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Preparation, Characterization of Ion Exchange Materials and Their Analytical Applications in
Indentification, Determination and Separation of Compounds
ABSTRACT
T H E S I S SUBMITTED FOR THE DEGREE OF
Bottor of $I|tlo£;op|)p IN
CHEMISTRY
BY
MOHAMMED R. KHAYER
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH (INDIA)
1997
*f "*cc No.
^bti tlu uutucaS
ABSTRACT
This thesis comprises of five chapters. In the
first chapter/ a detailed and uptodate literature of
the subject matter has been reviewed. Inorganic ion-
exchanger has received considerable interest due to its
high thermal and chemical stability/ selectivity for
certain ionic species and resistivity towards radiation
and now been well established. An elaborate study
reveals that mostly two component inorganic ion-
exchangers has low ion-exchange capacities compared to
those of three component ion-exchangers. Even in some
cases it shows selectivity compared to two component
ion-exchanger. These compounds find wide applications
towards high temperature separation of ionic components
in radioactive wastes/ pharmaceuticals/ as absorbents
and as catalysts. Also analytically potential for the
recovery and concentration of strongly absorbed trace
constituents which has made their study more
interesting. They are usually prepared in general as
gelatenous precipitate by mixing rapidly the oxides of
group IV to more acidic oxides of groups V and VI of
the periodic table at room temperature. Layered double
hydroxides(LDHs), structurally characterised as brucite
like layers (magnesium hydroxide)/ in which some
2+ 2+ 2+ divalent metal cations (Mg / Fe / C o ) have been
sv\bstituted by trivalent ion's (Al / Mn , Cr ) to
11
form positively charged sheets. The positive charge on
the metal hydroxide sheets is balanced by intercalated
-2 - -anions (CO- / Cl , NO ). These compounds are prepared
by coprecipitating their salt solution in basic medium.
The material is further calcined at temperature ranging
450°-550°C, in order to make convenient to intercalate
guest molecule. The mixed hydrous oxide is prepared by
coprecipitating higher valence cations as tetravalent
silicon, zirconium/ thorium/ titanium or tungsten with
that of lower valent cation as aluminium or zinc. The
resulting net positive charge is compensated by anion
radical. This material is obtained by hydrolyzing their
salt solution by base.
The chapter second describes the synthesis of
new three component ion-exchanger/ Zirconium(IV)
diethylenetriamine phosphate/ prepared by adding a
mixture which is IM diethylenetriamine and 2M
orthophosphoric acid to an aqueous solution of O.lM
zirconium oxychloride under varying conditions of pH/
stirring and refluxing time. The effect of
intercalation behaviour of the host molecule diethylene
triamine between the zirconium phosphate layers has
been carried out by x-ray diffraction (XRD)/ FT-IR,
thermogravimetry (TG) and differential thermal analysis
IIJ
(DTA). Among the samples of zirconium(IV)diethylenetri-
araine phosphate/ ZAP-1/ has been studied in detail due
to its maximum ion-exchange capacity and chemical
stability. The pH-titration curve of the material shows
two inflection points indicating that the material is
bifunctional. The chemical composition of the material
suggests that the mole ratio of zirconium, diethylene-
triamine and phosphate is 3:1:4. Distribution
coefficient values, Kd, of a large number of metal ions
on zirconium(IV)diethylenetriamine phosphate in
different solvent systems have been determined. On the
basis of their difference in Kd values of various metal
ions, it is analytically applied for a number of binary
separations by column chromatography.
In the third chapter an elaborate investigation
has been made on the use of zirconium arsenate ion-
exchanger to serve as coating material in thin-layer
chromatography (TLC), to identify and separate aromatic
nitro compounds, which are of carcinogenic importance.
To resolve 4-nitrophenol, 4-nitroaniline, l-chloro-2,4-
dinitrobenzene, 3,5-dinitrosalicyclic acid, 2,4-dini-
trophenylhydrazine, 3-nitrophenol, hexanitrodiphenyl-
amine, dir.itrobenzoic acid and m-dinitrobenzene various
solvent systems have been tried and their effect on Rf
IV
values have been studied in detail. The Rf values
obtained on ZrAs plates are compared with those
obtained on silica gel G layers which showed improved
result with compact and circular spot in most of the
solvent systems except few with tailing. The Rf values
obtained on ZrAs plates are discussed in terms of ion-
exchange property of the gel, activated surface of
zirconium arsenate and zirconium arsenate oxide surface
as adsorbent. This causes larger interaction of the
aromatic nitro compounds with zirconium arsenate
layers. On the basis of difference in their Rf values a
number of synthetic mixture of binary and ternary
compounds are separated successfully.
In the fourth chapter we describe the
preparation of layered double hydroxide of Mg(II)
Al(III)-carbonate and the behaviour of the guest
molecule ethylenediamine. The parent LDH is synthesized
as : a mixtiare containing 0.5M Mg(N02)2'6H20 and 2.5M Al(NO.) 3'3
.9H2O solution in 70 ml of deionized water was added
with stirring to a solution of 70 ml of 0.5 M NaOH
solution and 22.5 ml of 4M solution of Na-CO^ in 100 ml
of deionized water. Where the addition was done over a
period of one hour at pH maintained close to 10. The
preparation of the host material was done by
calcinating the Mg(II)Al(III)-carbonate at 450+10°C in
air for 6 hours. The guest molecule ethylenediamine
interacts with unsaturated surface of the calcined LDH,
resulting in pillared LDH-ethylenediamine without
-2 deplection of either NO^ or CO, anion species. The
intercalation of guest molecule is examined by
chemical analysis/ x-ray diffraction (XRD), FT-IR,
thermogravimetry (TG) and differential thermal analysis
(DTA). The study confirms that intercalation takes
place and resulted in increase gallery height for
ethylenediamine. Moreover, the ethylenediamine pillared
-LDH show complexing behaviour for transition metal
ions illustrated by sorption capacities and the pH-
titrations.
In the last chapter we describe the preparation
and characterization of mixed hydrous oxide of Al_0--
ZrO^-diethylamine. An aqueous solution of diethylamine
is added to a mixture of O.lM zirconium oxychloride and
O.lM aluminium nitrate in different ratio with
adjustment of pH. The adsorption behaviour of mixed
hydrous oxide of AljO-^-ZrO^ towards diethylamine are
studied by x-ray diffraction (XRD), FT-IR, thermogravi
metry (TG) and differential thermal analysis (DTA). One
of the sample Al202-Zr02-diethylamine, ZAA-9, has been
VI
studied in detail for high sorption capacity and
chemical stability. The chemical composition of the
material suggests that the mole ratio of zirconium,
aluminium and diethylamine is 4:1:1.
Preparation, Characterization of Ion Exchange Materials and Their Analytical Applications in
Indentification, Determination and Separation of Compounds
T H E S I S SUBMITTED FOR THE DEGREE OF
JBoctor of ^liilogoplip IN
CHEMISTRY
^'%> / ^ • ^ ' '
BY
MOHAMMED R. KHAYER
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH ( INDIA)
1997
SAIDUL ZAFAR QURESHI M.Sc.,Ph.O.,C.Chem. MRIC(London)
Professor of Anatytical Cfiemistry
Phone { Off. 0571-25515
Res 0571-20724
Department of Chemistry Aljgarh IMuslim University
Aligarli-202002 (INDIA)
Date
This is to certify that the thesis entitled
"Preparation, characterization of Ion-exchange
materials and their analytical applications in
identification, determination and separation of
compounds" is the original research work of
Mr. MOHAMMED R. KHAYER and is suitable for
submission for the degree of Doctor of Philosophy in
Chemistry.
(SAIDUL ZAFAR QURESHI) Supervisor.
ACKNOWLEDGEMENT
It gives me an immense delectation to express my sensibility and gratitude to
my supervisor Professor Saidul Zafar Qureshi, Department of Chemistry, Aligarh
Muslim University, whose able guidance and analytical thinking made this work a
rewarding experience.
I am grateful to Professor Mohd, Ulyas, Chairman, Department of Chemistry
for providing research facilities.
I awe my particular gratitude to Dr. Nafisur Rahman for his immense help,
affirmative respome and valuable suggestions in making this task fruitful.
I wish to thankmy colleagues and friends. Dr. IrshadBhai, Dr. Rasheed, Mr.
Murad, Mr. TalatandMr. Abdullah for their incessant help atuifriendly attitudes.
My thatikful appreciation goes to Shamim, Selim, Masood and well wishers
for their whole hearted co-operation and encouragement.
I am thankful to Vice-Chancellor (Aligarh Muslim Univeristy), Dean (Faculty
of Science) and Chairman (Department of Chemistry) for the award of University
Grant Commission Junior Research Fellowship.
I shall be ever be ifuiebted from my inner heart to my loving Parents and
Brother, withoutwhose affection ifwigorative encouragement, prudence and blessing
this endeavour could not have been a lucrative triumph in my academic pursuit.
Above All the God's Blessing led me to this path of Success.
(MOHAMMED R. KHAYER)
CONTENTS
Page No.
CHAPTER ONE
General Introduction ^ References 38
CHAPTER TWO
Preparation, Characterization and Analytical Applicatiorts SI of a New Semicrystalline Ion Exchange Material : Zirconium(l\/)Dieth^enetriamine phosphate
CHAPTER THREE
Thin layer Chromatographic BehaviourofSome Aromatic 83 Nitro Compounds on Zirconium Arsenate Layers
CHAPTER FOUR
Preparation and Characterization of Layered Double 100 Hydroxides: Intercalation ofEthylenediaminebyAdsorption Process
CHAPTER FIVE
Preparation andCharacterization ofl^ixedHydrousOxides i26 ofAlfi^-ZrO^ by Aqueous Base Diethylamine and its AdsorptionBehavourtowards Diethylamine
LIST OF TABLES
PAGE NO.
TABLE 1.1
TABLE 1.2
TABLE 2.1
TABLE 2.2
TABLE 2.3
TABLE 2.4
TABLE 2.5
TABLE 2.6
TABLE 3.1
TABLE 3.2
TABLE 3.3
TABLE 4.1
TABLE 4.2
TABLE 4.3
TABLE 4.4
TABLE 5.1
TABLE 5.2
TABLE 5.3
TABLE 5.4
Synthesis and properties of two-component inorganic ion-exchangers. 15-21
Synthesis and properties of some three component ion-exchange materials. 22-26
Synthesis of Zr(IV) diethylenetriamine phosphate under varying conditions. 60
Chemical stability of ZAP-1 in various solvent systems. 61
Ion-exchange capacity of ZAP-1 for various cations 62
X-ray diffraction data of ZAP-1 72
Distribution coefficient value . of metal ions on ZAP-1 in D^W and different concentration of HNO, and NH.NO- solutions 75
3 4 3
Separation of cations achieved on ZAP-1 exchanger . 77
Rf values of aromatic nitro-compounds together with the composition of the mobile phases studied on ZrAs-TLC plates. 87-89
Rf values of aromatic nitro-compounds on silica gel G coated plates. 90-92
Separation achieved using different solvents on Zirconium arsenate gel as coating
material on TLC plates. 93-95
X-ray diffraction data of parent-LDH 109
X-ray diffraction data of LDH-ethylene-diamine 110 Sorption capacity of some metal ions on LDH-ethylenediamine intercalated compound 120 Chemical composition of LDH-ethylenediamine 123
Synthesis of Al-O.-ZrO^-diethylamine gel under varying conaitions. 135
Chemical stability of ZAA-9 in various
solvent system. 136
Sorption capacity of metal ions on ZAA-9 137
X-ray diffraction data of ZAA-9 140
LIST OF FIGURES
PAGE NO.
FIGURE 2.1
FIGURE 2.2(a) FIGURE 2.2(b) FIGURE 2.2(c) FIGURE 2.3 FIGURE 2.4
FIGURE 4.1 (a & b)
FIGURE 4.2 (a & b)
FIGURE 4.3
FIGURE 4.4
FIGURE 4.5
FIGURE 5.1
FIGURE 5.2
FIGURE 5.3
FIGURE 5.4
pH-titration curve of ZAP-1. 64
FT-IR spectrum of ZAP-1 dried at 40°C 65 FT-IR spectrum of ZAP-1 dried at 37n°C 66 FT-IR spectrum of ZAP-1 dried at SIO^C 67 TGA and DTA curves of ZAP-1 69 X-ray diffraction fkattern of ZAP-1 71
X-ray diffractogram of parent-LDH and LDH-ethylenediamine 108
FT-IR spectrum of parent-LDH and LDH-ethylenediamine 112
TGA and dw/dt curves of LDH-ethylenediamine 117
DTA curve of LDH-ethylenediamine 118
pH-titration curves of LDH-ethylenediamine
intercalated compound 121
X-ray diffractogram of ZAA-9 139
FT-IR spectrum of ZAA-9 141
TGA and dw/dt curves of ZAA-9 143
DTA curve of ZAA-9 144
Chapter ^ife
GENERAL INTRODUCTION
GENERAL INTRODUCTION
With the growing global awareness in health
hazards and environmental pollution. Analytical
Chemistry has played a key role to unveil its causes
and day by day it has btoaden its spectrum with the
concerned situation. It is extensively and intensively
responsible for analytical measurements on variety of
materials* such as microbiological analysis of food,
pharmaceutical/ water, cosmetics/ agricultural
products/ environmental related species/ forensic
samples and products affecting public health and
welfare where qualitative, semiqualitative and quanti
tative analysis on macro to micro scale are performed.
In the recent decades Analytical Chemistry has reached
the pinnacle of precession with the modern
sophisticated instrumentation techniques which make
possible to elucidate the microstructure of molecular
species, determining antibiotic residues in milk and
tissues of food producing animals/ detection of complex
hydrocarbons/ studies of rare and artificial radiactive
elements and to obtain substances in the highest state
of purity. Moreover^ with the avent of the digital
computer the precision is further enhanced. However^ it
has always conceived the basic phenomenon for its
revealation despite the change in instrumentation.
Analytical excellence has been a great boon for
Chemists/ Microbiologist/ Entomologist and other
scientists working in food quality control and food
composition. Besides chemical methods/ other
extensively used techniques are distillation,
fractional precipitation and crystallization for
purification and separation of chemical compounds. But
problems relating to identification, separation and
quantitative determination of ionic as well as nonionic
species chromatography plays a vital role. The era of
chromatographic technique begins with the work of
Tswett in 1906 by the separation of coloured substances
on finely divided CaCO- adsorbent. Again another
evolution begins in 1931 unveiling the possibility for
the resolution of complex organic mixtures with an ever
lasting impact for the scientific world, utilizing the
chromatographic technique.
Eventhough chromatography is a universal
technique but their different principles greatly
segregate them from each other, namely high performance
liquid chromatography (HPLC), gas chromatography (GC),
ion-exchange chromatography (lEC), thin layer
chromatography (TLC) and high performance thin layer
chromatography (HPTLC).
Ion exchange chromatographic technique i s the
v e r s a t i l e technique among these which indiscr iminately
used in the separation of r a r e ear th and other metals /
a l l oys of multicomponents, i n d u s t r i a l e f f luents /
pharmaceuticals , biological substances and f i s s ion
products of radioactive elements.
Thin layer chromatography became popular
simultaneously with d is t inguished theo re t i ca l
i n t e r p r e t a t i o n , modernization of techniques and
v e r s a t i l e appl ica t ions . I t i s widely applicable for
separa t ion of pharmaceuticals, l i p i d s along with amino
a c i d s , bases , s te ro ids , p e s t i c i d e s , other carcinogenic
compounds and inorganic spec ie s . Some of the
successful ly used adsorbents a re s i l i c a gel and Chit in
l aye r s used for separation of amino acids (1) , mixture
of s i l i c a & Cg bonded - S i l i c a (1:1) and hydrophil ic
dyes ( 2 ) . A th in layer of mixed double layer hydroxides
and s i l i c a gel G (2:1) r a t i o , was used for
i d e n t i f i c a t i o n and separat ion of cephalosprin ( 3 ) .
S imi la r ly zirconium phosphate layers are used for the
rapid identification of carbamate pesticides and novel separatdon
of carbofuran (4). Layers of NaX molecular sieves are used for the
separation of cations (5). Commercial chiral plates
[C,o layers clipped into cupric acetate and a solution
of chiral [4-hydroxy-(2'hydroxydodecyl) proline] are
used for the separation of amino acids and 3-thiazali-
dine-4-carboxylic acid (6/7).
Ion exchange from the day of its discovery has
been embraced by analytical chemists to make use of
difficult separations possible and easier, eventhough
resolution of complicated mixture into its subsequent
determination can be achieved both by instrumental and
non-instrumental techniques.
Ion exchange phenomenon process was first
described by Thompson and Way in the naturally
occurring zeolites having structure of aluminosilicate.
Such as :
Analite Na[Si2A10g]*2H20/
Chabazite(Ca,Na) [Si^AlOg].SH^O/
Harmotone (K^Ba) [Si-AlOg].SH.O,
and Natrolite Na2 [Si2Al20j^Q] .2H2O
are the zeolites minerals having a three dimensional
frame work with uniform geometry have been widely used
as molecular sieves. But due to their certain
limitations, synthetic aluminosilicate with improved
properties took their place. The first applications of
synthetic zeolite for the separation and collection of
ammonia from urine is made by Folin and Bell (8).
Therefore/ synthesized ion exchange materials used
earlier are largely inorganic in nature. Shortly Cans
(9) developed synthetic sodium aluminosilicate
Na Al2Si,0,Q having cation exchange properties.
Ultimately now-a-days zeolites find extensive
application as catalysts along with transition metal
ions in the synthesis of many organic compounds (10). 'S
Thus inorganic ion - exchangers have played a
vital role and establisher! a distinguished position among
the ion-exchange materials. The prolified development
in nuclear energy/ hydrometallurgy of rare elements/
preparation of high purity materials/ water
purification/ catalysis etc. has forced to synthesize
new highly selective ion exchanger with enhanced ion
exchange capacities. The contribution for the synthetic
inorganic ion - exchangers from Kraus (11)/ Amphlett
(12-14)/ Pekarek and Vesley (15)/ Clearfield (16/17),
Alberti (18,19), Walton (20) and Volkhim (21)
etc. are noteworthy for elucidation of different
aspect of these materials other than the ion exchange
properties. Qureshi (22,23) synthesized a large number
of inorganic ion exchange materials and characterized
them with respect to t h e i r s t r u c t u r a l configuration,
thermal treatment, d i s t r i bu t i on coef f ic ien ts of ionic
and nonionic species e t c . and extensively applied them
for column and thin layer chromatographic separation of
inorganic and organic spec ie s . Moreover the authors
introduced a new chapter in ion-exchange methodology
t h a t i s "Resin Spot Test or Technique" of various
inorganic and organic compounds from macrogram to
microgram sca le . For the determinat ion of ani l ides (24),
a l i p h a t i c and aromatic aldehyde (25) , cation exchange
r e s i n in the hydrogen form ca ta lyze the reactions where
in a c id i c hydrolysis converts to an i l ine with the
appearance of pale yellow colour beads surface and in
the l a t t e r case converts the cyanohydrins to carboxylic
acid and ammonium ions, which i s fur ther detected by
N e s s l e r ' s reagent, whereas a l i p h a t i c (monoaliphatic)
amines and aromatic amines (po lya l ipha t ic ) amines are
d i s t inguished with p-dimethylaminobenzyldehyde and
v ice -versa (26) by appearance of deep yellow when cold
and blue green at hot in ac id i c medium, while the
former form very light colour (27).^ Another form of
de t ec t ion i s by loaded with mul t i l igand reagent i . e .
l -chloro-2,4-dini t roben2ene t o an anion-exchange r e s in
(28) . For the microdetection of the mercaptans with
p rus s i c s a l t as reagent and vice-versa has been
achieved, where NH- or H-O molecules of reagent groups
are being exchange with analyte (29). In consideration
of the organic solvent polarity and dielectric constant
a novel sensitive detection for m-dinitroaromatics is
performed due to its special ability to stabilize anion
species to form d'-complexes in alkaline medium (30).
Simultaneous microgram detection of sulphur,
chlorine, iodine and nitrogen in organic compound has
been determined. Where AgCl acts as reagent for
chlorine, sulfite with sodium nitroprusside^ NH. with
Nessler's Reagents, iodine by oxidation of iodine and
reaction with starch (31), whereas Uranyl(III) by
Erichrome Cyanine R (32). The detection of the various
salient functional groups which are present in the
organic molecules by the resin spot test is most
outstanding, where oxygen element of aldehyde groups
for aliphatic and aromatic is detected by sodium
cyanide by hydrocyanic acid mixture and Nessler's
reagent (25), of ketone group by l-chloro-2,4-dinitro-
benzene (33), of ester group by methyl red with
increased in acidity (34), of phenols and related
compounds by 4-amino antipyrineand hydrogen peroxide and
double action of the chlorinated sodium hypochlorite
solution (35,36). Similarly detection of nitrogen
element of aliphatic amines by reaction with 2/4-dini-
troaniline and dimethylsulfoxide (37), of nitriles by
sulphuric acid and Nessler's reagent (38) and also with
sulphuric acid sodium hydrochlorite and phenol with the
appearance of indophenol blue (39), secondly of amides
group by Nessler's reagent after catalytic hydrolysis
of resin and Berthelot's reagent after catalytic
hydrolysis with resin (39,40). Thirdly of amino acid
group by potassium permanganate and Berthelot's reagent
(41,42). Finally of nitro compound by interaction with
sodium sulphite and dimethylsulfoxide (30).
The element sulphur of thiols (Mercaptans) is
determined by reaction with l-chloro-2,4-dinitrobenzene
(43) and by indirect oxidation reaction and formation
of blue clathrate (44), and with sodium nitroprusside
(29).
Other organic compounds as anthranilohydrazide,
4-dimethylaminocinnamaldehyde, diphenylamine, ethylene
diamine tetra acetic acid, fructose, glycine, histidine
and picric acid has been detected by periodic acid,
diphenylamine, p-dimethylaminobenzaldehyde, potassium
chromate and 4-amino antipyrine, l-chloro-2,4-dinitro-
benzene, sodium hypochlorite and phenol, potassium
bromate and Nessler's reagent/ sodium hypochlorite
respectively (26-28, 45-50).
The resin spot test has been a wide scope of
application in the field of applied science like
biomedical/ analytical toxicology, drug control and
often qualitative information concerning the substance
impurity or component of a sample due to its simple,
quick/ economical and reliable technique it has drawn
considerable attentions.
In the pharmaceutical, the medicine salts has
an increasing use of ethylenediamine tetraacetic acid
(EDTA) since EDTA is not readily metabolize , most of
the injected CaNa^EDTA is finally removed in the urine
as mild toxic, which is easily detected by strong
acidic ion-exchanger by 4-amino antipyrine as a
colouring agent (46). Whereas various drugs containing
phenolic derivatives for drug formulation used as
antiseptic or germicides is adsorbed on strongly
anion-exchange resin, with colour producing reaction
with 4-aminoantipyrine in the presence of oxidizing
agent (35)/ and double action of the chlorinated sodium
hypochlorite solution oxidation in alkaline solution
and chlorination (36).
10
simultaneously the halides determination has
been superior to both Mohr's and Volhard's method by
the use of the resin in the p-dimethylaminobenzylidene
rhodanine form (51).
Synthetic inorganic ion-exchangers has been
classified into the following main groups according to
their salt composition.
(1) Hydrous oxides and insoluble salts .
(2) Quadrivalent metal oxides (oxides of group IV
with more acidic oxides of group V and VI of
the periodic table).
(3) Synthetic alumino silicate
(4) Salts of heteropolyacids
(5) Double layered hydroxides.
The insoluble materials with metal oxide-water
system has been widely used as "hydrous oxide". A wide
range of hydrous oxides exhibit excellent selectivity
with respect to certain elements or group of elements
due to their amphoteric nature. Hydrous oxides of Nb/
Ta, Sb(V), Mo(VI) and W(VI) exhibit cation exchange
properties. Whereas these show little or no anion
exchange character even in acidic solution. Anion
exchange properties were exhibited by oxides of Mg, Ca,
11
Bi and little cation exchange behaviour even at high pH
of 12. Therefore, hydrous oxide of ter-and quadrivalent
metals are mainly amphoteric ion-exchangers. The
dissociation reaction of an amphoteric exchange
reaction can be deduced by the following mechanism.
Anion exchange Reaction : M-OH; r:: M +0H
(Reverse reaction)
Cation exchange Reaction : M-OH ; :±. M-o"+H
(M-represents the central
metal atom)
Inorganic ion-exchange properties of oxides and
hydroxides :have been published in several reviews
(52,53). Some of its application has been the work of
Girandi et al. (54,55) who successfully used hydrous
antimonic(V) oxide in neutron activation analysis.
Additionally numerous papers have reported recently on
the subject with much emphasis of the adsorption
mechanism as well as their application in various
fields of interest. Numerous insoluble hydrous oxide
can exist in a number of forms with different chemical
and physical properties depending on their methods of
preparation and subsequent treatment. Mostly cations
of valency 3+ or higher gave rise to polynuclear species
12
in aqueous solution over an appropriate pH range. For
example^ the different hydrolyzed species of Zirconium
ZrOOH"*", [(ZrO-COH) ]" '''/ and [ (ZrO^COH)^]*"*" have been
observed depending upon the pH of mother liquor.
Acidic salts of multivalent metals produced
inorganic ion exchanger by mixing the acidic oxides of
the metals belonging to group IV to more acidic oxides
of group V and VI of the periodic table which result in
the production of insoluble white gelatinous material.
Their composition is nonstoichiometric and depends on
the condition under which they are precipitated..The
materials which have been synthesized so far include :
M(IV)-phosphate, arsenate, molybdate, tungstate,
silicate, vanadate and tellurate etc. Where M(IV)
stands for Zr(IV), Sn(IV), Ti(IV) etc. Potential
application of these materials are found in various
fields as hydrogen-oxygen fuel cell, desalination
process and artificial kidney machines to remove
ammonium ions (56).
The heteropolyacid salts have been prepared
belonging to the class of 12-heteropolyacids having the
general formula H XY^^O^.nU.O, where X may represent
one of the several elements including phosphorus.
13
arsenic and silicon, and Y a different element such as
molybdenum tungsten and vanadium. The heteropoly
compounds especially those of 12-molybdo compounds are
quite strong oxidizing agents.
Layered structures (<^-layered material) were
found among the acid salts of tetravalent metals.
oC-Zirconium monohydrogen phosphate (oC-ZrP) is the most
pertinent example of this type of materials. The
oC-layered material has been generally prepared by
refluxing the amorphous materials in concentrated
phosphoric acid (10-14M) for few days (14,16,57/58).
The degree of crystallinity increases with increase of
the refluxing time and the concentration of phosphoric
acid, as in the case of cC-ZrP, The structure is layered
and consists of a sheet of roughly coplanar Zr atoms
sandwiched between two-sheets of monohydrogen phosphate
group. Where each Zirconium atom is coordinated
octahedrally to six oxygen atoms. Each of these six
oxygen atoms belongs to one of six different
monohydrogen phosphate group. Very weak hydrogen bonds
or Van der Waals forces acts between the layers and the o
interlayer distance being 7.6 A . The layers are
arranged relative to each other in such a way that the
Zirconium atoms in one layer lie over the P atoms in
14
an adjacent layer and vice-versa. A water molecule
resides in the centre of each cavity and is hydrogen
bonded to phosphate groups. Whereas in the ^-phase of
Zirconium phosphate the structural features are
essentially the same as those of '^ -ZrP but the
difference is that the interlayer distance in this case
is 9.28 A°. The sequence of layer packing is such that
neighbouring HPO- groups from adjacent layers are
aligned opposite to one another to allow interlayer
hydrogen bonds of the type O3P-O. ^"^^3' " ^ structure
cf oC-ZrP is very closely related to that of ^-ZrP (59).
The most important two component ion-exchange materials
investigated are reported in Table (1.1).
Mixed salts of three components also possess
better ion-exchange properties compared to simple salts
or two component ion-exchangers. They exhibit
superiority over simple salts in terms of their (i)
stability towards thermal and chemical treatment1 (ii)
high selectivity and (iii) increased capacity. Some of
the three component ion-exchange materials with their
properties are summarized in Table (1.2).
Another important class of layered materials
are the layered double hydroxide with general formula.
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27
[MII^ M"I (OH) ] - Vn-2«2°
TT 7+ 5+ 7+ 2+ 2+ 2+ 2+
where M"" = Mq^ , Kn , Fe^ , Co^ , Hx , Cu" , Zn or
M " ^ = Al3\ Cr3^ Mn3^ Fe3\ Co^^, Sc^^ V^^ or
and X is the balancing anion. In its structure some of
the M(II) ions hydroxide layer M (OH.) are replaced by
M(III) ions/ and the total charge of the layer become
positive. The inorganic and anions x is exchangeable
by other inorganic and organic anion (158). The
outstanding reason for the importance of this class of
compounds is that they are the only inter-crystalline-
reactive layered materials consisting of positively
charge layers which can act as anion exchanger. They
can also serve as models of the binding of anionic
surface active agents on solid surfaces (159).
An extensive work has lead to the development of
many different M -M combination layered double
hydroxide, which has drawn much attention for its
potential use as ion-exchangers, pharmaceuticals ,
adsorbents, catalyst and anion scavangers. The
synthesis and characterization of polyoxovanadate
intercalated MgAl hydrotalcite has been achieved by the
28
exchange of the initial carbonate or terepthalate
anion, as well as reconstruction of the layered
structure from the previously calcined at SSCC.
Vanadate addation to MgAl-LDH at pH=4.5 leads to a
fibrous material with partial dissolution of magnesium
and total exchange of C0^7CgH^(COO)2~ takes place in
this LDH (160). Other LDH as [Zn2Al(OH)gCl.2H20,
[Zn2Cr(OH)g]C1.2H 0 and [Ni^Al(OH)g]Cl.2.3H2O has been
prepared by coprecipitation methods* and decavanadate
anion V-rtO o is utilized for pillaring agent. These
materials are further characterized by V MAS-NMR
spectrum (161). Exchange with organic anions with
double layer hydroxide has been investigated and lead
to the formation of compounds as dicarboxylic acids
(Zn ''"-Al- ' hydroxide), D,L histidine (Mg ' -Al '*')
2+ 3+ 3+ acetic acid (Ni -Fe )(Co ) • alkyl sulfates
(Zn ''"-Cr "*'), (Mg''"-Al"''") and hydrotalcite-Acrylate
compound has been investigated (162). Organic-anions
pillared hydrotalcites such as Mg.Al2{0H)-.(TA).nH.O
(TA=terepthalate) are synthesized by using coprecipita-
tion/digestion techniques. Under mild acidic condition
hepta - molybdate and decavanadate has been exchanged
with terepthalate. These isopoly-metalate pillared
hydrotalcites exhibit thermal stability over 500°C in
air (163). Another LDH compound has been synthesized
29
by V ion in the layers alongwith Mg , as Mg -V
are difficult to synthesize due to its instability of
oxidation state of vanadium (164). Recently Co -Fe
double layer hydroxide has been synthesized by
electrochemical oxidation with a metal ion ratio of
2.2:1 (165). Pillared hydrotalcite compound containing
Co(II) and Cr(III) has been prepared with the
interlayer anion as carbonate or decavanadate, and it
is being characterized by X-ray diffraction, XAS,
UV-Vis, FT-IR/ and Raman spectroscopies (166). Mg-Cr
and Ni-Cr layered double hydroxide with carbonate
anions in the interlayer were used as precursors to
synthesize pillared derivatives with decavanadate
anions with the use of any preswelling agent and
earlier Ni-Al-Co. LDH with decavanadate as the
pillaring agent has been synthezied (167/168).
Inorganic and organic ion exchanger has drawn
much attention due to their application as adsorbents.
Their adsorption and thermodynamic behaviour showed an
appreciable result and followed Freundlich or the
Langmuir or both isotherm.
Plotting of adsorption isotherms is the most
convenient way of studying and understanding the nature
30
of adsorption taking place in a particular system. The
isotherms are obtained by plotting the amount adsorbed
against the equilibrium concentration at any instant at
a particular temperature. Thus different types of
curves with different slops and initial portion of the
curve are obtained.
Ion-exchangers incorporated with chelating
group provides a convenient analytical technique to
concentrate and remove many toxic metal ions which
form complexes in the exchanger phase in a selective
manner. To this purpose the development of complexing
ion-exchanger have been taken place where the
complexation equilibrium will play an important role.
Ion-exchange resin, having a trade mark of Lewatit
TP-207 is used for the recovery of heavy metals from
polluted area (169). Another chelating
exchanger has been prepared by deacetylation of chitin
and oligoglucosamine. These chitin showed appreciable
adsorption of Hg " , Cd^'^, Pb ''" and Cr "*" (170). Highly
selective adsorption resins were prepared by chitosan
derivatives containing 2-Pridylmethyl,2-thienylmethyl
and 3-(Methylthio)propyl groups. The amino group of the
active adsorptive site of chitosan was protected by
Schiffs base formation prior to being crosslinked by
31
2-(chloromethyl)oxirane, and the final chitosan
derivatives were obtained by reducing the amine moiety
of the Schiffs bases with sodium borohydride. These
chitosan derivatives exhibit high selectivities and
excellent loading capacities for Au, Pd/ Pt (171).
Uranium is adsorbed by Temodsid-SCTiOj) adsorbent from
a carbonate solution of pH 7.85 and 8.15 (resembling
seawater) at 20-60°C, where emperical equation was
derived for calculating thermodynamic parameters(172).
Another uranium selected chelate resin was prepared by
bonding with maelic acid-isobutane copolymer loaded
with polyetheneamine to N/COOH equation ratio of
1.7-2.2 and chelate resins containing 0-aminophenol/
thiophenol/ benzoic acid, aminoethyl phosphonic acid/
8-aminoanthraquine/ 5,8-diaminoanthraquine are used as
adsorbent for recovering heavy metal from water (173).
By introducing secondary, tertiary amine and quaternary
ammonium group, the resins exhibit a high selectivity
for Ge and Sb (174). A silica gel bonded with an
N-based cationic polymer, poly[N-xylylene N,N'-dicyclo-
hexylethylene diammonium dibromide] with Ferron
[7-iodo-8-hydroxyquinoline-5-sulfonic acid] as counter
ion. This renders an extremely stable stationary phase.
It is analytically applied as sorbent for metal ions,
Cu " , Cd " , Zn " , Pb " , Co " , Ni " and Fe"'' and
32
purification of supporting electrolyte/buffer required
for voltametric detection (175). The adsorption of
Co(II) is studied on HTTA impregnated polyurethane foam
and follows Freundlich and Langmuir isotherm of concen-
-5 —2 tration range 10 to 10 M of metal solution (176).
Adsorption of nickel ions on macroporus ion-exchanger
is studied snd the recovery of metal ions from wastewater
is particularly achieved on this material (177).
Novel inorganic exchanger still commands
attention due to its various use but few have been
commercialized especially in HPLC. Noteworthy among
these are titanium dioxide (178), titanium phosphate
(179), Callidinium molybdoarsenate (180), stannic
vanadoarsenate (181) and Zirconium oxide (182).
Ion-exchange process reported for many separation often
involve mixed mechanisms in which sorption effect plays
an important part. The elution behaviour of Li and
Mg ions with nitric acid on crystalline antimonic
acid, a cation exchanger has been studied by Mitsu Abe
(190). On the basis of relevant distribution
coefficient for various metal ions in the resin and
crystalline antimonic acid, an effective separation of
Li from large amount of other metal ions can be
performed quantitatively on the double column which
33
consist of an upper column of Dowex 50W-X8 and lower
column of cyrstalline antimonic acid. Separations of
rare earths and other fission products from mineral
acids have been achieved on Zirconium titanium
phosphate (191, 192). Zirconium arsenophosphate cation
exchange column is used for quantitative separation of
uranium from some metal ions which generally interfere
in its spectrophotomeric determination using sodium
diethyldithiocarbamate as reagent (193). The complex
forming ability of EDTA at various pH values and the
ion-exchange behaviour of Sn(IV) arsenosilicate and
Sn(IV) arsenophosphate cation exchanger have been
combined in thin layer chromatography in order to study
the separation of metal ions (194). The distribution of
some anionic species on Zirconium(IV) phenylethylamine
anion exchanger has been studied and this exchanger,
modified with chromeazurol-S has been further studied
3+ 2+ for the separation of Al from Mg in some synthetic
mixture of antacid formulations (195). Selenophosphate
and iodomolybdate of zirconium • were used for
ternary and quaternary separation of metal ions
'^ 183/184). Zirconium arsenate-vanadate has been used
for the removal of fluoride ion as well as phenolic
compounds (185-187). Mercury selective exchanger,Zirco-
nium(IV) piperidimethioglycolate and Zirconium (IV)
34
4-amino-3-hydroxy napthalene sulphonate have been
synthesized and used for the separaticai of mercury metal
ions. (188). Whereas arsenate ion being separated on
Zirconium(IV) phenylethylamine exchanger (189).
Ion exchange materials have been extensively
fabricated for developing a large number of ion
selective electrodes in which these materials are
impregnated into polymeric inert matrices which serve
as ion-selective membrane. Monovalent ion-selective
electrode has been prepared by the use of a variety of
weak cation exchanger (196). Zirconyl ion-electrodes
(197/ 198) is developed by the incorporation of
Zirconium tungstoarsenate into a polystyrene matrix.
Using antimonate in an araldite matrix* lead ion-
selective electrodes has been developed (199), and
cerium selective electrode is developed using pressed
disks of zeolite ion-exchangers in an epoxy based
support (200, 201).
Ion-exchanger is the growing field for their
application as catalyst, sensors, ion-conductor etc. To
this need new ion-exchanger has been developed over the
years by new methods of preparation, intercalation with
various amine group or other organic compounds, and
characterized by elemental analysis, IR, NMR, FTIR
35
thermal studies, x-ray diffractions. A layered
compound with amine, Zirconium N-(phosphonomethy1)
iminodiacetate is developed, which shows a structural
similarity to that T-ZrP revealed by MAS, NMR, XRD. A
mixed phosphate/phosphonate compound is obtained by the
ratio variation of phosphoric acid to diacetoimino-
phosphoric acid and heating with Zirconyl chloride in
the presence of HF (202). Porous titanosilicate
[Na-Ti-0-SiO..2H^0] containing unidimensional is
synthesized hydrothermally. An elaborate framework
structure study reveals that the number of molecules in
the unit cell in this case is 8, where the channels are
occupied by the water molecules in the acid form, which
involved in hydrogen bonding among themselves as well
as with the framework oxygens. The titanium atoms are
octahedrally coordinated and they are grouped as
clusters of four. These clusters are linked by the
silicate groups along the a & b directions and by
Ti-O-Ti bonds along the c directions. This structural
data explains for the ion-exchange behaviour and ion-
2+ 2+ selectivity for Cs and Sr (203). A new microporous
lewis base having cC-layered structure, Zr(0_P(CH2)^NH-)2
(CI )2 with an interlayer spacing of 15.3 A" and Zr(0-P
(CH2)3NH2)Q 2 ^ -'s ^ s l 8'^^2° ^^^^ interlayer spacing
of 10.4A° has been synthesized, which allows facile
36
protonation of the amine and inclusion and subsequent
exchange of anions. This compound shows an ability to
coordinate metals to produce microporous materials with
built in active centres for active catalysis (204).
Another inorganic-organic polymer# Zirconium
phosphite (3,3',5,5'-tetramethylbiphenyl) diphosphonate
has been prepared and characterized which shows an
appreciable application as molecular sieve/ "shape
selective" catalysis and protonic conductors. These
material with specific interlayer porosity has been
prepared by simply changing the length of the organic
group intercalated in order to obtain their maximum
practical potential (205). The other type of ion-
exchangers are complex tubular Uranyl phenyl
phosphonate ("©2)3 (H03PCgHg)2 (03PCgH^)2.H20 which
shows a novel channel structure of a Uranyl compound
containing 50 non-hydrogen atoms in the asymmetric unit
(206) and two lamellar arylenebis(phosphonates)
Cu[H03P(CgH^)2P02H] which exhibit high stability (207).
Also three layered metal(IV) hydrogen phosphate with
formula <<l-M(HPO )2.H20 (M = Ti, Sn, Pb), has been
optimized to yield single phases of highly crystalline
material (208). Amine intercalated compound has also
drawn much interest due to its ambiguous use.
37
Intercalation compounds of eC-Zirconium phosphate with
hexamethylenetetramine (CH2)gN- has been prepared and
characterized (209). A new class of remarkable
complexing agent Zirconium Polyimine phosphonates/ has
been prepared by the intercalation of various amine
groups. These compounds were mainly phosphonates
because the P-C bond is more stable to hydrolytic
cleavage than the P-0 bond of phosphonates. Both mono-
and diphosphonic acids of polyamines were synthesized
and its general procedure involves reaction of
polyamine, NH2[CH2CH2NH) -H, with (Chloromethyl) phos-
phonic acid, ClCH-PO-H^/ in basic solution. Where an
excess use of phosphonic acid yields diphosphonic acids
(210). In addition various other compounds like
azaheterocyclic compounds, alcohols, tertiary amines
and diamines has been intercalated, and elaborate study
of intercalation chemistry of Zirconium phosphate has
been reviewed (211).
38
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PREPARATION, CHARACTERIZATION AND ANALYTICAL APPLICATIONS OF A NEW
SEMICRYSTALLINE ION EXCHANGE MATERIAL : ZIRCONIUM(IV) DIETHYLENETRIAMINE PHOSPHATE
51
There has been a continuous e f fo r t to
synthesize new inorganic ion-exchangers due to i t s high
thermal and chemical s t a b i l i t y , s e l e c t i v i t y for cer ta in
ionic species and r e s i s t i v i t y towards r ad ia t ion (l-8)-».
An exhaust ive study of ion-exchangers based on Zr(IV)
possessing layered s t ruc tu re has been ca r r i ed out (9) .
Another recen t area of in te res t i s the i n t e r c a l a t i o n of
guest molecules i n t o layered s t r u c t u r e . Layered
c(-Zirconium phosphate (10-12) has been used as a host
for i n t e r c a l a t i o n of a number of guest molecules. A
number of organic^ inorganic and organometal l ic guest
molecules have been in tercala ted i n t o cC~zirconium
phosphate/ most commonly via ion-exchange or acid-base
react ion with the ac id ic phosphate. Amines are found
spec ia l ly more e f fec t ive guest molecules due to the i r
high b a s i c i t y .
Haregawa e t a l . have studied i n t e r c a l a t i o n of
alkylamines and cyclohexylamine and discussed the
r e l a t i o n between the chain length of amine and the
i n t e r l a y e r d i s t ance of zirconium phosphate (13,14).
Ferargina e t a l . (15) have reported the i n t e r ca l a t i on
of some cf-diamines such as 2 ,2 ' b ipyr id ine and 1,10-
phenanthrol ine i n t o t"-zirconium phosphate l ayers .
Tomita f u r t h e r studied the uptake of Cu{II) on
52
^ - z i r c o n i u m p h o s p h a t e i n t e r c a l a t e d w i t h 2 , 2 ' - b i p y r i d i n e
and t h e e f f e c t i v e p i l l a r i n g by t h e g u e s t m o l e c u l e s
a l l o w e d more up t ake of C u ( I I ) i o n t h a n i n t h e c a s e of
s i m p l e ^ - z i r c o n i u m p h o s p h a t e ( 1 6 ) . K o b a y a s h i e t a l . (17) have
s y n t h e s i z e d i:-NH.ZrH(PO ) and s t u d i e d t h e i o n -
e x c h a n g e p r o p e r t i e s . Hahn and K l e i n (18) have
i n t r o d u c e d o r g a n i c amine i o n i n p l a c e of p o t a s s i u m i o n
i n p o t a s s i u m c o b a l t ( I I ) h e x a c y a n o f e r a t e ( I I ) and found
t h a t amine compounds have e x c e l l e n t exchange p r o p e r t i e s
137 . .
f o r C s . Kobayashi e t a l . have s y n t h e s i z e d m i c r o -
c r y s t a l l i n e i o n - e x c h a n g e r w i t h t h e fo rmu la of
Zr(RNH)^H2_^(P0 J ^ . Y H j O . F i r s t l y , RNH.H2P0^ was
p r e p a r e d by t h e r e a c t i o n of p h o s p h o r i c a c i d w i t h
t e r t i a r y amines and t h e n Zr(RNH) H j , (P0.)2.YH2O was
fo rmed by a h y d r o t h e r m a l r e a c t i o n be tween RNH.H^PO. and
ZrOCl i n an a u t o c l a v e .
In t h i s c h a p t e r , we have r e p o r t e d t h e s y n t h e s i s
o f a new s e m i c r y s t a l l i n e i o n - e x c h a n g e r ^ Z i r c o n i u m ( I V )
d i e t h y l e n e t r i a m i n e p h o s p h a t e . The i o n - e x c h a n g e
c h a r a c t e r i s t i c s of t h e m a t e r i a l have been s t u d i e d by
column and p H - t i t r a t i o n m e t h o d s . The m a t e r i a l h a s been
c h a r a c t e r i s e d on t h e b a s i s of c h e m i c a l c o m p o s i t i o n ,
x - r a y d i f f r a c t i o n p a t t e r n , FTIR and TGA. The
d i s t r i b u t i o n c o e f f i c i e n t o f s i x t e e n m e t a l i o n s h a s been
53
determined and on the basis of difference in the Kd
values, separation of metal ions has been carried out
on its column.
54
EXPERIMENTAL
REAGENTS :
Zirconium Oxychloride (CDH), orthophosphoric acid
(BDH) and diethylenetriamine (S.d. fine chemicals) were
used for the synthesis of ion exchange materials. All
other chemicals were of AR grade.
APPARATUS :
Spectronic 20 (Bausch & Lomb) spectrophotometer,
pH was measured on ELICO LI-10 pH meter, Remi 2LH magnetic
stirrer for stirring, x-ray diffraction pattern (XRD) on
Philips APO 1700 instrument, with Ni-filtered Cu-KcC
radiation, FTIR on Perkin-Elmer 1730 spectrometer and
thermogravimetric analysis (TGA) on Rigahu Denki
Thermoflex-type thermal analyzer, model 8076 were
recorded.
SYNTHESIS :
The ion-exchange materials were prepared by
mixing IM of diethylenetriamine and 2M of orthophosphoric
acid and put on stirrer plate for 1 hour. To this O.lM
zirconium oxychloride was added and maintained the
condition of synthesis as indicated in Table 2.1. The
resulting products were filtered off and washed with
55
several small volumes of distilled water to remove
excess of the reagents until a pH of 6 was obtained.
The material was dried at 40°C in an oven and allowed
to break down into small particles by immersing in
distilled water. The ion-exchange granules which
showed cationic properties were converted into the H
form by treating with 0.5M HCl for 24 hours. The
granules were finally washed with distilled water until
pH = 6, and dried at 40°C. Sample ZAP-1 was chosen for
further studies owing to its high ion-exchange
capacity.
ION-EXCHANGE CAPACITY :
A 0.5 gm exchanger in H form was packed into a
class column (0.6 cm/ i.d.) provided with a glass-wool
support. The ion-exchange capacity was determined by
passing a IM solution of different uni- and bivalent
metal salts and the flow rate was adjusted to 1 ml
min . The effluent was then titrated against a
standard solution of NaOH.
CHEMICAL COMPOSITION :
A 0.10 gm of the exchanger material ZAP-1 was
dissolved in minimum volume of concentrated sulphuric
56
acid and diluted to 100 ml with distilled water. The
zirconium ions by chelometric titration (21) using
xylenol orange indicator and phosphate (22) were
determined by the standard methods. To determine the
content of diethylenetriamine another (0.5 g) sample of
the exchanger was introduced into a Kjeldahl digestion
flask which contained concentrated hydrochloric and
sulphuric acids and potassium sulphate as catalyst.
After digestion, 30 ml sodium hydroxide solution (50%)
was added dropwise to release amine which was trapped
in 50 ml hydrochloric acid solution (1%). The amount of
diethylenetriamine released into the solution was
determined titrimetrically using a mixed indicator
(Bromo-Cresol Green and Methyl Red) (24).
The mole ratio of zirconium : diethylenetriamine :
phosphate was found to be 3 : 1 : 4.
CHEMICAL STABILITY :
The dissolution of various samples of exchanger
were studied in mineral acids, bases and organic
solvents. A 0.5 g of the exchanger (ZAP-1) in H form
was shaken with 50 ml of solution/solvent of interest
for 24 hours. The amount of zirconium ion, phosphate
ion and diethylenetriamine released into the solution
57
were determined spectrophotometrically vising alizarine red
S, hydrazine sulfate and ninhydrin as chromogenic
reagents, respectively (22,23). The results are
summarized in Table 2.2.
pH TITRATION :
The pH titrations of the ion-exchange material
(ZAP-1) in H form were carried out by equilibrating
several samples of exchanger (0.5 gm) with 50 ml of
O.lM NaCl-NaOH solutions (25). The pH was determined
after 24 hours and plotted against the ml of NaOH
added.
DISTRIBUTION COEFFICIENT :
The distribution coefficient vlaues (Kd) for
various metal ions in different solvent systems were
determined. A 0.2 gm of exchanger in H form vas
treated with 50 ml of desired O.OlM metal salt solution
in a 250 ml Erlenmyer flask using various concentration
of nitric acid, ammonium nitrate and distilled water
for each metal ion. The mixture was shaken in water
bath shaker for 8 hours. After equilibration, the metal
ion were determined by titrating against the standard
solution of EDTA.
58
The distribution coefficients (Kd values) were
calculated using the following equation .
mmoles of metal ionic species in the exchanger Kd = phase/gm of exchanger
mmoles of metal ionic species left in the aqueous phase/ml of the total volume of resultant solution.
QUANTITATIVE SEPARATION OF CATIONS :
Quantitative separation of cationic species
were accomplished on a small glass colxiran (i.d, 0.6 cm)
packed with an exact 2.0 gm exchanger (ZAP-1) in
H form. Synthetic two component mixtures of metal ions
of known volume were transferred into the column and
allowed to stand for 15 mins. to reach the equilibrium
state followed by elution with appropriate eluent at a
flow rate of 0.5 ml min.~ .
59
RESULTS AND DISCUSSION
Various samples of zirconiumdv) diethylene-
triamine phosphate ion-exchanger are prepared by mixing
aqueous solutions of zirconium oxychloride/ diethylene-
triamine and orthophosphoric acid under varying
conditions. It is observed from table 2.1/ among the
various samples, sample ZAP-1 prepared at pH ^ 4.7
possessed the highest ion-exchange capacity. The
chemical stability of zirconium(IV) diethylenetriamine
phosphate (sample ZAP-1) has been studied in moderate
concentrations of mineral acids, bases, ammonium
chloride solutions and ethanol. The results are
summarized in Table 2.2. The material is stable at low
concentration of hydrochloric acid and nitric acid and
therefore may be used for colximn chromatography.
The ion-exchange capacities for alkali and
alkaline earth metal ions are determined by column method.
The results are reported in Table 2.3. It clearly
indicates that the ion-exchange capacity increases
along with a decrease in the hydrated ionic radii of
the ingoing metal ions. The behaviour is in agreement
with the findings of Nachod and Wood (16), who
investigated the exchange of alkali and alkaline earth
metal ions on zeolites.
(X W K K O O O Z fc t P S <: \ < CC > O ' K U El Q) U X M E X ft! U * - ' W
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61
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62
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63
The pH titration curve of the sample ZAP-1 dried at
40°C (Fig. 2.1 ) shows two inflection points which
indicates that the exchanger is bifunctional. The
first end point occurs at 0.35 meq/g and the second end
point at 2.05 meq/g exchanger.
SPECTRUM (FTIR)
The FTIR spectrum shows a strong band in the
region 3600-3200 cm" which may be assigned to the
interstitial water molecules. The N-H stretching
vibration of secondary aliphatic amine (>NH) also lies
in the same region. The symmetric and asymmetric - CH_-
stretching vibration appeared at 2863 cm and 2933
cm respectively. Weak N-H stretching vibration is
shown at 2428 cm . The asymmetry deformation peak
arises at 1670 cm owing to protonated -NH_+ groups
(27). The peak appearing at 1487 cm may be due to C-H
deformation vibration. The Zr-0 stretching vibration
falls in the region 1120-920 cm~ (28).
FTIR spectra of the sample ZAP-1 dried at 60<>C,
370°C and 510°C were recorded and shown in Fig.
2.2 (a,b/c). The peak due to protonated -NH- +
deformation vibration at 1670 cm" gradually becomes
short in size at 370°C and almost vanishes at 510°C.
64
Ur
AO'C
1 2 3 4
OH~ added (meq/g exchanger)
Fig . 2.1 pH- t i t r a t i on of zirconium(IV)
diethylenetriamine phosphate (ZAP-1)
exchanger.
65
I
O o
1 •
o • 1 •
0 0
' 1 • • 1 ' • 1 '
C v j
• 1 '
o ' i '•
C O
• 1 •
CD CO
1 I • ' 1
C M ^ «
^ l — i _ ( 0 C ( n t - t - + - n J C O < D
66
67
68
There is shift in the position of peak towards 1630
cm , Fig. 2.2 (a & c). This shows the degradation/
combustion of diethylenetriammonium ion molecule which
is also supported by DTA studies. Another supporting
point is the decrease in its ion-exchange capacity. The
peak due to N-CH vibration at 1487 cm and the N-H
stretching vibration at 2428 cm" disappeared
completely. Fig. 2.2(ci/When the sample was heated at
510°C.
The thermal method which include TGA and DTA
analysis of the ion-exchange material (ZAP-1) are shown
in Fig. 2.3. The material released the water of
crystallization at 65°C-117°C (corresponding to weight
loss of 14%) appeared on DTA and upto 115°C on TGA.
Three different exothermic peaks at 490°C, 498°C-538°C
and 540°C appeared on DTA owing to the degradation/
combustion of the different type of amine group that is
-NH^+ (protonated) and -NH. The decrease in
ion-exchange capacity from 1.98 meq/g to 0.31/g
supports this fact. The weight loss is again observed
from 370-510°C corresponding to the total weight loss
of 21% indicates further decomposition of diethylene-
triamine. The loss of the ion-exchange sites (absence
of the ethylenediamine peak at 1488 cm" , primary-NH.
deformation peak at 611 cm and shorterning of peak at
69
IT) o N o
_ J _
in •rt
o _L_
o _ l _
in o o
_J_
o o
I I I I I I I I I I I o o
o o m
0) +J (0 x: to o -04
d •1-1
<0 •H U +J 0)
c (U >1 x: 0) •H
-r >
I I I I I I I I I I I I I I I I I I I I I I I I i I I I I I I I I I I I I I I I f O
in o in o in 0 1 0 1 CD CD rN
u
01 c ZJ -M ID c 0)
a e 0) 1 -
H ^ , _ , j
E 13
•H C 0 o w •H N
«4-l 0
0} (U > u s o < E-i • c -
i H eB 1
CU < < O K: EH —
• • •
CM
• •H
(X) :)MBTaM
7C
1631 cm is in good agreement with the above fact. The
decrease in the ion-exchange capacity is found to be
almost negligible that is 0.04 meq/g.
The x-ray diffraction pattern of the ion-
exchange material (ZAP-1) dried at 40oC (Fig. 2.4 ,
Table 2.4 ) reveals its semicrystalline nature. The
peaks appeared at different angles having d-values of
10.92, 1.23, 1.22, 1.12 and 1.03 A° in the x-ray
diffraction pattern. Comparing the first d-value of
c(-zirconium phosphate 7.6 A°^it clearly shows the
gallery height increase by 3.32 A°, which suggests the
diethylenetriamine molecule intercalation between the
zirconium phosphate layer (Scheme 2.2).
The ion-exchange capacity of the material may
be related to the presence of phosphoric group (-POOH)
will provide the free proton giving the cation-exchange
capacity to a number of different cations such as Li ,
Na , K after regenerating the exchanger to their
respective form. The ion-exchange capacity in terms of
different cations are determined(Table 2.2).
As described in the procedure a mixture of
phosphoric acid and diethylenetriamine is stirred for
one hour and then an aqueous solution of zirconium
71
(0 0) 0)
u
•D
<D
c B 10
•H U 4J (U c 0) i-H
>1
+> 0)
•H
>
H
•H c o o
•H es3
o c 0) +> +> <0
O i H •H I
<a N H w
M-l 0) •H +J «0 10
X
10 m U O I JC
X O4
CM
•H
AiiisNaiNi aAiivnan
72
Table 2 .4 : X-ray d i f f r a c t i o n da t a for Zirconium(IV)-d i e t h y l e n e t r i a m i n e phosphate (ZAP-1). Ca l cu l a t i on of d - v a l u e s . Monochromatic Rad ia t ion Used Cu-Kc( = 1.54 A°
ANGLE OF OBSERVATION 2e degree)
8.09
77.56
77.94
87.21
97.00
SPACING BETWEEN THE PLANES (d-values in A°)
10.92
1.23
1.22
1.12
1.03
I/I {%) max
100.00
88.36
37.21
42.25
21.16
73
oxychloride is transferred into it. The whole contents
are stirred on magnetic stirrer for six hours. The
final pH is found 4.7. The pH value gives an
indication that the acid hydrolysis has taken place
instead of a base hydrolysis due to the presence of
diethylenetriamine. A gel structure containing
phosphate group in the form of sheets of phosphate
units results later on weak physical interaction
between -OH group of metal ion and -NH of amine group
forming hydrogen bond. The lone pair on
the nitrogen atoms provides the possibility of interca
lation (Scheme 2.1). The Kd value of the transition
metals is supporting fact to this effect/ whereas the
-POOH group provides cation exchange to the metal ions.
The values of distribution coefficients are
determined at 25+ l°C which are summarized in Table 2.5
The result suggests the uptake of metal ions in two
different ways.
1. By ion exchange process : The H"*" ions of -POOH
sheets are responsible for exchange of metal ions such
„ 2+ r, 2+ „ 2+ .. 2+ „ 2+ „.2+ „ 2+ ^,2+ „, as Mg , Sr , Ba , Mn , Cu , Ni , Zn , Cd . The
Kd values of the three metal ions are comparatively
high in distilled water, in the nitric acid and ammonium
nitrate solutions there is a decrease in these values
74
/
Coordination Site
I N
V9 /
CH-
HO
I OPO3H
H2O
L
/ H - N : \
lon-exchonge site
[OP03H;
1 ^ 2 ° | ^ H 2 0 Zr 0 Zr— 0 - ^
I OPO3H
SCHEME 2 . 1
OPO3H
J n
/ I \ I n t e r c a l a t i o n of , ^^ g2A° 1 I 7 .6A° i - > » ' / ^ I ' d i e t h y l e n e t r i a m i n e \ /
V//////777A Shows cC-zirconiun phospha te I n t e r c a l a t e d S t r u c t u r e
SCHEME 2.2
.
en O
V ^
o 2:
n O
CM '*
O 12
m O
2 !Z r-l ^ • X O Z
m S O r 2 o ^ • tc o Z
S n rH O
o tc
z i-i m o o o BC
3 c
•J < w £-< !2 K O S H
m CM
1-1
CO ^ I^
o CM
O iH
VO ac KC •^
VO
<x> CM
CM
^
o t-i
t^ iH
O
+ CM
tT> 2
iH O
'*•
IT) r^
00
CN
r CM CM
IT,
r-
oc VO
'T IT
iH iH
1^
<n
n CM
n 00
in
^
+ N (C u
CTi OC
r-
^ in
«H iH
n n m m
00 r CM r-
o o IT)
<ri IT
O CM
^ VO
00 in
+ rM-U
w
CO iH
iH ^
r-i 00
^ VO
r in
n o r-t
<ri VO
00 o iH
in CM
«*
CM O
CTi iH
O o iH CO
+
CM O
<" n
<ri CM
VO ^
CM m
o r»
o • ^
in r~
n in
iH
m VO
in iH
m rr iH Tj*
+
iH ^ VO o in
in 00
m o CM
CO
n
n ** fH
00 CM
<n 00
00 00
VO 'ij"
o o
o in n
in t
o r-
+ rM CM n «0 CO
c s
0) PM
o o
o VO
r» CO
iH o
n en
n CM CM
CM VO
CM r r->
It iH
in in
o in
i^ 00
VO r-o en
+ CM 0 U
1^ CM
O CM
00 r-
r» CM
o i-(
^ n
CM iH
xr ^
in CM
VO
00 r t CM
n VO
CM in
+ M •H
z
CN ro CM in
ro CO
n 00
CM <n CM iH H
CTi iH
VO CM CM
in ^
o «H
ro o
ro in
in VO
CTl 00 iH
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CM VO
in t-\
in VO
00 iH
VO VO
VO in
in in
VO ^ iH
VO en
iH iH
c n
^ CM
t r>-r CM
+ CM c N
O
r Tf iH
O iH
VO CM
in CM
iH en
o en rH (N iH
O 00
CM
<y> o 'S' fH
in ^ 00 iH
+ CM T) U
CM VO
r-<n
CM O
fH O
m
o o
o 1^ • *
00 r-i
00 VO in
m CM
CTi VO CM
H cri
o o H
VO
r 00
o CM CM
+ CM D> sc
rH 00
CTi 00
1^ r-
<n 00 CM
in tH
VO o\ tn
VO CM
in in 00
r-in
00 CM
00 00
VO 'if
en en en 00
+ CM Xi Pn
VO in
en VO in
o r-
^ fH
cn
VO fH
CM 00
in '* VO in
VO VO
CM
o in
CM VO
00 iH
iH en iH
+ en fH <
O
o
o CM iH
CM
^ in en iH
** 00
VO en CM
en CM
a\ rH cn
CD o
•* o
VO 00
I^ iH
o o o
+ ^ (I) O
o o in
o iH
<n CM
r VO CM fH
O rH
cn in iH CM
VO VO
VO VO VO
00 in
en
r cn in
iH ** <n CM
+ rn •H CO
75
76
owing to the competition of H and NH.+ with respect to
metal ion.
2. Coordination sites of intercalated diethylenetri-
amine molecule : Metal ions Fe /Co / Hg ,Pb
Al "*", Ce " and Bi show substantially a high Kd values
suggesting a strong bond formation between metal ions
and nitrogen atom of diethylenetriamine having a lone
pair of electron.
On the basis of difference in Kd values of
various metal ions, some separations of analytical
utility have been successfully achieved on
Zirconium(IV)diethylenetriamine phosphate column. The
results are summarized in Table 2.G.
77
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• H V4 +J <U c (U
H
£ +J (U
•H
> H
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• H C o u u
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c o V
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H I
<
Z EL) Q
D W t-:i W
O E-> Z
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REFERENCES
1. S.Z. Qureshi and N. Rahman/ Bull. Chem. Soc. Jpn./ 60, 2627 (1987).
2. S.Z. Qureshi and N. Rahman/ Bull. Soc. Chim. France/ 959 (1987).
3. S.Z. Qureshi, S.T. Ahmad and N. Rahman, Chem. Anal. (Warsaw), 37, 21 (1992).
4. S.Z. Qureshi, M.A. Khan and N. Rahman, Water Treatment, 9, 27 (1994).
5. S.Z. Qureshi, M.A. Khan and N. Rahman, Bull. Chem. Soc. Jpn., 68, 1613 (1995).
6. S.Z. Qureshi, M.A. Khan and N. Rahman, Water Treatment, 10, 307 (1995).
7. S.Z. Qureshi, R.M.A.Q. Jamhour and N. Rahman, Ann. Chim., Fr. 21, 60S (1996).
8 . S . Z . Q u r e s h i , I . Ahmad, G. A s i f and N. Rahman, Ann. Chim. F r . / 21 / 593 ( 1 9 9 6 ) .
9 . A* C l e a r f i e l d / C.Y. O r t i z - A v i l a , i n S u p e r m o l e c u l a r A r c h i t e c t u r e . B e i n . T. E d s . , ACS Symposium S e n s e s 499: American Chem. S o c , Washington D .C . ( 1 9 9 2 ) .
1 0 . A . C l e a r f i e l d , and J . A . S t y n e s , J . I n o r g . N u c l . Chem. 26/ 117 ( 1 9 6 4 ) .
11. A'Clearfield/ Chem. Rev./ 88, 125 (1988).
12. G. Alberti, U. Costantino, In Inorg and Phys. Aspects of Inclusion, J.L. Atwood., J.E.D. Davies and D.D. MacNicol., Eds. Inclusion Compound. Vol. 5, Oxford Univ. Press/ New York/ (1991).
13. Y. Hasegawea and I. Tomita, Trends in Inorg. Chem., 2, 171 (1991).
14. Y. Hasegawa, K. Sasaki and H. Tanaka, Bull. Chem. Soc. Jpn./ 61/ 413 (1988).
79
15. C. Ferragina, M.A. Massucci and A.A.G. Tomlinson, J. Chem. Soc./ Dalton Trans., 1191 (1990).
16. I. Tomita, C. Takeo and Y. Hasegawa, J. Inclusion Phenom Mol. Recogn. Chem., 9, 315 (1990).
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18. R.B. Hahn and H.C. Klein, Anal. Chem., 40, 1135 (1968).
19. D.K. Singh and P. Mehrotra, Bull. Chem. Soc. Jpn., 63, 3467 (1990).
20. D.K. Singh and A. Darbari, Bull. Chem. Soc. Jpn., 61, 1369 (1988).
21. F.J. Welcher : "The Analytical Uses of EDTA", n. Van Nostrand Company, Inc., Princeton, New Jersey, pp. 188-189 (1958).
22. F.D. Snell and C.T. Snell. "Colorimetric Methods of Analysis," D. Van Nostrand Company, Princeton, New York, 2 (1957) .
23. D.F. Boltz : "Colometric Determination of non-metals", Interscience Publishing Inc, New York, Interscience Pub. Ltd. London, pp. 33-34 (1958).
24. J.J. Mitchell, I.M. Kotthoff, E.S. Proskaner and A. Weisberger : "Organic Analysis", Interscience, New York, 3, 140 (1956).
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26. F.C. Nachod and W. Wood, J. Am. Chem, Soc, 66, 1380 (1944).
27. G. Socrates, "Infrared Charac te r i s t ics Group Ffequen-c i e s " , A. Wiley Interscience Pub. (1980).
2 8 . F.A. M i l l e r and C.H. W i l k i n s , A n a l . Chem. , 2 4 , 1281 ( 1 9 5 2 ) .
THIN LAYER CHROMATOGRAPHIC BEHAVIOUR OF SOME AROMATIC NITRO COMPOUNDS ON
ZIRCONIUM ARSENATE LAYERS
80
A hand book of thin layer chromatography (1)
contains a comprehensive collection of Rf values of
organic and inorganic substances. TLC plates coated
with variety of sorbents have been utilized for
identification and separation of a variety of
substances. Silica gel (unmodified, chemically modified
and impregnated with organic ligands or organic salts)
have been the coating materials. The application of
synthetic inorganic ion-exchangers hag been extended
to TLC analysis to resolve a large number of organic
compounds with improved results (2-4). We have tried
Zirconium phosphate and layered double hydroxide for
the separation of carbamate pesticides and
cephalosporins drugs, where the results were found
promising (5,6).
Detection and determination of nitroaromatic
compounds have received considerable attention as most
of them show carcinogenic activity (7-9). Aromatic
nitro-compounds have been detected by liquid
chromatography (10) and separated from aqueous solution
using supercritical carbondioxide (11). m-Dinitroben-
zene have been detected on silica gel plates and the
effect of different solvents on Rf values have been
studied in detailed (12). The solvent polarities have
been related to Rf values of various nitrocompounds. On
81
the basis of the Rf values, the polarity of unknown
solvent or mixed solvent can be determined (14).
The silica gel is the most widely used
adsorbent in TLC and more than sixty nitro compounds
and their reduction products are analyzed on TLC plates
(15). A number of nitrocompounds have been separated
by TLC on silica gel plates in different solvent
systems such as chloroform-cyclohexane (80:20, 50:50)
and hexane-dimethylketone (80:20). The resolved
components are detected after converting them into
primary aromatic amines with TiCl. (16). It has been
observed that solvent's composition effect to a great
extent the Rf values of aromatic nitrocompounds. The
selectivity is improved on dilution of the polar
solvent (17). A molecular model of adsorption is
suggested for nitro-derivatives of benzene, naphthalene
and biphenyl on magnesium silicate layers developed
with solution of polar solvent in cyclohexane. In most
cases Rm values are found to be related linearly to the
logarithm of the mole fraction of the polar solvent.
The slope of linear plots were interpreted in terms of
configuration of the adsorbed molecules (18,19).
Polycyclic aromatic hydrocarbons may react with
nitrogen oxides (NOx) or nitric acid present in
82
atmosphere resulting in the formation of nitro
derivatives of polycyclic aromatic hydrocarbons. A thin
layer chromatographic method is developed for the
detection of the possible nitro derivates of polycyclic
aromatic hydrocarbons (20). A number of nitro
derivatives of biphenyl-2-carboxylic acid are detected
on silofol UV-254 TLC plates by separating with l:{5-7)
25% NH.OH-dioxane as developer. The separated nitro-
derivatives are reduced by spraying with 1% SnCl^ in 5%
HCl and then the reduced product is detected with
Ehrlich's reagent or 10% ^6^3 solution (21).
Nitrobenzene derivatives are separated on silica gel.
The separated nitro-derivatives are converted to nitro-
amines by treating with TiCl« and then detected by
spraying with 0.5% solution of p-dimethylaminobenzal-
dehyde in methanol-HCl [19:1] (22). Volkmann (23) has
studied the chromatographic behaviour of some
hydrocarbons and some of their nitro-derivatives on
silica gel preconditioned with vapour of cyclohexane.
Under this condition, the separation of sample pairs
is improved. Another method is also developed for
sorption and recovery of aliphatic and aromatic nitro
compounds on Amberlit XAD-2 and Amberlit XAD-7, after
desorption with a suitable solvent, Amberlit XAD-2 gave
80-100% recovery of nitroaromatics (24).
83
In this manuscript we describe the behaviour of
some nitroaromatic compounds on zirconium arsenate
layers in various solvent systems.
84
EXPERIMENTAL
MATERIALS :
Zirconium oxychloride (Loba Chemia India) and
sodium arsenate (Robert Johnson) were used for the
synthesis of gel. The nitrocompounds were either from
BDH (Anal R)/ E. Merk or Koch Light. The solvents were
used without further purification.
TESTING SOLUTIONS AND DETECTION REAGENTS :
The test solution of nitrocompounds (2%)
were - prepared in ethanol. The detection of
4-nitrophenol, 4-nitroaniline, 2,4-dinitrophenylhydra-
zine, hexanitrodiphenylamine and m-dinitrobenzene was
obtained by their self intense colouration from yellow
to red. Compounds such as 1 chloro 2,4-dinitrobenzene,
3-nitrophenol, 3,5-dinitrosalicyclic acid and dinitro-
benzoic acid were detected by spraying a 2% alco
holic solution of diethylenetriamine.
PREPARATION OF TLC PLATES :
Zirconium arsenate layers were prepared by
mixing 50 ml of O.lM zirconium oxychloride with 50 ml
of O.lM sodium arsenate. A 0.06M calcium sulphate as
85
binder was added to the resultant zirconium arsenate
gel and the mixture was stirred with a glass rod to
produce a homogeneous slurry. The TLC plates were
prepared on glass slides (7.5x2.5 cm) of uniform
thickness and then dried in an oven at SO^C. Spotting
are done with fine capillary and were run in different
solvent systems in airtight gas chambers.
PREPARATION OF SILICA GEL PLATES :
To a 20 gm silica gel, distilled water was
added slowly stirring with a glass rod continuously so
as to get a homogeneous slurry which was applied to the
glass plates of uniform thickness and then activated at
86
RESULTS AND DISCUSSION
The data svunmarized in Table 3.1 offer
potentialities for the separation of aromatic
nitrocompounds on Zirconium arsenate layers. The spots
are found small, compact, and circular in most of the
solvent systems except a few are with tailing. The
results obtained on Zirconium arsenate layers were
compared to those obtained on silica gel layers (Table
3.2). On the basis of a large difference in Rf values,
a number of synthetic mixtures of binary and ternary
compounds are separated successfully. The results are
reported in Table 3.3.
The mechanism of separation of aromatic nitro
compounds on Zirconium arsenate layers is some what
different from the mechanism of silica gel. The surface
activity of Zirconium arsenate may be discussed from a
different angle as given below :
I) Ion-exchange property of tho gel :
The As-OH sheet provides ionized protons to be
exchangeable with positively charged species, such as
protonated amine groups (-NH ).
87
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Table 3.2 : Rf values of aromatic nitrocompounds on silica gel G - coated plates.
to
» o o u EH
z
O
^1
^2
^3
^4
^5
^6
^7
^8
^9
^10
^11
^12
^13
^ 1 4
^ 1 5
1
H 0 c
0 u +> •H !2 1
0 . 8 9
0 . 9 2
0 . 9 1
0 . 5 3
0 . 9 6
0 . 0 7
0 . 9 4
0 . 0 0
0 . 9 8
0 . 9 8
0 . 9 2
0 . 9 8
0 . 9 4
0 . 2 2
0 . 0 0
c •H iH •H
c (0 0
u 4J •H Z 1
0.26*^
0 . 8 3
0 . 8 3
0 . 7 0
0 . 9 6
0 . 3 7
0 . 9 0
0 . 2 1
0 . 8 9
0 . 9 7
0 . 9 0
0 . 9 6
0 . 9 6
0 . 0 0
0 . 0 0
1 C <* 0)
- N CN C
(1) 0 XJ U 0 0 U
tH +J £ -H u c 1 -H
rH -D
T
0 . 3 1
0 . 8 4
0 . 9 6
0 . 9 5
0 . 9 2
0 . 9 6
0 . 9 0
0 . 0 0
0 . 9 6
0 . 9 5
0 . 9 3
0 . 9 0
0 . 9 8
0 . 0 0
0 . 4 7
C 0 1
•H iH m (0 0 n +J O •H < C
•H O Ci -H 1 iH
in V - > i
n o
0 . 9 5
0.17*^
0.23*^
0 . 0 0
0 . 0 9
0 . 0 0
0 . 1 5
0 . 0 0
0 . 9 6
0 . 2 1
0 . 9 6
0 . 8 9
0 . 0 0
0 . 0 0
0 . 0 0
M P 0 U 1 0 x: 0 C U -H 4-) N •H (C
c u •H -D O >i 1 £
•<t H ^ > i
<N C
0.21"^
0 . 7 5
0 . 8 4
0 . 8 8
0 . 9 6
0 . 9 4
0 . 9 4
0 . 0 0
0 . 9 6
0 . 9 6
0 . 8 9
0 . 9 3
0 . 9 6
0 . 9 4
0 . 0 0
N D S
iH 0
c
0 u +j •H !Z 1
n
0 . 6 9
0 . 8 7
0 . 7 4
0 . 3 8
0 . 9 6
0 . 2 6
0 . 9 3
0 . 3 6
0 . 9 3
0 . 9 8
0 . 8 2
0 . 9 4
0 . 8 9
0 . 0 0
0 . 0 0
1 0)
•H -0 0 0)
u c •H E C (C (0 X f-l <U >i E C
0 . 7 4
0 . 9 0
0 . 8 8
0 . 0 0
0 . 0 7
0 . 0 7
0 . 9 3
0 . 0 0
0 . 9 3
0 . 1 7
0 . 9 8
0 . 9 8
0 . 0 0
0 . 0 0
0 . 0 0
o •H 0 N
c 0 Xt 0 u
+J •H "O C -H
•H O D <0
0 . 8 1
0 . 7 8
0 . 7 5
0 . 0 0
0 . 9 8
0 . 0 8
0 . 8 7
0 . 0 0
0 . 9 0
0 . 9 8
0 . 8 9
0 . 1 8
Sp
0 . 8 0
0 . 0 0
1
c 0 u
•H
c •H 0) Q C 1 (U E N
0 . 0 0 1
0 . 9 0
0 . 8 8
0 . 8 8
0 . 9 5
0 . 1 5
0 . 5 0
0 . 0 0
0 . 9 6
0 . 9 7
0 . 8 6
0 . 9 4
0 . 9 6
0 . 0 0
0 . 0 0
TABLE 3 . 2 CONTINUED
91
•
^16
^17
^18
^ 9
^ 2 0
^ 2 1
^ 2 2
^ 2 3
^ 2 4
^ 2 5
^ 2 6
^ 2 7
^ 2 8
^ 2 9
^ 3 0
^ 3 1
^ 3 2
^ 3 3
" 3 4
^ 3 5
^ 3 6
^ 3 7
0 . 0 9
0 . 9 4
0 . 5 7
0 . 9 6
0 . 9 6
0 . 9 6
0 . 9 2
0 . 9 8
0 . 9 4
0 . 9 6
0 . 9 1
0 . 9 8
0 . 9 3
0 . 9 6
0 . 9 6
0 . 9 8
0 . 9 8
0 . 9 8
0 . 7 1
0 . 9 3
0 . 9 8
0 . 9 1
0 . 4 7
0 . 9 0
0 . 9 4
0 . 9 6
0 . 9 3
0 . 8 8
0 . 9 4
0 . 9 6
0 . 9 6
0 . 9 6
0 . 9 5
0 . 9 1
0 . 8 6
0 . 9 2
0 . 9 8
0 . 9 6
0 . 9 5
0 . 9 8
0 . 9 6
0 . 9 1
0 . 9 8
0 . 9 3
0 . 9 8
0 . 9 5
0 . 7 0
0 . 9 2
0 . 9 6
0 . 9 6
0 . 9 4
0 . 9 6
0 . 5 8
0 . 9 3
T 0 . 3 4
T 0 . 4 8
0 .48*^
T 0 . 3 3
D . 9 6
0 . 9 6
0 . 9 8
0 . 9 5
0 . 9 4
0 . 8 7
0 . 9 3
0 . 9 4
0 . 0 0
0 . 3 9 ^
0 . 2 0
0 . 9 6
0 . 7 9
0 . 8 9
0 . 0 9
0 . 0 0
0 . 0 6
T 0 . 2 3 ^
T 0 . 3 4
T 0 . 4 4
0 . 9 0
0 . 3 3 ' '
0 . 9 6
0 . 8 6
T 0 . 1 5
0 . 9 0
0 . 9 2
0 . 7 5
0 . 9 6
0 . 8 8
0 . 7 8
0 . 9 5
0 . 4 9
0 . 9 6
0 . 9 4
0 . 9 6
0 . 9 6
0 . 9 6
0 . 9 6
0 . 9 6
0 . 8 9
0 . 9 0
0 . 9 6
T 0 . 2 7
0 . 9 5
0 . 9 5
0 . 9 5
0 . 9 8
0 . 9 8
0 . 8 2
0 . 9 3
0 . 8 9
0 . 2 5
0 . 9 3
0 . 9 1
0 . 9 3
0 . 9 3
0 . 9 4
0 . 9 4
0 . 9 3
0 . 9 6
0 . 9 6
0 . 9 3
0 . 8 9
0 . 9 2
0 . 9 8
0 . 9 6
0 . 9 4
0 . 9 6
0 . 9 6
0 . 9 3
0 . 8 1
0 . 9 8
0 . 8 9
0 . 0 0
0 . 8 9
0 . 6 9
0 . 9 6
0 . 9 2
0 . 9 5
0 . 9 4
0 . 9 3
0 . 0 0
0 . 9 8
0 . 9 4
0 . 9 2
0 . 9 4
0 . 9 4
0 . 9 8
T 0 . 4 9
0 .25"^
0 . 9 6
T 0 . 2 8
T 0 . 1 5
0 . 9 0
0 . 3 1 ' ^
0 . 0 9
0 . 8 0
0 . 3 4
0 . 9 4
0 . 8 1
0 . 7 8
0 . 8 7
0 . 7 5
0.26*^
0 . 9 2
0 . 9 1
0 . 9 1
0 . 9 2
0 . 8 8
0 . 9 4
0 . 9 1
0 . 9 4
Sp
0 . 8 9
T 0 . 1 3
0 . 9 0
0 . 7 8
0 . 9 0
0 . 8 6
0 . 5 4
0 . 9 7
0 . 9 6
0 . 9 6
0 . 9 5
0 . 9 5
0 . 9 4
0 . 9 0
0 . 8 1
0 . 9 5
0 . 9 4
0 . 8 6
0 . 9 4
0 . 9 6
0 . 9 6
0 . 9 6
0 . 9 5
0 . 8 4
0 . 9 7
0 . 8 6
92
TABLE 3.2 CONTINUED
^38
^39
^4 0
^ 4 1
^4 2
0 . 9 6
0 . 9 5
0 . 8 5
0 . 8 7
0 . 9 5
0 . 9 5
0 . 9 4
0 . 9 1
0 . 9 1
0 . 8 5
0 . 9 8
0 . 8 0
T 0 . 2 8
0 . 4 7 ^
Sp
0 . 9 8
0 . 8 8
0 . 9 5
0 . 9 5
0 . 9 1
0 . 9 6
T 0 . 1 6
0 . 8 3
0.39*^
0 . 8 5
0 . 9 8
0 . 8 9
T 0 . 2 2
0.17*^
0 . 2 2 ^
0 . 9 8
T 0 . 1 7
T 0 . 2 2
0.48"^
0 . 8 1
0 . 9 8
0 . 7 7
0 . 9 1
0 . 2 1
0 . 4 7
0 . 9 6
0 . 8 3
0 . 7 6
0 . 3 9
0 . 3 7
a) Mixing ratio (v/v) of different solvents are given in parenthesis,
T Tailed spot
Sp Spreading.
m 10
r i (I) 0^
0) +J to
c 0) to u n e 0
•H C 0 o u •H N
c 0
(0 •p
c 0) >
1-H 0 (0
+J c 0) u 0) •
4-1 n M 0) •H +J "C «
H cna c •H U 10 i J 3 Fi
"0 C (U 0 > 0) <H
•H ns £ -W U V4 10 0
+> C 10 0 e
•H +> o* « c U-H <0 4^ Qi iO « 0 cc u
en m H •-3
§
El Z H > tJ O w
,_ (0 2 o ac u* Q K H < ( t < &< W
w
w c Sz D o (X
s o u
• 0
z • w
o\ ro
W
0) c •H
e--10 O i-< ID >1 " ^ C o vo 0 %^Tj< £ Oi 0) o
^ c ^ •0 -H 0 N (U M a c •P (4 (U •H "0 N C > i C (0 £ OJ X H j a fl) > i 0 X C VJ
0) -P - £ - H
^ a c i n 0 -H «<• k -0
• +> 1 O 'r\ ^ >- c »
•rl fN H "0 0 1 0
c^ u «) «. 0 X! rsi iH ft £ 0 * 0 n ^ » 4J 00 iH •H ^ C • 13 1 O C
»* - (0
1 o •H O H • <c o (0 ^^ 0 U -0 4J -H 1-1 0 c <o
iH D 0 1 -H • r - l
in 0 « > i
m 0
« H
O n
to
^ "D 1 i n - H 0 • O u o n + j ^
•H O C dJ-H
•H C 0 •C -H N 1 E C
^ (0 (1) ^ iH J3
fN > i O C U
0 (U -P M £ - H 0 Q« C
iH -H -H £ TJ "C O 0 1 U "D
iH +> C •H (0
» C — ( 0 - - -O X rH i n Q) r -
• £ • o o «—' »-..^
< - v
r-l 00 iH 0 i n > i C • C W O O ^ • - . x : 04 a 0 (U 0 1 C M ' -
4-1 (U -P (7) •H N -H m
c c c • 1 0) 1 o
^r X3 rn v. '
o 1 O
•H • iH O (0 ^—' n> 0 "0 U -H +J 0 •H (0
c •H 0 C -H 1 r-l
i n o » > i
n o
• H H
00 CM
W
V
^ 1 «3" 0 CN U
• 4J O -H ^ C
•H r-l -O 0 C -D (U C
£ «0
a 0 ' -U 00 +J r>j •H • C O I ^ -
"<* 0)
* c ' — - H
o e - -m nj i n • r-\ m
o >, . — C O
(!)>_ r-l £ o 04 -0 C -H -H fl) -O O
£ 0 <0 O4 V4 0 +» 0 > -H -rl +J C 0 •H «0 N C X C 1 0) (1)
ro J3 X}
- 0
1 0 •H •
<U rH 0 C «0 > -
•H to •-^ 0 - 0 •r l "O 4 -rl C C 4J 0 •0 (0 -r l (0 0 C Ul ' - -H 0 +J 0 "O -H •H 0 1 rH Z • i n 0 1 0 * > ,
Tf - ^ n 0
• _ M M M
C^ CM
w
rH 0 ; C (1)
£ QA 0 M 4J •H C >
' i '
"0
c <0
-- 0 n
• 0 *^«^
•0 •H 0 (0
0 •H 0 N
c (1) X! 0 H '-> 4-> fS •H »*
c • •H 0 •D —
1 •H '— C 0 1
•H 0 0 "0 •0 • P -H 1 0 +) 0
^ >-' -H «0 c
(N (U -H 0 C " D - H
0 (U 1 rH H N i n 0
0 C - > i ' -rH 0) n 0 0 x : j a - H O 0 0 "O r-l • - M C ro 0
rH 4J 10 to "-^
• > H
93
El » H > ^ o tn
,_ (0 s o ff Ji4
o H t^ <; p; < Pk H (A
(Q O S D O 04 s o u
• 0 2 •
Ui
CM (N
w
«.-H ' ^ C n -H Oi "O
• 1 rH -0 O ^ 0 C w «, C (0
W 0) <u x : ^ C * DjiT)
•H --^ 0 OC iH m »-l • •H r +) o C " H w «o o c 0 w 1 C) M m c 4J (1) -H •H c - e c d) ^ nJ 1 N CM iH
• * c o o > i QJ • C
^ X l O (U — •^ 0 ^ JCCt C«4 V Qt<T\ CTi +J (U -H •
• -H C "O O O C -H 0 w ^-^ -H N H
•O 10 -P 0) iH 1 h -H C 0 ^ "0 C Q) C - > , (0 N (U CM ^ X C £ 1 H 0) 0) 04 0 P h x : XI o n e 0 U 0 Q) -^ U •p rH x : ' - +> •H X; 0 *00 ' H C O 0 00. C 1 \ U C) I
•"J- iH +>>-^ E
^ O O - H
1 O 0 •H • N iH O C ( C - - dJ (0 X> 0 - 0 0 - -M -H n H •P O +> iH •H (0 ' H • C C O
•H O -rl w 13 •ri'd \ t-l "D
i n o "0 -H * > i C O
n o (0 10
• >
n w
1 n •H 00 C • iH 1
•H O 0 0 •O - ' C M 1 (1) -P
'S' rH X: -H * 0 D» C
CM C 0 1 (D J-t ^
* x: -p ^ Qj -H "O o 0 c c r - n 1 nj
• +J ^ O -H •— «— C - o
1 - ^ ^ IT) <U n o • C CTi O (I) » • V--N ' — O C O w . QJ (U 00 C X3 • <P 0) 0 O C N VJ - " H C +J g <U •H Q) fd X3 C C r-l 0
•ri -H >i U •O N C +) 1 (0 0) ' H '—
" * M XI C 00 " '0 Qj -H r»
CM > i - H "O • x: "D 1 o
% r-H 0 E "— 0 > i h 4 C +J » <U
0 0) -H ' - C iH £ C O -H x : Oi «J 00 iH O 0 X • -H 1 M (U o C
rH +J x : > - ro
^ 0 O -H
1 o 0 •H • N iH O C ro w (u (0 X} O -O 0 ' -V< -H VJ VD +J O +J rH •H HJ ' H • C C O
•M O -H ^ ^ •O -H "O 1 r-l "O
i n o "0 -H «• > i C O
n o ro «0
• H >
CM (fi
•>. 1 "^ *-> 0 00 C 4 00 r~ +> •
• -H O
o c — - 1 n QJ
0) C C ^ - H
• H ^ E rH CM (0 •H 00 rH C • >1 fC O C O^- - <U VJ XI •p (u a •H C -H ^ c QJ <a o 1 N 0 00
•«t c n - QJ + J O
- U - H ^ ' - 0 C a\ U <a Q) n +) X C
• -H 0) (1) o c x: N — - H C
Xi - 0 r-i 1 ' -^XJ 0 ^ rH -H C -CTl P QJ CM • +) x: o c a o-^-H O P -0 P 0 H 1 +J H 0 E •H XI C C O (1) "0 1 1 x: c
'«' H a ic
' - U O -H
1 o 0 •H • N H O C ( 0 ^ (1> to X3 ona 0 ^ P -H P ^ +J 0 + J H •H (0 -H • C C O
•H 0 -H N-* •D ' H "O 1 iH <0
i n 0 "0 -H * > i C O
n 0 ro (0
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W
w
^ ^~v %
O — r- c • r-
o • — o «o
^ C <U (0
c o <U C ^ ' N -H iH C iHOO ^ QJ -H • fH X3 c o c 0 « 0 - ^ • p 0 o +J P 0) ^ •H +J C C -H (U (U 1 C N C E 1 C -H
^ QJ N X I 10
- - ^ 0 P VD ^ P "0 Tf n jp > ,
• n -H x; O . C tH ^ ' O -H > i
W . O C 1 O
iH t-l « f x : O 0 » 04 C C CM 0 QJ QJ P x: x: * -p Q4 O4 0 -H 0 0 p c p p 0 -H •P +J iH -O •H -H s: 1
c e o - * 1 r 1 « n ^ H CM
- • o ^->.H QJ 0 0 c
1 0 (0 1 -H •H • n3 E iH 0 0 X «0 (0 ^ - -H QJ r-H 03 0 x : > i 0 <0 N C P -H C "0 QJ •p 0 dJ c x: •H to Xi to CU C 0 - H
•H 0 P ' ^ "O ^ •O -H +J i ^ 0 en 1 r-l ' H 0 P CM
i n 0 T 2 • - P • ^ >Tta 0 "H C3
n 0 >0 c ^
•
M M >
94
z > o
o
(A
O
m < < On H CO
o
(0
00 I r-
'^ c o H - H ^ '
• I r-l o <• 0 - ' * C
c * •H - ^ i H i H •H O^
c CO O
o
I o u •p •H
c x: -o o e
•H C
U •P •H c I
0) CO C «oo 0 ) ^ . N 'S' O
0) .
o u o c
fH I O 'sr C -0) ra
x: Q . 0 0 U U O 4Jr - l •H Xl
c o 1 I
0)
c •H E 10 iH >1
c (I) /-»
_ a<yi
JC "D O
c +> £ C 04 10 O X U 0)
c •H N 10
CO
I 0 u •P (U •H C C -H I N
«* «D
' ^ > t «* s:
• > i o c >- (1)
s: (1) Q4 c o <U M N -P C -H O C
c N
c XJ — O <x)
<ri
ro
en c . (1)
o £
O -D iH
• * iH +) x :
0) c a; N c
X5
U I 4J ^ •H «. C CN
•H •D * I -->
^ iH " 0 0
cs • o
o U (U o c
r-i -H
x : i-i
» c
O 0
c > x : - H a c O (0 M X
•H x: c «* c
•0
IT) VD c^ 00
o o
CO
c <0
«3
01 c (U N C ' ^ <U O XI o^ o • U O
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CM
0 u o
0)
c N
c XI o > +J •H c
x: -H U "O I I
CO
I <ri O • U O
+> ^ •H "O C 0) C
•H C (0 •O -H ) iH - ^
r r -H O - C r-
CM (0 •
o o +J •H C
• I o ^
CM 0) C
N
c -» 0) Q) ' - X 3
C <M 0 •H 00 M -— E • +) in <C o 'H in iH * - ' C • > i - H O C 0) 13 «- ' (1) c r
x : -H ^ t- i O4 N •> O •H (0 C-J C
> i 0
x: M iH O > i r H
c x: (U O x: I Q41H
O M 4J •H C «0
<u x :
x : o (-1 +> •H c I
CO
o
0)
c Q) N C (U X3 • 0 O U ^ +> • H OJ
c c 1 -H E E
«0 - iH
— > i O C CO Q)
• X
o a
o M -P •H C
o c 0}
X! O4 (0 O X u +J •H c I
n
(U
x :
c (0
CO D
D O P< S
o
o I o
•H • 1-1 O ( 0 - ' CO O'O
4J •H C
•H
I iH in D
» >1
U 10
O
1 vo rfl iH (0 • 0 0 u •p • H
c • H •D 1
i n ^
en
>_> 0
• H i H 0 > 1 0
•H r i
o I O >1 •
t-t O ( 0 - ' (0 0 -O U -H +1 •H
•d I r-i
in o « > i
n cj
o o
•H o (0
o I O
•H • iH O ( 0 ^ (0
o -o •H C
•H
in o
CO O
o I O >1 •
iH O «0 w CO 0 -0 ^ -H 4J O •H (0
c •H O
1 iH in o
- > i
n o
0
t
CO X H X X
H M X
H H H X
96
II) Activated surface of zirconium arsenate :
During the activation/ the zirconium arsenate
layer may loose the hydroxy1 group with elimination of
water molecule and produces dehydroxylation of oxide
surface.
OH
Zr
OH
Zr
0
Zr Zr + H2O
The dissociative chemisorption has been observed with
dehydroxylated oxide surface with many organic as well
as inorganic molecules. For example N-H bond rupture
has been observed for CH-NH^ and (CH_)-NH according to
(25).
A M M
/ 1 \ /|\
+ (CH2)2NH
(CH,)-
N
M +
OH \ M
In the above reaction, not only the chemisorption of
the compound on the surface result, but also there is
the production of the surface 0-H group.
Ill) Zirconium arsenate oxide surface as adsorbent :
The aromatic nitrocompounds which contain the
carboxylic or phenolic group may be attached by
97
hydrogen bonding with dehydroxylation of the oxide
surface.
From the above observation it is clear that the
interaction of the nitrocompounds with zirconium
arsenate surface is large enough and therefore the
possibility of separation is greater. We have tried to
take into account the role of polarity with Rf values
of different solvents in the separation of aromatic
nitrocompounds but the results are found irrelevant.
The increasing order of polarity of carbontet-
rachloride > hexane > toluene > benzene > diethylether
> 1,4-dioxane > ethylacetate > chloroform > methylace-
tate > acetonitrile > propan-2-ol > butanol > acetic
acid > ethanol > methanol :5 > 30.9 > 33.9 > 34.5 >
34.6 > 36 > 38.1 > 39 > 40 > 46 > 48.6 > 50.2 > 51.2 >
51.9 > 55.5, shows a rising trend in Rf values en
silica gel only.
98
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2. S.A. Nabi/ W.A. Farooqui, Z.M. Siddiqui and R.A.K. Rao/ J. Liq. Chromatogr., 6, 109 (1980).
3. M. Qureshi/ S.A. Nabi and N. Zehra, Sep. Sci., 10,
801 (1975).
4. M. Lederer, Chromatogr. Rev., 4, 83 (1962).
5. S.Z. Qureshi, R.M.A.Q. Jamhour and N. Rahman, J. Planar Chrom., 9, 466 (1996).
6. S.Z. Qureshi, R.M.A.Q. Jamhour and N. Rahman, Chem. Anal. (Warsaw), 42, 41 (1997).
7 . S .A. N a b i , A. Mohammed and P.M. Q u r e s h i , T a l a n t a , 26 , 1179 ( 1 9 7 9 ) .
8 . M. Q u r e s h i , S.A. Nabi , I . A . Khan and P.M. Q u r e s h i , T a l a n t a , 29 , 757 ( 1 9 8 2 ) .
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1 0 . Y . L i n , R .K . Zhang, E l e c t r o a n a l y s i s ( N . Y . ) , 6 ( 1 1 / 1 2 ) , 1126 ( 1 9 9 4 ) .
11. T. Nakai, Z. Lu, Y. Satoh, and Y. Kotoh, Nippon Kagaku Kaishi 11, 1012 (1994).
12. S.M. Petrovic and E. Loncar, J. Planar Chromatogr., Mod.TLC, 5(5), 359 (1992).
1 3 . V . F . T i m a f e e r a , E.V. T o l s t y k h , L . B . I r i s k i n a and K.A. Z h u b a n o v . Zh. A n a l . Khim. 4 8 ( 3 ) , 456 ( 1 9 9 3 ) .
1 4 . A. Ahmed, Q a s i m u l l a h , S.M.A. A n d r a b i and P.M. Q u r e s h i , J . C h r o m a t o g r . , S c i . 3 4 , 376 ( 1 9 9 6 ) .
1 5 . M . R . B a g i e v a and S . P . Soko lov , Zh. A n a l . Khim., 2 8 ( 8 ) , 1 6 3 1 ( 1 9 7 3 ) .
1 6 . H. S c h u e t z and A. S c h i n d l e r , F r e s e n i u s Z. A n a l . Chem., 2 7 0 ( 5 ) , 350 ( 1 9 7 4 ) .
99
17. E. Soczewinki, W. Golkiewiez and W. Warkowski/ Chromatographia, 8(1)/ 13 (1975).
18. E. Soczewiski, W. Golkiewiez and T. DzidO/ Chromatographia, 10(5), 221 (1977).
19. E. Soczewiski, T. Dzido and W. Golkiewiez,
Chromatographia, 10(6), 298 (1977).
20. J. Jager, J. Chromatogr., 152, 575 (1978).
21. G.I. Migachev and A.M. Terentev, Zh. Anal. Khim., 35(5), 1027 (1980).
22. K. Yasuda, Osaka-furitsu Kogya Gijutsa Kenkyesho Hokoku, 74, 1 (1979).
23. D. Volkmann, J. High Resolut. Chromatogr., Chromatogr. Commun., 5(3), 134 (1982).
24. K. Anderson, J.O. Levin and C.A. Nilsson, Chemosphere, 12(3), 377 (1983).
25. B.A. Morrow and I.A. Cody, J. Phys. Chem., 81, 1998 (1976).
PREPARATION AND CHARACTERIZATION OF LAYERED DOUBLE HYDROXIDES : INTERCALATION OF ETHYLENEDIAMINE BY ADSORPTION PROCESS
100
Layered double hydroxides(LDHs) can be regarded
to contain brucite MgCOH)- like layers in which a
partial replacement of some of the octahedrally
+2 . . coordinated divalent Mg cation with trivalent cations
+3 +3 +3 (Al f Cr , Mn etc.). The resulting positive charge
on the metal hydroxide sheets is balanced with
-2 -2 - -intercalated anions (CO-/ SO , CI , NO. ) and water
molecules (1-5) which are present into the interlayer
region of the structure (6). The naturally occurring LDH
or the so called hydrotalcite has the formula
Mg_Al_(OH).-(CO^) .4H 0. However, when considered as
derived from brucite like layers [Mg(OH)^]/ the above
formula may be written as
tW50.75^l0.25^°»^2^^^^^^0.1250-5«2^
Thermal transformation or calcination of LDHs is
carried out at temperature ranging 450-550°C, which
evolves CO^ and water from interlayer and favours the
formation of micropores in the solid and therefore
making the surface more unsaturated. This is a most
suitable host material to occupy the incoming guest
molecule either by ion-exchange or adsorption process.
Decarbonation and dehydroxylation is a reversible
process at room temperature and is accompanied by
restructuring the brucite to regain carbonate groups and
101
water molecules in its interlayer (7). Recently various
attempts have been made to intercalate bulky anions
between brucite layers by ion-exchange process.
Thermally transformed double layer hydroxide have been
pillared with decavanadate isopolyanions (8).
Decavanadate anion ^^-irPoR ^ (9)/ polyoxometalate
anions TagO^gOH"^, Nbg .Oj gOH" , PMOgVgO^p" (10),
«<^-P2Wl8°62'^^°4(V^2(P^°34^2^°^^^ ^-"2^12°2o"^ ^^^^'
4,7-diphenyl 1,10-phenanthroline disulfonate (12) and
-4 -4
Mo(CN)g or Fe(CN)g (13) are the few examples of
intercalation by ion-exchange process. A few organic
anions such as dodecylsulphate, sebacic acid, P-(SO,) _2
CgH-Me and Cr^O- (14) have been intercalated by the same process.
The above studies of intercalation of anionic
guest molecules are based on ion-exchange with
carbonate, chloride or nitrate and therefore would be
regarded unidirectional. The exchange of anion initially
present in the LDH, and the use of organic swelling
agent (to expand the interlayer spacing) to improve the
exchange of bulky anions have also been considered (15).
In this present studies attempts have been made to give
a new thrust and direction by considering the
unsaturated metallic -OH groups. They may occupy
102
different basic and acidic sites which can facilitate
the adsorption of non-anionic species in between the
layer and get intercalated without exchange with
carbonate or otherwise anionic species. Intercalation of
dodecylamine and sulfamic acid into LDHs was our first
successful attempt in this direction (16).
The present studies describe the subject in a
more precise and rationalize way to intercalate non-
anionic organic species into host material after thermal
decomposition or calcination process.
103
EXPERIMENTAL
REAGENTS AND TECHNIQUES :
All s t a r t i n g m a t e r i a l s were e i t h e r from BDH or
Merk ( a n a l y t i c a l g r ade ) . E l i c o Ll-10 pH meter was used
f o r pH measurements. Remi 2IiH magnetic s t i r re r for st irr ing ..Powder
x - r a y d i f f r a c t i o n (PXRD) p a t t e r n was recorded using a
P h i l i p APO 1700 i n s t rumen t , wi th N i - f i l t e r e d Cu-Koc
r a d i a t i o n . The FT-IR s p e c t r a of t he m a t e r i a l was
r e c o r d e d on a Perkin-Elmer FT-IR 1730 spec t rometer .
D i f f e r e n t i a l thermal a n a l y s i s (DTA) and thermogravimetry
(TG) of t h e sample were c a r r i e d out with a Rigaku Denki
t h e r m o f l e x - t y p e thermal a n a l y z e r , model 8076 a t a
h e a t i n g r a t e of 10°C min in n i t r ogen atmosphere by
u s i n g cC-Al-0^ as the r e f e r e n c e m a t e r i a l .
SYNTHESIS OF THE LAYERED DOUBLE HYDROXIDE OF Mg(II)
A l ( I I I ) - C O j " ^
The parent . LDH was syn thes i zed by the method
e s t a b l i s h e d by Reichle ( 1 7 ) . A Mg/Al r a t i o c lose t o 2
was chosen s ince o ther s t u d i e s show t o give sample of
good c r y s t a l l i n i t y . A s o l u t i o n c o n t a i n i n g 20 ml of 0.5M
s o l u t i o n of Mg(N02)2-6H20 and 20 ml of 2.5M s o l u t i o n of
Al(NO ) .gHjO in 70 ml of d e i o n i z e d water was added with
104
Vigorous stirring to a solution of 70 ml of 0.5M
solution of NaOH and 22.5 ml of 4M solution of NajCO.
(anhydrous) in 100 ml of deionized water. The addition
was done for a period of one hour at room temperature at
pH maintained close to 10. The resulting slurry was then
crystallized at 65°C for 18 hours followed by cooling
and washing several times with deionized water.
Synthesis of the host material was carried out
by calcination the Mg(II) Al(III)-carbonate in air at
450°j l0°C for 6 hours. One gram of the calcined material
was then added to a 100 ml of O.IOM alcoholic solution
of ethylenediamine. The mixture was kept on stirring for
3 days at room temperature. The product were then
separated by filtration and washed with hot distilled
water. Once incorporated the ethylenediamine-LDH appears
stable.
SORPTION CAPACITY :
The sorption capacities of various metal ions
were carried out. Two grams of the intercalated-LDH
material were kept in 100ml of O.OIM hydrochloric acid
overnight. After washing with distilled water, 0.2 gm of
the material were treated with 25 ml of O.OlM solution
of metal ions. The mixture were left for 12 hours, with
105
intermittent shaking, at room temperature. The amount of
metal ion left were determined titrimetrically.
pH-TITRATION :
The pH-titrations were carried out by batch
method. A set of 0.2 gm of material in H form with
-2 2+ . .
O.lOMNaOHand 1.0x10 M Cu solution were equilibrated.
The pH were recorded after 24 hours and plotted against
the meq of NaOH.
SURFACE AREA :
The surface area (A) of the sample were deter
mined by the method proposed by Dyal and Hendricks (18).
To this purpose 2 g of the sample was taken in a small
watch glass and placed in a dessicator over P2* ';" "^^^
weight of the dried sample was measured. The sample was
then wetted with ethyleneglycol and added from a pipette
dropwise and placed in a dessicator at 25+1°C to
evaporate excess of ethyleneglycol. This sample is
weighedseveral times till a constant weight is observed.
Surface area was then calculated from the equation,
w - w Surface area (A) = l_
W^ X 0.00031
Where W, and W^ are weight (g) of the dried sample and
106
sample wetted with ethyleneglycol respectively and
0.00031 is the Dyal and Hendricks values for the grains
of ethylene-glycol required to form a monolayer on one
m surface area.
CHEMICAL COMPOSITION :
For the determination of chemical composition of
the sample, O.lOgm sample was dissolved in the minimum
volume of hot IM hydrochloric acid. The solution was
then diluted to 100 ml with distilled water. The metal
ion, magnesium and aluminium, was determined titrimetri-
cally using standard O.OIM EDTA solution (19). While
ethylenediamine was determined spectrophotometrically by
preparing a buffer of pH 5 containing 21.00 gm of citric
acid monohydrate and 200 ml of 4 percent sodium
hydroxide. This is diluted to 500 ml of citric buffer.
Add this to 20 gm of ninhydrin in 500 ml and mixed. To 2
ml of ninhydrin reagent add 10 ml of a sample solution
to be determined. Shake and heat in boiling water for 20
minutes. And add 5 ml of ethanol with mixing. After 15
minutes it is read at 570 m>i against reagent blank (20).
107
RESULTS AND DISCDSSION
X-RAY DIFFRACTION ANALYSIS :
The x-ray diffractogram of two samples, parent-
LDH and LDH-ethylenediamine are shown in Fig. 4.1. Fig.
4.1(a) shows three harmonics ^QQO* ^n06 ' ^ ^009 9- ®
sharp intensity peaks corresponding to the basal spacing
of 26 angles at 7.6h°, 3.8A°, 2.5A° respectively. The
other two low intensity harmonics cl.. and d,, at
higher 29 angles are 1.52 and 1.49A° respectively (Table
4.1). It is observed, when parent-LDH interacts with
guest molecule substantial variation in the basal
spacing occurs. In the LDH-ethylenediamine Fig. 4.1(b)
the peaks due to d^Q^' ^006 ^"^ * 009 ^^® shifted to a
lower 26 angles when compared with XRD of Fig. 4.1(a).
The diffraction lines at ^QQ^' *^O06 ^^'^ ^009 ^ ^ '' from
7.6 to 8.2 4A°, 3.8 to 4.ISA", 2.5 to 3.75A° respectively
(Table 4.2). This suggests that ethylenediamine is
intercalated to the LDH layered material.
FTIR-STUDIES :
The FTIR spectra of the parent-LDH is shown in
Fig. 4.2(a). A broad absorption band in the form of a
maximum corresponding to the frequency range 3800-3200
, fi.24 ! (003)
108
1
i
n j i
3 . 7 5 i ( 0 0 9 ) • 2 . 5
!l
I I ! I I I I I I I .' ! ! I ' ' 4 15 I,' i (006)J, i • II II,' .
(i f I
( 0 1 2 )
!l
n
2 e N (010)1 j \
I ', \! I ! ,-4
I'l
( b )
I' II II,' i . 1 ', V 1 . / ••! I'll
1 . 5 1 I ( 1 1 0 )
Ji !•" II ( 1 1 3 ) III! !lll Mil I'm
ill ^Vy/-t-T •'-•C
> IH
< 7 . 6 ( 0 0 3 )
-,
, 3 . 8 i ( 0 0 6 )
i\
, 2 . 5 ll ( 0 0 9 )
%^' V*>«v/>W-w<'-'^
(i A 2 . 2 ( 0 1 5 )
1 . 5 2 ( 1 1 0 )
1 . 9 ( 0 1 8 )
1 . 4 9 ( 1 1 3 )
v»4>J>^'
(a)
^''V •••' • • * ^ i » .
2 0 40 60 2© degrees
Fig. 4.1(a) : X-ray diffraction of parent-LDH
80 ]80
X ^ : X-ray diffraction of LDH-ethylenediamine
109
Table 4.1 : X-ray data for parent-LDH: Calculation of d values. Monochromatic Radiation used Cu-Kct = 1.54 A°.
PLANE OF REFLECTION
d-._^(lst order)
d^-.g(2nd order)
d^pgOrd order.)
^015
' OlS
^110
^113
ANGLE OF OBSERVATION (29 degree)
11.55
23.39
34.8
39.4
46.8
60.7
62.0
SPACING BETWEEN THE PLANES (d values in A°)
7.6
3.8
2.5
2.2
1.9
1.52
1.49
110
Table 4.2 : X-ray data for LDH-ethylenediamine : Calcula-tion of d values. Monochromatic Radiation used Cu-Kcc=1.54 A°
PLANE OF REFLECTION
1 d p Q ^ d s t o r d e r )
i
<3pQg(2nd o r d e r ) i
d p p g O r d o r d e r )
^ '^OlO
^^012
^ 1 1 0
^ 1 1 3
ANGLE OF OBSERVATION (26 degree)
1 0 . 7
2 1 . 3
2 3 . 6
3 1 . 4
3 4 . 7
6 1 . 0
6 2 . 4
SPACING BETWEEN THE PLANES (d v a l u e s i n A**)
8 . 2 4
4 . 1 5
3 . 7 5
2 . 8
2 . 5
1 . 5 1
1 . 4 8
Ill
cm" , is assigned to vibrational frequencies of free-OH
group of metallic oxides (MgO) 3752, 3610 cm and
(Al-0_) 3680, 3700 cm" . The adsorbed molecular water
also lies in the same frequency range (21). In addition
a second weak shoulder is also recorded at 2894 cm is
supported to be starting point and extended to below
2100 cm suggest strong perturbation in the LDH
skeleton due to a dense packing or cluster of -OH groups
at the metallic surface. The peak corresponding to V(OH)
stretching modes is due to interlayer water, for which
the adsorption peak appears at 1663 cm . However this
band may also be attributed to V (COO), corresponding
to asymmetric mode and a strong band at 1394 cm
to symmetric mode, 1) (COO) (22). This vibrational
frequency at 1394 cm" overlaps with a characteristics
absorption band of NoT present in the interlayer as
residual or impurities during the synthesis of LDH (16).
In the spectrum of LDH-ethylenediamine Fig. 4.2(b) a
shifting of frequencies, 1664 to 1670 cm" and 1394tol381
cm /is observed due to a monodentate or bidentate
bridging between (COO) and N-0 (from NO^" ) with -OH
groups of metallic oxide layers to hold them firmly. In
calcination process, decarbonation occurs (release of -2
CO- to CO2, a reversible process at room temperature)
which could partially destroy the bridging due to (COO).
112
« T r a n s m f t t a n c •
4000
Wave nunbe-s (era* ) F i g . 4 . 2 ( • ) : FTIR-spectrum of parent-LDR
l b 2 : FTIR-spectrom of LDH-ethylenediamine compound.
113
At this juncture the NO. bridging, to some extent play
the role of holding up the metallic oxide layers, until
the reversible process of carbonation retained its
original position.
The sharp band at 953 cm due to M-0 stretching
vibration and a number of other sharp bands at 788, 669,
558 and 460 cm""'- (M = Mg"*" , Al"*" ) suggest the dehydroxy-
lation of some of the metallic free -OH groups resulting
in unsaturated surface M-O-M. Moreover the decarbonation
also favour the formation of active surface. The guest
molecule ethylenediamine interacts with unsaturated
surface by chemiporption, resulting in pillared LDH-
ethylenediamine without deplection of either NO, or -2
CO^ anion speciesfScheme 4.1).To support intercalation
of guest molecule three bands at 1670-1550 cm , 1380
cm and 953 cm are observed suggesting the presence
of vinylidine compound. A slightly broad band 1670-
1550 cm" is attributed to C-C stretching. Similarly a
distinct and strong band at 1380 cm" suggests C-O
stretching as well as -OH deformation other than N0~
bridging with -OH groups at metal surface. A shoulder at
953 cm is assigned to C-N vibration of aliphatic
amine. During dehydroxylation, magnesium oxide may have -2
strong basic site, 0 (23) of nucleophilic character.
114
X
y — z o<:
- | s—\ -o o» ®
/ 3 z
-J O
a u)
o _ Z A
X z — u
•o o z
/ V - ^ o=z" I X
lo / - * ^ '
z o_ 5\ " c 5 " :
^ w O O "5t> u z I
r c w o •- O^
O
=4 O
Z f i
u
115
which may causes the opening of TL bond of C-C double
bond of ethylene and thus result the formation of
polymeric chain. The weak lewis acid sites are probably
+3 associated with Al ion surface (22) which may form a
hydrogen bonding with -NH . This may be ruptured at the
time of coordination which takes place between
transition metal ions and -NH2 group. The proposed
arrangement of interlayer anions and intercalated guest
molecule is shown in Scheme 4.1.
During chemisorption, regeneration of surface
-OH groups arises in accordance with Webster Studies
(24). Suggesting the presence of clusters of -OH groups
on the surface of partially hydroxylated MgO. Scheme
4.2 shows the proposed mechanism.
0-C2«(NH2)2 ^OH
M-OH + (C2H2)(NH2)2 > M H2O M
Scheme 4.2
116
THERMAL STUDIES :
Fig. (4.3 and 4.4) shows the thermal behaviour
of LDH-ethylenediamine. The TGA diagram (Fig. 4.3)
shows the presence of two weight losses, the first one
upto Ca.250''C (15% weight loss) and the second cxie upto
Ca.450*>C (37% weight loss). The corresponding two
weight losses with respect to rate of weight loss per
degree centigrade (dw/dt) are 0.2154 %/»C at 234°C and
0.2423 %/°C at 422°C respectively. The first weight
losS/ as reported earlier, should correspond to the
removal of molecular water from interlayer, while the
second corresponds to dehydration, dehydroxylation
(removal of water from condensation of layer -OH
groups) and decarbonation that is the partial release -2
of CO- anions in the form of CO gas. Therefore, a
decarbonation process can overlap to some extent the
dehydroxylation. Beyond 450"*C the decomposition of
intercalated material goes on increasing resulting in
formation of metallic oxide surfaces. The corresponding
DTA profile (Fig. 4.4) shows two endothermic peaks at
237°C and 412°C which support the facts discussed in
TGA. An endothermic inflection point at 450°C may be
indicated to a phase transition to be accounted by +3 the fact that Al cation occupy octahedral from
tetrahedral sites.
117
iDo/%) ^UBiaM -ATjaa
in o OJ
in o N-l
IT) O
O O
{%] ^M6jaM
118
- n -
o
o -in
o -m •in
u 0
o -in (u
ID
a o a
-in I -tn
• o -in
o
I I ' I I I I I I I I I r in o
o f
o I o
I
o
o I
in
(6ui/3«) BDuaja iHG ajn^ejadujai
119
When LDH-ethylenediamine sample is soaked
overnight in dilute hydrochloric acid, the primary
amine groups of ethylenediamine due to the lone pair of
electron present on the nitrogen atom of amine, get
protonated and form a coordinative ionic sphere with
positive charge hydronium ion. In the case of
transition metal ions, this coordinative ionic sphere
is exchanged with transition metal leaving behind the
hydronium ion in the mother liquor which has been
determined against standard sodium hydroxide solution
by pH — metry Which culminates for the sorption
capacities and summarized in Table 4.3.
Simultaneously the LDH-ethylenediamine has been
found to exhibit a remarkable complexing behaviour with
transition metal ions. Which is illustrated by the pH-
2+ titration curves for the Cu ions (Fig. 4.5). The
2+ shape represent the increasing amount of Cu ions
uptake by the LDH-ethylenediamine/ which is indicated
also by the transformation of white LDH-ethylenediamine
material to bright blue during the process. This
further assures the formation of topper(II) complex
with amino group of ethylenediamine molecule in the
aquo-metal coordination sphere (16,25).
120
Table 4.3 : S o r p t i o n capaci ty of some meta l ions on LDH-e thy lened iamine compounds.
S.No. METAL ION SORPTION CAPACITY (mmol/g)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Cu 2+
Ni 2+
Co 2+
Al 3+
Zn 2+
Mn 2+
Cd
Bi
2+
3+
Fe
Ag
Pb
Cr
3+
2+
2+
3+
Zr 4+
Ce 4+
0.14
0.16
0.14
0.10
0.06
0.04
0.08
0.21
0.23
0.03
0.10
0.24
0.35
121
A 6 MEQ BASE/6
8 10
Fig. 4.5: pH titrations of {A) LDH-ethylenediamine
and the same compound with (B) O.OIM of
.2+ Cu added.
122
The specific surface area of LDH-ethylene-
diamine as determined by the Dyal and Hendrick's method
is 85.96 mVg-
The chemical composition of LDH-ethylenediamine
compound was determined and the result has been
2+ 3+ summarized in Table 4.4. The atomic ratio Mg /Al is
found 1.93.
123
0 •H
ro 4J O «0
c«i U t H < U \ «0 O f* 01 0 S E
0 •H +>
+ «0 CO K
rH < O \ - H
+ E r>4 0 01+> X <
ty\
1 U Q) ^^ ^f-i * )
•H 0 4 - -'-' E 1-1 «0 •H n E
OiflJ \ r H iH Qi 0 E i « E to
\ (D C 0 "C
•H C 3
.-1 0 (0 Q< +> E <U 0 S O
00 CM eri • .
vo
00 00
• tvj
+ CN tP S
>£) m •
i H
m <ri •
i H
00 00 in •
n
CO m •
rH
+ CO f-H
<
1
i H
• i H
C •H E (0
•H •O 0) c (U
i H > 1
124
REFERENCES
1. R. Allmann, Chimia/ 24, 99 (1970).
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3. W. FeitJcnecht, Helv. Chim. Acta, 25, 131 (1942).
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18, 555 (1935).
5 . S . Miya ta , C l ays C l a y M i n e r , 3 1 , 305 ( 1 9 8 3 ) .
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34, 5114 (1995).
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1 2 . E . P . G i a n n e l i s , D.G. Nocera and T . J . P i n n a v i a , I n o r g . Chem,, 2 6 , 203 ( 1 9 8 7 ) .
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Chim. Fr., 21, 231 (1996).
1 7 . W.T. R e i c h l e , C l a y s M i n e r , 35 , 401 ( 1 9 8 5 ) .
1 8 . R . S . Dyal and S . B . H e n d r i c k , T r a n s . 4 t h I n t e r . Congr . S o i l S c i . , 2 , 71 ( 1 9 5 0 ) .
125
19. F.J. Welcher, 'Analytical uses of EDTA", D. Van Nostrand Co., Inc., Princeton, New Jersey, (1957).
20. F.D. Snell and C.T. Snell, 'Colorometric methods of Analysis', D. Van Nostrand Co. Inc., Princeton, New Jersey, Vol. II A, 109 (1967).
21. J.R. Anderson and M. Boudart, 'Catalysis', Vol. IV, Springer Verlag, Berlin Heidelberg, New York (1983), p. 46, 49.
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(Chapter ^ive
PREPARATION AND CHARACTERIZATION OF MIXED HYDROUS OXIDES OF Al O^-ZrO^ BY
AQUEOUS BASE DIETHYLAMINE AND ITS ADSORPTION BEHAVOUR TOWARDS
DIETHYLAMINE
126
Metal hydrous oxide have been studied
extensively as adsorbent for many years. The
ion-exchange properties shown by them somewhat
neglected in comparison to their absorption
properties. In addition, some hydrous oxides are found
selective towards certain elements or group of
elements. Several reviews on metal hydrous oxide have
been published (1-6) .Alargenurriber of papers have been
reported recently on this subject related to analytical
problems. Thus the quadrivalent metal oxides such SiO-,
SnOj, TiO^/ ThO„, ZrO_ and MnO_ have drawn attention as
cation or anion exchanger depending upon the basicity
of the central metal atom and the strength of the M-O
bond relative to that of the O-H bond in the hydroxyl
group. Sorption of bivalent cations on different SiO^
preparation has been investigated (7-10). Hydrous
stannic oxide is selective for alkali metal ions (11)
and successfully applied for the decontamination of
water from ^^S, " P (12) and •'"° Ru(NO)' ^ (13).
Hydrous zirconium oxide has been prepared from
the salt solution of zirconium oxychloride which is
precipitated by adding excess base at an adjusted pH
between 1 and 2.5, produces amorphous zirconium
hydroxide. If heated, the same amorphous gel in
127
presence of NaOH or KOH produces cubic hydrous oxide
(14). This material is found amphoteric in nature and
used as absorbents for the extraction of uranium from
seawater (15).
Mixed metal hydrous oxides have also drawn
interest as ion-exchanger and adsorbents but not to the
extent of metal oxides. A modified form of sorbent has
been prepared by coprecipitation of hydrated Ag o and
Fe(OH)-, which is found to have high sorption capacity
for Ru and radiocobalt (16,17). Crystalline hydrous
silicon(IV)-titanium( IV) oxide ion-exchanger has been
synthesized and characterized (18). Moreover the
titanium and magnesium oxide Mg TiO (m = 0.5-0.42,
n = 2.50-2.42) has been prepared by treating hydrated
TiO- with a Mg salt and calcining the resulting product
at 180-200°C for 5-6 hours. It is used for the removal
of iron from carbonate solutions (19). Mixed oxides of
Bi : Th, Al : Th and Cr : Th in various ratios have
been synthesized and used for analytical purposes(20).
Another mixed oxides prepared by soaking activated
Al-O^ or PiOj in an aqueous suspension of hydrated
TiOj or Zr02 at an adjusted pH of 3-8, exhibits good
mechanical strength (21). While heat resistant ion-
exchanger is made by impregnating Al O with hydrolyzed
Ti compound to Ti02 or Ti(OH)^ (22). In addition, the
128
preparation and properties of some metal oxides are
reported in which a second cation of higher charge than
the parent cation is introduced into the structure. The
resulting net positive charge is compensated by adding
anion radical. Examples of such materials include
Zn(OH) -Al(OH)- and Ti''" /Zr"'" /Si''' - A K O H ) ^ which are
obtained by hydrolyzing their salt solutions by NaOH
and act as anion exchanger (23).
In the present chapter we describe the
preparation and characterization of mixed hydrous oxide
of Al^O« - ZrO which is hydrolyzed by an aqueous
solution of a base amine, followed by adsorption of
amine at the surface of M-0 layers. The excess of the
charge due to the introduction of Zr(IV) makes the
material to act as anion-exchanger. This may be less
significant compared to the coordinate site of nitrogen
atom of the amine. Sorption capacities of some of the
metal ions have been reported from analytical point of
view.
129
EXPERIMENTAL
REAGENTS :
Zirconium oxychloride (BDH), aluminium nitrate
(S.d fine chemicals) and diethylamine (s.d. fine
chemicals) were used for the synthesis of the
material. All other chemicals were of analytical
grade.
APPARATUS :
A Bausch and Lomb Spectronic-20 Spectrophoto
meter, Elico pH meter model LI-10 for pH measurements/
Remi 2LH magnetic stirrer for stirring, x-ray diffrac
tion (PXRD) pattern was recorded using a Philip APO
1700 instrument, with Ni filtered Cu-KcC radiation. FTIR
spectra were recorded on a Perkin Elmer FTIR 1730
spectrometer. Differential thermal analysis (DTA) and
thermogr a vi metric analysis (TGA) of the sample were
carried out with a Rigaku Denki thermoflux type thermal
analyzer, model 8076 at a heating rate of 10° min in
nitrogen atmosphere by using ct AljO-i as the reference
material.
130
SYNTHESIS :
Various samples of AljO.-ZrO -diethylamine were
prepared by mixing aqueous solution of zirconium
oxychloride, aluminium nitrate and diethylamine with
constant stirring under varying conditions as indicated
in Table 5.1. The white gel was filtered off, washed
with demineralized water to remove excess of reagent
till the filtrate attains v a-pH-7, and dried at 40°C. The
material is broken into small particles when immersed
in water- This showed cationic properties and converted
into H by treating with 0.5 M HCl for 24 hours. The
granules were finally washed with distilled water
untill pH-6, and dried at 40*>C. Sample ZAA-9 has been
found to be superior as compared to other and therefore
selected for further studies.
SORPTION CAPACITY :
The sorption capacities of Al-Oo-ZrO.-diethyl-
amine for metal ions were determined by the
batch method. A mixture of 0.5 gm of the sample of the
gel material and 2 5 ml of an aqueous solution
-2 containing metal ions 1x10 M were kept in Erlenmyer
flask for 24 hours to allow the attainment of
equilibrium. The g6l material was then
131
removed by filtration. The concentrationsof the metal
ions in the filtrate were determined by titrating
against standard EDTA solution. The results are
reported in Table 5.2.
CHEMICAL STABILITY :
A 0.2 gm of each sample of the materials were
equilibrated with 25 ml aqueous solution of acid, base
and organic solvents which is kept for 24 hours at room
temperature with intermitte t shaking. Zirconium
released in the solution was determined spectrophoto-
metrically using Alizarine Red S as chromogenic reagent
(24) ,v*iile aluminium by titration against standard EDTA
solution (25), The released diethylamine was determined• spectro-
photometrically (26). The results are summarized in
Table 5.3.
CHEMICAL COMPOSITION :
A 0.2 gm of the material (ZAA-9) was dissolved
in the minimum volume of concentrated nitric acid and
make up to a volume of 100 ml by diluting with
distilled water. Zirconium was determined spectropho-
tometrically (24), aluminium by titrating against
standard EDTA solution (25), while diethylamine was
132
determined by taking another (0.5 gm) sample of the gel
material and introduced into a Kjeldahl digestion
flask which contains concentrated hydrochloric and
sulphuric acid and potassium sulphate as catalyst.
After digestion 25 ml sodium hydroxide solution (50%)
was added dropwise to release amine which was trapped
in 50 ml hydrochloric acid solution (1%). The amount of
diethylamine released into the solution was determined
titrimetrically using a mixed indicator (Bromo-cresol
green and Methyl red) (27). The mole ratio of Zr : Al :
diethylamine is found to be 4 : 1 : 1.
SURFACE AREA :
The surface area (A) of the material was
determined by the method proposed by Dyal and Hendricks
(28). Where 2 gm of the sample was taken in a small
watch glass and placed in a dessicator over P2^5' " ^
weight of the dried sample was measured. The sample
was then wetted with ethyleneglycol and added from a
pipette dropwise and placed in a dessicator 25j l°C to
evaporate excess of ethyleneglycol. This sample is
weighed several times till a constant weight is
observed. Surface area was then calculated from the
equation. W - W
Surface area (A) = 2 1 Wj X 0.00031
sample wetted with ethyleneglycol respectively and
0.00031 is the Dyal and Hendricks value for the grams
of ethyleneglycol required to form a monolayer on one 2
m surface area. The area of sample (ZAA-9) was found
to be 98 m /g.
134
RESULTS AND DISCUSSION
Various samples of Al-0- - ZrOj - diethylamine
have been prepared by mixing aqueous solut ion of
zirconium oxychloride, aluminium n i t r a t e and
diethylamine under varying condit ions(Table 5 . 1 ) . From
t h i s t ab le i t i s observed t h a t the sample ZAA-9
prepared a t pH-10.5 possessed the highest sorpt ion
capaci ty and has ion-exchange capaci ty , and a lso found
to be s table below 250°C which i s revealed through the
e f fec t of var ia t ion in temperature s t u d i e s . The
chemical s t a b i l i t y of AljO- - ZrO^-diethylamine (ZAA-9)
in d i f ferent concentration of organic and inorganic
solvents has been summarized in Table 5.2. The sample
ZAA-9 has been selected for fu r the r s tud ies .
The sorption capaci ty of Al20--Zr02-diethylamine
for some metal ions has been studied and
summarized in Table 5 .3 .
The x-ray powder d i f f r a c t i o n pat tern reveals
t ha t the material (ZAA-9) i s semi-crys ta l l ine a t room j s j s j q
temperature. Fi5.5.1 shows four harmonics 001, 002, 003
and 004 give sharp intensity peaks corresponding to
the basal spacing of 20 angles at 4.7 A°, 4.4 A°,
3.2 A* and 2.2 A° respectively. The other harmonics
135
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Table 5.3; Sorption capacity of metal ions on Al O.-ZrO^-diethylamine (ZAA-9) ' '' ^
S.No. METAL ION SORPTION CAPACITY (mmol/g)
1.
2.
3.
4.
5.
6.
7.
8.
Cu 2+
Ni
Al
2+
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Mn 2+
Co 2+
Zn 2+
Pb 2+
Cd 2+
0.125
0.095
0.145
0.045
0.112
0.088
0.168
0.103
138
^021 and * 024 at medium 20 angles are 1.76 A** and 1.72
A°, While the harmonics at 110, 113 and 118 at
higher 20 angles are 1.56 A°, 1.46 A° and 1.13 A"
respectively (Table 5.4).
The FTIR spectrum of Al20--Zr02-diethyl-
amine is shovm in Fig. 5.2. The sharp peaks at 3664,
3539 and 3427 cm corresponds to V (OH) stretching
modes and also associated with V(OH) of interlayer
water. The N-H stretching vibration for the secondary
amine of diethylamine is also observed at 3427 cm
For C-H stretching the symmetric vibration, V is
attributed at 2940 cm and asymmetric vibration, S)^_
at 2829 cm" respectively. The peak corresponding to
V(OH) stretching modes is due to interlayer water, for
which the absorption peak appears at 1644 cm . The
weak broad band at 1545 cm is attributed by the N-H
deformation vibration of the secondary amine group
(29). While the sharp absorption band due to C-H
deformation mode is observed at 1394 cm , and this
vibrational frequency also overlap with the overtone of
Al-0 lattic vibration. The stretching vibration of C-N
for secondary amine is attributed at 1058 cm . The
sharp absorption band recorded at 992 cm" is due to
Zr=0 terminal stretching mode. This band may also be
attributed due to Al-0 vibration. In addition the
139
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o 00
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140
Table 5 .4 ; X-ray d a t a f o r Al-O^-ZrOj-die thylamine (ZAA-9)
C a l c u l a t i o n of d - v a l u e s . Monochromatic R a d i a t i o n Used Cu-KoC = 1.54 A°
PLANE OF REFLECTION
^ OOl ^^^^
^002 ^2nd
doQ3 (3rd
<3oo4 (4th
^021
^ 024
^110
^ 113
* 118
order)
order)
order)
order)
ANGLE OF OBSERVATION (29 degree)
18.55
20.06
27.57
40.38
51.62
52.97
59.02
63.58
85.22
SPACING BETWEEN THE PLANES (d values in A">)
4.7
4.4
3.2
2.2
1.76
1.72
1.56
1.46
1.13
141
142
various bands at 992, 815 and 545 cm is attributed
due to the various modes of M-0 and 0-M-O (M = Zr, Al)
of zirconium oxide and aluminium oxide (30, 31).
However, the weak shoulders for N-H deformation
vibration is also attributed at 710 cm , while the C-C
skeletal rocking vibration is attributed at 775 cm
with appearance of medium shoulder. And the shoulders
at 450 cm and 42 5 cm are assigned to C-N-C deforma
tion vibration of secondary aliphatic amine.
Fig (5.3 and 5.4) show the thermal behaviour
of Al-O^-ZrOj-diethylamine. The TGA diagram (Fig. 53)
shows the presence of three weight losses, the first
one upto Ca. 250°C (22% weight loss) and the second one
upto Ca. 280°C (27% weight loss), and in the final
stage upto Ca. 440°C (30% weight loss). The two weight
losses with respect to rate of weight loss per degree
centrigrade (dw/dt) are 0.2476 at 46oc and 0.1853 at
269°C respectively. The first weight loss, correspond
to the removal of the inter layer molecular water, while
the second corresponds to dehydration, dehydroxylation
(removal of water from condensation of layer -OH
groups) and decomposition of the diethylamine. The
corresponding DTA profile (Fig. 5.4) shows two
endothermic peaks one at 67°C and second at 268°C and
then the decomposition of the sample takes place.
143
"7
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144
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145
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