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STUDIES ON SYNTHETIC INORGANIC ION-EXCHANGERS AND THEIR APPLICATIONS TO SEPARATION AND
DETECTION AND DETERMINATION OF ENVIRONMENTAL POLLUTANTS
DISSERTATION Submitted in Partial Fulfilment of the Requirenncnts
for the Award of the Degree of
Muittv of $I|tIos(opI|p IN
Chemistry
BY
MUBEEN AHMAD KHAN
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
A L I G A R H ( I N D I A )
1990
^ f .
DS1552
,J^ec/u/ ^iz/ai' C^-teo/if^ M.Sc, Ph.D., C. Chem.. MRIC (London)
Professor of Analytical Chemistry
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH-202002, INDIA
vm^HmAt 8-^-3o
M wt^ u my <- 9«<TIW
Xtiis i s to etiCtlfy tHat feho disMMrtatiun
•atltlttd **atia4i«s on syath«%ie xneaenaiiiQ xon - jeetiangejca
<uia tsheir o^^lieatioiis to g«|>aaratioii and aetootion «iift
<l«t®icaiiafttioii of wm%xwiamtk%»X jPolXiatant*** i « tiio
Phll090|)hy i n ctMMii«tiy«
ACKNOWLEDGEMENTS
I egress with great sense of gratitude, my thanks
to Professor Saldul Zafar Qureshi, my dissertation advisor
whose guidance and criticism has been indispensible to the
completion of this task. I am also grateful to Professor
S.A,A.Zaidi, Chairman, Department of Chemistry for research
facilities.
I acknowledge my dept to many of my friends especially
to Dr.Ahsan Saeed, Mr, S.Munawwar Pazal and Ch.Durga Prasad
as well as Mr.Abdul uuadir for valuable suggestion and help
in the completion of this task. I also express my thanks to
ray colleagues who provide me a considerable insight and a
cordial atmosphere.
I owe particular gratitude to Dr. Nafisur Rehman for his
constant help and fruitful suggestions.
Finally a considerable dept of appreciation is owed to
my Papa/ Dr.Zaheer Ahmad Khan* without whose encouragement
this effort could not have been possible.
( MUBEEN AHMAD KHAN )
C O N T E N T S
P a g e
1 . L I S T OF TABLES
2 . L IST OF FIGURES
3 . CHAPTER-I
GENERAL Il^TRODUCTION
REFERENCES
4 . CHAPTER-II
II>.TRUiJUCTION
EXPERIMENTAL
RESULTS
DISCUSSION
REFERENCES
i
l i
1
25
24
35
SYNTHESIS AND CHARACTERIZATION OF NEW THREE COMPONENT ION-EXCHANGE MATERIAL J Zr (IV) AKSEi>iOVAl>JADATE
36 - 37
38
42
5Q
58
- 41
- 49
- 57
- 60
(O
1. Table-1
LIST OF TABLES
Page
Selected zeolites with their "+
composition and exchange capacities.
2. Table-2
3. Table-3
Properties of some two component
Ion-exchangers. 9-12
Properties of some three component 13-15
Ion-exchangers.
4. Table-4 Classification of Pollutants 18-20
5. Table-5 Synthesis and Proper t i es of Zirconlxun (IV) arsenovanadate
^2
6, Table-6 Ion-exchange capacity (meq/g-dry
exchanger) of Zirconium (IV)
arsenovanadate for various cations.
3
7. Table-7 Chemical stability of Zirconium (IV) ^
arsenovanadate in different
solutions.
8. Table-8 Distribution coefficients of metal
ions on Zirconium (IV) arsenovanadate
9. Table-9 Kd values and separation factor of
metal Ions for which the separation
is achieved.
4-7-
10. Table-10 Separation of metal ions achieved -8- 9
on zirconixjun (IV) arsenovanadate.
rii)
LIST OF FIGURES Page
1. Flgxire-l 52
p H - t i t r a t i o n curve of Zirconiiim(IV)
ar senovanadate.
2 . Figuure-2 53
I.R. spectrum of Zirconium (IV)
arsenovanadate.
3. Figure-3 56-57
Elution profiles
aj;s;i;:i:;:i;j::5;:::;;;«;:::i:y;-::::::::a:!;;s;:;:::;5;;;::"K:::;:::::::::;:::::;;:;::K!s;::;
CHAPTER-I
I N T R O D U C T I O N
«;iiiiS--i:iiiS;:;;5:a=:;:-i;i'i--iS;i:;!i=inS:i:-n!U
INTRODUCTION
Analytical chemistry is an Indlspenslble tool
in advancing the state of )cnowledge in the fields of
modem branches of science/ dealing with the separa
tion and analysis of chemical substances* Identifi
cation and estimation of a compound are the two most
pompauB steps in analysis. A large number of methods
have been used to obtain and identify the substance in
the high state of purity. Besides* chemical methods
like fractional precipitation, distillation and crystalli
zation have extensively been used for separation and
purification of the chemical compounds. However* chroma
tography plays a very important and significant role in
solving all such problems. This method is so fruitful and
common that this method can be applied in almost every
type of compound and fields. Amongst all the chromato
graphic techniques* ion-exchange chromatography is consi
dered to be very versatile method and is particularly
helpful in the separation of ions of similar properties.
The separation is achieved on the basis of the differences
between the sorbabilities of ionic species. It has proved
to be an excellent tool for solving many complicated
problems, in the fields of biological, organic and inorganic
z
chemistry. In the biological fields a versatile achie
vement has been made regarding the separation of hydro-
lysed products of nucleic acid.
The recognition of phenomenon of ion-exchange was
generally attributed with base exchange in minerals
present in the soil (1)• It was found when soils were
treated with ammonium salt solutions, ammonia was taken up
by the soil and an equivalent quantity of calcium was
released, it was also shown that a number of other salts
besides those of ammonia are capable of doing ion~exchange
phenomenon.
Ca-Soil+NH^SO^ <" NH^-Soil+CaSO^
Harm U> in 1896 successfully applied the lon-«xchange
for commercial purposes. He removed sodium and potassium
ions from sugar beat juice by using a naturally occuring
cation exchange silicate mineral. Later on (3) Gans deve
loped large scale amplications of cation exchange phenomenon
on inorganic material such as soditun altiminosilicate,
(Na2Al2Si30jQ) which was synthesized by him. To a large
scale his synthetic cation exchanger replaced the naturally
occuring exchangers such as zeolites.
The zeolites may be regarded as being drived from
the formula (slOj) by replacing silicon by alxaminium to
varying extents. The few selected zeolites with their
cooq?osition and exchange capacities are listed below in
table.
Zeolites which are crystalline aluminosilicates are
3cnown as molecular sieves and have the ability to selecti
vely remove ions from solution. A recent application of
zeolite selectivity involves the use of synthetic ultra-223
marine to separate the francium Isotopoes Fr from its
actinixjm parents and other activities (4).
During the last 20-30 years the inorganic ion-
exchangers have firmly occupied their own position among
the ion-exchange materials. A rapid development in nuclear
energy, hydrometallurgy of rare elements, preparations of
high purity materials, water purification etc. has enforced
atten^ts to find and synthesize new and highly selective
ion-exchange materials, resistant to chemicals, temperature
changes and radiation, and of more convenient properties
than ccdKoercial organic or natural inorganic (Soil, Clay
mineral etc) ion-exchangers.
Kraus et al (5,6) and Amphlett (7,8) in this field,
have done the excellent work. The work on these material
upto 1963 has been svimmarized by Amphlett (9) in his book
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"Inorganic Ion Exchangers". The latter work upto 1970
has been condensed by Pekarek and Vesley (10). Clear
field (11#12) Alberti (13,14) and Walton (15,16) have
also worked on different aspects of synthetic inorganic
ion->exchangers. Qoreshi and co-workers have prepared a
large nxmdber of such materials and studied their ion-
exchange behaviour during the last twenty years (65,67,
68,69,74,75,88).
A large nvunber of synthetic inorganic ion-exchangers
has been discribed, which may be divided into the following
headings (17).
1. Hydrous oxides,
2. Acidic salts of multivalent metals/
3. Salts of heteropoly acids,
4. Insoluble ferrocynides,
5. Synthetic aluminosilicates.
A large number of papers dealing with the ion^exchange
properties of these substances has been published. The
hydrous maganese dioxide with rather xjmusual slectivity
sequence for alkali metals has been described by Tsuji (18).
Study of prepration of hydrous tin (iv) oxide ion-exchangers
has been made. Inove and co-workers (19) have studied the
isotopic exchange rate of sodium ions between the hydrous
tin (iv) oxide in the nt form and aqueous solution of sodium
salt.
Mixed oxides can be prepared in which a second
cation of higher charge than the present cation
introduced into the strxicture* the resulting net positive
charge being balanced by the presence of anions other
than oxide and hydroxide; many of these are found to exchange
the balancing anions reversibly (20), Examples of such
+2 matarials include Zn(0H)2 in which Zn is partly replaced
by Al ''' and A1(0H)3 containing Si*** Ti*"*" or zr "*", the
general formulae being Zn. 1-n Aln (OH) 2 3S and Alj -n MO^
(OH), l/n where M is a tetravalent cationSoc a monovalent
anion.
Quadrivalent laetal oxide may be have either as cation
or anion exchangers^ depending upon the basicity of the
central atoms and the strength of metal- oxygen bond relative
to that of oxygen - hydrogen bond in the hydroxyl group.
Little attention has been made to other hydrous oxides of
quinoque and sexivalent metals. Hydrous VjOc (21) in mix
ture with hydrous zirconia absorbs K*", Hat Bat CaiT h^t
FIT d t Nif pit Zn?'*"c "*'and AJ. Hydrous tantalum oxides is
cation exchanger (22«23#24) suitable for the purification of
nuclear reactor cooling water at high temperatures upto
300* C.
A wide range of con?>o\ancis of acidic salts of
multivalent metals has been described as lon-exchangers«
Among metals studied hare been zirconium* thorium,
tltanlxim cerium (Iv) • tin (iv) etc, and anions employed
Include phosphate, arsenate, antlmonate, vanadate,
sllcate etc. These salts acting as catlon-eflcchangers are
gel like or mlcrocrystalllne materials and possess mostly
a high chemical, teii5>erature and radiation stability (8,25,
26)• The cation exchange properties arise from the presence
of readily exchangeable hydrogen Ions, associated with the
anionic groups present In the salts.
The acidic salts of quadrivalent metals have been
most intensively studied group of synthetic Inorganic
ion-exchangers. Zlrconlxim phosphate shows amorphous
(8,25,27) semi-crystalline (28,29) and crystalline proper
ties (30). Clearfield and others (28,30,31,32,33,34) have
tried to solve the structure of < -zlrconlvim phosphate.
StrelJco (35) has given the formula of H form and salt
forms of zirconium phosphate as -
Zr (OH)^. {HPO^)2-2x. YHjO (x=0-2)
Zr (OH)j f(MP0^)^(HP0^)n3 2-2X.YH2O.respectively.
8
A few analytically Important applications of
zirconlxim phosphate exchanger have been cited belowi-
(1) Purification of reactor coolants (36)
(2) Decontamination of D2O (37)
(3) Decontimination of radioactive waste water (38)
137 (4) Cs from an reprocessing solution (39)
4+ (5) Pu , from irradiated xiranixira (40),
A ntiraber of three component ion-exchangers have also
been prepared in which the parent acid belong to the class
of 12-heteropoly acids having the general formula H^ X ^^^2^40^
nH2p where X may be phosphorous^ arsenic* silicon* gerroa-
niiim and boron and Y different element such as molybdenum
tungsten and vanadium* Much of sxibsiquent investigation
of the ion-exchange properties of these salts have been
carried out by smith & Robb (41)• Three component ion-
exchangers show superiority over sin5>le salts niainlJC/ in
three aspects. They are more thermally and chemically stable,
more selective (42), A detailed account of synthesis and
properties of two component and three con^onents ion-exchangers
have been summarized in table-1 and i , respectively.
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various novel inorganic ion-exchangers such as
titanium oxide (110),titanium phosphate (111)# hydrated
stannic oxide (112), and iron (Hi) antiroonate (113) have
been used especially in HPLC, Counter ion effects in
ion-exchange chromatography were studied by Dieter and
Walton (114), Qureshi and Qureshi (115) have presented
a review on the applications of ion-exchange methods in
radiochemical separations which is needed in activation
analysis, waste processing, fuel processing or reactor
coolant water purifications.
2 +
Fe is determined by ion-exchange chromatography
on Zr (IV) arsenophosphate column (116). J.S.Fritz and
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separated on a cation exchange column of low capacity and
are detected with a conductivity detector.
17
In recent years great concern has been universally
voiced regarding environmental pollution arising as a
side effect of industrial activities. The sxibstances or
agents which are called pollutants, contaminate or ulti
mately dissipate our natuural environment and pose occupa
tional heatth hazards. Many of these chemicals are toxic
to human beings and may produce chronic effects on the
htiman organs like lungs, kidney and heart. Besides, even
cancer results from some type of occupational exposure.
Pollution, is, therefore, an undesirable change in the
physical, chemical and biological characterstics of our
environment i.e., air, water and soil.
Various toxic chemicals used in industry affect the
living organism. These toxic sxibstancqs may enter the human
body either directly or indirectly. Table-3 shows a list of
such substances which are hazardous to mankind. Many chemi«»
cals and other type of industrial discharge-industrial
effluent in lacks, rivers, oceans, which without any treatment
causes water pollution can be due to textile units, because
of dyeing, printing and bleaching processes, animal or
vegetable processing industries such as metallurgical, mining,
ore processing, cement, paper and fertilizer.
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The toxic contaminants of potable water are usually
metals* jt'ttsnoles and toxic substances. The conventional
water purification process remove only part of the metals
present, many of them in critical concentration so that
excessive harmful concentration of trace metals* can be
imbibed into hximan organisms with drinking water. Many
organic confounds affecting the quality of water, produce
a high incidence of hepatocellular carcinoma (a malignant
txixnor). Water available for domestic and industrial use
is soft and always contains considerable acid in.the form of
heterogenous condensation of decomposed plant material (134)•
The water taste and odoxir is affected by the presence of
inorganic and organic constituents (135) such as chlorinated
benzenes, anilines and phenols.
Basically the control of pollution is accompalished
by prevention and control. Control and reduction of pollu-
tAnts from their source is necessary. Efforts are being
made in this respect. Various methods and analytical tech
niques are being applied to monitor the extent of pollution
and for this purpose first the recognition of pollutants,
sampling and their estimation are carried out to evaluate the
levels of contaminants present. The degree, existing levels
of toxic chemicals and extent of exposure to the workers in
2J
the industrial working environment is estimated.
Protection starts with the measurement and method of
eliminating j>ollution or reducing waste to levels unharmful
to the public and ecological balance. New methods of
monitoring are being applied with vigour and determination
both by industry and public authorities.
Measurement by a variety of analytical techniques is
the only way to ensure that the methods are effective and
also to detect when and where pollution occurs so that more
preventive action can be initiated. Ion-exchange methods
have also occupied a firm position in controlling the pollu
tion. Various toxic elements can be removed using the
process of ion-exchange. Fluorine and nitrobenzene have been
removed from xirine.
Koerts (136) have discussed the use of ion-exchange for
the selective removal of Hg* Pb etc. and concentration of
trace metal from effluent streams. Pawlowski et al have
used the ion-exchange method for the purification of waste
water from tne manufacture of nitrogen compound (137). Zinc
is removed from pickling liquor by metal separating ion-
exchange process in which the Znclj is sorbed as ZnCl.7
eluted with water and converted to Zinc sulphate (ZnSO^)
by liquid ion-exchange extraction and elution by HjSO.(138),
Caiman has reviewed the process of ion-exchange for the
removal of murcury* recently (139)•
23
Ambrus has described the applications of ion-exchange
processes for the control of pollution for low level
pollutants in water including heavy metals (Pb,Cu,Ni/Cd,Zn)
from metal plating processes* organics such as phenolic
compoxind/ waste acids etc. (140).
lon-chromatographic method, a form of ion-exchange
chromatography have been developed for the analysis of
anions and cations in environmental samples. This method
has been fotind useful for the determination of SO3 ", So\f
and SjO^ in acqueous solution (141). Walton (142) has
discussed the method of ion-exchange as an analytical tool
in controlling pollution. lon-ectchange method currently
employed to the determination of Cd, Zn,Cu, Tl^Be, Co,Mn,MO/V,U
and Th in natural water, including drinking water, river
water) sea water have been successr-fully achieved. The tech
nique is based on an-ion-exchange enrichment of the metals
as their anionic complexes (143).
Selective ion-exchangers Lewatite Oc, 1019, 1034 are
found ideal for the immobilization of heavy metal ions in
soil (Zro^*, Cu "*",Pb "*") (144). Zirconium phosphate (25,30,
43,44,45) and zirconlxjm hydroxide are directly used for the
removal of ionic ij^urities from water at high temperature
in pressurized water reactors.
24
Hydrous aluminium oxide and hydrous ferric oxide
have also been used for the removal of arsenic (V) (145).
Connor has described a method for the removal of Hg from
water utilizing the radio tracer, Hg * in the form of
raurcury (II) chloride using adsorbents such as hydrous
aluminixim and iron oxides aa well as roontmorillonite clay
(146). Hydrous tantalum oxide is a cation exchanger (23,24)
suitable for the purification of nuclear reactor cooling
water at high temperat\are upto 300°C. Zirconitom (IV) seleno*
phosphate/a cation exchanger has been used for the removal
of low molecular weight carboxilic acid from water recently
(99).
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o 0
78. K»H,Konnlng and E.Meyn, J.Inorg. Nucl, Chem, 29,,
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79. E.M. Larsen and W.A.Cilley/ J.Inorg. Nucl. Chem.
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90, C.S.Czibloly/ L. Szirtes and L,2isdLnka/ Radicx:h«n.
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91. y.Yazawa/ T.Eguchl/ K.Takaaguchl and I.Tomlta, Bull/
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92. R.G.Safina, N.E.Denisova and E.S.Boichinova, Zh.
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94. K,G,Varshney and A,Preraadas/ Sep. Sci. Tenchnol,/
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105. S.A.Nabi/ Z.M,Slddiqul and W.U.Farooqui, Bull.
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107. S.A.Nabi, A.R. Siddiqui and R.A.K.RaO/ J. Liq.
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33
118, H.Peavy, D.R, Rawe and G,Technobanoglous# Environmental
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119, B.T.Starr, J.E.Grisbson, Ann. Rev. Pharmaco, Toxicol.,
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120, hUB.Abu.Donia, Ann. Rev. Pharmaco, Toxicol,, 2 .,
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121, J,H,Scinfield, "Air Pollution" (Physical & Chemical
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122, H.M.Clayton, Dev. P.V.C. Prod. Process, 1*43 (1977),
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124, J,F.Kopp and ^<,C,Korner, Trace Metals in waters of
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125, N,I, Sax, "Hand Book of the Dangerous Materials"
Reinhold, New York p,331 (1951).
126, H,B. Elkins, "The Chemistry of Industrial Toxicology",
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1093 (1974).
128, W.E.Robert/ C.jpatterson, Environ. Sci, Res, 17/
(Polluted Rain), 391 (1980),
129, B,B,Ewing, E,S,Pearson, Adv, Environ, Sci. Technol,
2/ 126 (1974).
34
130. O.J.jjriagu/ Cadmium in the environment/ John ITiley/
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131. J.R.Brown, NTIS Gov.Rep, Announce. Index, (U.S.)
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(1968) .
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15 May (1979).
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139. C.Caiman, Ibid, 1, 173-89 (1979)
140. P.Ambrus. inf.Chim., 124, 203, 207 (1973).
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3cl.Technol, 13_(7), 804-9.(1979).
142. H.P.Walton, Ion exch. Pollut.Control 2,, (1979)
143. J. Korkish, Pergamon, Ser. Environ. Sci. 3(Anal,Tech.
Environ.Chem.), 449 (1980).
35
144. C.Asschevan, P. Uyttebroek, Agri. Wastes, 2, * '
279 (1980). I
145. J .H.Gul ledge and J . T , 0 Connor/ J.Am wat , Wks.
Ass . 65(8) 548 (1973) .
146. J .T,O'Connor and Ebersole^Am. Wat.Wks. Assoc, Annual
meet ing , Chicago, I l l i n o i s , Jxine (1972) .
CHAPTER-II
SYNTHESIS AND CHARACTERIZATION OF NEW THREE COMPONENT ION-EXCHANGE MATERIAL J Zr (IV) ARSENOVANADATE
3G
UNTRQDUCTIQN
Analytical applications of synthetic inorganic
ion-exchangers have now been well established (1). These
materials are widely used for pxirification of nuclear
fuels* waste disposal, enrichment and purification of
usefxil radioactive isotopes and ammonium ion removal
from portable renal dialysis unit. Zirconium phosphate
is directly used for the removal of ionic impurities from
water at high temperatures in pressurized water reactors.
(2,3) • >ioreover, they are very effective in the removal
of trace . inorganic constituents of water which are
—4 commonly found in concentration range of 10 mole/1 (4),
Generally the gels of inorganic ion-exchange material
do not show reproducible characteristics as their behaviour
depends upon the conditions of aging and crystallinity.
Phosphates and arsenates of zirconium are showing a good
thermal and chemical stabilities (5,6). While the little
work has been done on zirconium vanadate (7). Since the
mixed salts are found to show ion-exchange properties (8-20)
different to the simple salts, therefore, it is important
to study the properties of the dovible salts synthesized by
mixing vanadate and arsenate with zirconium.
In this chapter, we describe the synthesis*
composition* ion-exchange properties and sorption
behaviour of zirconium (IV) arsenovanadate. It has
been successfully used for the quantitative
separation of Cr "*".
37
EXPERIMENTAL
a::c:uiS:::::::s:s:i::a:h::::::;s:::::::i:::-::n::;:i;;-nH::::::Ui;H;:::::a:a
38
EXPERIMENTAL
Reagents i Zirconium (IV) bis (chloride) Oxide (BDH)#
Sodium hydrogen arsenate (E.Merk) and sodium metavanadate
(E.Merk) were used for the synthesis of ion-exchange
material. All other chemicals were of analytical grade.
Apparatus t Toshniwal (India) Single electrode pH meter
was used for pH measurement, A Bouch and Lomb spectronic
20 colorimeter* a Bouch and Lomb spectronic—1001 and a
Perkin Elroer-137 spectrophotometer were used for spectro-
photometric and IR studies respectively.
Synthesis i Various samples of zirconium (IV) arseno-
vanadate ion-exchanger were prepared by mixing an aqueous
solution of which is 0.05 M (1M«1 mol«/dm ) in sodixun
hydrogen arsenate and 0,05 M sodium metavanadate to an
aqueous solution of 0,05 M in zirconium (IV) bis (chloride)
oxide. The desired pH was adjusted by adding dilute hydro
chloric acid or sodium hydroxide. The gel so formed was
allowed to settle down for 24 hr., washed several time
with distilled water to remove excess reagents and finally
filtered xinder suction. It was then dried at 40* C for 7d
in an oven. The dried material was then treated with
distilled water, which resulted in the cracking of the
substances into small particles with slight evolution of
3i
heat. To convert the sample into H form the material
was kept for 24 h in 1.0 M HNO3 solution. It was then
washed with distilled water to remove excess acid and
dried at 40^c.
Ion-exchange capacity t A 0.50 g of exchanger material in
H form was taken into the column with the glass wool
support. It was washed with distilled water to remove
excess acid remained sticking on the particles. One molar
solution of different metal salts (\ini and bivalent) were
passed through the colvunn. The H so liberated was deter
mined, (21), The ion-exchange aapacities thus detexmined
were, therefore, those at neutral pH condition (pH~6,5).
Chemical stability : A 0,50 g of exchanger material
(ZAVg), table 5 was equilibrated with 50 ml of the solution
of Intrest at room temperature and kept for 24 h. with
occasional shaking. Zirconium released in the solution
was determined titrimetrically using xylenol orange (22).
Arsenic and vanadium were determined spectrophotometrically
using ammonium moliiDdate-hydrazine sulphate (23) and sodixom
tungstate (24) as colouring reagents respectively. The
results are summarised in table-7.
40
pH T i t r a t i o n t The t i t r a t i o n of ion-exchange m a t e r i a l
(saiTple ZAVg) was c a r r i e d o u t by the method of Topp and
Pepper (25) e q u i l i b r a t i n g s e v e r a l samples of exchanger
(0.50 g) wi th 50 ml of 0*1 M l4aCl - NaOH and 0 , 1 M KCl-KOH
s o l u t i o n s .
Chemical cofoposition : For the determination of chemical
composition of the sanple 0.10 g of exchanger was dissolved
in hot concentrated sulphxiric acid. Then the solution was
diluted to 100 ml with distilled water. The zirconium was
determined titrimetrically (22) while arsenic and vanadium
was determined spectrophotometrically (23#24) respectively.
The mole ratio of Zr# As and V was foxind to be 3.1:2»1,
Infrared Spectrum : Infrared analysis of zirconium (IV)
arsenovanadate was performed using KBr technique.
Distribution coefficient » The distribution coefficient
(Kd) for 21 metal ions in different system were determined.
A 0.50 gm of exchanger in H"*" form (40-50 mesh) was treated
with 50 ml of IXICT M metal salt solution in 250 ml Erlen-
meyer flask. The mixture was then shaken for 6h at 25 + 2 C
in a shaker incxibator. The amount of metal species left
in the solution was then deteirmined by titrating against
41
the standard solution of EDTA. The Kd values were
calctilated according to the forraula-
Kd a M»moles of metal species/gm of exchanger
M«moles of metal species/ml of the total volume of resultant solution
The result of Kd values are summarised in table-8
separations of Metal Ions : Quantitative separation of
metal ions were achieved on a 0.6 Cm(i.d,) glass colvimn
using J .O gm exchanger (4Q~50 mesh) in H form, A metal
ion mixture was poured on tlie top of the column. The
flow rate of the effluent was maintained at 1 ml min"
through out the elution process.
;::;;::==:i:::i;;::i:::::::;is:i:::::J::-i::;::::::::i;::a:::::::::::::::u:!)!;::ii:!y;
RESULTS
:yii::~::^U::::K:-:iiiii:::::ft:-:::ui:::;u:i::::-i::;::ii::i::::::::::;i::::::!:-ii:J:a
g e < < <
e g CJ
< Is)
o • o Oi
o • o m
o • o tn
o • o Ui
o • o y
o • o tn
O • o IT
o • o U1
o • o tn
O • o Ol
o • o tn
o • o tn
o • o i/\
o • o u>
o • o tn
tu lO to
«o
M
lO
«Q K h y ft H ffi I-" » 0
< U3 K a (0 H 3 -
(Q m h a a H CD t - -0 0
< (0 K ar CD K ET S »<;
£.»^ t r (D H- H
© 0 «
«Q K
{L&
! ' < 3" (D K f -rt H « 0
C tt M-ST 0) H-ET 0 K
o
H E T
h »
s o
s
»-• • u o
o • VO O
o • 09 OD
o « ox \o
O • to a\
o
0
to h o
n 0
O
(D <
o o 01 vQ f t »
S fl* 0)
f t
0)
'D 0 > K H > ' D
0» "O B f t h » 0 (D M
n 0)
I O 0
01 01 O > f t H» HtfO
f t i»k 0
O h
« ? ^ K
no o o» 0) a o> 0 0 0 0 \ f t
0
tJ
O O h
42
& M 0 I tn
t«
0 0) H-U
•0 h o •D 0
f t
(p (0
o l-h
o 0 0
H
h CO 0 V o
0) a a* ft 0
43
Table-6 : Ion-exchange capacity (meq/g-dry exchanger) of zirconixim (IV) arsenovanadate (sample 2AVc)for various cations at pH-^S.S and 25 + 5oc.
^^^ Cation Ionic Hydrated Ionic Ion-exchange • potential radius (A©) capacity (meq/g-
dry exchanger)•
0.87
1.20
1.30
0.65
0.87
0»8d
0.93
1.
2 .
3 .
4 .
5 .
6 .
7 .
L i *
Na"*"
K*
m^ Ca-^
Sr-^*
Ba*-^
1.47
1.02
0 . 7 5
3 . 0 8
2 .02
1.77
1 .48
10
7 . 9
5 . 3
1 0 . 8
9 . 6
9 . 4
8 . 8
44
Table-7 Chemical stability of Zirconium (IV) arsenovanadate
(ZAVg) in different sol utions.
S o l u t i o n s
H2O
IM Hcl
2M HCl
4M HCl
IM HNO3
2M iUaO^
IM H2S04
2M H2SO4
IM HCIO4
2M HCIO. 4
O.IM CHjCOOH
0 . 2 5 M CH3COOH
O.Stt M CH3COOH
0.60M CH3COOH
l.OM CH3COOH
2.0M CH3COOH
l.OM HCOOH
O.IM NaOH
l.OM NaOH
2.0M NaOH
O.IM NH4OH
1 - b u t a n o l
E t h a n o l
1 4 -Dioxane DMSO
Z i r c o n i u m ( I V ) r e l e a s e d mg/50 ml
0 . 0 0
0 . 2 7
0 . 0 3
1.36
0 . 2 2
0 . 8 2
3 . 1 9
3 . 9 9
0 . 2 2
0 . 4 5
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 1 3
0 . 0 0
1.2
4 . 6 5
10 .74
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0 0 . 0 0
A r s e n i c r e l e a s e d mg/50 ml
0 . 0 0
0 . 9 0
0 . 8 0
2 .00
1.10
2 .80
3 .0
4 . 1
0 . 1 3
0 . 2 9
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 1 5
0 . 5 0
0 . 9 8
2 . 7 0
5 .40
0 . 7 0
0 . 0 2
0 .00
0 . 0 0 0 . 0 5
Vanadium r e l e a s e d mg/50 ml
0 . 0 0
0 . 1 4
0 . 1 8
0 . 2 9
0 , 0 0
0 . 2 1
1.20
2 .40
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0
0 . 1 2
0 . 0 0
0 . 7 0
2 . 8 7
6 . 9 5
0 . 0 0
0 . 0 0
0 . 0 0
0 . 0 0 0 , 0 2
(AI fO »-* o
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l-» »J
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NJ <T> it)
l-» 0^ ON
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H» ON ON
M ON
£ ( j j
+
M ON ON
M A
h-» •(»
I-* >•-O
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3 •(^
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CD 00
tn OD
t n
a>
u> ON
»-' •(
^ •t^
+
to VO
U) 00 ^
to 03 v j
• J CD ^ O
H» 00 Ui o
Cfl • 0 •
H- t V SJ
!-•
a: to
O
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O JC O
to • O to
o a o to • O rf^
8=
X o ( j j •
8g
to
to • J
ON
M O O
•( Oi
U) CD
-0 «J
to to
to O
••-Ov O
tn VD O to VO
to O
VD tn
M O O
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47
Table-9 Kd values and separation factor of metal ions
for which the separation is achieved.
S.No, Separation achieved
1. Mg
Cr
2. sr
Cr
3. Co
Cr
4. Ni
Cr ++
5. Cu +-H-
Cr ++
6. Zn +•••+
Cr •H-
7. VO Cr
•M-H-8. Zr
H
Cr H
9. Hg
10. Th
Cr
Kd values in water
23
300
33
300
78
300
43
300
76
300
67
300
14
300
29
300
13
300
13
Separation factor
CO
13.0
9.09
3.85
6.97
3.94
4.47
21.42
10.34
23.07
23.07 Cr" "" 300
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(0 H) Ml H c (5 a f t
0 CO a
43
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49
DISCUSSION
so
DISCUSSION
Table-5 describes the prepration of samples of
zirconium (IV) arsenovanadate and It is apparent from
the table that Ion-exchange capacity increases with the
increase of arsenic content of the reactants in the
mixture. Sample ZAV^ is chosen for further studies due
to its high ion-exchange capacity and chemical stability.
The ion-exchange capacities for alkali and alkaline
earth metal ions are given in table-6« It is apparent
from the table that ion-exchange capacity increases with
decrease of the ionic potential (Vir) of the ingoing
alkali and alkaline earth metal ions. This exhibit a
similar relationship because ion-exchange capacity should
decrease with the increasing ionic radii and increase with
the electric potential. This is in agreement with the
findings of Nachod and Wood (26) while investigating the
exchange of alkali and alkaline earth metal ions on a
carbonaceous zeolite. Jeny (27) has also found that the
relative degree of eeichange of alkali and alkaline earth
metcil ions on colloidal alumlnltun silicates is less for the
ion with smaller (unhydrated) radius. In earlier studies
(28) some observations were also reported for the exchange
of alkali and alkaline earth metal ions on zirconium (IV)
lodonolybdate.
51
The ion-exchange material is found to be fairly
stable in dilute mineral acids. The sample is also
quite stable in organic acid like acetic acid and
formic acid and organic solvents like 1,4— dioxane but in
soditun hydroxide the solxibility of exchanger is increased.
The pH titration curve of zirconium (IV) arsenovanadate
(fig,l) shows two inflection points* which indicate that
the exchanger is bifunctional with an inflection point at
about a half of the theoritical ion-exchange cpacity. This
shows that the exchanger replaces hydrogen ion with alkali
metal in two steps. The end point occured at 1,3 meq/g
of exchanger is exactly the value required for the replace
ment of three hydrogen atom. The second end point occured
at 2,60 and 2,45 meg for K & Na* respectively. Which is
in good agreement with the theoritical ion-exchange capacity
of the ion-exchanger (2,63 meq g" ) calculated by considering
six exchangeable hydrogen per jnole formula.
The IR ftpectrvun of zirconium (IV) arsenovanadate in
H"*" form is shown in fig, 2. A very strong peak in 3800-2900
cm" region with a maximxun at 3400 cm** represents the
interstitial water, free water and OH groups (29), Another
peak in the region 1700-1580 cm" is the characteristics
of interstitial water molecule. The strong peak in the
region 1000-750 cm" is due to the presence of vanadate and
arsenate (30 ),
X
0 1 2 3 ^ 5
meq. of OH ad d e d / O . 5 gm o f e x c h o n g e r
Fig. I pH Titration curve of zirconiunn(IV)arsenovanadate
53 TRANSMITTANCE (V . )
21 i5'
•o
o o
3 o < D o a o
n
5 .
On the basis of chemical composition^ pH titration,
and IR studies, a tentative formula of the exchanger
material is proposed as follows:
(2rO)g(HA^^) (V30g.l,5H20) (OH)3.nH20
It is clear from the table—8 that the distribution
coefficient (Kd values) vary with the composition and
the natxire of contacting solution, Kd values of metal
ions are decreasing in general with increase in 1, 4 —
dioxane content of the system. It has been obsejrved that
in most of the cases Kd values increase with increase in
the concentration of acetic acid and for rare earth, the
increase in concentration of acetic acid has a little
effect.
The sorption studies on zirconium (IV) arsenovanadate
for different metal ions Conclude that a number of impor
tant separations are possible. Table-9 described the
separation factor. Separation is dependant on the difference
in the adsorbabilities of the two metals.
Separation factor c/ a 1
ss
Thus if, KdM > KdM2/ Mj wi l l appear before M . The gre
a t e r the value of K, / more e f f i c i en t the resolu t ion (31). Some
of the more important separat ion of i ndus t r i a l and ana ly t ica l
u t i l i t y have been successful ly achieved on zirconium (IV)
arsenovanadate column (30 Cm length and 0,6 Cm i . d , ) , Results
are summarized in t ab le 10 and the e lu t ion p ro f i l e s are shown
in f igure-3 ( a- j ) .
There are large number of toxic metals such as As, Cd, Pb,
Hg, Se and Ag which have been found as ca t ion ic or anionic species
in acqueous so lu t i ons . Chromium also comes under t h i s category.
The concentrat ion of chromium in water has been found 9,lKg/l
which i s supposed t o be high with respect t o UsPHS (United s t a t e s
Public Health Standards) l imi t of 50 V^k,' I t i s said t o be tox ic
t o humans. The pr inc ipa l acqueous species of chromium are 2
O r ( I I I ) , Cr(IV), and Cr-O. This work i s in progress and we
are developing some sens i t ive methods in order t o determine i t
a t low concentrat ion l e v e l .
5o
•»>
o ' 8 0 K
< 6 0 o UJ
o
t 2 0 o ^ 0 0
—
HjO
^ n 2 -
1 1 1 \ ,
1 OM CH3COOH
^ r 3 *
' 1 1 V--<,-j
8 0
6 0
i, 0
2 0
n n
H^O
- 2 r ^ *
1 1 \
1 OMCH3COOH
C r 3 »
/ I 1 1 N ) 10 20 30 40 50 60 70 80
Vol of e f f l u e n t ( m l )
( a )
10 20 30 40 50 60 70
Vol of e f f l u e n t ( m l )
(b)
'2 8 0 X
< 6 0 »— 0 UJ 4 0
0
M 2 0 V
F ft n
H20
_ J^C02-
I I \
1 0 MCH3COOH
• C r ^ -
' 1 1 1 ^ 1
1 OM CH3COOH
»0 20 30 40 50 60 70
Vol of e f f l u e n t ( m l )
( C )
10 20 30 40 50 60 70 80 90
Vol of e f f l u e n t ( ml )
(d )
1 OM CHjCOOH
10 20 30 40 SO 60 70
1 OM CHjCOOH
10 20 30 40 50 60 70 80
Vol of e f f l u e n t ( ml ) (e )
Vol of e f f l u e n t ( m l ) ( f )
Fig 3 ( a ) Separat ion of Zn^-Cr3*(b) Separation of Zr^*-Cr3*,(c ) Separationof Co2*-Cr3*, (d)Separat ionof Cu2*-Cr3»,(e)SeparQtion of Mg2».Cr3% (f )Separat ion of Sr2* -Cr3*,(g )Separation of Th^*-Cr3*(h)5eparat ion of Hg2* -Cr3* ( i )Separa t ion of N|2*-Cr3* and( j )Separat ion of V02*-Cr3^
m
2 8 0 X
<r 6 0 » -o i^ 4 0 ••-o t 2 0 o ^ n n
-
-
HpO
Th^'
1 1 1 N
1 OM CH3COOH
^ - A C r 3 -
/ 1 1 1 \ 0 10 20 30 40 50 60 70 80
Vol of e f f l u e n t ( ml )
8 0
6 0
i, 0
2 0
r\ n
H2O
- . H g ^ -
- / \
/ 1 1 N
1 0MCH3COOH
C r 3 '
' 1 1 1 \ 0 10 20 30 4 0 SO 60 70
Vol of e f f l u e n t ( ml )
( h )
0 10 20 30 40 50 60 70 80
Vol of e f f l u t n t ( m l )
( 1 )
'
8 0
6 0
4 0
2 0
n n
_
_
-
0 5 M CH3COOH
vo'
1 J .1 ,>
1 OM CH3COOH
. C r 3 '
. . 1..., .,_L,._ rnia^j 0 10 20 30 40 5 0 6 0 70 80
Vol of e f f l u e n t ( ml )
( ) )
5S
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BU
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