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
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2) Schindewolf ,U Angew,chem. ,69 226 (1957).
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6) Mindler A.B in ion exchange Tech ,F.c .Nachod and J.Schubert (ed) p-235 Academic press in Newyork (1956).
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10) KBrajter.T.Chromatogr ,102,385(1974).
11 )H.J Fisher and K.H .Lieser, Freseneius Z. Analchem 335,738(1989).
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83
