2009 – 213 –
13. V.M. Gun'ko, R. Leboda, J. Skubiszewska-Zięba, Heating Effects on
Morphological and Textural Characteristics of Individual and Composite
Nanooxides, Adsorption, 15 (2009) 89.
14. V.V. Sydorchuk, V.A. Zazhigalov, S.V. Khalameida, K. Wieczorek-Ciurowa,
J. Skubiszewska-Zięba, R. Leboda Investigation of physicochemical
transformation at mechanochemical, hydrothermal and microwave treatment of
barium titanyloxalate., Journal of Alloys and Compounds, 482 (2009) 229.
15. V.V. Sydorchuk, V. Zazhigalov, S. Khalameida, J. Skubiszewska-Zięba,
B. Charmas, R. Leboda, Deposition of tungsten heteropolycompounds on
activated silica surface. Coll. Surf. A., 341 (2009) 53.
16. O. Makota, Yu. Trach, R. Leboda, J. Skubiszewska-Zięba, The study of
cyclooctene oxidation with molecular oxygen catalyzed by VSi2, Central
European Journal of Chemistry, 7(4) (2009) 731.
17. V.M. Gun’ko, V.M. Bpogatyrev, R. Leboda, J. Skubiszewska-Zięba, L.V.
Petrus, Y.M. Nychiporuk, O.I. Oranska, O.A. Dudarko, V.D. Osovski, Y.G.
Ptushinski, Titania deposits on nanosilicas, Annales Universitatis Mariae
Curie-Sklodowska Lublin-Polonia, LXIV, 3 (2009) 21.
18. A.Yu. Petin, V.M. Gun’ko, A.V. Turov, V.V. Turov, R. Leboda,
Clusterization of water at a surface of nanosilica A-380. Annales Universitatis
Mariae Curie-Sklodowska Lublin-Polonia, LXIV, 3 (2009) 184.
19. V.M. Gun'ko, V.I. Zarko, V.V. Turov, O.I. Oranska, E.V. Goncharuk, Y.M.
Nychiporuk, E.M. Pakhlov, G.R. Yurchenko, R. Leboda, J. Skubiszewska-
Zięba,V.D. Osovskii, Y.G. Ptushinskii, A.G. Derzhypolskyi, D.A. Melenevsky,
J.P. Blitz, Morphological and structural features of individual and composite
nanooxides with alumina, silica, and titania in powders and aqueous
suspensions, Powder Technology, 195 (2009) 245.
20. V.M. Gun'ko, V.I. Zarko, V.V. Turov, E.V. Goncharuk, Y.M.Nychiporuk, A.A.
Turova, P.P. Gorbik, R. Leboda, J. Skubiszewska-Zięba, P.Pissis, J.P. Blitz,
Regularities in the behaviour of nanooxides in different media affected by
surface structure and morphology of particles, in: Physicochemistry of
Nanomaterials and Supramolecular Structures, (A.P. Shpak, P.P. Gorbik, Eds.),
Springer, 2009, pp. 93-115.
21. V.V. Turov, V.M. Gun’ko, O.V. Nechypor, A.P. Golovan, V.A. Kaspersky,
A.V. Turov, R. Leboda, M. Jablonski and P.P. Gorbik Self-Organization of
Water–Organic Systems in Bone Tissue and Products of Its Chemical
Degradation, in: Physicochemistry of Nanomaterials and Supramolecular
Structures, (A.P. Shpak, P.P. Gorbik, Eds.), Springer, 2009, pp.79-92.
22. V.M. Bogatyrev, V.M. Gun’ko, M.V. Galaburda, M.V. Borysenko, V.A.
Pokrovskiy, O.I. Oranska, E.V. Polshin, O.M. Korduban, R. Leboda, J.
Skubiszewska-Zięba Synthesis and characterization of Fe2O3/SiO2 nanocom-
posites, J.Coll. Int. Science, 338 (2009) 376.
Publications – 214 –
Department of Theoretical Chemistry
1. W. Płazinski, W. Rudziński, Kinetics of adsorption at solid/solution interfaces
controlled by the intraparticle diffusion: a theoretical analysis, Journal of
Physical Chemistry C, 113 (2009) 12495.
2. W. Płaziński, W. Rudziński, Modeling the Effect of Surface Heterogeneity in
Equilibrium of Heavy Metal Ion Biosorption by Using the Ion Exchange
Model, Environmental Science and Technology, 43 (2009) 7465.
3. W. Płaziński, W. Rudziński, A. Plazińska, Theoretical models of sorption
kinetics including a surface reaction mechanism: A review, Advances in
Colloid and Interface Science, 152 (2009) 2.
4. K. Nieszporek, Application of the Statistical Rate Theory of interfacial
transport to investigate the kinetics of mixed-gas adsorption onto the
energetically homogeneous and strongly heterogeneous surfaces, Applied
Surface Science, 255(8) (2009) 4627.
5. K. Nieszporek, M. Drach, P. Podkościelny, Theoretical studies of hydrocarbon
homologous series adsorption on activated carbons: Adsorption equilibria and
calorimetry, Separation and Purification Technology, 69 (2009) 184.
6. M. Szymula, J. Narkiewicz-Michałek, Ascorbic Acid Oxidation in SDS
Micellar Systems, Journal of Applied Electrochemistry, 31 (2009) 681.
7. W. Nowicki, G. Nowicka, J. Narkiewicz-Michałek, Monte Carlo Study of the
Translocation of a polymer chain through a hole, Polymer, 50 (2009) 2161.
8. W. Nowicki, G. Nowicka, J. Narkiewicz-Michałek, Monte Carlo Study of the
Translocation of a polymer chain through a hole, European Polymer Journal,
46 (2010) 112.
9. J. Baker, K. Wolinski, M. Malagoli, D. Kinghorn, P. Wolinski, G. Magyarfalvi,
S. Saebo, T. Janowski, P. Pulay, Quantum Chemistry in parallel with PQS, J.
Comp. Chem., 30(2) (2009) 317.
10. A. Książek, P. Borowski, K. Wolinski, Theoretical analysis of the solvent
effects on the nitrogen NMR chemical shift in oxazoles and xadiazoles, J. Mag.
Res., 197(2) (2009) 153.
11. K.Wolinski, J. Baker, Theoretical predictions of enforced structural changes in
molecules, Mol. Phys., 107(22) (2009) 2403.
12. M. Barczak, A. Dąbrowski, M. Iwan, Z. Rzączyńska, Mesoporous
organosilicas functionalized by alkyl groups: synthesis, structure and
adsorption properties, Journal of Physics: Conference Series, 146 (2009)
012002.
13. M. Barczak, P. Borowski, A. Dąbrowski, Structure-adsorption properties of
ethylene bridged polysilsesquioxanes functionalized with different groups,
Colloids and Surfaces A Physicochemical Aspects, 347 (2009) 114.
14. M. Barczak, A. Dąbrowski, Synthesis and structure of ethylene bridged
polysilsesquioxanes functionalized with different groups, Annales UMCS, sect.
AA, LXIV (2009) 1.
F.Ch. UMCS Report 2009 – 215 –
15. M. Barczak, S. Pikus, B. Skrzydło-Radomańska, A. Dąbrowski, Synthesis,
structure and adsorption properties of nanoporous SBA-15 materials with
framework and surface functionalities, Adsorption, 15 (2009) 278.
16. V. Stolyarchuk, I.V. Melnyk, Yu.L. Zub, M. Barczak, A. Dąbrowski, B.
Alonso, Bridge polysilsesquioxane xerogels with a bifunctional surface layer of
the ≡Si(CH2)3NH2/≡Si(CH2)3SH composition, Protection of Metals and
Physical Chemistry of Surfaces, 45 (2009) 169.
Department for Modeling of Physico-Chemical Processes 1. M. Borówko, W. Rżysko, S. Sokołowski, T. Staszewski, Density functional
approach to adsorption and retention of spherical molecules on surfaces
modified with end-grafted polymers, J. Phys. Chem. B, 113 (2009) 4763.
2. S. Hlushak, W. Rżysko, S. Sokołowski, Density functional study of flexible
chain molecules at curved surfaces, J. Chem. Phys., 131 (2009) 094904.
3. Z. Sokołowska, P. Warchulska, S. Sokołowski, Trends in soil fractal
parameters caused by accumulation of soil organic matter as resulting from the
analysis of water vapor adsorption isotherms, Ecol. Complex, 6 (2009) 254.
4. S. Hlushak, A. Trokhymchuk, S. Sokołowski, Direct correlation function of the
square-well fluid with attractive well width up to two particle diameters,
J. Chem. Phys., 130 (2009) 234511.
5. L. Pusztai, H. Dominguez, O. Pizio, S. Sokołowski, Detailed structural analysis
of a 2 molal aqueous rubidium bromide solution: A combined molecular
dynamics and Reverse Monte Carlo approach, J. Mol. Liq., 147 (2009) 52.
6. O. Pizio, H. Dominguez, Y. Duda, S. Sokołowski, Microscopic structure and
thermodynamics of a core-softened model fluid: Insights from grand canonical
Monte Carlo simulations and integral equations theory, J. Chem. Phys., 130
(2009) 174504.
7. O. Pizio, H. Dominguez, L. Pusztai, S. Sokołowski, A core-softened fluid
model in disordered porous media. Grand canonical Monte Carlo simulation
and integral equations, Physica A, 388 (2009) 2278.
8. A. Patrykiejew, W. Rżysko, S. Sokołowski, Dynamics of monolayer films
formed on a substrate of square symmetry, Adsorption, 15 (2009) 254.
9. O. Pizio, L. Pusztai, Z. Sokołowska, S. Sokołowski, Solvation force between
surfaces modified by tethered chains: A density functional approach, J. Chem.
Phys., 130 (2009) 134501.
10. K. Bucior, A. Patrykiejew, S. Sokołowski, O. Pizio, Adsorption of chain
molecules in pores with crystalline walls: a density functional approach,
Condens. Matter Phys., 12 (2009) 51.
11. P. Bryk, M. Bryk, Effective interactions in polydisperse colloidal suspensions
investigated using Ornstein-Zernike integral equations, J. Colloid Interf. Sci.,
338 (2009) 92.
Publications – 216 –
12. M. Oettel, H. Hansen-Goos, P. Bryk, R. Roth, Depletion interaction of two
spheres-Full density functional theory vs. morphometric results, EPL-
Europhys. Lett., 85 (2009) 36003.
13. L. Sałamacha, A. Patrykiejew, S. Sokołowski, Ground-state properties of two-
dimensional symmetrical mixtures in an external field of square symmetry, J.
Phys. Chem. B, 113 (2009) 13687.
Department of Chemical Technology
1. Z. Hubicki, E. Zięba, G. Wojcik, J. Ryczkowski, FT-IR/PAS and SEM EDX
studies on aluminosilicates modified by Cs(I), Th(IV) and U(VI), Acta Phys.
Polonica A, 116 (2009) 312.
2. D. Kołodyńska, Z. Hubicki, S. Pasieczna-Patkowska, FT-IR/PAS Studies of
Cu(II)-EDTA Complexes Sorption οn the Chelating Ion Exchangers, Acta
Phys. Polonica A, 116 (2009) 340.
3. P. Rusek, Z. Hubicki, G. Wójcik, A. Dębczak, Application of the FT-IR/PAS
and DRS Methods for Studying Heavy Metal Ions Sorption on the Inorganic
Sorbents, Acta Phys. Polonica A, 116 (2009) 407.
4. G. Wójcik, Z. Hubicki, J. Ryczkowski, Investigations of chromium(III) and
(VI) ions sorption on SIR by using photoacoustic and DRS methods, Acta
Phys. Polonica A, 116 (2009) 432.
5. G. Wroński, A. Dębczak, Z. Hubicki, Application of the FT-IR/PAS Method in
Comparison of Ga(III) and In(III) Sorption on Lewatit OC-1026 and Amberlite
XAD-7 Impregnated D2EHPA, Acta Phys. Polonica A, 116 (2009) 435.
6. W. Gac, A. Denis, T. Borowiecki, L. Kępiński, Methane decomposition over
NiO-MgO-Al2O3 catalysts, Appl. Catal. A, 357 (2009) 236.
7. W. Grzegorczyk, A. Denis, W. Gac, T. Ioannides, A. Machocki, Hydrogen
Formation via Steam Reforming of Ethanol Over Cu/ZnO Catalyst Modified
with Nickel, Cobalt and Manganese, Catal. Lett., 128 (2009) 443.
8. A. Machocki, M. Rotko, W.Gac, Steady state isotopic transient kinetic analysis
of flameless methane combustion over Pd/Al2O3 and Pt/Al2O3 catalysts, Topics
in Catalysis, 52 (2009) 1085.
9. J. Goworek, A. Kierys, W. Gac, A. Borowka, R. Kusak, Thermal degradation
of CTAB in as-synthesized MCM-41, J. Therm. Anal. Calorim., 96 (2009) 375.
10. M. Rotko, A. Machocki, B. Stasińska, Wykorzystanie trwałych izotopów tlenu
(16
O2 i 18
O2) i węgla (12
C i 13
C) do badania katalitycznego procesu całkowitego
utleniania metanu, Przem. Chem., 88 (2009) 815.
11. M. Cichy, T. Borowiecki, Reforming parowy gliceryny, Przem. Chem., 88
(2009) 995.
12. B. Stasińska, S. Napieraj, Zagospodarowanie metanu z powietrza
wentylacyjnego kopalń węglowych, Przem. Chem., 88 (2009) 1121.
13. U. Prokop, E. Franczyk, W. Wróbel, A. Gołębiowski, T. Borowiecki,
Katalizatory do reaktora typu GHR, Przem. Chem., 88 (2009) 1292.
F.Ch. UMCS Report 2009 – 217 –
14. K. Stołecki, A. Gołębiowski, K. Michalska, T. Borowiecki, Przyczyny
dezaktywacji niklowego katalizatora uwodornienia benzenu w reaktorze
przemysłowym, Przem. Chem., 88 (2009) 1297.
15. M. Szukiewicz, K. Kaczmarski, K. Stołecki, A. Gołębiowski, T. Borowiecki,
R. Sylwestrowicz, Dezaktywacja niklowego katalizatora uwodornienia benzenu
w złożu przemysłowym, Przem. Chem., 88 (2009) 1302.
16. T. Borowiecki, M. Pańczyk, J. Ryczkowski, K. Stołecki, A. Gołębiowski,
Odporność na zawęglanie katalizatorów niklowych, Karbo, LIV(1) (2009) 39.
17. W. Próchniak, P. Kowalik, T. Borowiecki, Badania wpływu składu
chemicznego katalizatorów Cu-Zn-Al do parowego reformingu metanolu na
przebieg ich aktywacji termicznej, Karbo, LIV(1) (2009) 45.
18. M. Rotko, A. Machocki, B. Stasińska, Analiza kinetyczna izotopowych
zaburzeń w stanie ustalonym reakcji katalitycznej, Materiały: Nauka i
przemysł-metody spektroskopowe w praktyce, nowe wyzwania i możliwości.
UMCS, Wydział Chemii, Lublin 2009, (ISBN 978-83-227-2934-2), 290.
19. P. Rusek, Z. Hubicki, G. Wójcik, S. Pasieczna-Patkowska, Zastosowanie
metod FT-IR/PAS do badań procesów sorpcji jonów metali ciężkich i amonu
na naturalnych sorbentach nieorganicznych z wód osadowych z komunalnych
oczyszczalni ścieków, Materiały: Nauka i przemysł-metody spektroskopowe w
praktyce, nowe wyzwania i możliwości. UMCS, Wydział Chemii, Lublin 2009,
(ISBN 978-83-227-2934-2), 432.
20. A. Lesiuk, Wybrane metody badań odpadów komunalnych, in: Odpady i
opakowania – nowe regulacje i obowiązki – praktyczny poradnik dla
wytwórców i odbiorców odpadów i opakowań, (L. Wachowski, Ed.),
Wydawnictwo FORUM, 2009, (ISBN 978-83-260-0300-4), pp. 1–18.
21. M. Rotko, A. Machocki, B. Stasińska, Badania in situ bezpłomieniowego
katalitycznego spalania metanu, Chemik, 6 (2009) Suplement – VI Kongres
Technologii Chemicznej, Warszawa, 21-25.06.2009, vol. 2, pp. 393-396.
22. A. Machocki, Wodór z bio-etanolu. Efektywna droga produkcji wodoru na
nowych katalizatorach reformingu, Chemik, 6 (2009) Suplement – VI Kongres
Technologii Chemicznej, Warszawa, 21-25.06.2009, vol. 2, pp. 435-438.
Department of Radiochemistry and Colloid Chemistry
1. A. Komosa, E. Madej, M. Piekarz, Determination of a supported radon activity
concentration in bottled mineral waters. Chemia Analityczna – Chemical
Analysis, 53 (2008) 835-843.*
2. W. Janusz, A. Sędłak, M. Matysek-Nawrocka, Experimental study of
cadmium-citrate ions coadsorption onto TiO2 (anatase)/electrolyte solution
interface, Adsorption Sci. Technol., 26 (2008) 599.*
3. W. Zgłobicki, M. Kozieł, L. Lata, A. Plak, M.Reszka, Próba wykorzystania
wskaźników geograficznych do oceny natężenia współczesnej sedymentacji
deluwialnej i aluwialnej, Annales sectio B, LXIII (2008) 87.*
Publications – 218 –
4. St. Chibowski, E. Grządka, J. Patkowski, Influence of a Type of Electrolyte
and its Ionic Strength on the Adsorption and the Structure of Adsorbed
Polymer Layer in the System: Polyacrylic Acid/SiO2, Croatica Chemica Acta,
82 (2009) 623.
5. St. Chibowski, J. Patkowski, E. Grządka, Adsorption of polyethylenimine and
polymethacrylic acid onto synthesized hematite, Journal of Colloid and
Interface Science, 329 (2009) 1.
6. E. Grządka, S. Chibowski, Influence of a kind of electrolyte and its ionic
strength on the adsorption and zeta potential of the system: polyacrylic
acid/MnO2/electrolyte solution, Physicochemical Problems of Mineral
Processing, 43 (2009) 31.
7. J. Solecki, Migracja 90
Sr w układach glebowych, Wiadomości Chemiczne, 63
(2009) 7.
8. A. Komosa, K. Ślepecka, Study on quenching effect for 14
C and 3H
measurement parameters using a Quantulus spectrometer. LSC 2008, in:
Advances in Liquid Scintillation Spectrometry, (J. Eikenberg M. Jäggi, H.
Beer, H. Baehrle, Eds.), Radiocarbon, Tucson, USA 2009, pp. 161-172.
9. A. Komosa, M. Piekarz, Study on migration rate of beta-radiating 241
Pu in soils
using liquid scintillation spectrometry. LSC 2008, in: Advances in Liquid
Scintillation Spectrometry, (J. Eikenberg M. Jäggi, H. Beer, H. Baehrle, Eds.),
Radiocarbon, Tucson, USA 2009, pp. 321-329.
10. A. Komosa, I. Kitowski, R. Kowalski, G. Pitucha, Z. Komosa, J. Grochowicz,
Total mercury concentration in kidneys of birds of prey from different part of
Poland –some interspecies and geographical differences, Ecological Chemistry
and Engineering S, 16(1) (2009) 19.
11. Z. Ziembik, A. Dołhańczuk-Śródka, A. Komosa, J. Orzeł, M. Wacławek,
Assessment of 137
Cs and 239,240
Pu distribution in forest soils of the Opole
Anomaly, Water Air and Soil Pollution, (2009), doi: 10.1007/s11270-009-
0107-8.
12. A. Komosa, I. Kitowski, S. Chibowski, J. Solecki, J. Orzeł, P. Różański,
Selected radionuclides and heavy metals in skeletons of birds of prey from
eastearn Poland, Journal of Radioanalytical and Nuclear Chemistry, 281
(2009) 467, doi: 10.1007/s10967-009-0029-3.
13. M. Wiśniewska, St. Chibowski, T. Urban, Adsorption and Thermodynamic
Properties of the Alumina – Polyacrylic Acid Solution System, Journal of
Colloid and Interface Science, 334 (2009) 146.
14. A.W. Marczewski, A. Deryło-Marczewska, I. Skrzypek, S. Pikus and M.
Kozak,
Study of structure properties of organized silica sorbents synthesized on
polymeric templates, Adsorption, 15 (2009) 300.
15. M. Szymula, J. Narkiewicz-Michałek, Ascorbic Acid Oxidation in SDS
Micellar Systems, Journal of Applied Electrochemistry, 31 (2009) 681.
F.Ch. UMCS Report 2009 – 219 –
16. D. Kołodyńska, E. Skwarek, Z. Hubicki and W. Janusz, The Effect of
Adsorption of Pb(II) And Cd(II) Ions in the Presence of EDTA on
Characteristic of Electrical Double Layer at the Ion Exchanger/NaCl
Electrolyte Solution Interface, J Colloid Interface Sci., 333 (2009) 448.
17. W. Janusz, E. Skwarek, The study of the properties of the hydroxyl-
apatite/electrolyte interface, Annales sectio AA, LXIV (2009) 11.
*Edited in 2009.
Department of Crystallography
1. B. Modzelewska-Banachiewicz, B. Michalec, T. Kamińska, L. Mazur, A.E.
Kozioł, J. Banachiewicz, M. Ucherek, M. Kandefer-Szerszeń, Synthesis and
biological activity of (Z) and (E) isomers of 3-(3,4-diaryl-1,2,4-triazole-5-
yl)prop-2-enoic acid, Monatshefte fur Chemie, 140 (2009) 439.
2. M. Struga, J. Kossakowski, B. Mirosław, A.E. Kozioł, A. Zimniak, Synthesis
of new 1,3-thiazepine derivatives, Journal of Heterocyclic Chemistry, 46
(2009) 298.
3. M. Struga, J. Kossakowski, A.E. Kozioł, T. Lis, E. Kędzierska, S. Fidecka,
Synthesis and pharmacological activity of thiourea derivatives of 1,7,8,9-
tetramethyl-4-azatricyclo [5.2.1.02,6
]dec-8-ene-3,5-dione, Letters in Drug
Design and Discovery, 6 (2009) 445.
4. K. Sztanke, K. Pasternak, M. Sztanke, M. Kandefer-Szerszeń, A.E. Kozioł, I.
Dybała, Crystal structure, antitumor and antimetactatic activities of
disubstituted fused 1,2,4-triazinones, Bioorganic and Medicinal Chemistry
Letters, 19 (2009) 5095.
5. M. Struga, J. Kossakowski, A.E. Kozioł, E. Kędzierska, S. Fidecka, P. La
Colla, C. Ibba, G. Collu, G. Sanna, B. Secci, R. Loddo, Synthesis,
pharmacological and antiviral activity of 1,3-thiazepine derivatives, European
Journal of Medicinal Chemistry, 44 (2009) 4960.
6. B. Jasińska, M. Kędzior, M. Śniegocka, A.E. Kozioł, I. Wawrzycka-Gorczyca,
Investigation of the free volume in olanzapine by PALS, Physica Status Solidi
C, 6 (2009) 2432.
7. A. Kultys, M. Rogulska, S. Pikus, K. Skrzypiec, The synthesis and
characterization of new thermoplastic poly(carbonate-urethane) elastomers
derived from HDI and aliphatic-aromatic chain extenders, Eur. Polym. J., 45
(2009) 2629.
8. M. Barczak, S. Pikus, B. Skrzydło-Radomanska, A. Dąbrowski, Synthesis,
structure and adsorption properties of nanoporous SBA-15 materials with
framework and surface functionalities, Adsorption, 15 (2009) 278.
9. A.W. Marczewski, A. Deryło-Marczewska, I. Skrzypek, S. Pikus, M. Kozak,
Study of structure properties of organized silica sorbents synthesized on
polymeric templates, Adsorption, 15 (2009) 300.
Publications – 220 –
10. R.M. Grudzień, J.P. Blitz, S. Pikus, M. Jaroniec, Cage-like mesoporous
organosilicas with isocyanurate bridging groups synthesized by soft templating
with poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) block
copolymer, J. Colloid Interf. Sci., 333 (2009) 354.
11. R.M. Grudzień, J.P. Blitz, S. Pikus, M. Jaroniec, Cage-like ordered mesoporous
organosilicas with isocyanurate bridging groups: Synthesis, template removal
and structural properties, Micropor. Mesopor. Mat., 118 (2009) 68.
12. R. M. Grudzień, S. Pikus, M. Jaroniec, Synthesis and Properties of Ordered
Mesoporous Organosilicas with Vinyl and Mercaptopropyl Surface Groups:
The Effect of Ligand Concentration on Pore Structure, J. Phys. Chem. C, 113
(2009) 4875.
13. M. Majdan, M. Bujacka, Eyup Sabah, A. Gladysz-Plaska, S. Pikus, D. Sternik,
Z. Komosa, A. Padewski, Unexpected difference in phenol sorption on PTMA-
and BTMA-bentonite, J. Environmental Management, 91 (2009) 195.
14. E. Olszewska, B. Tarasiuk, S. Pikus, New powder diffraction data of some
derivatives of N-(hydroxyalkyl)-4-chlorophenoxyacetamide – potential
pesticides, Powder Diffraction, 24(4) (2009), 327.
15. M. Majdan, Eyup Sabah, M. Bujacka, S. Pikus, A. Gładysz-Płaska, Spectral
and equillibrium properties of phenol-HDTMA- and phenol-BDMHDA-
bentonite as a response to the molecular arrangements of surfactant cations, J.
Mol. Struct., 938 (2009) 29.
16. J. Kossakowski, M. Pakosińska-Parys, M. Struga, I. Dybała, A.E. Kozioł, P. La
Colla, L. E. Marongiu, C. Ibba, D. Collu, R. Loddo, Synthesis and Evaluation
of in Vitro Biological Activity of 4-Substituted Arylpiperazine Derivatives of
1,7,8,9-Tetrachloro-10,10-dimethoxy-4-azatricyclo[5.2.1.02,6
]dec-8-ene-3,5-dione,
Molecules 14 (2009), 5189.
Department of Organic Chemistry
1. K. Glegoła, C. Midrier, K.M. Pietrusiewicz, E. Framery, Palladium-catalyzed
asymmetric allylic alkylation using phosphine-amide derived from chiral trans-
2-aminocyclohexanol, Phosphorus, Sulfur, and Silicon, 184 (2009) 1065.
2. N. Vinokurov, I. Baumgardt, K.M. Pietrusiewicz, H. Butenschoen, (SP,SP)-(-)-
(E)-Ethene-1,2-diylbis[methyl(phenyl)phosphine] Dioxide, Acta Cryst., E65
(2009) o517.
3. O. Demchuk, K.M. Pietrusiewicz, New and efficient protocol for arylation of
quinones, Synlett, (2009) 1149.
4. J. Holt, A.M. Maj, E.P. Schudde, K.M. Pietrusiewicz, L. Sieroń, W.
Wieczorek, P. Jerphagnon, I.W.C.E.' Arends, U. Hanefeld, A. Minnaard, On
the resolution of Secondary Phosphine Oxides via Diastereomeric Complex
Formation: the Case of tert-Butylphenylphosphine Oxide, Synthesis, (2009)
2061.
F.Ch. UMCS Report 2009 – 221 –
5. N. Vinokurov, K.M. Pietrusiewicz, H. Butenschön, Asymmetric Diels-Alder
Cycloaddition of a Di-P-stereogenic Dienophile with Cyclopentadiene,
Tetrahedron: Asymmetry, 20 (2009) 1081.
6. M. Stankevič, K.M. Pietrusiewicz, Birch reduction of aryldialkylphosphine-
boranes, Tetrahedron Letters, (2009) 7093.
7. E. Olszewska, B. Tarasiuk, S Pikus, New powder diffraction data of some
derivatives of N-(hydroxyalkyl)-4-chlorophenoxyacetamide potential
pesticides, Powder Diffraction, 24 (2009) 327.
8. W. Charmas, M. Topyła, J. Nowak, Nowe pochodne bisfenolu-A oraz sposób
otrzymywania nowych pochodnych bisfenolu-A, Patent PL 201912 (2009).
Department of Polymer Chemistry
1. B. Gawdzik, McReynolds method for stationary phase classification, in:
Encyclopedia of Chromatography, Third Edition, (J. Cazes, Ed.), Taylor &
Francis 2009, 1434, (ISBN 978-1-4200-8459-7 hardback); (ISBN 978-1-4200-
8483-2 electronic).
2. M. Grochowicz, A. Bartnicki, B. Gawdzik, New tetrafunctional monomer 1,3-
di(2-hydroxy-3-methacryloyloxypropoxy)benzene in the synthesis of porous
microshpheres, J. Polym. Sci. Part A: Polym. Chem., 47 (2009) 3190.
3. A. Kultys, M. Rogulska, S. Pikus, K. Skrzypiec, The synthesis and
characterization of new thermoplastic poly(carbonate-urethane) elastomers
derived from HDI and aliphatic–aromatic chain extenders, Europ. Polym. J.,
45 (2009) 2629.
4. A. Podkościelna, A. Bartnicki, B. Gawdzik, Porous microspheres of bis[4(2-
hydroxy-3-methacryloyloxypropoxy)phenyl]sulfide and divinylbenzene as
stationary phase for HPLC, J. Appl. Polym Sci., 111 (2009) 1257.
5. M. Podgórski, Network structure/mechanical property relationship in
crosslinked dimethacrylates of different chain lengths, J. Appl. Polym. Sci, 112
(2009) 2942.
6. M. Worzakowska, Chemical modification of unsaturated polyesters. Influence
of polyester’s structure on thermal and viscoelstic properties of low styrene
content copolymers, J. Appl. Polym. Sci, 114 (2009) 720.
7. M. Worzakowska, Thermal and dynamic mechanical properties of IPNs formed
from unsaturated polyester resin and epoxy polyester, J. Mater. Sci., 44 (2009)
4069.
8. K. Plesz, Ł. Szajnecki, B. Gawdzik, Synthesis of molecularly imprinted
copolymer and its application as a SPE sorbent for preconcentration of
metoprolol and vitamin B6 from water, J. Liq. Chromatogr. & Rel. Technol., 32
(2009) 1831.
9. M. Worzakowska, The influence of chemical modification of unsaturated
polyesters on viscoelastic properties and thermal behavior of styrene
copolymers, J. Therm. Anal. Calorim., 96 (2009) 235.
Publications – 222 –
10. M. Worzakowska, Studies on the cure reaction and thermal properties of
NADIC/ phthalic modified unsaturated (epoxy) polyesters, J. Therm. Anal.
Calorim. (2009), doi: 10.1007/s10973-009-0153-x.
11. M. Podgórski, J. Księżopolski, Badania wpływu struktury sieci polimerowej na
właściwości termo-mechaniczne usieciowanych (met)akrylanów – pochodnych
bezwodnika cis-heksahydroftalowego, Polimery, 55 (2010) 34.
12. R. Zaleski, W. Stefaniak, M. Maciejewska, J. Goworek, Porosity of polymer
materials by various techniques, J. Porous Mat., 16 (2009) 691.
13. R. Zaleski, J. Goworek, M. Maciejewska, Positronuim lifetime in porous VP-
DVB copolymer, Phys. Status Solidi, 6 (2009) 2445.
14. A.M. Puziy, O.I. Poddubnaya, B. Gawdzik, M. Sobiesiak, C.A. Reinish, M.M.
Tsyba, T.P. Segeda, M.I. Danylenko, Solid phase extraction using
nanostructured carbons obtained by template method, Annales UMCS sectio
AA, LXIV (2009) 64.
15. M. Worzakowska, Synteza i charakterystyka nienasyconych (epoxy) poliestrów
na bazie CHDM oraz ich styrenowych kopolimerów, in: Modyfikacja
Polimerów. Stan i perspektywy w roku 2009, (R. Steller, D. Żuchowska, Eds.),
Oficyna Wydawnicza Politechniki Wrocławskiej, (ISBN 978-83-7493-482-4),
Wrocław 2009, pp. 143-147.
16. M. Worzakowska, Przebieg reakcji sieciowania liniowych nienasyconych
epoxy poliestrów z metakrylanem metylu, in: Modyfikacja Polimerów. Stan i
perspektywy w roku 2009, (R. Steller, D. Żuchowska, Eds.), Oficyna
Wydawnicza Politechniki Wrocławskiej, (ISBN 978-83-7493-482-4), Wrocław
2009, pp. 139-142
17. A. Kultys, A. Puszka, B. Podkościelna, Nowe termoplastyczne elastomery
poliuretanowe modyfikowane DMPA- synteza i charakterystyka, in:
Modyfikacja Polimerów. Stan i perspektywy w roku 2009, (R. Steller, D.
Żuchowska, Eds.), Oficyna Wydawnicza Politechniki Wrocławskiej, (ISBN
978-83-7493-482-4), Wrocław 2009, pp. 65-68.
18. M. Rogulska, A. Kultys, A. Puszka, B. Podkościelna, Synteza i charakterystyka
nowych termoplastycznych elastomerów poli(estro-uretanowych) pochodnych
HDI i MDI, in: Modyfikacja Polimerów. Stan i perspektywy w roku 2009, (R.
Steller, D. Żuchowska, Eds.), Oficyna Wydawnicza Politechniki
Wrocławskiej, (ISBN 978-83-7493-482-4), Wrocław 2009, pp. 105-108.
19. B. Podkościelna, Termo- i fotoinicjowana polimeryzacja metakrylowych
monomerów pochodnych naftaleno-2,7-diolu, in: Modyfikacja Polimerów.
Stan i perspektywy w roku 2009, (R. Steller, D. Żuchowska, Eds.), Oficyna
Wydawnicza Politechniki Wrocławskiej, (ISBN 978-83-7493-482-4), Wrocław
2009, pp. 351-354.
20. W. Charmas, M. Topyła, J. Nowak, Nowe pochodne bisfenolu-A oraz sposób
otrzymywania nowych pochodnych bisfenolu-A, Patent PL 201912, (2009).
21. B. Gawdzik, J. Księżopolski, T. Matynia, Środek inicjujący polimeryzację wolnorodnikową oraz sposób otrzymywania środka inicjującego polimeryzację wolnorodnikową, Patent PL 201217, (2009).
F.Ch. UMCS Report 2009 – 223 –
Department of Optical Fibres Technology
1. G. Luyckx, E. Voet, T. Geernaert, K. Chah, T. Nasilowski, W. De Waele, W.
Van Paepegem, M. Becker, H. Bartelt, W. Urbanczyk, J. Wójcik, J. Degrieck,
F. Berghmans, H. Thienpont, Response of FBGs in microstructured and bow tie
fibers embedded in laminated composite, IEEE Photonics Technology Letters,
21(18) (2009) 1290.
2. T. Geernaert, G. Luyckx, E. Voet, T. Nasilowski, K. Chah, M. Becker, H.
Bartelt, W. Urbanczyk, J. Wójcik, W. De Waele, J. Degrieck, H. Terryn, F.
Berghmans, H. Thienpont, Transversal load sensing with fiber Bragg gratings
in microstructured optical fibers, IEEE Photonics Technology Letters, 21(1)
(2009) 6.
3. B. Kibler, T. Martynkien, M. Szpulak, C. Finot, J. Fatome, J. Wójcik, W.
Urbanczyk, S. Wabnitz, Nonlinear femtosecond pulse propagation in an all-
solid photonic bandgap fiber, Optics Express, 17(12) (2009) 10393.
4. T. Martynkien, A. Anuszkiewicz, G. Statkiewicz-Barabach, J. Olszewski, G.
Golojuch, M. Szczurowski, W. Urbanczyk, J. Wójcik, P. Mergo, M. Makara, T.
Nasilowski, F. Berghmans, H. Thienpont, Birefringent photonic crystal fibers
with zero polarimetric sensitivity to temperature, Applied Physics B: Lasers and
Optics, 94(4) (2009) 635.
5. O. Frazão, T. Martynkien, J.M. Baptista, J.L. Santos, W. Urbanczyk, J. Wójcik,
Optical refractometer based on a birefringent Bragg grating written in an H-
shaped fiber, Optics Letters, 34(1) (2009) 76.
6. G. Statkiewicz-Barabach, A. Anuszkiewicz, K. Durakiewicz, W. Urbanczyk, J.
Wójcik, Sensing characteristics of rocking filters fabricated in microstructured
birefringent fibers, 2009 Conference on Lasers and Electro-Optics and 2009
Conference on Quantum Electronics and Laser Science Conference,
CLEO/QELS 2009, (2009) art. no. 5196275.
7. T. Martynkien, B. Kibler, C. Finot, J. Fatome, M. Szpulak, J. Wójcik, S.
Wabnitz, W. Urbanczyk, Nonlinear femtosecond pulse propagation in all-solid
photonic bandgap fiber, 2009 Conference on Lasers and Electro-Optics and
2009 Conference on Quantum Electronics and Laser Science Conference,
CLEO/QELS 2009, (2009) art. no. 5225383.
8. R. Kotynski, K. Panajotov, M. Antkowiak, T. Nasilowski, P. Lesiak, J. Wójcik,
H. Thienpont, Interplay of form and material birefringence in photonic crystal
fibers: Application for sensing, Proc. of IEEE 6th International Conference on
Transparent Optical Network, 2 (2009) 95.
9. J. Wójcik, M. Matusewicz, P. Mergo, M. Makara, „Wytrzymałość mechaniczna
światłowodów fotonicznych”, Pomiary Automatyka Komputery w Gospodarce
i Ochronie Środowiska, listopad nr 4/2009
10. G. Luyckx, E. Voet, T. Geernaert, K. Chah, T. Nasilowski, W. De Waele, M.
Becker, H. Bartelt, W. Urbanczyk, J. Wójcik, J. Degrieck, F. Berghmans, H.
Thienpont, Benchmarking the response of Bragg gratings written in micro-
Publications – 224 –
structured and bow tie fiber embedded in composites, Proceedings of SPIE,
7503 (2009) art. no. 75035P.
11. M. Kadulová, P. Hlubina, D. Ciprian, G. Statkiewicz-Barabach, W. Urbańczyk,
J. Wójcik, Birefringence dispersion in elliptical-core fibers measured over a
broad wavelength range by interferometric techniques, Proceedings of SPIE,
7357 (2009) art. no. 73570C.
12. T. Geernaert, G. Luyckx, E. Voet, T. Nasilowski, M. Becker, H. Barteltc, W.
Urbanczyk, J. Wójcik, W. De Waele, J. Degrieck, F. Berghmans, H.
Thienponta, Fiber Bragg gratings in microstructured optical fibers for stress
monitoring, Proceedings of SPIE, 7357 (2009) art. no. 73570I.
13. K. Kalli, T. Geernaert, C. Koutsides, M. Komodromos, T. Nasilowski, W.
Urbanczyk, J. Wójcik, F. Berghmans, H. Thienpont, Point-by-point Bragg
grating inscription in single-mode microstructure fibre using NIR femtosecond
laser, Proceedings of SPIE, 7503 (2009) art. no. 75037O.
14. F. Berghmans, H. Thienpont, P. Van Daele, P. Dubruel, W. Urbanczyk, J.
Rayss, D.J. Webb, J. Vlekken, K. Kalli, K. Sugden, Photonic skins for optical
sensing: Highlights of the PHOSFOS Project, Proceedings of SPIE, 7503
(2009) art. no. 75030B.
Department of Environmental Technology
1. D. Olszewska, A. Marcewicz-Kuba, The Elimination of SO2 and NOx Emission
from Hard Coal Combustion by the Use of DESOXNOX Catalysts with
Vanadium, Polish J. Environ. Studies, 18(1B) (2009) 166.
2. W. Ćwikła-Bundyra, A comparative study of PGM catalysts for catalytic
reduction of nitrogen oxide by methane for emission control, Polish J. Environ.
Studies, 18(1B) (2009) 35.
3. M. Kuśmierz, B. Czech, Preliminary study on CO2 hydrogenation over Pd/ZnO
catalysts prepared by the DIM method, Polish J. Environ. Studies, 18(1B)
(2009) 86.
4. B. Czech, M. Kuśmierz, Advanced oxidation methods in removal of recalcitrant
pollutants from wastewater and water, Polish J. Environ. Studies, 18(1B)
(2009) 31.
5. B. Czech, The effect of H2O2 addition on the phenol removal from wastewater
using TiO2/Al2O3 as the photocatalyst, Polish J. Environ. Studies, 18(1B)
(2009) 995.
6. W. Ćwikła-Bundyra, Wpływ odpadów elektrycznych na środowisko
przyrodnicze, Ekonatura, 9(70) (2009) 5.
F.Ch. UMCS Report 2009 – 225 –
Department of Chemical Education
1. R.M. Janiuk, Refleksje nad kształceniem chemicznym – co, w jaki sposób i w
jakim celu należy w nim zmienić? Materiały IX Konferencji: Nowe wyzwania
dydaktyki chemii, 25-27.04. 2008, Ciążeń k. Poznania, pp. 226-235.
2. A. Kamińska-Ostęp. Trudności i problemy uczniów dyslektycznych w uczeniu
się chemii w opinii nauczycieli, Materiały IX Konferencji: Nowe wyzwania
dydaktyki chemii, 25-27.04. 2008, Ciążeń k. Poznania, pp. 82-84.
3. Z. Kloc, Badania poziomu wiedzy z chemii ogólnej studentów I roku,
Materiały IX Konferencji: Nowe wyzwania dydaktyki chemii, 25-27.04. 2008,
Ciążeń k. Poznania, pp. 236-239.
4. A. Kamińska-Ostęp, H. Gulińska, Teaching methods and aids assisting
dyslexic pupils in learning chemistry, Journal of Baltic Science Education, 7(3)
(2008) 147.
5. A. Kamińska-Ostęp, Wyniki badań nauczycieli chemii na temat kształcenia
uczniów z dysleksją, Materiały III Międzynarodowej konferencji: Badania w
dydaktyce przedmiotów przyrodniczych, Uniwersytet Pedagogiczny im. KEN,
Kraków 26-28.06. 2008, pp. 182-185.
6. A. Persona, T. Gęca, J.W. Dymara, Computer-aided classes In Analytical
Chemistry, Materiały III Międzynarodowej konferencji: Badania w dydaktyce
przedmiotów przyrodniczych, Uniwersytet Pedagogiczny im. KEN, Kraków
2008, pp. 294-297.
7. A. Kamińska-Ostęp, H. Gulińska, The use of information technologies in
teaching chemistry to dyslexic students, in: Research, Reflections and
Innovations in Integrating ICT in Education, Lisbon, Portugal, 20-26.04.2009.
Vol. 2, pp. 1184-1188.
8. R.M. Janiuk, Edukacja przyrodnicza w opinii członków polskich towarzystw
naukowych, Materiały 52 Zjazdu PTChem i SiTPChem, Łódź 2009, S13-OC-
13-07, p. 309.
9. R.M. Janiuk, H. Gulińska, Rozwój dydaktyki chemii w Polsce, Materiały 52
Zjazdu PTChem i SiTPChem, Łódź 2009, S13-SL-13-01, p. 307.
10. A. Persona, J.W. Dymara, Kalibracja analityczna w analizie instrumentalnej,
Materiały 52 Zjazdu PTChem i SiTPChem, Łódź 2009, S13-PC-13-13, p. 314.
11. R.M. Janiuk, Wiedza o nauce w kształceniu chemicznym, Proceedings of the
19th International Conference on Chemistry Education, Vol. 1, Hradec
Kralove, IX. 2009, pp. 50-63.
12. J.W. Dymara. Rozwijanie zainteresowań uczniów chemią poprzez zajęcia
pozaszkolne, Proceedings of the 19th International Conference on Chemistry
Education, Vol. 2, Hradec Kralove, IX. 2009, pp. 80-86.
13. A. Kamińska-Ostęp, Teoria i praktyka w świetle badań dotyczących pracy
domowej ucznia. Chemia bliżej życia. Dydaktyka chemii w dobie reformy
edukacji, Poznań 2009, pp. 146-153.
PART 5
CONFERENCE
CONTRIBUTIONS
F.Ch. UMCS Report 2009 – 229 –
Department of General and Coordination Chemistry 1. A. Kula, Z. Rzączyńska, A. Szybiak, Budowa, właściwości spektroskopowe i
termiczne kompleksów lantanowców (III) z kwasem 2,3-naftaleno-dikarboksy-
lowym, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
2. Z. Rzączyńska, A. Kula, P. Szaruga, 2,6-Naftalenodikarboksylany
pierwiastków ziem rzadkich. Synteza i właściwości 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
3. J. Rayss, A. Borkowski, Z. Rzączyńska, A. Kula, Kompleksy europu i terbu w
fotoutwardzalne matrycy polimerowej do zastosowań w światłoczułych
czujnikach UV, XII Konferencja „Światłowody i ich zastosowania”, October,
14-17, 2009, Lublin-Krasnobród (Poland) – (komunikat).
4. A. Dziewulska-Kułaczkowska, W. Ferenc, The influence of the number of
methoxy- groups in benzene ring on the properties of the complexes with the
choosen d-block elements, International Conference On Coordination And
Bioinorganic Chemistry, June 7-12, 2009, Smolenice, (Slovakia) – poster.
5. W. Ferenc, A. Dziewulska-Kułaczkowska, Synthesis and characterization of
Co(II), Ni(II), Cu(II) and Mn(II) complexes with chromone-3-carboxaldehyde,
32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
6. W. Ferenc, A. Dziewulska-Kułaczkowska, J. Sarzyński, Thermal, spectral and
magnetic properties of mono-, di- and trimethoxybenzoates of Ho(III), 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
7. W. Ferenc, A. Dziewulska-Kułaczkowska, The influence of kind of solution on
the structure of 2,3-dimethoxybenzoate of Cu(II), 10th Conference on
Calorimetry and Thermal Analysis, 30 August – 3 September 2009, Zakopane
(Poland) – poster.
8. A. Dziewulska-Kułaczkowska, W. Ferenc, Synteza i charakterystyka nowej
zasady Schiffa i jej kompleksów z miedzią(II) i niklem(II), 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
9. W. Ferenc, A. Dziewulska-Kułaczkowska, B. Cristóvão, The influence of
substituent positions in benzene ring on the magnetic, thermal and spectral
properties of chloronitrobenzoates of copper(II), European Conference on
Molecular Magnetism ECMM 2009, October 4-7, 2009, Wrocław (Poland) –
poster.
10. W. Ferenc, B. Cristóvão, Synteza oraz badanie właściwości fizykochemicznych
kompleksów kwasu 5-chloro-2-nitrobenzoesowego z wybranymi pierwiastkami
d-elektronowymi, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – poster.
Conference contributions – 230 –
11. B. Cristóvão, L. Mazur, W. Ferenc, Synthesis, crystal structure, spectral and
magnetic properties of Cu(II) complex with Schiff base, XXII International
Conference On Coordination And Bioinorganic Chemistry, June 7-12, 2009,
Smolenice, (Slovakia) – poster.
12. B. Cristóvão, W. Ferenc, Synthesis and thermal studies of the Schiff base
complex with copper(II)–gadolinium(III), 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
13. W. Ferenc, B. Cristóvão, J. Sarzyński, Thermal and magnetic behaviour of 5-
chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II), 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
14. B. Cristóvão, W. Ferenc, Thermal and magnetic characterization of 5-chloro-
2-nitro- and 5-chloro-2-methoxybenozates of Co(II), Ni(II) and Cu(II), 10th
Conference on Calorimetry and Thermal Analysis, 30 August – 3 September
2009, Zakopane (Poland) – poster.
15. R. Łyszczek, Thermal Behavior of Lanthanide–Pyridine-3,5-dicarboxylate
Frameworks, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
komunikat.
16. Z. Rzączyńska, R. Łyszczek, A. Lenard, A. Marzec, M. Iwan, Thermal
investigations of Mn(II), Co(II), Cu(II) and Zn(II) complexes with biologically
active carboxylic acids, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
17. R. Łyszczek, Adsorption Properties of Lanthanide(III) Dinicotinates, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
18. Z. Rzączyńska, A. Ostasz, M. Iwan, R. Łyszczek, Reversibility of solvation
process of polymeric benzenepolycarboxylates of lanthanides, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
19. R. Łyszczek, Synteza, struktura krystaliczna i właściwości trójwymiarowych
dinikotynianów lantanowców(III), 52 Zjazd PTChem. i SITPChem., September
12-16, 2009, Lódź (Poland) – komunikat.
20. J. Górka, M. Jaroniec, R. Łyszczek, S. Pikus, A. Ostasz, Z. Raczyńska,
Zastosowanie techniki mikrofalowej w syntezie nowych związków
mikroporowatych, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
21. Ł. Popiołek, M. Dobosz, L. Mazur, M. Pitucha, A. Pachuta-Stec, N. Trosko,
Reakcje cyklizacji 1-[(4,5-difenylo-4H-1,2,4-triazol-3ylo) sulfanylo]acetylo
tiosemiarbazydów do pochodnych układu 1,2,4-triazolu, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
F.Ch. UMCS Report 2009 – 231 –
22. A. Pachuta-Stec, L. Mazur, Ł. Popiołek, M. Pitucha, Synteza i struktura
nowych pochodnych N-(fenylotioureido)aminobicyclo-dikarboksyimidów i
3,4-dipodstawionych 1,2,4-triazolino-5-tionu, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
23. A. Kultys, M. Rogulska, A. Puszka, H. Głuchowska, Effect of polymer diol
soft segments on thermal properties of new thermoplastic segmented
polyurethanes derived from MDI and 3,3`-[methylenebis(1,4-
phenylenemethylenethio)]dipropan-1-ol, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
24. Z. Rzaczyńska, A. Danczowska-Burdon, H. Głuchowska, Thermal properties
of light lanthanide(III) complexes with 2,4-pyridinedicarboxylate anion, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
25. M. Pitucha, B. Cristóvão, J. Sarzyński, Ł. Popiołek, A. Pachura-Stec, Synteza i
właściwości chemiczne kompleksów Cu(II) z pochodnymi semikarbazydu, 52
Zjazd PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
Department of Inorganic Chemistry 1. J. Jachuła, Z. Hubicki, D. Kołodyńska, The influence of the presence of
glycolic acid on sorption of Pb(II) and Cd(II) complexes on different ion
exchangers, ХХ Українського семінару ‘Мембранні і сорбційні процеси і технології’, February 24-25, 2009 – poster.
2. M. Gęca, Z. Hubicki, D. Kołodyńska, Baypure DS 100 as an effective
complexing agent of new generation in sorption of heavy metal ions on ion
exchangers, ХХ Українського семінару ‘Мембранні і сорбційні процеси і технології’, February 24-25, 2009 – poster.
3. Sz. Padło, Z. Hubicki, D. Kołodyńska Sorption of heavy metal ions in the
presence of polyelectrolytes based on acrolein and acrylic acid (POC) on
chelating ion exchangers, ХХ Українського семінару ‘Мембранні і сорбційні процеси і технології’, February 24-25, 2009 – poster.
4. D. Kołodyńska, Biodegradable complexing agents as an alternative to chelators
in sorption of heavy metal ions, ХХ Українського семінару ‘Мембранні і сорбційні процеси і технології’, February 24-25, 2009 – poster.
5. M. Siek, Z. Hubicki, D. Kołodyńska, The role of NTMP in sorption of heavy
metals on polystyrene anion exchangers, ХХ Українського семінару
‘Мембранні і сорбційні процеси і технології’, February 24-25, 2009 –
poster.
6. D. Kołodyńska, Comparison of applicability of EDTA and EDDS in sorption
of heavy metal ions on anion exchangers, XII Scientific Conference ,,Lviv
Chemical Reading – 2009, June 1-4, 2009, Lviv (Ukraine) – lecture.
Conference contributions – 232 –
7. Z. Hubicki, J. Jachuła, D. Kołodyńska, Studies on cadmium removal in the
presence of glycolic acid by ion exchange method, XII Scientific Conference
,,Lviv Chemical Reading – 2009, June 1-4, 2009, Lviv (Ukraine) – poster.
8. M. Gęca, Z. Hubicki, D. Kołodyńska, Zastosowanie spektroskopii w
podczerwieni w badaniu procesu sorpcji kompleksów Cu(II) i Zn(II) z kwasem
poliasparaginowym na anionitach poliakrylowych, Ogólnopolskie Sympozjum
„Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości” June 6-10, 2009, Lublin (Poland) – poster.
9. M. Gęca, Z. Hubicki, D. Kołodyńska, Badania sorpcji kompleksów metali
ciężkich z kwasem metawinowym na jonitach chelatujących z wykorzystaniem
metod spektroskopowych, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
10. J. Jachuła, D. Kołodyńska, Z. Hubicki, Wykorzystanie metod spektro-
skopowych w badaniach wpływu kwasu glikolowego na sorpcję Cd(II) i Pb(II)
na jonitach różnego typu, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
11. J. Jachuła, D. Kołodyńska, Z. Hubicki, Zastosowanie metod spektroskopowych
w badaniach procesu sorpcji kompleksów Cu(II) z MGDA na mocno
zasadowych anionitach, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
12. D. Kołodyńska, Z. Hubicki, A. Dębczak, Zastosowanie metod
spektroskopowych w badaniach sorpcji jonów metali ciężkich w obecności
Dissolvine GL-38 na jonitach różnego typu, Ogólnopolskie Sympozjum
„Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości” June 6-10, 2009, Lublin (Poland) – poster.
13. M. Siek, D. Kołodyńska, Z. Hubicki, Zastosowanie spektroskopii FT-IR w
badaniach procesu sorpcji kompleksów Cu(II), Zn(II), Pb(II) i Cd(II) z NTMP
na mocno zasadowych anionitach, Ogólnopolskie Sympozjum „Nauka i
przemysł – metody spektroskopowe w praktyce, nowe wyzwania i możliwości”
June 6-10, 2009, Lublin (Poland) – poster.
14. D. Kołodyńska, J. Jachuła, Z. Hubicki, MGDA as a new biodegradable
complexing agent for sorption of heavy metal ions on anion exchanger Lewatit
MonoPlus M 600, XIV International Symposium on Physicochemical Methods
of Separation, ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój
(Poland) – poster.
15. D. Kołodyńska, Z. Hubicki, Studies of sorption of heavy metal complexes with
biodegradable ligands of new generation on ion exchangers of various types,
XIV International Symposium on Physicochemical Methods of Separation,
ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland) – lecture.
F.Ch. UMCS Report 2009 – 233 –
16. G. Wójcik, Z. Hubicki, Investigation of chromium(III and VI) ions sorption on
the solvent impregnated resin, XIV International Symposium on
Physicochemical Methods of Separation, ARS SEPARATORIA, June 15-18,
2009, Kudowa Zdrój (Poland) – poster.
17. G. Wójcik, Z. Hubicki, M. Górska, Recovery of gold (III), palladium (II) and
platinum(IV) ions from chloride solutions on solvent impregnated resin -
Purolite® MN 202, XIV International Symposium on Physicochemical Methods
of Separation, ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój
(Poland) – poster.
18. G. Wójcik, Z. Hubicki, S. Pasieczna-Patkowska, Investigation of platinum(IV)
ions sorption on acrylic anion-exchanger in hydrochloric acid media by using
Photoacoustic method, 38th Winter School on Wave and Quantum Acoustics –
14th Winter Workshop on Photoacoustics and Thermal Wave Methods,
February 25-28, 2009 Korbielów (Poland) – oral.
19. P. Rusek, Z. Hubicki, G. Wójcik, Sorpcja jonów metali ciężkich na sorbentach
nieorganicznych, Chemistry for Agriculture, 29 November-02 December 2009,
Karpacz (Poland) – poster.
20. P. Rusek, Z. Hubicki, G. Wójcik, Zastosowanie metod FT-IR PAS do badań
procesów sorpcji jonów metali ciężkich i amonu na naturalnych sorbentach
nieorganicznych z wód osadowych z komunalnych oczyszczalni ścieków,
Ogólnopolskie Sympozjum „Nauka i przemysł – metody spektroskopowe w
praktyce, nowe wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) –
poster.
21. B. Czech, S. Pasieczna-Patkowska, G. Wójcik, Usuwanie zanieczyszczeń
organicznych z wód i ścieków w reaktorze wstęgowym, VI Kongres
Technologii Chemicznej, June 21-25, 2009, Warsaw (Poland) – poster.
22. P. Rusek, Z. Hubicki, G. Wójcik, S. Pasieczna-Patkowska, Zastosowanie
metod FT-IR Pas do badań procesów sorpcji jonów metali ciężkich i amonu na
naturalnych sorbentach nieorganicznych z wód osadowych z komunalnych
oczyszczalni ścieków, VI Kongres Technologii Chemicznej, June 21-25, 2009,
Warsaw (Poland) – poster.
23. M. Wawrzkiewicz, Z. Hubicki, Badania procesu sorpcji żółcieni
pomarańczowej z roztworów wodnych na anionicie polistyrenowym Amberlit
FPA-51M, Ogólnopolskie Sympozjum „Nauka i przemysł – metody
spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10, 2009,
Lublin (Poland) – poster.
24. M. Wawrzkiewicz, Z. Hubicki, Zastosowanie metod spektroskopowych w
badaniu sorpcji błękitu kwasowego 29 na mocno zasadowym anionicie
poliakrylowym, Ogólnopolskie Sympozjum „Nauka i przemysł – metody
spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10, 2009,
Lublin (Poland) – poster.
25. M. Wawrzkiewicz, Z. Hubicki, M. Greluk, Application of strongly basic anion
exchanger for removal of acidic dye, Дванадцята наукова конференція “львівські хімічні читання-2009”, June 01-04, 2009, Lviv (Ukraine) – poster.
Conference contributions – 234 –
26. M. Wawrzkiewicz, Z. Hubicki, M. Greluk, Equilibrium modeling and kinetic
studies on the adsorption of allura red by weakly basic anion exchanger,
Дванадцята наукова конференція “львівські хімічні читання-2009”, June
01-04, 2009, Lviv (Ukraine) – poster.
27. M. Greluk, Z. Hubicki, M. Warzkiewicz, Adsorption of anionic textile dye-acid
red 88 from aqueous solution onto strong base anion exchanger, Дванадцята наукова конференція “львівські хімічні читання-2009”, June 01-04, 2009,
Lviv (Ukraine) – poster.
28. M. Greluk, Z. Hubicki, M. Warzkiewicz, Adsorption removal of reactive dye
from aqueous solution by strongly basic anion exchanger: kinetic and
equilibrium studies, Дванадцята наукова конференція “львівські хімічні читання-2009 June 01-04, 2009, Lviv (Ukraine) – poster.
29. M. Wawrzkiewicz, Z. Hubicki, M. Greluk, Application of strongly basic anion
exchanger Purolite A-850 for removal of Acid Blue 29, XIV International
Symposium on Physicochemical Methods of Separation, ARS
SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland) – poster.
30. M. Greluk, Z. Hubicki, M. Warzkiewicz, Kinetic study on the removal of
Reactive Black 5 from aqueous solution using strongly basic anion exchangers,
XIV International Symposium on Physicochemical Methods of Separation,
ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland) – poster.
31. M. Greluk, Z. Hubicki, M. Warzkiewicz, Sorption of Acid Orange 7 and Acid
Orange 10 from aqueous solution on Amberlite IRA-900 XIV International
Symposium on Physicochemical Methods of Separation, ARS
SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland) – poster.
32. A. Wołowicz, Z. Hubicki, Zastosowanie spektrofotometrii absorpcyjnej UV-
Vis oraz metody spektroskopii w podczerwieni w badaniach procesu sorpcji
jonów palladu(II) na anionitach Amberlyst, Ogólnopolskie Sympozjum „Nauka
i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości” June 6-10, 2009, Lublin (Poland) – lecture.
33. A. Wołowicz, Z. Hubicki, Badnia spektroskopowe procesu sorpcji jonów
palladu(II) na anionicie średnio zasadowym Lewatit MonoPlus MP-64
Ogólnopolskie Sympozjum „Nauka i przemysł – metody spektroskopowe w
praktyce, nowe wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) –
poster.
34. A. Wołowicz, Z. Hubicki, Zastosowanie spektroskopii w podczerwieni (FT-
IR) w badaniach sorpcji jonów palladu(II) na anionitach słabo zasadowych
firmy Rohm and Hass, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
35. A. Wołowicz, Z. Hubicki, Recovery of palladium(II) ions from the chloride-
nitrate solutions using anion exchange resins Amberlite IRA-92 and Amberlyst
A-24, XII Scientific Conference ,,Lviv Chemical Reading – 2009”, June 1-4,
2009, Lviv (Ukraine) – lecture.
F.Ch. UMCS Report 2009 – 235 –
36. A. Wołowicz, Z. Hubicki, Kinetic investigation of palladium(II) ions
adsorption onto the phenyl-phormaldehyde resin Amberlyst A-23, XII
Scientific Conference ,,Lviv Chemical Reading – 2009”, June 1-4, 2009, Lviv
(Ukraine) – poster.
37. A. Wołowicz, Z. Hubicki, Effect of macrocomponent addition on the sorption
of palladium(II) from the HCl-NaCl-Pd(II) solutions, XII Scientific Conference
,,Lviv Chemical Reading – 2009”, June 1-4, 2009, Lviv (Ukraine) – poster.
38. A. Wołowicz, Z. Hubicki, Application of the anion exchange resin Lewatit
MonoPlus M-600 in sorption of palldium(II) from acidic solutions, XII
Scientific Conference ,,Lviv Chemical Reading – 2009”, June 1-4, 2009, Lviv
(Ukraine) – poster.
39. A. Wołowicz, Z. Hubicki, Paladium(II) sorption behaviour onto the acrylate gel
resins, XII Scientific Conference ,,Lviv Chemical Reading – 2009”, June 1-4,
2009, Lviv (Ukraine) – poster.
40. A. Wołowicz, Z. Hubicki, The study of possibilities of selective recovery of
palladium(II) from the chloride-nitrate solutions by weakly basic anion
exchangers, XIV International Symposium on Physicochemical Methods of
Separation, ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland)
– poster.
41. A. Wołowicz, Z. Hubicki, Ion exchange removal of palladium(II) from
multicomponent chloride solutions using Amberlyst A-26 – kinetic studies,
XIV International Symposium on Physicochemical Methods of Separation,
ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland) – poster.
42. A. Wołowicz, Z. Hubicki, Application of Lewatit MonoPlus MP-500 in
preconcentration of palladium ions from hydrochloric acid- sodium chloride
solutions, XIV International Symposium on Physicochemical Methods of
Separation, ARS SEPARATORIA, June 15-18, 2009, Kudowa Zdrój (Poland)
– poster.
43. M. Greluk, Z. Hubicki, Removal of azo dye from aqueous solution onto weakly
basic anion exchanger, XII Scientific Conference ,,Lviv Chemical Reading –
2009”, June 1-4, 2009, Lviv (Ukraine) – oral.
44. M. Greluk, Z. Hubicki, L. Lata, Sorption of Cu(II), Co(II), Ni(II) ions onto
Amberlite IRA-458 modified by SPADNS, XII Scientific Conference ,,Lviv
Chemical Reading – 2009”, June 1-4, 2009, Lviv (Ukraine) – poster.
45. M. Greluk, Z. Hubicki, Application of polymeric sorbents for removal of
SPADNS from different acid solutions, XII Scientific Conference ,,Lviv
Chemical Reading – 2009”, June 1-4, 2009, Lviv (Ukraine) – poster.
46. M. Greluk, Z. Hubicki, Zastosowanie metod spektroskopowych w badaniu
procesu sorpcji barwników kwasowych na anionicie Amberlit IRA-910,
Ogólnopolskie Sympozjum „Nauka i przemysł – metody spektroskopowe w
praktyce, nowe wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) –
lecture.
Conference contributions – 236 –
47. M. Greluk, Z. Hubicki, Zastosowanie spektroskopii w podczerwieni w badaniu
procesu sorpcji SPADNS z roztworów wodnych na anionitach styrenowo-
diwinylobenzenowych, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
48. M. Greluk, Z. Hubicki, Zastosowanie metody FT-IR w badaniach sorpcji
Oranżu G oraz Oranżu II na słabo zasadowym jonicie Amberlyst A-21,
Ogólnopolskie Sympozjum „Nauka i przemysł – metody spektroskopowe w
praktyce, nowe wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) –
poster.
49. G. Wroński, Z. Hubicki, S. Pasieczna-Patkowska, Application of FT - IR\PA
method in hydrometallurgical process recovery of metals from mobile phones,
38th Winter School on Wave and Quantum Acoustics – 14th Winter Workshop
on Photoacoustics and Thermal Wave Methods, February 25-28, 2009
Korbielów (Poland) – poster.
50. Sz. Padło, Z. Hubicki, Badanie sorpcji jonów miedzi(II)w obecności
polielektrolitów polialdehydokarboksylowych na chelatujących jonitach
aminometylofosfonowych, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
51. Sz. Padło, Z. Hubicki, Zastosowanie spektroskopii w podczerwieni w
badaniach sorpcji jonów cynku w obecności polielektrolitu
polialdehydokarboksylowego na chelatujących różnego typu, Ogólnopolskie
Sympozjum „Nauka i przemysł – metody spektroskopowe w praktyce, nowe
wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) – poster.
52. A. Kaczor, R. Kalityński, M. Makarska-Białokoz, G. Żukociński, K. Kacprzak,
A. Bartyzel, D. Bartuzi, D. Matosiuk, Allosteric modulation of G protein-
coupled receptors as novel approach to the treatment of CNS disorders, II
Konwersatorium Chemii Medycznej, September 8-10, 2009, Lublin (Poland –
poster.
53. A. Gładysz-Płaska, M. Majdan, O. Maryuk, M. Iwan, Thermal analysis of
organobentonite, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
54. A. Gładysz-Płaska, M. Majdan, D. Sternik, S. Pikus, E. Zięba, Sorptive and
Thermal Properties of red-mud in relation to Cr(VI), 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
55. D. Sternik, M. Majdan, A. Deryło-Marczewska, Thermal analysis of
aluminosilicates modified by selected dyes, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
F.Ch. UMCS Report 2009 – 237 –
56. M. Majdan, D. Sternik, M. Bujacka, A. Gładysz-Płaska, Studies of phenol
influence on thermal stability of clays modified by surfactant, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
57. M. Bujacka, M. Majdan, Amazing result in adsorption of phenol on BTMA and
PTMA-bentonite, VI Warszawskie Seminarium Doktorantów Chemików
(ChemSession), May 15, 2009, Warsaw (Poland) – poster.
58. A. Lipke, M. Majdan, M. Trytek, J. Fiedurek, Widma FT-IR i Ramana żeli
krzemionkowych interkalowanych porfirynami, VI Warszawskie Seminarium
Doktorantów Chemików (ChemSession), May 15, 2009, Warsaw (Poland) –
poster.
59. A. Gajowiak, H. Krzyżanowska, J. Żuk, S. Pikus, M. Majdan, Characterization
of the uranium(VI) sorption by HDTMA-bentonite, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
Department of Analytical Chemistry and Instrumental Analysis 1. A. Nosal-Wiercińska and G. Dalmata, Adsorption of methionine at
mercury/aqueous solution of chlorate (VII) interface; dependence on the
supporting electrolyte concentration, Modern Electroanalytical Methods 2009,
December 9–13, 2009, Prague (Czech Republic) – poster.
2. J. Saba, D. Sieńko, J. Nieszporek, D. Gugała-Fekner, Zn2+
electroreduction
mechanism at mercury interface/concentrated NaClO4 solutions in the presence
of tetramethylthiorea, Modern Electroanalytical Methods 2009, December
9–13, 2009, Prague (Czech Republic) – poster.
3. J. Saba, D. Sieńko, M. Klin, D. Gugała–Fekner, J. Nieszporek, Adsorption of
tetramethylthiorea at mercury electrode in the presence of 1–decanesulfonic
acid, Modern Electroanalytical Methods 2009, December 9–13, 2009, Prague
(Czech Republic) – poster.
4. D. Sieńko, J. Saba, M. Klin, J. Nieszporek, D. Gugała–Fekner, Adsorption of
1–decanesulfonic acid at mercury electrode in 1M NaClO4 solution, Modern
Electroanalytical Methods 2009, December 9–13, 2009, Prague (Czech
Republic) – poster.
5. K. Tyszczuk, M. Korolczuk, M. Grabarczyk, The determination of diazepam,
temazepam and oxazepam at the lead film electrode by adsorptive stripping
voltammetry, Modern Electroanalytical Methods 2009, December 9–13, 2009,
Prague (Czech Republic) – poster.
6. M. Grabarczyk, M. Korolczuk, K. Tyszczuk, Stripping voltammetric
determination of As(III) in natural water samples with complicated matrix,
Modern Electroanalytical Methods 2009, December 9–13, 2009, Prague (Czech
Republic) – poster.
Conference contributions – 238 –
7. M. Korolczuk, A. Stępniowska, K. Tyszczuk, Stripping voltammetric
determination of methylmercury in the presence of inorganic mercury, Modern
Electroanalytical Methods 2009, December 9–13, 2009, Prague (Czech
Republic) – poster.
8. M. Korolczuk, I. Rutyna, M. Grabarczyk, K. Tyszczuk, Determination of
nickel by adsorptive stripping voltammetry at an in situ plated bismuth film
electrode, Modern Electroanalytical Methods 2009, December 9–13, 2009,
Prague (Czech Republic) – poster.
9. J. Lenik, Properties of ion–selective electrodes with polymeric membranes for
ketoprofen determination, Modern Electroanalytical Methods 2009, December
9–13, 2009, Prague (Czech Republic) – poster.
10. A. Kaczor, D. Matosiuk, A. Persona, Computer classes on computer-assisted
drug design, case studies: virtual screening towards novel monamine oxidase B
(MAO-B) inhibitors, Research, theory and practice in chemistry didactics, 19th
International Conference on Chemistry Education, September, 2009, Hradec
Kralove (Czech Republic) – poster.
11. A. Kaczor, D. Matosiuk, A. Persona, Computer classes on computer-assisted
drug design, case studies: estimation drug-likeness and calculation of admet
properties for novel noncompetitive glur5/6 receptors antagonists, Research,
theory and practice in chemistry didactics 19th International Conference on
Chemistry Education, September, 2009, Hradec Kralove (Czech Republic) –
poster.
12. A. Persona, T. Gęca, S. Drejka, Development of Web-based prelabs and
postlabs in analytical chemistry course, Research, theory and practice in
chemistry didactics 19th International Conference on Chemistry Education,
September, 2009, Hradec Kralove (Czech Republic) – poster.
13. A. Nosal-Wiercińska and G. Dalmata, Wpływ aktywności wody na
elektroredukcję jonów Bi(III) w chloranach (VII), IX Konferencja
„Elektroanaliza w Teorii i Praktyce”, June 3-4, 2009, Kraków (Poland) –
poster.
14. A. Nosal-Wiercińska, G. Dalmata and R. Dobrowolski, Oznaczanie In(III) w
obecności Cd(II) i Pb(II) metodami woltamperometryczną i absorpcyjnej
spektrometrii atomowej, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – poster.
15. M. Klin, J. Saba, D. Gugała–Fekner, J. Nieszporek, D. Sieńko, Adsorpcja
dekano–N–metyloglukamidu na kapiącej elektrodzie rtęciowej z roztworu 1M
NaClO4, IX Konferencja „Elektroanaliza w Teorii i Praktyce”, June 3-4, 2009,
Kraków (Poland) – poster.
16. J. Saba, M. Klin, D. Gugała–Fekner, J. Nieszporek, D. Sieńko, Adsorpcja
tetrametylotiomocznika na kapiącej elektrodzie rtęciowej w obecności dekano–
N–metyloglukamidu, IX Konferencja „Elektroanaliza w Teorii i Praktyce”,
June 3-4, 2009, Kraków (Poland) – poster.
F.Ch. UMCS Report 2009 – 239 –
17. J. Lenik, C. Wardak, Konstrukcja i właściwości elektrody jonoselektywnej do
oznaczania ibuprofenu w preparatach farmaceutycznych, II Ogólnopolskie
Sympozjum „Nowoczesne techniki badawcze w ocenie jakości produktów
leczniczych”, 2009, Lublin (Poland) – poster.
18. M. Grabarczyk, M. Korolczuk, K. Tyszczuk, Prosta i szybka
woltamperometryczna metoda oznaczania Se(IV) w obecności wysokich stężeń
interferentów, IX Konferencja „Elektroanaliza w teorii i praktyce”, June 3-4,
2009, Kraków (Poland) – poster.
19. K. Tyszczuk, M. Korolczuk, M. Grabarczyk, Nowa procedura oznaczania
witaminy P na błonkowej elektrodzie ołowiowej metodą adsorpcyjnej
woltamperometrii stripingowej, IX Konferencja „Elektroanaliza w teorii i
praktyce”, June 3-4, 2009, Kraków (Poland) – poster.
20. K. Tyszczuk, M. Korolczuk, Wykorzystanie błonkowej elektrody ołowiowej w
oznaczeniach cytrynianu syldenafilu (viagry) metodą analizy stripingowej, IX
Konferencja „Elektroanaliza w teorii i praktyce”, June 3-4, 2009, Kraków
(Poland) – poster.
21. K. Tyszczuk, M. Korolczuk, Zastosowanie elektrody ołowiowej do oznaczania
substancji biologicznie czynnych metodą adsorpcyjnej woltamperometrii
stripingowej w lekach, II Ogólnopolskie Sympozjum „Nowoczesne techniki
badawcze w ocenie jakości produktów leczniczych”, 2009, Lublin (Poland) –
poster.
22. R. Dobrowolski, M. Marzec, Analiza frakcjonowana – zastosowania w
analityce środowiskowej, Specjacja Chemiczna – możliwości i kierunki
rozwoju, March 27-28, 2009, Poznań (Poland) – lecture.
23. M. Otto, R. Dobrowolski, A. Adamczyk, J. Kuna, Problemy analityczne
oznaczania cyny w glebach i osadach techniką dozowania zawiesiny GF AAS,
XVIII Poznańskie Konwersatorium Analityczne, April 16-17, 2009, Poznań
(Poland) – poster.
24. A. Adamczyk, R. Dobrowolski, M. Otto, Modyfikatory długotrwałe w
oznaczaniu wanadu techniką dozowania zawiesiny do atomizera
elektrotermicznego, XVIII Poznańskie Konwersatorium Analityczne, April 16-
17, 2009, Poznań (Poland) – poster.
25. M. Marzec, R. Dobrowolski, T. Dulęba, Ekstrakcja sekwencyjna wybranych
pierwiastków śladowych z odpadów kopalnianych, XVIII Poznańskie
Konwersatorium Analityczne, April 16-17,2009, Poznań (Poland) – poster.
26. R. Dobrowolski, M. Kuryło, Adsorbenty mikroporowate w analityce
pierwiastków szlachetnych, Sympozjum Zielona Chemia – Nowe Wyzwania
Analityki, GBC Polska, May, 2009, Ślesin (Poland) – lecture.
27. A. Adamczyk, R. Dobrowolski, M. Otto, Wzbogacanie selenu na
modyfikowanym węglu aktywnym w pomiarach absorpcji atomowej z
wykorzystaniem techniki generowania wodorków, Ogólnopolskie Sympozjum
„Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości” June 6-10, 2009, Lublin (Poland) – poster.
Conference contributions – 240 –
28. R. Dobrowolski, M. Otto, A. Adamczyk, Węgle aktywne w analityce
śladowych ilości selenu, Konwersatorium Spektrometrii Atomowej, September
28–30, 2009, Ustroń (Poland) – lecture.
29. R. Dobrowolski, A. Adamczyk, K. Prudzyńska, Oznaczanie metali śladowych
w roślinach leczniczych metodą absorpcyjnej spektrometrii atomowej,
Sympozjum „Horyzonty Chemii”, „Bioaktywni”, October 10, 2009, Lublin
(Poland) – lecture.
30. I. Malinowska, B. Marczewska, Zastosowanie metod spektroskopowych w
analizie TLC, Ogólnopolskie Sympozjum „Nauka i przemysł – metody
spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10, 2009,
Lublin (Poland) – lecture.
31. B. Marczewska, A. Persona, T. Gęca, D. Smolarz, Wyznaczanie parametrów
fizykochemicznych kwasów fenolowych w aspekcie ich aktywności
biologicznej, Ogólnopolskie Sympozjum „Nauka i przemysł – metody
spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10, 2009,
Lublin (Poland) – komunikat.
32. A. Persona, J.W. Dymara, Kalibracja analityczna w analizie instrumentalnej.
Wykorzystanie e-learningu w systemie prelab, 52 Zjazd PTChem.
i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
33. A. Persona, T. Persona, e-learning, repetytorium z Chemii ogólnej dla
studentów studiów przyrodniczych, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
Department of Interfacial Phenomena 1. M. Jurak, E. Chibowski, L. Hołysz, Energetic changes of lipid layers on mica,
7th International Symposium Effects of Surface Heterogeneity on Adsorption
and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
2. K. Terpiłowski, E. Chibowski, Effect of different solids on free energy of some
polymers, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – poster.
3. M. Mirosław (Gołąbek), E. Chibowski, L. Hołysz, Changes in wetting and
energetic properties of glass caused by different lipid adsorption, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – oral.
4. M. Jurak, E. Chibowski, Interaction energy of model lipid membranes with
water, The 4th Annual Conference on the Physics, Chemistry and Biology of
Water, October 22-25, 2009, West Dover, Vermont (USA) – poster.
5. A. Szcześ, Effects of static magnetic field on water and electrolyte solutions
properties, The 4th Annual Conference on the Physics, Chemistry and Biology
of Water, October 22-25, 2009, West Dover, Vermont (USA) – poster.
F.Ch. UMCS Report 2009 – 241 –
6. E. Chibowski, K. Terpiłowski, Surface free energy of polypropylene and
polycarbonate solidifying at different solid surfaces, 13th International
Conference on Surface & Colloid Science / 83rd
Colloid & Surface Science
Symposium, June 14-19, 2009 New York (USA) – oral.
7. E. Chibowski, M. Jurak, Influence of enzymes lipases on properties of solid
supported lipid layers, 13th International Conference on Surface & Colloid
Science / 83rd
Colloid & Surface Science Symposium, June 14-19, 2009 New
York (USA) – oral.
8. K. Terpiłowski, L. Hołysz, E. Chibowski, Superhydrophobic layers obtained by
deposition polymeric fillers on glass substrate, 13th European conference on
applications of surface and interface analysis, October 18-23, 2009, Antalya
(Turkey) – poster.
9. M. Wiśniewska, K. Terpiłowski, S. Chibowski, E. Chibowski, T. Urban,
Influence of polyacrylic acid adsorption on alumina suspension stability, pH
effect, 13th European conference on applications of surface and interface
analysis, October 18-23, 2009, Antalya (Turkey) – poster.
10. K. Szymczyk, B. Jańczuk, Właściwości adsorpcyjne i zwilżające mieszanin
dwóch surfaktantów anionowych, 52 Zjazd PTChem. i SITPChem., September
12-16, 2009, Lódź (Poland) – oral.
11. A. Zdziennicka, Wpływ alkoholi krótkołańcuchowych na właściwości
adsorpcyjne Tritonu X-100 na granicy faz woda-powietrze, 52 Zjazd PTChem.
i SITPChem., September 12-16, 2009, Lódź (Poland) – oral.
12. A. Zdziennicka, K. Szymczyk, B. Jańczuk, Wpływ rodzaju surfaktantu na
zwilżalność kwarcu, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – oral.
Department of Adsorption 1. A. Borówka, G. Żukociński, Thermogravimetric investigations of Al-MCM-41
molecular sieves, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
2. J. Goworek, R. Zaleski, W. Buda, A. Kierys, Positron annihilation study of free
volumes evolution during desorption of n-heptane from silica with regular pore
geometry, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland)
– poster.
3. A. Borówka, J. Goworek, Influences of synthesis modifications on porosity of
MCM-41, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
4. A. Borówka, G. Żukociński, Kinetyka temodesorpcji z mezoporowatych
materiałów Al-MCM-41, Nowoczesne Techniki Badania Powierzchni i
Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
Conference contributions – 242 –
Department of Planar Chromatography 1. I. Malinowska, B. Marczewska – zastosowanie metod spektroskopowych w
analizach TLC, Ogólnopolskie Sympozjum „Nauka i przemysł – metody
spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10, 2009,
Lublin (Poland) – lecture.
2. Malinowska, L. Pobłocka Olech, M. Krauze-Baranowska, TLC-OPLC Analysis
of salicyc compounds in the willow bark, 5th Conference by Nordic Separation
Science Society, August 26-29, 2009, Tallin (Estonia) – poster.
3. M. Janicka, D. Pietras-Ożga, Chromatographic Evaluation of Hydrophobicity
using Micellar TLC and OPLC, 8th Balaton Symposium on High Separation
Methods and 15th International Symposium on Separation Sciences, Hungary –
poster.
4. M. Janicka, Chromatographic Evaluation of Hydrophobicity – the Effect of
Stationary Phase, 8th Balaton Symposium on High Separation Methods and 15
th
International Symposium on Separation Sciences, Hungary – poster.
5. I.Malinowska, H.Malinowski, M. Studziński, A Niewiadomy, J. Matysiak, TLC
in Strong Magnetic Fields, 8th Balaton Symposium on High Separation Methods
and 15th International Symposium on Separation Sciences, Hungary – poster.
6. K. Niezabitowska, I. Malinowska, I. Cichosz-Pośladek, The Influence of the
Electric Field on the Retention and Hydrophobicity of some PAH, 8th Balaton
Symposium on High Separation Methods and 15th International Symposium on
Separation Sciences, Hungary – poster.
Department of Physicochemistry of Solid Surface 1. M. Tęcza, E. Magner, P. Staszczuk, A. Deryło-Marczewska, D. Sternik,
Adsorption and activity of cytochrome c onto SBA-15 and TiO2, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
2. D. Sternik, M. Majdan, Thermal analysis of aluminosilicates modified by
selected dyes, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
3. A. Deryło-Marczewska, M. Błachnio, Adsorption of 2,4-D and MCPA from
aqueous solutions on activated carbon, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
4. A. Deryło-Marczewska, A. W. Marczewski, S. Winter, D. Sternik, Adsorption
of selected dyes from aqueous solutions on carbonaceous materials, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
F.Ch. UMCS Report 2009 – 243 –
5. A. Deryło-Marczewska, D. Sternik, G. Żukociński, Thermogravimetric analysis
of intermediate products of MCM-41 and MCF syntheses, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
6. W. Janusz, E. Skwarek, D. Sternik, A study on thermal behavior of
hydroxyapatite syntheses by various methods, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
7. W. Janusz, E. Skwarek, D. Sternik, Thermal decomposition of yttrium citrates
prepared in water medium, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
8. A. Gładysz-Płaska, M. Majdan, D. Sternik, S. Pikus, E. Zięba, Sorptive and
thermal properties of red mud in relation to Cr(VI), 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
9. M. Majdan, D. Sternik, M. Bujacka, A. Gładysz-Płaska, Studies of phenol
adsorption influence on thermal stability of clays modified by surfactant, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
10. M. Błachnio, P. Staszczuk, Studies of adsorption and total heterogeneity
properties of pure and modified carbon nanotube surfaces, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
11. A. Borówka, G. Żukociński, Thermogravimetric investigations of Al-MCM-41
molecular sieves, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
12. P. Staszczuk, B. Tomaszewska, D. Sternik, M. Błachnio, G. Grodzicka, G.
Żukociński, Influence of heavy metals activation on physico-chemical
properties of carbon multiwall nanotubes, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
13. P. Staszczuk, Thermogravimetry Q-TG in studies of sufrace properties of lunar
nanoparticles, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
14. P. Staszczuk, D Sternik, J. Jamroz, P. Czerwieniec, Studies of physicochemical
properties of starch nanomaterials by means of the complex techniques, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
Conference contributions – 244 –
15. A. Deryło-Marczewska, A. Świątkowski, Z. Malinowska, B. Buczek, Effects of
activated carbon surface oxidation on its sorptive properties towards selected
chlorinated phenols, 7th International Symposium Effects of Surface
Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
16. Deryło-Marczewska, A.W. Marczewski, Sz. Winter, D. Sternik, Studies on
adsorption equilibria and kinetics in the systems: aqueous solution of dyes –
mesoporous and microporous carbons, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
17. A.W. Marczewski, A. Deryło-Marczewska, K. Mirosław, D. Sternik, Studies of
adsorption equilibria and kinetics of o-, m-, p-nitro- and chlorophenols on
microporous carbons from aqueous solution, 7th International Symposium
Effects of Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-
11, 2009, Kazimierz Dolny (Poland) – oral.
18. A. Deryło-Marczewska, M. Błachnio, A.W. Marczewski, A. Świątkowski,
Adsorpcja wybranych herbicydów z roztworów wodnych na mikroporowatym
węglu aktywnym, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – oral.
19. D. Sternik, A. Deryło-Marczewska, M. Majdan, G. Żukociński, A. Gładysz-
Płaska, Wpływ adsorpcji barwników na niejednorodność powierzchni
naturalnych glinokrzemianów, Nowoczesne Techniki Badania Powierzchni i
Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
20. A. Borówka, G. Żukociński, Kinetyka termodesorpcji z mezoporowatych
materiałów Al-MCM-41, Nowoczesne Techniki Badania Powierzchni i
Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
21. A. Kaczor, R. Kalityński, M. Makarska-Białokoz, G. Żukociński, K. Kacprzak,
A. Bartyzel, D. Bartuzi, D. Matosiuk, Allosteric modulation of G protein-
coupled receptors as novel approach to the treatment of CNS disorders, II
Konwersatorium Chemii Medycznej, September 8-10, 2009, Lublin (Poland –
poster.
22. P. Staszczuk, B. Tomaszewska, D. Sternik, Influence of various modifying
agents on physical and chemical properties of carbon nanotubes, X Vedecká
Konferencia Doktorandov a Mladých Vedeckých Pracovníkov, April 2-3, 2009,
Nitra (Slovakia) – oral.
Department of Chromatographic Methods 1. K. Kondzioła, A. L. Dawidowicz, Oznaczanie wolnej frakcji indometacyny w
osoczu ludzkim z wykorzystaniem techniki HPLC/UV-VIS, I Podlaskie
Spotkania Chromatograficzne, September 20-23, 2009, Reymontówka-Kotuń,
Chlewiska (Poland) – poster.
F.Ch. UMCS Report 2009 – 245 –
2. E. Rado, A. L. Dawidowicz, Ekstrakcja przegrzaną wodą w procedurze
chromatograficznego oznaczania składu olejku eterycznego tymianku, I
Podlaskie Spotkania Chromatograficzne, September 20-23, 2009,
Reymontówka-Kotuń, Chlewiska (Poland) – poster.
3. P. Borowski, M. Pitucha, K. Pilorz, Wykorzystanie metod SQM i ESFF do
interpretacji widm IR wybranych związków z układem 1,2,4-triazolu (The use
of SQM and ESFF scaling procedures in the interpretation of IR spectra of
selected 1,2,4-triazole compounds), 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
4. A. Brzyska, P. Borowski, K. Woliński, Quantum Chemical Calculations of the
Solvent Effects on Nitrogen NMR Chemical Shifts in Oxazoles and
Oxadiazoles, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
5. J. Skubiszewska-Zięba, M. Jabłoński, K. Turżańska, R.Leboda, DSC analysis
of rat spine elements. Case study, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
6. J. Skubiszewska-Zięba, Application of microwave energy to modification of
porous structure and surface chemistry of silica gel, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
7. S. Khalameida, V. Sydorchuk, J. Skubiszewska-Zięba, R. Leboda, V.
Zazhigalov, Synthesis, thermoanalytical and spectroscopical studies of
dispersed barium titanate, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
8. J. Skubiszewka-Zięba New possibilities of vanadium-phosphorous oxide
catalysts preparation. Effect of surface chemistry7th International Symposium
Effects of Surface Heterogeneity on Adsorption and Catalysis on Solids, July
4-11, 2009, Kazimierz Dolny (Poland) – poster.
9. V. Sydorchuk, S. Khalameida, V. Zazhigalov, J. Skubiszewska-Zięba, R.
Leboda, Influence of mechanochemical activation in various media on structure
of porous and non-porous silicas, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
10. S. Khalameida, J. Skubiszewska-Zięba, R. Leboda, V. Sydorchuk, V.
Zazhigalov, Pecularities of microwave synthesis of bulk and supported
vanadium-containing catalysts, 7th International Symposium Effects of Surface
Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
11. E. Skwarek, S. Khalameida, V. Sydorchuk, W. Janusz, V. Zazhigalov, J.
Skubiszewska-Zięba, R. Leboda, Influence of presence of nickel on
electrokinetics properties of milled vanadium phosphates, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
Conference contributions – 246 –
12. V.M. Gun’ko, V.V. Turov, V.I. Zarko, R. Leboda, Influence of nonuniformity
of pre-adsorbed water on the adsorption of organic compounds, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
13. V.M. Gun’ko , V.M. Boratyrev, M.V. Borysenko, M.V. Galaburda, I.Y. Sulim,
V.S. Sergeev, L.V. Petrus, O.M. Korduban, E.V. Polshin, R. Leboda, J.
Skubiszewska-Zięba, J.P. Blitz, Structural and adsorptional nonuniformity of
nanocomposites with Fe2O3 and TiO2 grafted onto different matrices, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – oral.
14. J. Skubiszewska-Zięba, E. Skwarek, W. Janusz, R. Leboda, Influence of
heteroatoms on carbosil surface on adsorption of Nickel and cobalt ions, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
15. W.Janusz, S. Khalameida, V. Sydorchuk, E. Skwarek, V. Zazhigalov, J.
Skubiszewska-Zięba, R. Leboda, Adsorption of Zn (II) ions at the
Ti02/Electrolyte Solution Interface, Nowoczesne Techniki Badania
Powierzchni i Obszarów Międzyfazowych, October 22-23, 2009, Lublin
(Poland) – poster.
16. V. M. Gun'ko, V. I. Zarko, E. M. Pakhlov, N. V. Guzenko, J. Skubiszewska-
Zięba, R.Leboda, Thermal and Structural Properties of Nanooxide Core – PEG
or PVP Shell Composites, Nowoczesne Techniki Badania Powierzchni i
Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
17. V. Sydorchuk, S. Khalameida, J. Skubiszewska-Zięba, R. Leboda, Synthesis
and Some Physicochemical Properties of Ammonium MolybdophosphateSilica
Compositions, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
18. V. Sydorchuk, J. Skubiszewska-Zięba, S. Khalameida, R. Leboda, V.
Zazhigalov, Mechanochemical Modification of Hydro- and Xerogels of Silica.,
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
19. O. Makota, R. Leboda, J. Skubiszewska-Zięba, Yu. Trach, AFM Investigation
of Molybdenum Disilicide – Catalyst of Olefin Oxidation Reaction,
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
20. R. Typek, А.E. Кobylyanskyy, R. Leboda, V.V. Strelko, V.V. Lapko, Removal
of sulphur-containing compounds from diesel fuel by modified zeolites,
International Symposium “Progress in oilchemistry and gas industry”, June
9-12 June, 2009, Lviv (Ukraine) – poster.
F.Ch. UMCS Report 2009 – 247 –
Department of Theoretical Chemistry 1. A. Brzyska, P. Borowski, K. Wolinski, Solvent effects on nitrogen NMR
chemical shift in oxazoles and oxadiazoles – quantum chemical study,
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
2. M. Drach, J.Narkiewicz-Michałek, M.Szymula, J.Jabłoński, Co-adsorption of
Surfactants and Propyl Gallate on the Oxide Surface, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
3. A. Bieganowski, J. Cieśla, J. NarkiewiczMichałek, M. Szymula, Determination
of Agglomerates Size in the Sds/Water/Pentanol/Vitamin E System by the
Dynamic Light Scattering Method, Nowoczesne Techniki Badania Powierzchni
i Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
4. M. Drach, J. Jabłoński, J. Narkiewicz-Michałek, M. Szymula, Co-adsorption
of Surfactants and Propyl Gallate (PG) on the Oxide Surface, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
5. J. Cieśla, J. Narkiewicz-Michalek, M. Szymula, A. Bieganowski, The Use of
Dynamic Light Scattering Method for Determination of Agglomerates Size in
the SDS/ Water/ Pentanol Microemulsion, EUROANALYSIS, September 6-10,
2009, Innsbruck (Austria) – poster.
6. P. Podkościelny, K. Nieszporek, Influence of the surface energetical
heterogeneity on adsorption of phenols on activated carbons, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
7. K. Nieszporek, P. Podkościelny, The application of Dubinin-Astakhov
isotherm equation to study the hydrocarbon homologous series adsorption on
activated carbons: adsorption equilibria and calorimetry, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
8. P. Podkościelny, K. Nieszporek, Heterogeneity effects accompanying
adsorption of simple aromatic compounds from aqueous solutions on activated
carbons, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – poster.
9. K. Nieszporek, P. Podkościelny, Application of the statistical rate theory of
interfacial transport to investigate the kinetics of mixed-gas adsorption onto the
energetically homogeneous surfaces, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
Conference contributions – 248 –
10. T.P. Warzocha, T. Panczyk, W. Rudzinski, Badanie właściwości
nanourządzenia zbudowanego z nanorurki węglowej i nanocząsteczek
magnetycznych metodą Monte Carlo, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – lecture.
11. W. Płaziński, W. Rudziński, Theoretical description of the adsorption kinetics
onto porous particles: model involving the surface reaction kinetics, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
12. W. Płaziński, W. Rudziński, Heavy metals binding to biosorbents. Theoretical
modeling of the effect of pH, The second international environmental best
practices conference and AGFES educational workshop, September 14-18,
2009, Kraków (Poland) – poster.
13. T.P. Warzocha, T. Pańczyk, W. Rudziński, Physicochemical properties of
novel nanodevice composed of carbon nanotube and magnetic nanoparticles. A
Monte Carlo study , 3rd
Warsaw School of Statistical Physics, June 27–July 04,
2009, Kazimierz Dolny (Poland) – poster.
14. T.P. Warzocha, T. Pańczyk, W. Rudziński, Unique properties of novel
nanodevice composed of carbon nanotube and magnetic nanoparticles. A
Monte Carlo study, 7th International Symposium Effects of Surface
Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
15. M. Barczak, A. Dąbrowski, S. Pikus, Structural and adsorption properties of
nanoporous SBA-16 organosilicas, International Conference Functional
Materials and Nanotechnologies, March 31–April 04, 2009, Ryga (Latvia) –
poster.
16. M. Barczak, A. Dąbrowski and E. Skwarek, Synthesis, structure and adsorption
properties of SBA-15 organosilicas functionalized with different groups, 5th
Pacific Basin Conference on Adsorption Science and Technology, May 25-28,
2009, Singapur – poster.
17. M. Barczak, A. Dąbrowski, S. Pikus, Structural and adsorption properties of
SBA-16 organosilicas, 5th Pacific Basin Conference on Adsorption Science and
Technology, May 25-28, 2009, Singapur – poster.
18. M. Barczak, A. Dąbrowski, S. Pikus, SBA-15 nanomaterials as sorbents of
toxic metal ions, 42nd
IUPAC Congress, August 2-7, 2009 Glasgow (United
Kingdom) – poster.
19. 19.M. Barczak, A. Dąbrowski, S. Pikus, Functionalized SBA-15 materials as
sorbents of heavy metal ions from wastewaters, International Conference on
Functionalized and Sensing Materials, December 6-9, 2009, Bangkok
(Thailand) – poster.
F.Ch. UMCS Report 2009 – 249 –
Department for Modeling of Physico-Chemical Processes 1. Z. Sokołowska, P. Warchulska, S. Sokołowski, Changes in soil surface fractal
dimension due to accumulation of soil organic matter as resulting from the
analysis of water vapor adsorption isotherms, European Geosciences Union
General Assembly 2009, April, 2009, Vienn (Austria) – oral.
2. M. Borówko, A. Patrykiejew, S. Sokołowski, Z. Sokołowska, The influence of
modification of pore walls by organic molecules on adsorption, solvation
forces and fluid transport in slit-like pores, European Geosciences Union
General Assembly 2009, April, 2009, Vienn (Austria) – poster.
3. T. Zientarski, D. Chocyk, Ewolucja naprężeń i struktury w cienkich warstwach:
symulacje metodą dynamiki molekularnej, XI Seminarium: Powierzchnia i
Struktury Cienkowarstwowe, May, 2009, Szklarska Poręba (Poland) – poster.
4. P. Bryk, Theoretical investigations of effective interactions in colloidal
suspensions, Planer-Smoluchowski Soft Matter Workshop on Liquid Crystals
and Colloidal Dispersions, June, 2009, Lviv (Ukraine) – invited lecture.
5. S. Sokołowski, Density functional approach to adsorption of spherical
molecules on surfaces and in pores with the walls modified with end-grafted
chains, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – oral.
6. A. Patrykiejew, Two-dimensional symmetrical mixtures in an external field of
square symmetry, 7th International Symposium Effects of Surface
Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – oral.
7. M. Borówko, W. Rżysko, S. Sokołowski, T. Staszewski, Adsorption and
retention of spherical molecules on chemically bonded phases, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
8. P. Bryk, W. Rżysko, Critical wetting transition for short-ranged forces
revisited. New results of Monte Carlo simulations, 3rd
Warsaw School of
Statistical Physics, June 27–July 04, 2009, Kazimierz Dolny (Poland) – poster.
9. M. Borówko, W. Rżysko, S. Sokołowski, T. Staszewski, Density functional
approach to adsorption and retention of spherical molecules on surfaces
modified with end-grafted polymers, 3rd
Warsaw School of Statistical Physics,
June 27–July 04, 2009, Kazimierz Dolny (Poland) – poster..
10. P. Bryk, W. Rżysko, Critical wetting transition for short-ranged forces
revisited. New results of Monte Carlo simulations, 3rd
Warsaw School of
Statistical Physics, June 27–July 04, 2009, Kazimierz Dolny (Poland) – poster.
11. L. Sałamacha, A. Patrykiejew, S. Sokołowski, Ground state properties of two-
dimensional symmetrical mixtures in an external field of square symmetry, 3rd
Warsaw School of Statistical Physics, June 27–July 04, 2009, Kazimierz Dolny
(Poland).
Conference contributions – 250 –
Department of Chemical Technology
1. J. Ryczkowski, Application of CO2 in chemistry, E-MRS Fall Meeting 2009,
Warsaw University of Technology, September 14, 2009, Warsaw (Poland),
Workshop “Carbon dioxide: a new material for energy storage and challenge
for european industry” – invited lecture.
2. A. Machocki, Wodór z bio-etanolu. Efektywna droga produkcji wodoru na
nowych katalizatorach reformingu, VI Kongres Technologii Chemicznej, June
21-26, 2009, Warsaw (Poland) –lecture.
3. A. Dębczak, J. Ryczkowski, Adsorption of biodegradable chelating compounds
on inorganic oxides, 38th Winter School on Wave and Quantum Acoustics –
14th Winter Workshop on Photoacoustics and Thermal Wave Methods,
February 25-28, 2009 Korbielów (Poland) – oral.
4. G. Wójcik, Z. Hubicki, S. Pasieczna-Patkowska, Investigation of platinum(IV)
ions sorption on anion-exchanger in hydrochloric acid media by using
photoacoustic method, 38th Winter School on Wave and Quantum Acoustics –
14th Winter Workshop on Photoacoustics and Thermal Wave Methods,
February 25-28, 2009 Korbielów (Poland) – oral.
5. A. Dębczak, S. Pasieczna-Patkowska, J. Ryczkowski, J. Patkowski, Adsorpcja
soli EDTA na tlenkach metali, 41 Kolokwium Katalityczne “Kataliza w
ochronie środowiska”, March 30-April 01, 2009, Kraków (Poland) – oral.
6. M. Rotko, A. Machocki, B. Stasińska, Analiza rezultatów izotopowego
przełączenia pomiędzy 12
CH4/Ar/O2/He a 13
CH4/Kr/O2/He w stanie ustalonym
reakcji całkowitego utleniania metanu na Pd(PdO)/Al2O3, 41 Kolokwium
Katalityczne “Kataliza w ochronie środowiska”, March 30-April 01, 2009,
Kraków (Poland) – oral.
7. W. Gac, W. Zawadzki, T. Borowiecki, A. Denis, Tempereature-programmed
studies of methane decomposition in the presence of Ni-Cu/SiO2 catalysts, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – oral.
8. M. Rotko, A. Machocki, B. Stasińska, Analiza kinetyczna izotopowych
zaburzeń w stanie ustalonym reakcji katalitycznej, Ogólnopolskie Sympozjum
„Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i
możliwości” June 6-10, 2009, Lublin (Poland) – oral.
9. P. Staszczuk, B. Tomaszewska, D. Sternik, Influence of various modifying
agents on physical and chemical properties of carbon nanotubes, X Vedecká
Konferencia Doktorandov a Mladých Vedeckých Pracovníkov, April 2-3,
2009, Nitra (Slovakia) – oral.
10. T. Borowiecki, M. Pańczyk, A. Gołębiowski, K. Stołecki, R. Narowski, Wpływ
zatrucia siarką katalizatora niklowego na przebieg reakcji rozkładu i
reformingu parowego metanu, VI Kongres Technologii Chemicznej, June 21-
26, 2009, Warsaw (Poland) – oral.
F.Ch. UMCS Report 2009 – 251 –
11. T. Borowiecki, M. Pańczyk, J. Ryczkowski, A. Gołębiowski, K. Stołecki,
Katalizatory reformingu gazu wieloskładnikowego dla reaktora ogrzewanego
gazem procesowym (GHR), VI Kongres Technologii Chemicznej, June 21-26,
2009, Warsaw (Poland) – oral.
12. P. Kowalik, W. Próchniak, T. Borowiecki, Wpływ składu na właściwości
katalizatorów Cu/Zno/Al2O3 do parowego reformingu metanolu, VI Kongres
Technologii Chemicznej, June 21-26, 2009, Warsaw (Poland) – oral.
13. K. Stołecki, A. Gołębiowski, K. Michalska, R. Sylwestrowicz, T. Borowiecki,
Dezaktywacja w warunkach przemysłowych niklowego katalizatora
uwodornienia benzenu, VI Kongres Technologii Chemicznej, June 21-26,
2009, Warsaw (Poland) – oral.
14. M. Rotko, A. Machocki, B. Stasińska, Badania in situ bezpłomieniowego
katalitycznego spalania metanu, VI Kongres Technologii Chemicznej, June 21-
26, 2009, Warsaw (Poland) – oral.
15. J. Ryczkowski, Infrared photoacoustic spectroscopy in catalysis and surface
science, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – oral.
16. B. Stasinska, A. Marcewicz-Kuba, Catalytic oxidation of methane, VIII
International Conference “Mechanisms of Catalytic Reaction”, June 29-July
02, 2009, Novosibirsk (Russia) – oral.
17. M. Kuśmierz, A. Lesiuk, B. Chmiel, B. Czech, S. Pasieczna-Patkowska,
Problematyka nowoczesnych technologii chemicznych w pracach licencjackich
i magisterskich studentów ochrony środowiska UMCS, 17 Konferencja
Metodyczna „Ochrona środowiska na uniwersyteckich studiach
przyrodniczych”, August 31-September 02, 2009 Łagów (Poland) – oral.
18. G. Wroński, Z. Hubicki, S. Pasieczna-Patkowska, Application of FT-IR/PA
method in hydrometallurgical process recovery of metals from mobile phones,
38th Winter School on Wave and Quantum Acoustics – 14
th Winter Workshop
on Photoacoustics and Thermal Wave Methods, February 25-28, 2009
Korbielów (Poland) – poster.
19. P. Rusek, Z. Hubicki, G. Wójcik, S. Pasieczna-Patkowska, Application of the
FT-IR/PAS and DRS methods for studying heavy metal ions sorption on the
inorganic sorbents from waste waters, 38th Winter School on Wave and
Quantum Acoustics – 14th Winter Workshop on Photoacoustics and Thermal
Wave Methods, February 25-28, 2009 Korbielów (Poland) – poster.
20. K. Stołecki, A. Gołębiowski, W. Wróbel, K. Michalska, T. Borowiecki, Wpływ
depozytów węglowych na aktywność i selektywność niklowego katalizatora
uwodornienia benzenu, 41 Kolokwium Katalityczne “Kataliza w ochronie
środowiska”, March 30-April 01, 2009, Kraków (Poland) – poster.
21. M. Rotko, A. Machocki, B. Stasińska, Wyznaczanie liczby cząsteczek ditlenku
węgla obecnych na powierzchni katalizatorów palladowych „pracujących” w
reakcji utleniania metanu, 41 Kolokwium Katalityczne “Kataliza w ochronie
środowiska”, March 30-April 01, 2009, Kraków (Poland) – poster.
Conference contributions – 252 –
22. K. Stołecki, A. Gołębiowski, K. Michalska, T. Borowiecki, Specyfika
pomiarów aktywności katalizatora uwodornienia benzenu w warunkach
przemysłowych, 41 Kolokwium Katalityczne “Kataliza w ochronie
środowiska”, March 30-April 01, 2009, Kraków (Poland) – poster.
23. P. Rybak, B. Tomaszewska, A. Denis, W. Grzegorczyk, A. Machocki,
Konwersja etanolu na katalizatorach tlenkowych z aktywną fazą kobaltową, 41
Kolokwium Katalityczne “Kataliza w ochronie środowiska”, March 30-April
01, 2009, Kraków (Poland) – poster.
24. J. Ryczkowski, M. Pańczyk, K. Stołecki, A. Gołębiowski, T. Borowiecki,
Ocena stabilności katalizatorów niklowych dla reaktora typu GHR, 41
Kolokwium Katalityczne “Kataliza w ochronie środowiska”, March 30-April
01, 2009, Kraków (Poland) – poster.
25. W. Próchniak, P. Kowalik, T. Borowiecki, Wpływ cynku na właściwości
impregnowanych katalizatorów Cu/Al2O3 do parowego reformingu metanolu,
41 Kolokwium Katalityczne “Kataliza w ochronie środowiska”, March 30-
April 01, 2009, Kraków (Poland) – poster.
26. A. Dębczak, J. Ryczkowski, Adsorpcja biodegradowalnych chelatów na
nośnikach nieorganicznych, 41 Kolokwium Katalityczne “Kataliza w ochronie
środowiska”, March 30-April 01, 2009, Kraków (Poland) – poster.
27. A. Dębczak, J. Ryczkowski, The application of FT-IR/PA spectroscopy in
study of interactions between chelating compounds and inorganic oxides, 2009
in GAP NANOCAT, ECTN Summer School, June 21-26, Trondheim (Norway)
– poster).
28. M. Cichy, Novel applications of glycerol waste fraction – main byproduct of
biodiesel production, 2009 in GAP NANOCAT, ECTN Summer School, June
21-26, Trondheim (Norway) – poster).
29. W. Gac, A. Machocki, S. Piwko, Redox properties of the Co/CeO2-ZrO2
catalysts, 32nd
International Conference on Vacuum Microbalance and
Thermoanalytical Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) –
poster.
30. B. Stasińska, Ograniczenie emisji metanu z kopalń węglowych poprzez
katalityczne oczyszczanie powietrza wentylacyjnego, Konferencja naukowa
"Paliwa - Energia - Ochrona Środowiska", May 27-29, 2009, Kraków (Poland)
– poster.
31. B. Czech, S. Pasieczna-Patkowska, G. Wójcik, Usuwanie zanieczyszczeń
organicznych z wód i ścieków w reaktorze wstęgowym, VI Kongres
Technologii Chemicznej, June 21-26, 2009, Warsaw (Poland) – poster.
32. M. Rotko, A. Machocki, B. Stasińska, Wykorzystanie 12
CH4 i 13
CH4 do badań
katalitycznego procesu całkowitego utleniania metanu, VI Kongres
Technologii Chemicznej, June 21-26, 2009, Warsaw (Poland) – poster.
33. K. Stołecki, A. Gołębiowski, K. Michalska, R. Sylwestrowicz, T. Borowiecki,
Selektywność niklowego katalizatora uwodornienia benzenu w reaktorze
przemysłowym, VI Kongres Technologii Chemicznej, June 21-26, 2009,
Warsaw (Poland) – poster.
F.Ch. UMCS Report 2009 – 253 –
34. K. Stołecki, A. Gołębiowski, K. Michalska, T. Borowiecki, Ocena właściwości
zużytego niklowego katalizatora uwodornienia benzenu KUB-3, VI Kongres
Technologii Chemicznej, June 21-26, 2009, Warsaw (Poland) – poster.
35. M. Cichy, T. Borowiecki, Kierunki wykorzystanie odpadowej frakcji
glicerynowej z produkcji biodiesla, VI Kongres Technologii Chemicznej, June
21-26, 2009, Warsaw (Poland) – poster.
36. W. Próchniak, P. Kowalik, T. Borowiecki, Ocena aktywności katalizatorów
parowego reformingu metanolu w obszarze kinetycznym, VI Kongres
Technologii Chemicznej, June 21-26, 2009, Warsaw (Poland) – poster.
37. B. Stasinska, M. Rotko, A. Machocki, Steady State Isotopic Transient Kinetic
Analysis of Catalytic Process of Complete Methane Oxidation, VIII
International Conference “Mechanisms of Catalytic Reaction”, June 29-July
02, 2009, Novosibirsk (Russia) – poster.
38. A. Marcewicz-Kuba, B. Stasinska, A. Machocki, M. Rotko, A. Debczak,
Catalytic Utilization of Methane from Coal Mine Ventilation Air, VIII
International Conference “Mechanisms of Catalytic Reaction”, June 29-July
02, 2009, Novosibirsk (Russia) – poster.
39. W. Gac, S. Pasieczna-Patkowska, W. Zawadzki, A. Vaz, The influence of
water vapour on the oxidation of CO in the presence of the cryptomelane-type
silver-manganese catalyst, 6th World Congress on Oxidation Catalysis
“Towards an integrated approach in innovation and development”, July 5-10,
2009 Lille (France) –poster.
40. M. Rotko, A. Machocki, B. Stasinska, Determination of kinetic parameters for
complete methane oxidation over supported palladium catalysts by means of
the SSITKA method, 6th World Congress on Oxidation Catalysis “Towards an
integrated approach in innovation and development”, July 5-10, 2009 Lille
(France) –poster.
41. A. Dębczak, J. Ryczkowski, J. Patkowski, Adsorption of biodegradable
chelating compounds on inorganic oxides, 7th International Symposium Effects
of Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11,
2009, Kazimierz Dolny (Poland) – poster.
42. S. Pasieczna-Patkowska, B. Czech, J. Ryczkowski, J. Patkowski, Removal of
recalcitrant pollutants from wastewater, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
43. M. Rotko, A. Machocki, B. Stasińska, Studies of catalytic process of complete
oxidation of methane by SSITKA method, 7th International Symposium Effects
of Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11,
2009, Kazimierz Dolny (Poland) – poster.
44. A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, Nano- and micro-powder of
zirconia and ceria-supported cobalt catalysts for the steam reforming of
bioethanol, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – poster.
Conference contributions – 254 –
45. Z. Surowiec, M. Wiertel, B. Bierska-Piech, M. Budzyński, W. Gac, J.
Goworek, Effect of a reduction on transformation of superparamagnetic iron-
cobalt oxide nanoparticles, International Conference on the Applications of the
Mössbauer Effect, July 19 - 24, 2009, Vienna (Austria) – poster.
46. M. Rotko, A. Machocki, B. Stasińska, Isotopic transient study of catalytic
oxidation of methane on palladium catalysts, 9th European Congress on
Catalysis EUROPACAT-IX, August 30-September 04, 2009, Salamanca
(Spain) –poster.
47. A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, J. Cieniuch, A high-efficient
Co/ZnO catalyst for conversion of ethanol to hydrogen, 9th European Congress
on Catalysis EUROPACAT-IX, August 30-September 04, 2009, Salamanca
(Spain) –poster.
48. A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, W. Niemiec, Influence of
cerium modifier of cobalt-based catalysts on the steam reforming of bio-
ethanol process, 9th European Congress on Catalysis EUROPACAT-IX,
August 30-September 04, 2009, Salamanca (Spain) – poster.
49. B. Czech, S. Pasieczna-Patkowska, M. Kuśmierz, W. Ćwikła-Bundyra, Wpływ
preparatyki katalizatorów na efektywność usuwania związków organicznych z
wody, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland)
– poster.
50. A. Marcewicz-Kuba, B. Stasińska, Katalizatory dopalania węglowodorów, , 52
Zjazd PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
51. W. Ćwikła-Bundyra, S. Pasieczna-Patkowska, Zeolity dotowane Fe jako
aktywne i selektywne katalizatory procesu redukcji tlenków azotu, , 52 Zjazd
PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
52. B. Czech, S. Pasieczna-Patkowska, M. Kuśmierz, Badanie prekursorów
katalizatorów fotoutleniania metodami FT-IR i FT-IR/PAS, , 52 Zjazd
PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
53. B. Czech, S. Pasieczna-Patkowska, M. Kuśmierz, Zastosowanie nowych
chelatów w preparatyce katalizatorów metodą DIM, , 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
54. M. Kuśmierz, B. Czech, S. Pasieczna-Patkowska, Uwodornienie dwutlenku
węgla na katalizatorach Pd/ZnO/Al2O3, , 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
55. W. Gac, W. Zawadzki, Z. Surowiec, An application of nanocasting technique
for the preparation of cobalt and iron oxides, Nowoczesne Techniki Badania
Powierzchni i Obszarów Międzyfazowych, October 22-23, 2009, Lublin
(Poland) – poster.
56. A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, Cobalt catalysts with nano-
and micro-dispersed supports for the steam reforming of etanol, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
F.Ch. UMCS Report 2009 – 255 –
57. M. Rotko, A. Machocki, B. Stasińska, Steady state isotopic transient analysis
of the process of complete methane oxidation over palladium catalysts,
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
58. P. Rybak, B. Tomaszewska, A. Denis, W. Grzegorczyk, A. Machocki,
Conversion of etanol over potassium-promoted cobalt catalysts, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
59. B. Tomaszewska, P. Rybak, A. Machocki, W. Grzegorczyk, A. Denis, Cobalt-
based catalysts for selective production of hydrogen in the etanol steam
reforming, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
Department of Radiochemistry and Colloid Chemistry
1. J. Solecki, J. Orzeł, Oznaczanie radionuklidów 137
Cs i 90
Sr w zbożach i
handlowych produktach zbożowych, K-13, V Krajowa Konferencja
Radiochemii i Chemii Jądrowej, May 24-27, 2009, Kraków-Przegorzały
(Poland) – poster.
2. J. Solecki, Badanie zawartości radionuklidów 137
Cs i 90
Sr w próbkach osadów
dennych z Morza Barentsa, P-17, V Krajowa Konferencja Radiochemii i
Chemii Jądrowej, May 24-27, 2009, Kraków-Przegorzały (Poland) – oral.
3. A. Komosa, J. Orzeł, S. Żądełek, Migracja i biodostępność plutonu w glebach
Lubelszczyzny, V Krajowa Konferencja Radiochemii i Chemii Jądrowej, May
24-27, 2009, Kraków-Przegorzały (Poland) – oral.
4. A. Komosa, I. Kitowski, J.W. Mietelski, J. Orzeł, Z. Komosa, Ptaki jako
przedmiot badań radioekologicznych. V Krajowa Konferencja Radiochemii i
Chemii Jądrowej, May 24-27, 2009, Kraków-Przegorzały (Poland) – poster.
5. M. Piekarz, A. Komosa, Optymalizacja warunków selektywnej ekstrakcji
plutonu od uranu i toru z użyciem chlorku metylotrioktyloamoniowego i
pomiaru z ciekłym scyntylatorem, V Krajowa Konferencja Radiochemii i
Chemii Jądrowej, May 24-27, 2009, Kraków-Przegorzały (Poland) – poster.
6. A. Komosa, K. Ślepeczka, Badanie wpływu objętości scyntylatora na
parametry pomiaru 3H i
14C przy użyciu spektrometru Quantulus, V Krajowa
Konferencja Radiochemii i Chemii Jądrowej, May 24-27, 2009, Kraków-
Przegorzały (Poland) – poster.
7. M. Piekarz, A. Komosa, Oznaczanie plutonu, uranu i toru metodą ciekłoscyntylacyjną, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – poster.
8. S. Żądełek, A. Komosa, J. Orzeł, M. Piekarz, Badanie dystrybucji plutonu
pomiędzy frakcjami otrzymanymi w wyniku sekwencyjnej ekstrakcji próbek
profili glebowych, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – poster.
Conference contributions – 256 –
9. A, Komosa, J. Orzeł, M. Piekarz, Badania obecności i przemieszczania się izotopów plutonu w glebach Lubelszczyzny, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
10. M. Wiśniewska, The Temperature Effect on the Adsorption Properties of Silica
– Polyacrylic Acid Interface, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
11. M. Wiśniewska, St. Chibowski, T. Urban, Investigation of the Alumina
Properties with Adsorbed Polyvinyl Alcohol, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
12. M. Wiśniewska, K. Terpiłowski, St. Chibowski, E. Chibowski, T. Urban,
Influence of Polyacrylic Acid Adsorption on Alumina Suspension Stability, pH
Effect, 13th European conference on applications of surface and interface
analysis, October 18-23, 2009, Antalya (Turkey) – poster.
13. M. Wiśniewska, St. Chibowski, T. Urban, The Temperature Influence on
Adsorption Properties of PVA-ZrO2 and PEG-ZrO2 Systems, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
14. A. Dębczak, S. Pasieczna-Patkowska, J. Ryczkowski, J. Patkowski, Adsorpcja
soli EDTA na tlenkach metali, 41 Kolokwium Katalityczne “Kataliza w
ochronie środowiska”, March 30-April 01, 2009, Kraków (Poland) – oral.
15. W. Janusz, E. Skwarek, D. Sternik, A study on thermal behavior of
hydroxyapatite syntheses by various methods, 32nd
International Conference on
Vacuum Microbalance and Thermoanalytical Techniques, June 21-24, 2009,
Kazimierz Dolny (Poland) – poster.
16. W. Janusz, E. Skwarek, D. Sternik, Thermal decomposition of yttrium citrates
prepared in water medium, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
17. M. Drach, J. Jabłoński, J. Narkiewicz- Michałek, M. Szymula, Co-Adsorption
of surfactants and propyl gallate (PG) on the oxide surface, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
18. M. Drach, J. Jabłoński, J. Narkiewicz- Michałek, M. Szymula, The Influence of
microenvironment on the electrochemical behavior of selected antioxidants,
23th Conference of the European Colloid and Interface Society, September 06-
11, 2009, Antalya (Turkey).
19. M. Drach, J. Narkiewicz-Michałek, M.Szymula, J. Jabłoński, Co-adsorption of
Surfactants and Propyl Gallate on the Oxide Surface, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
F.Ch. UMCS Report 2009 – 257 –
20. A. Bieganowski, J. Cieśla, J. Narkiewicz-Michałek, M. Szymula,
Determination of Agglomerates Size in the Sds/Water/Pentanol/Vitamin E
System by the Dynamic Light Scattering Method, Nowoczesne Techniki
Badania Powierzchni i Obszarów Międzyfazowych, October 22-23, 2009,
Lublin (Poland) – poster.
21. J. Cieśla, J. Narkiewicz-Michalek, M. Szymula, A. Bieganowski, The Use of
Dynamic Light Scattering Method for Determination of Agglomerates Size in
the SDS/ Water/ Pentanol Microemulsion, , EUROANALYSIS, September 6-
10, 2009, Innsbruck (Austria) – poster.
22. A. Deryło-Marczewska, A.W. Marczewski, Sz. Winter, D. Sternik, Adsorption
of selected dyes from aqueous solutions on carbonaceous materials, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
23. A.W. Marczewski, Kinetics and Equilibrium of Adsorption of Organic Solutes
on Mesoporous Carbons, 7th International Symposium Effects of Surface
Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
24. A. Deryło-Marczewska, A. W. Marczewski, Sz. Winter and D. Sternik, Studies
of Adsorption Equilibria and Kinetics in the Systems: Aqueous Solution of
Dyes - Mesoporous and Microporous Carbons, 7th International Symposium
Effects of Surface Heterogeneity on Adsorption and Catalysis on Solids, July
4-11, 2009, Kazimierz Dolny (Poland) – poster.
25. A.W. Marczewski, Adsorption Kinetics – Optimization of Measurements and
Data Analysis, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
26. A.W. Marczewski, A. Deryło-Marczewska, K. Mirosław and D. Sternik,
Studies of Adsorption Equilibria and Kinetics of o-, m-, p- Nitro- and
Chlorophenols on Microporous Carbons from Aqueous Solutions, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – oral.
27. Deryło-Marczewska, M. Błachnio, A. W. Marczewski, A. Świątkowski,
Adsorption of selected herbicydes from aqueous solutions on microporous
activated carbon, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – oral.
28. S. Pasieczna-Patkowska, B. Czech, J. Ryczkowski, J. Patkowski, Removal of
recalcitrant pollutants from wastewater, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
29. J. Patkowski, Influence of magnetic field on zeta potential od magnetite',
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
30. J. Skubiszewska-Zięba, E. Skwarek, W. Janusz, R. Leboda, Influence of
heteroatoms on carbosil surface on adsorption of nickel and cobalt ions, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
Conference contributions – 258 –
31. W. Janusz, E. Skwarek, Comparison of adsorption of ion of nickel on nano-
Al2O3 and polycrystalline- Al2O3, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
32. E. Skwarek, S. Khalameida, V. Sydorchuk, W. Janusz, V. Zazhigalov, J.
Skubiszewska-Zięba, R. Leboda, Influence of presence of nicel on
electrokinetic’s properties of milled vanadium phosphatese, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
33. W. Janusz, E. Skwarek, A. Dąbrowski, M. Barczak, Functionalized sba-15
organosilicas as sorbents of zinc(II) ions, 7th International Symposium Effects
of Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11,
2009, Kazimierz Dolny (Poland) – poster.
34. W. Janusz, S. Khalameida,V. Sydorchuk, E. Skwarek,V. Zazhigalov, J.
Skubiszewska-Zięba, R. Leboda, Adsorption of Zn (II) ions at the
TiO2/electrolyte solution interface, Nowoczesne Techniki Badania Powierzchni
i Obszarów Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
35. W. Janusz, E. Skwarek, The study of the electrochemical properties of the
hydroxyapatite/electrolyte interface, Nowoczesne Techniki Badania
Powierzchni i Obszarów Międzyfazowych, October 22-23, 2009, Lublin
(Poland).
36. St. Chibowski, M. Reszka, Sorpcyjno-desorpcyjne właściwości żywicy
syntetycznej przy usuwaniu izotopów promieniotwórczych z roztworów, V
Krajowa Konferencja Radiochemii i Chemii Jądrowej, May 24-27, 2009,
Kraków-Przegorzały (Poland) – oral.
Department of Crystallography
1. A. Drzewiecka, A.E. Kozioł, Analiza strukturalna i spektroskopowa
pochodnych benzofuranu, Ogólnopolskie Sympozjum „Nauka i przemysł –
metody spektroskopowe w praktyce, nowe wyzwania i możliwości” June 6-10,
2009, Lublin (Poland) – oral.
2. A. Drzewiecka, A.E. Kozioł, T. Pena Ruiz, M. Fernandez Gomez, M. Struga, J.
Kossakowski, Structural studies on benzofuran derivatives with biological
activity. Methyl ester of 6-acetyl-5-hydroxy-2-methyl-3-benzofurancarboxylic
acid, 51 Konwersatorium Krystalograficzne, June 25-27, 2009, Wrocław
(Poland) – poster.
3. A.E. Kozioł, L. Mazur, B. Modzelewska-Banachiewicz, Rozdział racematu w
czasie krystalizacji z DMSO, 51 Konwersatorium Krystalograficzne, June 25-
27, 2009, Wrocław (Poland) – poster.
4. I. Dybała, A.E. Kozioł, K. Sztanke, Badania strukturalne 3-podstawionych
pochodnych 4-okso-8-arylo-tetrahydroimidazo[2,1-C][1,2,4]triazyny, 51 Kon-
wersatorium Krystalograficzne, June 25-27, 2009, Wrocław (Poland) – poster.
F.Ch. UMCS Report 2009 – 259 –
5. A. Drzewiecka, A.E. Kozioł, M. Struga, J. Kossakowski, Structural analysis of
derivatives of coumarin, 51 Konwersatorium Krystalograficzne, June 25-27,
2009, Wrocław (Poland) – poster.
6. T. Pena Ruiz, A. Drzewiecka, M. Fernandez Gomez, A.E. Kozioł, Structural
studies on Kv1.3 potassium channel blockers: visnaginone and khellinone, X
International Conference on Molecular Spectroscopy, September 6-10, 2009
Kraków-Białka Tatrzańska (Poland) – oral.
7. A. Drzewiecka, A.E. Kozioł, T. Pena Ruiz, M. Fernandez Gomez, M. Struga, J.
Kossakowski, Structural studies of 7-acetyl-6-methoxy-3-methyl-2-benzo-
furancarboxylic acid and its sodium complex, X International Conference on
Molecular Spectroscopy, September 6-10, 2009 Kraków-Białka Tatrzańska
(Poland) – poster.
8. A.E. Kozioł, M. Pitucha, Modyfikacje oddziaływań międzycząsteczkowych w
kryształach pochodnych 4-etylo-1,2,4-triazolo-5-tionu, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
9. A. Drzewiecka, A.E. Kozioł, M. Struga, J. Kossakowski, Analiza konfor-
macyjna pochodnych kwasu benzofuranokarboksylowego, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – oral.
10. M. Struga, J. Kossakowski, S. Rosołowski, J. Stefańska, M. Kulas, A.E.
Kozioł, New triazole derivatives as compounds with potential biological
activity, II Konwersatorium Chemii Medycznej Polskiego Towarzystwa
Chemii Medycznej, September 8-10, 2009, Lublin (Poland) – poster.
11. S. Pikus, E. Celer, M. Jaroniec, L. A. Solovyov, M. Kozak, Studies of intrawall
porosity in hexagonally ordered mesostructures of SBA-15 by small ange X-
ray scattering and nitrogen adsorption, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
12. M. Zienkiewicz, S. Pikus, E. Olszewska, M. Barczak, Mezoporous ordered
organosilicas containing Zr and Ti species, XXI Conference on Applied
Crystallography, September 20-24, 2009, Zakopane (Poland) – oral.
13. E. Olszewska, L. Pająk, M. Majdan, S. Pikus, High quality powder diffraction
data and structural refinements for Mg, Ca, Sr and Ba mordenites, XXI
Conference on Applied Crystallography, September 20-24, 2009, Zakopane
(Poland) – poster.
14. E.Olszewska, M. Kozak, M. Zienkiewicz, S. Pikus, TEM, XPS and XRD study
of mesoporous ordered organosilicas containing Zr and Ti ions, Nowoczesne
Techniki Badania Powierzchni i Obszarów Międzyfazowych, October 22-23,
2009, Lublin (Poland) – poster.
Department of Organic Chemistry
1. O.M. Demchuk, K. Kielar, K.M. Pietrusiewicz, Atropoisomeric phosphorus
ligands for the asymmetric X-coupling and C-H activation reactions, 42nd
IUPAC Congress, August 2-7, 2009 Glasgow (United Kingdom).
Conference contributions – 260 –
2. O.M. Demchuk, K. Kielar, K.M. Pietrusiewicz, Novel Bulky and Electronically
Rich Atropoisomeric Phosphorus Ligands: Synthesis and Application in X-
coupling and C-H Activation Reactions, The XIIth European Symposium on
Organic Reactivity (ESOR XII), August 6-11, 2009, Haifa (Israel).
3. O.M. Demchuk, K. Kielar, K.M Pietrusiewicz, The straightforward approach to
sythesis of new phosphorus ligands and their further application in the X-
Coupling as well as C-H activation reactions, The XXII Conference on
Advances In Organic Synthesis (AOS 2009), July 8-12, 2009, Karpacz
(Poland).
4. A. Włodarczyk, M. Stankevič, K.M. Pietrusiewicz, Reactions of
organophosphorus compounds possessing P-N bonds with alkali metals, VII
International Congress of Young Chemists, YoungChem 2009, September 14-
18, 2009, Zegrze (Poland).
5. K.M. Pietrusiewicz, O.M. Demchuk, K. Glegoła, G. Wójciuk, Olefin
Metathesis as a Tool Syntheis of Novel Chiral Diphosphine Ligands, 15th
IUPAC International Symposium on Organometallic Chemistry Directed
Towards Organic Synthesis (OMCOS 15), July 26-30, 2009, Glasgow (United
Kingdom) – poster.
6. S. Sowa, K.M. Pietrusiewicz, M. Stankevič, A. Szmigielska, BH3 as a
convenient reducing agent for the reduction of P=O bonds in the synthesis of
functionalized phosphorus(III) compounds, XII Regional Seminar of PhD
Students on Organometallic and Coordination Chemistry, September 3-7, 2009,
Szklarska Poręba (Poland) –oral.
7. K.M. Pietrusiewicz, S. Sowa, M. Stankevič, A. Szmigielska, Redukcja
wiązania P=O za pomocą kompleksów BH3 w funkcjonalizowanych tlenkach
trzeciorzędowych fosfin, fosfinianach i fosfonianach, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland).
8. M. Stankevič, K. M. Pietrusiewicz, Redukcja Bircha w chemii związków
fosforoorganicznych, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – lecture.
9. S. Sowa, K. M. Pietrusiewicz, M. Stankevic, A. Szmigielska, BH3 as
convenient reducing agent for the reduction of P=O bonds in the synthesis of
functionalized phosphorus(III) compounds, XII Ogólnopolskie Sympozjum
Sekcji Chemii Heteroorganicznej PTCh – Postępy w Chemii Związków
Heteroorganicznych, November 27, 2009, Łódź (Poland) – poster.
10. A. Włodarczyk, M. Stankevič, K.M. Pietrusiewicz, Reactions of
organophosphorus compounds possessing P-N bonds with alkali metals, XII
Ogólnopolskie Sympozjum Sekcji Chemii Heteroorganicznej PTCh – Postępy
w Chemii Związków Heteroorganicznych, November 27, 2009, Łódź (Poland)
– poster.
11. O.M. Demchuk, M. Topyła, K. Kielar, K.M. Pietrusiewicz, Synteza i
zastosowanie nowych atropoizomerycznych ligandów fosforowych, XII
Ogólnopolskie Sympozjum Sekcji Chemii Heteroorganicznej PTCh – Postępy
w Chemii Związków Heteroorganicznych, November 27, 2009, Łódź (Poland)
– poster.
F.Ch. UMCS Report 2009 – 261 –
Department of Polymer Chemistry
1. M. Worzakowska, Relationship between network structure and thermo-
mechanical properties of cured polyesters, 10th Conference on Calorimetry and
Thermal Analysis, 30 August – 3 September 2009, Zakopane (Poland) –
invited lecture.
2. M. Worzakowska, Succinic/ or glutaric anhydride modified unsaturated
(epoxy) polyesters, 10th Conference on Calorimetry and Thermal Analysis, 30
August – 3 September 2009, Zakopane (Poland) – poster.
3. M. Worzakowska, Thermal properties of copolymers based on modified
unsaturated (epoxy) polyesters, 10th Conference on Calorimetry and Thermal
Analysis, 30 August – 3 September 2009, Zakopane (Poland) – poster.
4. M. Grochowicz, B. Gawdzik DSC and IGC applications for the studies of
crosslinked polymeric microspheres, 10th Conference on Calorimetry and
Thermal Analysis, 30 August – 3 September 2009, Zakopane (Poland) – poster.
5. M. Worzakowska, Network structure/property relationship in cross-linked
blends prepared from unsaturated polyester resin and epoxy polyester,
European Polymer Congress (EPF’09), July 12-17, 2009, Graz (Austria) –
poster.
6. M. Worzakowska, Synthesis, characterization and properties of adipic/ or
sebacic acid modified unsaturated epoxy polyesters, European Polymer
Congress (EPF’09), July 12-17, 2009, Graz (Austria) – poster.
7. M. Podgórski, J. Księżopolski, M. Worzakowska, A study of the relationship
between network structure and thermo-mechanical properties of crosslinked
di(metyl)acrylates-substituent derivatives of glicerol dimethacrylate, European
Polymer Congress (EPF’09), July 12-17, 2009, Graz (Austria) – poster.
8. B. Podkościelna and A. Bartnicki, Photoinitiated polymerization of
methacrylate monomer: 4,4’-thiodiphenole and 1-vinyl-2-pyrrolidinone,
European Polymer Congress, EPF’09, July 12-17, 2009, Graz (Austria) –
poster.
9. B. Podkościelna and Ł. Szajnecki, Application of poly(MMA-co-EGDMA) as
a sorbent for solid phase extraction of selected pesticides, European Polymer
Congress, EPF’09, July 12-17, 2009, Graz (Austria) – poster.
10. B. Podkościelna, B. Gawdzik and A. Bartnicki, Synthesis, structure and
properties of the new polymeric microspheres derivatives of naphthalene-2,7-
diol and DVB, European Polymer Congress, EPF’09, July 12-17, 2009, Graz
(Austria) – poster.
11. M. Worzakowska, Curing reaction of unsaturated (epoxy) polyesters based on
different aliphatic glycols, 32nd
International Conference on Vacuum
Microbalance and Thermoanalytical Techniques, June 21-24, 2009, Kazimierz
Dolny (Poland) – poster.
12. M. Worzakowska, Thermal properties of unsaturated (epoxy) polyesters, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
Conference contributions – 262 –
13. B. Podkościelna, B. Gawdzik, M. Worzakowska, Studies of synthesis and
thermal resistance properties of acrylate copolymers, 32nd
International
Conference on Vacuum Microbalance and Thermoanalytical Techniques, June
21-24, 2009, Kazimierz Dolny (Poland) – poster.
14. M. Grochowicz, M. Sobiesiak, B. Gawdzik, Use of IGC in determination of
glass transition temperature of crosslinked polymeric microspheres, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
15. M. Maciejewska, B. Podkościelna and M. Rogulska, Effect of crosslinker on
thermal properties porous copolymers of 1-vinyl-2-pyrrolidone, 32nd
International Conference on Vacuum Microbalance and Thermoanalytical
Techniques, June 21-24, 2009, Kazimierz Dolny (Poland) – poster.
16. B. Podkościelna, B. Gawdzik, Studies of influence of diluent compositions on
the porous structure of copolymers methacrylate derivatives aromatic diols and
divinylbenzene, 7th International Symposium Effects of Surface Heterogeneity
on Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland) – poster.
17. M. Maciejewska, B. Gawdzik, Influence of crosslinker on the porous structure
and polarity copolymers of 1-vinyl-2-pyrrolidone, 7th International Symposium
Effects of Surface Heterogeneity on Adsorption and Catalysis on Solids, July
4-11, 2009, Kazimierz Dolny (Poland) – poster.
18. M. Sobiesiak, B. Gawdzik, A.M. Puziy, O.I. Poddubnaya, Analysis of structure
and properties of active carbons and their copolymeric precursors, 7th
International Symposium Effects of Surface Heterogeneity on Adsorption and
Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
19. M. Sobiesiak, B. Podkoscielna, Comparison of structure and physico-chemical
properties of porous DVB copolymers, 7th International Symposium Effects of
Surface Heterogeneity on Adsorption and Catalysis on Solids, July 4-11, 2009,
Kazimierz Dolny (Poland) – poster.
20. C.A. Reinish, A.M. Puziy, O.I. Poddubnaya, B. Gawdzik, M. Sobiesiak, M.M.
Tsyba, One-pot functionalisation of nanostructured carbons, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
21. A.M. Puziy, O.I. Poddubnaya, B. Gawdzik, M. Sobiesiak, C.A. Reinish, M.M.
Tsyba, Nanostructured carbons for solid phase extraction, 7th International
Symposium Effects of Surface Heterogeneity on Adsorption and Catalysis on
Solids, July 4-11, 2009, Kazimierz Dolny (Poland) – poster.
22. M. Sobiesiak, Mesoporous active carbons for SPE-HPLC analyses of aqueous
samples obtained by the template method, 2nd
International Environmental Best
Practices Conference and AGFES Educational Workshop, September, 14-18,
2009, Kraków (Polska) – poster.
23. A.M.Puziy, O.I.Poddubnaya, B.Gawdzik, M.Sobiesiak, C.A.Reinish,
M.M.Tsyba, T.P.Segeda, M.I.Danylenko, Solid Phase Extraction Using
Nanostructured Carbons Obtained by Template Metod, Carbon 2009, June
14-19, 2009, Bearritz (France) – poster.
F.Ch. UMCS Report 2009 – 263 –
24. M. Sobiesiak, Zastosowanie skaningowej mikroskopii elektronowej i
mikroskopii sił atomowych do badania powierzchni i topografii materiałów
porowatych, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
25. J. Osypiuk-Tomasik, M. Maciejewska, B. Podkościelna, B. Gawdzik, Synteza i
ocena właściwości fizykochemicznych matryc polimerowych DMGE-DVB i
VP-DVB, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
26. M. Grochowicz, B. Gawdzik, Synteza i struktura metakrylowych mikrosfer
polimerowych, Nowoczesne Techniki Badania Powierzchni i Obszarów
Międzyfazowych, October 22-23, 2009, Lublin (Poland) – poster.
27. M. Maciejewska, B. Podkościelna, J. Osypiuk-Tomasik, Studies on
physicochemical properties of highly porous polymeric microspheres,
Nowoczesne Techniki Badania Powierzchni i Obszarów Międzyfazowych,
October 22-23, 2009, Lublin (Poland) – poster.
28. B. Podkościelna, B. Gawdzik, A. Bartnicki, Synthesis, structure and properties
of the new methacrylate microspheres, Nowoczesne Techniki Badania
Powierzchni i Obszarów Międzyfazowych, October 22-23, 2009, Lublin
(Poland) – poster.
29. M. Sobiesiak, Analiza spektroskopowa w podczerwieni struktury chemicznej
kopolimerów BM-DVB i ich węglowych pochodnych Ogólnopolskie
Sympozjum „Nauka i przemysł – metody spektroskopowe w praktyce, nowe
wyzwania i możliwości” June 6-10, 2009, Lublin (Poland) – poster.
30. B. Gawdzik, J. Osypiuk-Tomasik, M. Maciejewska, A. Kultys, Polimerowe
fazy stacjonarne VP-DVB i DMGE-DVB do HPLC, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
31. M. Podgórski, J. Księżopolski, Synteza i charakterystyka właściwości nowych
dimetakrylanów o różnej długości łańcucha jako potencjalnych monomerów
dentystycznych, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009,
Lódź (Poland) – poster.
32. M. Podgórski, J. Księżopolski, Synteza i właściwości metakrylowych
pochodnych bezwodnika ftalowego, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – poster.
33. M. Podgórski, J. Księżopolski, Wpływ wewnątrzcząsteczkowych cyklizacji
oraz międzycząsteczkowego sieciowania na strukturę sieci polimerowej
wielofunkcyjnych (met)akrylanów, 52 Zjazd PTChem. i SITPChem.,
September 12-16, 2009, Lódź (Poland) – oral.
Department of Optical Fibres Technology
1. J. Wójcik, J. Pędzisz, G. Wójcik, A. Walewski, J. Kopeć, P. Mergo, J.Klimek,
K. Poturaj, K. Skorupski, M. Makara, L. Czyżewska, Technologia
światłowodów mPOF w Polsce, XII Konferencja „Światłowody i ich
zastosowania”, October, 14-17, 2009, Lublin-Krasnobród (Poland).
Conference contributions – 264 –
2. J. Rayss, A. Borkowski, Z. Rzączyńska, A. Kula, „Kompleksy europu i terbu w
fotoutwardzalnej matrycy polimerowej do zastosowań w światłowodowych
czujnikach UV, XII Konferencja „Światłowody i ich zastosowania”, October,
14-17, 2009, Lublin-Krasnobród (Poland).
3. P. Mergo, J. Wójcik, Rozwój technologii światłowodów mikrostrukturalnych ze
szkła kwarcowego, XII Konferencja „Światłowody i ich zastosowania”,
October, 14-17, 2009, Lublin-Krasnobród (Poland).
4. T. Martynkien, J. Olszewski, G. Statkiewicz-Barabach, W. Urbańczyk, J.
Wójcik, P. Mergo, M. Makara, T. Nasiłowski, F. Berghmans, H. Thienpont, R.
Piramidowicz, P. Gdula, Interferencyjny pomiar dyspersji chromatycznej we
włóknach fotonicznych z podwójnym koncentrycznym rdzeniem, XII
Konferencja „Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-
Krasnobród (Poland).
5. A. Anuszkiewicz, G. Statkiewicz-Barabach, W. Urbańczyk, J. Wójcik, Siatki
długookresowe wytworzone różnymi metodami w światłowodach fotonicznych
o wysokiej dwójłomności, XII Konferencja „Światłowody i ich zastosowania”,
October, 14-17, 2009, Lublin-Krasnobród (Poland).
6. P. Mergo, J. Wójcik, K. Poturaj, J. Klimek, L. Czyżewska, Światłowód
polaryzujący na zasadzie efektu plazmonowego, XII Konferencja
„Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-Krasnobród
(Poland).
7. J. Wójcik, P. Mergo, J. Klimek, G. Wójcik, K. Skorupski, J. Pędzisz, J. Kopeć, Technologia światłowodów mPOF o wysokiej dwójłomności, XII Konferencja
„Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-Krasnobród
(Poland).
8. J. Wójcik, P. Mergo, M. Makara, K. Poturaj, K. Skorupski, J. Klimek,
Światłowód fotoniczny o wysokiej dwójłomności typu V do czujników
ciśnienia, XII Konferencja „Światłowody i ich zastosowania”, October, 14-17,
2009, Lublin-Krasnobród (Poland).
9. J. Wójcik, A. Strzałka, K. Poturaj, J. Klimek, M. Makara, Projekt palnika OVD
z generacją aerozolu do syntezy szkieł high silica, XII Konferencja
„Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-Krasnobród
(Poland).
10. J. Wójcik, M. Matusewicz, P. Mergo, M. Makara, Wytrzymałość mechaniczna
światłowodów fotonicznych, XII Konferencja „Światłowody i ich
zastosowania”, October, 14-17, 2009, Lublin-Krasnobród (Poland).
11. M. Gil, A. Dębczak, J. Rayss, W. Podkościelny, A. Gorgol, J. Widomski,
Badania metodą FTIR procesów fotopolimeryzacji polimerów do zastosowań w
fotonice, XII Konferencja „Światłowody i ich zastosowania”, October, 14-17,
2009, Lublin-Krasnobród (Poland).
F.Ch. UMCS Report 2009 – 265 –
12. T.R. Woliński, D. Budaszewski, M. Chychłowski, A. Czapla, R. Dąbrowski, A.
W. Domański, S. Ertman, P. Lesiak, E. Nowinowski-Kruszelnicki, K.
Rutkowska, M. Sierakowski, M. Tefelska, J. Wójcik, Fotoniczne światłowody
ciekłokrystaliczne – stan badań i perspektywy rozwoju, XII Konferencja
„Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-Krasnobród
(Poland).
13. J. Wójcik, G. Wójcik, K. Poturaj, K. Skorupski, A. Walewski, Technologia
światłowodów mPOF o niskiej dwójłomności, XII Konferencja „Światłowody i
ich zastosowania”, October, 14-17, 2009, Lublin-Krasnobród (Poland).
14. M. Tefelska, T. R. Woliński, S. Ertman, M. Chychłowski, R. Dąbrowski, J.
Wójcik, Propagacja światła w światłowodach fotonicznych wypełnionych
nematykami chiralnymi, XII Konferencja „Światłowody i ich zastosowania”,
October, 14-17, 2009, Lublin-Krasnobród (Poland).
15. J. Hunicz, J. Wójcik, P. Kordos, Badanie procesu tworzenia mieszanki w
silniku benzynowym z wykorzystaniem czujnika światłowodowego, XII
Konferencja „Światłowody i ich zastosowania”, October, 14-17, 2009, Lublin-
Krasnobród (Poland).
16. J. Wójcik, P. Mergo, Krzysztof Skorupski, Lidia Czyżewska, Grzegorz Wójcik,
"New side hole fiber for 1550 wavelength”, Integrated Optical Sensors,
Korbelów, Polska, 23 – 26.02.2009
17. J. Wójcik, P. Mergo, M. Makara, K. Poturaj, J. Klimek, K. Skorupski, A.
Walewski, Development of high birefringent photonic crystal fibers technology,
Integrated Optical Sensors, February 23-26, 2009, Korbelów (Poland).
18. J. Wójcik, P. Mergo, K. Poturaj, M. Makara, K. Skorupski, J. Pędzisz, Aktywne
światłowody fotoniczne o wysokiej dwójłomności ze szkła kwarcowego,
Sympozjum Techniki Laserowej, September 21-25, 2009, Świnoujście
(Poland).
19. J. Wójcik, P. Mergo Technology of high birefringent microstructured fibers for
sensing applications, COST 299 Meeting, March 30-April 01, 2009, Larnaca
(Cyprus).
20. J. Wójcik, Technologia światłowodów specjalnych ze szkła kwarcowego, XL
Zjazd Fizyków Polskich, September 06-11, 2009, Kraków (Poland).
21. J. Wójcik, P. Mergo, Fabrication of Highly Birefringent mPOF for Sensing
Applications, COST 299 Meeting, September 09-11, 2009, Wrocław (Poland).
Department of Environmental Chemistry
1. D. Nazimek, E-MRS FALL MEETING 2009, September 14, 2009, Warsaw
(Poland).
2. D. Nazimek, Międzynarodowa Konferencja Naukowa: Stan pozyskiwania
odnawialnych źródeł energii w Polsce, April 17-18, 2009, Łomża (Poland).
3. D. Nazimek, V Międzynarodowe Seminarium Naukowe „Energetyka węglowa,
a problem dwutlenku węgla”, December 11, 2009, Kraków (Poland).
Conference contributions – 266 –
4. D. Nazimek, Innowacyjne technologie produkcji paliw I i II generacji ze źródeł
odnawialnych, May 27, 2009, Opole (Poland).
5. D. Nazimek, Rogóźno - wczoraj i dziś, October 14, 2009, Zgierz (Poland).
6. A. Marcewicz-Kuba, VIII International Conference Mechanisms of Catalytic
Reactions, June 29-July 02, 2009, Nowosybirsk (Russia).
7. B. Czech, 7th International Symposium Effects of Surface Heterogeneity on
Adsorption and Catalysis on Solids, July 4-11, 2009, Kazimierz Dolny
(Poland).
8. A. Marcewicz-Kuba, Paliwa-Energia-Ochrona Środowiska, May 28-29, 2009,
Kraków (Poland).
9. A. Marcewicz-Kuba, W. Bundyra-Ćwikła, M. Kuśmierz, B. Czech, 52 Zjazd
PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland).
10. W. Bundyra-Ćwikła, M. Kuśmierz, B. Czech, VI Kongres Technologii
Chemicznej, June 21-26, 2009, Warsaw (Poland).
11. M. Kuśmierz, B. Czech, 17 Konferencja Metodyczna „Ochrona środowiska na
uniwersyteckich studiach przyrodniczych”, August 31-September 02, 2009
Łagów (Poland).
Department of Chemical Education
1. A. Kamińska-Ostęp, The use of information technologies in teaching chemistry
to dyslexic students, V International Conference on Multimedia and ICT in
Education, April 22-24, 2009, Lisbon (Portugal) – poster.
2. R.M. Janiuk, Refleksje nad nauczaniem chemii – do czego może być przydatna
uczniom wiedza chemiczna?, VIII Konferencja Dydaktyka Chemii, April 3,
2009, Rzeszów (Poland) – lecture.
3. R.M. Janiuk, Wiedza o nauce w kształceniu chemicznym, 19th International
Conference on Chemistry Education, Vyzkum, teorie a praxe v didaktice
chemie. September, 2009, Hradec Kralove (Czech Republic) – lecture.
4. J.W. Dymara, Rozwijanie zainteresowań uczniów chemią poprzez zajęcia
pozaszkolne, 19th International Conference on Chemistry Education, Vyzkum,
teorie a praxe v didaktice chemie. September, 2009, Hradec Kralove (Czech
Republic) – oral.
5. R.M. Janiuk, Edukacja przyrodnicza w opinii członków polskich towarzystw
naukowych, 52 Zjazd PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – oral.
6. H. Gulińska, R.M. Janiuk, Rozwój dydaktyki chemii w Polsce, 52 Zjazd
PTChem. i SITPChem., September 12-16, 2009, Lódź (Poland) – lecture.
7. A. Persona, J.W. Dymara, Kalibracja analityczna w analizie instrumentalnej.
Wykorzystanie e-learningu w systemie prelab, 52 Zjazd PTChem. i
SITPChem., September 12-16, 2009, Lódź (Poland) – poster.
PART 6
VISITORS AT FACULTY
OF CHEMISTRY IN 2009
F.Ch. UMCS Report 2009 – 269 –
Prof. Kurt Binder Johannes Gutenberg University,
Mainz, Germany
Prof. Nikołaj Kartel National Academy of Sciences, Kiev,
Ukraine
Prof. Valentin Tertykh National Academy of Sciences, Kiev,
Ukraine
Dr Duncan Carmichael Ecole Polytechnique, CNRS, France
Dr Stepan Petrovych Hlushak National Academy of Sciences of
Ukraine, Ukraine
Dr Yaroslav Ilnytskyy National Academy of Sciences of
Ukraine, Ukraine
Dr Irina L. Odinets Russian Academy of Sciences, Russia
Dr Volodymir Sydorchuk National Academy of Sciences, Kiev,
Ukraine
M.Sci. Kostiantyn Kulyk National Academy of Sciences of
Ukraine, Ukraine
PART 7
AWARDS
F.Ch. UMCS Report 2009 – 273 –
Prime Minister medal of honour „For make a great contribution to inventiveness”
Prof. dr hab. Roman Leboda
Dr Jadwiga Skubiszewska-Zięba
Prime Minister medal „Distinction for Inventions”
Prof. dr hab. Barbara Gawdzik
Knight’s Cross
Prof. dr hab. Emil Chibowski
Golden Medal for Many Years’ Public Service
Dr Jerzy Jabłoński
Mgr Marek Reszka
Silver Medal for Many Years’ Public Service
Mgr Teresa Urban
Medal of National Education Committee
Prof. dr hab. Tadeusz Borowiecki
Dr hab. Jan Rayss prof. UMCS
Dr hab. Janusz Ryczkowski, prof. UMCS
Dr hab. Ryszard M. Janiuk
Dr hab. Jan A. Solecki
Dr Renata A. Kurpiel-Gorgol
Medal of National Ucrainian Academy of Sciences for Contribution to Science Development
Prof. dr hab. Roman Leboda
Award for scientific achievement in calorimetry and thermal analysis for young scientists
Dr Marta Worzakowska