ir.amu.ac.inir.amu.ac.in/7782/1/T 3817.pdfACKNOWLEDGEM:;NT It is with great indebtness and gratitude...

STUDIES ON INORGANIC ION EXCHANGERS AND

CHELATE EXCHANGERS

NEELAM SHARMA DEPARTMENT OF CHEMISTRY A11GARH MUSLIM UNIVERSITY

A11GARH

A THESIS SUBMITTED IN FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN THE

FACULTY OF SCIENCE OF THE ALIGARH MUSLIM UNIVERSITY ALIGARH 1989

c_7x 9dic h cp. Cf:Za wa t M.Sc., Ph.D,

READER IN CHEMISTRY

CERTIFICATE

Ph. Office : 6515

DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY

ALIGARH-202002 INDIA

This is to certify that the work embodied in this thesis

entitled, "Studies on inorganic ion exchangers

and chelate exchangers" is original, carried out by

Ms.Neelam Shilrma under my supervision and is suitable

for submission for the award of Ph.D. degree in Chemistry

of this University.

.i i ( i ~~- I( / I\_

.1

t;'' .. , 1 .. l ~

;(-J.P. RAWAT)

M^Ciyi/C/i

c

yoviA/Vi

'V

ACKNOWLEDGEM:;NT

It is with great indebtness and gratitude that I pay

my thanks to Dr. J.P. Rawat v;ho served as a beacon of light

v>rhile I v;as canoeing in ever increasing and turbulent ocean

of chemical sciences. His timely advice, fatherly interest,

healthy criticism and constant encouragement enabled me to

give the work its present shape„

I am grateful to Professor S.M. Osman, Chairuian,

Department of Chemistry for providing the necessary research

facilities.

I would be failing in my duties if I don't acknowledge

my friends especially Miss. Archana Agarwal and Mrs. Sangeeta

Kumar for their continued help and cooperation. I am thankful

to my lab colleagues for maintairinc a congenial atmosphere.

Mr. Rakesh Kumar, my husk and, deserves to be praised

highly who while cooperating witi me becomes the very source

of strength to me.

I also thank Ui:iiversity Grants Commission for a

research grant.

(NEELAM

C O N T E N T S

1. List of Publications

2. List of Tables

3. List of Figures

Chapter - I

5. Chapter - II

Chpater - III

Paae r;o,

Introduction

References

Stannic phthalojihosphate a nevi cation exchanger for the removal and recovery of Pb(II)

Introduction 72

Experimental 73

Results 75

Discussion 95

References 99

Ion exchange equilibria of alkaline earth metal ions on stannic phthalophosphate

Introduction lOl

Experimental 102

Results 105

Discussion 137

References 14i

7. Chpater - IV

8. Chapter - V

Tin thioglycola-::e as a new material for the recovery and removal of mercury

Introduction 14 3

Experimental 14 5

Results 150

Discussion 158

References 161

Ferroin sorbed zinc silicate in the in the deterrnination of cerium in presence of rare earth

Introduction 162

Experimental 163

Results 165

Discussion 168

References 171

LIST OF PUBLICATI QMS

1. Stannic phthalophosphate a nev; cation exchanger for the

removal and recovery of Pb(Il)

Indian Journal of Chemistry (Communicated).

2. Ion exchange equilibria of alkaline earth metal ions on

stannic phthalophosphate

(Communicated).

3. Tin thioglycolate as a new material for the recovery and

removal of mercury.

(Communicated).

4. Ferroin sorbed zinc silicate as indicator in the determi-

nation of cerium in presence cc rare earth

(Commsunicated) .

- 1 1

LIST OF TABLES

TABLE 1.1 S y n t h e s i s and I o n - e x c h a n g e p r o p e r t i e s of

M u l t i v a l e n t m e t a l s a l t s

Pane I'vO,

1 n

TABLE 1.2 Some of the important Chelate exchange

resins 39

TABLE 2,1 Conditions of preparations of stannic

phthalophosphate 74

TABLE 2,2 Solubility of stannic phthalophosphate 77

TABLE 2.3 pH titration of stannic phthalophosphate 81

TABLE 2,4 Kd values of different metal ions 85

TABLE 2.5(a) Uptake of Pb(ll) by stiinnic phthalophosphate from solutions of diffs^rent concentrations 85

2,5(b) Uptake of Pb(II) at lover concentration 87

2,5 (c) Uptake of Pb(II) from solutions containing

same amount of Pb(II) c.t various concentra-

tions 87

TABLE 2.6 Rate of Sorption of Pb(II) 8b

TABLE 2,7 Some separations on stannic phthalophosphate

columns 9 0

+ '̂ TABLE 3,1 Ionic fractions of Mg , Selectivity

coefficients and thermodynamic equilibrium + 2 +

constants for Mg -H exchange on stannic

phthalophosphate 105

TABLE 3.2 Ionic fractions of Ca"̂ *", selectivity

coefficients and thermodynamic equilibrium + 2 +

constants for Ca -H exchange on stannic


- IIX -

+ 2 TABLE 3,3 Ionic fractions of Sr , selectivity

coefficients and thermc'clynaniic equilibrium + 2 +

constants for Sr -H exchange on stannic


+ 2 TABLE 3.4 Ionic fractions of Ba , selectivity

coefficients and thermodynamic equilibrium + 2 + constants for Ba -H exchange on stannic


TABLE 3.5 Thermodynamic parameters for Hydrogen-

Magnesium exchange on stannic phthalo-

phosphate at constant iDnic strength 123

TABLE 3.6 Thermodynamic parameteis for Hydrogen-

calcium exchange on ste::inic phthalophosphate

at constant ionic strer. jth 123

TABLE 3.7 Thermodynamic parameters for Hydrogen-

Strontium exchange on scannic phthalo-

phosphate at constant i Dnic strength 124

TABLE 3.8 Thermodynamic parameter,? for Hydrogen-

Barium exchange on stannic phthalophosphate

at constant ionic strength 124

TABLE 3.9 Equilibrium constants and selectivity + 2 +

coefficients for Mg -H exchange on

stannic phthalophosphate 125

TABLE 3.10 Equilibrium constants and selectivity + 2

coefficients for Ca -H exchange on

stannic phthalophosphat(i 128

TABLE 3.11 Equilibrium constants and selectivity + 2 coefficients for Sr -H exchange on

stannic phthalophosphate 13 1

TABLE 3.12 Equilibrium constants and selectivity + 2 coefficients for Ba -H e;:change on

stannic phthalophosphate; 134

- IV

TABLE 4.1 Synthesis of Tin thioglycolate under

different conditions 14 6

TABLE 4.2 Uptake of Fig (II) fro.n its solutions of

different concentrations by tin thiogly-

colate 15 3

TABLE 4.3 Rate of sorption of Hg(II) 154

TABLE 4.4 Reduction of As(V) to As(III) 156

TABLE 4.5 Study of Precision for Hg(Il) uptake by

tin thioglycolate 157

TABLE 5.1 Determination of Cerium(IV) 165

TABLE 5.2 Determination of Cerium in presence of

other metal ions 166

TABLE 5.3 Reproducibility of determination of

Cerium 167

- V

LIST OF FIGURES

Page No.

FIGURE 2.1

FIGURE 2.2

FIGURE 2.3

FIGURE 2.4(a)

FIGURE 2.4(b)

FIGURE 2.5

FIGURE 2.6

FIGURE 2.7

FIGURE 2.8

FIGURE 2.9

FIGURE 2.10

FIGURE 2.11

FIGURE 3.1

FIGURE 3.2

FIGURE 3.3

FIGURE 3.4

FIGURE 3.5

Plot of Ion-exchange capacity against

number of regeneration cycles

Capacity and % weight losses of exchanger

at different temperatures

pH titration curve of stannic phthalo-

phosphate using O.IN NaCl"*" O.IN Na CO

solutions

IR spectrum of phthalic anhydride

IR spectrum of stannic phthalophosphate

exchanger

Rate of Sorption of Pb'.Il)

+ 2 +? Separation of Zn -Pb

+ 2 + • Separation of Sr -Pb

4-2 +.'' Separation of Co -Pb

+ 2 +'' Separation of Ni -Pb

+ 2 +2 Separation of Cu -Pb

+ 2 +'' Separation of Mg -Pb

+ 2 Ion exchange isotherm of Mg ion on


+ 2 Ion exchange isotherm of Ca ion on


+ 2 Ion exchange isotherm cf Sr ion on


Ion exchange isotherm cf Ba ion on


Selectivity coefficients Vs equivalent + 2

fractions of Mg ion :.n exchanger phase

76

78

82

84

84

89

92

92

93

93

94

94

106

109

112

115

118

VI

FIGURE 3.6

FIGURE 3.7

FIGURE 3.8

FIGURE 3.9

FIGURE 3.10

FIGURE 3.12

FIGURE 3.13

FIGURE 4.1

FIGURE 4.2

FIGURE 4.3

Selectivity Coefficients Vs equivalent + 2 .

fractions of Ca ion m exchanger phase

Selectivity Coefficients Vs equivalent + 2

fractions of Sr ion in exchanger phase

Selectivity Coefficients Vs equivalent + 2 fractions of Ba ion in exchanger phase

Plot of In K Vs l/T for alkaline earth

metal ions

Mass action plot for Hydrogen Magnesium

exchange on stannic phthalophosphate

Mass action plot for Hydrogen-strontium


Mass action plot for Hydrogen-Barium


X-ray diffraction c:; Tin thioglycolate

Uptake of Hg(II) from its solution of

different concentra-;ions

Rate of Sorption of Hg(ll)

119

120

121

122

126

132

135

151

152

155

CHAPTER - I

Introduction

1 CHAPTER ~ I

I N T R O D U C T I O N

Analytical chemistry deals with the solving of quali-

tative and quantitative problems. Qualitative analysis deals

with the finding what constituent or constituents are in an

analytical sample^ and quantitative analysis deals with the

determination of how much of a given substance is in the

sample. With today's instrumentation and with the large

variety of chemical measurements available, specificity or

sufficient selectivity can often bp. achieved so that a qua-

ntitative measurement serves as a c[ualitatlve measurement.

The development of methods for these analyses is the main

aim of analytical chemistry.

Analytical chemistry, like other areas of chemistry

and of all sciences, has gone thrc-ugh a period of rapid

growth and change. At present, new areas such as chemical

physics, biophysics and molecular biology are rapidly deve-

loping. Many advances in these ar>;'as were made possible by

analytical results.

The importance of analytical chemistry in related

scientific areas can be illustratec by considering its

impact on clinical analysis, in phcrmaceutical research

and quality control, and in envirormental analysis.

2

In the past, the medical profession used clinical

results qualitatively and many of their diagnosis were

based on symptoms and/or X-ray examinations. The tests

were improved to the point where it became possible to

quantitatively determine these components. Now these

test results play a major role in influencing the diag-

gnosis.

Currently, quite a large number of tests are per-

formed in clinical laboratories. The major portion of

these tests deal with blood and urine samples and include

the determination of glucose, urea nitrogen, protein nit-

rogen, sodium, potassium, calciT-im, UCO^A^J^^s' "^^^^ acid,

and pH, etc.

In the pharroaceutical industry the quality of the

manufactured drugs in tablets, solution and emulsion

forms must be carefully controlled. Slight changes in

composition or in the purity of the drug itself can

affect the therapeutic value. Accurate and sensitive

tests must be developed since the level that are being

determined are often as little .;s 1 nano gram.

Analytical methods providt; the basis for the

studies including the application of science and tech-

nology toward the control and in.provement of environ-

mental quality. The development of analytical methods of

3

separation, identification, and subsequent determination

have provided information about the presence of dust and

suspended particulate matter in air as lime, limestone,

and cement dust from kilning operations, coke dust and

polycyclic aromatics from coking operations, and fluorides

from metallurgical processes. Other contaminants are fly

ash from coal-fired electrical power plants and wind-blown

slag and insulation from industrial operations. Water is

also as complex a system as air, when it comes to environ-

mental monitoring. As in the study of air, analytical

chemistry has played a major rola in the environmental

science of water.

There are various methods in analytical chemistry

that are employed for separation. Some of them are*chro-

matography, electrophoresis, ion-exchange, solvent extra-

ction, ring oven technique and dialysis. Out of them

ion-exchange has come to be recognised as an extremely

valuable technique. Ion-exchange had a great impact on

analytical chemistry.

Ion-exchange is a reversible, stoichiometric ex-

change between the ions in the mobile liquid phase and

the ions on the exchange sites on the stationary phase.

The major application of ion excJiangers is the separation

of ionic or partially ionic mixtures. But recently, Sepa-

4

ration of nonionic organic molecules on ion exchangers has

also been reported. The retention of these kinds of mole-

cules on ion exchanger depends upon the highly polar chara-

cter of ion exchanger and the se-.ection of eluting condi-

tions.

Ion exchangers can separate the micro ( < 1 - mg

quantities) as well as the macro (> 1 - g quantities)

samples. Because of the macro application, ion exchangers

can also be used on industrial scale. A wide variety of

very complex mixtures have been separated on ion exchangers.

These includes the separation of rare earths in hitherto

unknown purity (1-7). Ion-exchange chromatography has played

an important role in the isolation and identification for

the concentration and extraction of the most important

metals and of the new transuranium elements (8-13) and has

even been used for enrichment of isotopes (14-19), Organic

substances such as amino acids (20-28), peptides (29,23,30),

proteins (23,31), nucleic acids (32), alcohols (23,33,34),

glycols (33,35,36), carbonyl compounds (23,33,37,38), car-

bohydrates and derivatives (23,39-43), ethers (38,44),

amines (23,44-46), hydrocarbons (38,47) and phenols (38,48)

have also been separated in ion-e:

r) concerned, organic resins are by far the most important ion

exchangers. The more recent analytical applications of ion

exchange resins include the collection of selenium (IV)(49),

ppb level of aluminium (50), preconcentration of cobalt (51),

trace determination of trimethylselenonium in urine (52),

molybdenum (53) and iron (54), preparative, fractionation

of petroleum heavy ends (55), determination of pt and pd (56),

analysis of metamict mineral containing U, Ti, Nb and rare

earths (57) and the determination of low level bromide in

fresh water (58). Ion exchange has also been used with

success in the food industry (59) and for determining polar

organics in shell process v/ater;; (60).

The water pollution is increasing day by day. However,

the methods based on ion-exchange are becoming of promising

success when applied to this fi:-̂ ld. The use of ion exchangers

on large scale may provide mankind v.'ith pure water and may be

useful for the concentration and extraction of the most

important metals and ra\\' materials v.'hich is becoming more and

more difficult to produce.

The English agriculturist H.S.Thompson(61) was the first

to observe and to publish descriptions of the phenomenon

of ion exchange by the name of base exchange. Thompson

found that the ammonium sulfate absorbed by soils

could not be washed out by water and that much of

the absorbed ammonium sulfate was converted to calcium sulfate,

It v/as VJay (62), who thoroughly explored the phenomenon and

6

demonstrated the underlying mechanism to be one of base ex-

change involving the complex silicates present in the soil.

Ca - Soil + (NH4)2SO^ = NH^ - Soil + CaSO^

The first attempt to employ ion exchange for commer-

cial purposes was made by Harm in 1896 (63). In his patent.

Harm claimed to have a successful process utilising a natu-

rally occurring cation exchanging silicate for removing

sodium and potassium from sugar beet juice. However, success-

ful large-scale applications of cation exchange were developed

by Cans (64) who synthesized inorganic materials of the type

Na^Al„Si-O^Q in which the Na was exchangeable. He success-

fully applied his inorganic synthetic cation exchanger to

water softening and sugar treatment on a technological scale.

To a large exlent his synthetic exchanger replaced the natu-

rally occuring exchangers or zeolites.

One decided shortcoming of the inorganic exchangers

at that time resided in the fact that they were acid sensi-

tive and did not lend themselves to any exchange reactions

in which hydrogen ions were taking part.

It is only in the past forty years that ion exchange

has reached the point where it should be considered a unit

process at par with tne traditional ones such as distillation,

precipitation, and adsorption. Adams and Holmes (65) in 1935,

English Chemists discovered and appreciated the potentialities

of the ion exchanging properties of synthetic resins. They

synthesized both anion and cation exchange resins thus making

it possible to deionize water in the cold for the first time.

The really modern era in ion exchange technology began

in 1944 when D'Alelio of the General Electric Company's Pitts-

field laboratories synthesized resins from preformed polyst-

yrene (66), These resins were the forerunners of the currently

available line of polystyrene resins which, compared to

earlier resins, possess greatly improved capacity and chemical

and mechanical stability.

The application of organic ion-exchange resins are

also limited under certain conditions i.e. they are unstable

in aqueous systems at high temperatures and in presence of

the ionizing radiations. For these reasons there has been

a revived interest in inorganic ion-exchangers in recent

decades, as they are unaffected by ionizing radiations and

are also sensitive to higher temperatures. The structure of

these inorganic ion exchangers is stiff; therefore they are

more selective and suitable for the separation of ions on

the basis of their different pore sizes. Being stable towards

ionizing radiations, they can be: used advantageously in

reactor technology. Inorganic ion exchange membranes have

also recently been used preferably over organic ones because

of the ability of inorganic membranes to withstand higher

temperatures and their high selectivity for cetain ions.

8

Inorganic ion exchangers also find applications in

the analysis of alloys (67,68) and silicate rocks (68,69)

separation of metals from drugs 170,71) and in the detec-

tion of iron and molybdenum (72,•/3).

The selectivity of inorganic ion exchangers has been

utilized for the preparation of ion selective electrodes

(74). The ion selective electrodes have now come to be

recognized as an important tool for solving various analytical

problems (75-77).

In order to understand the applications and in order

to improve upon them, systematic and fundamental studies are

being persued of these materials. This new interest in inor-

ganic ion exchangers may be said to begin in 194 3. It was

shov/n by Boyd (78) that columns containing finely divided

zirconium phosphate supported on silica wool could be used

to separate uranium and plutoniurii from fission products by

ion exchange process. In addition to zirconiiim phosphate

many other similar substances may be prepared by containing

oxides of group IV with more acidic oxides of group V and VI

of the periodic table.

The various inorganic ion exchangers reported upto

1963, have been summarized by Amphlett (79) in his classical

book, "Inorganic Ion-exchanger". The relevant work from 1962

to 1970 has been reviewed by Pekerek (80) and Vesely (81).

!)

Marinsky has summarised the theoretical aspects of exchange

in inorganic ion exchange materials (82) , The synthesis and

application of inorganic ion exchangers have been reviewed

by Walton (83-88), Recent reviews on the applications of

ion exchange have been edited by Marinsky (89) and Walton

(90), Recent literature on these materials has been covered

by Clearfield in his monograph in 1982 (91). Zirconium

phosphate is a most extensively studied material in this

family and a large number of research papers have been

published on it. The ion-exchange properties of some of the

more important inorganic ion-exchangers of the zirconium

phosphate type have been summai'ised in Table 1.1

(0 V)

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?.3

Ion exchangers can be utilized :.n the laboratory in many

other ways:

1) Interfering ions can be removed.

2) Group separations are possible,

3) Samples can be concentrated.

4) Charges on ions can be established.

5) Samples can be purified.

6) Standard solutions can be prepared.

7) Formation constants of complexes can be determined.

8) They can be used as acid and base catalysts.

If v/ater is passed through two columns, the first

containing a cation exchanger in the hydrogen form and the

second an anion exchanger in tt- hydroxide form, deionized

water can be prepared. The reactions, assuming all salts in

the '^ater are univalent cations (M ) and anions (X ) are

Cation exchanger: Resin - SO~H''"+MX ;^=±LResin-S03M"^-fHX.

Anion exchanger : Resin - NR30K'-VHX^=^ Resin-NR3X""+H20

Water purification for the laboratory using this procedure

has two advantages in comparison to distillation.

1) The ion-exchange procedure is faster and cheaper .

2) It easily Satisfies the pui-ity requirements of a

scientific laboratory.

Ion exchangers can be utilized in the preparation

of solutions in several ways, I'or example, ionic salts can

C'4

be removed from organic reaction mixtures. This often faci-

litates purification of the organic compounds through crys-

tallization, A solution of a metal chloride or some other

anion can be prepared by passing a metal nitrate solution

through a colum.n of an anion exchanger charged in the

chloride form or anion form of interest. If a vjeiqhed

amount of KCl is passed through a cation exchanger in the

hydrogen form, and the effluent is collected and diluted

to a known volume, a standard solution of HCl is prepared.

This is possible since the exchange of ions is stoichio-

metric. Conversion of salts to an acid (or base if an anion-

exchanger hydroxide form is used) can also be used for

analysis.

The properties of ion exchangers facilitate the

selection of the correct ion exchanger for the particular

problem. The more important properties are colour, density;

mechanical strength; particle size; capacity; selectivity;

amount of crosslinking, swelling; porosity-surface area;

and chemical resistance. The exchange of univalent ions

may be represented by the following equation

(A+)^+ (B-^)^ ^ . ^ (A-*-) 3 . (B-^)^

where R and S refer to the cation being in the resin phase

and solution phase, respectively. Since the reaction

reaches an equilibrium position, an equilibrium expression

25

in terms of concentrations can be written as

R _ ^ s ^ ^ R

where the square brackets are for equilibrium concen-

tration .

If the experimental variables are held constant and

the concentrations of A and B are low, K is a constant

and is an indication of the preference the ion exchanger

shov7s for one ion over another.

For a good ion exchanger the rate of exchange should

be rapid. Several properties like particle size, mechanical

strength, crosslinking, swelling and porosity-surface area

influence the exchange rates.

Total capacity of an ion exchanger is a measure of

the total amount of exchangeable ions expressed per unit

weight of dry ion exchanger (mmol/g) or v/ater sv/ollen ion

exchanger (mmol/ml). It is determined by taking a weighed

sample of the ion exchanger, in column and passing a solu-

tion of KCl through the column in large excess. For the

cation exchanger in the H form, the effluent will be acidic

which can be titrated v;ith standard base. For the anion

exchanger, the solution v.-ill be basic, if the exchanger is

in OH form, and the effluent ip titrated with standard acid.

25

If the exchanger is in the Cl form/ a KNO solution is used

and the exchanged Cl" is determined by a Ag"̂ titration. From

the titration data and v/eight of the exchanger, the capacity-

can be calculated.

Separations of inorganic mixtures to a more or less

extent are based on one of the three different principles.

1. At low concentration the extent of exchange is directly

proportional to the valency of the exchanging ion.

2. At constant valence the extent of exchange is directly

proportional to the atomic number at lov/ concentration.

3. The extant of exchange highly depends upon the formation

of complexes.

Besides the above three factors some others such as

concentration, pH, temperature may influence the separations.

Distribution coefficient K, may be determined to

calculate the separation factor which may be regarded as a

measure of possible separation.

y _ Amount of ion (A) present in exchanger phase g M Amount of ion TAI present in solution phase ml

The separation between a given pair is possible or

not is predicted by comparing their K. values. It is also

possible to separate a trace quantity of a metal from a macro

amount of another metal ion.

27

Organic compounds that have ionic character (acidic

or basic) can be separated on anion and cation ion exchangers.

Many nonionic organic compounds are retained by ion exchangers

through adsorption, salting out, size and other exchanger-

solute interactions. By proper choice of eluting conditions

separations are possible. The total capacity of the exchanger

towards an organic solute may be quite different than found

for the exchange capacity for the exchanger.

Thermodynamics is a very important tool to study the

theory of ion exchange and also for :an insight to the under-

lying mechanisms involved. Two different approaches are usually

applied for this purpose (though ether meritable approaches

exist, these two are most widely accepted).

The first approach is based on the design of more and

more elaborate models. Tnis approach gives a semiquantitative

picture to a practical chemist who is interested in under-

standing the physical causes of the phenomena. Thermodynamics

is the appropriate means of explaining any equilibria.Rigorous

thermodynamics, however, is, inherently abstract. The rigorous

and abstract treatment of thermodynamics is'correct' and

universal, but it yields a minimum of information about the

physical causes of the phenomena to which it is applied.

28

In the second approach attempts have been made to

correlate the activities v;ith some measurable quantities with

the thermodynamic equations. Probably the tirst quantitative

formulation of ion exchange equilibria was made by Cans (239)

using the law of mass action in its simplest form. This

concept was extended by Kielland (240). A similar choice of

the general treatment was given by Gaines and Thomas (241).

The most acceptable model, however, is the semiquantitative

one of Gregor which relates selectivity to hydrated ionic

volumes.

The particular use of the thermodynamic equilibrium

constant is made to find out the free energy changes of the

ion exchange process, usually, by the expressions:

A F = - RT In ka

Where Z:̂ F is change in free energy. From the Ka values

at different temperatures, the enthalpy changes in the system

may be evaluated. The enthalpy change is directly related to

the changes in the number and the strength of the bonds

involved in the ion exchange reaction.

The therroodynamic studies cf alkali metal ions on

semicrystalline zirconium phosphate were performed by many

scientists (242-247). The thermodynamics for alkali and

alkaline earth metal cations on ferric antimonate (248-249),

?9

and niobium arsenate (250) were made in our laboratories.

The kinetics of simple homogeneous chemical reaction

is governed by their differential rate of the reaction depe-

nding on the concentrations of the reactants.

Ion exchange kinetics involves three types of processes.

1. Interdiffusion of counter ions in the adharent film,

2. Interdiffusion of the counter ions with in the ion

exchanger particles themselves, and

3. Chemical exchange reaction.

It is important to note that of all the studies on

ion exchange kinetics which have appeared in the literature

to date, none of them has been shown by chemical exchange

reactions.

Nachod and Wood (251) made the first serious study on

the kinetics of ion exchange. They studied the reaction rate

with which ions from solution are removed by the solid ion

exchanger or conversely the rate ^t wnich the exchangeable

ions are released from the exchanger, Boyd et al (252) have

later on studied the kinetics of metal ions on resin beads,

and nave given an elaborate understanding about particle and

film diffusion which are governed by ion exchange.

30

Costantino et al. (253) have studied the self diffusion

process of Na"̂ and K"*" ions on microcrystals of zr (NaPO^) 2. 3H2O

and Zr(KPO.)^.3H^0 and modified Picks equation to take into

account the non-uniformity of the particle size. The equation

so obtained was employed in tne study of self diffusion rate

of Na^ and K^ ions on the above mentioned exchangers.

Kinetic studies on inorganic ion exchangers were made

in our laboratories and kinetic studies on the exchange ot + 7+ 2+ 2+ 2+ 3+ 4 +

the cation Ag , Mg , Ca , Sr , Ba , Y and Th were

made on tantalum arseiiate (254). Similar studies were also

been made. The distribution of an ion between the exchanger

and solution phases can give a direct measure of their rela-

tive selectivities. Often, the ion exchanger takes up certain

ions in preference to other counter ions present. This sele-

ctivity depends mainly on.

1. The Donnan potential.

2. Sieve action.

3. Complex formation.

An inorganic ion exchanger can be prepared by intro-

ducing triethylamine group into the hydrous oxide of a

trivalent or tetravalent metal ion. The amine group may also

act as a chelating group to certain cations and hence such a

material may be useful in two ways: (1) as anion exchanger

and (ii) a chelating exchanger.

Si

Chelating ion exchangers show a definite selectivity

towards certain ions or groups of ions. Thus the chelating

ion exchanger may provide a convenient technique for the

analytical concentrations of many of the more interesting

trace elements from natural waters and collection of toxic

elements from industrial waste waters. The selectivity of

most complexing agents resides predominantly in their ability

to form chelates with certain cations. The maximum efficiency

in the separation can be achieved by variation of the pH.

Therefore the development of complexing ion exchangers have

taken place, where complexatior. equilibria plays an important

role, such studies can be directed to follov/ing three cate-

gories :

(i) An ion exchanger is used in appropriate metal ion form

and the complexing agent is present as a solute in the

liquid phase.

(ii) An exchanger containing e. complexing agent functional

group attached to the matrix, is used and the metal

ion is present in the liquid phase.

iii) The solid phase is a chelating and the liquid phase

also contain a complexinc agent as solute.

Implementation of the fi.rst and second possibilities

will involve directly the metal complex equilibria, but in

heterogeneous phase, whereas the third possibility is

mainly advantageous of chelate exchange systems. In This

32

field the succ;essful efforts have been made by Bayer and

Cov/orkers (255-258). Blausius and coworkers (259-268),

Gregor and Cov/orkers (262-267)and many others (269-297).

A complex has been defined as "a species formed by

the association of two or more simpler species each capa-

ble of independent existence"(298). When one of the simpler

species is a metal ion, the resulting entity is known as

metal complex. The metal ion occupies the central position.

When the central metal atom of a complex is bound to

its immediate neighbours by covalent bonds by accepting an

electron pair from each nonmetal atom, the metal ion is

called the acceptor atom and the nonmetal ion, donor atom,

A more generally used convention is to call the non metal

ion which is attached to metal ion, ligand (L) and the

bond between them, metal-ligand bond (M-L) , According to

lewis concept this is regarded as an acid base reaction

where the central metal ion is the lewis acid and the

ligand is the lewis base. -

Some ligands are attached to the metal atom by more

than one donor atom in such a manner as to form a hetero-

cyclic ring. This type of ring has been given a special

name "chelate ring" and the molecule or ion from which it

is formed is known as chelating agent. The process of

33

forming a chelate ring is known as chelation. An example of

such a ring is the one formed in fig. 1 by the glycinate ion,

H^C - NH^

C= C - 0

Cu

.NH^ - CH^

0 C=0

The first chelating moleculeswere discovered by

Morgen and Drew (299) with donor atoms and it was the

Caliper like mode of attachment of the molecule to the

metal atom.

Metal chelates may be examined from atleast three

points of view.

1. the central metal ion

2. the chelating molecule.

3. the nature of the bonds linking (l) and (2), and the

influence of each and all of these on the behavior of

the metal chelate as a whole.

If a molecule is to function as a chelating agent/

it must fulfil at least two conditions:

1. It must possess at least two appropriate functional

groups/ the donor atoms of which are capable of combi-

ning with a metal atom by donating a pair of electrons.

These electrons may be contributed by basic coordinating

34

groups such as NH_ or acidic groups that have lost a

proton. Some acidic groups that combine with metal

atoms by the replacement of hydrogen are:

- CCOH

- SC3H

OH (enolic and phenolic)

. H

- NCT

- SH

Coordinating groups include:

0

NH^

NH

N=0

—

=

-

_

0 - R

NOH

OH (alcohol ic)

S - ( t h i o e t h e r )

2. These functional groups must be so situated in the

molecule that they permit the formation of a ring

with a metal atom as the closing member.

Sometimes these two conditions are not always suffi-

cient for the formation of chelate ring. Under some condi-

tions, for example, in solutions of sufficiently low pH, a

potential chelating molecule may attach itself to a metal

atom through only one ligand atom (300).

35

Accordin(3 to Gregor et al. (273), the following pro-

perties are required for a chelate exchanger.

1. The chelat:.ng agent should yield a resin gel of suffi-

cient stab:Llity.

2. The chelating molecule must possess sufficient chemical

stability. So that during the synthesis of the resin

the functicnal structure is not changed by polymeri-

zation or any other reaction.

3. The steric structure of the chelating molecule should

be compact, so that the formation of the chelate rings

will not b«: hindered by the matrix.

4. Because the agents forming relatively stable complexes

are at least tridentate, it is necessary that the ligand

groups of the chelating molecule be situated appropria-

tely, so that the specific arrangement of the ligand

will be preserved in the resin.

The complex formation in such reactions is based,

mainly on the use of N, S, P, As, 0 as donor atoms. For the

formation of coordination bonding, a donor atom must be an

element of high electronegativity.

So far, only the simplest type of chelating molecule

has been discussed - the type that is attached to metal

35

atoms by two donor or ligand atoms. There are, however,

many molecules v/ith three or more donor atoms capable of

combining with metal atoms and forming interlocking or

fused chelate rings. According to the number of donor atoms

capable of combining with a metal atom, these are called

tridentate, quadridentate, quinquedentate, sexadentate

and octadentate chelating molecules respectively. In

forming a metal chelate, a multidentate chelating agent

may not use all its donor atoms.

Chelate exchangers that contain only nitrogen as

ligand atom is comparatively small. Gold and Gregor (269)

have prepared a chelating exchanger that contains aromatic

nitrogen as the only functional chelation proceeds with

eopper(I) and Silver(l).

Chelating ion exchangers with nitrogen and oxygen as

donor atoms have been prepared in large group. Klyachko(3 01).

prepared a material by fixing EDTA as a solid solution within

a phenolformaldehyde condensate. Many workers prepared such

materials by fixing ligands to the benzene nucleus of the

970 crosslinked polystyrene" . Blasius (261) prepared such

materials by the reaction of chloromethylated polystyrene

with various aliphatic amines and stamberg (294,297)

prepared several resins, with vicinal dioxime groups using

polystyrene as starting material. Incorporation of thiol

groups has also been applied to prepare such materials

(272/92) with sulphur as the sole donor atom.

The theory of complex formation on chelating exchan-

gers is a field needing further extensive study. The use

of a chelating resins in analytical chemistry appears to

be of advantage either when the separation problem cannot

be solved by simpler means or when time can be saved.

The reagents which form metal chelates are found

important both in qualitative as well as in quantitative

analysis.Dimethylglyoxime, 8-hydroxyquinoline, cupferron,

Fehling solution, 0-phenthroline and aluminon are examples

of substances v;hich are indispensable in analytical separa-

tions and precipitations. In physiological chemistry the

chelate compounds are useful in the biuret reaction, in

the amino acid salts of the heavy metals chlorophyll, blood

pigment, and cytochrome are special chelates v/hich play an

important role in life processes, "Two very important chelate

compounds, the alkali metal salts of ethylenediamine tetra-

acetic acid and the condensed phosphates are used v;here

the removal of metallic ions are required such as the sof-

tening of water, negative catalysis, and clarification of

solutions.

s»

The ace:ylacetonates of metals are cyclic complexes

which are widely used in the purification of metals because

of their high volatility and solubility in non-polar sol-

vents. Chelating agents in connection with cation exchange

resins and soi.vent extraction are useful in the separation

of radioactive metals.

Some of the important exchangers have been summarised

in Table 1.2

Table "1.2

Some of the Important chalate exchange resins

Si)

S.No. Type of Exchanger Sorption Capacity m mole/g

Selectivity Refs

1. Oxime and diethylamino 2.00 resin

2. 8-hydroxyquinoline and -8-hydroxyquinodine

resin

3. 0-hydroxyoxime resin

4. Thioglycolate resin

5. Aminoacid type resin

6. Phosphate type resin

7. N-Acylphenyl hydro- 0.4 5 xylamines

8. Aluminium oxide

9. Alumina and Silica gel

10. Microreticular resin

11. Cellulosic exchanger

12. Cation exchange resin

13. Sulphonatecfitype resin

14. Carboxylic ion exchanger

15. Chilosan

16. Dithiocarbamate

17. Acrylic resin

18. Semithiocarbazide

Cu(ll)

Cu(Il), Zn(II)

Cu(ll), Mo (VI)

A g d ) , Bi(IIl),Sn(IV) Sb(Ill) , Hg(Il) ,U(VI) from pH = 3.5

U(VI), Cu(II), Ni(II) Fe(lII)

U(VI), Th(IV)

NH4

Ag(l)

Ag(l)

Sb(IIl), CoCll)

Zn(II)

Ni(II)

CoCen)^"^

Cu(II)

Cu(II)

Cu(ll)

Pb(ll), Pt(lV), Rh(III), Ir(III)

302

303

304

305

306

306

307

308

309

310

311

311

312

313

314

315

316

317

40

Sorption S.No. Type of Exchanger Capacity Selectivity Refs,

m mole/g

19. Poly(Vinylbezylthio- 819 mg/g Au(III) 318 urea)

20. Poly(hydroxamic acid) - Cu(II), Cd(II), 319 Zn{ll)

21. Chelating resin - Mo(VI), W(VI) 320 U(VI), V(II)

22. Chelating resin 1.9 Cu(II) 324

41

The present work was undertaken to synthesize a nev/

ion exchange material/ stannic phthalophosphate, to carry

out experiments for its physical characterization, to study

its ion exchange behaviour with special reference to sele-

ctivity for heavy metal ions and to study the ion exchange

equilibria applying the laws of reversible thermodynamics,

for alkaline earth metal ions. Experiments were also carried

out to determine thermodynamic parameters AH, As & A c .

The work was extended to prepare a new chelate ion

exchanger, tin thioglycolate, to carry out experiments for

its physical characterization and to study the selective

behaviour on the basis of complex formation with mercury(II)

and to study the reproducibility for quantitative separa-

tion.

To study the application of inorganic ion exchanger

the ferroin sorbed zinc silicate was used as an indicator

in the form of. beads for the selective determination of

Ce(lV) in presence of rare-earth metal ions. A study of

reproducibility was also made in order to find the preci-

sion of determinations.

42

1. Ketelle, B.H. and Boyd, G.E.

J. Am. Chem. Soc. 1947, 69_, 28C0.

2. Spedding,, F,H., Voigt, A.F., Gladrow, E.M. and Sleight,N.R.

J. Am. Chem.. Soc. 1947, _69, 2777.

3. Spedding, F,.H., Voigt, A.F., Gladrow, E.M., Sleight, N.R.,

Powell, J,E„, Wright, J.M., Butler, T.A. and Figard, P.

J. Am. Chem„ Soc, 1947, 69, 2786.

4. Spedding, F.H.

Discussions Faraday S o c , 1949, 1_, 214.

5. Spedding, F.H. and Powell, J.E.

"Ion Exchange Technology" Acad. Press. Inc., New York,

1956, pp. 359.

6. Tompkins, E.R., Khym, J.X. and Cohn, W.E.

J. Am. Chem. S o c , 1947, 69, 2769.

7. Tompkins, E.R.

Discussions Faraday S o c , 1949, !_, 232.

8. Diamond, R.M., Street, Jr. K. and Seaborg, G.T.

J. Am. Chem. S o c , 1954, 76_, 1461.

9. Glass,R.A.

J. Am. Chem. S o c , 1955, 77__, 807.

10. Martin, W.J. and Perker, G.W.

J. Tenn, Acad. Sic. 1954, 29, 132.

43

11. Street, Jr. K., Thompson, S.G. and Seaborg, G.T.

J. Am. Chem. S o c , 1950, 17^, 4832.

12. Thompson, S.G., Harvey, E.G., Choppin, G.R. and

Seaborg, G.T.

J. Am. Chem. Soc. 1954, 7^, 6229.

13. Wish, L., Freiling, E.G. and Bunney, L.R.

J. Am. Chem. S o c , 1954, 76_, 3444.

14. Dickel, G.

2. Elektrochem., 1950, 54_, 353.

15. Gluekauf, E„, Barker, K.H. and Kitt, G.P.

Discussions Faraday S o c , 1949, 2' 199.

16. Lindner, R.

Z. Naturforschung, 1954, 9a, 798.

17. Lindner, R. and Bergdahl, T.

Z. Elektrochem., 1960, 64_, 919.

18. Spedding, F,H., Powell, J.E. and Svec, H.J.

J. Am. Chem. Soc 1955, 22' 1393, 6125.

19. Taylor, T.I,, and Urey, H.C.

J. Chem. Phys., 1938, 5, 429.

20. Hamitton, P.B.

Ion Exchangers in Organic and Biochemistry, Interscience

Pub. Inc., New York, 1957, pp. 255.

44

21. Hamilton P.B.

Anal. Chem. 1960, 3_2' 1779.

22. Hamilton P,.B., Bogue, D.C. and Anderson, R.A.

Anal. Chem.., 1960, 3^' 1782.

23. Miller, P.S. and Johnson, J.A.

Trans., Am. Assoc. Cereal Chem., 1954, _1_2, 29.

24. Moore, S. end Stein, W.H.

J. Biol. Chem., 1951, 192, 663.

2 5 . Moore, S . a n d S t e i n , W.H.

J . B i o l . Chem., 1948, r7j6, 3 6 7 ;

25a . Moore, S . and S t e i n , V;.H.

J . B i o l . Chem., 1949, 178, 5 3 .

26. Partridge, •̂ .M. and V^estall, R.G.

Biochem. J,, 1949, £4, 418.

27. Partridge, 3.M.

Biochem. J. 1949, 4_4, 521,

and Discuss. Faraday S o c , 1949, 1_, 296.

28. Talley, E.A. and Porter, VJ.L.

J. Chromatof^., 1960,_3_f 434.

29. Boardman, N.K. and Partridge, S.M.

Nature, 1953, r n , 208.

30. Schroeder, W.A.

''ion Exchangers in Organic and Biochemistry"

Interscience Publ. Inc., New York, 1957, p. 299,

45

31. Sober H.A., Kegeles, G. and Gutter, J.

J. Am. Chem. Soc., 1952, 74_, 2734.

32. v;ard, D.N. and Putch, J.D.

Makromol. Chem., 1960, 3£, 23 0.

33. Manalo, G.D., Breyer, A., Sharma, J. and Rieman III, W.

J. Phys. Chem. 1959, 6̂ / 1511.

34. Hahn, R.B., Backer, C. and Backer, R.

Anal. Chim. Acta., 1953, 9, 223.

35. Sargent, R. and Rieman III, W.

J. Phys. Chem., 1956, 6£, 1370.

36. Sargent, R. and Rieman III, W.

Anal. Chim. Acta., 1957, _16, 144,

37. Breyer, A. and Rieman III, VJ.

Anal. Chim. Acta., 1958, j^, 204.

38. Sherma, J. and Rieman III, v;.

Anal. Chim. Acta 1 58; 1^, 214; 1_9, 134 and 1959,_2£, 357.

39. Khym, J.X. and Zill, L.P.

J. Am. Cherr . S e e , 1951, 73_, 2399; 1952, 21' 2090.

40. Khym, J.X., Zill, L.P. and Cohn, W.E. "Ion Exchange in

Organic and Biochemistry" Interscience Publ., Inc.,

New York, 1957, pp. 392.

4 1. Lock, M.V. and Richards, G.N.

J. Chem. S o c , 1955, 3024.

46

42. Samuebon, C. and Sjostrom, E,

Svensk kem. Tidskr. 1952, 6£, 305.

43. Zill, L.P., Khym, J.X. and Cheniae, G.M.

J. Am, CheiT. S o c , 1953, 7Ei, 1339.

44. Sargent, R. and Rieman III, V;.

J. Org. Chem., 1956, 2_1_, 594; J. Phys. Chem. , 1957,

6^, 354; Anal. Chim. Acta, 1957, r7, 408; 1958, W, 197.

45. Helfferich, F.

J. Am. Chem. S o c , 1962, 84_, 3237, 3242.

46. V.'atkins, S.R. and VJalton, H.F.

Anal. Chim. Acta, 1961, 24_, 334.

47. Thomas C.L. (Sun Oil Co.)

U.S. Patent, 1958, 2' 865, 970.

48. Seki, T.

J. Chromatcg. 1960, 4_, 6.

49. Nakayama, M., Itoh, K., Chikuma, M., Sakurai, H,

and Tanaka, H.

Talanta, 1984, 31 (4), 269.

50. Sarzanini, C , Mentasti, E., Gennaro, M.C. and Marego, E,

Anal. Chem. 1985, 57(9), 1960.

51. Stella, R., Genzerli, V., and Maggi, L.

Anal. Chem. 1985, 57(9), 1941.

47

52. Blstcky, A.J. and Hansen, G.T.

Anal. Cherr.. 1985, 57(9) , 1937.

53. Kirlyama, T, and Kuroda, R.

Talanta, 1984, 31(6), 472.

54. Li Shi-Yu and Geo Wei-Ping,

Talanta, 1984, 3l(10A), 844.

55. Desbene, P-L,, Lambert, D,, Richardin, P. and

Basselier, J-J.and Kuc, A.Y. and Boulet, R.

Anal. Chem., 1984, ̂ , 313.

56. Brown, R.J. and Bicgs, W.R,

Anal. Chem. 1984, 5_6, 646.

57. Mazzucotelli, A., Vannuccu, R,, Vannucci, S, and

Passaglia, 2.

Talanta, 19B4, 31(3) , 185.

58. Lundstrom, U,, Olin, A. and Nydahl, F.

Talanta, 1984, 31(1) , 45.

59. Cristal, M.J.

Chem. Ind. (London) , 1983, (2J.) , 814-17,

Chem. Abst. 1983, £9, 211233 K.

60. Richard, J.J. and Junk, G.A.

Anal. Chem., 1984, 5_6, 1625.

61. H.S. Thompson,

J. Roy. Agr. Soc. Engl., 1850, 11, 68.

48

6 2 . J . T . Vvay,

J . Roy. A g r . S o c . E n g l . , 1850, _n , 3 1 3 ; 1852, l ^ , 1 2 3 .

6 3 . F . Harms and A. Rlimpler,

V. I n t e r n . K o n g r e s s f . angew. c h e m . , 1903 , 5 9 .

6 4 . R. G a n s ,

Jahrb. Preuss. geol. Landesanstall, 1905, 2Ji, 179.

65. B.A. Adams and E.L. Holmes

J. Soc. Chem. Ind. (Londonl, 1935, IT, 54.

66. D'Alelio, G.F.,

U.S. Patent, 2, 366, 007, 1945.

67. Mukerjee, A.K. and Mandal, S.K.

Talanta 1984, 31(3), 195.

68. Varshney, K.C, Agrawal, S. and Varshney, K.

J. Liq Chromatog. 1983, 6(8), 1535.

69. Varshney, X.G., Agrawal, S. and Varshney, K.

Sep. Sci. Technol., 1983, 18(1), 59.

70. Varshney^K.G., Agrawal, S. and Varshney, K,

Ind. J. Technol. (Accepted for publication).

71. Varshney, K.G., Agrav/al, S., Varshney, K. and Saxena, V.

Analyt. Lett. 1984, 17(B16), 2111.

72. Varshney, K.G., Rani, S., Anwar, S. and Sharma, U.

Analyt. Lett., 1985, 18(A16).

49 73. Varshney, K.G., Agrawal, S. and Varshney, K.

Analyt. Lett., 1983, 16 (A17).

74. Punger>E., Toth, K.and Nagy, G.

Essays Anal. Chem., 1977, 331.

75. Koryta, K.

Anal. Chim. Acta 1972, 6_1, 329.

76. Koryta,K.

Ion Selective electrodes,

Cambridge University Press, Cambridge (1975).

77. Lakshminarayanaiah, N.

Membrane Electrodes,

Academic Press, London (1976).

78. Russel, E.R., Adamson, A.W. Shubert, J. and Boyd, G.E.

U.S.A.E. Comm. Rep. CN-508, 1943 and Beaton, R.H.,

Copper, V.R., Fries, B.A. Chapelle, T.J., Scheft, I.,

Stoughton, R.A. and Truk, E.H.

U.S.A.E. Comm. Rep. CN-633, 1943.

79. Amphlett, C.B.

'^Inorganic Ion Exchangers'^ Else, Pub. Co., Amsterdam, 1964

80. Vesely, V. and Pekarek, V.

Talanta, 1972, j^, 219.

81. Pekarek, V. and Vesely, V.

Talanta, 1972, _12, 1245T

50

82. Marinsky, J.A.

"Ion Exchange". Marcel Dekker, Inc., New York, 1969.

8 3 . V J a l t o n , H . F .

A n a l . C h e m . , 1 9 7 0 , 4 ^ , 8 6 R .

8 4 . V J a l t o n , H . F .

A n a l . C h e m . , 1 9 7 2 , 4_4, 2 5 6 R .

85. Walton, H.F.

Anal. Chem., 1974, £6, 398R.

86. 'Walton, H.F.

Anal. Chem, 1976, 4_8, 52R-

87. VJalton, H.F.

Anal. Chem., 1978, 5^/ 36R.

88. VJalton, H.F.

Anal. Chem., 1980, 52_/ 15R.

89. Marinsky, J.A. and Marens, Y.

'̂ Ion Exchange and Solvent Extract ion" Vol. 6.

Dekker, New York 1974, pp. 301.

90. Walton, H.F.

Techniques and Applications of "Ion Exchange Chromo-

tography", in "Chromatography". E. Hefftman, Ed.,

3rd ed.. Van K'ostrand Reinhold, Nev; York, 1975, pp.344

91. Clearfield,, A.

Inorganic Ion Exchange Materials, CRC. Press. Inc.

Boca Raton, Florida, USA, 1982.

:u

92. Parrish, J.H.

Chem & Ind. (London), 1956, 127.

93. Churms, I.S.C.

S, African Ind. Chemist. 1965, 19, 26, 48, 68, 87, 148.

94. Prospert, J.

Comm. Energie, At (France). Rappt CEA-R, 1966, 2835.

95. Tikavyi, V.F. and Tsukorova, L.I.

Izv. Akad. Nauk. SSSR, Neorg. Mater. 1965, I., 108,

96. Savel'eva, V.I. and Minaev, V.A.

Tr. Mosk. Khim. Tekhnol. Inst. 1963, 43_, 82.

97. Nancollas, G.H. and Pekarek, V.

J. Inorg. Nucl. Chem. 1961, 22, 259.

98. Garbauskas, G. and Sharmaev, V.I.

Zh. Neorg. Khim. 1970, 15_, 33.

99. Hont, M.D. and Baetsle, L.H.

Mededel. Koninkl. vlaam. Acad. Wetenschap, Belq

KI VJestor Schap. 1965, 21_, 31.

100. Ahrland, S. and Oskarsson, A.

J. Inorganic. Nucl. Chem. 1970, 3/2^, 2069.

101. Horwitz, E.P.

J. Inorg. Nucl. Chem. 1966, 2£, 1469.

102. Nancollas, G.H. and Tilak, B.V.K.S.R.A.

J. Inorg. Kucl. Chem. 1969, 31, 3643.

52

103. Albertsson, J.

J. Acta Chim. Scand. 1966, 2_0_, 1689.

104. Perevazova, V.A. and Boichinova, E.S.

Zh. Prikl. Khim. (Leningrad.) 1967, £0, 2679.

105. CVjeticanin, D. and Milic, N.

Bull. Boris Kidrich Inst. Nucl. Sci. 1964, 1^, 73.

106. Konig, K.H, and Demel, K.

J. Chromatogr. 1969, 3_9/ 101.

107. Konig, K.H. and Schefer, H.

Radiochim., Acta. 1963, 1, 213.

108. Konig, K.H. and Hoyer, F.

Atompraxis. 1965, VL' 275.

109. Biochinova, E.S, and Podgorelva, T.I.

Zh. prikl. Khim. (Leningrad). 1967, £0, 1833.

110. Biochinova, E.S. and Kharitonova, E.V.

Zh. Prikl. Khim (Leningrad) 1965, 38_, 674.

111. Biochinova, E.S. and Kharitonova, E.v.

Zh. Prikl. Khim (Leningrad). 1965, 3^/ 674.

112. Brigevitch, R.F. and Kuznetsov. R.A.

Vestn. Leningr. Univ. Fiz. Khim. 1969, 145.

113. Feuga, J.R. and Kikindai, T.

Compt. Rond. Acad. Sci. (Paris), Ser. C. 1967, 8, 264.

53

114. Clearfield, A. and Smith, G.D.

J. Inorg. Nucl. Chem. 1968, 3_0/ 277.

115. Toracca, E.. and Constantino, U. and Mossucci, M.A.

J. Chromatogr. 1967, 3^, 584.

116. Clearfield, A. and Blessing, R.H.

J. inorg. Nucl. Chem. 1972, 3±, 2643.

117. Ahrland, S., Albertsson, J., Nihlg, B. and Nilson, L.

Acta Chim. Scand. 1964, 1_8, 707.

118. Osipora, N.O. and Biochinova, E.S.

2h. Prikl. Khim. (Leningrad) 1968, 4_1, 2186.

119. Kraus, K.A.

U.S. Patent.. 1968, 3, 382, 034.

120. Rahman, M.K. and Hug. A.M.S.

J. Chromatogr. 1970, 53_, 613.

121. Zsinka, L. and Szirtes, L.

Proc. Second Hungarian Conf. Ion Exchange , Balatovzeplak,

1969, 2, 627.

12 2. Medeiros.

J. Inorg. Nucl. Chem. 1966, 2_8, 599,

123. Tang, T.P., Sun, P. and Chan, K.Y.

Hua - Hsuch 1965, 3_3.'

124. Tang, T.P., Sun, P. and Chan, K.Y.

Hua-Hsuch 1967, 9.

fi4

125. Gill, J.S. and Tandon, S.N.

J. Radioanal. Chem. 1973, J^, 391.

126. Alberti, G., Costantino, U. and Gupta, J.P,

J. Inorg. Nucl. Chem. 1974, 3_§' 2013.

127. Hallaba, E., Misak, N.Z. and Salama, H.N.

Indian. J. Chem., 1973, n_, 580.

128. Ruvarac, A.L. and Trtanj, M.I.

J. Inorg. Nucl. Chem., 1972, 3_i' 3893.

129. Albert!, G. ana Costantino, U.

J. Chromatogr. 1970, 5^, 482.

130. De, A.K. J. Chromatogr. 1974, 101, 63, 73.

131. Alberti, G. and Costantino, U.

J. Inorg. Nucl. Chem. 1970, 3_i' 1719.

132. Qureshi, M. and Husain, W.

J. Chem. Soc. (A.). 1970, 1204.

133. De. A.K. and Chaudhury. K.

Talanta, 1976, 23(2), 137.

134. Qureshi, K. and Nabi, A.

J. Chem. Soc. (A). 1971, 139.

135. De, A.K. and Dass, K.S.

J. Ind. Chem. Soc. 1976, 53(10), 1063.

136. Belg. Batent. 1964, 64 9, 389.

5n

137. Nerth. Appl. 1966, ^, 603, 607.

138. Michel, E. and VJeiss, A.

Z. Naturforsch, B.,1967, 22_, 1100.

139. Alberti, G,, Cardini, P. and Torracca, E.

J. Inorg. Nucl. Chem., 1967, 29^, 571.

140. Kurbatov, UI, and Pavlova, S.A.

Tr. Inst. Khim. Akad. Nauk,SSSR, Ural Filial.

1966, _10, 73.

141. Piret, J., Heunry, J., Balon, G. and Beaudet, C.

Bull, Soc. Chim. France.^ 1965, 3590.

142. Dolique, R. and Quenovn, F.

Tra.v. Soc. Pharm. Montpel lier^ 1966, 2e_, 353.

143. Dubos. D. and Kikindai, T.

Cenpt. Rend. Acad. Sci. (Paris) Ser C, 1970, 270, 1833

144. Alberti, G. and Torracca, E.

J. Inorg. Nucl. Chem., 1968, 3_0' 3075.

145. Quresfti, M. and Nabi, S.A.

J. Inorg. Nucl. Chem., 1970, 3_2/ 2059.

146. Qureshi, M. and Rav.at, J.P. and Sharma, V.

Talanta, 1973, 2_2' 267.

147. Qureshi, M.. Zehra, N., Nabi, A. and Kumar, V.

Talanta, 1973, 2£' ^09.

148. Qureshi, M. and Kumar, V.

J. Chem. S o c , 1970, (A), 1488.

f\0

149. Gill, J.S. and Tandon, S.N.

J. Radioanal. Chem., 1974, 2£, 5.

150. Qureshi, M. and Kumar, R. and Rathore, H.S.

Anal. Chem., 1972, 4_4, 1081.

151. Qureshi, M., Varshney, K.G. and Kabiruddin, S.K.

Can. J. Chem., 1972, 5_0 , 2071.

152. Sasaki, T., Komatsu, Y. and Fujiki, Y.

Sepn. Sci. Technol. 1983, 18(1), 49.

153. Qureshi, M. and Rathore, H.S.

J. Chem. S o c , 1969, (A), 2515.

154. Qureshi, M, and Gupta, J.P.

J. Chem. s o c , 1969, 1755.

155. Qureshi, M. Varshney, K.G, and Khan, F.

Separ. Sci., 1971, 6, 559.

15 6. Husain, S.v;.

Analusis, 1972, 1_, 314.

157. Szirtes, L. and Zsinka, L.

J. Chromatogr., 1974, 102, 105.

158. Lieser, K.H. Bastian, J., Hecker_, A.B. H. and Hild, V}.

J. Inorg. Mucl. Chem., 1967, 22, 815.

159. Desai, G.T. and Baxi, D.R.

Indian J. Technol., 1978, 16(5), 204.

57 160. Konig, K.H„ and Meyn, E.

J. Inorg. Nucl. Chem. 1967, _22' 1153.

161. Konig, K.H. and Meyn, E.

Anal. Chem„ Acta. 1968, £2, 540.

162. Larson, E.M. and Cilley, VJ.A.

J. Inorg. Uucl. Chem. 1968, 3_0, 207.

163. Konig, K.H, and Meyn, E.

J. Inorg. Nucl. Chem. 1967, _22' 1519.

164. Tomata^N. and Ichiro, F.

Asahi Garasju Kogyo Gijutsu Shorei Kaikenhyyu

Ho Ko Ku 1968, U_, 563.

165. Albert!, G.,, Costantino, U., D\ Gregorio, F. and

Torracca, E.

J. Inorg. Nucl. Chem. 1968, 3^/ 295.

166. Konig, K.H.. and Eckstein, G.

J. Inorg. Nucl. Chem. 1969, 2i' 1179.

167. Alberti, G., Costantino, U., Di Gregorio and

Torracca, E.

J. Inorg. Nucl. Chem. 1969, 3_1' 3195.

168. Zsinka, L. and Szirtes L.

Radiochem. Radioanal. Lett., 1974, j^, 271; r7, 257.

169. Tandon, S.N. and Gill, J.S.

Talanta, 1972, 19, 1355.

58

170. Srivastava, S.K. , Singh, R., Agarv;al, S. and Kumar, S

J. Radioanal. Chem. 1977, 40(1), 7.

171. De, A.K. and Dass, S.K.

J. Indian Chem. Soc.^ 1976, 53 (10) , 1063.

172. Rawat, J.P.^ Khan, M.A. and Thind, P.S.

Bull. Chem. Soc. Jpn.-1984, 57(6), 170.

173. Kabi, S.A. and Rao, R.A.K.

J. Ind. Chem. Soc.^1981, 58(11) , 1030.

174. Bhattacharyya, D.K. and De, A.

J. Radioanal. Chem.^ 1983, 76(1), 109.

175. Tandon, S..N. and Gill, J.S.

Talanta, '.972, _2£' ̂ 85.

176. Alberti, G., Costantino, U., Di Gregorio, F. and

Torracca, E.

J. Inorg. Nucl. Chem.^ 1964, ^ , 224.

177. Qureshi, M., Kumar, R. and Rathore, H.S.

J. Chem. SoC; (A). 1970, 272.

178. Qureshi, M., Kumar R. and Rathore, H.S.

J. Chem. Soc.^ (A). 1970, 1986.

179. Qureshi, M. and Rawat, J.P.

J. Inorg. Nucl. Chem.^ 1968, _3£' 305.

180. Qureshi, M. and Varshney, K.G.

J. Inorg. Nucl. Chem.^ 1968, 3_£/ 3081.

59

181. Qureshi, M., Kumar, V. and Zehra, N.

J. Chromatogr. 1972, 67, 351.

182. Qureshi, M. and Nabi, S.A.

Talanta, 1972, r9, 1355.

183. Qureshi. M., Varshney, K.G. and Israili, A.H.

J. Chromatogr. 1971, 5^, 141.

184. Qureshi, M., Nabi, S.A. and Zehra, N.

Can. J. Chem. 1977, 55_/ 1667.

185. Qureshi, M., Rav/at, J.P. and Gupta, A.P.

ind. J. Technol. 1977, 15(2), 80.

186. Chaudhry, R.K. and Dhar, D.

J. Inst. Chem. (India). 1983, 55(6), 246.


Indian J. Technol. 1978, 16(5), 201.

188. Szirtes, L., Zsinka, L., Zaboranko, K.B. and lofa, B.S

Acta. Chlm. Acad. Sci. Hung. 1967, 54^, 215.

189. Belteridge, D. and Stradling, G.N.

J. Inorg. Nucl. Chem. 1967, 22, 2652.

190. Qureshi, M., Kumar, R. and Rathore, H.S.

Talanta. 1972, r9/ 1377.

191. Malik, V/.U., Srivastava, S.K., Bhandari, V.M. and

Kumar, S.

J. inorg. Nucl. Chem. 1976, 2§' ^43.

60

192. Rawat. :'.P. and Thind, P.S.

Can. J. Ohem. 1976, 54(12), 1892.

193. Greko, S.D. and Leitsin, V.A.

Zh. Neorg. Khim. 1968, 13_, 1133.

194. Rawat, J.P. and Singh, J.P.

Can. J. Chem. 1976, 54_, 2534.

ig'S. Walton, H.F.

Anal. Chem., 1970, 4_2, 86R.

196. V. Kourim, J. Rais and B. Million,

J. inorg. Nucl. Chem., 1964, ^ , 1111.

197. Rawat, J,P. and Singh, D.K.

Anal. Chim. Acta. 1976, £7, 157.

198. Rawat J.?., Khatoon, T. and Shankar, H.

Annal di Chimica, 1978,. 68., 913.


Indian J, Technol., 1979, r?/ 157.

2 00. Kobayashi, E. and Goto, T.

Kogyo Kagaku Zasshi, 1970, 23/ 692.

201. Bittles, J.A.

U.S. Patent, 1970, 3_, 499; 537.

202. Rawat, J.P. and Singh, J.P.

Chromatocraphia, 1977, 10, 205.

61

203. Rawat, J.P, and Singh J.P.

Annali di Chimica 1976, ^ , 585.

204. Williams, L.E. and Mays, R.K.

U.S. Appl. 1974, 1_1/ 522.

205. Rav/at, J.P. and Mujtaba, S.Q,

Can. J. Chem. 1975, 53_» 2685.

206. Qureshi, M., Ravjat, J.P. and Sharma, V.

Anal. Chem. 1973, 45(2), 1901.

207. Qureshi, K., Rav/at, J.P. and Gupta A.P.

Chromatographia. 1978, 11(4), 202.

208. Qureshi, F., Rawat, J.F. and Gupta, A.P.

J. Chromatogr. 1976, 118, 167.

209. Qureshi, K., Gupta, A.P. and Khan, T.

J. Chromatogr. 1977, 14£, 231.

210. Qureshi, M., Gupta, A.P. Thakur, J.S. and Singh, V.P.

Sepn. Sci., Technol. 1980, 15(5), 1255.

211. Gupta, J.P., Novell, D.V., Qureshi, M. and Gupta, A.P,

J. Inorg. Nucl. Chem., 1978, £0, 545.

212. Qureshi, M., Varshney, K.G. and Khan, P.

J. Chromatogr., 1972, £5, 547.

213. Baestle, L.H., Deyck, V.V. and Huys, D.

J. Inorg. Nucl. Chem., 1978, 40, 545.

62

2 1 4 . J a i n , A . X . , S i n g h , R . P . and Chand, B .

J . RadiOc-anal. Chem. 1982, 75 ( 1 - 2 ) , 8 5 .

2 1 5 . Shen , X. and VJang, VJ.

Huaxue Xi:ebao 1981 , 3 9 ( 7 - 8 y 9 ) , 7 1 1 .

216 . Abe, -M, and I t o , T .

Bull. Chem. Soc. Japan 1968, 4Ĵ , 333.

217. Ganev, S,. and Arsova, A.

Pochivozen. Agrokhim. 1983, 18(2) , 30.

218. Pekarek, V., Vesely, V. and Ullrich. J.

J. Bull. Soc. Chim. France. 1968, 1844.

219. Volkhira, V.V., Tatlieve, T.N. and Zilleman, M.V.

Izv. Akad. Nauk SSSR Neorg. Mater 1975, 11(8), 1476.

220. Kritel, J.

J. Inorî ,. Nucl. Chem. 1965, 22, 1862.

221. Williams, L.E. and Mays. R.K.

U.S. Appl. 1974, n^, 522.

222. De, A.K. and Chodhury, N.D,

Chromatographia, 1978, 11 (10), 586.

223. Rav,'at, J.P. and Muktawat, K.P.S.

Chromatographia. 1978, 11 (9), 513.

224. Kourim, V., Rais, J. and Million, B.

J. Inorg. Nucl. Chem. 1964, 26, 1111

63

225. Thind P.3. and Bindal, T.K.

J. liq. Chromatogr. 1980, 2JA^) , 573.

226. Gonzaliz, C.G. and Carvallio; R.A. and Guedes de.

J. Chromatogr. 1977, 136(1), 176.

227. De, A.K. and Charabarty, P.

J. Liq. Chromatogr. 1981, 4 (12), 2223.

228. Kritil, J.

J. Chromatogr. 1965, 2_£. 384.

229. Rawat, J.P. and Iqbal, M.

J. Liq. Chromatograpy, 1980/ _3' 591.

230. Simona, M.G., Balsenc, L.R. and Jorgensen, C.K.

Helv. Chim. Acta. 1978, 61(6), 1984.

231. Qureshi, M. and Kaushik, R.C.

Anal. Chem., 1977 49(1), 165.

232. Barsukova, K.V. and Radionova, G.N.

Radiokhimiya, 1972, 14_, 228.

233. Vinter, I.K., Biochinova, E.S., Darisova, N.E. and

Chitverina, R.B.

Z'h. Prinkl. chim., 1973, 4_6, 269.

234. Caletika, R. and Konecky, C.

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