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STUDIES OF ION-EXCHANGE MATERIALS AND THEIR ANALYTICAL APPLICATONS DISSERTATION SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF THE DEGREE OF ^ IN CHEMISTRY By SHALINI GAUTAM DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY ALIGARH-202002 (INDIA) 2006 ^ ^^^ J ' II • i I '•I'll '^"liiiTTir^JCliH
Transcript

STUDIES OF ION-EXCHANGE MATERIALS AND THEIR ANALYTICAL APPLICATONS

DISSERTATION

SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF THE DEGREE OF

^ I N

CHEMISTRY

By

SHALINI GAUTAM

DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY

ALIGARH-202002 (INDIA)

2006 ^ ^ ^ ^ J ' II • i I '•I'll '^" l i i iTTi r^JCl iH

z^/

2 0 JUL ?009

DS3632

OEblCATEb TO MY LOVING PARENTS

Sued "Jls/ifa^ 0Ca6/ M.Sc. M.Phl.. Ph.D.

Professor of Analytical Chemistry

0) (OFF.) 0091-571-703515 (RES.) 0091-571-404014

E-mail [email protected] DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY

ALIGARH -202002 (INDIA)

1G-XO'06

CERTIFICATE

Certified that the work has embodied in the dissertation entitled

**Studies of Ion Exchange materials and their Analytical Applications" is

original research work carried out by Miss Shalini Gautam under my

supervision and is suitable for submission for the award of Master of

Philosophy degree in Chemistry by this university.

(Pl-of. Syed Ashfaq Nabi)

Supervisor

Acknowledgement

I n the name of Omnipotent, Omniscient, Omnipresent God, the most

beneficent and the most merciful.

I am privileged to take this opportunity for recording my deep

indebtness to all those in bringing this dissertation to a satisfactory

completion. I t is my f i rs t privilege to acknowledge with deep sense of

gratitude and humble submission, the enthusiastic support and never failing

encouragement, extended by my supervisor Prof. Syed Ashfaq Nabi, who

made it possible for me to bring the dissertation in hand to a glorious

furnish. Besides providing guidance and assistance he have been a constant

source of strength and inspiration to me throughout the work. I am heavily

indebted to him for his benevolent attitude.

I owe a deep sense of gratitude to Prof. Kabiruddin, Chairman,

Department of Chemistry, A.AA.U for providing me all research facilities I

would like to express my deep gratitude to all the teachers of my

department.

The acknowledgement will remain incomplete without expressing heartiest

thanks to Dr. Amjad Khan and my seniors, who provided me motivation,

encouragement and moral support throughout the period of my research.

I am extremely impressed by the generosity and genuine help

extended to me by all Lab colleagues- Shaheena Khan, Abid, and Sajjad in

successfully carrying out my work. I would be failing in my duty if I do not

express my thanks to all my friends Yusuf Khan, Meraj Jaf fery, Altaf, Rafey

and Sana who from time to time provided me moral support and enquired

about the progress of my work.

My special thanks to my loving parents and siblings for their love,

support and constant source of encouragement paved this way for me to

carry on this work all through the time it has taken. Without which this work

would have not been existed.

I also appreciate the assistance of my sister Malini Gautam for her

timely suggestions and answering my numerous computer questions and

acting as my observational co-advisor who took great interest in my work.

Special mention must be to the staff members of the seminar library for

providing me books and literature. Storeroom members for providing

chemicals and other equipments, Department of chemistry A.M.U for their

significant contribution towards a frui t fu l completion of my research work. I

would also thanks to print point for composing my thesis.

Last but not least this work, I believe would have not been possible in its

present shape without the benign mercy and inspiration from God Almighty.

( Shalini gautam).

CONTENTS

Acknowledgement

PageNo.

ListofFisiires —

Chapter-1

INTRODUCTION 1-44

REFERENCES 45-56

Chapter-2

^Studies of ion exchange materials and their analytical

applications**.

INTRODUCTION 57-59

EXPERIMENTAL 60-65

RESULT AND DISCUSSION 66-81

REFERENCES 82-83

LIST OF TABLES

Table -1 Basis of separation method.

Table -2 Applications of partition chromatography.

Table -3 Important years in the history of TLC.

Table-4 Classification of column chromatography.

Table -5 Some of Key contributors in the field of chromatography.

Table-6 a Commercially available cation exchangers, b Commercially available anion exchangers.

Table-7 Selected zeolites with their composition and exchange capacities.

Table-8 Some ion exchanger with their trade name and manufacturer.

Table-9 List of important ion exchange resin loaded with different chelating

agent, their selectivity and their applications.

Table-10 Toxic traces elements in natural water, their effect.

Table-] 1 Some research papers.

Table-12 List of metal ions and their salts.

Table-13 The solvent system used for study of distribution coefficient (Kd) of the metal ions.

Table-14 Distribution coefficient of metal ion between solvent system Si-S? based on Polarity factor on Amberlite IRA-400 (CI') treated with cresol red.

Table-15 Distribution coefficient of metal ion between solvent system Si-Sg based on Acid dissociation constant on Amberlite IRA-400 (CI") treated with cresol red.

Table-16 Binary Separations of Bi , Sn'* ' Zr"* ' and Hg ^ fi-om other metal ions (cations) on cresol red modified Amberlite IRA- 400(Cr) anion exchange resin column.

Table-17 Selective separation of Hg^^ fi^om an synthetic mixture of Cu^^,Al^,Fe^ , Ni * on a Column of cresol red dye loaded Amberlite IRA-400 (CI") resin

LIST OF FIGURES

Figure-l Co-polymerisation of styrene divinyl benzene followed by sulphonation to give polstyrene cation exchange resin.

Figure-2 Polycondesation of parasubsituted phenol with formaldehyde yield linear Polymer

Figure-3 Dipicrylamine.

Figure-4 Metaphenylenediamine by condensation with formaldehyde

Figure-5 Structure of Cresol-red.

Figure-6 Effect of concentration on the amount of the Cresol-red adsorbed by Amberlite IRA-400 resin.

Figure-7 EflFect of equilibration time on the amount of the Cresol-red adsorbed by Amberlite IRA-400 resin

Figure-8 Effect of pH on the amount of the Cresol-red adsorbed by Amberlite IRA-400 resin

Figure-9 Effect of temperature on the amount of the Cresol-red adsorbed by Amberlite IRA-400 resin

Figure-l 0 Elution profile diagram for binaiy separation of Mg ' ,Ca^, Sr , Ba^ , Zn^^,and Mn' resin column Zn^^,and Mn ^ on cresol red modified Amberlite IRA-400 anion exchange

Separation of-: a) Mg ^ firom Hg * b) Ca^" from Hg^' c) Sr ^ from Hg ^ d) Ba ^ from Hg ^ e) Mn ^ from Hg^"

Figure-l 1 Elution profile diagram for binary separation of Mn JZn ,Pb ,Ni ' and Co' ' on cresol red modified Amberlite IRA-400 anion exchange resin.

Separation of-: a) Mn^' b)Zn^^ c)Pb' ' d)Ni' ' e)Co'^

from from from from from

Bi ^ Bi ^ Bi'^ Bf^ Bi ^

CHAPTER'1

INTRObUCnON

INTRODUCTION

I t is always difBcult to decide what to omit and what to delete. The words analytical and

instrumental are not amenable to definition. With respect to this (1) H.A Laitmer has

written, "The vital point here is that if the research is aimed at methods of solution of

measurement problem, it is properly classified as analytical chemistry, whereas the

interpretation of the result of the measurement infiinges upon the other fields of

chemistry". The use of instrumentation is an exciting and fascinating part of chemical

analysis that interact with chemistry and other field of pure and applied sciences.

Analytical chemistry may be defined as the science and art of determining the

composition of material in terms of the elements or compounds contained in them. In the

closing decades of the 19* century the invention of the spectroscopy brought with it an

analytical approach that proved to be fiuitful in qualitative and quantitative on macro or

micro level. There were many methods used like Gravimetric, Volumetric, Colorimetric

and Turbidimetric were introduced then it was found that electrical measurement could be

used to advantage to detect and points in titration since about 1930, the rapid development

of electronics has resulted in a major revolution in analytical instrumentation. This

instrumentation provides the lower detection limits require to assure safe food, drugs, water

and air. Thus the analyst is free to examine component of the analytical system such as

sampling methods, data treatment and the evaluation of results. There are number of

analytical methods but the important principal areas are:

Spectroscopy.

Chromatography

Hyphenated method and last but not least the Ion exchange technique.

A no of existing techniques have been combined to expand the utility of the component

methods. Some of the principal types of chemical instrumentation are as follows.

1. Spectroscopic Techniques.

> Ultraviolet and visible spectroscopy.

> Fluorescence and phosphorescence spectrophotometry. > Atomic spectrometry (emission and absorption). > Infrared spectroscopy > Raman spectroscopy. > X-ray spectroscopy. > Radiochemical methods including activation analysis. > NMR spectroscopy. > ESR spectroscopy.

2 Electroanaiytical techniques.

> Potentiometry (PH and ion selective). > Voltammetry. > Voltammetric techniques Stripping techniques. > Amperometric techniques. > Coulometiy and many others.

3 Chromatographic techniques.

> Gas chromatography. > HPLC (High performance Uquid chromatography).

4 MisceUaneous techniques.

> Kinetic technique. > Thermal analysis. > Mass spectrometry.

5 Hyphenated technique.

> (GC-MS)Gas Chromatography. > (ICP-MS). > (GC-IR). > (MS-MS).

In analytical chemistry we are mainly concerned with the various types of Separation.

Separation, Detection and Determination: The detection and determination sometimes

requires its separation from interfering impurities. The separation is the basis of analysis

from interfering impurities or of analj^ical chemistry too. It is important for an analj^ical

chemist to separate different constituent of a sample prior to chemical analysis. There were

variety of separation method that are in common use, including

1) Chemical or electrolytic precipitation.

2) Distillation.

3) Solvent extraction

4) Ion exchange

5) Chromatography.

6) Electrophoresis.

7) Field flow fiactionation.

The basis of separation mediod is mentioned in table number (1).

Separation Method Basis of Method

1) Mechanical phase separation

2) Precipitation and fiactionation

3) Distillation

4) Ion exchange

5) Solvent extraction

6) Chromatography

7) Field flow fi-actionation

Difference in solubility of compound.

Difference in volatility & solubility of

compound.

Difference in volatility & solubility of

compound.

Difference in interaction of reactant with

Ion exchanger.

Difference in solubility of two immiscible

hquids.

Difference in rate of movement of a

solute through a stationary phase.

Difference in interaction with a field

or gradient applied perpendicular

to the transport direction.

Detection is most probably more important than separation or determination, therefore it

usually precedes them. There are number of procedures used for the determination of

organic substances.

Some of the most important of these are

1) Instrumental techniques (2-8).

2) Chromatographic methods (9).

3) Ion exchange methods (10-11).

4) Spot testing (12).

Instrumental Method- IR, UV, NMR, ESR can be used to detect substances which are

otherwise difficult to identify .The importance of photo acoustic spectroscopy (13) to the

solution of analytical chemistry is now realized.

The main drawback of the instrumental techniques is the high cost

of instrument and the expertise needed to handle them. Moreover the instrument cannot be

used where full detectiwi is required.

The Non-Instrumental Metiiod-:

These have definite advantage of being fest, simple and expensive .The chromatographic

methods are being used more and more to solve the problem of detection .The simplest

approach to detection of organic fiinctional group is provided by ion exchange methods.

These methods are fest, simple, selective and in expensive.

A simple example will illustrate the eflBciency of ion exchange techniques or metiiods-:

Feigl (14,15) first described the spot test, which is the most versatile non instrumental

techniques. Fujimoto et al (16) proposed the use of resins for test technique to make these

test more elegant, which depend on the intense coloration of the few grains of light colored

ion exchange resin produced by the uptake fi"om the reaction medium of ions having

characteristic colors .The test have the following advantages-:

1. They are more sensitive because the colored ionic species is concentrated on the

resin surface.

2. The coloration is often more stable in the resin phase and sometimes become

3. progressively more intense on standing.

4. These test are more selective, thus ion having a charge opposite to that of ionic

species absorbed by the resin usually do not interfere.

5. These tests need very little equipments and require very little training on the part of

investigator.

The Resin Spot technique-: It has been widely used for the detection of inorganic ions by

using color reaction (17-19). However resin beads can also be used to develop to new color

reaction as described by Qureshi (20) for diphenylamine picric acid (21-23) and for EDTA

in human urine (24,25) Fujimoto (26) described very sensitive test for the detection of

fluoride using ion exchange beads. Balton (27) has described an ion exchange method for

the detection of N, S, P, & Halogens.

Another important phenomenon is to combine the hydrolysis and catalytic

reaction of the resin beads with the resin spot technique. Example- Detection ester amide

(28), amide anilides (29) and nitriles (30). Qureshi et al (31) extended the use of the ion

exchange resin as a catalyst and as an ion exchanger simultaneously for the determination

of amide and ester. The use of solid ion exchangers have a number of advantages when

compared with electrolytes-:

a The ion exchanger is more selective i.e., it distinguishes more sharply between the

various reactant molecules and it may be considered to be half v«iy in the selectivity

between dissolved electrolytes and enzymes.

Q The catalyst can be readily removed from the reaction products by nitration or

decantation.

Q The purity of the product is better since side reactions are minimized.

a No new ions are introduced in the reaction except the ions, which are produced as a

result of hydrolysis.

Although there are many methods of determination of trace metal ions, such procedures

often result in tedious extraction and separation (32). With the development of modem

analytical techniques it has become possible to elucidate the structure of these ion exchange

materials and correlates with the mechanism of ion exchange. Infra red spectrum predicts

the presence of water molecules, OH group and metal oxygen bonds.

Analytical chemistry is a science of a set of a powerful ideas and method that are useful in

all fields of science; it also deals with the chemical composition of samples of matter

qualitatively and quantitatively. Qualitatively yield information about the identity of atomic

or molecular species or the functional group sample. Quantitative data include the required

accuracy precision and range of expected analyte concentrations and detection limits for

the analyte. With the growing global awareness in health hazards and environmental

pollution analytical chemistry played key role to unveil it causes. Modem analytical

instrumental techniques make everything possible in the field of structure elucidation,

studies of rare and artificial radioactive elements. Although I have mention many

techniques before but chromatography, electrophoresis and ion exchange are the modem

and the most versatile techniques used for the purpose of separation The various analytical

techniques mentioned earlier are summarized in brief as:

Q Ultraviolet and visible spectroscopy: Molecular ultraviolet visible absorption

methods are the most widely used of all quantitative analysis technique in chemical

and clinical laboratories throughout the world It has find wide application for the

identification and determination of inorganic and organic species The act of

identifying material based on their colour was probably one of the earliest example

of qualitative molecular absorption spectrophotometry, even the colour intensity

can be an indicator of concentration was probably the earhest application absorption

spectroscopy. Further improvement came with use of prism and gratmg

monochromators for lambda isolation Photoelectric detectors were soon developed

and replaced by phototubes and photomultipliers.A wide range of

spectrophotometers are now available featuring ultraviolet and visible

measurements.Low straight light, small effective bandwidth, digital data acquisition

etc The ultraviolet region of this spectmm is generally considered to the range fi-om

200 to 400 run and visible region fi-om 400 to 800 nm.The basic ftinction is to use

transmittance and absorbance.

• Fluorescence and phosphorescence spectrometry: It has major role in analysis,

particularly in the determination of trace contaminants in our environment,

industries and bodies because of its high sensitivity and high specificity It has more

rigorous constraints on molecular structure that is absorption. Many dmgs has been

detected like quinine, LSD etc aslng/ml can be detected in a sample of blood

plasma or urine and carcinogens like benzopyrene can be determined

fluorometrically in air by pollution analysis.

Q Atomic spectrometry (emission and absorption): It is standard method for metal

analysis both FFS and AAS have been used for the determination of trace metal

especially in liquid samples .It is simple, inexpensive and sensitive method for

detecting common metals including alkali, alkaline and transition metals such as Fe,

Mn, Cu, H, B, C, N, P, As, O, S, Se, Te, halogens and Nobel gases. It also has wide

application in agriculture and envirormiental analysis, industrial analysis of ferrous

metals and alloys as well as glasses and ceramic material and clinical analysis of

body fluids.

a Infra red spectroscopy: It is the absorption measurement of different IR

frequencies by a sample position in the path of an IR beam.Infrared radiation

spends a section of the electromagnetic spectrum having wave number from 13000

to 10cm or lambda from 0.78-1000 micrometer IR absorption is presented in the

form of spectrum with lambda or wave number with wavelength or wave number as

the X-axis and absorption intensity or transmittance as y-axis It is used in the

identification of the functional groups in organic compounds and also identify

compounds whose spectra are generally complex and provide numerous maxima

and minima that are useful. This identification has been extended to such diverse

application as the determination of steroid hormones and pharmaceuticals other

spectroscopy provides a unique fingure print which is readily distinguished from the

absorption patterns of all other compound .By this techniques many compound like

lipids, carbohydrates, amino acids, proteins, nucleic acids, enzymes and many other

biochemical compounds.

• Raman spectroscopy: It began in the early 20* century and was named in the

honour of its discoverer, C.V. Raman who along with K.S. Krishnan published the

first paper on this technique .In 1928 C.V. Raman discovered that the visible

wavelength of a small fraction of the radiation scattered by certain molecules differs

from that of the incident beam and the shifts in wavelength depends upon the

chemical structure of the molecules responsible for scattering .He was awarded

1931 Noble Prize in physics for the discovery and systematic exploration of the

phenomenon(34-38) .It has also been applied to structural studies of both organic,

inorganic and biological systems (39-43). It is superior for studying inorganic

systems. Daimay et al. have pubhshed a comprehensive treatment of Raman

fimctioiuil group frequencies (44).

a X-ray Spectroscopy : It is based upon the measurement of emission, absorption,

scattering, fluorescence and dififtaction of electronu^netic radiation such

measurement provide much usefiil information about the composition and structure

of matter. X-rays are short wavelength electromagnetic radiation produced by the

deceleration of high energy electron or by electronic transition of electron in the

inner orbital of atom .The wavelength range of X-ray is from about 0.1 A*' to 100 A"

.Only three laboratories in the united states haves fecilities to produce X-rays from

synchrotron radiation (45) It is used for both qualitative and quantitative

determination of elemental composition of a variety of samples for solids and

liquids .It is used in determination of sulphur in diesel friel, quality control and

consumer support for catalyst manufacture, for process control of cement

production and forensic application in evaluating evidence .

a N.M.R Spectroscopy: N.M.R is based on the measurement of absorption of

electromagnetic radiation in the radio frequency region of roughly 4-900 mega hertz

.The basis of spectroscopy was proposed by W. Pauli in 1924 who suggested that

certain atomic nuclei should have the properties of spin and magnetic moment

which on exposure to magnetic field lead to splitting of there energy levels In 1946

Bloch at Stenford and Purcell at Harvard worked independently on the postulates

and verified experimentally.(46-50).They demonstrated that nuclei absorb

electromagnetic radiation in strong magnetic field As a consequence of energy

level sphtting that is induced by magnetic field They share Noble Prize for their

work .It has been used to identification and structure elucidation of organic, metal

organic and biochemical's however this method is often usefiil for quantitative

determination of absorbing species, ftinctional groups such as phenol, alcohols.

aldehydes, carboxylic acids, olefins, acetylenes, amines, and amides.(51-53). It is used to

determine the total concentration of a given NMR active nucleus in a sample. The great

utility of NMR is the identification of pure substance of unknown structures. (54). Mollis

has described a method for determination of aspirin, phenacitin, and caffeine, is

commercial analgesic preparation. NMR is one of the most powerfiil tools available to the

chemist and biochemist for elucidating structure of both organic and inorganic species. (55-

58).

There are number of electrochemical techniques used in analytical chemistry for the

detection of elements qualitatively and quantitatively like flame photometry is only used to

detect elements of group I and n of Periodic table i.e. Na, K, Mg, Ca, Sr, Ba etc (59)

Turbimitry and colomitry, Nephelometiy are the technique used on gaseous liquid or even

transparent solid samples, inorganic analysis, for the determination of sulphates as Baso4,

carbonate, chloride and many more application.(60). It is used in organic analysis of

turbidity in sugar products and for clarity of citrus juices .For biochemical analysis to

measure the amount of growth of bacteria in a nutrient medium, amino acid, vitamins and

antibiotics It is also used for the determination of protein yeast glycogen, beta, gamma

globulin in blood serum and plasma. (61). Flourimetry and Phosphorimetry are used in the

determination of uranium in salts and for vitamins in the food samples like meat, cereal etc.

Organic analysis for the determination of benzopyrene in the nanogram range. Polaromitry

is the quantitative method of analysis for the determination of plant control in the

pharmaceutical industry. Conductometric titrations. High fi-equency titrations used in both

qualitative and quantitative determination with the help of calibration curve prepared from

known solutions. Under the heading of electrochemical analysis other method are

Polarography and Amperometric titrations etc. (62,63). Polarography is that method in

which the measurement of potential difference as current flows in solution and the result

obtained can thus be interpretated in terms of nature and concentration of mass substances.

The method can be used for the determination of several

organic functional groups and also used for the estimation of cations, anions in the presence

of interfering ions in pharmaceuticals analgesics, antipyretics etc.

Amperometric titration is the basis of polarography. It is considered to be more accurate

than the polarographic method because it is less dependent upon the characteristics of the

capillary and supporting electrolyte. The utihty of NMR is the study of dynamic systems

and in conformational analysis (64). The development of powerful superconducting

magnets and the introduction of the pulsed fourier transform(ft) technique vastly increased

the sensitivity and resolving power of the method (65). Two-D techniques were discovered

rapidly to provide the chemist with the ability to map nuclear connectivity's.

Voltammetry and polarography: -

These are the techniques, which involves information about the analyte derived from the

measurement of current as a function of applied potential obtained under conditions that

encourage polarization of the indicator or working electrode. Historically the field of

voltametry developed from the discovery of polarography by Czechoslovakian chemist

Jarsolav Herovasky in the early 1920s(66). The application of voltammetric methods to the

qualitative and quantitative determination of a host of inorganic and organic species.

Besides all these techniques i.e. Spectroscopies, Electro analytical techniques

and miscellaneous technique involve long and complicated operations.Chromatography,

Electrophorosis and Ion exchange technique have been emerged as a very important

analytical tool. They have played a very significant role of identification, separation and

quantitative determination of ionic and non-ionic species and purification of chemical

compounds.

CHROMATOGRAPHY: -

It is relatively a new technique which was invented by (67) Mikhail Tswett a Russian

botanist in 1906.He applied this technique for the separation of coloured substances mto

individual components since then it has gone tremendous modification so that various types

of chromatography are in use to separate almost any given mixture, whether colored or

colorless into its constituents and to test the purity of these constituents. The 1952 Nobel

Prize that was awarded to A.J.P Martin and R.L.M Synge for their discoveries in the field

attests the tremendous impact of these methods on science.(68). In chromatography a

mixture is applied in a narrow zone to a stationary porous sorbent and components are

caused to undergo differential migration by the flow rate of mobile phase, a liquid or gas

phase.

It can be classified as:

CHROMATOGRAPHY

COLUMN

Gas Liquid

4.iquid-Liquid

— Liquid-solid

— Ion-exchange

_Size-exculsion

-Affinity

-Chiral

~ Gas-solid

jGas-liquid

PLANAR

Supercritical

Electro Thin

chromatography

Paper

Column Chromatofiraphy: M.S Tswett the Russian polish botanist, in 1906 used

adsorption columns in his work of plant pigments. (69). The base for column

chromatography is adsorption chromatography. In this mixture to be separated is dissolved

in a suitable solvent and allowed to pass through a tube containing the adsorbent, the

component having greater adsorbing power is adsorbed in the upper part of column. The

next component is adsorbed in the lower portion of column and as a result the material are

partially separated and adsorbed. For analytical purpose column chromatography finds

11

limited applications. It is mainly used in the separation of geometrical isomers,

diastereoisomers, and separation of tautomeric mixtures.

A brief explanation of all Column Chromatographic methods is summarized as

under:

Gas Chromatography:

The concept of gas-liquid chromatography was first described in 1941 by Martin and Synge

who were also responsible for the liquid partition chromatography. (70), Three 503 later m

1955 the first commercial apparatus for gas liquid chromatography appeared on the market

since that time the growth in application is phenomenal (71). By 1985 it was estimated that

as many as 200,000 gas chromatographs were in use throughout the world (72-74). It is a

type of technique for separation of thermally stable and volatile organic and inorganic

compounds The two types of gas chromatography are GLC and GSC In Gas liquid

chromatography the separation of components of a chemical mixture between a moving

mobile gas phase and a stationary liquid phase held on a solid support. While Gas Solid

Chromatography uses a solid adsorbent as a stationary phase.

The availability of versatility of hyphenated technique fiirther enhance the usefulness of

gas chromatography It provides the scientist with a powerfiil method for separating

complex mbrtures It is much less usefiil, however as a tool for identifying separated

components, usually the separated components is more easily identified by spectroscopies

through several chromatographs.

James and Martin in their first publication on gas chromatography employed an automatic

titration cell as a detector for volatile fetty acids and later it was applied to mixtures of

aeromatic and aliphatic amines.

The technique and application of gas chromatography are almost completely independent

of other chromatographic techniques .Gas chromatography can provide more information

in a directly, supplanted mass spectrometry to somewhat lesser extent, IR for online

analysis of multi component streams It was originally developed in 1941 by A.J.P. Martin,

R.L.M Synge (awarded Noble Prize in 1952 for the discovery of gas chromatography) as a

purely analytical method A.J.P. Martin and A.T. James (1952) were the first to separate

fatty acids by this technique.

12

Gas-liquid chromatograpiiy lias main advantages:

1) The technique has strong separating power and even complex mixture can be resolved

into constituents.

2) The sensitivity of the method is quite high It is a micro method and a few mg of

the sample is sufficient for analysis.

3) It has good precision and accuracy.

4) The analysis is completed in short time.

5) The cost of instruments is relatively low and its life is generally long.

6) This technique is suitable for routine analysis. Even it has wide use in forensic

laboratory.

7) Identification of drug samples.

Liquid chromatograpiiy: It refers to the chromatographic technique in which the mobile

phase is liquid such as liquid solid sorption chromatography and column chromatography.

This has been extensively used for the fractionation and separation of organic mixtures

both for preparative and analytical purposes. Liquid-liquid distribution is also called

partition chromatography .It is used for nonionic, polar compounds of low to moderate

molecular wt.

Typical application of partition chromatograpiiy mentioned in table (2).

Field Typical mixtures

> Pharmaceuticals > Biochemical > Food products

> Industrial chemicals

> Pollutants > Forensic chemistry

> Clinical medicine

Antibiotics, sedatives, steroids, analgesics. Amino acid, proteins, carbohydrates, lipids. Artificial sweeteners, antioxidants, aflatoxins,

additives. Condensed aromatics, surfactants, propellants,

dyes. Pesticides, hebicides, phenols, PCBs. Drugs, poisons, blood alcohol, narcotics

Bile acids, drug metabolites, urine extracts, estrogens

13

Liquid-solid or adsorption chromatography is classic form of liquid chromatography first

introduced by Tswette at the beginning of 20* century (75).

The advancement in liquid chromatography first come to the attention in 1969 but had a

begirming in the late 1950's with the introduction of automated amino acid analysis by

Speckman Stein and Moore (76,77). Modem liquid chromatography has been called high

performance liquid chromatography or HPLC .It has become the standard technique for

column separation because of its increased speed, resolution, sensitivity and its

convenience for quantitative analysis. There is no diflFerence in the basic mechanism, only

the apparatus employed and the practice of the technique are different The versatility of

the technique has lead to publication of numerous books and review articles dealing with

its theory, instrumentation, and apphcation. HPLC is not limited by sample volatility and

thermal stability .It is a technique that is able to separate macromolecules, ionic species,

labile natural products, polymeric material and high molecular weight polyfimctional

groups. This technique is useful in separation of drugs and their metabolites, in the analysis

of normal constituents of cells as steroids nucleotides. Many pharmaceuticals used this

technique for the separation of vitamin D and its metabolites. With the development of

HPLC it has become possible to solve almost all the problems of separation in short time.

There are many hyphenated technique, which has been applied in the identification of

peaks in complex biologicals mixtures.

Ion Exchange chromatography: This was the first of the various liquid chromatography

methods to be used under modem LC condition. Automated high resolution ion exchange

chromatography dates from the early 1960s with introduction of the routine aminoacid

analysis.(78). The technique was later extended to the analysis of literally hundreds of

different compounds in physiological fluid. It has also proved to be extensively useful for

the separation of inorganic ions specially rare earths, multicomponents of alloys, heavy

metals in industrial effluent and fission products of radioactive elements.

Size Exculsion : It is also called gel permeation gel filtration chromatography h is

particularly applicable to high molecular weight species such as nucleic acid proteins

etc.(79).It has been applied to solve widely different separation problems This is

14

commonly divided into two techniques of gel filtration chromatography using aqueous

solvents and gel permeation chromatography using organic solvents for application to

water soluble and organic samples respectively It is also used for fi^ctionating and

obtaining the molecular weight distribution of cellulose and its derivatives

Supercritical-fluid chromatography: During the past two decades, two new techniques

have been developed and play an important role in the analysis of environmental,

biomedical and in food samples .It is a hybrid of gas and liquid chromatography that

combines some of the best features of each and. These methods are:

• Supercritical-fluid chromatography

• Supercritical-fluid extraction

This technique is important for industrial processes that is based upon the high solubility of

organic species.(80). Supercritical carbon dioxide has been employed for extracting

caffeine from coffee beans to give decaffeinated coffee and for extracting nicotine from

cigarette tobacco .The importance of this chromatography is that its supercritical fluids are

inexpensive iimocuous and non-toxic substances that can be allowed to evaporate into the

atmosphere with no harmful environmental effect (8 l).It is of importance because it

permits the separation and determination of a group of compounds that are not

conveniently handled by gas or liquid chromatography .These compounds are either non­

volatile or thermally labile and which contain no functional group.(82-85).

2) PLANAR CHROMATOGRAPHY;

a) Electro chromatography: It is a hybrid of capillary electrophoresis and HPLC that

offers some of the best features of technique. Since 1980 two types of electro

chromatography developed called packed column and micellar electro kinetic capillary.

The capillary electro chromatography has advantage over the parent technique like HPLC

and electrophoresis. The capillary electrophoretic methods are not applicable to the

separation of uncharged solutes. In 1984, however, Terabe and collaborators described a

modification of the method that gives the separation of low molecular weight aromatic

phenols and nitro compounds.

15

b) T.L.C (Thinlayer chromatography): The technique was first introduced by a Izmailov

and Schreiber (86) inl938, they used this technique for separating plant extracts on 2mm

thick and firm adhesive layer of alumina set on glass plates, lot of attempts were made by

different scientist using adsorption chromatography. The discovery of TLC is usually

described to Iszmailer and Schreiber who utilized layers of alumina on glass plates for the

separation of extracts of medicinal plates. However the first publication with the title "Thin

Layer Chromatography" appeared in 1956 by stahl.

Kirchener (87) in 1950 was first to do this for the identification of terpenes. TLC is often

called as drop, strip, and spread layer, surfece chromatography. TLC is used for the various

purposes like

a) Identification of substance

b) Separation of two or more component of mixture

c) Determination of amount of particular species present in a sample

d) Preconcentration or preparation of sample or

e) Study of relative polarity of any solid sample or liquid-liquid phase.

This technique is similar in some regards to both column chromatography and paper

chromatography (88). TLC has been successfiiUy used for characterizing and isolating the

organic compounds Acids. The cis-trans acids can be separated on the layers of silica gel

'G' with benzene methanol acetic acid (89).

From the historical point of view, countable achievements made in the history of TLC are

enlisted in Table (3).

Table-3 Important years in the history of TLC:

Year Chromatographers and their work

193 8 Izamaliov and schraiber made unbound alumina layer and applied

16

the drops of solvent to the plate to separate certain medicinal

compounds.The procedure was called "drop chromatography".

1949 Meinhard and Hall,using drop chromatography;separated Fe and

Zn^^ on microscopic slides coated with alumina (adsorbent)

and starch (binder).

1951 Kirchner etal used plates to support the layer,developed the plates by

ascending technique and coined the term chromastrip for his layers.

1958 E.Stahl introduced the term chromatography and standardized the

materials .procedures and nomenclature involved in TLC.

1965 Przybylowicz etal discussed the importance of precoated TLC plates.

1976 Zlatiks and Kaiser modernized TLC in the form of a highly instrumental

technique and named as HPLC.

1979 Tyihak etal applied extra pressure, force for the movement of solvent

introduced over pressurized layer chromatography (OPLC).

c) Paper Chromatography: It is a type of partition chromatography in which the

substances are distributed between two liquids i.e. stationary phase and moving phase.

Originally it was used to separate mixtures of organic substances such as dyes and amino

acids only but now this is perfect to separate cations & anions of inorganic substances. The

movement of substances relative to the solvent is expressed in terms of RF value i.e.

migration parameters.

RF = Distance traveled bv the solute from the original line

Distance traveled by the solvent from the original line.

Where RF is a retention fector.

17

Classification of column chromatographic method is mentioned under table no.4

General

Classification

Specific

Method

Stationary

Phase

Type of

Equilibrium

Liquid Liquid-Liquid Liquid adsorbed

Chromatography or partition on a solid

Partition between

immiscible liquid

Liquid bonded Organic species Partition between

Phase

Liquid-solid or

Adsorption

Ion exchange

Size exclusion

Gas Gas-liquid

Chromatography

(Mobile phase:gas)

Gas-bonded

Phase

Gas-solid

Supercritical- Fluid

Chromatography

bonded to a solid

surfece

Solid

Ion exchange

Resin

Liquid in

Interstices of a

Polymeric solid

Liquid adsorbed

on a solid

Organic species

bonded to a

Solid surface

Solid

Organic species

bonded to a solid

surface

liquid & bonded sui

Adsorption

Ion exchange

Partition/Sieving

Partition between

gas &liquid

Partition between

liquid & bonded

surfece

Adsorption

Partition between

Supercriticalfluid

& bonded surface.

18

Electrophoresis: (90) It is a separation method based on the differential rate of migration

of charged species in a buffer solution across which has been applied a DC electric field. A

Swedish scientist Ame Tiselius in the 1930, s for the study of serum proteins, developed

this technique; he was awarded the Nobel Prize in 1948 for his excellent work (91).

Electrophoresis has been applied to a variety of difficuh analytical separations problems,

inorganic anions and cations, amino acid, catecholamines, drugs, vitamins, carbohydrates,

peptides, proteins.nucleicacid etc. For many years electrophoresis has been the powerhouse

method of preparation of proteins, enzymes, hormones, antibodies and RNA, DNA.

Electrophoresis separations are performed in two ways one is slab electrophoresis and the

other capillary electrophoresis. The advance in electrophoresis leads to the development of

capillary electrophoresis, which gives the acceptance for the rapid and eflficient separation

of especially biopolymers and in the field of DNA and Pharmaceuticals analysis. Capillary

electrophoresis is more advantageous than slab electrophoresis. C.E. separations are

performed in several ways called modes. These include isoelectric focusing

isotechphoresis, capillary zone electrophoresis. (92). CZE is one in which the buffer

composition is constant throughout the region of separation .The applied field causes the

each of the different ionic components to migrate according to own mobility and to

separate it to zones that may be completely resolved or partially overlapped. Completely

resolved zones have regions of buffer between them .It helps in the separation of small ions

in the range of nanolitre, whereas microlitre or large sample are usually needed for other

types of small ion analysis example alkaline earth metals, alkali's, lanthanides. This

method is also used for the separation of molecular species like small synthetic herbicides,

pesticides, pharmaceuticals that are ions and can be derivatized to yield ions, proteins,

amino acids and carbohydrates all been separated in minimum time by CBZ.(93) Capillary

gel electrophoresis is performed in porous gel polymer matrix, the pores of which contain a

buffer mixture in which the separation is carried out(94). Most common gel used is a

polyacrylamide and polyethylenglycol It is a promising technique for the separation of

nucleic acid as well as biopolymers. Capillary electrophoresis has been assuming a

increasingly important role in forensic DNA identification of blood siemns, saliva and hair.

19

The chronological listing of some key contributors table no. 5 outlines the brief

history of chromatography

Year Contributors Contributions

1848

1850-1900

1903

1935

Way and Thompson

Range and Schoenbeen

Tsweet

Adams and Homles

Recognized the phenomenon c exchange in soil.

Studied capillary analysis

Invented chromatography with

use of pure solvent to develop

the chromatogram used mild

adsorbent to resolve chloroplast

pigments.

Synthesized synthetic organic

ion exchange resin.

1938 Reichrtein hitroduced the liquid or flowing

chromatogram thus extending

application of chromatography

to colourless substances.

1939 Brown For the first time he used circular

paper chromatography.

1940-1943 Tiselius Devised frontal analysis method

displacement development.

1941

1944

Martin and Synge

Consden, Gordon and

Martin

Introduced column partition

chromatography.

First developed paper partition

chromatography

20

1948 Lederer and Linstad Applied paper chromatography

to inorganic compounds.

1951 Kirchner

1952

1956

1959

James and Martin

Sober and Peterson

Porath and Flodin

Introduced thin layer

chromatography.

Developed gas chromatography

Prepared ion exchange cellulose.

Introduced cross-linked dextran

for molecular sieving.

1964 Moore Gel permeation chromatography

as practical method.

Other than spectroscopic method, electroanalytical and chromatographic techniques there

are thermal methods which have been widely accepted in analytical chemistry. Till we have

studied the method based on single thermal analysis which do not provide the complete

information of a system. However additional information may be provided by the thermal

methods if required they are DTA, TGA, DTG, DSC, DRS, and TMA etc

Thermal method we mean those techniques in which some physical parameter is measured

as a function of temperature. (95-98). TGA is a technique where by the mass of a sample m

controlled atmosphere is recorded continuously as a function of temperature and time. The

techniques provide a great help in establishing the structure and thermal stability of

compounds. A plot is made between weight and furnace temperature, called thermo gram

or a thermal decomposition curve (99). It has wide application area especially on analytical

chemistry:

> Evaluation of gravimetric precipitates.

> Testing of purity of samples etc.

21

> Organic compounds, oxides, mixtures, glass technology and building materials.

DTA: Differential thermal analysis It is oldest method first used by Lectatelier(100) in

1887 and later by Robert Austin in 1899.1t is more versatile and yields data of a

considerably more fundamental nature. It is a technique in which the difference in

temperature between a substance and a reference material is measured as a function of

temperature while the substance and reference material are subjected to a controlled

temperature program. It is plotted against sample temperature to give a differential thermo

gram .It has wide application areas like qualitative analysis, quality control of large number

of substances like cement, glass soil catalyst textiles explosives resins etc It is used for the

characterization of gypsum and corcidolit .It is used in inorganic chemistry to study the

thermal stability of a large number of inorganic compounds and complexes like mixed

clays, lubricating greases, perchlorates, acetates and oxalates .Purity of mixtures

investigation of solid phase reaction kinetic and polymerization.(101-102).The first

inorganic material to be analyzed by DTA were clays and microcrystalline materials .With

the advancement in DTA technology the study of phase transition in organic and polymeric

material began in 1950 .DTA is a sensitive tool for the detection and measurement of

Gibbsite .A method has been devised by J. Cice 1964 for measuring isothermal crystalline

rates of high polymer .A method has been developed by W. Lodding and L. Hammell to

investigate the reaction and phase changes during thermal analysis of metal hydroxides M

J. Jonish and D.R Bailey (1960) have investigated the system phinanthrene and anthracene

by zone melting and DTA .Charles maziers in 1964 has designed a DTA apparatus which

permits micro and semi micro determination .E.S. Freeman and V.D. Hogon in 1964 have

investigated the thermal behavior of several inorganic fluorides and silicofluorides at 1

atmosphere pressure over the temperature range of 25"C to SOO C.

DSC (Differential Scanning Calorimetry) :It is a method where by the energy necessary

to establish a 0 temperature difference between a substance and a reference material is

recorded as a function of temperature or time when both are heated or cooled at a

predetermined rate (103). It has found many applications in industry and indetermination

22

purity of a compound. There are number of miscellaneous thermal methods which is used

for studying heterogeneous decomposition reaction.

Ion Exchange Chromatography and Ion Exchange Technique:

Though the history of this technique is of ancient time but it is of recent origm. This

technique came into existence in late 1960s with introduction of routine amino acid

analysis. It is a process of nature occurring throughout the ages from even the dawn of

human civilization. (104). Aristotle stated that "the seawater loses a part of the salt content

when pass out through certain types of soil". The ion exchange properties of wood

cellulose is the first case when the bitter water converted to drinking water and that of

silicate is the second case the role for the improvement of the taste of water. Among all

chromatographic technique ion exchange chromatography is considered to be most

versatile method. It is particularly helpful in the separation of ions of similar properties.

The separation is based on the difference between the sorbabilities of ionic species. It has

an excellent tool for rapid and accurate determination of constituents of all biological

substances and fission products. It has been used for the separation of inorganic ion

especially rare earths.The work on Ion pair chromatography as a new HPLC owes much

work by Schill et al the current popularity of IPC arises mainly fi-om the limitations of ion

exchange chromatography and tiie difficulty in handling certain samples by other liquid,

chromatographic method. It permits the rapid selective separation of ionizable drugs,

biogenic amines, dyestufifs, and proteins, complex ions even isotopes. Industrial

applications of ion exchange have been limited in the metal finishing, water softening,

extraction of metals from ores and transition metals.

On the basis of ion exchange chromatography the phenomenon of ion exchange was first

reported by two British agriculture chemist Thompson(105) & Way(l 06)1850. who proved

that soil can remove potassium ammonium salts from water with release of Ca salts

Ca- Soil + NH4SO4 ^ NH4-S0U +CaS04.

After the work of G^s ifi 1913 natural and synthetic inorganic cation exchanger were used

for softenmg hard water.Moderfi ion exchange resin were first used in 1935 by Adams and

Holmes. The fiindamental work on chromatographic separation by use of ion exchange

23

resin is derived from studies carried out in U.S.A. Ion exchange can be defined as a

reversible reaction in which free mobile ions of a solid called ion exchanger are exchanged

fr)r different ion of similar charge present in the solution .It is based on exchange equillibna

between ions in solution and ions of like sign on the surfece of an essentially insoluble,

high molecular weight solid. Ion exchange resin are porous synthetic organic polymers

containing charged groups which are capable of holding positive or negative ions they are

usually insoluble in water and have open permeable molecular structure so that ions and

solvent molecules can move freely in and out.

First synthetic granular ion exchange resin Phenol formaldehyde

condensation resin was described by B.A Adams, E.L Holmes (109) in 1935 although

naturally occurring zeolites had been in use for purification of water since 19* century.The

phenol formaldehyde resin was weak exchanger due to the presence of ionized phenolic

group this lead to recognition in introducing more efficient ionic group on a polymer

backbone.In 1950 Styrene were made on commercial scale. There are large number of new

synthetic ion exchange resins have been introduced which has new chemical structure and

specific selectivity.

Some common properties of ion exchange of value in analysis are as follows-

1 They are almost insoluble in water and other solvent.

2 Complex in nature infect they are polymeric, polar.

3 Reversibility and no permanent change are the key properties.

4 Physicochemical properties are determined by the cross-linking. Swelling is limited

cross-linking.

5 Fouling of resin can be an important factor to avoid this the ion exchange resm are used

ION EXCHANGE: This Phenomenon was successfully applied for commercial purposes

by Harm. (110) He removed Na and K ions from sugar beat juice by using a naturally

occurring cation exchange silicates minerals. The ion exchanger made possible the

isolation of Promethium (111) and the analytical and technical separation of rare earths.

Classical method of analysis involves long and complicated separations but using ion

exchangers separation can be carried out with a smaller amount within a shorter time and

the compound can be determined using rapid titrimetric method. Ion exchangers are

24

insoluble solid materials, which cany exchangeable cations or anions. These ions can be

exchanged for a stoichiometrically equivalent amount of other ions of the same sign when

the ion exchanger is in the contact with an electrolyte solution. There are two types of ion

exchangers called

Cation exchanger.

Anion exciianger. Carriers of exchangeable cations are called cation exchangers and

carriers of anion exchanger are called anion exchangers. Certain materials are capable of

exchanging both cation and anion and term as amphoteric ion exchangers.

CATION EXCHANGERS: It is an crosslinked polymer containing fimctional groups as

phenolic, sulphonic, carboxylic, and phosphoric groups.The strong acid cation exchangers

have sulphonic acid group SO3H which are strong acids. The weak acid cation exchangers

have carboxylic acid groups CO2H, which are only partially ionized. Other cation

exchangers with different properties and acid strength have been developed like PO3,

HP02, AsCh.SeOa. There are many of ion exchange resin, which contain two or more

different types of fixed ionic groups called bifunctional or poly functional. When a cation

exchanger is kept in solution and equivalent amount of cations of the salt get attached to

the resin. This reaction may be represented as:

HnR + nNa ^ Najl +nH

Resin Soln Resin Sol

The reaction with calcium ion is represented as: -

NaR+2Ca ^ Ca2R + Na

Resin Sol Resin Sol

Some commercially available cation exchangers are given in table (6).

Trade name Functional groups Framework material

• Amberlite -SO3H Syrenedivmylbenzene

• Dowex

• Zeolite

-SO3H

-SO3H

Copolymer

Copolymer

25

• Amberlite 200

• SE Cellulose

• AmberlitelECSO

• CM

-SO3H

-C2H4SO3H

-COOH

-CH2COOH

Copolymer

Cellulose

Methacrylicacid/divinyl

Cellulose, Fibrous Anion Exchangers:

Resin anion exchangers are cross-linked polymers containing basic groups such as

amino group, quaternary amino group as integral parts of the resin and equivalent

amount of such as CI, S04, OH" ions etc. These ions are mobile and exchangeable

which can be represented as:

nRzNR*^ + OIT ^ (RzNR3)n + nOH"

nRZNRsOH+AN •>(RzNH3)nA+ nOIT

Where R represents organic groups, usually methyl.

Some commercially available anion exchangers are given below in table (6).

Trade name Framework material Functional groups

1 AmberiitIRA400 Styrenedivinylbenzene -CH2N^(CH3)3

2 Zeolite FFIP Copolymers (homo) -CH2>r(CH3)3

3 Amberlite IRA400

4 Zeolite N-IP

Styrenedivinyl

Isoporpus

-CH2-N"- CH2-CH2 I I

CH3 CH3

CH2 - N - CH2-CH2

CH3 CH3

5 QAE Sephadex A-25 Dextran -N-

26

There are number of diflFerent natural and synthetic product which show ion exchange

properties. In 1934 two new types of material were invented. The first was a sulphonated

coal developed in Germany and the second was a Phenol formaldehyde resin invented by

Adams And Holmes at the national physical laboratories in England. The simultaneously

development of relatively stable synthetic cation and anion exchanger made the

demineralization process of water possible this has since become the most used and

important application of ion exchange. Adams and Holmes found considerable industrial

application. It was so rapid progress that the first industrial scale demineralization plant in

this world was built in Great Britain in 1937.

The feats of ion exchange resin had been more spectacular than in the field of ion exchange

chromatography. Ion exchange technique have been used for the isolation of trace amount

of actinides and in the study of protein hydrosilates. Industrial applications of ion exchange

have been limited in the metal fi^om ores and separations of rare earth metals. Later Gans

(114) gave large-scale application of cation exchanger on inorganic material such as

sodium alumnosilicate which was synthesized by him. Gallium and germanium analogues

have been prepared e.g.; gallogermanate and aluminogermanate (115), Silicates of

zirconium (116), titanium (117), Bismuth (118), iron (119), Zinc (120), have also been

prepared. Gans synthetic cation exchanger replaced the naturally occurring exchanger such

as Zeolites. Ion exchange is a process by which ions held on porous, essentially msoluble

solid are exchanged for ions in solution that is brought into contact with the solid. The ion

exchange properties of clay and Zeolites have been recognized and studied. Synthetic ion

exchanged resin were first produced in 1935 and have found wide application in water

softening deionization solution purification and ion separation.

Zeolites are crystalline aluminosilicates and known as molecular sieves and have ability to

remove ions (selectivity) fi-om solutions The recent application of Zeolites selectively

involves the use of synthetic ultra mine to separate the ftancium isotopes Fr ^ ' fi^om its

actinium parents and other activities. (121) The first attempt to synthesise ion exchangers

resembling with zeolites were made more then SOyrs.The first cation exchangers were

prepared by ftision of mixture of soda and potash, feldspar and kaolin. From last 20-30 yrs

27

the inorganic ion exchangers have formally occupied their own position .the term inorganic

ion exchangers is used in the title of monograph by Amphlett (122) which give rise to rapid

development to these materials and their applications because of property resistant to heat

and radiation it is receiving much attention. They can be used for high temperature

separation of ionic components in radioactive waste as solid electrolytes and catalysts.

Selected zeolites with their composition and exchange capacities: table (7).

Zeolites

1. Analyte

Composition

Na(AlSi206).H20

Exchange capacity

(Meq/gm)

4.50

2. Chabazite (Ca, NaXSi2A106).6H20 4.00

3. Harmotome (K, Ba)(Si5Al20i4). 5H2O

4. Henlandite Ca(Al2Si206).H20 3.30

5. Natrolite Na2(Si3Al20,6).2H20 5.30

6. Edingtonite Ba(Al2Si30i6).4H20 3.30

7. Strlbite NaCoi/2(AlSi308). 2H20

Kraus et al (123,124) and Amphlett(125,126), in this field have done the excellent work

.The work upto 1970 has been condenced by Peparek and Vesely(127), Clearfield(128-

130), Alberty(131,132), and Walton(133,134) have also worked on different aspects of

synthetic inorganic exchanger. Quershi and co-workers have prepared a large no. of such

material and studied their ion exchange behavior during last 20 years(135-141) .Ion

exchange resins can be obtained fi-om various companies with their trade name .

28

Some ion exchangers with trade name and manufacturers are listed in table no. (8)

Trade Name Manufacturer

1) Amberlite Rohn and Hass Co., Philadelphia.

2) Dowex Dow chemicals Co., Midland.

3) Nalcite National aluminate corporation, Chicago, JR.

4) Permutit Permutit Co., New York.

5) Resex, Resanex Jos, Crossfield & Sons Ltd., Washington Lances,

England

6) Wofetit VEB, FARBENFABRDC Wolfen, K.R. Bitterfield,

Germany East

7) Zeolits United water softeners, London, England.

In organic ion exchanger material classified on the basis of chemical characteristics of the

ion exchanging species appears still useftill as proposed by Vesely et al. (142).

> Hydrous oxide.

> Acidic salt of multivalent metals

> Salts of hetropoly acids

> Insoluble ferrocyanides,

> Synthetic aluminosilicates.

Qureshi and Qureshi (143) have presented a review on the application of ion exchange

methods in radiochemical separations, which is needed in activation analysis, waste

processing, fuel processing or reactor coolent water purifications.

Aluminosilicates can be divided into three main categories or groups:

> Amorphous substances

> Two dimensional layered aluminosilicates

> Three-dimensional structure zeolites.

Inorganic ion exchanger have too many application in analytical chemistry .

29

1. Water pollution control, removal of air pollutant.

2. Removal of interfering ion.

3. Recovery of precious metal.

4. Preparation of dionized water.

5. Water softening.

6. Determination of total salt.

7. Separation of metal ions.

8. Separation of organic and biologically important substances.

9. Cone of trace constituents.

10. Specific spot test

11. Location of end point in titration.

12. Gas chromatography, electrophoresis separation.

13. Preparations of ion selective electrode.

14. Preparation ofion exchange fuel cell.

In 1931 KuUgre (144) observed that sulphide cellulose work as an ion exchangers for

the determination of Cu. In 1935 Adams & holmes (145) found ion exchange properties

in crushed phonograph.The interesting led to the synthesis of organic ion exchange

resin which have much better properties and investigator developed ion exchange

resin. After world war second these resin were developed and improved by companies

U.K England and also Farben industries in Germany .Nearly all current industrial and

laboratories application of ionexchange are based on these resins. At the same time the

synthesis of organic resin made it possible to vary the properties of ion exchanger in a

synthetic manner .A large number ofion exchanger we synthesized by polymerization

methods

Therefore synthetic organic ion exchanger can be prepared by condensation of phenol

(Resorcinol, hydroquinone. Para and meta phenol sulphonic acid etc) with

formaldehyde or other aldehyde in the presence of acid or base as catalyst

Polmerisation of Styrene and divinylbenzene.

30

CH=CH2 CH^CHj

Styrene CH=CH2

Divinyl Benzene

-CH — CHj—CH—CH2—CH—CH2

H2SO4

-CH—CH,—CH—CH2—CH—CHj-

Copolynnerisation of Slyrene and divinyl benzene(Cross linked polystyrene)

^SOgH

CH2 CH — CHj-

SO3H SO3H

-CH CH2 CH CHj CH — CH2

SO3H

Polystyrene Cation exchange resin

Figure-1

The synthesis of ion exchange resin must yield 3-D cross-linked matrix of hydrocarbon

chains carrying fixed ionic groups.

Polycondensation of Para substituted phenol with formaldehyde yield linear polymer.

OH OH OH

HCHO CH

R

Para-substituted phenol

R R

Linear polymer Figure-2

31

OH OH

HCHO

Figure-3

It is important to note that the product should be made under identical and degree of

condensation should be identical The degree of cross linking of the product can be

controlled to some extent by choosing proper base material .A common disadvantage of

condensation type of ion exchange resin is that they also contain phenolic hydroxyl group

besides the strongly acidic or weakly basic groups.

The polymerization type products are superior to condensation type to ion exchange resin.

The polymerization product are more uniform and there production is more controllable

The first polymerization type of ion exchange was produced by D.A. Lelio (146) The

polymeric ion exchangers which are commercially available are based mainly on cross

linked polystyrene (147). In essence one part is a large permeable insoluble, non-dififiisible

ion containing mainly of the basic resin structure its counter part is an ion of equal but

opposite charge .The ion group attached to the skeleton of the resin determines the nature

of the exchange characteristics. Cation exchangers are produced when acidic functional

groups are introduced into the resin structure. Anion exchanger are produced when basic

functional group are introduced .A representative type of strong cation exchange resin is

Dowex 50 WXB manufactured by Dow chemical company.

Styrene divinyl benzene cation exchange resin are classified as follows:

Strong acidic:

RSO3H, Dowex 50, IR 12 Amberlite

Weak Acidic:

-RCOOH, Wofetite, Amberlite 45-C.

Similarly Anion exchange resin can be classified as: -

32

Strong base type: Dowex-lx8, Dowex 21k, Amberlite IRA-400

And weak base type: Dowex-3, Amberlite IR 48, Wulfenite-m,

By wearing the divinely benzene content the degree of cross linking can be adjusted in a

simple reproducible manner .The monomer DVB content is used indicate the degree of

cross linking It refers to mole % of DVB in the polymerization mixture Resin with low

DVB content swell strongly and are soft gelatinous Resin with very high DVB content can

swell hardly at all and more stable A number of other similar ion exchangers are known in

which styrene has been replaced by one of its derivative such as methyl styrene, vinyl

anisole(148) or phenylacetylene .There are some specific types of cation exchangers in

concern with counter ion species to others .Many attempt have been made to develop resin

which prefer one particular counter ion species The first attempt to put this idea into

practice was made by Skogseid (149) .He synthesized a resin containing groups with a

configurations similar to that of dipicrylamine.

NO,

Figure-4

Chelating agents can also be used into styrene type resin by polycondensation with phenol

and aldehyde .Ion exchangers of this type are stable than the condensation.

An ion exchange was developed almost exclusively with synthetic organic resins The first

anion exchange resin were prepared from aromatic amines such as m-Phenylenediamine by

condensation with formaldehyde (150).

33

NH,

HXO3

-NH—CH

NH —CH,

Meta-phenylene diamine

Figure-5

There are many anion exchanger which can be prepared from cross Hnked polymers of

alicyclic vinyl compounds carrying amino group or cyano group However, anion

exchangers with many different kinds of ionic groups have been made According to

Lindsey and D'Amico (151), the resin are insoluble in all common solvents including

aliphatic and aromatic hydrocarbons .Organic ion exchangers also suffers from certain

limitations, they are unstable in aqueous system at high temperature and in the presence of

ionizing radiation this led to a revide interest in inorganic exchangers .The properties of ion

exchange facilitates the selection of the correct ion exchanger for solution of a particular

problem The more important properties are color, density, mechanical strength , particle

size, capacity, selectivity, amount of cross linking, swelling, porosity, surface area and

chemical resistance.

Amphoteric resin: Materials which contain both acidic and basic groups are called

amphoteric. (152). Various ion exchangers of this type have been prepared, but applications

have been found for only a few several amphoteric resin with strong acid groups. However

most of the product were not cross linked .The most resent and most important amphoteric

resin are so called snake "Cage polyelectrolytes" prepared by converting a strong base

anion exchangers (Dowex) to the acrylate form and then polymerizing the acryl ate anions

in the resin .The difference between the snake cage polyacrolytes from other amphoteric

resin is the ionic groups of the polywinter ions are not attached to the matrix .It is not

34

necessary for the resin to contain counter ion just to fix ionic groups and to make balance

between them.

In most applications ion exchangers are used as coherent gels in the form of small particles,

but in ion exchange electro dialysis requires thin membrane with large surfece areas and

excellent mechanical stabilities, in such cases the ordinary coherent ion exchange gels are

unsatisfectory.

The first ion exchange membrane was introduced in late 1950's and 60's as an efficient and

economic technique for the desahnation of blackish water (JR. Wilson 1980) .The

principle of the process has been known for more than 100 years (W.Oswald 1950). The

first ion exchange membrane were produced by Juda and Marac(153).The term ion

exchange "membrane" is comprised of solid films, disks, ribbons, tubes, plugs etc .In short

we can say any material that can be used as a separating wall between two solutions .

The ion exchange membrane is of six types:

1) Ion exchange membrane.

2) Homogeneous membrane.

3) Heterogeneous membrane.

4) Interpolymer membrane

5) Graft copolymer membrane.

6) Impregnated membrane.

The first basic studies related to ions selective membranes in 1925 were given by L.

Michaelis et.al with homogeneous weak acid colodium membrane. Later polystyrene cross

linked with divinyl benzene become more and more the basis of ion exchange membranes

(F.Helflferich 1962). Electrodylasis (154-158) is rapidly became a relevant mdustrial

process for demineralising and concentrating electrolyte solutions.

Ion exchange membrane have been prepared by various method. Homogeneous

membranes; are coherent gels they can be reinforced by incorporating supportmg wide

mesh plastic tissues, only few ion exchangers can be prepared in the form of such

membrane. Heterogeneous membranes are prepared by incorporating colloidal ion

exchanger particles into on inter binders. Interpolymer membranes are prepared by

35

evaporation of solution containing a linear polyelectrolyte and a linear inter polymer. Graft

copolymer membrane; are prepared by impregnating plastic films with monomer such as

styrene, grafting these monomer fixed ionic group. Ion exchanger can also be prepared by

made by impregnating colloidan films with polyelectrolyte.

Ion exchange membranes are characterized in a quantitative manner by their capacity

called ion exchange capacity, \^ich is most fundamental characterization of ion exchange

material. For a strong ion exchanger the capacity can be readily be determined by direct

titration. Various types of capacities can express in different manner. Nfajority of the

synthetic inorganic ion exchanger and therefore direct titration is not reliable. Inthis case

ion exchange capacity is determined by replacement of H^ ion fix)m the exchanger phase by

the counter ion of a neutral solution and equilibrium ion exchange capacity is determined

by PH titrations.

The uptake of metal ions in preference to other by an ion exchanger is called selectivity.

Selectivity depends upon the charge on the metal ions the ionic radii of metal ion; the

formation of insoluble substances with the exchanger and on complex formation .The

selectivity reveals possibility for the separation of different metal ions fi-om one another.

In recent years the nature ion exchange resins are being modified but incorporating them

with certain chelating agents? These modified resins show a definite selectivity towards

certain ions or groups of ions. Thus the chelating ion exchangers are useful in removal of

trace metals and toxic elements from industrial wastewater. These chelating resins prepared

by immobilization of chelating agents on various supports.

A no. of research have been done with different dye loaded with resin for separation of

metal ions, aromatic complexing agents with sulphonic acid group is usefiil treated with

exchange resin .The selectivity of these modified resins depends upon the nature of

fiinctional group of the ligand .Various studies have been done which are given below m

table (9).

36

11

12

13

14

Dowex-1

Ambeilite IRA-400

Amberiite IRA-400

Amberiite IRA-120

Amberiite IRA-120

Exchanger

Strongly basic anion exchanger.

Strongly basic anion exchanger

Strongly basic anion exchanger

Strongly basic anion exchanger

7-iodo-8-hydroxy quinoHneS-sulphonic acid (IHQS)

Congo-red (sodium diphenyl napthayl amine sulphonate).

Alizarin red's

Crystal violet

Toluidine blue

Hg^ ' Cr ^ Zr ^

Hg^ Al ^ Fe^^

Hg^^ Al ^ Fe^^

Ag

Pb^ -Mn^"-Cu^* Fe'"-Cr'-Pb'-Ni'"-Zn'^-Cr^^ Fe'^-Mn'^-Cu^, Ca'^-Cd^-Zn^-Pb'^-Cu'^ Hg^^-Cd", Zr^^Cd'\ Hg^^-Pb^,Cr^-Mn'^ Hg^^-Zn',Cr^-N,' Zr'*-U'\Cr'-Al^' Fe^"-Al^\Hg^^-Pb^^ Fe'^e'"'Hg'^-Zn' Fe ' -Co ' A]^-Mg'" Fe'"-Zn'^''Al'^-Ca ^ Fe^-Cu'^ Fe^"-Zn^"'Fe^ Mn^^ Fe^^Co^^Al^-Co'^ Al'^-Zn'^Al^ - Pb'^ Al' -Hg^^Zn^^-Ni2+

Co '^Zn^Hg^-Zr ^

Ca'^-Zr'Mh^--Zr^^ Th^"-Ba'*,Mn' Zr^\ Cd2^-Zr^,Zn^-Ag; La - Ag ,Zn' -

There are many other factors responsible in the ion exchange techniques like swelling,

selectivity, ion exchange equlibria, ion exchange capacity, ion exclusion, sorption of solute,

ligand exchange.

38

Ion exchangers, both inorganic and organic are able to sorbs solvents in which they are

placed. While taking up solvents, the ion exchanger usually expands or swells in water and

polar solvents, but only to a limited degree. Resins and other gels swell when taking up the

solvents .So from here we can say that solvent plays an important metal role on the

adsorption behavior of metal ions on ion exchangers .The ion exchanger behavior of almost

all metal ions on aqueous mineral acids of different concentration have been studied

extensively. Solvents other than mineral acids have also been used as eluent example

formic acid, citric acid, oxalic acid, tartaric acid, perchloric acid and many other common

eluent are used for column chromatography.

Elution of metal ions is usually enhanced because of complex forming agent

has studied been in the separation of As, Mn, Zn, Ni & Cu.from one another. (159)

According to Somuelsons (160) and cowoilcers these complex forming organic acid and

sometime absorb on a strong basic anion exchanger and such an exchanger can be treated

as cation exchanger and they can be successfully used for selectivity separations.

Ion exchange can be used not only for replacing one ion by another but also

for complete removal of electrolyte from solutions (deionization, demineralization

Deionization can be carried out as a two stages process (160-164), the solution first passed

trough a cation exchange bed in H* form and then through a anion exchanged bed in OH"

form cation are removed in the first bed then the solution becomes more acidic The

accumulation of HT ions in the solution discourages the process (165,166) and in this way

the cation ,anion are excluded. Ion exclusion is a elegant method for separating strong

electrolyte from weak electrolyte and non electrolyte (167,168). No actual ion exchanger

occurs, the ion exchanger acts as merely as a sorbent. It can also be used for separating

electrolytes from one another, provided that they differ sufficiently in their degree of

dissociation or their ionic valences. The basic principle of ion exclusion is same as that of

chromatography i.e. on a non-ionic species. The separation is effected by the difference in

sorption strength of the solute.

Ion exchange technology is perhaps the best means for the removal of the toxic species in

natural water and effluent from industries.

39

Various toxic chemicals used in industry affect the living organism. Table (10) listed below

showing toxic elements, which causes chronical effects to human beings.

TABLE: 10

Toxic trace elements in natural water and wastewater

Elements

Arsenic

Cadmium

Chromium

Copper

Flourine

Lead

Mercury

Zinc .

Manganese

Sources

Miningproduct,pesticides,ch«nical waste.

Industrial discharge mining waste metal plating,water pipes.

Metal plating,tanning found as Cr (IV) in water.

Metal plating Industrial and domestic wastes mining,mineral leaching.

Natural geological sources,industrial wastes,water additive.

Industry ,mining,plumbing,coal gasoline.

Mining industrial wastes,pestcides.

Industrial waste metal plating,plumbing.

Mining industrial waste,acid mine damage.

Effects and Significance

Toxic ,Carcinogenic.

Causes high blood pressure,Kidney damage destruction of testicular tissue and RBC.

Ulceration and perforation of nasal system and carcinogen.

Toxic to plants algae high concentration in water causes death.

Present tooth decay at 1 mg/1 causes mottled teeth and bone damage at about 5mg/l.

Toxic, anaemia,kidney,disease nervousdisoder,wild life destroyed.

Highly toxic,mercury compounds are more toxic than elements.

Toxic to plants at higher level.

Toxic to plants at higher level

40

Ion exchange technology is perhaps the best means for the removal and determination of

the toxic species in natural water effluent from industries and environment too. An

understanding of the nature of the environment and of human interaction with it is a

necessary prerequisite to control environment pollution effectively (169). According to

International register potentially chemicals of the United Nations Environment

Programme.There are 4 millions known chemicals in the world today and another 30,000

new compounds are added every year .These substances effect the environment and many

of these chemicals have toxic effects on human beings.Envionment sanitations defined by

WHO as the control of all those fectors in mans physical environment which may exercise

a harmful effect on his physical development ,health and survival. Human interact with

their environment, sometimes adversely impacting the environment and sometimes being

adversely affected by pollutant in the environment Many toxic chemicals and other types

of industrial discharge, industrial effluent in lakes, oceans, rivers which without any

treatment causes water pollution and this all because of industries. There are number of

objectionable components of industrial waste water, their effect on the environment like

biooxidisable. Primary toxicants As, Cn, Cr, Cd, F, Hg, Pb, Zn, acid, alkalies, disinfectants,

H2O2CI2 ionic forms Fe, Ca, Mg, Mn, CI, and many other various analytical methods are

being applied to monitor the extent of pollution. First the recognition of pollutants,

sampling and their estimation are carried to evaluate the level of contaminants present Ion

exchange has resolved the most difficult problem in chemical analysis i.e. separation of

components having similar properties Ion exchange can separate the micro (Igm quantity)

as well as the macro (less than Igm quantity) The removal of Hg, Pb using the ion

exchanger discussed by (170), Koertus (171) Powlosky (172) et al have used the ion

exchange technique for the purification of waste water from the manufacture of nitrogen

compound .Zn is removed from pickling liquor by metal separating ion exchange process

in which the ZnCb is sorbed and eluted with water and converted to zinc sulphate by liquid

ion exchange method For the removal of Hg Caiman (173 ) has reviewed the process of

ion exchange .Ambrus (174) describes the control of pollution for low level pollutants in

water such as Pb, Cu, Ni, Cd, Zn using ion exchange method Ion exchange method

currently employed to the determination of Cd, Zn, Cu, Be, Co, Mn, Mo .V, U, and Th in

natural water including drinking water, river water, sea water has been successftilly

41

achieved The technique is based on ion exchange enrichment of the metals as their anionic

complexes .Selective ion exchangers Lewatte(175,176) 1019,1034 and found ideal for the

immobiUzation of heavy metal ion in soil (ZT02^^ CU^^ JPb ^ ) Ion exchange resm has

been used for the isolation of selenium (V)(177) PPB level of aluminum (178 ) and pre-

concentration of cobalt, Ur and sea water (179-184).

Ion exchange have been used with success in food industries also .The ion

processing of wine is commonly practiced by large manufacture in U.S.A It was worth

recoding that the use of strong acid cation exchanger resins in the H^ form and one is Na

form may produce a wine, removing calcium, copper and undesirable metals (185).

In recent years ion exchange method has wide application in every field

of pure and applied sciences like biochemistry, medicine, material science, agriculture

science etc. There are number of examples.

1) Ion exchange treatment of sea water (186-188).

2) In environmental analysis (189) and distillation of water (190).

3) Removal of heavy metals from river water (191) determination of Ca^ and

Mg* ( 192) CI2 and N2 determination in water (193) for the production of water used

in pharmaceutical purpose (194). Treatment of waste water containing Hg^^ (195)

for separation heavy by chelating resin .In separation perconcentration of Cr(VI)

from Cr([IIX196), for the chromatography of biopolymer (197). Separation amino

acid (198) and phenol compound (199). In clinical and pharmaceutical process

(200) and extraction of Uranium (201).

There are various methods for analysis of trace metal ions: -

1) Ion exchange in impregnated papers.

2) Ion exchange resin beads.

The resin loaded papers suffer from the problem of unequal distribution of metal ions

within the paper membrane subjected low capacity and very long equilibrium So this

method does not have much advantage Ion exchange beads are used further.

Aromaric complexing agents (202-204) containing sulphonic acid groups have already

shown analytical competence and are particulariy useful for the separation of metal ions or

ion exchange resin (205-206 ).These compounds display a high affinity for anion

exchangers and as a consequence of their structure when retained on the exchange resm

42

transformed into a selective exchanger .The selectivity of the species depends upon the

character of the functional group of the ligand incorporated with the resin .Resins modified

with sulphuric acid group have been studied .Recently Whetall (207) reported the

immobilization of an 8-hydroxyquinoline chelate on controlled pore glass .Hercules (208)

reported the use of an immobilized lithiocarbamate for trace analysis .In this connection

Brajter (209) recommended exchange method with highly selective resin .The chelating

resins prepared by immobilization of chelating agent on various support (210) .A very

efficient system is provided by immobilization of the sulphonic acid derivative of an

aromatic complexing agent on an anion exchange resin (211).

Recently there are number of research papers pubhshed every year in the

advancement of ion exchange technology which are as foUows: - table (10)

• Selective separation and recovery of heavy metal ions using water-soluble N-

benzoylthiourea modified PAMAM polymers (212).

• Novel ion exchange material for the separation of Y fi"om Sr^ including

Clinoptilolilite, Potassium titanosilictae pharmacosiderate, sodium

titanosilicate and sodium nanoatitanate. (213).

• Recent advancement in ion exchange technology specifically the development

of glass fibers coated with ion exchange resin are described. These are used for

the removal of lead mercury and arsenate ions, fibers were also synthesized and

tested for selective removal of monovalent, divalent ions specifically nitrate

over sulphate. (214).

• Sorptive properties of Shungite, organic acids are sorbed substantially better

than the sorption of aromatic acids by shungite i.e. selective (215).

• Ion exchange process for the production of glucose (216).

• Synthesis of new organic compounds by ion exchange reaction. New limonite

type compound LiNbOs, LiSbOs, AgSbO? and AgBiOs were synthesized for

the first time by the ion exchange resins (217).

• Synthesis of new chelating ion exchange resin developed from guar and study

of its exchange behavior (218).

• New ion exchanger process for brine purification have been developed The

PDF (precipitator dust purification), BDS (brine desulphurization) process

43

removes the impurities. While another a novel brine softening process is

utilized to remove Ca and Mg hardness from brine used for regeneration of

brackish water softeners (219).

• Volume 13, 351125X synthesis and development of selective ion exchange

resins for the removal of toxic metal ions from water in the environment. (220)

• Volume 7708d application of some complexing ion exchanger for Cu recovery

from natural water, wastewater .The rational use of water is one of the urgent

environmental control problems. These problems can be solved by the

treatment of sewage; removal of different nonferrous heavy metal ions

wastewater is of great importance. Besides the selective complexing ion

exchanger are of interest because of their good sorption properties The

following carboxylic resins were studied, the cation exchanger KB-2T, KB-4

and amphoteric ion exchanger ANKB35, AMF-2T and AMF-2.5.

(Manufacturer=TOKEM COMPANY-Kemerovo Russia) (221).

• Apparatus for regeneration of used ion exchange resins (222).

• First difficult problems of chemistry like separation of the components of a

mixture having similar properties, thus this separation method is in position to

identify and removing toxic elements present in like fluorine and Nitrobenzene

from urine. Ion exchanger separate the micro < Img as well as macro >lmg

quantities (223).

44

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56

CHAPTER-2

'^Studies of ion exchange materials and tlieir analytical

applications''.

Introduction

In recent years the nature of ion exchange resin are being modified by incorporating them

with the certain chelating agents. These modified resin often show a definite selectivity

towards certain ion or groups of ions. These chelating resins prepared by immobilization of

chelating agents on various supports. The studies have been done for loaded resins for

separation. Aromatic complexing agents with sulphonic acid group when treated with

exchange resin have been found useftil for separation of metal ions. The selectivity of these

modified resins depends upon the nature of the fiindamental group of the ligand.

Ion exchange operations are carried out in columns. A solution is passed through a bed of

ion exchanger beads where its composition is changed by ion exchange or sorption. The

composition of effluent and its changed with time depends upon the properties of ion

exchanger (ionic form, capacity, degree of cross-linking etc). Ion exchange is often used

for removing a certain ion from a solution or for replacing it by another ion. For Examples-

removal of phosphate ions, which interfere with standard quantitative inorganic analysis

(I).

For quantitative estimation the replacement of alkali metal ions by H*, w^ich is readily

titrated (2-5). Industrial application of this kind is water softening, metal recovery from

waste treatment of plating solutions (6-8).

Ion exchange materials occur in definite ion form it form, Na', CI" and NO3 etc Its size is

quoted in nm, size and their volume depends on the medium exchangers with chelate

forming groups are known as chelate ion exchangers. The utility of these modified resins

has prompted us to start a search for a new chelate forming resm bead on the same idea and

to check its selectivity towards the metal ions. The potential of chelating ion exchanger

resins for the separation and pre-concentration of metal has been firmly established (9-13).

These chelate forming groups are usually prepared by incorporation of complexing groups

on the ion exchange resin. The resin beads adsorb metal ion and give the characteristic

color of the complex. It is possible to detect even traces because of small surface area of

beads. Griesbach and Hieses (14) describes the preparation of a chelating resin by chemical

reaction and studied about fifteen adsorbent. Example-; Dowex 1x8 containing adsorbed

58

sulphonated azo dyes (15) have been found useful to separate copper and nickel

Azothiopyrene disulphonic acid (16) has been incorporated on to an anion exchange resin

and the product has been used for the uptake of Hg^, Cu ^ and Cd ^ from aqueous solution

Similar use of pyrogalol sulphonic acid (17) enabled the separation and enrichment of Mo

and Fe^ . The incorporation of thiol (18) fiinctional group resulting in chelating resm with

high selectivity towards heavy metal ions. Nabi et al synthesized a variety of chelate

forming resin by incorporating complexing agents such as Bromophenol (19), EBT (20),

Congo red (21), Alizarin red (22), Crystal violet blue (23,) and Toludine. (24).

Metal ions can be selected for separation on the basis of distribution coefficient (K<i). In

feet metal ions can be separated from each other if there is a significant difference in Kd

values.

Kd = Amount of ion (A) present in exchanger phase per em of resin

Amount of ion (A) present in solution phase per gm of resin

The general use of Kd is made in elution technique in separation. The rate at which ions

move in ion exchange column is proportional to their distribution coefficient. It is also

possible to separate a trace quantity of a metal from a macro amount of another metal ion.

The resin sorbed with different chelating agents may show marked selectivity towards a

particular metal ion. It is for this reason effort have been made to develop new chelate form

of exchange resin and to find their specificity for the detection, determination and

separation of metal ions as well as anions

The present work was undertaken as an effort to develop the new modified ion exchanger

resin using different chelating agents. The strong acid anion exchanger resin Amberlite

IR400 (CI") has been modified by adsorption of cresol red. The analytical application of the

material has been explored.

59

Experimental

"Studies of ion exchange materials and their analytical applications".

Apparatus-:

A Genesysis spectronic 20 U V visible spectrometer.Elico Ll-IOT digital pH meter.

Electronic balance and electronic shaker incubator with a stainless body and an oven

were used.

Test solutions-:

O.IM solution of NaOH, 2M and O.IM solution of HCl, O.IM, 0.2M and IM solution of

CHsCOONa and 0.0IM solution of EDTA were prepared in demineralized water.

Reagents-:

Amberlite IR-400 (CI") resin (mesh size 16-45, 8% by wt) in the protonated form was

obtained from Merck (India) Ltd. (Germany) and the di sodium salt of EDTA from S.D

fines chemicals (India). Ethanolic solution (1%) of l-(l-hydroxy-2-naptholazo)-5nitro-2-

napthol-4-sulphuric acid sodium salt (Erichrome Black-T) C2oHi2N3Na07S. Molecular

weight 461.38 and l-(2-pyridylazol) 2-napthol (PAN), C15H11N3O, molecular weight

249.27 (gm/mole) and an aqueous solution of (1%) of 0-Cresol sulphonapthalein-3.

Cresol-Red Dye S.D fines chemicals (India). PH range 1.0-10

Molecular weight 382-404, Melting Point 250-290

Formula C: 1H1 yNaOsS

Structure: Cresol Red

H,C,. o II

II n

- H j

Figure- 6

60

Table 11

Cation Studied-: A list of the metal ions investigated and their salts.

Cation Salt used (O.IM aqueous solution)

1. Ca 2+

2. Mg-2+

3. Ba 2+

4. Sr' ,2+

5. Hg 2+

6. Pb

7. Cd

8. Zn

2+

2+

2+

9. Mn 2+

10. Cu 2+

11. Co 2+

12. Ni

13. Fe

14. Al

15. Sn

2+

3+

3+

4+

3+ 16. Ag

M.Zx'

18. Th"' 44 19. Ce

20. La^"

Calcium Nitrate

Magnisium Nitrate

Barium Nitrate

Stroncium Nitrate

Mercurous Nitrate

Lead Nitrate

Cadmium Nitrate

Zinc Nitrate

Manganese Chloride

Copper Nitrate

Cobalt Nitrate

Nickel Nitrate

FerrousNitrate

AluminiumNitrate

TinNitrate

Silver Nitrate

Zirconium Oxychforide

Thorium Nitrate

Cesiumsulphat

LanthnamNitrate

Solvent System-:

The solvent system used for the study of the distribution coefficient (Kd) of the metal ions

is given in the table. (12), all are of AR grade.

61

Table-; 12

Solvent System Notation

1) O.lMAcetonitrile

2) O.IMDMSO

3) O.IM Methanol

4) 0.1M Formamide

5) O.IM Acetone

6) O.IM Acetic acid

7) O.IM Formic acid

8) O.IM Boric acid

9) O.IM Succinic acid

10) O.IM Tartaric acid

11) O.IM Phenol

12)0.1MTCA

13) O.OIM Nitric acid

14) 0. IM Disodium tetra Borate

15) O.IM Water

S,

S2

S3

S4

Ss

S6

ST

Ss

S9

Sio

Sii

Sl2

S,3

Sl4

S,5

Eluent used-:

0.1 M Methanol

0.01 M Nitric acid

Preparation of modified resin-:

The modified cresol-red resin was prepared by treating Amberlite IR-400 (CI") resin with

aqueous solution of Cresol-red for 24 hours at pH 1.0. The resin was washed several times

with demineralised water to remove access reagent from the supernatant liquid. The sorbed

resin was finally dried in an oven at 60°C to remove moisture.

Study of adsorption Isotherm-:

62

Effect of concentration of the reagent-:

To study the sorption of Cresol-red under a state conditions resin in the protonated form

(0.3g) was equilibrated with Cresol-red (30ml) of diflferent concentration (74-198nmol/l) in a

temperature controlled electronic shaker incubator at constant pH 1.0 for 2 hours The

equilibrium concentration of the reagent was then determined spectrometrically at

435run.The adsorption isotherm shown in figure (7).

Effect of pH-:

To determine the eflfect of pH on the sorption of Cresol-red, 0.3g of resin was shaken

continuously with 30ml of 198fimole/litre Cresol-red solution for two hours. The pH of

solutions were adjusted by adding an appropriate acid, base or buffer of the desired pH The

equilibriiun concentration of the reagent in the supernatant liquid was determined

spectrophotometrically in the pH range 1.0 to pH 8.0 at wavelength 435m.hi the region PH

(9.0 tol 0) the absorbance were recorded at 575 nm figure (8).

Effect of Time-:

The equilibrium time for sorption of Cresol-red on the resin was established by performing a

series of adsorption experiments at constant pH 1.0. A constant mass 0.3gm of Amberlite IR-

400 (Cr) was stirred with an aqueous solution of Cresol-red (30ml) for different times. The

amount of Cresol-red taken by the resin was determined by analyzing the supernatant

solution spectrophotometrically at 435nm. Figure (9).

Effect of Temperature-: The optimum temperature for adsorption of cresol red on the resm

was established by performing a series of adsorption experiment at PH 1.0. A fixed mass

0.3gm of Amberiite IRA-400 (CI) was stirred for 2 hrs with aqueous solution of cresol red

(30) ml for different temperature i.e. room temperature to 70 degree centigrade at bath. The

amount of cresol red taken up the resin was determined by analyzing the supernatant solution

spectrophotometrically at 435 wavelength (10).

Distribution coefficient (Kj) of metal ions-:

0.3g of modified resin beads were loaded with 1 Oml of 0. lOM metal ion solutions and 29ml

of the appropriate solvent in 250ml Erlenmeyer flask. The solvent systems studied are given

63

in table number (12). The mixture was shaken continuously in a shaker incubator at 25*'C for

two hours. The amount of anion in solution before and after equilibrium was determined by

EDTA titration.The mixture was shaken continuously in a shaker at 25 c for 2 hrs.The

amount of cation in the solution before and after equilibrium was determined by EDTA

titration.

In case of Mg, Ca, Ba, Sr, Pb, Hg, Zn, Mn, Cd. Titration was performed in the presence of

Erichrome black-T (EBT) and ammonia buffer at PH -10. At the Equivalence point the colour

of the solution changes from wine red to blue.

Cu, AI, Fe, Co, Ni, Sn, Ag was titrated in the presence of PAN indicator at PH 3.75 at 60 C.

The equivalence point was indicated by a colour of solution, changes fi^om red to yellow. Zr,

Th, Bi, Ce was titrated in the presence of 1.0 molar nitric acid using Xylenol orange as

indicator. Th is used with PH 2.as indicator at 80"C a change in colour of the solution from

red to lemon yellow indicates the end point .Kd values for each metal ion were calculated by

the formula-:

Kd = l-F/03gmxlOO

F/30ml

Where I =Volume of EDTA used for complete titration of the metal ion solution before

Treatment with the resin (ml).

F= Volume of EDTA used after the treatment of the metal ion solution with

the resin (ml).i.e. (amount of metal ion left in the solution after treatment

with resin).

I-F= Amount of metal ion in the resin phase (ml) The Kd value for each metal ion in

Various solvent systems have been calculated and presented in table (13-14).

Quantitative Separation of Metal ions-: The separations of metal ions were carried out by

an elution technique; 1.5 gm of modified resin was packed into a glass column of 1 feet long

and 8mm,i.d. Width with a glass wool support at the end. It was washed 2-3 times with

DMW.2.0ml of binary mixture of the metal ion to be separated was poured on the top of the

column and the solution was allowed to flow gently at the rate of 8-10 drops per minute till it

reaches just above the surfece of the r^sin The column was rinsed with DMW The elution

64

technique was carried out at a constant flow rate of 18-20 drops/mint using appropnate

eluting reagent. The eluted metal ion fractions were detemiined titnnetrically using a 0.01 M

disodiumsalt of EDTA as a titrant. Elution profile for binary separations of metal ions are

shown in figure (10-11). Selective binary separation of Bismuth, Mercury Zirconium & Tm

from other metal ion on cresol red modified amberlite IRA-400 (CI) ion exchange resin

columns are presented.

65

Result & Discussion

Ion Exchange resin with a large surfece area and a macro porous structure have been treated

with a variety of complexing agents to enhance their selectivity for the separation and

recovery of metal ions.

Cresol red, which has three aromatic rings probably responsible to interact with the resin

matrix (styrene-divinyl benzene) owing to the presence of hydroxyl group and -SOsNa group

which react selectively with metal ions. It is imperative to include that the dye cresol-red,

which contain three aromatic rings, was attached to the polystyrene skeleton by physical

adsorption and pi-pi dispersion forces arising from the aromatic nature of the resin and the

dye is responsible for this adsorption.

Before going for the detailed studies of different parameters,both Amberlite IRA-400

(Cr )and Amberlite IR-120 were tested for adsorption of various chelating agents. It was

observed that only Amberlite IR-400 adsorb cresol-red, the color of the resin bead changed

from light yellow to red .The IRA-400 resin shows that maximum sorption of cresol red

occurs at PH 1.0 when the concentration of the dye was 198/umol/l .The hydrophobic nature

of styrene divinyl benzene matrix of a Amberlite IRA-400 resin appears to be an excellent

support for the sorption of cresol red. The IRA-400 resin bead show different colures with

different PH ranging from 1 to 10 i.e.

> PH 1 to 3 orange red beads.

> PH 4 to 6 reddish brown beads

> PH 7 to 8 purple beads.

> PH 9 & 10 dark purple beads were found.

The time required to reach equilibrium for the adsorption of cresol red by the resin was

found to be 2 hrs and adsorption was constant up to PH 1.0. No fiirther adsorption occurs on

increasing the time. Therefore an equilibrium time of 2 hr was chosen to complete adsorption

throughout these experiments. The isotherm for adsorption of cresol red on the resin was

almost linear and followed langmuir adsorption isotherm It is seen from the distribution

coefficient values given in the table (13-14) that cresol red has different selectivity for metal

ions possibly because of the formation of metal complexes with different stability constants,

66

The type of solvents used was based on the Acid dissociation constant and polarity factor

which effect the ease of complexion Sorption studies of different metal ion or cations in

different solvent systems revealed many interesting features. It was found that almost all the

metal ions exhibited low Kd value in most of the solvent systems studied except Mercury and

BisAiuth which show exceptionally high value of Kd in every solvent system and made it

possible to separate them from other metal ion .The Kd values for each metal ion in various

systems has been calculated and presented in table (13-14). It is clear from the table that

Methanol is the only solvent in which the Kd valve for both Hg and Bi is zero, otherwise for

all other metal ions the value increases this will help out in the selectivity and separation .On

the basis of differences in Kd values several binary, ternary separations of metal ions were

performed by selecting appropriate eluting reagent. The quantitative separations of metal ions

perfbnned i.e. of Mn, Zn, Ni, Co, from Bi have been successfiilly achieved and of Ni, Pb,

Sn,Zn from Zr and finally Mg, Ca, Ba, Sr, Zn, Mn, from Hg. Ternary separation Bi, Mg, and

Ca. The results of separations of metal ions achieved are given in table (15-16) and elution

profiles are shown in figure (11-15).

CONCLUSION-: To check the selectivity and the reproducibility of the method. Separation

of different amounts of Hg^ has been achieved from a synthetic mixture consisting of Hg^^

and Fe^ (5.58 mg), Cu^ (6.35 mg), Al ^ (2.69 mg) and Ni^ (5.68 mg). The results on table

16 show that the method may be used for the removal of Hg^ from industrial wastes and

domestic water discharge. It can also be used as a packing material in column

chromatography and for preconcentration and for the recovery of metal ions from industrial

effluents and wastewater.

67

5.5-

5.0-

1 4.5-01

"b K _ fo 4 . 0 -o

& I 3.5-i

I 2.5-

2 0 -

Amount loa<l>d()imol x lo'x mL '|

Figure-6 Effect of cresol red concentration on the amount of dye adsorbed by Amberlite IRA-400(C1"') resin.

2.20

215

2 1 0 -

1 2 05 3 •D

I 8 2 00

I 195

1.90 I ' I ' I ' I ' I ' I • I • I ' r ' I ' r 20 40 60 80 100 120 140 160 180 200 220

Time(minutes)

Figure- 7 Effect of equilibration time on the amount of cresol red adsorbed by Amberlite IRA-400(C1"') resin.

68

2.20

o. 219

2- 2 18-o E

S e I 2.17

2 . 1 6 -

W 10

PH

Figure- 8 Effect of pH on the amount of the cresol red adsorbed by Ambedite IRA-400(Cr') resin

2.20

2.18

i 3 5 2 14-€ 8

2 1 2 -

2 10

20 30 40 —r-50 60 70

Temperature! °C)

Figure- 9 Effect of temperature on the amount of the cresol red adsorbed by Amberlite IRA-400(Cr') resin

69

0.1 M Nitric acid 0.01 M Nitric acid

I I

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170

Volume of effluent (ml)

Figure 11 (a). Separation of Mg ^ from Hg'*

Elution profile di^^ram for binary separation of Mg^,Ca^^ Si , Ba^ , Zn ' ,and Mn^ on cresol red modified amberlite IRA-400 anion exchange resin column.

Separation of-a) Mg'" b) Ca ^ c) Sr " d) Ba'^ e) Mn ^

from from from from from

Hg Hg Hg Hg Hg^

2+

,2+

2+

2+

> Elution flow rate-18-20 drops /min.

> Bed length-3cm.

> Column diameter-0.6 cm (i.d).

> Column length - 11.0cm.

> Modified Resin loaded -1.5g.

70

0.1 M Formic acid 0.01 M Nitric acid

10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170

Volume of effluent (ml)

Figure 11 (b) Separation of Ca^* from Hg *

0.1M Acetonitrile 0.01 M Nitric acid

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

Volume of effluent (ml)

Figure 11(c) Separation of Sr ^ from Hg ^

71

0.1 MFormic acid 0.01 M Nitric Acid

1 -

lU

E O >

T ' r

0 10 20 30 40 50 60 70 90 10) 110 120 130 140 150 160 170

Volume of effluent(mO

Figure 11(d) Separation of Ba * from Hg**

0.1M Acetonitr i le 0.01 M Nitric acid

o Q>

E

0 10 20 30 40 SO 60 70 80 90 100 110 120 130 140 150 160

V o l u m e of efflusnt (ml)

Figure 11 (e) separation of Mn from Hg 2+

72

0.1MDMSO 10 T4

S

J

0.01 M Nitric acid

0 10 2 0 3 0 4 0 5 0 6 0 70 80 90 100110 120130140 150 160

Volume of effluent (ml)

Figure 12 (a) separation of Mn^^ from Bi**

, ^ ^^2-^ mJ+ XT;2+, , -2+ Elution profile diagram for binary separation of Mn'^^''^J*b^^,Ni^^' and Co^^ on cresol red modified Amberlite IRA-400 anion exchange resin. Separation of-: a)Mn^ from Bi * b)Zn^* from Bi^^ c)Pb d)Ni e)Co

2+

2+

2+

fiom from from

Bi Bi Bi

3+

3+

3+

Elution flow rate-18-20 drops /min.

Bed length -3cm.

Column diameter-0.6 cm (i.d).

Column length- 11.0cm.

Modifed resin loaded-1.5gm

73

10 -9 -

f 8-< 7-^ c a 6 -UJ "^ 5 • o o 4 -E „ s 3 -1 2-

1 - 0«

^ •^r

0.1M Boric acid

Zn*"

^ w

0.01 M Nitric acid .^ . . .^ ^ w

Bi'*

(—,—,—•—• 7 ^ 9 » — , 0 10 20 30 40 50 60 70 80 90 100 110 120 1KJ140 150160 170 180

Vohime of dfluent (ml)

2+i Figure 12 (b) Separation of Zn' from Bi .3+

.1 M Formamide 0.1 M methanol - • M •

E

Q 1X1 *•— o at E _2 o >

Bl

10 20 30 40 50 60 70 80 90 100 110 120 130 140

Volume of effluent (ml)

Figure 12 (c) Separation of Pb^ from Bi »•>+

74

0.1 M Boric acid 0.01 M Nitric acid

0 10 20 30 40 50 S3 70 80 a) 100 110 120 130 140 150 160 170

Volume of efnuent(ml)

Figurel2 (d) separation of Ni ^* from Bi**

0.1 M Boric acid 0.01 M Nilric acid

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190

Volume of efFluent (mi)

Figure 12 (e) separation of Co from Bi .M

IS

10 -,

9 -

8 -

f 7-? 6-a Ul »- 5 -o E * • 3 O 3 -

2 -

1 -

0 *

• • ^

Sn*^

1 —

0.1 M Formamide h r

^•» <

"^

/

/ .

0.01 M Nitric acid

fir

\ v_^ -1 1 1 T—^ ^ f .

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

Volume of effluent (ml)

Figurel3 (a) separation of Sn* from Ni "

g

I I

10 -]

9 •

8 -

7 •

6 •

5 -

4 •

3 •

2 •

1 -

0 <

Q.I M Formamide ^

Pb'*

1 1 1 1 T " ^

h w

0.01 M Nitric acid

^

Sn*"

' — 1 — 1 1 1 1 1 — - ^

P

'—t—, 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140150 160 170

Volume of effluent (ml)

Figure 13 (b) separation of Pb*^ from Sn 4+

76

10

9

8

7

6

5

4

3

2

1

0

0.1 M Boric acid

Zn

0.01 M Nitric acid

Zr*

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

Volume of Effliieiiit(ml)

Figurel4 -: separation of Zn * from Zr ^

6 l ^ 0.1 Boric acid 0.01 Nitric acid

/' X^ .x\>

iv* .\»' '^^Jt^^iL

It^ *" V

' ^ • . ^ > ^ Univet*'^-'

"I r I 1 1 1 I r

0 30 60 90 120 150 180 210 240 270 300

Volume of effluent (ml)

Figure-15 Separation of Mg ' Ca from Bi

77

Table-: 13 Distribution coefficients of metal ions between solvent systems I based on Polarity factor and Amberlite IRA- 400 resin treated with cresol red.

Metal ions

Mg^^

C^

s/' Ba^^

H g ^

Pb^^

Mn^"

Zn^^

Cd^^

Cu^

M'^

Fe^

Ni^^

Co^"

Sn^^

Ag^^

ZT''

Th"*

Ce'"

Bi^^

SI 00

2.7

13.8

19.8

155

24.5

00

1.7

00

0.9

0.9

0.9

9.8

9.3

50.0

16.6

0.8

15.3

8.3

377,5

Distribution coefficient for solvrat systems

S2 2.2

0.8

0.9

1.8

216.6

0.9

0.9

1.7

5.4

8.0

17.1

10.4

1.9

9.1

4.1

-

68

-

17.3

200

S3 18.3

5.4

4.1

00

00

8.3

8.8

9.2

00

1.8

1.0

6.0

2.9

3.0

100

-

18.0

7.6

-

00

S4 1.8

1.7

10.4

21.8

56.5

00

0.9

14.4

8.5

7.8

70

56.3

00

4.7

116.6

-

18.0

7.6

-

00

S5 1.6

13.5

00

1.8

233.3

2.7

00

1.9

-

42.5

11.4

17.2

36.6

33.3

-

1.9

22.2

-

358.3

126.6

S6 11.7

16.8

15.0

9.1

135.5

5.5

0.9

00

6.0

0.9

00

3.7

0.9

7.5

83.3

-

122

27.7

188.8

33.3

S7 22.4

00

24.4

0.9

157

23.5

1.9

7.6

3.8

9.0

15.3

0.9

0.9

26.2

22.2

-

70

60

0.9

122.2

S1 -0.1M Acetonitrile. S3-0.1M Acetone

S2-0 IM DMSO Sfi-O.lMAcieticacid.

S3-O.IM Methanol S7-0.1 M Formic acid

S4-0.1M Formamide.

78

Table-: 14 Distribution coefficients of metal ions between solvent systems II based on Acid dissociation constant and Amberiite IRA 400 resin treated with cresol red.

Metal ion

M g -

Ca^'

Sr ^

Ba^"

H g "

Pb^

Mn^"

Zn^^

Cd^"

Cu^^

Al^"

Fe^"

Ni^"

Co^"

Sn^"

Ag^^

Zr*"

Th''"

Ce'"

Bi'"

Distribution coefficient for solvent systems

SI

11.5

0.9

16.4

22.3

24.4

20.0

2.9

00

1.8

1.9

9.1

21.4

1.9

3.8

-

11.1

425

193

500

621

S2

00

2.0

1.9

2.9

17.7

1.8

00

00

25.5

3.8

12.5

26.5

13.5

85

-

-

23.8

00

7.1

76.6

S3

15.2

5.1

12.3

26.9

300

9.8

2.8

-

00

6.0

53.0

177.7

00

209.0

-

-

193.3

422

-

70

S4

25.2

15.0

10.3

6.3

183.3

3.7

7.5

7.5

8.1

5.8

11

1

00

3.9

37.5

50

"*

-

90.4

177.7

S5

0.8

00

4.7

46.4

256.6

19.1

37.3

4.6

00

11.1

14.2

3.2

40

43.3

11.1

-

"•

5.0

-

128.5

S6

00

17.1

3.0

17.7

1285

11.1

00

5.4

2.0

5.1

12.7

6.5

2.2

11.7

128.5

-

31.3

46.6

1.1

151.2

S7

6.0

5.7

1.9

0.9

129.1

5.7

2.8

12.7

7.8

5.2

46.6

16.6

4.9

3.8

33.3

420.8

-

76.6

25.7

135.5

S8

2.1

-

-

-

17.6

2.3

16.4

-

-

546.6

-

00

00

-

-

-

-

-

-

-

Si 0.1 M Boric acid

52 0.1 M Succinic acid

53 0.1 M Tartaric acid

S4O.IM Phenol

S5O.IMTCA

SeO.OI MNitncacid

S7 0.1 M Water

Sg 0.1 Disodiumtetraborate

79

Table:lS Binary Separatioiis of Bi^, Sn* , Zr**, and Hg from other metal ions (cations)

on cresol red modified Amberlite IRA- 400 Anion exchange resin column.

Binary Mixtures

B ^

Br

Zr*" Zn ^

H g -

Hg-B a -

Hg-Zn2' H g -M n -

Amount Loaded (n»g) 20.9 20.7

20.9 5.49 20.9 6.53 20.9 5.87

20.9 5.89 11.86 5.87 11.86 20.7 9.12 6.53 20.05 2.43 20.05 4.01 20.05 13.73

20.05 8.76 20.05 6.53 20.05 5.49

Amount Recovered

(mg) 14.2 17.3

16.3 4.39 18.6 6.53 17.4 4.34

13.3 4.71 5.45 5.75 8.53 15.7 8.21 6.01 8.8 2.43 18.4 4.01 18.0 11.81

14.0 8.45 15.6 6.53 12.2 5.49

Recovery Percentage %

67.91 83.50

78.00 81.30 88.99 100.00 83.20 73.91

63.62 79.91 45.95 97.95 71.92 75.83 90.13 96.72 42.92 100.00 89.75 100.00 89.77 86.01

69.82 95.89 77.80 100.00 60.84 100.00

Volume of Elu«at (ml)

70 70

70 70 90 90 80 80

80 80 80 80 80 80 70 70 80 100 70 70 80 80

70 80 80 80 70 80

Eluent Used

0.1 MFonnamide 0.1 M Methanol

0.1 M Acetonitrile 0.01 M Nitric acid 0.1 M Boric acid 0.01 M Nitric acid 0.1 M Boric acid 0.01 M Nitric acid

0.1 M Boric acid 0.01 M Nitric acid 0.1 MFonnamide 0.01 M Nitric acid 0.1 MFonnamide 0.1 M Nitric acid 0.1 M Boric acid 0.01 M Nitric acid 0.01 M Nitric acid 0.1 M Ntric acid 0.1 M Fonnic acid 0.01 M Nitnc acid 0.1 M Fonnic acid 0.01 M Nitric acid

O.IMDMSO 0.01 M Methanol O.OIM Nitric acid 0.1 M Ntnc acid 0.01 M Nitric acid 0.1 M Ntric acid

80

2+_ Table: 16 Selective separation of Hg from (Cu =6.35nig), (Al =2.69mg),

(Fe^^=5.58nig),( Ni ^ =5.68 mg).

S.No

1

2

3

4

Metal

ion

Hg ^

Hg ^

Hg^^

Hg^*

Amount

loaded mg

20.05

40.11

60.15

80.20

Amount

Found mg

15.99

25.68

36.47

56.58

Percentage

Recovery

79.75

64.02

60.63

70.54

Eluent Used

ml

0.1m Nitric acid

0.1m Nitric acid

0.1m Nitric acid

0.1m Nitric acid

Volumeof eluent

used ml

160

160

180

200

REFERENCES

1) Samuelsons,0 "Ion Exchange in Analytical chem. P.45 117,136,196.John Wiley and Sons Inc.NewYork(l 953).

2) Schindewolf ,U Angew,chem. ,69 226 (1957).

3) Calmon c.and A.W King Bury in "Ion exchange technology".F.C Nachod and J.Schubert (eds) p-231,Academic Press Jnc Newyork (1956).

4) Kumin R and F.X .M.C Garvey in "Ion exchange technology" F.C Nachod and J.Schubert (eds) p-95 (academic press)Inc Newyork,(1956).

5) Gerster,F,Z,Electrochem 57,221,(1953)Chem IngTechnik ,26 264,(1954) in ion exchange and its apphcation p,64 society of chemical Industry London.

6) Mindler A.B in ion exchange Tech ,F.c .Nachod and J.Schubert (ed) p-235 Academic press in Newyork (1956).

7) Morrison W.S in "Ion exchange tech" F.C Nachod and J.Schubert (eds) p-321 , Academic press.Newyork (1956).

8) Swope,H.G in "Ion exchange tech" F.C.Nachod and J.Schubert eds ,p-458 Academic press ,in Newyork (1956).

9) E.Holmes,S.Ballesters and RFukai ,Talanta 26,79,(1979).

10) KBrajter.T.Chromatogr ,102,385(1974).

11 )H.J Fisher and K.H .Lieser, Freseneius Z. Analchem 335,738(1989).

12)H.Hiroshi ,Japan ,Kokai Tokkyo Koho JpApp,l55,3,(1992).

13)R.Brown and T.Edward Diss,Abstr,IntB,54,1524 (1993).

14)M.Griesbach and K.H.Liseir. ,Angew,Makro .chem.,90,368,(1980).

15)M.Peasvnto and A.Prolvino ,Talanta35,431,1988.

16)M.Nakayama and M.Chikuma and T.Talanta,Talanta 29,503,(1982).

17) J.L.Pillai and Siyasankara .analyst 114,439,(1989).

18) A.Dertani and B.Sebille,Anal chem. 53,1742 (1981).

19) S.A Nabi,A.Bano,and Usmani,J.Indiana Chem Soc 34A,33) (1995).

20) S.A Nabi,S. Usmani ,N.Rehaman and A.Bano J.Indiana Chem Soc 73A,301 (1996).

82

21)S.A Nabi,A.Gupta and A.Sikawar ,AnnaIi di Chimica 89,419,(1999).

22) S.A.Nabi ,M.A.Khan and A.Islam,Acta Chromatographica 11,130,(2001).

23) S. A.Nabi, E.Laiq and A.Islam,Acta Chromatographica 11,118,(2001).

24)S.A.Nabi and A.M.T.Khan ,Acta Chromatographica 12,29,(2002)

83


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