DEVELOPMENT OF ION EXCHANGE RMTERIALS AND THEIR ANALYTICAL
APPLICATIONS
ABSTRACT THESIS
SUBMITTED FOR THE AWARD OF THE DEGREE OF
Bottor of ^Iiilosiopdp IN
CHEMISTRY
BY
AM J AD M.T. KHAN
Under the Supervision of
Prof. SYED ASHFAQ IMABI
DEPARTIVIENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
AUGARH (INDIA)
2004
Abstract
The process of ion exchange is defined as exchange oi" ions oi" liJvc charges
between the solutions and generally solid, which are highly insoluble bodies.
Thompson and Way in 1850 laid the foundation of ion exchange by Base
Exchange in soil. Adam and Holms discovered in 1935 that crushed
phonograph records exhibit ion exchange properties. This led researchers to
develop synthetic ion exchange resin. Organic resins, which have been used
for long time for ion exchange column chromatography, have high
mechanical and chemical stability. However they are decomposed at elevated
temperature and in the presence of strong radiations .The typical structure of
inorganic ion exchangers frequently permits separation of metal ions on the
basis of their different size. They can also be used as ionic or molecular
sieves. Furthermore the synthesis of such ion exchangers involves simple
procedures. A cation exchange resin is a high molecular weight cross linked
polymer having sulphonic, carboxylic, phenolic groups etc as an integral part
of the resin and an equivalent amount of cations to maintain the electro
neutrality .An anion exchange resin, on the other hand is a polymer containing
an amine or quaternary ammonium groups as an integral part of the polymer
lattice and an equivalent amount of anions such as chloride, hydroxyl or
sulphate ions. The first polymerization type of organic ion exchange resin was
prepared by D. Alelio in 1945. Since then these organic ion exchangers have
been used both in laboratories and in industries for the separation and
preconcentration of metal ions, recovery of metals, removal of permanent
hardness of water, demineralization of water, concentration of electrolytes and
elucidating the mechanism of reactions.
The use of chelating resins for the removal and separation of traces of metal
ions from industrial wastes is of great interest owing to simplicity, elegance
and a wide range of variations in methodology. Moreover they often exhibit
selectivity towards certain metal ions or groups of ions. The aromatic
complexing agents containing the sulphonic acid group are particularly useful
for the separation of metal ions on an anion excliange resin. The selectivity of
these modified resins depends on the nature of the functional analytical
groups of the ligand.
Chromatography is a method of analysis in which the How of solvent or gas
promotes the separation of substances by differential migration from a narrow
initial zone in a porous sorptive medium. Michael Tswett discovered the
principle of chromatography and their wide applicability in 1906,which
applied this technique for the separation of chlorophyll pigments using finely
divided calcium carbonate as an adsorbent.
Ion exchange chromatography was the first of the various liquid
chromatographic method used under modern LC conditions. Partition
chromatography is the second major innovation in the field of
chromatography. Reversed phase paper chromatography (applicable for
substances sparingly soluble in water) in which paper is impregnated with a
hydrophobic substances and the aqueous phase becomes the moving phase
was described by Kritchersky and Tiselius.
Thin layer chromatography (TLC) is considered to be the most simple, rapid,
versatile and low cost method which is applicable to the characterization and
separation of variety of multicomponent mixtures (both ionic and non-ionic)
except those which are volatile or reactive substances .TLC was first reported
by Izmailov and Shraiber in 1938 who utilized thin layers of alumina on glass
plates for the separation of plant extracts. Attempts were made using
adsorption chromatography on impregnated filter paper and later glass fiber
paper coated with silica acid or alumina. In TLC, a large number of coating
materials such as silica gel, alumina, Kieselguhr and cellulose have been
widely used as adsorbents.
Zirconium oxide was used for the first time by Zabin and Rollins. Zirconium
phosphate was used as a medium for thin layer chromatography of cations.
Separation of noble metals on stannic phosphate layers in ammonia -
hydrochloric acid-acetone-butanol -pyridine systems are reported. Nabi et al
have reported quantitative thin layer chromatographic separation of Uranium
from other metal ions on stannic sulphosalicylate layer. Analytical
applicability of heteropoly acid salts has been a recent trend.
Chapter 2 describes the modification of Amberlite IR-120, a strong acid
cation exchange resin by the sorption of dye; toludine blue .The effect of
time, pH, concentration of reagent on the adsorption of the dye has been
carried out. The maximum uptake of toluidine blue was found to be 2.58
jimole X IOVO.4 g resin at pH 6.0 .The interaction of toluidine blue with the
ion exchange resin may be through hydrogen bonding as represented by the
following structure:
NaOsS
SOsNa
Distribution coefficients (Kd) of important metal ions have been determined
in diverse solvent systems viz 0.05M Hydrochloric acid+O.lM Ammonium
Chloride (l:lv/v), O.IM Ammonium Chloride, O.IM Citric acid, O.IM Citric
acid+O.lM Sodium Citrate (l:lv/v), O.IM Sodium Citrate, O.IM Formic acid,
O.OIM DMSO, O.OIM DMSO+ O.OIM Nitric acid (l:lv/v), O.OIM Nitric acid
and O.IM Tartaric acid .On the basis of Kd values, important binary
separations of metal ions Ca -Zr''" , Cu -Bi ^ Zn ' -Bi"'*, Zn^'-Ag^, La ' -Ag ,
III
Cd ' -Zr'*" , Mn '*'-Zr''" , Th' ' -Ba ' and Th' -Zr''"*' have been achieved. Ag^ ions 9-4- n 1
has been selectively separated from a synthetic mixture containing Ca , Ba ,
Sr " , Pb^ , Cd " and Zn " . The analytical importance of this modified resin has
been explored in the separation of Zn " , Mg^ , Mn"' and Cu^^ contents of a
pharmaceutical preparation (Zincovit, a multivitamin capsule).
Chapter 3 gives an account of two new inorganic ion exchangers, Stannic
Selenoiodate and Stannic Selenosilicate synthesized under identical
conditions; their thermal and chemical stabilities have been examined. The
ion exchange capacities of stannic selenoiodate and stannic selenosilicate for
K' was found to be 1.84 and 1.23 meq/g respectively. To establish the
structure of the materials, chemical analysis, TGA, DTA, DSC, FTIR X-ray
and SEM studies have been performed. The X-ray diffraction study suggests
semi crystalline nature of Stannic selenoiodate with an intense peak at 26-
28°29 while its scanning electron microscopy shows spherical morphology.
This also indicates the absence of impure phases. The pH titration studies
revealed monofunctional and bifunctional behavior for stannic selenosilicate
and stannic selenoiodate respectively. Distribution coefficients of the metal
ions have been studied in a number of solvent systems namely O.IM DMF,
O.lMHCl, O.lMDMF+O.lMHCl (l:3v/v), O.lMDMF+O.lMHCl (l:4v/v),
O.IMDMF+O.IMHCI (2.iv/v), O.IM Formamaide, O.IM Formamide+O.IM
HCl (l:lv/v), O.IM Formamide+O.IM HCl (l:2v/v), O.IM Formamide+O.IM
HCl (l:3v/v), O.IM Formamide+O.IM HCl (l:4v/v), O.IM Formamide+O.IM
HCl (2.iv/v). Quantitative separations of metal ions in binary mixtures, Mn -
Co ' \ Cu^^-Ni^^ Cr^"-Ni'^ Th'^-Zr''^ Pb^^-Cd^^ Ni^^Co^^ Cd^^-Ag^ Pb^^
Ag^ Cu^^-Ag^ Cd^^-Sn ""• and La^ -Zr'*'' as well as in ternary mixtures, Cd^ -
Fe^"-Sn^ Cu'"-Cr^"-Ni2\ Al^^Co'^-Zr''^ Cd^^-Co^^-Zr^^ Cd^^Co^^-Sn' "
and Cd ' -Ag' -Zr'*'*' have been achieved on Stannic selenoiodate columns.
Selective separations of Sn"*" from a synthetic mixture of Zr , Th *, Al ^,
Cr^^ Fe^", Pb^" & Cd - , Co^" from Cd^^ Mn^^ Cr^^ La^^ Zr' ^&AP"; Ni^"
from Cd^^ Pb'^ Mn^^ La'\ Cv'\ Zr' ' &Ap^ Ag" from Cd^^ ?b'\ Fe^\ Th''^
Al'^ Cr'", Zr'"&Co'" and Zr'" from Cd^", Cu'", Ni'", Mn^", Al'", Cr'", Co'" &
Ag" have been perfonned. The material also utilized in the quantitative
separation and determination of metal ions in electroplating waste sample.
In chapter 4 a new phase of inorganic ion exchanger, Stannic Arsenate has
been synthesized by mixing 0.2M solution of Stannic Chloride pentahydrate
with 0.4M Sodium Arsenate in the volume ratio 3:1 at pH 0.4. The
reproducibility of the material has been checked in terms of ion exchange
capacity and chemical composition. The ion exchange capacity for Ba " was
found to be 2.73-meq/g dry exchanger. In order to characterize the material,
Chemical and thermal stabilities, Chemical Composition, pH titrations, FTIR,
TGA, DSC and X-ray studies of the material have been performed. The X-ray
diffraction study of the material reveals a semi crystalline nature with
intermittent peaks of weak intensities. The material was utilized in the thin
layer chromatographic separations of metal ions in solvents having varying
polarity viz. acetone, acetic anhydride, ethanol, methanol, nitrobenzene,
nitromethane, acetonitrile, N, N, dimethyl formamide and formamide and also
in mixed systems; DMSO-HCl and DMSO-HNO3. On the basis of Rf,
analytically important quantitative binary and ternary separations of metal
ions have been achieved on stannic arsenate cellulose layer. The analytical
potential of this material has been exploited by separating and determining of
metal ions in glass industry waste.
Finally chapter 5 presents the synthesis of a new phase of stannic
silicomolybdate at pH 0.63 .The experimental parameters like order of mixing,
mixing volume ratio, pH, stirring time, drying temperature has been
established for the synthesis of the material. The ion exchange capacity for
Ca"*" has been improved from 0.53 to 1.73 meq/g for this newly synthesized
material. The reproducibility of the product formed has been checked. The
exchanger was characterized on the basis of chemical composition, thermal
(fechemical stability, FTIR, TGA, DSC, X-ray and SEM analysis .The
scanning electron microscopy of the material shows regular diamond shape
morphology. The presence of uniform morphology also indicates the absence
of impure phases. The X-ray diffraction study shows amorphous nature.
Distribution coefficients studies of the metal ions on this material were
performed in solvents having different acid dissociation constants namely
trichloroacetic acid, formic acid and acetic acid. The effect of dielectric
constants of solvents has also been studied by using dimethylsulfoxide; formic
acid, acetic acid& tricholroacetic acid .The effect of temperature on the
distribution coefficient has been explored. It was finally concluded that 45°C
appears to be the most favourable temperature. Important quantitative
separation of metal ions in ternary mixtures include Ni ' -Co '*'-Pb ' ,Cu " -Cr " -
?h'\Cu''--¥e''-?h'\Th'^-Z/^-Sn'\Cr''.Ki-^-¥e'\Cn''-Ki'^-Ag^ and Fe^"-
Zn " -Al " . The practical potential of stannic silicomolybdate has been •74- "JA-
explored by separatiilg Cu and Zn quantitatively in synthetic mixtures as
well as in commercially available brass sample.
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T6229
DEVELOPMENT OF ION EXCHANGE MATERIALS AND THEIR ANALYTICAL
APPLICATIONS
THESIS SUBMITTED FOR THE AWARD OF THE DEGREE OF
iEottor of $I)tIo£op()P IN
CHEMISTRY
BY
AMJAD M.T. KHAN
Under the Supervision of
Prof. SYED ASHFAQ IMABI
DEPARTMENT OF CHEMISTRY AUGARH MUSLIM UNIVERSITY
ALIGARH (INDIA)
2004
^)iyecl CTlsnfat/ jCafti M.Sc. M.Phil.. Ph.D
Professor of Chemistry
(OFF (0091-571-703515 THESIS ( (RES.) 0091-571-404014
E-mail sanabi(®rediffmail.coni DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH-202002 (INDIA)
Certificate
This is to certify that the work presented in this thesis
entitled "'Development of Ion Exchange Materials and
Their Analytical Applications" is original, carried out by
Mr. Amjad Mumtaz Tahir Khan under my supervision
and is suitable for submission for the award of Doctor of
Philosophy in Chemistry of this university.
(Prof. Syed Ashfaq Nabi)
Acknowledgement
To write am acknowledgement is indeed a very difficult task but I
will try my level best to put my feelings rightly into words. Firstly
I would like to thanks Almighty Allah in the completion of my
research work. My guide Prof. Syed Ashfaq Nabi, (Sectional
Incharge, Analytical Chemistry), Department of Chemistry,
Aligarh Muslim University, Aligarh was not only a supervisor to
me but rather acted in a parental manner especially in the hour
of crisis, distress. No words can express my feelings or gratitude
to him. I pay my humble and sincere thanks for his scholarly
attitude and advise which was provided to me throughout my
research work. I also appreciate his gesture for being very
accommodative in the time schedule of my presence in the
laboratory.
The reseai'ch facilities provided by the Chairman,
Prof. Kabir-Ud-Din, Department of Chemistry, Aligarh Muslim
University, Aligarh is highly appreciated.
I am very thankful to my senior colleague Ms. Esmat Laiq and
my juniors Ms. Sheeba Nasim Khwaja, Ms. Nuzhat Jahan
Fatima, Mr. Mu. Naushad Ghauri and Mr. Alimuddin for
providing support and cordial atmosphere in the laboratory. My
special thanks and appreciation goes to my friends
Mr. Shahnavvaz Ahmad and Mr. Mohd. Farhat for their
wholehearted cooperation and encouragement.
Last but not the least, it will be my pleasure to express my
appreciation to the staff members of Seminar library and
departmental store. Kr. Rifaquat Ali Khan, Incharge depart-
mental store has been very kind and helpful throughout my
research work.
My brothers Arshad M.T. Khan and Asjad M .T. Khan and
sister Ms. Deeba Tahirah contributed a lot with their moral
support.
Financial assistance provided by Aligarh Muslim University,
Aligarh for junior and senior research fellowships is deeply
acknowledged.
I feel obliged to pay my sincere thanks and appreciation to
Mr. Salimuddin Ahmad for providing excellent cartographic
services.
Finally, I would like to thank Mr. Modabbir Azam, M/S Global
Air Services, Aligarh for providing typesetting facility.
Mr. Farhan Tajryab did the typing work in bringing this thesis
in print form.
(Amjad Mumtaz Tahir Khan)
Contents
Page No.
Chapter 1
Introduction 1-60
Chapter 2
Sorption Studies of Metal Ions and Selective 61-83
Separation of Ag+ Ion on Strong Acid Cation
Exchange Resin Modified with Toluidine Blue
Chapter 3
Comparative Studies on Stannic Selenoiodate and 84-123
Stannic Selenosilicate as New Ion Exchangers:
Metal Ion Separations on Stannic Selenoiodate.
Chapter 4
Synthesis sind Characterization of A New Phase of 124-155
Stannic Arsenate as Ion Exchanger and its Use in
TLC Separations of Metal Ions
Chapter 5
Synthesis, Ion Exchange Properties and Analytical 156-194
Applications of Stannic Silicomolybdate. Effect of
Temperature on Distribution Coefficient Studies.
Research Publication
Research Paper Published
1. Studies of the adsorption of metal ions and the selective
separation of the Ag+ ion on a strongly acidic cation
exchange resin modified with toluidine blue, Acta
chromatographica, 12,129 (2002).
Research Papers Communicated
1. Comparative Studies on Stannic Selenoiodate and Stannic
Selenosilicate as New Ion Exchangers: Metal Ion
Separations on Stannic Selenoiodate.
2. Synthesis and Characterization of A New Phase of Stannic
Arsenate as Ion Exchanger and its Use in TLC Separations of
Metal Ions.
3. Synthesis, Ion Exchange Properties and Analytical Applications
of Stannic Silicomolybdate. Effect of Temperature on
Distribution Coefficient Studies.
apiier -1
ii ucimn
Ion Exchange
The process of ion exchange is defined as exchange of ions of Hke charges
between the solutions and generally solids, which are highly insoluble body. The
solids, which contain the ion of their own for the exchange to take place rapidly
with electrolyte solution, are called ion-exchangers. For practical value the solid
has an open, permeable molecular structure so that ions and solvent molecules
can move freely in and out.
Ion exchange is basically a process of nature occurring throughout the ages from
even before the dawn of human civilization. So the process is mentioned in the
Holy Bible [1]. Aristotle stated that the seawater loses part of salt content when
filtered through certain types of soil [2]. The ion-exchange process could be
noted when wood cellulose convert bitter water into drinkable water, in the first
case and silicate which play the role for the improvement of taste of water in the
second case. Today ion exchange pervades many fields of human activity and its
ever-expanding uses bring man closer to his dream of comfort. Historically
speaking, ion exchange was not recognized till the middle of eighteen century,
when two papers by two different investigators working independently were
published, ironically in the same issue of same journal. So Thompson [3] and
Way [4] in 1850, laid the foundation of ion exchange by Base Exchange in the
soil. They observed that the calcium and magnesium ions of certain types of soil
could be exchanged for potassium and ammonium ions. Later Eichorn [5]
showed that the ion- exchange properties of solids arise from zeolites. The first
synthetic aluminium based ion exchanger was made by Harms and Rumpler [6]
in 1903. Gans [7] did the major work on ion exchangers in the field of industrial
production and technical applications. The first industrial product applicable for
technical purposes was sodium permutite, which was produced by fusing a
mixture of clay minerals and alkalis. The first application of synthetic zeolite for
collection and separation of ammonia from urine was made by Folin and Bell [8].
Adam and Holms [9] discovered in 1935 that crushed phonograph records
exhibit ion-exchange properties. This led the researcher to develop synthetic ion-
exchange resin. These resins were developed and improved by companies in the
United States and England after World War II. Nearly all-current industrial and
laboratory applications of ion-exchangers are based on these resins. At the same
time, the synthesis of organic resins made it possible the properties of ion-
exchangers in systematic manner.
Organic resins which have been used for a long time for ion-exchange column
chromatography (lECC) have high mechanical and chemical stability. However,
they are decomposed at elevated temperature and under the presence of strong
radiations. It is due to these reasons there has been a revived interest in inorganic
ion-exchangers in recent years as they are unaffected by ionizing radiation and
are less sensitive to higher temperatures. The structure of these inorganic ion-
exchangers are more selective and suitable for separations of ions on the basis of
their different size. They can also be used as ionic or molecular sieves.
Furthermore, the synthesis of such ion-exchangers involves simple procedures.
Kraus et al. [10,11] at Oak Ridge National Laboratory and C.B. Amphlett [12,13]
in United Kingdom did the excellent work on these materials at the initial stages.
The work upto 1963 has been summarized by Amphlett [14] in his classical book
"Inorganic Ion Exchangers". The later work upto 1970 has been condensed by
Pekarek and Vasely [15]. Clearfield [16,17], Alberti; [18,19] and Walton [20-23]
have also worked on different aspects of synthetic inorganic ion-exchangers. In
India Qureshi and co-workers have prepared a large number of such inorganic
materials and studied their ion-exchange behavior.
Characterization of Ion-Exchange Process
An important feature differentiating the ion-exchangers from other type of gel is
the presence of ionogenic groups. The ionogenic groups are attached to slceleton
either directly or by means of another groups (composed group). The process of
ion exchange is most typical interaction between the ions in the solution and
takes place on these ionogenic groups. The exchange of ion between the ion-
exchangers and solution is a physiochemical process and has the following
properties.
1. The process takes place between like charges and is reversible.
2. The exchange reaction takes place on the basis of equivalency and in
accordance with the principle of electro neutrality.
Synthetic Inorganic Ion-Exchangers
The inorganic ion-exchangers have drawn considerable attention during the last
two decades due to increase in interest for analytical and industrial uses.
Inorganic ion-exchangers are a vast field for study and are materials of ever-high
selectivities. These materials were explored for their suitability for the treatment
of nuclear wastes solution and purification of water all over the world. The
analytical importance of synthetic inorganic ion-exchangers is now firmly
established. Synthetic inorganic ion-exchangers may classify into following five
categories;
1. Acidic salts of polyvalent metals
2. Oxides and hydrous oxides
3. Exchangers based on heteropolyacids
4. Insoluble ferrocyanides
5. Various insoluble materials
Inorganic ion-exchangers of first category arc produced by mixing the acidic
oxides of the metals belonging to IV, V and VI groups of the periodic table. Acid
salts of quadrivalent metals are most studied group of this class. They are
extremely insoluble. The chemical compositions of these salts depend upon the
method of preparation. The well-known member of this class, which has been
known for the last one hundred years, is zirconium phosphate [24]. However it
has been used as an ion-exchanger much later [25]. It is highly selective for Cs
ion in acidic inedium. Cesium can be separated from almost all elements of
periodic table using zirconium phosphate [26]. The discovery of a crystalline
phase of zirconium phosphate in 1964 made it possible to explain its observed
ion-exchange behavior in structure terms [27,28]. It has also found applications
in areas such as hydrogen-oxygen fuel cell, desalination and artificial kidney
machines.
The oxide and hydrous oxides of some metals have also been the well-
established materials for ion-exchange purposes. Freshly precipitated trivalent
metal oxides are of particular interest. For example, hydrous ferric oxide and
ferric hydroxide readily adsorb alkaline earth cations according to the law of
mass action [29]. Other bivalent cations [30] were adsorbed above pll. in this
process, the alkali metals and alkaline earths are adsorbed on the surface and are
readily eluted while more highly charged cations Ce (III), Y (III), Pm (III), Ru
(IV) are sorbed in bulk and eluted only with difficulty [31]. The ion-exchangers
of this class shovv' an amphoteric behavior depending upon the pH of the solution.
The process can be described by the following equilibria [32].
A1(0H)2'' + OH- ^ A1(0H)3 ^ A10(0H)-2 + H"
Hydrous zirconium oxide is typical representative of this class [33]. Hydrous
titanium oxide shows high selectivity for Cs" and can be used for the
preconcentration of uranium [34]. Hydrous cerium oxide [35], tin dioxide
[36,37], iron (III) oxide [38] and manganese dioxide [39,40] are useful for
cesium separation. Freshly precipitated magnesium oxide shows the scavenging
properties towjird fission products in solution [41-43]. Mixed sah can be
prepared in which a second cation of higher charge than the parent cation is
introduced into the structure. The resulting positive charge is balanced by the
presence of anions other than oxides and hydroxides. Example of such materials
include Zn (0H)2 in which Zn " is partly replaced by Al " and A1(0H)3
containing Si ^ Ti'* , or Zr'*'*' ,the general formulae Znn.iAIn(0H)2Xn and Al„.
iMn(0H)3Xn.i where M"*" is a tetravalent oxide and X is a monovalent anion.
Quadrivalent metal oxides are also commonly used as inorganic ion-exchangers
such as Sn02, SiOa, ThOi and Zr02. Actually these materials do not possess
simple oxide formula as given above unless they are ignited at a high
temperature. They are found to contain varying amounts of water, which is not
present as water of hydration since on heating it is lost continuously over a range
of temperatures. Consequently these oxides are usually described as hydrous
oxides. Inoue et al. [44-46] and A.K.et al [47-49] have done important work on
hydrous oxides.
Heteropolyacid salts can be used as inorganic ion-exchangers. A number of such
compounds have been prepared. This group of exchangers is derived from 12-
heteropolyacids of general formula Hn XYi204o.nH20 where X may be P, As, Si,
B or Ce and Y may be one of elements such as Mo, W or V. The heteropoly
compounds especially those of 12-molybdo compounds are quite strong
oxidizing agents. Insoluble ammonium salts of these acids have been applied in
some cases. The exchangers of this type are stable in moderately concentrated
acid. However they dissolve in the solution of alkali. The heteropolyacids exhibit
high affinity to heavy alkali metals, thorium and silver. The sizes of univalent
ions of these elements are suitable for their retention in the crystal lull ice of
heteropolyacids. Ammonium molybdophosphate is very selective for large
monovalent cations in acidic condition [50]. Despite its high selectivity for
cesium, pH limits the use of ammonium molybdophosphate to acidic solutions
because dissolution of molybdenum from the framework occurs at pH>6 [51].
Buchwald and Thistlewaits first recognized that the addition of foreign ions into
ammonium molybdophosphate structure during precipitation occurred by a
potentially usefol cation exchange process. They showed the sorption of macro
quantities of K , Cs^ and if by ammonium molybdophosphate from acidic
nitrate media at room temperature. Much of the subsequent investigations of the
ion-exchange properties of these salts have been carried out in laboratories of
Van R. Smith, Robb and Jacobs and their co-workers [52-55].
Insoluble metal Ferro cyanides can also be used as inorganic ion-exchangers.
They are easily prepared and usually have high ion-exchange capacity. They are
also known as scavengers for alkali metals. They are useful in the separation of
radioactive wastes and fissionable materials [56] with less damage to radiation
than their organic counter parts. Ferro cyanide molybdate was studied by
Baetsley et al [57], who determine its structure by X-ray studies. They also used
molybdenum and tungsten Ferro cyanide for the separation of Cs-137 and Sr-90
from fission products in acidic medium. Large range of separation applications
have been reported for cobalt Ferro cyanides as well as for copper, zinc and
nickel Ferro cyanides [58,59]. A recent trend has been in the study of ion-
exchange properties of Ferro cyanides adsorbed on silica gel [60] or resin beads
[61]. They are reported to have reasonably good stability in acids and alkalis and
a higher selectivity for alkali metals especially Cs-137 as compared to the simple
salts. Amine based metals Fen'o cyanide have also received attention. They were
first introduced by Hahn and Clein [62], who prepared a cobalt amine Ferro
cyanide. Later on Sn(ll) and Sn(lV) amine 1 'erro cyanides hiave also been
prepared in these laboratories.
Various insoluble ion-exchanging materials are also of interest. A large number
of such compounds have been prepared. These materials have been prepared by
precipitation from metal salt solution with Na2S or H2S. The ion exchange
properties of insoluble suphides (eg. Ag2S, SnS, CuS, PbS, FeS, NiS, AS2S3,
Sb2S3) have been investigated. The suphides are selective towards cations
forming insoluble sulphides, the exchange reaction occurs through metathetical
reactions in which the metal of sulphide is displaced by appropriate ion from the
solution. Quantitative adsorption of TI , Ni , Co , Mn , Cu and Pb have
been reported on ZnS , CdS, and PbS [63], uranium on PbS [64], separation of
Cu ^ from Zn " and Cd ^ on SnS [65] and noble metal on CuS [66,67]. Some of
the important two component ion exchangers with their composition, ion
exchange capacity and selectivity of metal ions have been reported in table 1.
Apart from the heteropolyacid salts many other substances like mixed sahs have
also been synthesized and studied in detail for ion-exchange properties. It has
been found that double sahs or mixed salts of some of the metal ions possess ion-
exchange properties different from that of simple salts. Usually they show
superiority over simple salts mainly in three aspects. They are more thermally
and chemically stable, secondly they are selective in nature and finally their ion-
exchange capacities are higher as compared to their simple salts. It is with this
view; attention has been given to synthesize and to investigate ion-exchange
properties of this class of ion-exchangers. Some mixed salts or double salts
prepared earlier have been reported in Table 2.
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24
Characterization of Inorganic Ion-Exchanger
In order to characterize a new substance as an inorganic ion-exchanger, its utility
in various fields and its limitation, the following properties may be studies as per
given order of preferences.
1. Ion-exchange capacity
2. Chemical and thermal stabilities
3. Selectivity
4. Composition
5. Structural studies
6. Analytical applications
Uses of Inorganic Ion-Exchangers
Few important uses of inorganic ion-exchangers arc;
1. Separation of metal ions.
2. Separation of organic compounds.
3. Removal of air and water pollutants.
4. Preparation of ion selective electrodes.
5. The preparation of artificial kidney machines.
6. Preparation of fuel cells.
The organic ion-exchange resins are beads of highly polymerized cross-linked
organic materials containing a large number of acidic or basic groups. The
backbone is generally a styrene-divinylbenzne copolymer. Copolymers of acrylic
acid derivatives and divinyl benzene are also frequently used. For use with
biological, macromolecules, it is usual to introduce charge groups into cellulose
fibers. For several years, cross-linked dextrin (Sephadex) has also been used as
carrier material. A list of commercially available ion-exchange resins along with
their chromatographic applications is given in Table-3
25
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27
A cation exchange resin is a high molecular weight crosslinkcd polymer having
sulphonic, carboxylic, phenolic group etc as an integral part of the resin and an
equivalent amount of cations.
A typical cation exchange reaction may be represented as:
nRS03"H^ + M'"" = (RS03),M '" nH^
Where, R is the resin matrix and M is the exchanging cation.
An anion exchange resin, on the other hand is a polymer containing an amine or
quaternary ammonium groups as an integral part of the polymer lattice and an
equivalent amotmt of anions such as chloride, hydroxy] or sulphate ions.
A typical anion-exchange reaction may be represented as:
nR^4* McaCr + X"" = (RNMej) X ^ nCF
Where, R is the resin and X is the exchanging anion.
The first polymerization type of organic ion-exchange resin was prepared by
D'Alelio [310] in 1945. Since then, these organic ion-exchangers have been used
both in laboratories and industries for the separation and preconcentration of
metal ions, recovery of metals, removal of permanent hardness of water,
demineralization of water concentration of electrolytes and elucidating the
mechanism of reactions [311]. Resins of strongly basic type having chlorine
atom are more resistant to oxidation than weakly basic resins of phenolic type
[312]. The organic resins are insoluble in all common solvents including
aliphatic and aromatic hydrocarbons.
The use of chelating resins for the removal and separation of traces of metal ions
from industrial wastes is of great interest due to the simplicity, elegance and a
greater range of variation of the method. Chelating ion-exchange resins show a
definite selectivity towards certain metal ions or a group of ions. The properties
of some resins bearing chelate forming groups and ion-exchange groups have
28
been studied in detail. These resins are prepared by immobilization of chelating
agents on various support [313]. The aromatic complexing agents containing the
sulphonic acid group are particularly useful for the separation of metal ions on an
anion exchange resin. These compounds display high selectivity for anion
exchangers. The selectivity of these modified resins depends on the nature of the
functional analytical groups of the ligand. In recent years, various papers have
been published related to the study of modified resins in different fields of
separation science. A list of some important chelate ion-exchange resins with
their selectivity and chromatographic applications has been shown in Table-4.
The distribution coefficient (Kd) is of great value as a practical guide to the
separation procedures in chromatography. On the basis of distribution
coefficient, it is possible to predict the separation of one ion from the other. The
distribution coefficient of an ion (A) is given by the equation:
Amount of ion (A) present in the exchanger phase/g of exchanger Kd =
Amount of ion (A) present in the solution phase/ml of solution
The general use of distribution coefficient is made in elution technique for the
separation of metal ions. The rate at which ions move in ion-exchange
chromatography is directly proportional to their distribution coefficients.
Chromatography is a method of analysis in which the flow of solvent or gas
promotes the separation of substances by differential migration from a narrow
initial zone in a porous sorptive medium. Chromatography can be divided into
two major classes (i) gas chromatography and (ii) solution chromatography. The
latter may be further divided into paper chromatography, column
chromatography, thin Layer chromatography, ion-exchange chromatography and
electro chromatography.
29
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The principle of chromatography and their wide applicability were discovered by
Michael Tswett in 1906 who applied this technique for the separation of
chlorophyll pigments using llnely divided calcium carbonate as an adsorbent
[314]. He also published a detailed monograph in 1910 [315]. Very little
chromatographic work was published between 1910 and 1931. In 1931, Richard
Kuhn and coworkers [316] resolved plant carotenes into several components.
Rimington and co-workers [317] worked out detailed technique for the
separation of porphyrins and bile pigments. M.L. Wolform and coworkers [318]
separated mixtures of sugars on adsorption columns, locating the sugar zones by
streaking the extruded columns with an alkaline permanganate reagent. Moore
and Stein [319, 320] have separated amino acids obtained by hydrolysis of
proteins first on starch columns and later on ion-exchange resin columns. The
importance of rigid standardization of technique, solvents and adsorbents has
been discussed by H.H. Strain [321] and by Brockinann and Schodder [322],
since the original discovery of adsorption chromatography. Three major
advances have been introduced viz. ion exchange chromatography, partition
chromatography and gas chromatography.
Ion-exchange chromatography was the first of various liquid chromatography
methods to be used under modem LC conditions and its application came into
existence in late 1960s [323]. Partition chromatography is the second major
innovation in the field of chromatography. Silica gel packed columns was used
as a support for a stationary phase by Martin and Synge [324], paper
chromatography, a form of partition chromatography in which strips or sheets of
filter paper are used as a support for the stationary phase was introduced by
Consden, Gorden and Martin [325]. They described two-dimensional systems
which are particularly useful where one solvent system is inadequate for the
resolution of all the components in a mixture. Reversed phase paper
chromatography (applicable for substances sparingly soluble in water), in which
34
the paper is impregnated witli a hydrophobic substance and the aqueous phase
becomes the moving phase was described by Kritchevsl<y and Tiselius [326].
Because of its inherent simplicity and versatility, the low equipment cost and its
ability to handle micro quantities, paper chromatography became popular very
rapidly. Further advancements, both in theory and equipment lead to the
development of gas chromatography in 1952 by James and Martin [327, 328] for
which they got a Nobel Prize. This technique is particularly used for mixture of
gases or for volatile liquid and solids.
Liquid chromatography (LC) refers to any chromatographic technique in which
moving phase is a liquid. Modem liquid chromatography has been named high
performance or high-pressure liquid chromatography (HPLC). In HPLC, closed
reusable columns are employed so that hundreds of individual separations can be
carried out on a given column in a matter of few minutes. The technique finds
it's beginning in late 1950s with the introduction of automated amino acid
analysis by Spackman, Stein and Moore [329]. Detection and quantitation were
achieved with continuous detectors of various kinds, which yield a final
chromatogram without intervention by the operator. The newest of all liquid
chromatographic methods is the size exclusion liquid chromatography or gel
permeation cliromatography. This separates molecules according to their
effective size in the mobile phase. The technique has been used for the separation
of high molecular weight species particularly those which are non-ionic. The
macromolecules such as proteins and nucleic acids are best separated by gel
permeation method. The technique uses either rigid or non-rigid column packing.
Rigid packing are required for high-pressure liquid chromatography while some
samples are better separated on non-rigid gels.
Among various chromatographic techniques discussed above, thin layer
chromatography (TLC) is considered to be most simple, rapid, versatile and low
cost method which is applicable to the characterization and separation of a
35
variety of multicomponent mixtures (both ionic and non ionic) except those
which are volatile or reactive substances. The TLC technique has been applied
since years, in the analysis of organic and inorganic substances and to the
analysis of biological, pharmaceutical, and environmental samples [330-337].
An improved version of TLC called high performance thin layer chromatography
(HPTLC) has been introduced by Pretorius [338] in 1974, who described this
technique as high speed thin layer chromatography. It is based on electro osmotic
flow and has been used frequently for the separation and determination of a large
number of substances [339-344]. Izmailov reported thin layer chromatography
first of all and Shraiber in 1938 who utilized thin layers of alumina on glass
plates for the separation of plant extracts [345]. The attempts were made using
adsorption chromatography on impregnated filter paper and later glass fiber
paper coated with silicic acid or alumina. Kirchnar [346] in 1950 was one of the
first to do this and was able to separate and identify terpenes. The technique
received due attention only in 1958 as a resuh of pioneering work of E. Stahl
[347] who was mainly responsible for developing a standard method for thin
layer chromatography. Thin layer chromatography closely resembles to those of
column and paper chromatography. In TLC, partition occurs on a layer of finally
divided adsorbent supported on a glass plate. The technique has certain
advantages over paper chromatography and gas chromatography e.g. resulting
separations are much better than in classical liquid chromatography and require
less time. It can handle several samples simultaneously and has a higher loading
capacity. Moreover, corrosive reagents and acids can be sprayed without any
adverse effect.
In TLC, a large number of coating materials such as silica gel, alumina,
kieselguhr and cellulose have been widely used as the adsorbents. Other
materials, which can be used as adsorbents in TLC include magnesium silicate,
calcium phosphate, activated charcoal, polyamide, silica gel-alumina (1:1),
36
acetylated cellulose and hydrated ferric oxide. Alumina is preferred for the
separation of weakly polar compounds while silica gel is preferred for polar
compounds like sugars, amino acids etc. TLC recommends cellulose powder as
an adsorbent for the separation of cations even though the separations may be
slower than those obtained on silica gel.
Inorganic ion-exchangers in particle size of 40-80 |j.m have also been used as the
stationary phase in thin layer chromatography. For the preparation of the
stationary phase, slurr}' of ion-exchange material is prepared in water or alcohol,
usually with a binder such as gypsum or plaster of Paris. The slurry is dispersed
on the glass plates with the help of an applicator in the form of a thin film of 0.1-
0.3 mm uniform thickness. Sherma and Fried [348] in their review described the
analytical capabilities of synthetic inorganic ion-exchange materials in thin layer
chromatography. Adsorption and ion exchange occurs simultaneously resulting
better resolution of the separating species. Inorganic ion exchange materials that
have found their use in thin layer chromatography can be classified into
following four groups:
(1) Thin layers of hydrated oxides.
(2) Thin layers of insoluble metal salts of polybasic acids.
(3) Thin layers of metal Ferro cyanides.
(4) Thin layers of heteropoly acids.
Zirconium oxide was used for the first time by Zabin and Rollins [349] for the
separation of Ni "", Co^^ Pb^^ Fe^^ Ag^ Hg^^ Cd ^ and Cu^^ Berger [350] used
this material for the study of Ferro cyanide, ferricyanide, sulfocyanide, iodate,
borate and chlorate in concentrated acidic medium. The resolution of Bi from
ternary and quaternary synthetic mixtures was achieved by Sen and coworkers
[351] in combinations of O.IM HCl, O.IM HNO3, acetone and dioxane and
separated upto 20 fig of bismuth by this method. The same authors have also •J !
chromatographed some anions and separated Cr from other metal ions on
37
stannic oxide layers [352]. Cremer and Seidal [353] also studied the movement
of various anions on indium oxide plates.
Zirconium phosphate was used as a medium for thin layer chromatography of
cations by different workers like Zabin and Rollins [354], Keonig and Demiel
[355] and Alberti [356]. Separation of noble metals on stannic phosphate layers
in ammonia-hydrochloric acid and acetone-butanol-pyridine systems was
reported by Yin et.al. [357]. Qureshi and coworkers [358] prepared stannic
tungstate thin layers for the study of 15 binary metal ion mixtures and reported
the separation of gold from other cations. Chromatography of fifty-seven metal
ions on stannic arsenate layers was performed by Hussain and coworkers [359].
Qureshi et.al. [360] have also reported the separation of 20 binary metal ions on
non-refluxed stannic layers. They also achieved the separation of uranium from
48 metal ions on stannic antimonate layers [361]. Nabi et.al. [362] Have reported
quantitative thin layer chromatographic separation of uranium from other metal
ions on stannic sulphosalicylate layer using mixed dimethyl formamide systems
as mobile phase. De and coworkers [363] have isolated Au " from other cations
on thorium (IV) phosphate layers. Ammonium molybdate impregnated silica gel
has been utilized by Srivastava et.al [364] for thin layer chromatography of 32
synthetic dyes.
Fogg and Wood [365] prepared zinc Ferrocyanide layers and chromatographed
16 samples of sulfonamides in various concentrations of acetic acid. The same
material was used by Kawamura et.al [366] for the analysis of various
combinations of alkali metal ions in ammonium nitrate eluents and suggested
some useful separations on the same materials.
Analytical applicability of the heteropoly acid salts (double salts) has been a
recent trend. Alkali metals were chromatographed by Lesigang and coworkers
[367, 368] on thin plates of ammonium phosphodeca molybdate. arsenododeca
38
molybdate, germanododeca molybdate and oxinium and pyridinium
germanododeca molybadates in ammonium nitrate system. Lepri and Desideri
[369] have presented exhaustive explorations of ammonium molybdophosphate
and tungstophosphate layers for thin layer chromatographic separations of
aromatic amines. Kaletca and Koneeny [370] have utilized silica gel supported
ammonium phosphomolybdate layers for the separation of cesium. Srivastava
et.al [371, 372] have successfully separated metal ions and amino acids on thin
layers of pyridinium tungstoarsenate. Varshney and coworkers [373, 374]
performed separations of alkaline earths, transition metals and amino acids on
Tin (IV) arsenosilicate and Tin (IV) arsenophosphate layers in buffered ED'l'A
solutions.
The following pages summarize findings on the synthesis, characterization and
analytical application of inorganic ion exchange materials namely stannic
selenoiodate, stannic selenosilicate and stannic silicomolybdate. Studies on
Amberlite IR-120, a strong acid cation exchange resin modified with toludine
blue has also been done.
39
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60
aDier -2
CJmdles o,
^WldJ 9i on§ a m
'eiecime (3eparaMon o^
+ on on
mn x^xcma.
9 /I 9
^jommme i ue
Suminary
Cation exchange resin Amberlite IR-120 has been modified by sorption of
toluidine blue. The effect of time, pH and concentration of the reagent on the
ailsv>rplion of dye has been studied. I lie luiisiniuiu upUikc DI loluidiiic blue
was found to be 2.58|^mole X10V0.4g of resin at pH6.0.On the basis of Kd
values in diverse solvent systems, important quantitative binary separations of
metal ions namely Ca '"-Zr'' Cu^^-Bi^^ Zn^*--Ri^^ 7.n^^-A^\ La^^-Ag' 'Cd '-
Zr'^, Mn'^-Zr''^, Th ' -Ba ^ and Th '-Zr'" have been achieved .Ag' ion has
exceptionally high Kd value and therefore it has been selectively separated
from a synthetic mixture of other metal ions. The analytical importance of the
modified resin has been explored in the separation of Zn^', Mg^' Mir'and
Cu " contents of a pharmaceutical preparation (Zincovit, a multivitamin).
61
Iiitrodiiclioii
Now a day's attention has been paid for the removal of heavy metals from
industrial effluents and wastewaters. The focus is mainly due to increasing
environmental problems due to excessive and indiscrimale induslriali/.alion.
The potentiality of chelating ion exchange resins for the separation and
preconcentration of metal ions has been firmly established [1-6]. These
chelating ion exchange resins are prepared by incorporating of complexing
groups on the resins. The selectivity of these modified resins for metal
depends on the nature of functional groups of the complexing agents. New
poly(styrene-p-hydroxamic acid) have been synthesized and characterized,
and their physio -chemical properties have been determined. These polymers
are used as chelating ion exchange resins for the separation and determination
of rare earths lanthanum, cerium, neodymium and yttrium in synthetic,
standard and environmental studies [7].
Studies have also been reported on dye impregnated polystyrene resins and
dye coated cellulose for the chelating ion exchange [8]. The properties of
some resins, bearing chelate forming groups have been widely studied.
Dowexl-X8 containing sulphonated azo dyes [9] have been found to separate
copper and nickel. The recovery of mercury from wastewater utilizing a
chelating a chelating strong and weak base, containing imidoacetic acid and
thiol groups [10] is also reported. Nabi et al synthesized a variety of chelate
forming resins by incorporating complexing agents such as bromophenol blue
[11], Eriochrome Black-T [12], Congo red [13], Alizarin red [14] and crystal
violet [15]. Besides the separation of metal ions, chelating resins have also
shown other analytical applications such as adsorption of bile salts [16] and
decoloration of lactic acid [17]. The successful utility of these modified resins
have prompted us to start a search for a new chelate forming group for
differential selectivity towards metal ions
62
Experimental
Apparatus
Spectronic 1001 -spectrophotometer ,Elico digital pH meter model Li-IOT
and Electronic shaker with a temperature controlled body was used.
Reagents
Ambcrlite IR-120 (11" ) resin (mesh size 16-45,8% divinyl benzene by weight)
in hydrogen form was obtained from BDH (U.K), Toluidine blue from
E.Merck (Germany), Disodium salt of EDTA from S.D Fine chemicals
(India), ammonium chloride, citric acid, sodium citrate, formic acid, dimethyl
sulfoxide and tartaric acid (all AR grade).
1% ethanolic solutions of l-[l-hydroxy-2-napthol azo]-5-nitro-2-napthol-4-
sulfonic acid sodium salt (Eriochrome BlackT),l-[2-pyridyl azo]-2-
napthol(PAN) and 1% aqueous solution of o-cresolsulfonapthlein 3'-3'-bis
[methylUiminodiacetic acid sodium salt] (XylenolOrange) were used as
indicators and O.OIM solution of disodium salt of ethylenediaminetetraacetic
acid (EDTA) was used as titrant. A list of metal ions investigated is given in
table 1.
Adsorption Stodies
Preparation of Modified Resin
The modified toluidine blue resin was prepared by treating 50g dried
Amberlite IR-120 (H" ) with 1 liter of 65ppm solution of toluidine blue for 24
hours at pH 6.0 with intermittent shaking (Fig.4). The excess reagent was
removed by washing the resin several times with demineralised water. The
treated resin was finally dried in an oven at 60°C.
63
Table: 1 List of cations (O.IM aqueous solutions) studied
Cations
Ag^
Mg^^
Ca^*
Ba^^
Sr ^
Hg^^
Pb^^
Cd'"
Zn^^
Mn^"
Cu^^
Co'*
m'*
Fe^^
AP^
Bi^^
La^^
Sn^^
Zv''
Th''"
Salt used
Silver nitrate
Magnesium nitrate
Calcium chloride
Barium nitrate
Strontium chloride
Mercurous nitrate
Lead nitrate
Cadmium chloride
Zinc nitrate
Manganese chloride
Copper chloride
Cobalt nitrate
Nickel Nitrate
Ferric nitrate
Aluminum nitrate
Bismuth nitrate
Lanthanum nitrate
Stannous nitrate
Zirconium oxychloride
Thorium nitrate
64
Effect of Time
The equilibration time for the adsorption of toluidine blue by the resin was
established by performing a series of adsorption experiments at constant pH
6.0 at 25+2°C (pH was-i»edtfied by mean of an Elico Ll-IOT digital pH
meter). A constant mass (0.4g) of Amberlite IR-120 resin was stirred with an
aqueous solution of toluidine blue (40ml) for 1-6 hours. The amount of
toluidine blue adsorbed was determined spectrophotometrically at 625nm.
Effect ofpH
To determine the effect of pH on the adsorption of toluidine blue, 0.4g of
resin was shaken continuously with 40ml of 30ppm toluidine blue solution for
6 hours. The pH values of the solutions was adjusted by adding an appropriate
acid, base or buffer of the desired pH .The equilibrium concentration of the
reagent in the supernatant liquid was determined spectrophotometrically at
625nm.
Effect of Concentration of Reagent
To study the adsorption of toluidine blue under static conditions, 0.4g of resin
(I^) was equilibrated with 40ml of toluidine blue solulion at dilTcrcnt
concentrations (30-90) ppm in a temperature controlled electronic shaker-
incubator at constant pH-6 for 6 hours. The equilibrium concentration of the
reagent was then determined spectrophotometrically at 625nm.
Distribution coefficient (Kd) of metal ions
0.4g of modified resin beads were treated with 1 ml of metal ion solution and
39 ml of appropriate solvent in 250 ml Erlenmeyer flask. The list of solvent
systems used for the determination of Kd values is given in table 2. The
mixture time was shaken continuously in a shaker at 25+2°C for 6 hours .The
amount of cation in the solution before and after equilibration was determined
by using 0.0 IM EDTA as tirtant. Kd values for each metal ion was then
calculated by the formula
65
Table: 2 List of solvent systems for distribution coefficient (Kd)
studies of metal ions.
Solvent systems
O.O5M+O.IMNII4CI
O.IMNH4CI
O.IM Citric acid
O.IM Citric acid+0.1 M Sodium citrate
O.IM Sodium citrate
O.IM Formic acid
O.OIMDMSO
O.OIM DMSO +0.01M HNO3
O.OIM HNO3
O.IM Tartaric acid
Composition
1:1
-
-
1:1
-
-
-
1:1
-
-
Notations
Si
S2
S3
S4
S5
S6
Sv
Ss
S9
S,o
66
Amount ormclal ion in Ihc resin pliasc/g of resin K d -
Amount of metal ion in the solution phase/ml of solution
I-F/0.4g I-F = X 100
1740 ml
Where 1= volume of EDTA used before treatment,
F= volume of EDTA used after treatment with the resin
Quantitative Separation of Metal Ions
The separation of metal ions was carried by an elution technique. 1.5g of
modified resin was packed into a glass column of id 0.6 cm with a glass wool
support at the base. The column was washed 2-3 times with demineralized
water.2.0 ml of binary mixture of the metal ions to be separated was poured
on the top of the column and the solution was allowed to flow gently at the
rate of 4-8 drops / min till it reaches just above the resin surface. The column
was then rinsed with limited quantity of demineralized water and recycled.
The elution process was carried out at a constant flow rate of 8-10 drops /
minute using appropriate mobile phase (table 3). The eluted metal ion
fractions were determined titrimetrically using 0.0 IM disodium salt of EDTA
solution as titrant.
To demonstrate the practical utility of the material for selective separation of
metal ion, synthetic mixtures were prepared - Ca ' (0.240mg), Ba '* (0.40mg),
Sr '"(0.87mg), Pb^^(0.58mg), Cd^^(0.91mg) and Zn^^ (0.65mg) with varied
amount of Ag"* (5.19 mg, 6.48, 7.78mg) for selective separation of Ag" . The
recovery percentage has been calculated.
67
Table: 3 List of eluting electrolytes for metal ions.
Eluting electrolytes
0.1 MHNO3
O.IMNH4NO3+O.IMHNO3
O.I MHCOOH
O.IMDMSO
0.1 MNH4CI+0.05 MHCl
0.1 M DMSO +0.1 M IICOOH
0.1 M NH4NO3 +0.05 M HNO3
Composition (v/v)
1:1
-
-
1:2
2:1
1:1
68
Determination of Metal Ions in Pharmaceutical Sample
One capsule or 5ml ofmultivilamin was treated with 10 ml oiXonc. IICI and
filtered, the clear solution thus obtained was diluted to 250ml with
deminerlized water (DMW). 1 ml of this solution was evaporated to dryness
and the residue was taken in 1 ml demincralised water.2.0 g of the ion
exchange material was loaded into a column having an internal diameter of
0.6 cm .The effluent was recycled through the column to ensure complete
adsorption of the metal ions .Zn" was eluted with a mixture of 0.1 NH4NO3
+0.1 M HN03(1:1 v/v), Mg^ by 0.4 M NH4NO3, Mn^^ by 0.1 M HCOOH and
Cu " was eluted by using O.IM DMSO as solvent. The rate of elution was
kept at 8-10 drops/minute and the metal content of the effluent was
determined by conventional EDTA titration.
Result and Discussions
The effects of equilibration time, pH and toluidine blue concentration on the
amount of the dye adsorbed by the resin are shown Figs. 1-3, respectively.
The maximum uptake of toluidine blue was found to be 2.58).i mole X 10 Vo.4
g of resin at pH 6. hitcraction of toluidine blue with the ion exchange resin
might be by hydrogen bonding as represented by the structure.
CH3
SOsNa
NaOaS
69
Figure: 1
2 3 4 5 6 7 Time (hrs.)
Effect of time on the adsorption of toluidine blue on Amberlite
IR-120 (H* form) resin
70
2.58
0; u cn
• ^
en O r— X vT d "~-o e •^
•V Oi -D L.
o to •o <
2.56
2.54
2.52
2.50
c o 2.48 e
0.0
Figure: 2 Effect of pH on adsorption of toluidinc blue on Amberlite IR-
120 (H"" form)
71
0.5A0
0.480
c
S 0 .420 u en
"O -
o 2 0.360 d ~--o ^ 0 .300 :;
• D
<U XI ^ 0.2A0 (/I
•o a c ^ 0.180 v -
i i -' c D 0 0.120 e <
0 . 0 6 0
-
_
-
-
^^-k 2.6
1.2 1.6 2.0 2.A 2.8 3.2
Amoun t l oaded ( ; jmol Xl0>.mL~^ )
3.A
Figure: 3 Effect of loading of toluidine blue on Amberlite IR-120
(H^ form)
72
It is apparent from the distribution coefficient valves that tokiidine blue
modified cation exchange resin shows a differential selectivity for metal
ions. This may be due to the formation of metal complexes with different
stability. The ease of complexation will of course depend upon the reaction
medium. Toludine blue modified resin posses both the sulphonic groups to act
as ion exchange as well as chelate forming groups, which arc responsible for
the adsorption of metal ions. The bulky size of toludine blue molecule
increases its strength of interaction with the sorption matrix and enhances the
affinity of cation exchanger for toluidine blue and its complexes with the
metal ions. The Kd value for each metal ion in various solvent systems have
been calculated and presented in table 4.
Amberlite IR-120 sorbed toludine blue resin has been found promising for the
separation of metal ions due to differential affinity. Adsorption studies on
different metal ions in diverse solvent system reflects many interesting
features in Dimethyl sulfoxide-Nitric acid mixture (1:1 v/v) [S8]. All the
metal ions are poorly adsorbed with the exception of Zr"* .
On the other hand Zr'*' behaves in an exceptional manner by showing very
high Kd values in almost all the solvent systems studied viz ammonium
chloride -HCl mixture, citric acid sodium citrate, sodium citrate ,formic acid,
nitric acid, and tartaric acid. While very low Kd values were observed in
ammonium chloride and dimethyl sulfoxide medium (Table 4).
It is apparent from table 4 that the distribution coefficient values in pure
DMSO medium is higher for most of the metal ions as compared to values in
pure nitric acid medium with the exception of Zr"*" ion. This might be because
of a reduction in the strength of complexation ability of toluidine blue with
this metal in the presence of nitric acid medium. It is also interesting to note
from Kd values for most of the metal ions are exceptionally high in tartaric
acid and sodium citrate medium. This behavior of metal ions may be
attributed due to the formation of more stable complex with toluidine blue as
compared to metal tartarate or metal citrate complexes.
73
Table: 4 Distribution coefficients of metal ions between different
solvent systems Si-Sio* on Amberlite IR-120 [H ] resin
treated with toluidine blue.
Metal ions
Ag^
Mg^^
Ca ^
Ba ^
Sr ^
Hg^^
Pb'"
Cd'"
Zn^^
Mn^"
Cir'
Co^^
Ni^^
AP^
Fe^^
La^*
B\''
Sn'"
Zv''
Th""
s,
636.0
2966
10.0
725.0
215.0
424.0
553.0
788.0
36.00
990.0
314.0
878.0
975.0
412.0
111.0
37.00
10.00
1441.0
4460
1120
S2
666.0
2200
132.0
450.0
206.0
390.0
603.0
56.0
255.0
1716
2800
241.0
400.0
241.0
82.00
1960
23.00
488.0
456.0
1642
Distribution coefficients for solvent systems*
S3
308.0
5.70
115.0
115.0
98.0
270.0
215.0
207.0
4.00
0.00
987.0
242.0
532.0
310.0
458.0
505.0
5150
242.0
3700
1425
S4
9100
922
135.0
135.0
10.0
375.0
510.0
53.0
4.00
2625
1640
505.0
1094
4000
125.0
0.00
2525
2983
5600
838.0
Ss
8300
124.0
110.0
II.O
80.0
310.0
662.0
21.0
123.0
2080
2800
1857
138.0
4000
3066
1.00
2000
4525
4460
52.00
S6
662.0
53.0
41.0
41.0
215.0
533.0
137.0
5.00
140.0
9.00
335.0
270.0
194.0
412.0
313.0
692.0
5750
611.0
7500
10.00
Sv
155.0
1433
83.0
83.0
74.0
162.0
232.0
125.0
84.00
2080
987.0
226.0
975.0
105.0
375.0
87.00
707.0
311.0
62.00
114.0
Ss
31.0
22.6
7.0
7.0
46.0
52.0
94.0
1.00
3.00
31.00
14.00
87.00
13.00
9.00
6.00
128.0
303.0
85.0
1653.0
662.0
S9
196.0
33.0
4.0
4.0
304.0
78.0
94.0
14.0
7.00
9.00
10.00
242.0
18.00
9.00
28.00
157.0
303.
10.00
7500
248.0
Sio
7033
2200
1830
1830
197.0
210.0
1043
27.00
71.00
21.00
4250
21X3
7066
2633
1800
415.0
2000
3600
7500
357.0
The identities of solvent system SI to SIO are given in Table 2.
74
Elution profiles for binary separations of metal ions are shown in Fig. 4.
Binary separations achieved are listed in table 5 and result from separation of
Ag from mixture of Ca ,Ba' Sr" Pb Cd and Zn are given in table 6.
The practical utility of this material has been demonstrated by achieving
separation of metal ions in multicomponent metal containing pharmaceutical
in Zincovit (Tabic?).
7^
Table: 5 Binary separations of Ag^, Zr"* and Zn^^ from other cations
on toluidine blue modified Amberlite IR-120 [H^] resin.
Binary mixture
Ca^* Zr"
Cu^' Bi^'
Zn '
Bi^^ Zn^^
Ag^
La^^
Ag^
Cd^"
Zr "
Mn^" Zr''"
Th""
Ba^"
Th'*"
Zr''
Amount loaded
("•«) 3.82
9.10
5.10
8.62
7.50
8.62
7.50
10.95
11.62
10,94
10„22
9.10
5..30
9.10
12.24
8.92
12.24
9.10
Amount found"
(•"«) 2.95
9.00
5.05
7.99
7.30
7.99
7.30
10.94
11.0
10.94
9.00
9.00
5.13
9.00
11.79
8.80
11.79
9.00
Recovery (%)
77.2
98.9
99.4
92.6
97.3 "
92.6
97.3
99.9
94.6
99.9
97.0
98.9
96.7
98.9
96.32
98.6
96.32
98.6
Volume of Eluent
(mL) 50 80
50 60
" 4 5
65 45
75
45
55
30
70
25 75
50
60
40
60
Mobile Phase
O.IMDMSO O.IMDMSO-O.IM HCOOH, 2:1 (v/v) OJMDMSO O.lMllCOOII 0.1MNll,,NO,r0.1M PINO3, 1:1 (v/v) O.IM HCOOH O.IMNH4NO3-O.IM HNO3, 1:1 (v/v) O.IMHNO3-O.IM DMS0,2:1 (v/v) O.IMNH4CI-O.5HCI, 1:2 (v/v) O.IMHNO3-O.IM DMSO, 2:1 (v/v) O.IMNH4NO3-0.05MHNO3,l:l(v/v) O.IMDMSO-O.IM HCOOH, 2:1 (v/v) O.IM HCOOH O.IMDMSO-O.IM HCOOH, 2:1 (v/v) O.IMDMSO-O.IM HNO3, 1:1 (v/v) O.IMNH4NO3-0.05MHNO3,l:l(v/v) O.IMDMSO-O.IM HNO3, 1:1 (v/v) O.IMDMSO-O.IM I1C00H,2:1 (v/v)
* Average of five replicate determinations.
76
2+ Table: 6 Selective separation of Ag from synthetic mixtures of Ca ,
Ba^\ Sr^\ Pb^^ Cd ^ and Zn^^
Sample No.
1.
2
3.
Amount of Ag^ Loaded
(mg)
5.20
6.35
8.72
Amount of Ag^ Found**
(mg)
5.04
6.20
8.51
Recovery (%)
96.9
97.6
97.5
Mobile phase* volume (mL)
65
70
75
* The mobile phase was O.IM HNO3-O.IM DMSO, 2:1 (v/v)
** Average of five replicate determinations.
k r ; ^ » ^*-^H LiTr.
T- 6ZZ9
•r, in.''
• ^
77
Table: 7 Separation of Zw^^, Mg , Mn ^ and Cu ^ present in
pharmaceutical preparation Zincovit on a column of
toluidinc blue modified Amberlite IR-120 resin.
Ions
Mn""*'
A A 2 +
Mg
Zn^
Cu^
Label amount*
(mg)
2.8
30.0
63.0
2.0
Composition found **
(mg)
2.7
29.5
62.0
1.9
Recovery (%)
96.4
98.3
98.4
95.0
Mobile Phase
Components
O.IMHCOOH
O.IMNII4NO3
O.IMNH4NO3+ O.lMMNOsCl:!)
O.IMDMSO
Vol.
25
30
40
50
* Per 5 mL or per tablet of drug;
** Each result is the mean from three replicate analyses
78
O.TM DM SO 0.1MDMSO + 0.1MHCOOH (2:1 v/v
< o u
o
o
£
"o > 10 20 30 AO 50 60 70 80 90 100 110 120 130 KO
Volume of ef f luen t ( ml )
O.TM DM SO 0.1M H C O O H
5 < I— a Ui 1
o £
"o >
10 20 30 AO 50 60 70 80 90 100 110 120 130 Volume of e f f l u e n t ( m l )
0 10 20 30 AO 50 60 70 80 90 )00 110 120 Vo lumeo i e f f l u e n t ( m l )
Figure: 4 Elution profile diagrams for binary separation of metal ions on
toluidine blue sorbed Amberlite IR-120 (H^) ion exchange resin 2+ 4+ 2+ :3+. 2+ (a) Ca^" from Zr"" (b) Cn^ from Bi'"(c) Zn'^ from Bi .3+
79
a (jj
2
o
e
Q
Of
£ 2 o >
5
A
3
2
1
0.1MNH(,N03 + 0,1MHNO3
Zn2^
-A
O.IMHNO3 +O.IM DMSO (2:1 )
Ag +
/ r 1 1 1 1 1
(a)
•1 \
> 0 10 20 30 40 50 60 70 80 90 100 110 120 Volume of e f f l uen t ( m l )
E
< 5
A
3
2
1
O.IMNH^Cl + _0.5M HCl
L Q 3 +
- - — T i 1
0.1M HNO3 +0.1MDMSO(2:1)
Ag +
—( . 1 1 1 1 V ,
(b
10 20 30 40 50 60 70 80 90 100 110 Volumeof e f f l u e n t ( m l )
< Q
2
o
e
>
5
4
3
2
1
O.IMNH4NO3 C).5MHN03 '
- Cd^^
-
- •-
/ , \
+ 0.1M DMSO+ 0.1MHCOOH ( 2:1 v /v )
2r4+ (c)
r'—^'^v / \
, / 1 1 1 1 1 1 \ • 1 1
10 20 30 40 50 60 70 80 90 100 110 120 „ Vo lumeof e f f l u e n t ( m l )
Figure: 4a Elution profile diagrams for binary separation of metal ions on
toluidine blue sorbed Amberlite IR-120 (H^) ion exchange resin
(a) Zn "" from Ag^ (b) La " from Ag^ (c) Cd^^ from Zr"^
80
£ < o HI
o
E 2 >
0.1M HCOOH 0.1M OMSO -t-O.IM HCOOH ( 2: 1 v/ v
e 5
10 20 30 40 50 60 70 80 90 100 110 V o l u m e o f e f f l u e n t ( m l )
0.1M NH4NO3+0.O5MHNO3 O.IMDMSO + O.IMHNO3
o >
E
< 5
4 \-
10 20 30 40 50 60 70 8 0 90 100 l l 'o Volume of e f f l u e n t ( m l )
Q.IMDMSOt 0.1 M QMS 0 + 0.1 M HCOOH (2:1 v/v "O.IM HNO3
o >
10 20 30 4'0 50 6 0 70 8 0 90 ^l5o~riO
• Volume of effluent (ml)
Figure: 4b Elution profile diagrams for binary separation of metal ions on
toluidine blue sorbed Amberlitc IR-120 (H^) ion exchange resin 2+
(a) Mn^ from Zr'^ (b)Th'^ from Ba'"- (c) Th'^ from Zr'^
81
Acknowledgements
The author is grateful to Prof. M. Illyas, Chairman Department of Chemistiy
for providing the necessary research faciHlies. The author is also thankful to
Dr S.A.Abidi, Lecturer Department of Zoology for spectrophotometric
facilities.
82
References
[1] E.I-Iolms S.Ballesters, R.Fukai, Talanta, 26, 79 (1979).
[2] K.Brajter, J.Chromatogr, 102, 385 (1974).
[3] H.J.Fischer, K.H.Leiser, Fresenius. Z.Anal.CHEM, 335, 738 (1989).
[4] H.Hubicka Hung, J.Ind.Chem. Soc, 17, 355(1989).
[5] U.Hiroshi, Jpn Kokai Tokkyo Koho Jp Apll, 155, 3 (1992).
[6] R.Brownc, T.Rdward, Diss.Abslr. Inl.B, 54, 1524 (1993).
[7] Y.K.Agarwal, H.Kaur, S.K.Menon, React .Fund. Polym, 39 (2), 155,
1998,(1999).
[8] R.M.C.Sutton, S.J. Hill, P.Zones, J. Chromatogr.A, 739, 81 (1996).
[9] M.Peasvento, A.Profumo, Talanta, 35, 431(1998).
[10] N.S.C.Becker, R.J.Eldridge, Water, 19 , 33, 36 (1992).
I l l] S.A.Nabi, A.Bano, S.lJ.smani, J. Ind .Chcm. Soc, 34A, 330 (1995).
[12] S.A.Nabi, S.Usmani, N.Rahman, A.Bano, J. Ind. Chem .Soc, 73A, 301
(1996).
[13] S. A. Nabi, A. Gupta, A. Sikarwar, Annnalidi Chimica, 89, 419 (1999).
[14] S. A .Nabi, M A Khan, A.Islam, Acta Chromatographica, 11, 130
(2001).
[15] S.A.Nabi, E.Laiq, A.Islam, Acta Chromatographica, 11, 118 (2001).
[ 16] W.Gaoming, Diss.Abs. Int. B, 54, 3646 (1994).
[17] R.Ql, D.Sui, Shcngli Kexue Jisnzhan , 25, 47 (1994).
amer ~3
'L-M^npiirmme CJinid ie§ on
mmc y^eiiem),
ind ana '^jfUMnmc
9/1 9
•nBsmctmje as v 'LJ&H^
on v^xemmgers:
Cyeparaiio. on ^.ufeoarauons on
mmc
Summary
Two new inorganic ion exchangers, Stannic selenoiodate and Stannic
selonosilicate have been synthesized under identical conditions and their
thermal and chemical stabilities have been examined. The ion exchange
capacities of stannic selenoiodate and stannic selenosilicate for K^ was found
to be 1.84 and 1.23 meq/gm respectively. To establish the structure of the
materials, chemical analysis, TGA, DTA, DSC, FTIR, X-ray and SEM studies
have been performed. The X-ray analysis shows semi crystalline behavior for
stannic selenoiodate while amorphous in case of stannic silicosilicate. The
SEM analysis shows uniform globular morphology for stannic selenoiodate.
The presence of uniform morphology shows the absence of impure phases.
pll titration studies reveal monolunctional and bifunctional behavior for
sliinnic selenosilicate and stannic selenoiodate respectively. Uistributioii
coefficients of metal ions in DMF-HCL and Formamide-HCL systems have
been evaluated. Some important and analytically difficult quantitative binary
and ternary separations of metal ions have been achieved on stannic
selenoiodate columns. The practical utility of the material has been
demonstrated by analyzing metal ions in synthetic mixtures and in
electroplating waste.
84
Introduction
Today ion exchange technology is considered as an established analytical tool
for analysis of complex mixtures in diverse fields. The different types of
inorganic ion exchangers and their applications in various fields are
documented in a book by Clcarndd | 1 | . llt)vvcver, (he dcvclopmcnl of new
inorganic ion exchangers vvilh charactcrislic jiropcrdcs is slill needed
attention and their utility in diverse fields is yet to be explored. Amorphous
and crystalline forms of tetravalent metal acids salts, generally called single
salts with the general formula [M (IV) (HXO4) 2] nH20. Where M represents
Zr , Ti , Sn etc and X represents P, W, Si, Mo, Se, As, etc have been studied.
Stannic tungstate layers have been utilized for quantitative separation of gold
from other metal ions [2]. Silicates of tin were prepared and ion exchange
properties studied [3]. Synthetic isoflavones were separated chromato-
graphically on stannic molybdate papers [4]. Separations of amino acids were
performed on stannic tungstate [5]. Semi-crystalline layer of stannic tungstate
was utilized to study the movement of phenolic compounds in various solvent
systems [6].
Previous studies showed that mixed salts have better ion exchange capacity,
thermal and chemical stabilities as compared to single salts. These mixed salts
may have tetravalent metals such as Zr (IV), Sn (IV), Ti (IV) etc in
combination with any two anions from W, P, Mo, Si, V etc. These mixed salts
are called double salts. Tin (IV) molybdoarsenate, semi-ciystalline tin (IV)
selenophosphate, tin (IV), vanadoarsenate, tin (IV) vanadotungstate, tin (IV)
selenoarsenate, tin (IV) arsenosilicate, tin (IV) molybdosilicate and tin (IV)
tungstoselenate have been studied previously [7-14]. Apart from these,
zirconium [15-16] and titanium [17] based double salts have been synthesized
and their properties investigated. The paper chromatographic behavior of
some pesticides and toxins has been studied using stannic molybdosilicate
impregnated papers [18]. The present work has been stimulated by the
following considerations.
«5
1. The hclcropolybusic ticiti sails show bcllcr ion exchange properties
than their corresponding single salts.
2. Both the exchangers i.e. tin (IV) selenoiodate and tin (IV)
seienosilicatc have not been studied earlier.
3. Tin (IV) selenoiodate showing higher thermal and chemical stability
and enhanced ion exchange capacity has been chosen for detail studies.
Experimental
Reagents and chemicals
Stannic chloride pentahydrate (Loba chemie, India), potassium iodate (E.
Merck, India) sodium selenite (E. Merck, India), sodium meta silicate (CDH,
India). All other reagents and chemicals used were of Anal R grade.
Apparatus
Per kin Elmer FTIR spectrophotometer for IR analysis, a Philips Martin
Holland (Model PW 7030/10) for X-ray diffraction, Elico, India (EL-10) for
pH measurements, Spectronic 20 Genesis Spectrophotometer for absorbance
measurement. Per kin Elmer thermal analyzer (model pyris diamond) for
TGA DTA and DSC studies and Cambridge instruments (stereoscan
360,made in U.K) for scanning electron microscopy.
Syntheses
Tin (IV)- selenoiodate
This compound was prepared by adding a mixture of 0.3 M aqueous solutions
of potassium iodate and sodium selenite drop wise to 0.3M aqueous solution
of stannic chloride pentahydrate while stirring the mixture continuously in 1 .T
volume ratio. The pH (<1) of the resulting mixture was maintained by gradual
addition of IM HNO3. The resulting precipitate was digested in mother liquor
overnight. The liquid is separated from the precipitate by decantation. The
86
precipitate was washed several times with deminerlized water; filtered and
washed again to remove reagents adhered with the precipitate under suction.
The final product was dried at 40+20°C in an electrically controlled oven. The
material was cracked into line particles when immersed in water. It was
converted into H" form by treating it with IM HNO3 solutions. It was
Iranslcrrcd in a column and washed with deminerlized water to remove excess
acid and finally dried in the oven at 40+2''C.
Tin (IV)- Selenosilicate
It was prepared by adding gradually a mixture of 0.3M aqueous solutions of
sodium selenite and sodium metasilicate into 0.3 M aqueous solution of
stannic chloride pentahydrate in the volume ratio of 1:1. The pH of the
resulting mixture was adjusted below 1, by adding IM HNO3 solution. The
subsequent steps were the same as described in earlier synthesis to obtain the
final product.
Ion Exchange Capacity
1.0 g (dry mass) of the material in H^ form was packed in glass column with a
glass wool support at the base. A 0.1 M NaNOs solufion was passed through
the column maintaining at flow rate 9-10 drops/min. The effluent containing
H" ions was carefully collected. The complete replacement of W^ from the ion
exchanger by Na" was checked. The collected effluent was titrated with a
standard NaOH solution. The ion exchange capacities of stannic selenoiodate
and stannic selenosilicate are reported in table 3.
pH Titration
Topp and Pepper method was utilized for pH titration using NaCl-NaOH,
KCl-KOH, CaCl2-Ca(OH)2 and BaCl2-Ba(OH)2 systems [19]. For this
purpose, a 0.5 g (dry mass) of ion exchanger in II"* form was treated with 50
ml of the concerned solution. pH titration curves are shown in figures 1 and 2.
87
Chemical Stability
The chemical stabilities of stannic selenoiodate and stannic selenosilicate
were examined in mineral acids HCl, HNO3 and H2SO4 and bases NaOH and
KOH.
A 500 mg (dry mass) of each ion exchanger was treated with 50 ml of the
solvent of interest and kept for 24 h at (30+2°C). Tin, iodate, silica and
selenium contents of the solutions were determined using suitable
spectrophotometric methods [20-23].
Chemical Composition
The stiochiometry of the constituents in stannic selenoiodate and stannic
seleno silicate were determined. For this purpose 0.15 g (dry mass) of sample
was dissolved in 15 mL hot concentrated nitric acid. The solution was cooled
and diluted to 100 mL with demineralized water. The components of each
sample in the solution were estimated spectrophotometrically using standard
methods [20-23].
Thermal Stability
The effect of diying temperature on the ion exchange capacity was studied by
heating each material from 100-900*^0 for 1 h in a muffle furnace .The ion
exchange capacity of each product was determined and the results are
reported in figure 3.
IR Analysis
111 analysis of both the materials in ll ' form was performed separately. 10
mg (dry mass) of each material was taken and was then thoroughly mixed
with lOOmg (dry mass) of KBr and grounded to a very fine powder. A
transparent disc was formed by applying a pressure of 80,000 psi (1 psi
=6894.76 pa) in a moisture free atmosphere. The FTIR absorption spectra
88
were recorded in the range 400 to 4000 cm''. The resuUs are given in figures 7
and 8.
Thermal Studies
A 15 mg (dry mass) each of stannic selenoiodate and stannic selenosilicate
was analyzed for TGA, DTA and DSC with sample holder made of AI2O3 in
N2 atmosphere. The heating rate and chart speed were maintained at lO C
/min and 20cm/h respectively. Alumina powder was used as reference
material. The DSC and TGA curves are shown in figures 4, Sand 6.
X-ray Analysis
For X ray diffraction analysis, powder method was employed with a
manganese fihered CuKa radiation (k =1.5418A) source. The instrument was
equipped with graphite monochromator operating at 40 KV and 30 mA. The
crystalline nature of stannic selenoiodate was ascertained by comparing the
intensity of different peaks with the most intense peak at (26-28* ) 29. The
study was done in the range 10 to 70 20 values while the speed of the recorder
was maintained at lOmm/sec 20. The X -ray diffraction pallcrns is sliown in
figure 9.
SEM analysis
Electron micrographs were recorded for stannic selenoiodate and stannic
selenosilicate by scanning electron microscope operating at 20.0 KV. The
details are shown in SEM photographs (figure 10).
Ion Exchange Equilibration Studies
In order to check the equilibration time for the ion exchange reaction, 0.5g
ion exchange material in H"*" was treated with 20 ml of O.IM potassium nitrate
solutions in a 100 ml conical flask. The mixture was then shaken for 1-6 h in
a shaker incubator at 30+2°C. The amount of metal ion adsorbed by the
89
exchanger in mcq/g was csliniatcd by (ilration of the siipcnialant lic|iii(l
against EDTA solution. The results are shown in figure 11.
Elution Profile for H^ Ion
250 ml solution of 0.1 M potassium nitrate was percolated through a glass
column containing l.Og of ion exchange material in H" form with a glass
wool support at the end. I'hc How rale of the erilueut collected was
maintained at 8-10 drops/min. The amount of H"* ions released in each 5 ml
fractions of the effluent was determined titrimetrically using a standard NaOH
solution. The results are shown in figure 12.
Distribution Studies
Distribution coefficients (Kd) for Ag^ Mn^^ Ni^^ Ca^^ Cd^^ Cu^^ Co^^
Pb "", Fe "", U^\ Cr^^ k?\ Th''^ Sn'*\ and Zr ^ were determined in
dimethylformamide, formamide, hydrochloric acid and mixed systems.
0.5g (dry mass) of stannic selenoiodate in H" form were put into 100ml
conical flasks each containing 50 mL .solution of 2x10"'' M concentration of
metal ion. The mixture was continuously shaken for 3h in a siiaker incubator
at 30+2°C. The amount of metal ion left in the solution was determined by
titration against disodium salt of ethylene diaminetetracetic acid using
standard procedure [24].
The Kd values were calculated using the following formula.
Amount of metal ion in the exchanger phase /g exchanger Kd=
Amount of metal ion in the solution phase /mL solution
In our case (I-F)/0.5g (I-F)
Kd = = X 100 l-l''/50ml V
90
Where I is the volume of EDTA used before Ireatmenl, f" is the volume of
EDTA used in the solution phase after treatment with the exchanger, I-F =
corresponding amount of metal ion in exchanger phase.
Separations
In order to demonstrate the separation potential of stannic selenoiodate in
column chromatography, a number of binary and ternary separations of metal
ions were practically achieved.
l.Og of stannic selenoiodate in H'*' form (50-lOOmesh) were packed in a glass
column of inner diameter 1.1 cm with a glass wool support at the end. A
mixture of metal ions solution to be separated was then poured into the
column. The solution was allowed to move through the column at the rate of
8-1 Odrops/min and recycled at least three times. The column was washed with
dimineralized water to rinse the sides of the column. The adsorbed metal ions
were then eluted with appropriate eluents. The flow rate of the effluent was
maintained at ImL/min throughout the elution process. The effluents WQXQ
collected in 10ml fractions and metal ions content was determined
titrimetrically against EDTA solution.
Several ternarj' separations of metal ions were also achieved in a similar
manner..
Selective separations of Ag^, Ni " , Co^\ Sn"* and Zr" from a mixture of other
metal ions were successfully achieved on columns of stannic selenoiodate
(Tables 7-11).
Separation and Determination of Metal Contents in Electroplating Waste
Sample preparation
5.0g of the waste material collected from the electroplating plant were
dissolved in 15ml of aqua regia. The mixture vv'as stirred thoroughly till a
clear solution was obtained. It was diluted to 100ml with dcmineralizcd water
91
and was then used as a stock solution. The atomic absorption spectroscopic
analysis of the sample gave the following results Cu^^ (38.0pg/ml), Cr' "
(22.0)Lig/ml) and Ni^"^(14)ig/ml) respectively.
Methodology
Appropriate volumes ranging from 2.0 to 5.0 ml of the stock solution was
poured into a glass column packed with stannic selenoiodate having inner
diameter of 1.0 cm packed with stannic selenoiodate having bed height of
5.0cm with a glass wool support at the base. The solution was allowed to flow
through the column at a rate of 0.3-0.5ml/min. The effluent was recycled at
least three times. Finally the column was rinsed with demineralized water.
The sorbed metal ions were then eluted with O.IM DMF+O.lMHCl as eluting
reagent. The flow of the effluent was maintained at Iml/min through out the
elution process, The fractions of each metal ion collected were determined
titrimetrically using 0.0 IM disodium salt solution of EDTA.
Results and Discussion
Table 1 summarizes the synthesis of single sails; slannic iodalc, slaniiic
selenite, stannic silicate and corresponding double salts stannic selenoiodate
and stannic selenosilicate under identical conditions. It appears from the data
(Table 2) that double salts show superiority over their single salts in terms of
exchange capacity, thermal and chemical stability. It was therefore considered
worthwhile to concentrate our studies on double salts
It is evident from table 3 that stannic selenoiodate has higher ion exchange
capacity than stannic selenosilicate prepared under identical conditions (1.84
and 1.23 meq/g, respectively for K^). The affinity sequence for alkali metal
ions is K^>Na^>Li^ and for alkaline earth is Ba ''>Sr^^>Ca '">Mg^^ This
sequence is in accordance with the hydrated radii of the exchanging ions. 'I'he
ions with smaller hydrated radii easily enter the |)()res of the cxcliaiigcr,
resulting in higher adsorption [25]. Figures 1 and 2 show pH titration curves
92
Table: 1 Synthesis of single and double salts of tin (IV).
Synthesis Conditions
Cone.
Order of mixing
PH
Stirring time
Mixing ratio
Cone, of HN03 for
eonversion
r'wasiiing
2nd
washing
Drying temp, of fmai pnuliicl
Stannic selenite
0.3M
Anion in cation
<1
Ih
Cation: anion 1:1
IM
51/4! ppt solution
81/41 ppt solution
40+2 °C
Single salts
Stannic-iodate
0.3M
Anion in eation
<1
Ih
Cation: anion 1:1
IM
51/41 ppt solution
81/41 ppt solution
40+2"C
Stannic silicate
0.3M
Anion in cation
<1
Ih
Cation: anion 1:1
IM
51/41 ppt solution
81/41 ppt solution
40+2"C
Double salts
Stannic-selenoiodate
0.3M
Anions in cation
<1
Ih
Cation: anion 1:1
IM
51/41 ppt solution
81/41 ppt .solution
40+2"C
Stannic selenosilicate
0.3M
Anions in eation
<1
Ih
Cation: anion 1:1
IM
51/41 ppt solution
81/41 ppt solution
40+2 "C
93
Table: 2 A comparison of few properties of single and double salts of
tin (IV).
Properties
Ion exchange capacity for Na"" ion
Ion exchange capacity for Na"" ion after drying al 300"C
Solubility
Single
Stannic Sclcnite
0.4] m eq/g
0,16 meq/g
Tin=2.4
Seleniiim=4.6
Am
Salts
Stannic iodatc
0.24 meq/g
0.10 meq/g
Tin=1.8
Iodale=2.5
cunt released,
Stannic silicate
0.32 mcq/g
0.21 meq/g
Tin=2.8
Silicale=i.48
mg/50 ml in 1.0^
Double Salts
Slannic selenoiudate
0.97 meq/g
0.57 meq/g
Tin=0.56
SelcniLim=0.18
Iodate=1.56
/I HTvIOi
Stannic sclcnosilicate
0.71 mcq/g
0.42meq/g
Tin=3.4
Sclenium=6.2
Silica=8.9
94
Table: 3 A comparison of ion exchange capacity data of stannic
sclcnoiodatc and stannic selcnosilicatc for different metal
ions
Exchanging metal ions
Lr
Na
K"
Mg ^
Ca ^
Sr^"
Ba'"
Hydrated Radii (A)
10.0
7.90
5.30
10.80
9.60
9.40
8.80
Ion exchange capacity (meq/g exchanger)
Stannic selenoiodate
0.97
1.27
1.84
0.84
1.09
1.16
1.37
Stannic selenosilicate
0.88
0.99
1.23
0.77
0.85
1.00
1.12
95
13
Stannic S e l e n o l o d a t e
N Q O H - N Q C I
K O H - K C l
C a ( O H ) 2 - C a C l 2
0.5 1.5 2.5 3.5 /.,5 5.5
OH added , m eq / 0.5 g exc hanger
Figure: 1 pH titration curves of stannic selenoiodate.
96
stannic Seleno Silicate
N Q O H - N Q C I
KOH-KCl C a ( O H ) 2 - C a C l 2
BQ{OH)2-BaCl2
15 2.5 3.5 i.5
OH added, meq/0.5g exchanger
5.5
Figure: 2 pH titration curves of stannic selenosilicate.
97
for NaCl-NaOH, KCl-KOIl, CaCh-CiKOIl). and na(^lrl^a(OI I), syslcnis
revealed a mono functional ion exchange characteristic for stannic
selenosilicate and bifunctional for stannic selenoiodate. The pH titration
curves of stannic selenoiodate indicate thai at pi 1-6, the sequence ol' ion
exchange capacity was found to follow K" <Na" <Ca ^ while in the case of
stannic selenosilicate the ion exchange capacity trend was
Ba^^<Na''<K^<Ca^"'.
from the chemical treatment data (table 4), it can be concluded that stannic
seleno iodate is highly stable upto 1.0 M concentration of mineral acid
solutions. However, in alkalis it is fairly stable up to 0.1 M concentration
whereas stannic selenosilicate shows lesser chemical stability as compared to
stannic selenoiodate. Both the material was analyzed for its constituents. The
Sn: Se:Io3 ratio in stannic selenoiodate was found to be 3:1:2 and that in
stannic selenosilicate the Sn:Se:Si ratio was 3:2:3.
In order to observe the resistance towards heat, the materials were dried in
the temperature range 100-900*^0. It has been observed that stannic
selenoiodate experiences a sharp decrease in ion exchanger capacity as the
drying temperature is increased up to 500 "C and the capacity becomes almost
negligible after 700 C. Whereas in the case of stannic selenosilicate no
significant loss in ion exchange capacity is observed upto 500 'C (figure 3).
The pyrolysis curve (figure 4) of stannic selenoiodate shows a sharp
continuous loss in weight upto 100°C and is attributed to the elimination of
water molecules. After that a gradual loss in weight is observed which
continues uplo 424V is probiibiy cnuscd by Ihc viipori/iilioii of srk'iiiu-
group. On raising the temperature further a sharp decrease in weight is
rellected in the temperature region 424 to 750"C, as a result of decomposition
reaction of the material. Further loss in weight is almost negligible due to
formation of stannic oxide as the final product. These interpretations are also
supported by the appearance of two endothermic peaks in the DTA curve
98
able: 4 Solubility of Slaunic sclcnuiudate and Stannic seleno-silicate
in various solvents at 30+2 C.
Solvents
DMW
O.IMKOH
l.OMKOH
O.lMNaOH
l.OMNaOH
I.OMHNO3
l.OMHCl
I.OMH2SO4
Amount released nig/50 ml
Stannic Selenoiodate
Sn
0.00
1.00
3.70
0.78
4.20
3.56
4.95
6.24
Se
0.00
0.90
4.00
0.14
0.84
2.18
1.00
2.66
IO3
0.00
2.00
3.56
1.20
3.28
1.56
2.75
2.24
Stannic Selenosilicate
Sn
0.00
4.20
7.20
4.80
8.20
8.40
10.30
14.86
Se
0.00
3.95
8.70
5.50
4.80
6.20
4.40
4.36
Si
0.00
4.50
9.60
7.20
10.20
8.90
5.60
12.86
99
^ 2.0 en c o x: u
\ cr
e >; 1.2 u o Q. O
u 0) 0.8 C71 C o u X
LU C
+
0.4
Stannic Seleno Silicate Stannic Seleno iodate
0.0 L 200 400 600 800 1000
Temp. ( C!
Figure: 3 Effect of drying temperature ou tUe ion exchange capacity of
ion exchanger materials.
100
o o en
o o 0 0
O
o c^
O O U3
O O i n
o o ~*
C J
o o CN
o o
, . u
o
0)
•3 •*-'
a
a. b
(—
H u
+ ffi
o o o <u V3
U
s a W)
O
t 3
H Q
1
O H
S _bX)
to
o o o i n ro
O O O O n
o o O I f ) rsi
O
P O O CM
A (I)
o o o i n T -
"Via
o o o o T -
o o d in
— - o
o o
101
(figure 4) and the ion exchange capacity data at different temperatures
(figures).
The thermo grams of stannic sclenosilicate arc shown in figure 5. It can he
readily concluded that the first sharp weight loss occurs up to 100"C which
corresponds to loss of water molecules per mole of the material. Then gradual
decrease in weight up to 450°C occurs probably due to volatilization of
selenite group. Further loss in weight occurs on increasing the temperature is
caused by decomposition reaction of intermediate product leading to the
formation of residual oxide of tin as final product. The DSC curve (figure 6)
of stannic selenosilicate also shows two endothermic peaks and an exothermic
peak. The endothermic peaks with a maximum at 104.22"C and 392.42"C
correspond to dehydration reactions and decomposition of intermediate
product. The exothermic peak with maxima at 214°C supports the TGA
findings.
The infrared absorption spectra of stannic selenoiodate and stannic
selenosilicate in H" form are shown in figures 7 and 8. The strong and broad
band for both the compound in the region 3500-3100cm'' may be assigned to
interstitial water molecules. Another strong and sharp peak with a maximum
at 1633cm" is due to HO-H- bending. The spectrum of stannic selenoiodate
shows a strong and a weak band at 723cm'', and 460cm'',respectively
indicates the presence of iodate and selenite groups |26]. The infrared
spectrum of stannic selenosilicate shows two bands in the region 1100-900
cm'' represent silicate groups while three week bands with a maxima at 714
cm'', 510 cm'' and 458 cm'' characteristic of oxides of selenium [26].
The X-ray diffraction patterns (figure 9) suggest semi crystalline nature of
stannic selenoiodate with an intense peak at (26-28") 20. On (he other hand
stannic selenosilicate shows amorphous behavior.
102
t£> o O
0; i -D O I . 0) Q. E o I -
E
+
ITS
o I/) o a <u
«
o
W)
o
IT)
u 3 bD
(7.)ssonm6!dM/;p/Mp
103
X
T3
'o c —
c c C3
O
U CO
Q
MUJ ) M O l d }D3H
104
r^/:6'6S7
16'ZZL
o o
o
o o in
o e z z v E
o o o (Nl
o o i n
1
E
•—* 1_ Ol
X)
E 3 C (U
> o 5-
o o en
o Lf>
Lf) »J
o v l
\n ro
O on
LT)
(Nl
o CM
o o o
'o c
a a
E 3
01
a
I—(
H fa
3
(o/o) 3 D U D ) } ! U U S U D J i
105
o o i n
O O O fNl
o o
a o o CI
O O i n
<—, *"" e "—
0/ n e D
c > a 3:
C
<u - ^ r f
O C 0)
a; (» CJ
C
C/3
(»> o p 3
(J
H
0 0
u> in O cr> <0 t~- ID
(%) e o U D U l U J S U D J i
o o o •J-
106
l/l
c c OS
t3 C 03
0)
'o c <u
c
I / l
c L. Oi
- ^ -iw
ra c c o
• *—»
••J
•a 1 H
'5 >» 05 U 1
X
CTN
O • - 4
bl;
i i .
^2 en O S U
(/I
X H S U 8 } U |
107
Scanning electron micrographic studies revealed irregular rod like structure
for stannic selenosilicate (figure 10b) and spherically regular shape for stannic
sclcnoiodate (figure 10a) On the basis of chemical composition, pll titration,
thermal and IR studies, the following tentative formula may be assigned to
stannic selenoiodate.
[(Sn02)3 (SeOj) ( H2lO-3)2]. nHzO (1)
If all the external water molecules are lost up to 100°C then the weight loss as
calculated from the 1"GA curve was 10%. The number of water molecules (n)
per mole of the material can be computed from Alberti equations [27].
X(M+18n) 18n =
100
Where X is the percent water contents and M+18 is the molecular weight of
the material. It gives the value of'n' ~ 3
The above formula can then be rewritten as
[( Sn02)3 ( Se03) (H2IO-3 )2] .3H2O (2)
Similarly a tentative formula for stannic selenosilicate can be suggested.
[(Sn02)3. (H2Se03)2. (1128103)3] .6II2O
The resuhs of ion exchange equibration studies revealed that stannic
selenoiodate requires shorter time (3h) for equilibration as compared to 4h in
the ease of stannic selenosilicate (figure 11).
Figure 12 shows the elution profile curves for hydrogen ions release for these
ion exchange materials. The release of hydrogen ions is faster in the case of
stannic selenoiodate (figure 12a) as compared to stannic selenosilicate
(figure 12b). The most of the H" ions are released within 100 ml of the effiuent
in both the cases.
108
Figure: 10 Scanning electron micrographs of (a) Stannic selenoiodate
and (b) Stannic selenosilicate at magnification (17,000 X)
109
1.5 u 0) CT C
o
t 1.2 X 0) O)
cr
e +
•+-
o
o - • - ' Q. 3
0.8
0.4
0,0
S t a n n i c Seleno Silicate
S tann ic Se leno lodate
2 3 L
Time ( h rs .)
Figure: 11 Uptake of K' \vi(li time.
110
0.15
O.U-
0,12-
0.10-
0.08-
^ 0.05-
C71 C o i : u X 0)
ai
cr a* e
X) OJ <Ji
a
n X u 0.04.
0.02
u en c o r u K 0;
0.14 •
0.12-
0.10-
0.08-
0.05-
C7
e
x>
O i_
^n 0.0^. X u
0.02-
(a)
(b)
50 T
150 10 0
Vol.of effluent (m'
200 2 50
— I 1 1 50 100 150
Vol.of effluent (ml
200 250
Figure: 12 Elution behaviors of hydrogen ions using l.OM K (NOj):-
111
In order to explore the separation potentiality of stannic selenoiodate,
dislribulion cocnicicnls of important niclal ions were determined in various
solvent systems. It has been observed that with gradual increase in
hydrochloric concentration in UMl'-llCI systems decreases the Kd valve for
most of the nietal ions studied (tableS) The similar behavior has been
observed in formamide-hydrochloric acid systems. This is an expected trend.
An increase in H' ions concentration in the equilibration mixture prevents the
uptake of exchanging ions from the solution phase. However Cr"' , Al' , and
Sn " shows exceptional behavior in these systems. In these cases the uptake
increases in the beginning reaching to the highest valve at composition
formamide: hydrochloric acid, 1:3.On further increasing the concentration of
hydrochloric acid, decreases the distribution coefficient values (table6). It can
be readily predicted from the data of Kd values that Ag" and Sn"*" can be
separated from the rest of the metal ions in O.IM DMF-HCl (1:1), systems
and formamide-HCl (1:3) systems. Very high Kd values of Co " and Ni ^
permit their separations from Mn^^ Cd^^ Pb^^ Cu^\ Fc^', Cr^^ La^\ 'fh"'
and Zr"* in DMF-HCl, (1:2) systems. On the other hand very high Kd value of
Zr in formamidc-llcl (1:4) is found lo be useful for its sclcclive separation
from the mixture of other metal ions studied. Based on the distribution
coefficient values several analytically important separations of binary and
ternary mixtures of metal ions have been actually achieved on small columns
of stannic selenoiodate (table 12and 13). Selective separation of Sn"* , Co" ,
Ni" , and Ag from a synthetic mixture of other metal ions have been
successfully performed. The results are shown in tables 7,8,9 10 andl 1. These
separations can be utilized in situations where one of these metal ions has to
be isolated from a natural or environmental samples containing metal ions as
impurities and subsequently determined .In certain instances interfering metal
ions can be conveniently eliminated prior to its determination. Stannic
selenoiodate was successfully utilized in the determination of Cu , Zn and
Cr' ' ions in real matrix i.e electroplating waste. Table 14 shows the separation
results.
112
Table: 5 Distribution coefficient of metal ions in DMF-HCL systems
(Kd/mLg"') at SO+zV.
Metal ions
Ag^
Mn^"
Co ^
Cd'^
Pb^"
Ni^"
Cu'^
Fe^^
Cr^^
Al^^
La^^
Th"
Zr^"
Sn^^
O.IM DMF
2966
320
470
122
510
333
443
280
953
228
390
542
395
9150
O.IM HCI
2528
373
585
196
63.0
65.0
156
102
122
245
930
3()9
591
741
O.IM D M F + O.IM HCI
1:1 (v/v)
3580
194
1612
128
150
395
190
239
1011
740
930
388
208
6066
1:2 (v/v)
3580
395
4466
105
245
5110
181
265
567
1540
472
352
660
3600
1:3 (v/v)
1214
251
953
128
165
285
123
179
700
645
635
213
2433
1056
1:4 (v/v)
1433
336
756
45
195
235
116
179
203
382
930
3()()
280
1056
2:1 (v/v)
1572
336
585
450
226
206
142
171
852
272
390
J0()
1420
1323
113
Table: 6 Distribution coefficients in formamidt -IICL systems (Kd
niLg-')at30+2''C
Metal ions
Ag^
Mn^^
Co ^
Cd "
Pb^"
Ni^^
Cu^^
Fe^^
Cv''
Al^"
La^^
Th"^
Zr"^
Sn^^
O.IM Formamide
1740
626
495
1233
245
352
383
332
388
173
415
570
2750
1750
O.IM HCl
2528
374
585
1042
63
65
156
102
122
215
930
369
591
741
O.IM Formamide + O.IM HCl
1:1 (v/v)
1315
354
1145
70
233
167
164
179
525
228
348
352
3700
1955
1:2 (v/v)
2528
354
756
110
158
316
211
197
769
720
329
336
1420
2212
1:3 (v/v)
3580
354
1857
57
165
215
211
252
900
720
312
369
1241
2983
1:4 (v/v)
1740
374
954
14
81
258
190
197
700
583
348
369
4460
2983
2:1 (v/v)
1944
374
448
63
289
246
222
216
174
164
390
369
2433
2983
114
41 Table: 7 Selective separation of Sii ion from syntlietic mixture of
Zr^^ Tli^\ A\^\ Cr^\ Fe " Pb^', Cd'"
S.No.
1.
2.
3.
Amount of Sn'* loaded
(mg)
3.24
5.00
6.50
Amount of Sn** found*
(mg)
3.22
5.00
6.48
% Recovery + S.D
99.38+0.06
100.00±0.02
99.69+0.04
Vol. of Eluent (ml)
45
70
85
Eluent: 0.5M HNO3 + O.l M DMSO (l:lv/v/)
2+ i2+ Table: 8 Selective separation of Co from synthetic mixture of Cd ,
M n ' \ Cr'", La^^ Zr'*" and Al'^
S.No.
1.
2.
3.
Amount of Co^^ loaded
(mg)
2.50
3.00
3.50
Amount of Co found
(mg)
2.44
3.01
3.45
% Recovery + S.D
97.60+0.12
100.33+0.02
98.57+0.03
Vol. Of Eluent (ml)
35
50
65
Eluent: l.OM HNO3
115
Table: 9 Selective separation of Ni ^ ion from synthetic mixture of 2+ T - 3 + ^.3+ rT.J+ Cd , Pb , Mn , La^\ Cr^\ Zr"* and Al i3+
S. No.
1.
2.
3.
Amount of Ni ^ loaded
(mg)
1.00
2.00
3.00
Amount of Ni ^ found (mg)
1.02
2.00
2.99
% Recovery + S.D
102.00±0.46
100.00±0.05
99.66+0.02
Vol. of Eluent (ml)
20
45
65
Eluent: 0.5 M HNO3 + 0.1 M HCL (1:1 v/v)
Table: 10 Selective separation of Ag* from synthetic mixture of Cd^^
?b'\ ¥c'\ Th^^ A\'\ Cr^" Zr^" and Co'^
S. No.
1.
2.
3.
Amount of Ag^ loaded
(mg)
5.00
6.50
7.20
Amount of Ag^ found
(mg)
5.10
6.50
7.21
% Recovery + S.D
102.00+0.10
100.00+0.22
100.13+0.46
Eluent: 0.5 M HCl
Vol. of Eluent (ml)
60
105
130
116
Table: 11 Selective separation o l Z r " from synthetic mixture of Cd^',
Cu^^, Ni^ , Mn^^ A P ^ Cr^^ Co^^ and Ag^
S.No.
1.
2.
3.
Amount of Zr^^ loaded
(mg)
4.20
6.40
8.00
Amount of Zr'*^ found*
(mg)
4.10
6.32
8.00
% Recovery + S.D
97.61+0.03
98.75+0.08
100.00+0.01
Vol. of Eluent (ml)
50
75
90
Eluent: 2.0 M HNO3 + O.IM DMSO
Average of five replicate determinations
117
Table: 12 Quantitative separations of metal ions in binary synthetic
mixtures on a column of Stannic selenoiodate
s. No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Binary mixture
Pb ^
Ag^
Cd ^
Amount loaded (mg)
4.20
3.50
5.24
2.20
6.10
4.80
8.00
6.50
9.10
5.60
8.50
5.40
10.0
8.0
11.50
7.40
9.50
11.70
7.00
6.00
5.00
9.50
Amount found*
(mg)
4.10
3.39
5.22
2.18
6.12
4.80
7.89
6.60
9.00
5.55
8.44
5.28
10.0
7.89
11.41
7.28
9.40
11.50
6.99
5.96
5.0
9.3
Vol.of Eluent (ml)
25
60
40
70
20
45
35
65
30
55
25
65
30
90
35
50
45
80
50
110
45
85
Eluent used (ml)
O.lMPiNOj
0.5M IINO3
O.IMHNO3
I.OMIINO3
O.IMHNO3
O.5MHNO3
0.2M HNO3
1 .OM IINO3
O.IMHNO3
O.3MHNO3
O.O5MHNO3
0.2M IINO3
0.5M HNO3
IMHNO3
O.O5MHNO3
IMHNO3
O.IMHNO3
IMIINO3
O.O5MHNO3
IMHNO3
O.IMHNO3
2MHNO3
* Average of five replicate determinations.
118
Table: 13 Q'uantitative separations of metal ions in ternary synthetic
mixtures on a column of Stannic seleno iodate.
s. No.
1.
2.
3.
4.
5.
6.
Ternary mixture
Cd''
Fe^"
Sn^"
Cu^"
Cr ^
Ni -
Al^"
Co^"
Zv''
Cd^"
Co^^
Zr^^
Cd'^
Co^^
Sn^^
cd-*
Ag^
Zr"
Amount loaded
(mg)
2.50
3.00
5.00
6.00
5.00
4.00
4.50
7.40
9.50
11.00
6.50
7.40
6.20
4.50
7.00
3.80
5.20
9.60
Amount found*
(mg)
2.44
2.89
5.00
6.0
4.5
4.1
4.40
7.24
9.33
10.75
6.41
7.25
6.20
4.48
6.94
3.79
5.10
9.58
Vol.of Eluent (ml)
25
50
60
45
60
70
25
50
75
35
55
70
35
65
80
55
40
85
Eluent used (ml)
0.05M11N(>,
O.OIMHNO3
O.OIMHNO3
O.OIMHNO3
0.05M HNO3
0.05M HNO3
O.O5MHNO3
O.OIMIINO3
O.OIMHNO3
O.O5MHNO3
O.OIMHNO3
O.OIMHNO3
O.O5MIINO3
O.OIMHNO3
O.OIMI-INO3
O.OlMIINOi
0.05M HNO3
O.02MIINO3
* Average of five replicate determinations.
119
Table: 14 Results of analysis of metal ions in electroplating waste using
stannic selcnoiodate column
Metal ions
Cu^"
Ni^'
Cr ^
Cu^'
Ni^^
Cr^"
Cu^"
Ni ^
Cr "
Cu^^
Ni^"
Cr ^
Amount loaded* (mg)
76.0
28.0
44.0
114
42.0
66.0
162
56.0
88.0
190
70.0
110
Amount Found** (mg)
76.0
27.0
43.0
113.8
42.21
65.9
161.6
56.0
87.0
190.0
69.9
109.6
Recovery+S.D (%)
100.0 ±0.17
96.42+0.11
97.72 ±0.09
99.82 ±0.12
100.50±0.I6
99.80 ±0.21
99.75 ±0.14
100.0+0.45
98.86 ±0.32
100.0 ±0.56
99.85 ±0.14
99.63 ±0.23
* Rcsull.s arc coinparcti with iiloiiiic absorption .spcctro.scopy.
** Average of five replicate determinations.
120
Acknowledgement
The authors are thankful to Chairman, Department of Chemistry, Aligarh
Muslim University, Aligarh for providing necessary facilities. Cartographic
services provided by Mr. Salimuddin Ahmed are highly appreciated. One of
the authors (AMTK) gratefully acknowledges Aligarh Muslim University for
providing University research fellowship.
121
References
[I] A. Clearfield. G.H. Nanocollas and R.H. Blessing, Ion Exchange and
Solvent Extraction in J.A. Marinspy, Y. Marcus. (Eds), Vol. 5, Marcel
Dekker, N.J, (1973).
[2] M. Qureshi, K.G. Varshney, S.P. Gupta, and M.P. Gupta, Sep-Sci,
Techno!., 12 (6), 649 (1977).
[3] G.T. Desai, D.R. Baxi, Indian. J. Technol., 16 (5), 201 (1978).
[4] J.P. Rawat, T. Akhtar, K. Akthar , N. Mohammad, J. Liquid
Chromalogr., 3 (7), 1095 (1980).
[5] S. A. Nabi, W.U. Farooqui, Z.A. Siddiqui , R A. K. Rao., .1. Liq.
Chromatogr, 6(1), 109 (1993).
[6] S.A. Nabi, W.U. Farooqui, N. Rahman, Chromatographia, 20(2), 109
(1985).
[7] M. Qureshi, R. Kumar , R.C. Kaushik, Sep. Sci. Technol, 13(2), 195
(1978).
[8] S.A. Nabi, Z. M. Siddiqui , R.A.K. Rao, Bull. Chen. Soc. Jpn, 58 (8),
2380 (1985).
[9] P.S. Thind, J.P. Rawat, Chem. Anal (Warsaw), 24 (1), 65 (1979).
[10] M. Qureshi, R.C. Kaushik, Sep-Sci. Technol, 17(5), 739 (1982).
[II] S.A. Nabi, Z.M. Siddiqui , R.A.K. Rao, Sep. Sci. Technol, 17 (15),
1681 (1982).
[12] K.G. Varshney, A.A. Khan, A Maheshwari, S. Anwar, V. Sharma,
Indian, J. Technol, 22 (3), 99 (1984).
[13] M. Qureshi, A. P. Gupta, N. Rizvi, S. Abbas , N. Ahmad, React. Polym
Ion Exch, Sorbents, 3(1), 23 (1984).
[14] S. A. Nabi, Z. M. Siddiqui, Bull. Chem. Soc. Jpn, 58 (2), 724 (1985).
122
[ 15] P.V.Singh, J.P.Rawat, N.Rahman, Talanta, 59, 443 (2003).
[16] K.G.Varshney, V.Jain, N.Tayal, Ind, J.Chem.Technol, 10, 186 (2003).
[17] Z.M. Siddiqi, D.Pathania, J.ChromatogrA, 1, 147 (2002).
[18] M. Qureshi, A. Ahmad, A. Sulaiman, M. Shakeel , A. Naseem Ahmad,
Anal. Lett, 2(8), 1157(1987).
[19] N.E. Topp , K.W. Pepper, J. Chem. Soc, 3299 (1949).
[20] F.D. Snell , C.T. Snell, Colorimetric methods of analysis including
photometric methods Vol. IIA, D.Van. Nostrand, N.J, p. 135 (1959).
[21] F.D. Snell, C.T. Snell, Colorimetric methods of analysis including
photometric methods Vol. llA, D.Van. Nosrtand, N.J, p.741 (1959).
[22] F.D. Snell , C.T. Snell, Colorimetric methods of analysis including
photometric methods Vol. IIA, D.Van. Nostrand, N.J, p. 586 (1959).
[23] F.D. Snell , C.T. Snell, Colorimetric methods of analysis including
photometric methods Vol. IIA, D.Van. Nostrand, N.J, p. 680 (1959).
[24] F .J. Welcher, The Analytical uses of ethylenediamine Tetracetic acid,
D.Van.Nostrand, Princeton, New Jersey, (1957).
[25] S .A.Nabi S.Usmani ,N.Rahman,Ann.Chim.Fr 21,521(1996).
[26] G. Socrates, Infrared Characteristic Group frequencies, John Wiley,
NJ,p. 144(1980).
|27| G.AIbcrli, I'.Torocca , A.Coiilc, J. Iiiorg . Nucl.Chcin.28, 607 (1996).
123
apier -4
SIS a,
^h€ir€3cierismion of a
€ise Of ^^HMnmc
'XeiMimiier and its lULse
m CJLC^ (3eparaiions o^
9, ons
Summary
A new phase of inorganic ion exchanger, stannic arsenate has been
synthesized by mixing 0.2M solution of stannic chloride pcntahydratc with
0.4M sodium arsenate solutions in the volume ratio 3:1 at pi I 0.40. The
reproducibility of the material has been checked. The ion exchange capacity
of the material for Ba was found to be 2.73 meq/g of dry exchanger. In order
to characterize the material, chemical & thermal stabilities, chemical
composition, pH titrations, FTIR, TGA, DSC and X-ray studies have been
performed. The exact chemical composition was found to Sn 0.28: As, 0.30
(mmoles). The use of this material for thin layer chromatography of metal
ions has been explored. On the basis of Rp values in solvents having varying
polarity viz. acetone, acetic anhydride, ethanol, methanol, nitrobenzene,
nitromethane, acetonitrile, N, N, dimethyl formamide and formamide and
mixed systems; DMSO-HCl and DMSO-HNO3, important binary and ternary
quantitative separations of metal ions have been achieved on stannic arsenate
cellulose layer. The practical utility of this material bas been demonstrated by
achieving separations and determinations of metal ions in glass industry
waste.
124
Introduction
It has been found that ion exchange resins suffer from two limitations. Firstly
they are damaged by high ionizing radiations and secondly they get
decomposed when used at elevated temperatures. The inorganic ion
exchangers have drawn considerable attention owing to their high thermal and
chemical stability [1]. In addition they often exhibit selectivity towards
certain metal ions. Inorganic ion exchangers are being used in diverse fields.
Some of the worth mentioning applications are: amorphous zirconium
phosphate as a sorbent in portable dialysis systems [2], separation of
radioisotopes [3-6], the French atomic energy commission utilizes a mixed
bed exchanger of zirconium phosphate and ammonium phosphotungstate for
the recovery and packaging of cesium-137 [7], a patent has been granted for 94- 9-i-
the removal of Ca and Mg from wash water by the use of zirconium
phosphate in the presence of large amounts of Na^ introduced from detergent
builders Na2SO4.10H2O and Na2Si03, Organic compounds like amines[8-9]
chloroiiydrocarbons und incrcaplans were ciTcclivcly scpurulcd on a
crystalline potassium zirconium phosphate[10]. Catalytic uses on such
materials have also been explored [11-13]. It is for these reasons interest on
the investigation of new inorganic ion exchangers have been revived.
The selectivity of an ion exchange reactions depend on the nature of the ion
exchanger well as on the medium of exchange. Changing the reagent
concentration and reaction conditions can easily alter the nature of inorganic
ion exchanger material, 'fhcse materials have been mainly utilized for the
separation of heavy metals [14-25] and certain organic compounds [26-27J.
Qureshi and coworker in his book titled. "Inorganic ion exchanger in
chemical analysis" also gives a detailed account on the utility of synthetic
inorganic ion exchangers [28]. The applications of synthetic inorganic
exchangers have been further reviewed [29]. It appears from the literature that
most of the studies have been concentrated on ion exchangers based on
zirconium and titanium (IV) and only few studies have been reported on tin
125
compounds. Amorphous monofunctional inorganic ion exciiangers based on
tin (IV) have been developed [30]. However this material has not been
explored systematically for its applications. Nabi and Coworkers have utilized
the potential of stannic arsenate-silica gel layers for the separation of phenolic
byproducts in banana [31]. Few other studies on the utility of stannic arsenate
have been reported [32-36]. However the earlier studies on this material lacks
in two aspects. Firstly its reproducibility has not been checked and Secondly
distribution behaviors of metal ions in several solvents have not been
investigated in a systematic manner.
The present work deals with the synthesis and ion exchange properties of a
new phase of stannic arsenate. The material has been characterized on basic of
chemical composition, chemical and thermal stabilit>', and TGA, DSC and
FTIR studies. The potentiality of the ion exchanger has been demonstrated by
achieving a few analytically difficult separations and determinations of metal
ions in glass industry wastes using thin layer chromatography.
Materials and Methods
Apparatus
The various instruments used in this study are FTIR spectrophotometer
(Nicolet protege), X-ray diffractometer (Philips Model No. PL-82038, Made
in Holland), pH-meter (ELICO -LI-10, Elico India Ltd.), FGA (Perkin Elmer
Pyris Diamond), DSC (General V4.1C Du Pont 2100), Spectrophotometer
(Spectronic-20- Genesis), Elemental analysis (GBC -932 atomic absorption
spectrophotometer), Muffle-furnace (NSW, India), Microsyringc (sample
application) and Desaga TLC applicator for preparation ofTLC plates.
Reagents
Stannic chloride pentahydrate (Loba chemie, India) sodium arsenate (S.D.
Fine Chemical, India), Cellulose micro crystallite (CDIl, India) A number of
visualizing reagents were used for detection of spots namely 1% alcoholic
126
dephenyl carbazide, 0.1% alcoholic Alizarin Red-S, Yellow ammonium
sulphide, Fresh aqueous sodium rhodizonale in neutral medium, 2% thiourea
in 2 N HCL, 1% ammonical dimethyl glyoxime. Aqueous solution
K4Fe(CN)6, 1,10, Phenenthroline. Metal ion solutions in nitrate form were
used throughout the experiment. All others reagents used were of AR grade.
Preparation of Ion Exchange Material
Stannic arsenate was prepared by adding gradually 0.2 M. Stannic chloride
pentahydrate solution in 0.4 M sodium arsenate solution with continuous
stirring in 3:1 volume ratio at pH 0.4 at 18+2°C. The resulting white
precipitate was digested for 24 h. in the mother liquor. The supernatant liquid
was then removed by decantation. The precipitate formed was washed several
times with demineralized water. The product was filtered under suction pump
and washed again with demineralized water to remove excess reagents. The
precipitate so obtained was divided into two portions, the first one was
utilized for thin layer preparations and the second half was dried in an oven at
60"C. The dried product was immersed in water to gel granules, crushed into
fine particles. It was then converted into H" form by placing it 0.5M HCl
solutions overnight. The reproducibility of this product was checked and the
data are given in Table 1. This final material was studied for characterization
and ion exchange properties.
Preparation of Thin Layer Plates
10 g of cellulose micro crystallite was soaked in 50 cm of demineralized
water to allow the cellulose fiber to smell overnight at room temperature
(30+2°C). The wet compact precipitate of stannic arsenate obtained as
described earlier was mixed with presoaked cellulose in the ratio 1:5. It was
observed that for making a free ilowing slurry of excliangcr and cellniosc
mixture, 8.0 cm^ of demineralized water / 6 g total mass was required to
obtain a uniform thickness of the film. The slurry containing stannic arsenate
ion exchanger and cellulose was stirred for 5 min and immediately spread on
a 20 X 20 cm clean glass plate with the help of an applicator to obtain layer of
0.25 mm thickness. The coated glass plates were air dried at room
temperature (30±2°C) initially and then at (90+2*^0) in an electrically
controlled oven for 1 h. The glass plates were then cooled at room
temperature (30+2°C) and stored in an airtight chamber for TLC.
Ion Exchange/Hydrogen Ion Liberation Capacity
Ion exchange capacities of the material were determined by column process.
1.0 g exchanger in hydrogen form was taken in the column with a glass wool
support. The hydrogen ions were eluted by applying O.IM solutions of uni
and bivalent cations at the rate 6-8 drops/minute. The hydrogen ions in the
effluent were determined by titrating against standard sodium hydroxide
solution.
Chemical Stability
A 0.5 of sample (stannic arsenate) was shaken with 50cm'' of the solvent of
interest for 6h at (30+2°C). Tin and arsenic released in the solvent was
determined spectrophotometrically using hematoxylin[37] and ammonium
molybdate[38] as coloring reagents respectively.
Chemical Composition
A 0.15g of sample was dissolved in approx. 15 cm^ hot concentrated
hydrochloric acid. The solution was cooled and diluted to 100 cm with
dimineralized water. Tin and arsenic was estimated spectrophotometrically
[37-38]. On the basis of chemical analysis, the exact composition of the
material was found to be Sn, 0.28 mmol: As, 0.30 mmol.
Thermal Studies
The thermogravimetric analysis of the exchanger in hydrogen form was
performed at a heating rate of 10°C/min in nitrogen atmosphere from room
temperature (30+2°C) to 900°C. The effect of heating on the ion exchange
128
capacity of the material was also examined. The sample in the hydrogen form
was heated in the temperature range 100-1000°C for 1 h in a muffle furnace.
Differential scanning calorimetric study of stannic arsenate was under taken
in nitrogen atmosphere upto 600°C at heating rate of 10°C/m.
pH-titration
Topp and pepper's method [39] was used for pH-titrations using NaCl-NaOH,
KCl-KOH and BaCl2-Ba (0H)2 systems. For this purpose 0.5g of exchanger
was treated with 50cm of concerned solution.
IR-spectrum
The IR spectra of stannic arsenate in H^ form was obtained using KBr disc on
a Nicolet Fourier transform spectrometer.
X-Ray Analysis
The exchanger in H" form was analyzed for x-ray diffraction studies using
manganese filtered FeKa radiation at voltage of 40 KV and current of 20 mA.
The speed of recorder was 10 mm/sec 2 9.
Solvents Systems
Solvents were selected on the basis of difference in their polarity in order to
explore the possibility of differential mobility of metal ions. The following
solvents were used as mobile phases: Acetone, Acetic anhydride, Ethanol,
Methanol, Nitrobenzene, Nitromethane, Acetonitrile, N, N, Dimethyl-
formamide and Formamide.
Development
Approximately 0.05ml of test solution of metal ions was applied with the help
of microsysinge, The plates were developed in various solvent systems and
allowed to ascend 10cm from the point of application. Ry and RL values were
n o
measured after detection. Development time varied from 20-25 minutes
depending on the nature of solvent system.
Quantitative Separation of Cr^*, Cu^* and Zn ^ in Synthetic Mixtures On
Stannic Arsenate-Cellulose Layer
0.05ml mixture containing 5Pfig each Cr^\ Cu"* and Zn " metal ion solutions
were loaded with the help of micro syringe on thin layer. The dcvclopmciil
was performed in the appropriate solvent systems. A pilot plate was run
simultaneously in order to locate the exact position of spot on the plate. The
spotted area for Cr^\ Cu "" and Zn^^ was scratched and extracted with 0.5N
H2SO4, HNO3: H2O: H2SO4 (1:3:1) and 0.5N HNO3 respectively and filtered.
In the filtrate, Cr"*" was determined spectrophotometrically using diphenyl
carbazide.[40] Dithizone in carbon tetra chloride was used for determining
Cu^^andZn^^[40]
Determination of Elements In Glass Industry Waste
5g of semi solid waste from polishing and grinding unit of glass industry of
Firozabad U.P. India, was treated with 200ml aqua regia and stirred till a clear
solution was obtained. The amount of Cu^ , Cr' , and Zn " was found to be
4.4, 11.6 and 34.8 |.ig/ml respectively as determined by atomic absorption
si)cclropliolomclcr.
Quantitative Separation ofCr'' Cu ' and Zn ' /// OVc/.v.v hulii.slry Wcisic
200ml solution of the glass waste (5.0 g) was concentrated by heating the
solution on a water bath reducing the volume to approximately Iml. 0.05ml of
the pre-concentrated solution containing 348|ag/ml Zn^ , 44 ig/ml Cu '*" and
116|ig/ml Cr''" was applied with the help of microsyringe at the point of
application of the plate as thin layer with microsyringe.
130
Results and Discussion
Ion exchange capacity and chemical composition data establish that the
stannic arsenate Ibrmcd is reproducible (Table 1). The ion exchange
capacities for alkali and alkaline earth metal ions are shown in (Table 2). It is
evident from the table that the affinity sequence for alkali metal ions is
K' >Li' and for alkaline earth ions is Ba '*'>Ca "*'. This sequence is in
accordance with the hydrated radii of the exchanging ions. The ions with
smaller hydrated radii easily enter the pores of exchanger, resulting in higher
adsorption [41].
Figure 1 shows pH titration curves for the Na"^-H"^,KM-r and Ba^Ml^
exchange processes. The titration process occurs in one stage in all systems
studied suggesting its behavior as a mono functional weak acid.
The effect of heating on ion exchange capacity of stannic arsenate for Ba
ions is shown in Fig. 2. It is quite evident from the figure that the loss in ion
exchange capacity occurs in stages. Initially the decrease in capacity is slow
and gradual upto 500°C and becomes very sharp between 500-1000 **C. At
900^C the ion exchange capacity becomes almost negligible due to formation
of tin oxide. This is also reflected in the thermogram.
The material was found to be fairly stable in lower conccnlralioii of 11( 1,,
IINO3, II2SO4 and alkalis NaOH and KOll. It is also quite stable in organic
acids like acetic acid and formic acid. The material gets completely dissolved
in 2M NaOH/KOH (table3).
FTIR spectra of the sample (Fig. 3) shows a strong and broad band in the
region 3400-2300 cm'' which may be assigned to interstitial water molecule
and o n group [421. Anoliier slrong aiid sharp peak with a lua.viinum at 1627
cm'' may be due to H-OH bending. The spectrum also shows strong bands in
the region 850-450 cm'' indicating the presence of arsenate and metal oxide
band. [43]
Table: 1 Reproducibility data for the synthesis and ion exchange
capacity of stannic arsenate.
Siimplc No.
1.
2.
3.
4.
5.
Cone.
Sn:0.2M
As: 0.4 M
Sn:0.2M
As: 0.4 M
Sn:0.2M
As: 0.4 M
Sn:0.2M
As: 0.4 M
Sn:0.2M
As: 0.4 M
I'll
0.40
0.40
0.40
0.40
0.40
Stirriiin lillK-
1 h
Ih
1 h
1 h
Ih
Older of iiiixiiiK
Sii lo As
Sn to As
Sn to As
Sn to As
Sn to As
Mixiiin riill<»
Sn:As3:l
SnrAs 3:1
Sn:As3:l
Sn:As 3:1
Sn:As3:l
DryiiiU U-ii i |» .
6()i2"C
60±2°C
60+2''C
60±2"C
60+2''C
lou-i'xj;
('ll|)IU'll,V
lor Na' (nicq/g)
I..V1
1.50
1.50
1.54
1.52
I'XllCl
i'lu-llllcill
coiiip. Sn: As
(nimolc)
0.28:0,30
0.32:0.30
0.30:0.32
0.29:0.30
0.32:0.33
132
Table: 2 Hydrogen ion liberation capacities of mono and bivalent
metal ions.
S.No.
1.
2.
3.
4.
5.
Hj'drated radii (A)
10.0
7.90
5.30
9.60
8.80
Exchanging metal ion
Li"
Na""
r Ca'"
Ba^"
Hydrogen ion liberation capacity (meq/gm)
1.22
1.54
1.97
2.35
2.73
l^-^
Tabic: 3 Chemical stabilities oi'stannic arsenate (II i'oiin) in dilTerent
solutions.
Solutions
Dimineralized water
O.IMHCL
4MHCL
0.1MPINO3
2MHNO3
O.IMH2SO4
2 M H2SO4
1 M CH3COOH
1 M Formic Acid
O.lMNaOH
2MNaOII
O.IMKOH
2 M K 0 H
Tin released (mg/50ml)
0.000
1.43
Dissolve completely
0.10
2.10
0.24
1.24
2.24
1.45
2.20
Dissolve completely
3.10
Dissolve completely
Arsenic released (mg/50ml)
0.000
1.87
Dissolve completely
0.48
3.48
0.36
2.36
1.40
4.20
1.48
Dissolve completely
2.68
Dissolve completely
134
u
5
4
2
0
• N Q C I - N Q O H o KCl-KOH A BoCl2-Bo(OH)2
0 1 2 3 4 OH added,meq./0.5g exchanger
Figure: 1 pH titration curves of stannic arsenate in NaCl-NaOH, KCI-
KOH and BaClj-Ba (OH)2 systems.
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137
The thermogram of stannic arsenate (Fig. 4) shows continuous loss in weight
upto 400*'C. This may be attributed to the elimination of external water
molecules and water molecules arising from condensation of OH groups of
the material. Gradual loss in weight occurs as the temperature is further
increased from 400V-800''C and then sharply between 800V-900"C as a
result of decomposition of arsenate group leading to the formation of stannic
oxide as final product.
The DSC curve (Fig.5) shows a broad endothermic peak between 20-190''C
with a maximum at 51-130°C due to the loss of external water molecules. The
weak upward peaks between 220 to 600°C are due to exothermic burning of
arsenic as arsenic oxide vapors. These changes are also reflected in the TGA
curve.
The X-ray powder diffraction analysis of the material dried at 60 C shows a
semi-crystalline nature with intermittent peaks of weak intensities (i'ig.6).
It has been observed that for most of the metal ions studies, the Rf value
increases with the increase in dielectric constant of the solvent reaching to its
maximum value in nitromethane. However, further increase in the dielectric
constant of the solvent show no systematic trend (Fig. 7a, b).
In case of mixed DMSO-IINO3 systems, R)- value ol" metal ions namely 'An"',
Cd "", Cu^^ Ni "", La^ , Ce "", Cr ^ and Zr'' increases with the increase in the
nitric acid concentration upto solvent system 4 (DMSO+O.3MHNO3, 1:1 v/v).
But Th''"' beha ves differently (Fig.8a, b).
Rp value for Mn " and Fe "* remains constant in the beginning and then
increases shaiply as the hydrochloric acid concentration is increased in
DMSO-HCl system. It is interesting to note that Ba and Bi remain at the
point of application in solvents with compositions (DMSO+0.05M HCI 1:1
v/v and DMSO+O.IM HCI 1:1 v/v) respectively. Further increase in the
hydrochloric acid concentration enhances the movement of ions sharply and
138
1000 Temperature C
Figure: 4 Thermogram of stannic arsenate.
139
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then gradually. Cu " , Ni *, La''" and Th'' show an increase in the movement
with the increase in hydrochloric acid concentration. In these cases almost a
linear increase in the Rp value has been observed (table 4) as the hydrochloric
acid content in the composition is increased.
The above behavior of metal ions depends on the extent of exchange reaction
occurring between the hydrogen form of stannic arsenate and the external
solution. The presence of higher concentration of H" ions in the external
solution suppresses the exchange of metal ion with the exchanger and hence
an increases in the Rp value. On the contrary, at high pH the ion exchange
reactions will be facilitated as expected. As a result the metal ions are strongly
retained by the stationary phase (i.e. exchanger phase), which retards the
migration. On the basis of differential migration of metal ions, several binary
and ternary separations of analytical importance have been achieved (Table 5
and 6). The practical utility of this material has been demonstrated by
achieving separation and determination of metal ions in synthetic mixtures as
well as in glass industry waste. The results are reported in Tables 7 and 8.
146
Table: 4 R|, values of heavy iiielal ions in DMSO-IICL systems.
Metal ions
Mn^"
Zn^"
Cd "
Cu ^
Ba ^
Sr "
Co^"
Ni ^
Fc ^
La ^
Bi ^
Ce ^
Fe "
Cv''
Th^"
Zr "
DMSO+ 0.05M HCL
(1:1) VA^
0.10
0.00
0.56
0.22
0.00
0.60
0.15
0.32
0.10
0.00
0.00
0.00
0.00
0.00
0.00
0.00
DMSO+ O.IM HCL
(1:1) VA^
0.11
0.23
0.54
0.24
0.00
0.72
0.18
0.32
0.10
0.20
0.00
1.00
0.00
0.00
0.22
0.00
DMSO+ 0.2M HCL
(1:1) VA^
0.32
0.31
0.62
0.39
0.42
0.72
0.18
0.45
0.24
0.33
0.22
0.11
0.19
0.14
0.29
0.32
DMSO+ 0.3M HCL
(1:1) V/V
0.40
0.56
0.00
0.58
0.51
0.80
0.43
0.56
0.28
0.42
0.22
0.22
0.20
0.23
0.35
0.00
DMSO+ 0.4M HCL
(1:1)V/V
0.40
0.43
0.00
0.80
0.51
0.52
0.00
0.60
0.41
0.56
0.34
0.12
0.28
0.25
0.44
0.00
DMSO+ 0.5M HCL
(1:1) VA^
0.40
0.24
0.00
1.00
0.60
0.42
0.00
0.00
0.42
0.58
0.40
0.34
0.31
0.38
0.53
0.00
t d 7
Table: 5 Binary separations of important metal ions on stannic
arsenate- cellulose (1:5) blended layer
Metal ions
Zv''
Zx''
Th'"
Z/^
^r h^
h^
Cx''
Cu ^
Mn '
Cu ^
Fe ^
(RT-RL)
(0.10-0.28)
(0.31-0.55)
(0.23-0.40)
(0.23-0.32)
(0.39-0.52)
(0.34-0.48)
(0.21-0.38)
(0.25-0.38)
(0.33-0.64)
(0.24-0.56)
(0.22-0.41)
(0.25-0.54)
Metal ions
Th'"
• La^^
L^
C^
Zx''
Co''
Cx''
m''
Cr ^
Cr ^
Zxi''
Fe^^
(RT-RL)
(0.50-0.78)
(0.73-0.84)
(0.72-0.88)
(0.67-0.84)
(0.23-0.34)
(0.64-0.78)
0.70-0.85)
0.54-0.68)
(0.44-0.66)
(0.38-0.57)
(0.56-0.70)
(0.63-0.87)
Solvent Systems
0.1MDMSO + 0.1MI-iNO3(l:l v/v)
0.1MDMSO + 0.1MMNO3(2:l v/v)
O.IM Formic acid
0.2M Formic acid
O.IMIINO3
O.IM Formic acid
O.IMDMSO
0.1MDMSO + O.IM HNO3 (1:1 v/v)
O.IMHCL
O.IMMCL
0.1MDMSO + 0.1MH[NO3(l:2v/v)
0.1MDMSO + O.JM UNO, (3:1 v/v)
148
Table: 6 Ternary separations of heavy metal ions on stannic
arsenate-cellulose (1:5) layer
Metal ions
Th ' "
Cu^^
Ni^^
Cd'^
Mn'^
Cu^^
Cr^^
Zx'^
Yi'
( R T - R L )
(0.16-0.24)
(0.21-0.39)
(0.12-0.17)
(0.10-0.18)
(0.25-0.33)
(0.21-0.33)
(0.14-0.22)
(0.21-0.32)
(0.22-0.35)
Metal ions
Bi^^
Cr^^
Cu^^
Cu^^
Cr ^
Cd'^
Zn^^
Bi^^
NP^
( R T - R L )
(0.62-0.74)
(0.48-0.56)
(0.28-0.38)
(0.40-0.56)
(0.48-0.54)
(0.44-0.54)
(0.48-0.59)
(0.45-0.38)
(0.41-0.53)
Metal ions
La^^
Zn^^
C?'
Qx'*
Q^
Mn'V
Mn^
La ^
Fe ^
( R T - R L )
(0.80-0.93)
(0.74-0.91)
(0.66-0.82)
(0.78-0.86)
(0.77-0.88)
(0.70-0.80)
(0.84-0.93)
(0.76-0.88)
(0.67-0.88)
Solvents
O.IM Formic acid + 0.1MHNO3(l:l v/v)
O.IM Formic acid + O.IM HNO3(2:1 v/v)
O.IM Formic acid + O.IM HN03( 1:2 v/v)
O.IM Formic acid + O.IM HN03(1:1 v/v)
O.IMDMSO
O.IMHNO3
O.IMMHNO3+ 0.1MDMSO(1:1 v/v)
O.IM Formic acid + O.IM HNO3(2:1 v/v)
O.IM Formic acid + 0.iMIINO3(l:l v/v)
149
Table: 7 QuanU(a(ive separation of Cu , Cr and Zn ions on
stannic arsenate-cellulose (1:5) blended layer from synthetic
mixtures
S. No.
1.
2.
3.
Separation achieved
Cu'"
Cr "
Zn'"
Cu'"
Cr "
Zn'"
Cu'"
Cr "
Zn'"
Amount loaded
(^lg)
50
50
50
50
50
50
50
50
50
Amount Found"
48.6
49.0
50.1
49.8
49.9
49.2
50.00
49.0
50.0
% Recovery + S.D.
97.2+0.06
98.02±0.02
100.2+0.81
99.6+0.12
99.8+0.01
98.4+0.20
100.0+0.32
98.0+0.03
100.0+0.04
a. Average of five replicate determinations
150
Table: 8 Quantitative separation of Cu , Cr ^ and Zn ^ ions in glass
industry waste on stannic arsenate-cellulose (1:5) blended
layer
Separation achieved
Cu'"
Cr "
Zn'"
Amount loaded
44
116
348
Amount found "
44
115.2
344
% Recovery + S.D.
lOO.OiO.Ol
99.3+0.02
98.3.0±0.05
a. Average of five replicate determinations.
151
Conclusions
Stannic arsenate exhibit reasonable thermal and chemical stability. Its use in
thin layer chromatography shows interesting results in the separation of metal
ions. The potentiality of this material can further be explored for difficult
separations of metal ions and organic compounds in industrial wastes and
environmental samples using thin layer and column techniques.
Acknowledgements
The authors are thankful to Chairman, Department Chemistry, Aligarh
Muslim University, Aligarh for providing research facilities. One of the
authors (AMTK) gratefully acknowledge the award of University fellowship
(SRF) by Aligarh Muslim University, Aligarh
152
References
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155
-5
o
'SIS, ^on
J'^roperuei •xcmam/ie jr roDerims
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' icomOi
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oif LjesnpGf'mMre on
in isirmmmn K^Ami i lae. o o
IBS
Summary
Stannic silicomolybdate has been synthesized at pH 0.63 .The experimental
parameters like order of mixing, mixing volume ratio, pH, stirring time,
drying temperature has been established for the synthesis of the material. The
ion exchange capacity for Ca " has been improved from 0.53 to 1.73 meq/g
for this newly synthesized material. The reproducibility of the product formed
has been checked. The exchanger was characterized on the basis of chemical
composition, thermal & chemical stability, FTIR, TGA, DSC, X-ray and SEM
analysis .The scanning electron microscopy of the material shows regular
diamond shape morphology. The presence of uniform morphology also
indicates the absence of impure phases. The X-ray diffraction study shows
amorphous nature. Distribution coefficients studies of the metal ions on this
material were performed in solvents having different acid dissociation
constants namely trichloroacetic acid, formic acid and acetic acid. The effect
of dielectric constants of solvents has also been studied by using
dimethylsulfoxide; formic acid, acetic acid& tricholroacetic acid .The effect of
temperature on the distribution coefficient has been explored. It was finally
concluded that 45°C appears to be the most favorable temperature. Important
quantitafive separafion of metal ions in ternary mixtures include Ni^'-Co~'-
Pb^^ Cu^"-Cr^^--Pb' Cu''-¥c''-?h'\ Th'' -Zr'' -Sn'*^ Cr^"-Ni2^Fe^^ Cu^"-
Ni '*'-Ag" and Fe' ' -Zn^ -Al'' . The practical potential of stannic silico-
molybdate has been explored by separatmg Cu and Zn quantitatively in
synthetic mixtures as well as in commercially available brass sample.
156
Introduction
Inorganic ion exchangers are in general superior to organic exchangers in
some aspects as they are resistant towards high ionizing radiations [1-2] and
can be used at elevated temperatures without the danger of decomposition.
Moreover, thej often exhibit specificity towards certain metal ions. It is for
these reasons there has been a revolutionary growth in the field of synthetic
ion exchangers. [3] Studies have been made for their preparation, properties
and analytical applications to simple binary and ternary separations of metal
ions have been performed by different chromatographic techniques [4-15].
However their analytical and industrial applications in diverse fields is yet to
be explored. It has been observed that double salts often exhibit much better
ion exchange properties than simple salts [16-19]. Tin (IV) based ion
exchangers have received attention because of their excellent ion exchange
behavior. They are accepted to have radiation stability. Because of their
reproducible behavior and ion exchange properties, their utility has been
demonstrated for the separation of various metal ions [20-21]. Double salts
comprising of molybdoarsenate [22], vanadoarsenate [23], vanadotungstate
[24], selenoarsenate [25], arsenosilicate [26], tungstoselenate [27], iodophos-
phate [28], selenophosphate [29], pyrpphosphate [30], tungstophosphate [31],
molybdosilicate [32-33] and molybdophosphate [34] based on tin (IV) has
been synthesized.
The present work has been undertaken in an attempt to synthesize new phase
of stannic silicomolybdate. Efforts have been made to explore the effect of
temperature; dielectric constant and acid dissociation constants of solvents on
the distribution coefficient of metal ions have been extensively studied. The
practical utilitj' of the material has been demonstrated by separating and
analyzing the standard sample of brass.
IS7
Experimental
Reagents and Chemicals
Stannic (IV) chloride pentahydrate (LobaChemieJndia), Sodiummolybdate
(M&B,USA), Sodium metasilicate (CDH, India), Nitrates of metal ions
(E.Merck India) used were of analytical grade.
Apparatus
Specronic 20-Genesis for specrophotometric dereminations, Perkin Elmer
Spectronic BX FTIR for IR studies, a Philips (Martin HollandPW 7030/10)
for Xray diffraction, Elico (EL-10, India) for pH measurements, Perkin Elmer
(TGA7 & DSC7) for thermal analysis and scanning electron microscopy was
performed on Cambridge instruments (stereoscan360, U.K).
Syntheses
Stannic silicomiolybdate was prepared by adding mixture of 0.1 M aqueous
solutions of sodium molybdate and sodium metasilicate in O.IM aqueous
solution of stannic chloride pentahydtare with constant stirring in 1:1 volume
ratio. The pH (0.63) of the resulting solution was maintained by adding IM
HNO3. The yellow precipitate obtained was digested with mother liquor
overnight. The supernatant liquid was tested to ensure for the complete
utilization of the reagents. The liquid is separated from the precipitates by
decantation. The precipitate was washed with DMW several times; filtered
and washed again to remove reagents if any adhered with the precipitates. The
final product v/as dried at 40+2°C in an electrically controlled oven. The
material was cracked into fine particles when immersed in water. It was
converted into H" form by treating with l.OM HNO3 solutions. It was finally
rinsed with dimineralised water to remove excess acid in a column and dried
in an oven at 40+2°C.
Ion Exchange Capacity
A 1.0 g (dry mass) of stannic silicomolybdate in H^ form was packed in a
glass column having glass wool support at the base. A 0.1 M NaNOs solution
158
was passed slowly by adjusting Ihe cfnucnl rate at 9-10 drops/min.Thc
effluent was carefully collected in a 250 ml conical flask. The complete
replacement of H" from the ion exchanger by K was ciicckcd by comparing
the pH of the influent (O.IM NaNOs) and effluent. The collected effluent was
titrated against standard NaOH solution.
pH titration
Topp and Pepper method was used for pli studies in LiCl-LiOll, NaCl-
NaOII, KCl-KOII, CaCl2-Ca(OII)2, MgCl2-Mg(OIl)2 and BaCl2-Ba(011)2
systems [35]. For this 0.5 g exchanger was treated with 50 ml of concerned
solution.
Chemical Stability
The chemical stability of stannic silicomolybdate was examined in several
mineral acids like HCl, HNO3 and H2SO4 and in bases, NaOll and KOH. A
0.5g of ion exchange material was placed in 50ml solvent of interest and kept
for 24h at room temperature. Tin, molybdate and silica released in the
solution were determined spectrophotometrically using suitable reagents [36-
38].
Chemical Composition
A 0.15g of samiple was dissolved in 15 ml hot concentrated nitric acid. The
solution was cooled and diluted to 100ml with dcmincralizcd water .The
metal contents in the solution phase were determined spectrophotometrically
[36-38].
Thermal Stability
The effect of drying temperature of the material on the ion exchange capacity
was studied by heating stannic silicomolybdate from 100-1000°C for Ih in a
muffle furnace and subsequently the ion exchange capacity was determined
using standard NaOH solution.
159
IR Analysis
For IR analysis of the material, lOmg of the exchanger in H^ form was taken.
The ion exchanger was thoroughly mixed with lOOmg of KBr and grounded
to a fine powder. A transparent disc was formed by applying a pressure of
80,000psi (lpsi=6894.76) in a moisture free atmosphere. The disc formed
contained 50-100|ig of the ion exchanger. The IR absorption spectrum was
recorded between 400-4000cm''.
Scanning Electron Microscopy
Electron micrographs were recorded for stannic silicomolybdate by scanning
electron microscope at 20.0 Kv. The details are shown in SEM photographs.
X-Ray Studies
For x-ray diffraction analysis, manganese filtered CuKa radiation (X,=1.5418)
was used. The instrument was equipped with graphite monochromotor
operating at 40KV and 30mA. The X-ray studies were performed between 10
to 70°29 while the speed of the recorder was maintained at lOmm/sec20.
Distribution Studies
Distribution coefficient (Kd) for metal ions Ag^ Ca^*, Mg^^ Ba^^ Sr^^ Cd^^
Co^^ Ni^^ Pb^^ Zr?\ C?\ VQ'\ Cu'^ C^\ L^\ Zv'\ Th''^ Sn" and k?'
were determined in a number of solvents viz formic acid, dimethlyformamide
acetic acid, trichloroacetic acid and mixed systems .The effect of temperature
on the distribution coefficient was also studied. 0.5g of stannic
silicomolybdate in H form was put into 100ml conical ilasks each containing
50ml solution of 2*10' ' 'M concentration of metal ions. The mixture was
continuously shaken for 3h at 30°C, 45''C, 60''C and 75"C.The amount of
metal ion present in the solution was determined by titrating it against
disodiun salt of EDTA using standard procedures [39]. Distribution
coefficient valves were calculated by using the following relationship
160
The Kd values were calculated using the following formula.
Amount of metal ion in the exchanger phase /g exchanger Kd=
Amount of metal ion in the solution phase /mL solution
In our case (I-F)/0.5g (I-F)
Kd = = X 100 I-F/50ml F
Where I is the volume of EDTA used before treatment with exchanger
F is the volume of EDTA used after treatment
I-F Amount of metal ion in resin phase.
Separations
Quantitative separations of metal ions in binary and ternary synthetic mixtures
In order to explore the separation ability of stannic silicomolybdate by
column chromatography, a number of binary and ternary quantitative
separations of metal ions were practically achieved.l.Og of stannic
silicomolybdate in H" form (50-100 mesh) was packed in a glass column of
inner diameter 1.1 cm with a glass wool support at the base. Mixture of metal
ions solution to be separated was then poured into the column. The solution
was allowed to move through the column at the rate of 8-lOdrops/min and
recycled at least three times. The column was washed with demineralized
water to rinse the sides of the column. The adsorbed metal ions were then
eluted with appropriate eluents. The flow rate of the effluent was maintained
at ImL/min throughout the elution process .The effluents was collected in
lOmL fractions and metal ions contents were determined titrimetrically
against EDTA solution.
161
Quantitative Separation of Cu ^ and zn ^ in Commercially Available Brass
Sample
2.0 g of commercially available brass in the form of solid chip was dissolved
in minimum quantity of aqua regia. Thereafter the solution containing Cu '
and Zn "*" was diluted in a 100 ml standard volumetric flask. Now this stock
solution was utilized in the determination of the metal contents in the given
sample. Suitable volumes of stock solution were poured into the stannic
silicomolybdate column. The subsequent steps were the same as described
earlier in section
Results and Discussions:
Table 1 shows the synthesis of single and double salts of stannic
silicomolybdate .It is quite evident from the data that double salts shows
superiority over their single counterparts in terms of ion exchange capacity.
Table 2 shows the reproducibility data in terms of ion exchange capacity,
composition and yield. Only the pH of the resultant mixture was varied while
the rest of the experimental conditions remain the same. I Icncc sample no 5
was chosen for detailed studies.
The ion exchange capacities for mono and bivalent metal ions are represented
in table 3. The alkali metal shows decreasing trend for ion exchange capacity
in the following order K' >Na" >Li ^ while the alkaline earth metal ion follow
the sequence Ba " >Sr " >Ca '*'> Mg " . This sequence is in accordance with the
hydrated radii of the exchanging ions. The ions with smaller hydrated radii
easily enter the pores of the exchanger resulting in higher adsorption. [40].
Figures 1 and la represent the pH titration curves for mono and bivalent
systems namely LiCl- LiOH, NaCl-NaOH, KCl-KOH, CaCL2-Ca(OH)2,
MgCl2-Mg(0H);., BaCl2-Ba(OH)2 respectively. The uptake of alkaline earth
metal ion in the pH region 2-6 follows the order Mg "*">Ca" >Ba '*"> both in
acidic and basic regions whereas in case of alkali metal ions in the pH region
2.3-7.5,the trend is Li''>Na^>K^
162
^ i—(
'S c o
73 0) I / ]
03 A
• 4 - 1
7S
lU
2 s o
-o -o s
c ( / ]
C M
O
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BX)
e JS u ><
a
T 3
a C8 yi '33 .a s
03
^H
^ 3
pfl O ^"^ « « bl)
B 2 « o c
2 "« 'wD > 3 ^
a "o C^
C3 •* ->
O H
ffi a
u 2 s O V3
5 — bX)
03
C M
o *
.2 « • M - M
"2 ?* a b
' O
o §
S CI.
!?; o (J
a "cu^ Bl> OS «
oo ^ o
I > CN CN
o o CN
m ^ o
.S c
^ '—; o
<u •4—>
o
to
O
H CH c3
00
^
r-1 r n O
r o
r~; *—H
o o <N
m vq o
c C/J
:^ ^ o
(L) • 4 — »
E ^ 03 "o
(N
O >o o
r o O ^
o o ( N
m ^. o
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:§ '—; o
<u • i - j
eti
•1 6 S o S o
1 ^ ^
r n
oo MD
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o o CN
r<^ ^ o
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S '—' o
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fi o o • »-( 00
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^
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c«
ffi a
s o
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a
a o U (U
2- o S2: « o)
c^ CN MD
O O ^
(N CN O ro rn O
' " • ^ .
O
U o (N
+ 1 O >o
o o CN
r—1
^ • •
CN
x: r - H
m ^ o
r—1 '""' ' '
0 9 0
tit
r—{
0 CN VC)
0 ' — 1
^
^ H
CN 0
CN CO
0
'^ r t
d
U 0 CN + 1 0 ^
0 0 (N
.—I
^ • • CN
JD r—*
m MD
d
s§s d d 0 II II II
c/D :g c/D
CN
CN CN vb
0 0 ON
d
CN CN 0 CO
ro d on ^ d
0 0 (N + 1 0 VO
0 0 CN
» — 1
^ CN
x: T — <
m ^ d
sss d d 0 II II II
^ 2 ^
m"
CO
MD
0 CN ^
CN ( N
d m r<-|
d CN '^ d
U 0 CN + 1 0 •o
0 0 CN
.—H
rl^ • • ( N
X, r-~t
m MD
d
sss d d d II II II
00 ^ (/}
'^
0 CN >o
0 • — ;
^
CN r-1
d CN rn 0
• *
'^ d
U 0 CN + 1 0 "O
0 0 CN
r—1
' 1
CN
x: f — (
m MD
d
3S3 d ^ d II II II
c/D ;§ c/3
^n
164
Table: 3 Ion exchange capacity for mono and bivalent metal ions of
stannic silicomolybdate (drying temp 40 + l^C).
Exchanging metal ions
Lr
Na^
K"
Ca ^
Mg^^
Ba^^
Sr'"
Hydrated Radii (A)
10.0
7.90
5.30
9.60
10.80
9.90
9.40
Ion exchange capacity (meq/g exchanger)
0.30
0.40
1.00
1.73
0.92
0.95
0.88
165
u
0
LiCL-Li(OH; •— NaCl-NaOH • - • KCl-KOH
1.0 2.0 3.0 /..O
OH added/ meq/0.5gexchanger
5C
Figure: 1 pH titration curves for different alkali metal systems.
ififi
u
MgCl2 -Mg (0H)2
CQCl2^Ca {OHJ2 B Q C 1 2 - B Q ( O H ) 2
1-0 2.0 3.0 L.O
OH odded .meq/O.Sgexchonger
5.0
Figure: la. pH titration curves for different alkaline earth metal ions
systems.
167
The chemical analysis data in lahic 4 reveals Ihal slaiiiiie silicomolylxiale is
highly stable up to l.OM Concentration in alkalis and fairly stable in mineral
acids.
The chemical composition analysis reveals the Sn:Si:Mo ratio as 4:3:2. The
superiority of the newly synthesized Stannic silicomolybdate can be readily
emphasized from figure2 that it retains considerable ion exchange capacity
even at 800°C while the other material have negligible ion exchange capacity
even at 60''C.The ion exchange capacity of various materials dried at 40"C
shows the following decreasing trend, Tin (IV) silicomolybdate* >'fin (IV)
iodophospate [41] > Zr (IV) iodomolybdate [42] > Tin (IV) molybdoarsenate
[43] > Tin (IV) Tungstoselenate [44] > Tin (IV) silicomolybdate** [45] > Tin
(IV) Tungstosilicate [46]. It is also interesting to note that there is a decrease
in the ion exchange capacity in all cases as the drying temperature of the
material is increased except the previously synthesized stannic
silicomolybdate which shows abnormal behavior in the increase in the ion
exchange capacity with the increase in the drying temperature [45]. It is also
apparent in case of newly synthesized material that the loss in ion exchange
capacity is gradual with increasing drying temperature while in other cases
the loss in ion exchange capacity is sharp.
The infrared spectrum of stannic silicomolybdate in H* is shown in llgurc3.
The strong and broad band in the region 3500-300cm"' may be assigned to
interstitial water molecules and OH groups. Another strong and sharp peak
with a maximum at 1626cm'' is due to 11-0-11 bending .The spectrum of
stannic silicomolybdate shows a strong and weak band at 1104cm'' and
942cm' respectively indicates the presence of silicate and molybdate groups
[47]. Band at 585cm"' is due to metal oxide bond.
* Newly synthesized ** Synthesized earlier
168
Table: 4 Chemical solubility of stannic siliconiolybdato in various
solvents.
Solvents
O.IMKOII
l.OMKOH
O.lMNaOH
l.OMNaOH
l.OMHCl
I.OMHNO3
I.OMH2SO4
Tin (IV) (ms/SOmI)
0.0
0.26
3.21
1.54
5.40
4.80
6.20
Mo (niR/50ml)
0.00
0.80
2.20
8.00
4.26
6.50
3.89
Si (ni^/50uil)
0.00
1.74
0.80
4.06
6.75
5.40
4.50
16')
2.0 o Stannic S i l i c o m o l y b d a t e ^ • Stannic Si l icomoly bdote"*^'^ A Stannic lodophosphate A Zirconium lodomolybr lote Q Titanium Tungstosi l icate X Stannic Tungtosele note ^ Stannic Molybdoarsenate
400 GOO 800 1000 Temperature ( C
Figure: 2 Comparison of ion exchange capacity of ciilTcrenl ion
exchanger at different drying temperatures.
170
C O (J
c
3 U O
a-C/3
H u.
p
Si
171
The scanning electron microscopy of newly syntiiesi/xd stannic
silicomolybdate shows regular uniform diamond morphology. The presence
of uniform morjDhology also indicates the absence of impure phases [48]. The
results are shown in photograph 4. The X-ray diffraction study of the material
shows amorphous nature.
A broad endothermic peak in DSC curve (fig.6, 6a) in the temperature region
6O-I8OV is due to gradual loss of external water molecules from the material.
Two exothermic peaks with T,nax at 280 and another at 311"C may be caused
by physical transitions such as crystallization occurring during heating. These
conclusions are also supported by thermogram and a derivative thermogram
(fig.5), which show weight loss up to 200°C.No further loss in weight has
been observed. The ion exchange capacity data also supports these llndings.
On the basis of chemical composition, thermal and IR studies, a tentative
formula may be assigned for stannic silicomolybdate as
l(Sn02)4 .(I l2Si03)2. (112M0 0,)3j .nl bO
If all the external water molecules are lost upto 150"C,thcn the weight loss as
calculated from TGA curve was 08%. The number of water molecules (n)
per mole of the material can be calculated from Albcrti's equation [49|.
X(M+18n) 18n -
100
Where:
X: percent water content and M+18n is the molecular weight of the material.
It gives the value of n »6.
The above formula can be then rewritten as
[(Sn02)4 .(H2Si03)2 .(H2M0 04)3] .6H2O
The H^ attached to silicate and molybdate group seem to be responsible for
the exchange characteristic of this material.
172
l^tM
Figure: 4 SEM photograph of stannic silicomolybdate.
173
>
a. E <u
1—
>
P-
W w o
•*^
JZ CT
01
5:
10 1/) o
x: C7)
(U
$ o dl > ^-* o > i_
0) O •4^
n F
h-
>
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o 03 t ^
o C71 CD
O o I D
o ^mm
i n
O <M
^
—. u 0
O
o I . a> QL
F
•a X!
"o c o
t/1
CJ
c c l/l
<*-o f= C3 U 61) O
c
o in
^ - f - - T o o in
(Vo) s s o i j q S i a M / MP
i n O
H
o c^ o
O ^ r-j
U~t , . QJ Ttmt
fcC
u-
174
o CO CO
o ^ m
O O n
O <£> CM
O <N CM
O CO
/- u O 0; \-'J
••--O
(1-
a b
1—
•
•a
o c o
o c c 05 -w C/)
t+-O CU
3
u
IZ
o o
o
( M i i J ) M O i j } D e H
175
o
o r -m
( i CTl CN
o
CM
o t n
•— U o
<u
(_ D
O u
a e
1—
•a
o r C O
'H c +-C/3.
o Of • » -
;. 3 o
u Q
5X3
b-
o cvi
( M U J ) M O I J ; 0 3 H
176
It appears from figure? that pH of the solution decreases wilh increase in lime
of equibration due to release of hydrogen with sodium ions. It is evident that
the equibration time fro ion exchange is attained after 4h since there is no
further release of hydrogen ions in the solution phase.
The data in figures8,8a, show the variation in Kd valve with variation in
temperature in formic acid .All the metal ions studied exhibit a general trend
of highest Kd at 45°C and then a gradual decrease with the increase in
temperature .In some cases for example Ni ' ,Cr " ,Th''" and Sr^*), the Kd
remains constant with the increase in temperature beyond 45°C.In acetic acid
system, almost similar behavior has been observed (see figures 9, 9a &
9b).Therefore the optimum temperature for the sorption of metal ions is 45°C.
The distribution studies of metal ions in various organic acids with different
dissociation constants has been shown in figurelO .It has been found that
formic acid with dissociation constant (58.0) is most favorable for the uptake
of metal ions namely Al^^ Zx^\ l\i^\ Sn'*\ Mg^\ Pb^^ Zx^\ Ni^^ Ce^^ and
La " . Kd valves remains almost ineffective by the variation of dissociation
constant for k% , Q^\ Sr^^ Cd^^ Co "" and Fe^^
The effect of dielectric constant of the solvent systems on Kd has also been
studied. The results are shown in figure 11,1 la which revealed that in case of
Ag" ' Ca " , Mg " , Cd " , Pb " , Zn "*", Co^ , and Fe^ , there is no significant
variation with the change in dielectric constant. However Ce *", La " , Zr''" and
Th''" show interesting features. The Kd valve decreases with the increase in
the dielectric constant of the solvent systems studied (fig.9a). This decrease in
Kd docs not follow linearity.
It is apparent from table 5 that Kd values in O.IM DMSO are relatively high
as compared to formic acid medium. However on mixing formic acid in
DMSO there is decrease in Kd values for most of the metal ions with the
exception of Ce "*", La"'" and Sn'*" . This may probably be due to increase in
polarity of the mixed system.
177
Time (h
Figure: 7 Equilibration study as function of time.
178
C71 O
3.0
2.0
1.0
-
r^ — — ^
1 ' ^ J »
» ^ ' ' ' ^ " ^
1 1
^ . . . \
^ ^ • • • - • ^ • - - A
Ag + 8a 2-
- - Cd2/ — - Co2^
1 1 30 45
Temp, ( C 50 75
Figure: 8 Effect of temperature ou distribution coefncieut of metal
ions on stannic silicomolybdate in formic acid medium.
179
3.0
o
20
1.0
1
— — o
,.J.,.. 7S
Temp.
I'il'lirc: HA MllVrl ol |i-iii|H'i';iliii«- on disln ihnl ion < (x-niciciil ol iii('l:il
ions on ,sl:iiiiiic silicoinulylHhilc in luiriii*. acid incdinni.
180
3.0
2.0
X5
cn O
1.0
30 45 Temp. ("C
— Ce 3^
Co
50
/>
75
Figure: 9 Effect of temperature on distribution coefficient of metal
ions on stannic silicomolybdate in acetic acid medium.
181
3.0 -
2.0 -
-o
O
1.0 -
/
1 1
> 5
' ^ • A . -A
M g — - Cut2 — - Pb2-
.1 1 30 45
Temp. (°C ) 50 75
Figure: 9a Effect of temperature on distribution coefficient of metal
ions on stannic silicomplybdate in acetic acid medium.
182
Temp
Figure: 9b Effect of temperature ou distributiou coefficieut of metal
ions on stannic silicomolybdate in acetic acid medium.
183
Ag +
o
Co 2+ Mg 2 +
V J — I 1
0 1 2 3 0 1 2
Ba 2 +
1 2 3 0 1 2 3 0 1
Solvent Syste ms
Figure: 10 Effect of acid dissociation constant on distribution
coefficient of metal ions. The solvent systems are arranged
in increasing order of acid dissociation constant. 1.Acetic
acid 2. Formic acid. 3. Trichloroacetic acid
184
X3 is: a. 2 o
Fe 2+ Zn 2+
/. 0 1
0 1 ^ 1 1 I I I I
0 1 2 3 /; 0 1 2 3 t 0 1 -J
Mg 2 +
1 2 3 4
J I
3 Z,
Po 2^
i 1 1 i
Souen, Systems SoUen. Systems Soiven. 'sys.Ls'
Figure: 11 Variation of Kd value with dielectric constants of solvents.
The solvent systems are arranged in increasing order of
dielectric constants. 1. Trichloroaceticacid 2. Acetic acid
3. Dimethylsulfoxide 4. Formic acid.
185
•o
O
A r
en o
3+ 4
J I
LQ 3 +
V
0 1 2 3 ^ 0 1 2 3 c
Th^ +
0 1 2 3 ^ 0 1 2 3 4 Solvent Sys tems Solvent Sys tems
Figure: 11a Variation of Kd value with dielectric constants of solvents.
The solvent systems arc arranged in increasing order of
dielectric constants. 1. Tricliloroacelieacid 2. Acetic acid
3. Dimethylsulfoxide 4. Formic acid.
186
ruble: 5 Distribiilioii cocnkiciil Nliidics in some pure iiiul iiiixid
solvent systems.
Metal ions
Ag^
Ca''
Mg^'
Ba'
Sr^^
Cd'"
Pb'^
Zn^^
Co^"
Ni^*
Cu^^
Cr^^
Al^^
Fe^^
Ce^^
La^"
Zv''
Sn'"
Th^"
O.IM Acetic acid
860
94.0
233
116
215
197
917
280
234
94.0
31.0
160
158
150
252
212
443
1133
270
O.IM Trichloro acetic acid
392
97.0
170
727
180
155
298
224
281
389
292
550
1270
169
4833
6766
15100
585
144
O.IM AA-O.IM TCA
860
111
14.0
99.0
17.0
7.00
93.0
151
132
231
4.0
71.0
427
3.00
14700
20500
1529
825
42.0
O.IM DMSO-AA
292
118
23.0
27.0
1.00
57.0
205
17.0
78.0
82.0
78.0
8.00
32.0
200
21.0
36.0
175
444
18.0
O.IM
DMSO
1100
100
300
204
481
328
408
316
163
225
277
1200
204
128
270
232
891
263
249
O.IM Formic acid
392
67.0
23.0
148
132
189
221
122
163
52.0
63.0
300
52.0
110
17.0
43.0
245
160
51.0
O.IM DMSO-FA
433
56.0
22.0
84.0
33.0
10.0
771
49.0
52.0
103
75.0
171
37.0
556
14700
20500
635
1441
42.0
AA- Acetic Acid rCA-Trichloro accdc iicid F.A- Formic Acid DMSO-Dimethyl sulfoxide
187
Similar trend is observed in case of O.IM TCA-O.IM A.A systems. Table 6
shows the quantitative separation of metal ions in synthetic ternary mixtures.
It is evident from the data that metal ions of economic importance as well as
those which are industrial waste can be separated on a column of stannic
silicomolybdate acting as ion exchanger. After able to achieve ternary
separations in ternary mixtures by column chromatography, quantitative
separation of Cu andZn was undertaken in synthetic sample prior to its
determination in commercially available alloy sample ie brass. The result in
table 7 shows quantitative separation of Cu and Zn in brass at different
loadings. Table 8 shows the separation data.
188
Ijible: 6 QiiuiiiUljilivc separsilioiis of ineliil ions in ternary syndiclic
mixtures
Ternary mixtures
Ni^^
Co -
Pb'*
Cu^^
Cr ^
Pb'*
Cu^^
l^c"
Pb^"
Th"^
Zr"
Sn'^
Co"
Til ' '
Sn"
Cr^^
Ni^^
Fe- ^
Cu''
Ni^'
Ag'
IV^
/ i r '
M''
Amount loaded
(mg)
2.93
2.94
10.35
3.17
2.59
10.35
3.17
2.79
10.35
11.6
4.56
5.93
7,00
11.60
5.93
2.59
2.93
2.79
3.17
2.93
5.35
2.79
.1.26
1.44
Amount found*
(mg)
2.91
2.93
10.33
3.17
2.56
10.34
3.16
2.77
10.32
11.5X
4.55
5.92
(.,97
11.61
5.92
2.59
2.91
2.76
3,18
2.91
5.33
2.78
3,2'l
1.43
0 /
Recovery
99.3
99.6
100.0
100.0
98.8
99.9
99.6
99.2
99.7
99.8
99.7
99.8
99. >
100.1
99.8
100.0
99.3
98.9
100.0
99.3
99.6
99.6
99.3
99.3
Volume of
Eluent (mL)
25
50
60
30
45
70
40
55
80
3.5
60
80
Ml
70
85
55
70
90
30
.SO
65
45
60
90
Kluent u.sed
O.IMF.A
O.IMDMSO+O.IMA.A
O.IMDMSO+O.IMF.A
O.IMF.A
O.IMDMSO
0.1MTCA+0.1MA.A(l : lv /v)
O.IMF.A
0.1MTCA+0.1MA.A(l:lv/v)
IMHNO3
O.IMDMSO
i(),IMA.A(l:lv/v)
O.IMDMSO
O.IM l'',A
O.IM I'.A
0.1M DMSO +0.1M l''.A(l;lv/v)
O.IMF.A
O.IMDMSO+O.IM A.A(l:lv/v)
O.IM I'.A
O.IMTCA lO.IM A.A(l:lv/v)
O.IM I'.A
O.IM A.A
O.IM DMSO 1 O.IM A.A(1:I v/v)
O.IMTCA+O.IM A.A(l:lvA')
O.IM l)MSOlO.IMA.A(l:lv/v)
IMHNO3 d
* Average of live replieale delenniiuilions. TCA- Trichloroacetie acid, A.A - Acetic acid, !• .A - Formic acid
Table: 7 Quantitative separations of Cu^ and Zn ^ in synthetic
niixfnres
Metal ions
Amount loaded (mg)
3.15
3.26
6.30
6.50
9.45
3.26
Amount found* (mg)
3.10
3.24
6.12
6.50
9.42
3.22
Volume of Eluent (mL)
35
20
55
40
75
60
% Recovery + S.D
98.41+0.02
99.38+0.05
97.14+0.20
100.0+0.08
99.68+0.11
Eluentuse Cu : O.IM Trichloroacetic acid-O.IM Acetic acid (1:1 v/v)
Zn " : 1 .OM Acetic acid
* Average of five replicate determinations.
190
Table: 8 Quantitative separation of Cu ^ and Zn * in commercially
available brass on stannic silicomolybdate columns.
Metal ions
Zn '
Amount loaded (mg)
10.0
4.35
20.0
8.7
25.0
13.0
40.0
17.40
50.0
21.70
Amount found* (mg)
9.76
4.25
18.90
17.84
25.90
11.70
37.90
16.20
47.25
19.74
Eluent
0.1MTCA-0.1MAA(l:lv/v)
l.OMAA
0.1MTCA-0.1MAA(l:lv/v)
l.OMAA
O.IMTCA
l.OMAA
O.IMTCA
I.OMHNO3
O.IMTCA-O.O5MHNO3
I.OMAA-O.IMHNO3
Volume of
Eluent (mL)
40
20
55
30
40
50
55
65
60
80
/o Recovery +
S.D
97.60+0.22
97.70+0.08
94.50+0.06
90.11+0.12
103.60+0.20
90.0+0.41
94.75+0.31
93.10+0.40
94.50+0.14
90.96+0.21
* Average of five replicate determinations.
TCA- Trichloroacetic acid, A.A - Acetic acid
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