FACULTY OF CHEMISTRY - hektor.umcs.lublin.plhektor.umcs.lublin.pl/~chem/chem/raporty/Raport_2009.pdf · Complexes of Chosen D-Block Elements with 2-Amino-4,6-Dimethylo- pyrimidine

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


Department of Interfacial Phenomena

Katarzyna Szymczyk and Bronisław Jańczuk

Investigations of the Adsorption and Volumetric Properties of Anionic

and Nonionic Surfactants Mixtures..........................................................................59


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


and Ludomir Kwietniewski

A New Method for the Determination of Retention of Substance

in Ternary Mobile Phases ........................................................................................73


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


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


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


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


K. Michał Pietrusiewicz, Zbigniew Drzazga, Anna Flis,

Renata Parcheta and Elżbieta Łastawiecka

Reactions of Cyclic Organophosphorus Compounds with Nucleophiles ...............145

Contents – 10 –


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


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


Andrzej Dąbrowski, Mariusz Barczak, Władysław Janusz

and Ewa Skwarek

Functionalized SBA-15 Organosilicas as Sorbents of Zinc(II) Ions ......................161


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


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


Stanisław Chibowski, Małgorzata Wiśniewska

and Teresa Urban

Studies of Temperature Influence on Adsorption Behaviour

of Nonionic Polymers at the Zirconia-Solution Interface.......................................183


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


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



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.


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,


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.


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


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.


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


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.


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).


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.


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)

– 29 –

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


– 30 –

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.


– 31 –

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.


– 32 –

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).


– 33 –

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,


– 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.


– 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).


– 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-


– 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


– 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


– 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.


– 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


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


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


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).


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.


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


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


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


0

0,1

0,2

0,3

0,4

0,5

1800 2000 2200 2400 2600

Temperature [°C]

Ab

so

rba

nc

e


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.


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


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.


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


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.


THE CONSTRUCTION AND RESEARCH OF PROPERTIES OF CADMIUM ION-SELECTIVE ELECTRODES WITH SOLID

CONTACT

Cecylia WARDAK DEPARTAMENT OF ANALYTICAL CHEMISTRY


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


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.


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


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).


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.


DIGITAL SIMULATION OF CYCLIC RECIPROCAL DERIVATIVE CHRONOPOTENTIOMETRY WITH PROGRAMMED CURRENT

OF ADSORPTION SYSTEMS WITH SLOW CHARGE TRANSFER

Zygmunt FEKNER DEPARTMENT OF ANALYTICAL CHEMISTRY


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-potentials (∆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


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


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


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:


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.


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.


INVESTIGATION OF THE WETTABILITY OF POLYMERIC SOLIDS

BY AQUEOUS SOLUTION OF BINARY MIXTURES OF ANIONIC

AND NONIONIC SURFACTANTS



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


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.


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


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.


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.





EFFECTS OF STATIC MAGNETIC FIELD ON WATER

AND ELECTROLYTE SOLUTIONS PROPERTIES

Aleksandra SZCZEŚ, Emil CHIBOWSKI and Lucyna HOŁYSZ


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.


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.


PHOSPHOLIPID INFLUENCE ON CALCIUM CARBONATE

PRECIPITATION

Aleksandra SZCZEŚ


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


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.


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.


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


A NEW METHOD FOR THE DETERMINATION OF RETENTION

OF SUBSTANCE IN TERNARY MOBILE PHASES


and Ludomir KWIETNIEWSKI


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


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


THE APPLICATION OF LINEAR FORM OF OŚCIK’S EQUATION

FOR DETERMINATION OF HYDROPHOBICITY INDEX


and Ludomir KWIETNIEWSKI


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.


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


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.


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.


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.


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


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(trialkoxysilane) 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.


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


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.


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


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.


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.


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


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.


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.


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.


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.


DETERMINATION OF SURFACE PROPERTIES OF PALLADIUM CATALYST FOR THE REACTION OF COMPLETE OXIDATION

OF METHANE

Andrzej MACHOCKI, George AVGOUROPOULOS*

and Theophilos IOANNIDES*


*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


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-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/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.


INVESTIGATION OF ISOTOPIC DISTURBANCES OF OXYGEN IN THE REACTION OF METHANE OXIDATION

OVER PALLADIUM AND PLATINUM CATALYSTS

Marek ROTKO and Andrzej MACHOCKI


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


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


OPTIMIZATION OF ACTIVE PHASE PALLADIUM CATALYSTS

Beata STASIŃSKA


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).


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 [%

] .


STUDY OF ACTIVITY PALLADIUM CATALYSTS ON COMMERCIAL SUPPORT PRODUCED BY FERTILIZERS

RESEARCH INSTITUTE IN PUŁAWY

Beata STASIŃSKA


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.


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.


THE INFLUENCE OF THE PROJECTED TRANSPORT SYSTEM IN THE LUBELSKIE VOIVODESHIP ON THE QUALITY

OF THE ATMOSPHERIC AIR

Adam LESIUK


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


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).


PROMOTED NICKEL CATALYSTS IN THE HYDROCARBON REACTIONS

Tadeusz BOROWIECKI, Andrzej DENIS, Monika PAŃCZYK

and Czesława SIKORSKA


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


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.


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.


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.


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.


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.


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)


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.


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.


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 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.


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.


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.


SYNTHESIS AND APPLICATIONS OF CYCLIC

AND MACROCYCLIC ORGANOPHOSPHORUS COMPOUNDS

K. Michał PIETRUSIEWICZ, Anna SZMIGIELSKA, Anna FLIS,

Nikolai VINOKUROV* and Holger BUTENSCHOEN

*


*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.


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.


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.


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.


LARGE MODE AREA FIBERS WITH DEDICATED MODE

FIELD DIAMETERS – THEORY, FABRICATION

AND CHARACTERIZATION

Paweł MERGO, Jan WÓJCIK, Krzysztof SKORUPSKI, Krzysztof POTURAJ and Mariusz MAKARA


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


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


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.


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.


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


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.


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.


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.


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.


OPTIMIZATION OF PLUTONIUM EXTRACTION

WITH METHYLTRIOCTYLAMMONIUM CHLORIDE PRECEDING

ITS DETERMINATION BY LIQUID SCINTILLATION

SPECTROMETRY

Andrzej KOMOSA, Magdalena PIEKARZ and Jolanta ORZEŁ


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.


EFFECT OF LIQUID SCINTILLATION COCKTAIL VOLUME

ON 3H AND

14C MEASUREMENT PARAMETERS USING

THE QUANTULUS SPECTROMETER

Andrzej KOMOSA, Katarzyna ŚLEPECKA and Jolanta ORZEŁ


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).


REACTIONS OF CYCLIC ORGANOPHOSPHORUS

COMPOUNDS WITH NUCLEOPHILES

K. Michał PIETRUSIEWICZ, Zbigniew DRZAZGA, Anna FLIS,

Renata PARCHETA and Elżbieta ŁASTAWIECKA


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).


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%


STUDIES ON PHOTOPOLYMERIZATION KINETICS

Jan RAYSS, Małgorzata GIL, Wiesław PODKOŚCIELNY, Andrzej GORGOL and Jan WIDOMSKI


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


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.


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.


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


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


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)


A STUDY OF INTERACTIONS OF TERNARY SURFACTANT

SYSTEMS AT WATER-AIR INTERFACE



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


+ 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)


ELECTROKINETIC PROPERTIES

OF N-TETRADECANE/ETHANOL EMULSIONS WITH DPPC

AND ENZYME LIPASE OR PHOSPHOLIPASE A2

Agnieszka Ewa WIĄCEK, Lucyna HOŁYSZ and Emil CHIBOWSKI


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.


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)


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


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.


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)


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


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


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)


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.


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)


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


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)


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)


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)


HYDROGEN FROM BIO-ALCOHOLS. AN EFFICIENT ROUTE FOR HYDROGEN PRODUCTION

VIA NOVEL REFORMING CATALYSTS

Andrzej MACHOCKI, Andrzej DENIS, Wiesław GRZEGORCZYK

and Wojciech GAC


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


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.


A HIGH-SELECTIVE CATALYST FOR CONVERSION OF ETHANOL TO HYDROGEN

Andrzej MACHOCKI, Andrzej DENIS, Wiesław GRZEGORCZYK

and Wojciech GAC


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


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.


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


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.


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)


CATALYSTS FOR MULTICOMPONENT GAS REFORMING IN GAS HEATED REFORMER

Janusz RYCZKOWSKI, Tadeusz BOROWIECKI, Monika PAŃCZYK

Kazimierz STOŁECKI* and Andrzej GOŁĘBIOWSKI

*


*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.


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)


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 ENVIRONMENTAL CHEMISTRY

**DEPARTMENT OF RADIOCHEMISTRY


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


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)


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.


-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)


PROEKOLOGICAL TECHNOLOGY UTILIZATION COAL MINE METHANE

Beata STASIŃSKA, Agnieszka MARCEWICZ-KUBA*,

Monika PAŃCZYK, Marcin KUŚMIERZ, Wojciech GAC,

Marek ROTKO, Witold ZAWADZKI and Dobiesław NAZIMEK*



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


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, %


STUDIES OF TEMPERATURE INFLUENCE ON ADSORPTION BEHAVIOUR OF NONIONIC POLYMERS

AT THE ZIRCONIA-SOLUTION INTERFACE

Stanisław CHIBOWSKI, Małgorzata WIŚNIEWSKA and Teresa URBAN


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)


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)


X-RAY POWDER DIFFRACTION – NEW INORGANIC

AND ORGANIC COMPOUNDS IV

Elżbieta OLSZEWSKA, Stanisław PIKUS, Marek MAJDAN*

and Bogdan TARASIUK**


*DEPARTMENT OF INOGRANIC 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)


X-RAY POWDER DIFFRACTION – NEW INORGANIC

AND ORGANIC COMPOUNDS XII

Stanisław PIKUS, Elżbieta OLSZEWSKA, Marek MAJDAN

*

and Bogdan TARASIUK**


*DEPARTMENT OF INORGANIC 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


hydroxy-1,1-dimethylethyl)acetamide


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-


11. C14H18Cl3N3O2 N-(2-piperazin-1-ylethyl)-2-(2,4,6-

trichlorophenoxy)acetamide


12 C13H15Cl3N2O2 1-methyl-4-[(2,4,6-

trichlorophenoxy)acetyl]piperazine





15. C14H7Br3Cl3NO2 N-(2,4,6-tribromophenyl)-2-(2,4,6-


16. C14H12Cl2N2O2 2-(2,5-dichlorophenoxy)-N-(3-methylpyridin-

2-yl)acetamide

17. C15H9Br3Cl3NO2 N-(2,4,6-tribromophenyl)-2-(2,4,6-


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)


BORAN JAKO NOWY SELEKTYWNY ODCZYNNIK REDUKUJĄCY W CHEMII FUNKCJONALIZOWANYCH FOSFONIANÓW,

FOSFINIANÓW I TLENKÓW FOSFIN

Sylwia SOWA, Marek STANKEVIČ and K. Michał PIETRUSIEWICZ


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


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.



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


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%

-


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.


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


NOVEL BULKY AND ELECTRONICALLY RICH ATROPOISOMERIC PHOSPHORUS LIGANDS: SYNTHESIS

AND APPLICATION

Oleg M. DEMCHUK, Katarzyna KIELAR

and K. Michał PIETRUSIEWICZ


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.


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


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.


PPh2

NMe2

Fe

PCy2

02JACS116206TA2593

DC


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


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


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)


FROM STUDENT TO EXPERT – ENVIRONMENTAL

PROTECTION IN PRACTICE

Adam LESIUK, Marcin KUŚMIERZ*,

Joanna STRUBIŃSKA**

and Bożena CZECH*



**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


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



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



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.


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.


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.


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.


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


(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.


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.


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.


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.


analizie TLC, Materiały: Nauka i przemysł-metody spektroskopowe w


(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,


and BTMA-bentonite, Journal of Environmental Management, 91 (2009) 195.


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.


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.



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.


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.


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.


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

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Katalizatory do reaktora typu GHR, Przem. Chem., 88 (2009) 1292.


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

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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


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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


(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.

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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.


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.*


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

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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.

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15. M. Szymula, J. Narkiewicz-Michałek, Ascorbic Acid Oxidation in SDS

Micellar Systems, Journal of Applied Electrochemistry, 31 (2009) 681.


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.

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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,


polymeric templates, Adsorption, 15 (2009) 300.


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,


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,

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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.


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).


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-

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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.


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

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21. B. Gawdzik, J. Księżopolski, T. Matynia, Środek inicjujący polimeryzację wolnorodnikową oraz sposób otrzymywania środka inicjującego polimeryzację wolnorodnikową, Patent PL 201217, (2009).



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-


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.



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


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



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


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



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




24. Z. Rzaczyńska, A. Danczowska-Burdon, H. Głuchowska, Thermal properties

of light lanthanide(III) complexes with 2,4-pyridinedicarboxylate anion, 32nd



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.


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 –



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 –



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



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


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.


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


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.


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



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.


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,


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



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 –



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.


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,


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,



lecture.


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 –



48. M. Greluk, Z. Hubicki, Zastosowanie metody FT-IR w badaniach sorpcji

Oranżu G oraz Oranżu II na słabo zasadowym jonicie Amberlyst A-21,



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 –



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



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



55. D. Sternik, M. Majdan, A. Deryło-Marczewska, Thermal analysis of

aluminosilicates modified by selected dyes, 32nd





56. M. Majdan, D. Sternik, M. Bujacka, A. Gładysz-Płaska, Studies of phenol

influence on thermal stability of clays modified by surfactant, 32nd

International



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



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



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


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 –



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.


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


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


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




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.


analizie TLC, Ogólnopolskie Sympozjum „Nauka i przemysł – metody


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


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.,


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


3. M. Mirosław (Gołąbek), E. Chibowski, L. Hołysz, Changes in wetting and

energetic properties of glass caused by different lipid adsorption, 7th


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.


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



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


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.


Department of Planar Chromatography 1. I. Malinowska, B. Marczewska – zastosowanie metod spektroskopowych w

analizach TLC, Ogólnopolskie Sympozjum „Nauka i przemysł – metody


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



2. D. Sternik, M. Majdan, Thermal analysis of aluminosilicates modified by

selected dyes, 32nd



poster.

3. A. Deryło-Marczewska, M. Błachnio, Adsorption of 2,4-D and MCPA from

aqueous solutions on activated carbon, 32nd




4. A. Deryło-Marczewska, A. W. Marczewski, S. Winter, D. Sternik, Adsorption

of selected dyes from aqueous solutions on carbonaceous materials, 32nd




5. A. Deryło-Marczewska, D. Sternik, G. Żukociński, Thermogravimetric analysis

of intermediate products of MCM-41 and MCF syntheses, 32nd

International



6. W. Janusz, E. Skwarek, D. Sternik, A study on thermal behavior of

hydroxyapatite syntheses by various methods, 32nd




7. W. Janusz, E. Skwarek, D. Sternik, Thermal decomposition of yttrium citrates

prepared in water medium, 32nd




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



9. M. Majdan, D. Sternik, M. Bujacka, A. Gładysz-Płaska, Studies of phenol

adsorption influence on thermal stability of clays modified by surfactant, 32nd



10. M. Błachnio, P. Staszczuk, Studies of adsorption and total heterogeneity

properties of pure and modified carbon nanotube surfaces, 32nd

International



11. A. Borówka, G. Żukociński, Thermogravimetric investigations of Al-MCM-41

molecular sieves, 32nd



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




13. P. Staszczuk, Thermogravimetry Q-TG in studies of sufrace properties of lunar

nanoparticles, 32nd



poster.

14. P. Staszczuk, D Sternik, J. Jamroz, P. Czerwieniec, Studies of physicochemical

properties of starch nanomaterials by means of the complex techniques, 32nd




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,


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,


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,


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


20. A. Borówka, G. Żukociński, Kinetyka termodesorpcji z mezoporowatych

materiałów Al-MCM-41, Nowoczesne Techniki Badania Powierzchni i


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.


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.,


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


5. J. Skubiszewska-Zięba, M. Jabłoński, K. Turżańska, R.Leboda, DSC analysis

of rat spine elements. Case study, 32nd




6. J. Skubiszewska-Zięba, Application of microwave energy to modification of

porous structure and surface chemistry of silica gel, 32nd

International



7. S. Khalameida, V. Sydorchuk, J. Skubiszewska-Zięba, R. Leboda, V.

Zazhigalov, Synthesis, thermoanalytical and spectroscopical studies of

dispersed barium titanate, 32nd




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


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



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



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




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



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



14. J. Skubiszewska-Zięba, E. Skwarek, W. Janusz, R. Leboda, Influence of

heteroatoms on carbosil surface on adsorption of Nickel and cobalt ions, 7th



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


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


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


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,



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.


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,



2. M. Drach, J.Narkiewicz-Michałek, M.Szymula, J.Jabłoński, Co-adsorption of

Surfactants and Propyl Gallate on the Oxide Surface, 7th International



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,


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



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



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



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




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



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



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.


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


(Poland) – oral.

6. A. Patrykiejew, Two-dimensional symmetrical mixtures in an external field of

square symmetry, 7th International Symposium Effects of Surface


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



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).



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 –



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 –



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


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


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.


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


(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



22. K. Stołecki, A. Gołębiowski, K. Michalska, T. Borowiecki, Specyfika

pomiarów aktywności katalizatora uwodornienia benzenu w warunkach

przemysłowych, 41 Kolokwium Katalityczne “Kataliza w ochronie


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


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



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.


organicznych z wód i ścieków w reaktorze wstęgowym, VI Kongres


32. M. Rotko, A. Machocki, B. Stasińska, Wykorzystanie 12

CH4 i 13

CH4 do badań

katalitycznego procesu całkowitego utleniania metanu, VI Kongres


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.


34. K. Stołecki, A. Gołębiowski, K. Michalska, T. Borowiecki, Ocena właściwości

zużytego niklowego katalizatora uwodornienia benzenu KUB-3, VI Kongres


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


37. B. Stasinska, M. Rotko, A. Machocki, Steady State Isotopic Transient Kinetic

Analysis of Catalytic Process of Complete Methane Oxidation, VIII


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


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,


42. S. Pasieczna-Patkowska, B. Czech, J. Ryczkowski, J. Patkowski, Removal of

recalcitrant pollutants from wastewater, 7th International Symposium Effects of



43. M. Rotko, A. Machocki, B. Stasińska, Studies of catalytic process of complete

oxidation of methane by SSITKA method, 7th International Symposium Effects



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




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


54. M. Kuśmierz, B. Czech, S. Pasieczna-Patkowska, Uwodornienie dwutlenku

węgla na katalizatorach Pd/ZnO/Al2O3, , 52 Zjazd PTChem. i SITPChem.,


55. W. Gac, W. Zawadzki, Z. Surowiec, An application of nanocasting technique

for the preparation of cobalt and iron oxides, Nowoczesne Techniki Badania



56. A. Machocki, A. Denis, W. Grzegorczyk, W. Gac, Cobalt catalysts with nano-

and micro-dispersed supports for the steam reforming of etanol, Nowoczesne




57. M. Rotko, A. Machocki, B. Stasińska, Steady state isotopic transient analysis

of the process of complete methane oxidation over palladium catalysts,



58. P. Rybak, B. Tomaszewska, A. Denis, W. Grzegorczyk, A. Machocki,

Conversion of etanol over potassium-promoted cobalt catalysts, Nowoczesne



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



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


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,


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,



9. A, Komosa, J. Orzeł, M. Piekarz, Badania obecności i przemieszczania się izotopów plutonu w glebach Lubelszczyzny, 52 Zjazd PTChem. i SITPChem.,


10. M. Wiśniewska, The Temperature Effect on the Adsorption Properties of Silica

– Polyacrylic Acid Interface, 32nd




11. M. Wiśniewska, St. Chibowski, T. Urban, Investigation of the Alumina

Properties with Adsorbed Polyvinyl Alcohol, 32nd




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



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




16. W. Janusz, E. Skwarek, D. Sternik, Thermal decomposition of yttrium citrates

prepared in water medium, 32nd




17. M. Drach, J. Jabłoński, J. Narkiewicz- Michałek, M. Szymula, Co-Adsorption

of surfactants and propyl gallate (PG) on the oxide surface, Nowoczesne



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




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,


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



23. A.W. Marczewski, Kinetics and Equilibrium of Adsorption of Organic Solutes

on Mesoporous Carbons, 7th International Symposium Effects of Surface



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



25. A.W. Marczewski, Adsorption Kinetics – Optimization of Measurements and

Data Analysis, Nowoczesne Techniki Badania Powierzchni i Obszarów


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



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,


28. S. Pasieczna-Patkowska, B. Czech, J. Ryczkowski, J. Patkowski, Removal of

recalcitrant pollutants from wastewater, 7th International Symposium Effects of



29. J. Patkowski, Influence of magnetic field on zeta potential od magnetite',



30. J. Skubiszewska-Zięba, E. Skwarek, W. Janusz, R. Leboda, Influence of

heteroatoms on carbosil surface on adsorption of nickel and cobalt ions, 7th




31. W. Janusz, E. Skwarek, Comparison of adsorption of ion of nickel on nano-

Al2O3 and polycrystalline- Al2O3, 7th International Symposium Effects of



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



33. W. Janusz, E. Skwarek, A. Dąbrowski, M. Barczak, Functionalized sba-15

organosilicas as sorbents of zinc(II) ions, 7th International Symposium Effects



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


(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.


1. A. Drzewiecka, A.E. Kozioł, Analiza strukturalna i spektroskopowa

pochodnych benzofuranu, Ogólnopolskie Sympozjum „Nauka i przemysł –


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


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.


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


8. A.E. Kozioł, M. Pitucha, Modyfikacje oddziaływań międzycząsteczkowych w

kryształach pochodnych 4-etylo-1,2,4-triazolo-5-tionu, 52 Zjazd PTChem. i


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



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


14. E.Olszewska, M. Kozak, M. Zienkiewicz, S. Pikus, TEM, XPS and XRD study

of mesoporous ordered organosilicas containing Zr and Ti ions, Nowoczesne




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).


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.



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




12. M. Worzakowska, Thermal properties of unsaturated (epoxy) polyesters, 32nd




13. B. Podkościelna, B. Gawdzik, M. Worzakowska, Studies of synthesis and

thermal resistance properties of acrylate copolymers, 32nd

International



14. M. Grochowicz, M. Sobiesiak, B. Gawdzik, Use of IGC in determination of

glass transition temperature of crosslinked polymeric microspheres, 32nd



15. M. Maciejewska, B. Podkościelna and M. Rogulska, Effect of crosslinker on

thermal properties porous copolymers of 1-vinyl-2-pyrrolidone, 32nd



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


17. M. Maciejewska, B. Gawdzik, Influence of crosslinker on the porous structure

and polarity copolymers of 1-vinyl-2-pyrrolidone, 7th International Symposium



18. M. Sobiesiak, B. Gawdzik, A.M. Puziy, O.I. Poddubnaya, Analysis of structure

and properties of active carbons and their copolymeric precursors, 7th



19. M. Sobiesiak, B. Podkoscielna, Comparison of structure and physico-chemical

properties of porous DVB copolymers, 7th International Symposium Effects of



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



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



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.


24. M. Sobiesiak, Zastosowanie skaningowej mikroskopii elektronowej i

mikroskopii sił atomowych do badania powierzchni i topografii materiałów

porowatych, Nowoczesne Techniki Badania Powierzchni i Obszarów


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


26. M. Grochowicz, B. Gawdzik, Synteza i struktura metakrylowych mikrosfer

polimerowych, Nowoczesne Techniki Badania Powierzchni i Obszarów


27. M. Maciejewska, B. Podkościelna, J. Osypiuk-Tomasik, Studies on

physicochemical properties of highly porous polymeric microspheres,



28. B. Podkościelna, B. Gawdzik, A. Bartnicki, Synthesis, structure and properties

of the new methacrylate microspheres, Nowoczesne Techniki Badania



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


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,


32. M. Podgórski, J. Księżopolski, Synteza i właściwości metakrylowych

pochodnych bezwodnika ftalowego, 52 Zjazd PTChem. i SITPChem.,


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.


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).


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”,


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


(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


(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).


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


(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”,


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).


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).


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


(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).


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


PART 6

VISITORS AT FACULTY

OF CHEMISTRY IN 2009


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


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

Documents

FACULTY OF CHEMISTRY - hektor.umcs.lublin.plhektor.umcs.lublin.pl/~chem/chem/raporty/Raport_2009.pdf · Complexes of Chosen D-Block Elements with 2-Amino-4,6-Dimethylo- pyrimidine