SYNTHETIC AND CHROMATOGRAPHIC STUDIES OF NEW ION EXCHANGE MATERIALS

DISSERTATION SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR

THE AWARD OF THE DEGREE OF

Msissttt ot pl^ilosiop^v In

iSijpplteb t^tmisitxp

BY

SARDAR HUSSAIN

UNDER THE SUPERVISION OF

PROF. AU MOHAMMAD

DEPARTMENT OF APPLIED CHEMISTRY FACULTY OF ENGINEERING & TECHNOLOGY

ALiGARH MUSLIM UNIVERSITY ALIGARH (INDIA)

2012 0 9

DS4208

T)cdjiMtect

%

VemS/iO'P

Dr. AH Mohammad

Ph.D.,D.Sc.(FJ.A.Sc.)

EDrrOR: Chemical & Environmental Research

Faculty of Engineering & Technolog)',

Aligarh Muslim University, Aiigarh-202002, India

564^230 AMU IN (Telex).

91-571-700920, 700921 (Tel). 456 (Exl).

E-mail: mohammadali4u@rediHmail.com

DEPARTMENT OEAPPLIED ('HEMISTRY

Dated ^.U.il2J?\ U

Certificate

This is to certify that the work embodied in this dissertation

entitled, "Synthetic and chromatographic studies of new ion exchange

materials " is the original contribution of Mr. Sardar Hussain, carried

out under my guidance and supervision, and it is being submitted in

partial fulfillment of the requirement for the award of the degree of

Master of Philosophy in Applied Chemistry from Aligarh Muslim

University, Aligarh.

ALI MOHAMMAD ' (Supervisor)

first of aCC, Ij?rostrate in reverence Before JACmigfity J^CCafi, the

BenevoCent, the cfierisfier ancC sustainer. I am fiigfiCy indebted

and grateful to my Lord "JACmigfity" who BCessed me witfi

innumeraBCe favors to comjjCete tfiis academic work and its

Bringing in tfiisy)resentform.

I wouCd Cike to express my gratitude to my supervisor, Trof Ad

Mohammad, whose expertise added consideraBCy to my research

experience. 3{is truCy scientific intuition has made him a

constant oasis of ideas and passions in science, which

exceptionaCfy inspire and enrich my growth as a student, a

researcher and a scientist want to Be. JABove aCC and the most

needed, he provided me unflinching encouragement and support

in various ways. I wouCd aCso Cike to acknowCedge Dr.

Inamuddin of the Department of .AppCied Chemistry for Being

heCpfuCto me during my researchpCan.

I wouCd aCso Cike to thanks Dr. JABduC Mohem,an, Ms JArshi

JAmin, Ms JAsma, Ms J^ida Xhanfor their vaCuaBCe advices and

tHeir wiCCingness to sfiare tfieir 6rigfit tfioughts witfi me, wdicfi

were very fruitfuCfor sHoping up my ideas ancCresearcfi work.

y/Here wouCcC I Be without my famiCy? My jjarents deserve

speciaC m.ention for tfieir supj)ort andj)rayers. My father, Mr,

Mofmrnmad JAyyuB Stddiqui, aCways inspired me to achieve a

high status in the fieCd of education through continuous process .

My Mother, Mrs Sakina 'Begum, is the one who sincereCy raised

me with her caring and gentCy Cove. My eCder Brothers

especiaCCy, Mr. Zafar IsmaeiC & JAasif IqBaC aCso deserve speciaC

thanks for Being supportive and caring nature. Last But not the

feast my sister Mrs. Shahnaz 'Razvifor his fove and affection.

I afso fike to express thankfufness to aff the non-teaching staff of

Appfied Chemistry Department for their hefp and support

during my research tenure.

Jinaffy, I woufd fike to thank every Body who was important to

the successfuf reafization of dissertation, as weff as expressing

my apofogy that I coufdnot mention personaffy one By one.

CONTENTS

CONTENTS

CHAPTER -1

1.1 Introduction

1.2 Chromatography

1.3 Ion exchange chromatography

1.4 Ion exchange phenomenon and its historical background

1.5 Ion exchange process and its mechanism

1.6 The journey from synthetic ion exchangers to composite ion exchangers

1.7 Applications of ion-exchange materials

1.8 Aim ofthe present work

1.9 References

CHAPTER - 2

Preparation and physico chemical characterization of an organic-

inorganic composite cation exchanger poly vinyl alcohol Ce(IV)

phosphate

1.0 Introduction

2.0 Experimental

2.1 Chemicals and reagents

2.2 Instrumentation

2.3 Preparation of organic inorganic composite cation exchange material

2.3.1 Preparation of reagent solutions

2.3.2 Preparation of inorganic ion exchanger

2.3.3 Preparation of poly vinyl alcohol Ce(IV) phosphate hybrid cation exchanger

2.4 Ion exchange capacity for alkali and alkaline earth metals

2.5 Thermal effect on ion exchange capacity

2.6 Effect of eluent concentration

2.7 Elution behaviour

2.8 Selective sorption (Kj) studies

2.9 X-ray diffraction ( XRD) study

2.10 Fourier transform infra red (FTIR) study

2.11 Thermo gravimetric analysis (TGA) /differential thermal analysis (DTA) studies

2.12 Scanning electron microscopy (SEM) Studies

3.0 Results and discussion

4.0 Conclusion

5.0 References

Chapter 1

1.1 Introduction

Science has been derived from the Latin word Scientia which means

knowledge, gained through carefiil experimentation and reasoning. It is a

systematic enterprise that builds and organizes knowledge in the form of

testable explanations and predictions about the universe [1-4]. Analytical

Chemistry is an ancient branch of science, and regarded as the mother of all

sciences.

Analytical Chemistry involves the study of the separation, identification,

and quantification of the chemical components of natural and artificial materials

[5]. It is a multidisciplinary branch of science wherein a large number of

research workers have contributed to its development [6]. No other branch of

science finds such extensive applications as analytical chemistry purely for two

reasons; firstly, it finds numerous applications in various disciplines of

chemistry such as inorganic, organic, physical and biochemistry and secondly it

finds wide applications in other fields of related sciences such as environmental

science, agricultural science, biomedical and clinical chemistry, solid state

reseaixh and electronics, oceanography, forensic science and space research.

However, the identification of a substance, the elucidation of its structure and

quantitative analysis of its composition are the aspects covered by modem

analytical chemistry. Analytical methods are the fundamental tools of the

analyst.

The classical methods of analysis have dominated the scene of analysis for

the past few decades. Fortunately, with the discovery of modem methods of

analysis, mainly involving instruments, these methods have been relegated.

Neventheless, these methods will not be phased out in spite of the greater

advancement of newer methods of analysis as the new methods have their own

limitations. They cannot be applied if the substance is present in large

concentration and further in order to standardize the newer methods it is

absolutely essential to use classical (gravimetric or volumetric) methods of

analysis. According to the type of process used to perform the analysis, methods

used for chemical analysis can be categorized as given in (Figure 1). Another

trend is to designate newer methods involving instruments as instrumental

methods of analysis, which involves the use of burette, pipette or weighing

balance. In the present circumstances when speed, simplicity, selectivity and

sensitivity of analysis are of upmost importance, it is better to categorize such

methods as modem methods of analysis instead of instrumental methods of

analysis.

Chemical Anahsis

Classical Methods

Gravittietric Volumetric Anahsis Analvsis

lastriimeutal Methods

Optical Methods

Separation Methods

Electroanalvtical Methods

Figure 1. Major categories of chemical analysis

1.2 Chromatography

Chromatography derived from Greek word ypfhiia: chroma means color

and ypoLcpeiv: graphein means to write represents a collective term for a set of

qualitative and quantitative techniques used in separation of mixtures. It

involves passing a mixture dissolved in a "mobile phase" through a stationary

phase, which separates the analyte of interest from other molecules in the

mixture based on differential partitioning/sorption between the mobile and

stationary phases. The mobile phase may be either a liquid or a gas, while the

stationary phase is either a solid or a liquid. Each component has a characteristic

time of passage through the system, called a "retention time". The techniques

fmd use in the separation, purification and identification of compounds before

quantitative analysis is taken up.

Chromatography may be preparative or analytical. The purpose of

preparative chromatography is to separate the components of a mixture for

further use (and is thus a form of purification). Analytical chromatography is

done normally with smaller amounts of material and is for measuring the

relative proportions of analytes in a mixture. Since its invention, the

chromatography has become an essential part of bio-chemiical laboratories. A

simple classification of chromatographic methods is summarized in Table 1.

The identification and separation of various species can be achieved by

an an-ay of systematic procedures. Among the most versatile analytical

separation techniques, chromatography has wider applicability. In spite of the

populair belief and general acceptance of the contribution of Tswett as being the

real discoverer of chromatography, the starting of chromatography predated to

the work of F. Runge who investigated the separation of coloured substances

(i.e. dyes) on paper [7]. The work carried out by Goppelsroeder [8] and

Schonbein [9] on chromatographic separation of substances on filter paper has

Table 1. Classification of chromatographic methods

S. No. Type of Chromatography Examples

1. Adsorption chromatography

2. Partition chromatography

Modified partition (or

bonded phase)

chromatography

Ion-exchange

chromatography

Exclusion chromatography

6. Electro chromatography

Column chromatography, Thin-Layer

Chromatography (TLC), Gas-Solid

Chromatography.

Paper chromatography, Reversed-

Phase Thin Layer Chromatography

(TLC), Classical Liquid-Liquid

Chromatography.

High-Performance Liquid

Chromatography (HPLC) and High

Performance (HP) TLC.

Cation and Anion Exchange

Chromatography.

Ion-Exclusion and Gel Permeation

Chromatography, Molecule Sieve

Chromatography.

Capillary and Zone Electrophoresis.

been included in a report published by Fischer and Schmidner [10] in 1892.

However, the concept of separation on column may be attributed to

Reed's work, which was followed by Day who separated petroleum fractions

with the help of columns [11,12]. The paper published in 1906 by Tswett a

Lecturer of Botany at the University of Warsaw provided the first description in

nearly modem terms of chromatographic separation [13]. He described the

resolution of different components of pigments as coloured bands on a calcium

carbonate column like spectrum of light rays and termed it as "chromatogram".

The actual importance of Tswett's work remained dormant until about 1931,

when separations of plant carotene pigments were reported by prominent

organic chemist Kuhn [14,15]. His research attracted much attention and

adsorption column chromatography became invaluable tool in the field of

natural product chemistry. In 1941, Martin and Synge [16,17] laid another

milestone in development of chromatography by reporting their discovery of

liquid-liquid partition chromatography.

As for as the knowledge of Human civilization concerned to the science

and technology, a wide variety of instrumental and non-instrumental

chromatographic techniques have been developed since the pre historic time. As

the field is very diverse it is very difficult to elaborate all the chromatographic

techniques. Therefore, we have chosen particularly ion-exchange

chromatography to discuss.

1.3 Ion-Exchange Chromatography

Ion-exchange chromatography is a technique in which resolution of a

mixture is achieved by virtue of differences in migration rates of the

components in the packed column. The stronger the charge on the sample, the

stronger it will be attracted to the ionic surface and thus, the longer it will take

to elute. In particular, the stationary phase is usually: Positively charged ion-

exchanger {anion-exchanger) interacts with anions and Negatively charged

ion-exchanger {cation-exchanger) interacts with cations (Figure 2).

Artfocted to Negative Surface

Cation _ _ Exchanger , Stationary-phase , - . Particle -

Figure 2. Ion exchange chromatography

1.4 Ion exchange phenomenon & its historical background

The phenomenon of ion-exchange is not of a recent origin. The earliest of

the references were found in the Holy Bible establishing Moses's priority that

succeeded in preparing drinking water from brackish water [18], by an ion-

exchange method. Later on, Aristotle found that the seawater loses part of its

salt contents when percolated through certain sand [19]. Basically, ion-exchange

is a process of nature occurring throughout the ages before the dawn of

civilization, has been embraced by analytical chemists to make use of difficult

separations easier and possible.

Francis Bacon in 1623 brought the intentional use of ion-exchange,

Thompson and Way in 1850 described the exchange of calcium and magnesium

ions of certain types of soils for potassium and ammonium ions [20,21],

Eichorn (in 1858) demonstrated exchange processes in soils as reversible [22],

and Boedecker proposed an empirical equation describing the establishment of

equilibrium on inorganic ion-exchange sorbents in 1859. In the 20* century, the

majority chemists believed that the 'base exchange' m soils is nothing but a sort

of absorption. Strong supports to ion-exchange come out witii the synthesis of

materials from clay, sand and sodium carbonate by Gans [23].

Gans [23] developed the basis for the synthesis and technical application

of inorganic cation-exchangers at the beginning of the 20* century. He termed

the amorphous cation-exchangers based on aluminosilicate gels "permutites"

which were actually the first commercially available ion-exchangers. In 1917,

Folin and Bell developed an analytical method based on these materials for the

separation of ammonia [24]. During the period between the 1930s and 1940s,

inorganic ion-exchange sorbents were replaced in almost all fields by the new

organic ion-exchangers. The observation of Adam and Holms [25] that the

crushed phonograph records exhibit ion-exchange properties, eventually

resulted in the more significant development of synthetic ion-exchange resins

(high molecular weight organic polymers containing a large number of ionic

functional groups) in 1935.

Because of the limited applications of the organic resins due to breakdown

in aqueous systems at high temperatures and in the presence of high ionizing

radiation doses there had been a resurgence of interest in inorganic exchangers

in the 1950s. Pioneering work was carried out in this field by the research team

at the Oak Ridge National University led by Kraus, and by the English team led

by Amphlett. Further extensive research and study of inorganic ion-exchange

sorbents were carried out in the 1960s and 1980s. Clearfield and co-workers

made great contributions in this area. Since last two decades, intense research

has continued on the synthesis of a number of new 'organic-inorganic'

composite materials. An interest of inorganic as well as composite ion exchange

materials in ion-exchange operations in industries is increasing day by day as

their field of applicafions is expanding.

1.5 Ion exchange process and its mechanism

The ion-exchange process became estabHshed as an analytical tool in

laboratories and in industries, as it was studied chiefly by practical chemists

interested in effects and performance etc. The exchange of ion takes place

stoichiometrically [26], really by the effective exchange of ions between two

immiscible phases, stationary and mobile. A typical ion-exchange reaction may

be represented as follows:

AX + B(aq) :5==^ IBX + A (aq) 1.1

where A and B (taking part in ion-exchange) are the replaceable ions, and X is

the structural unit (matrix) of the ion-exchanger. Bar indicates the exchanger

phase and (aq) represents the aqueous phase.

1.6 The journey from synthetic inorganic ion exchangers to

composite ion exchangers

Synthesis of inorganic materials resembling to the natural zeolites was

started about six decades ago. The first commercially available inorganic

materials were prepared by fusion of mixture of potash, feldspar, soda, kaoline

etc which bear the resemblance to the natural zeolites with an exception of their

irregular structures [27]. Later on some modification in preparation methods

were tried to obtained the ion exchangers with improved properties. An example

to cite includes the precipitation with caustic from acidic solutions of aluminium

sulphate and sodium silicate, followed by drying of gelatinous precipitates. The

chemical structure of these gel-permutits was very similar to the natural

zeolites. These materials possessed irregular structure which resembles that of

silica and ion exchange resins. Nowadays, both fusion and gel permutits are

well known but are of historical interest.

8

Various zeolites have been syntiiesized by hydrothemiai techniques [28-

34]. The hydrothermal technique involves the crystallization at an elevated

temperature from solution containing silica, alumina and alkali. These zeolites

were of completely regular structure and exact counter parts of natural zeolites.

These materials possessed a little practical consideration as ion exchanger; but

their use as highly selective adsorbent has been reported [35-38]. Later on

various ion exchangers have been synthesized with a frame work other than

alumino silicates, in which silicon was partially or completely replaced by other

tetravalent elements (titanium, thorium and tin and aluminium) by other

trivalent elements (iron, vanadium, manganese and phosphorus). However, ion

exchange properties of these modified ion exchangers were not found to

acceptable level and hence their practical applicability has been unsatisfactory.

Hydrous oxides gels of iron, aluminium, chromium, bismuth, titanium,

thorium, tin, molybdenum and tungsten are of particular interest because most

of these gels can function as cation or anion-exchangers, and under certain

conditions, as amphoteric exchangers. Their dissociation may be schematically

represented as follows:

M-OH * M^ + OH" 1.2

M-OH • M - 0 " + H^ 1.3

(M represents the central atom)

Scheme '1.2' is favoured by acid conditions when the substance can

function as anion-exchanger and scheme '1.3' by alkaline conditions, when the

substance can function as cation-exchanger. Near the isoelectric point,

dissociation according to both schemes can take place and both types of

exchange may occur simultaneously. All of the hydrous oxide, except,

zirconium and tin, are chemically unstable as they are dissolved by acids and

bases easily. Therefore, hydrous oxides are of little practical importance.

Recently, various inorganic ion exchangers with much more satisfactory

properties have been prepared by combining salts of group III and IV such as

aluminium, antimony, bismuth, cerium, chromium, iron, titanium, tin, thorium

and zirconium with the more acidic salts of group V and VI such as silicate,

vanadate, arsenophosphate, arsenotungstate, arsenomolybdate, arsenosilicate,

arsenovanadate, phosphotungstate, phosphomolybdtate, phospahovanadate,

phosphosilicate, alkali phosphates, selenomolybdate, tungstophosphate,

molybdosilicate, vanadosilicate, phosphoric, arsenic, molybdic, and tungstic

acids etc.

These ion exchangers are extremely insoluble, non-stoichiometric and

possessed high ion exchange capacity (up to 12 meq g"' of ion exchange). The

materials also provided high rate of exchange and high thermal and radiation

stabilities as compared to organic ion exchange resins; however, they tend to

lose fixed ionic groups at higher pH due to hydrolysis and ion exchange

properties are reported to be not very much reproducible as well as ion

exchangers are not granular, thereby limiting their suitability for column

operations.

Recently, composite materials prepared by the combination of insulating

or conducting polymers as supporting materials with the matrices of inorganic

precipitates (prepared by combining cationic group salts such as cerium,

titanium, tin, thorium and zirconium with any of the anionic species) are

considered to be alternatives to overcome the limitations associated with the

organic resins and inorganic ion exchangers [39-49]. However, this dissertation

is aimed to review the recent advances in the study of composite cation

exchangers prepared by combining insulating or conducting polymers with

cerium salts as cationic part with various anionic parts. To be very precise, only

the insoluble poly basic salts of cerium have been reviewed (Table 2).

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1.7 Applications of ion exchange materials

Ion-exchange materials find applications in various fields including the

fuel cell [62], catalysis [63], wastewater treatment [64], water purification [65],

selective separation [66], concentration and recovery of toxic metal cation and

anions [67], chemical and biochemical separations [68], pharmaceuticals [69],

therapeutic [70] and electronics [71].

14

1.8 Aim of the present work

The present work was undertaken to explore the analytical applicability

of the newly synthesized composite ion-exchangers. In this direction the

following work was planned:

a. Synthesis of new composite ion-exchange material.

b. Characterization of the newly synthesized composite ion-exchange

material using various analytical techniques such as scanning electron

microscopy (SEM), thermo gravimetric analysis/differential thermal

analysis (TGA/DTA), fourier transform infra red (FTIR) and X-ray

diffraction (XRD).

c. Characterization of ion exchange material to validate the ion exchange

properties.

15

1.9 References

[ 1 ]. "Online Dictionary". Merriam Webster. Retrieved (2011).

[2]. K. R. Popper, The Logic of Scientific Discovery, Routledge, London

(2002)513.

[3]. Wilson, Edward, Consilience, The Unity of Knowledge, Vintage, New

York (1999).

[4]. L. Fleck, Genesis and Development of a Scientific Fact, The University

ofChicago Press (1935).

[5]. F. James, Skoog, A. Douglas, Fundamentals of analytical chemistry.

Philadelphia: Saunders College Pub, (1996).

[6]. K. Danzer, Fresenius, J. Anal. Chem. 343 (1992) 827.

[7]. F. Runge, "Der Biddhungstriebder stoffe" Verenschlaulicht in

Selbstaqndiggewachsenan Bedem. Sebsterlag Oranenberg, Germany

(1855).

[8]. F. Goppelsroeder, V. Naturforsch, Ces. Basel. 3 (1861) 268.

[9]. C. F. Schonbein, V. Naturforsch, Ces. Basel. 3 (1861) 249.

[10]. E. Fisher, E. Schmidner, Annalen. 272 (1892) 156.

[11]. L. Reed, Proc. Chem. Soc. 9 (1893) 123.

[12]. D. T. Day, Amer. Phil. Soc. 36 (1897) 112.

[13]. M. S. Tswett, Ber. Duet. Boatan. Ges. 24 (1906) 235.

[14]. R. Kuhn, E. Lederer, Ber. 64 (1931) 1349.

[15]. R. Kuhn, A. Winterstein, E. Lederer, H. Seyler'sz. Physiol. Chem. 197

(1931)141.

[16]. A. J. P. Martin, R. L. M. Synge, J. Biochem. 35 (1941) 91.

[17]. A. J. P. Martin, R. L. M. Synge, J. Biochem. 35 (1941) 1358.

[18]. The Second Book of Moses, Exodus, Ch. 15, Verse 25.

16

[19]. Aristotle, Works, about 330 BC, Clarenndon Press, London, 7 (1927)

933b.

[20]. H. S. Thompson, J. Roy, Agr. Soc. Engl. 11 (1850) 68.

[21]. J. T. Way, J. Roy, Agr. Soc. Engl. 11 (1850) 313.

[22]. E. Eichom, Pogg. Ann. Phys. Chem. 105 (1850) 126.

[23]. R. Gans, Jahrb. Preuss. Geol. Landesanstalt, Berlin, 26 (1905) 179; 27

(1906)63.

[24]. 0. Folin, R. Bell, J. Biol. Chem. 29 (1917) 329.

[25]. B. A. Adams, E. L. Homes, J. Soc. Chem. Ind, London. 54 (1935) 17.

[26]. F. Hellferich, Ion-Exchange, McGraw-Hill, New York (1962).

[27]. F. Helfferich, Ion Exchange, McGraw-Hill, New York. (1962) Chap-2.

[28]. R. M. Barrer, Hydrothermal Chemistry of Zeolites, Academic Press,

New York. (1982) Chap 3-5.

[29]. C. S. Cundy, Chem. Rev. 103 (2003) 663.

[30]. R. Szostak, Molecular Sieves - Principles of Synthesis and

Identification, 1st ed.. Van Nostrand Reinhold, New York. (1989); 2nd

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19

Chapter 2

Preparation and Physico-chemical characterization of

an 'organic-inorganic' composite cation-exchanger

poly vinyl alcohol Ce(IV) phosphate

20

1.0 Introduction

The presence of pesticides, radio-nuclides and most importantly heavy

toxic metal ions in the aquatic environment has been of great concern to

engineers, environmentalists and scientists because of their increased discharge,

toxic nature and adverse effects on receiving water. Some heavy metals - such

as cobalt, copper, iron, manganese, molybdenum, vanadium, strontium and zinc

are essential to health in trace amounts to maintain the metabolism of human

body [1]. The others are non-essential and can be harmful to health in excessive

amounts. These include cadmium, antimony, chromium, mercury, lead, and

arsenic - the last three being the most common in the cases of heavy metal

toxicity. Among the toxic metal species on the priority list of the Environmental

Protection Agency (EPA) the following are of great importance: aluminium,

antimony, arsenic, beryllium, cadmium, chromium, cobalt, copper, lead,

manganese, mercury, nickel, selenium, vanadium and zinc. Heavy metal

pollution exposure to humans may occur naturally or by human anthropogenic

sources which may include erosion of surface deposits of metal minerals,

mining of coal, natural gas, smelting, fossil fuel combustion and industrial

application of metals, among others, in chemical industry, production of paper,

plastics, plating and the manufacture of lubricants and chlor-alkali industries

[2,3]. The persons with heavy metal toxicity may experience the symptoms like

memory loss, chronic pain throughout the muscles, high blood pressure, chronic

malaise, sleep disabilities, brain fog, speech disorder, chronic infections such as

21

Candida, gastrointestinal complaints, such as diarrhea, constipation, bloating,

gas, heartburn, and indigestion, food allergies, attention/concentration deficits,

dizziness, migraines and/or headaches, visual disturbances, mood swings,

depression, anxiety and nervous system malfunctions [4].

Heavy metal toxicity can result in damaged or reduced mental and central

nervous function. Some metals inhibits the function of certain enzymes

necessary for the formation of hemoglobin in bone marrow, injuries of

gastrointestinal tract, lower energy levels, and damage to blood composition,

lungs, kidneys, liver, and other vital organs. Long-term exposure may result in

slowly progressing physical, muscular, and neurological degenerative processes

that mimic Alzheimer's disease, Parkinson's disease, muscular dystrophy, and

multiple sclerosis. Due to continuous exposure and human health hazards

caused by the heavy metals, several technologies such as thermal treatment,

precipitation, extraction, adsorption and ion exchange have been proposed for

the removal of these pollutants from the environment [5-18]. Among these

techniques, ion exchange is one of the most common and effective treatment

methods. Various inorganic and organic ion exchange materials have been used

for the removal and separation of heavy toxic metal ions. However, inorganic

ion exchangers and organic resins suffer some major disadvantages, such as less

chemical and radiation stabilities, mechanical stability, reproducibility and

granulometric properties. To overcome these obstacles organic-inorganic

composite ion exchange materials are considered as one of the most important

22

classes of engineered materials, as they offer several outstanding properties as

compared to conventional inorganic ion exchangers and organic resins. The

improvement in the properties of organic-inorganic composite ion exchange

materials make them more suitable for the application in environmental

remediation technology [19-42], In this study, an 'organic-inorganic' composite

cation-exchange material poly vinyl alcohol Ce(IV) phosphate was prepared

under varying conditions and characterized by various physico-chemical and ion

exchange methods to validate the ion structure and exchange process.

23

2.0 Experimental

2.1 Chemicals and reagents

The main reagents used for the synthesis were:

• Cerric sulphate, Ce(S04)2.4H20 (99%) Central Drug House (India)

• Ortho phosphoric acid, H3PO4 (88-93%) Fischer Scientific (India)

• Nitric acid, HNO3 (98-99%) E-Merck (India)

• Poly vinyl alcohol Central Drug House (India)

All other reagents and chemicals were of analytical reagent grade and used as

received.

2.2 Instrumentation

The following instruments were used for various studies made for

chemical analysis and characterization of the composite materials:

••• FTIR spectrometer — Interspec 20 by Spectre lab U.K.; was used for

recording FTIR spectra.

•> An X-ray diffractometer — Miniflex-II, Desktop,X-ray diffracometer

model Miniflex-II (Japan); was used for recording powder X-ray

diffraction pattern.

<• A digital muffle furnace — was used to heat the material at different

temperatures.

• TGA/DTA Recorder- DTG-60H by Shimadzu Japan; was used to record

TGA/DTA pattern.

24

• An air oven — Universal Oven (Mammart type) (India).

•:• An electronic balance (digital) — Sartorius (Japan), model 21 OS was used

for weighing purpose.

•> A magnetic stirrer.

<• A scanning electron microscope (SEM) (JEOL, JSM 6510 LV, Japan) was

used to examine the surface morphology.

2.3 Preparation of organic-inorganic composite catioii;;exchange

material

13A Preparation of reagent solutions

O.IM eerie sulpahte, Ce(S04)2.4H20 and 2M ortho plibsptefic" acid

(H3PO4) solutions were prepared in deminiralized water (DMW).

2.3.2 Preparation of inorganic ion exchanger

Various samples of inorganic ion exchanger Ce(IV) phosphate were

prepared using different mixing volume ratios by mixing aqueous solutions of

O.IM Ce(S04)2.4H20 into 2M H3PO4 at room temperature (25 ± 2°C). The

obtained gels were digested for 24 hours at room temperature. The supernatant

liquid was decanted and the gels were washed with DMW till the filtrate gave

negative test for H^ ions. After washing till neutral, the gels were dried in an

electric oven maintained at (45± 3°C). The dried product was cracked into small

granules (-125 ^m) and ion exchanger was placed in IM HNO3 for 24 hours

25

with occasional shaking intermittently replacing the supernatant liquid with

fresh acid. The excess acid was removed after several washings with DMW,

dried at 50°C.

For the determination of ion exchange capacity one gram of the dry

inorganic exchanger in the H^ form was taken into a glass column having an

internal diameter (i.d.) ~ 1 cm and fitted with glass wool support at the bottom.

The bed length was approximately 1.5 cm long. IM sodium nitrate (NaNOs) as

eluant was used to elute the H^ ions completely from the Ce(IV) phosphate

exchange column, maintaining a very slow flow rate (~ 0.5 ml min'). The

effluent was titrated against a standard O.IM NaOH solution using

phenolphthalein indicator.

2.3.3 Preparation of poly vinyl alocohol Ce(IV) phosphate

composite cation-exchanger

Various samples of organic-inorganic composite cation exchange

materials were prepared by mixing different masses of PVA dissolved in 30 ml

DMW into the inorganic precipitates of Ce(IV) phosphate having higher ion

exchange capacity (1.00 meq dry g'') as observed in Table 1. These slurries

were kept for 24 hours at room temperature (25 ± 2°C) for digestion. The

supernatant liquid was decanted and the excess acid was removed by several

washings with DMW and the materials were dried in an air oven over at 45°C.

26

The dried products were converted to H^ form as discussed above. A number of

samples of 'poly vinyl alcohol Ce(IV) phosphate' composite cation-exchanger

were prepared (Table 2 ) and on the basis of Na" ion-exchange capacity sample

S-1 was selected for detailed studies.

2.4 Ion-exchange capacity for alkali and alkaline earth metals

One gram of the dry cation-exchanger, sample S-1 in the rf"-form was

taken into a glass column having an internal diameter (i.d.) ~ 1 cm and fitted

with glass wool support at the bottom. The bed length was approximately 1.5

cm long. IM alkali and alkaline earth metal nitrates as eluents were used to

elute the iT ions completely from the poly vinyl alcohol Ce(IV) phosphate

cation-exchange column, maintaining a very slow flow rate (~ 0.5 ml min').

The eluent was titrated against a standard O.IM NaOH solution using

phenolphthalein indicator.

2.5 Thermal effect on ion-exchange capacity (lEC)

To study the effect of drying temperature on the ion exchange capacity,

Ig samples of the organic-inorganic hybrid cation-exchange material (S-1) in

the H^ form were heated at various temperatures in a muffle furnace for 1 hour

and the Na ion-exchange capacity was determined by column process after

cooling them at room temperature.

27

2.6 Effect of eluent concentration

To find out the optimum concentration of the eluent for complete

elution of H^ ions, a fixed volume (250 ml) of NaNOj solution of varying

concentrations ranging from 0.20 to 1.60M were passed through a column

containing Ig of the cation-exchange material (S-1) in the H -form with a flow

rate of- 0.5 ml min'\ The eluent was titrated against a standard alkali solution

of 0.1M NaOH for the ¥C ions eluted out.

2.7 Elution behavior

To find out the efficiency of column containing Ig of the cation-

exchanger (S-1) in Yt form was eluted with IM NaNOs solution in different

10.0 ml fractions with minimum flow rate as described above. Each fractions of

10.0 ml eluent was titrated against a standard alkali solution for the H^ ions

eluted out.

2.8 Selectivity sorption (Kj values) studies

The distribution coefficient (K ) values of various metal ions on poly

vinyl alcohol Ce(IV) phosphate was determined by a batch method in various

solvent systems. 200 mg of composite ion exchanger beads in the R" form was

taken in Erlenmeyer flasks and treated with 20 ml of different metal nitrate

28

solutions in the required medium. The initial metal ion concentration was

adjusted so that it did not exceed 3% of its total ion exchange capacity.

The mixture was kept for 24 hours with continuous shaking for 6 h in a

temperature controlled shaker incubator at (25±2°C) to attain equilibrium. The

metal ions in the solution before and after equilibrium were determined by

titrating against the standard 0.005 M solution of EDTA [43]. The distribution

coefficient (Kj) values were calculated using the formula given below:

where I is the initial amount of the metal ion in the solution phase, F is final

amount of metal ion in the solution phase, V is the volume of the solution (ml)

and M is the amount of exchanger (g).

2.9 X-ray diffraction (XRD) study

X-ray diffi-action pattern of the poly vinyl alcohol Ce(IV) phosphate

composite material was recorded by Miniflex-II X-Ray diffractometer (Rigaku

Corporation) with Cu Ka radiation.

2.10 Fourier transform infrared (FTIR) spectroscopic study

The FTIR spectra of poly vinyl alcohol Ce(IV) phosphate composite

material was recorded by Interspec 20 FTIR spectrometer, Spectrolab (UK).

The sample compartment was 200 mm wide, 290 mm deep and 255 mm high.

The entrance and exit beam to the sample compartment was sealed with a

29

coated KBr window and there was a hinged cover to seal it from the

environment.

2.11 Thermogravimetric analysis (TGA)/differential thermal analysis (DTA) studies

The degradation process and thermal stability of the poly vinyl alcohol

Ce(I V) phosphate composite was investigated using thermo gravimetric analysis

(TGA) (Shimadzu DTG-60H), under nitrogen atmosphere using a heating rate

of20°Cmin' from25 to 800°C.

2.12 Scanning electron microscopy (SEM) studies

Scanning electron microscopic image were taken by JEOL, JSM,

6510LV, (Japan) scanning electron microscope at an accelerating voltage of 20

kV. Sample was mounted on a copper stub and sputter coated with gold to

minimize the charging.

30

3.0 Result and discussions

In this study, various samples of poly vinyl alcohol Ce(IV) phosphate

were prepared by sol-gel mixing of poly vinyl alcohol solutions into inorganic

gels of Ce(IV) phosphate in different mixing volume ratios. It was observed that

the ion exchange capacity of inorganic ion exchanger increases by increasing

anionic part with fixed cationic part up to the mixing volume ratios of 1:3

(Table 1), however further increase in the ratio of an ionic part ion exchange

capacity decreases considerably.

Slurry of inorganic ion exchanger having high ion exchange capacity

(1.00 meq dry g'') was selected for the preparation of composite ion exchange

material. Different masses of poly vinyl alcohol dissolved in DMW were added

into various inorganic ion exchanger slurries and it was observed that the ion

exchange capacity was decreased with increase in the mass of poly vinyl

alcohol which may be due to the blockage of exchange sites (Table 2).

The composite material possessed higher ion exchange capacity of 1.54

meq dry g'' as compared to its inorganic counterpart Ce(IV) phosphate (1.00

meq diy g"'). The improvement in the ion exchange capacity may be due to the

binding of organic polymer poly vinyl alcohol with inorganic counterpart

leading to the formation of granular material suitable for column operation.

31

The material was found reproducible in behavior which is evident from

the fact that the material obtained in different batches did not show any

appreciable deviation in ion exchange capacity, colour and yield.

The charge and size of exchanging ions also play a vital role on the ion

exchange capacity of ion exchanger. The study of size and charge of eluent

showed that ion exchange capacity of this cation exchanger for the alkali and

alkaline earth metals increased with decrease in hydrated ionic radii of eluent as

shown in Table 3.

The rate of elution is always dependent upon the concentration of eluent

used for particular application. In this study NaNOs is used as eluent to elute

replaceable IT ions and found that IM NaNOa is required for the maximum

release of H^ ion from 1 gm of composite cation exchanger as shown in Table 4.

The elution efficiency of cation exchange column containing Igm of

cation exchanger is determined by the elution behaviour. The result showed that

the elution of replaceable ions is quite fast as all the exchangeable ions are

eluted out by 100 ml of eluent (IM NaNOs) with 2-3 drops/min as shown in

Figl.

Thermal stability experiment shows that the physical appearance and ion

exchange capacity of the composite cation exchanger material Ce(IV) phosphate

(S-1) was changed with increases in the temperature. The result shows that the

32

composite cation exchanger is thermally stable as the sample maintained about

45% of initial ion exchange capacity and mass 80% of mass by heating upto

350°C as shown in Table 5.

The distribution studies was performed for four metal ions in 8 solvent

systems (Table 6).The result showed that the material is highly selective for

Cu , which is a toxic environmental pollutant. Selective coefficient (Kd) values

is dependent on the concentration of electrolyte.

The X-ray diffraction of this cation exchanger poly vinyl alcohol Ce (IV)

phosphate (S-1) showed very small peaks of 20 values which indicated that the

composite ion exchange material is amorphous in nature (Fig. 2).

The FTIR spectra of this composite cation exchanger (Fig. 3) conforms

the presence of-OH stretching (3400 cm'') [44] , -CH2 scissoring (15II cm"'),

ionic phosphate and -CHOCH2O (1063 cm''), respectively [45,46] and assembly

of three sharp peaks in the region of 1618-428 cm'Vay be ascribed due to the

presence of metal oxygen bond [47], while a sharp absorption band around

(1634 cm') conforms the presence of water of crystallization [48].

The thermogram of Ce(IV) phosphate composite cation exchanger (Fig.

4) shov s two major weight loss at lOO 'C and 600°C which may be assigned due

to the removal of the water molecule present on the surface of the material and

complete conversion of the metals into metals oxides. Both the transformations

33

have also been supported by differential thermal analysis as the DTA curve

showed two exothermic peaks with maxima at 100°C and 600°C.

Scanning electron microscope (SEM) photographs showed the difference

in surface morphology of inorganic ion-exchanger Ce(IV) phosphate (Fig. 5)

and organic-inorganic composite poly vinyl alcohol Ce(IV) phosphate (Fig. 6).

It was observed that after binding of inorganic precipitate of Ce(IV) phosphate

with organic polymer morphology has been changed.

4.0 Conclusion

In this study organic-inorganic composite cation exchanger poly vinyl

alcohol Ce(IV) phosphate prepared by sol-gel method showed appreciably

enhance ion exchange capacity as compared to its inorganic counterpart Ce(IV)

phosphate. The composite cation exchanger showed granulometric and

reproducible behaviour, fast elution efficiency, thermal stability and selectivity

for a toxic heavy metal Cu" ^ which is a toxic environmental pollutant.

34

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39

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46

C/3

u C 3 ©

50 29/"

Figure 2. Powder X-ray diffraction pattern of poly vinyl alcohol Ce(IV) phosphate composite

80

47

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48

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Figure 4. Simultaneous TGA-DTA curves of poly vinyl alcohol Ce(IV) phosphate (S-1) (as-prepared).

49

Figure 5. Scanning electron microphotographs (SEM) of chemically prepared Ce(IV) phosphate at the magnification of 2,500 x.

50

WD18mm SS40 0000 21 Apr 2012

Figure 6. Scanning electron microphotographs (SEM) of chemically prepared poly vinyl alcohol Ce(IV) phosphate composite system at the magnification of 2,500 x.

51