Chemical Studies on Polyaniline Titanotungstate As a New Composite Cation Exchanger and Its Analytical Applications for Removal of Cesium from Aqueous Solutions

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CHEMICAL STUDIES ON POLYANILINE TITANOTUNGSTATE AS A NEW COMPOSITE CATION EXCHANGER AND ITS ANALYTICAL APPLICATIONS FOR REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS

A PhD Thesis Submitted

Chemistry Department Faculty of Science Ain Shams University

MAGDY KHALIL MOHAMED IBRAHIM M. Sc. (Inorganic Chemistry) Department of Nuclear Fuel Technology Hot Laboratories Center Atomic Energy Authority

2012

CHEMICAL STUDIES ON POLYANILINE TITANOTUNGSTATE AS A NEW COMPOSITE CATION EXCHANGER AND ITS ANALYTICAL APPLICATIONS FOR REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS

A PhD Thesis Submitted To

Chemistry Department Faculty of Science - Ain Shams University

For Degree doctor of philosophy of science (Chemistry)

MAGDY KHALIL MOHAMED IBRAHIM M. Sc. (Chemistry) Department of Nuclear Fuel Technology Hot Laboratories Center Atomic Energy Authority

Supervised By

Prof. Dr. M. F. El-Shahat Prof. Dr. I. M. El-Naggar Prof. of Analytical and Prof. of Physical Chemistry Inorganic Chemistry Hot Laboratories Centre Faculty of Science Atomic Energy Authority Ain Shams University

Prof. Dr. E. S. Zakaria Prof. Dr. I. M. Ali Prof. of Physical Chemistry Prof. of Physical Chemistry Hot Laboratories Centre Hot Laboratories Centre Atomic Energy Authority Atomic Energy Authority

2012

Approval Sheet for Submission

A Thesis Title

CHEMICAL STUDIES ON POLYANILINE TITANOTUNGSTATE AS A NEW COMPOSITE CATION EXCHANGER AND ITS ANALYTICAL APPLICATIONS FOR REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS

A thesis Submitted By MAGDY KHALIL MOHAMED IBRAHIM M.Sc. (Inorganic Chemistry) This thesis has been approved for submission by supervisors Thesis Advisors: Signature 1- Prof. Dr. M. F. El-Shahat ……………... Prof. of Analytical and Inorganic Chemistry Ain Shams University 2- Prof. Dr. I. M. El-Naggar ……………... Prof. of Physical Chemistry Atomic Energy Authority 3- Prof. Dr. E. S. Zakaria ……………... Prof. of Physical Chemistry Atomic Energy Authority 4- Prof. Dr. I. M. Ali ……………... Prof. of Physical Chemistry Atomic Energy Authority Credit Head of the Department of Chemistry

Prof. Dr. Maged S. Antanious

ACKNOWLEDGEMENT

I am deeply thankful to my ''ALLAH'', by the grace of whom, the progress and success of this work was possible. I would like to express my deep gratitude and appreciation to my thesis supervisor’s committee members:

Prof. Dr. Mohamed F. El-Shahat, professor of Analytical and Inorganic Chemistry, Faculty of Science, Ain Shams University for sponsoring this work, his continuous encouragement and help during the progress of this study.

Prof. Dr. Ibrahim M. El-Naggar, professor of Physical Chemistry, Nuclear Fuel Technology Department, Hot Laboratories Centre, Atomic Energy Authority for suggesting and planning the research project throughout the whole investigations, direct supervision, her unlimited help, continuous encouragement, valuable comments, and his insight on both the professional and personal levels which gave me the greatest helps to accomplish this study.

Prof. Dr. Essam S. Zakaria and Prof. Dr. Ismail M. Ali, professors of Physical Chemistry, Nuclear Fuel Technology Department, Hot Laboratories Centre, Atomic Energy Authority for direct supervision, continuous guidance, continuous advice, sincere help and significant encouragement during the experimental work, and preparation of the thesis.

I would like to thank all the staff members and colleagues of the Nuclear Fuel Technology Department, Hot Laboratories Centre, Atomic Energy Authority for their cooperation and useful help offered during this work.

Finally, I wish to thank all the members of my family, specially my parents, my wife and my sons for their assistance and patience during the program of this work. M. Khali

CONTENTS M. Khalil CONTENTS List of Tables…………………………………………………………... IV List of Figures…………………………………………………………. V List of Publications……………………………………………………. IX Aim of Work…………………………………………………………... X Abstract………………………………………………………………... XI

CHAPTER-1 INTRODUCTION 1.1. Inorganic Ion Exchangers…………..………………….. 2 1.2. Synthetic Organic Ion Exchangers……….………..…….. 4 1.2.1. Polystyrene divinylbenzene………………...………... 5 1.2.2. Phenolic………………………………..…...... 5 1.2.3. Acrylic……………………………………………….. 5 1.3. Composites Ion Exchangers……………………………… 6 1.3.1. Amines………………………………………………. 8 1.3.2. Nylon-6,6……………………………………………. 8 1.3.3. Polycarylonitrile……………………………………... 8 1.3.4. Polypyrrole………………………………………….. 9 1.3.5. Polymethyl methacrylate…………………………… 10 1.3.6. Polyaniline…………………………………………... 10 1.4. Characterization of Ion Exchangers…………….………… 11 1.4.1. Ion exchange capacity……………………………...… 11 1.4.2. Chemical and thermal stability …………………...... 13 1.4.3. Selectivity of ion exchanger…………………………. 14 1.4.3.1. Ion sieve effect……………………………………. 16 1.4.3.2. Steric effect……………………………………….. 16 1.5 Concepts of Ion Exchange….……………..………..……... 17 1.5.1. Kinetics of ion exchange…...…………...... 18 1.5.1.1. Mechanism of ion exchange………….…………….. 18 1.5.1.2. Rate-determining step…………………...... 22 1.5.2. Equilibrium isotherm………………………………… 25 1.5.2.1. Freundlich isotherm………………………………… 26 1.5.2.2. Langmuir isotherm…………………………………. 26 1.5.3. Thermodynamic of ion exchange.…………………… 28

1.5.4. Distribution coefficient (Kd)…………………………. 28 - I - CONTENTS M. Khalil 1.5.5. Column processes……………………………………. 30 1.6. Applications of Ion Exchangers...... 31 1.7. Ion exchangers Showing High Selectivity for Cesium…... 34 1.7.1. Organic ion exchangers with high selectivity for cesium. 34 1.7.2. Inorganic ion exchangers with high selectivity for 34 cesium………………………………………………... 1.7.2.1. Heteropolyacid salts………………………………... 35 1.7.2.2. Insoluble hexacyanoferrate(II) salts of transition 36 metals………………………………………………. 1.7.2.3. Insoluble hexacyanoferrate(III) salts of transition 37 metals………………………………………………. 1.7.2.4. Zeolites…………………………………………….. 38 1.7.2.5. Hydrous oxides…………………………………….. 39 1.7.2.6. Acid salts of metals…………...... 39 1.8. Recent Developments…………………………………….... 40

CHAPTER-2 MATERIALS AND METHODS

2.1. Chemicals and Reagents………………...………………… 44 2.2. Radioactive Materials …………………………………….. 44 2.3. Preparation of the Reagent Solutions …..…..……………. 44 2.4 Synthesis of Polyaniline……………………………………. 45 2.5. Synthesis of Titanotungstate (TiW)………………………. 45 2.6. Synthesis of Polyaniline Titanotungstate (PATiW)..…...... 45 2.7. Instruments and Characterization of Materials………….. 46 2.8. Elemental Composition…………………………………….. 47 2.9. Chemical Stability…...……………..……………………….. 47 2.10. pH Titration ……………………………….………………. 47 2.11. Ion-Exchange Capacity (IEC)…………………………….. 47 2.12. Distribution Studies …………………..………..…………. 48 2.13. Separation Factor …….…………………………………... 49 2.14. Kinetic Studies ……………………………….……………. 49 2.15. Sorption Isotherms…………………………………………. 50 2.16. Column Operations………………………………………… 51 2.17. Recovery of Cesium from Milk ……………………...……. 52

- II - CONTENTS M. Khalil CHAPTER-3 RESULTS AND DISCUSSION

3.1. Characterization of Materials………………..………….. 56 3.1.1. IR spectra ………………………...……..……..…… 56 3.1.2. X-ray diffraction patterns ……………..………..….. 60 3.1.3. Scanning electron microscopy (SEM) studies…….... 60 3.1.4. Thermal analysis ………………………………..…... 68 3.1.5. Elemental composition of PATiW…...……………… 68 3.1.6. Chemical stability………..………………..…….….... 70 3.1.7. pH Titration …………………………………..……... 70 3.1.8. Ion-Exchange Capacity (IEC)…...……..……….….... 73 3.2. Distribution Studies ………………………………………. 76 3.2.1. Separation factor………...………………………….... 86 3.3. Kinetic Studies……………………………………………... 87 3.3.1. Effect of initial concentration and contact time…….... 88 3.3.2. Effect of particle size.…………………………...... 93 3.3.3. Effect of contact time and reaction temperature……… 97 3.3.4. Effect of drying temperature.……………………….. 103 3.3.5. Sorption kinetics modeling…………………………... 103 3.3.5.1. Pseudo first-order model………………….…….….. 107 3.3.5.2. Pseudo second-order model………………………... 107 3.3.5.3. The homogeneous particle diffusion model (HPDM). 114 3.3.5.4. The shell progressive model (SPM)………………... 116 3.3.5.5. Intraparticle diffusion model……………………….. 131 3.4. Sorption Isotherms………………………………………… 133 3.4.1. Freundlich isotherm…………………………...... 137 3.4.2. Langmuir isotherm……………………….…...... 143 3.5. Column Operations………………………………….……... 151 3.6. Recover Cesium from Milk…………………………….…. 157 SUMMARY……………………………………………………………. 160 REFERENCES………………………………………………………… 165 ARABIC SUMMARY………………………………………………….

- III - CONTENTS M. Khalil LIST of TABLES

Table 1 Few applications of ion exchange materials including both well- 32 developed and experimental techniques………….. Table 2 Chemical stability of TiW and PATiW in various solvent 71 systems...... Table 3 Factors affecting on preparation of PATiW and the percent of 74 sorption of Cs+, Co2+ and Eu3+ ions at 10-4 M and at V/m 100...... + 2+ 2+ 2+ 2+ 3+ 4+ 5+ 5+ Table 4 Kd values of Cs , Co , Zn , Cd , Cu , Cr , Zr , As , V , 84 6+ Cs + + Mo and separation factors ()α B of Cs from other metal ions at o different concentrations of HNO3 on PATiW at 25 ±1 C………… Table 5 Thermodynamic parameters for the sorption of Cs+ on TiW and 102 PATiW at V/m 50 and at different reaction temperatures.……….. Table 6 The calculated parameters of the pseudo second-order kinetic 113 model for Cs+ onto TiW and PATiW at V/m 50 and at different reaction temperatures…….………………….. Table 7 Diffusion coefficients for the sorption of Cs+ onto TiW and 126 PATiW at V/m 50 and at different reaction temperatures...... Table 8 Kinetic parameters for the sorption of Cs+ onto TiW and 130 PATiW…. Table 9 Intraparticle diffusion rate constant for the sorption Cs+ onto TiW 136 and PATiW at V/m 50 and at different reaction temperatures…………………………….………………… Table 10 Freundlich and Langmuir isotherm parameters for the sorption of 147 Cs+ onto TiW and PATiW at V/m 50 and at different reaction temperatures…………………......

- IV - CONTENTS M. Khalil LIST of FIGURES

Figure 1 Equivalent character of ion exchange..…………….…. 19 Figure 2 Mass transfer at ion exchange process….…………..…. 20 Figure 3 General mechanism of the ion exchange process…...... 21 Figure 4 FTIR spectrum of a prepared polyaniline………………. 57 Figure 5 FTIR spectrum of a prepared TiW……………………… 58 Figure 6 FTIR spectum of a prepared PATiW composite material. 59 Figure 7 FTIR spectra of a prepared PATiW composite material at 61 different drying temperatures…………………………… Figure 8 XRD patterns of PATiW at different drying temperatures. 62 Figure 9 Scanning electron microphotographs (SEM) of chemically 63 prepared polyaniline at the magnification of 900×……… Figure 10 Scanning electron microphotographs (SEM) of chemically 64 prepared TiW dried at 50 oC at the magnification of 3000×…………………………………………………… Figure 11 Scanning electron microphotographs (SEM) of chemically 65 prepared TiW dried at 850 oC at the magnification of 3000×…………………………………………………… Figure 12 Scanning electron microphotographs (SEM) of chemically 66 prepared PTiW dried at 50 oC at the magnification of 2000×………………………………………………….. Figure 13 Scanning electron microphotographs (SEM) of chemically 67 prepared PTiW dried at 850 oC at the magnification of 3000×………………………………………………… Figure 14 TGA-DTA thermogram of PATiW…………………….. 69 Figure 15 The pH-titration curve of PATiW with 0.1M NaOH.…. 72 Figure 16 Plots of capacity versus pH for exchange of Cs+ on 75 PATiW at 0.1M, V/m 100 and 25 ±1 oC.…….………..… + Figure 17 Plots of log Kd versus pH for exchangeof Cs on TiW and 78 PATiW at 10-4M, V/m 50 and 25 ±1 °C…….…….. + Figure 18 Plots of log Kd versus pH for exchangeof Cs on TiW at 79 10-4M and V/m 50 at different reaction temperatures…… + Figure 19 Plots of log Kd versus pH for exchangeof Cs on PATiW 80 at 10-4M and V/m 50 at different reaction temperatures…. + Figure 20 Plots of log Kd versus pH for exchangeof Cs on PATiW 81

- V - CONTENTS M. Khalil at 10-4M and V/m 50 at different drying temperatures…… + 2+ 2+ Figure 21 Plots of Kd versus pH for exchange of Cs , Co , Zn , 83 Cd2+, Cu2+, Cr3+ , Zr4+, As5+, V5+ and Mo6+ at 25 ±1 oC on PATiW at 10-4M , V/m 50 of Cs+ and 10-5M , V/m 100 for other ions………………………………………………… Figure 22 Effect of initial ion concentration and contact time on the 89 amount sorbed of Cs+ onto TiW V/m 50 and 25 ±1 °C. Figure 23 Effect of initial ion concentration and contact time on the 90 amount sorbed of Cs+ onto PATiW at V/m 50 and 25 ±1 °C. Figure 24 Plots of F versus time for sorption of Cs+ onto TiW at 91 different initial ion concentration, V/m 50 and 25 ±1 °C… Figure 25 Plots of F versus time for sorption of Cs+ onto PATiW at 92 different initial ion concentration, V/m 50 and 25 ±1 °C. Figure 26 Plots of F and Bt versus time for sorption of Cs+ onto TiW 94 at different particular sizes, V/m 50 and 25 ±1 °C……….. Figure 27 Plots of F and Bt versus time for sorption of Cs+ onto 95 PATiW at different particular sizes, V/m 50 and 25 ±1 °C.. Figure 28 Plots of B versus 1/r2 for sorption of Cs+ onto TiW 96 and PATiW……………………………………………..... Figure 29 Plots of F and Bt versus time for sorption of Cs+ onto TiW 98 at V/m 50 and at different reaction temperatures……….… Figure 30 Plots of F and Bt versus time for sorption of Cs+ onto 99 PATiW at V/m 50 and at different reaction temperatures…. Figure 31 Relationship between Gibbs free energy change and 101 temperature of sorption of Cs+ onto TiW and PATiW at different reaction temperatures…………………………… Figure 32 Plots of F and Bt versus time for sorption of Cs+ onto TiW 104 dried at 50, 200, 400 oC, at V/m 50 and reaction temperature 25 ±1 oC Figure 33 Plots of F and Bt versus time for sorption of Cs+ onto 105 PATiW dried at 50, 200, 400 oC at V/m 50 and reaction temperature 25 ±1 oC.…………………………………. Figure 34 Pseudo first-order kinetic plots for the sorption of Cs+ onto 108 TiW at V/m 50 and at different reaction temperatures..

- VI - CONTENTS M. Khalil Figure 35 Pseudo first-order kinetic plots for the sorption of Cs+ onto 109 PATiW at V/m 50 and at different reaction temperatures.. Figure 36 Pseudo second-order kinetic plots for the sorption of Cs+ 111 onto TiW at V/m 50 and at different reaction temperatures. Figure 37 Pseudo second-order kinetic plots for the sorption of 112 Cs+ onto PATiW at V/m 50 and at different reaction temperatures……………………………………………….. Figure 38 Plots of -ln(1-F) as a function of time for the diffusion of 117 Cs+ onto TiW at V/m 50 and at different reaction temperatures……………………………………………….. Figure 39 Plots of -ln(1-F) as a function of time for the diffusion 118 of Cs+ onto PATiW at V/m 50 and at different reaction temperatures………………………………………………. Figure 40 Plots of -ln(1-F2) as a function of time for the diffusion 119 of Cs+ onto TiW at V/m 50 and at different reaction temperatures………………………………………………. Figure 41 Plots of -ln(1-F2) as a function of time for the diffusion of 120 Cs+ onto PATiW at V/m 50 and at different reaction temperatures……………………………………………… Figure 42 Plots of [3-3(1-F)2 / 3 -2F] as a function of time 122 for the diffusion of Cs+ onto TiW at V/m 50 and at different reaction temperatures……………………………. Figure 43 Plots of [3-3(1-F)2/3-2F] as a function of time for 123 the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures……………………….. Figure 44 Plots of [1-(1-F) 1 / 3 ] as a function of time for 124 the diffusion of Cs+ onto TiW at V/m 50 and at different reaction temperatures…………………………………….. Figure 45 Plots of [1-(1-F) 1 / 3 ] as a function of time for 125 the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures………………………… Figure 46 Arrhenius plots for the particle diffusion coefficients of 129 Cs+ sorbed onto TiW and PATiW……………………….. Figure 47 Morris–Weber kinetic plots for the sorption of Cs+ onto 134 TiW at V/m 50 and different reaction temperature…….. Figure 48 Morris–Weber kinetic plots for the sorption of Cs+ onto 135

- VII - CONTENTS M. Khalil PATiW at V/m 50 and at different reaction temperatures.. + Figure 49 Plots qe versus Ce for sorption isotherm of Cs ontoo138 TiW at V/m 50 and at different reaction temperatures……… + Figure 50 Plots qe versus Ce for sorption isotherm of Cs onto PATiW 139 at V/m 50 and at different reaction temperatures……… Figure 51 Freundlich isotherm plots for sorption of Cs+ onto TiW 141 at V/m 50 and at different reaction temperature………... Figure 52 Freundlich isotherm plots for sorption of Cs+ onto PATiW 142 at V/m 50 and at different reaction temperatures………. Figure 53 Langmiur isotherm plots for sorption of Cs+ onto TiW 145 at V/m 50 and at different reaction temperatures………... Figure 54 Langmiur isotherm plots for sorption of Cs+ onto PATiW 146 at V/m 50 and at different reaction temperatures…………

Figure 55 plots of separation factor, RL, versus initial concentration, 149 + Co, for sorption of Cs onto TiW at V/m 50 and at different reaction temperatures……………………………………….

Figure 56 plots of separation factor, RL, versus initial concentration, 150 + Co, for sorption of Cs onto PATiW at V/m 50 and at different reaction temperatures……………………………. Figure 57 Performance of PATiW column for cesium removal from 153 neutral solutions at different bed depth, 140 mg L-1 and flow rate 2.5 ml min-1…………………………………… Figure 58 Performance of PATiW column for cesium removal from 155 alkaline and acidic simulant solutions at bed depth 1cm,13 mg L-1 and flow rate 0.7 ml min-1………………………. Figure 59 Redaction of cesium-134 on PATiW as a function of 159 mixing time at V/m 50 and 25 ±1 oC……………………

- VIII - CONTENTS M. Khalil

Chemical Studies on Polyaniline Titanotungstate as a New Composite Cation Exchanger and Its Analytical Applications for Removal of Cesium from Aqueous Solutions

List of Publications

1. I.M. El-Naggar, E.S. Zakaria, I.M. Ali, M. Khalil, M.F. El- Shahat, Kinetic modeling analysis for the removal of cesium ions from aqueous solutions using polyaniline titanotungstate, Arabian Journal of Chemistry (2012) 5, 109–119. 2. I.M. El-Naggar, E.S. Zakaria, I.M. Ali, M. Khalil, M.F. El- Shahat, Chemical studies on polyaniline titanotungstate and its uses to reduction cesium from solutions and polluted milk, Journal of Environmental Radioactivity (2012) 112, 108-117.

- IX - CONTENTS M. Khalil Aim of Work

The latest developments of synthetic ion exchangers are the preparation and the application of inorganic-organic composite ion exchangers in order to obtain a combination of the advantages of inorganic and organic ion exchangers. These materials are used in analytical chemistry and in separation technology, because of their high selectivity's for metal ions and ease of preparation. Many inorganic- organic composite ion exchangers have been developed earlier by incorporation of organic polymers in the inorganic matrix. In order to increase interlayer distance of layered inorganic ion exchangers, to increase the selectivity's for the ions and to prepare larger particles with higher granular strength for column for the treatment of various aqueous solutions and radioactive waste from cesium. This may open new possibilities for their industrial applications. In this concern, efforts have been made to study and develop effective and economic materials for treatment cesium ion from aqueous solutions waste using polyaniline titanotungstate. The following items will be studied: • Synthesis of polyaniline titanotungestate. • Characterization of the prepared material using IR, XRD, SEM and DTA-TGA analysis. • Chemical stability, equilibrium studies and capacities of the prepared material for Cs+ at different operation conditions. • Determination of the diffusion mechanisms and selectivity of these materials. • Ion exchange isotherms. • Separation of Cs+ from other ions.

- X - CONTENTS M. Khalil Chemical Studies on Polyaniline Titanotungstate as a New Composite Cation Exchanger and Its Analytical Applications for Removal of Cesium from Aqueous Solutions

ABSTRACT

Polyaniline titanotungstate has been synthesized by incorporation of organic polymer polyaniline into the inorganic precipitate of titanotungstate. This material was characterized using IR, X-Ray, SEM and DTA-TGA analysis. The influences of initial concentration of metal ions, particle size and temperature have been reported. The material stability was investigated in water, acids, alkaline solutions, and at high temperature up to 850 oC. Ion-exchange capacity and distribution coefficients (Kd) for ten metal ions have been determined. It was found that the polyaniline titanotungstate has high affinity and high selectivity for Cs+. The material has high separation for Cs+ ion from other metal ions. The comparison of composite (PATiW) and inorganic material (TiW) was studied and indicated that the composite material is better than the inorganic one in selectivity of Cs+. Thermodynamic parameter of Cs+ exchange process, such as changes in Gibbs free energy (Go), enthalpy (Ho), and entropy (So) have been calculated. It was found that numerical value of G decrease with an increase in temperature, indicating that the sorption reaction of adsorbent was spontaneous and more favorable at higher temperature. The positive value of Ho corresponds to the endothermic nature of sorption processes and suggested that chemisorptions were the predominant mechanism. A comparison of kinetic models applied to the sorption rate data of Cs+ was evaluated for the pseudo first-order, pseudo second-order, homogeneous particle diffusion, shell model and intraparticle diffusion models. The results showed that Cs+ is sorption onto PATiW and TiW with particle diffusion mechanism. Self diffusion coefficient (Di), Activation energy (Ea) and entropy (S*) of activation were also computed from the - XI - CONTENTS M. Khalil linearized form of Arrhenius equation. Column studies in acid and alkaline solutions were studied. A kinetic study for removal cesium from milk was investigated.

KEYWORDS: Synthesis; Sorption; Separation; Kinetics; Ion exchange; Polyaniline titanotungstate; Cesium.

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INTRODUCTION M. Khalil

1. INTRODUCTION In science, analytical chemistry is an ancient branch, yet may be regarded as one of the youngest science with the growing global, awareness in health hazards and environmental pollution; it has played a key role to unveil the causes. So the scientists all over the world are paying great attention to analytical chemistry. Analytical Chemistry is basically concerned with the determination of chemical composition of matter. The aspects covered by modern analytical chemistry are identification of a substance, the elucidation of its structure, separation of different elements and synthesis of ion exchangers. Separation has very important applications in various fields namely medicine, agriculture and environmental analysis. Separation is basically a pre-treatment method which, usually proceeds any quantitative or qualitative analysis. Separation involves both classical and modern techniques. The examples of the classical methods are precipitation and distillation. The general methods of separation include distillation, extraction, precipitation, crystallization, dialysis, diffusion etc. The most modern and versatile techniques used for the purpose of separations are chromatography, electrophoresis and ion exchange. Ion exchange has emerged as a most versatile and standard analytical tool. Ion exchange is basically a process of nature occurring throughout the ages from even before the dawn of human civilization. The phenomenon of ion exchange is not of a recent origin. The earliest of the references were found in Holy Bible, which says ‘Moses’ succeeded in preparing drinking water from brackish water by an ion exchange method. In the beginning of 19th century, chemists were quite aware about ion exchange and were busy in new researches. By middle of 19th century sufficient experimental observations and information had been collected but principle of ion exchange had not yet been discovered.

- 1 - INTRODUCTION M. Khalil

Thompson and Roy (1850); Way (1850) laid the foundation of ion exchange by base exchange in soil. They observed that when soils are treated with ammonium salts, ammonium ions are taken up by the soil and an equivalent amount of calcium and magnesium ions are released. During 1850-55 the agrochemist way demonstrated the following mechanism to be one of the ion exchange methods involving the complex silicates present in the soil as described by formulated: − + − + Ca Soil( NH4)2 SO 4 NH 4 Soil CaSO 4 (1) The ion exchange process is reversible and alumino silicates (zeolites) are responsible for the exchange in soil, established by Eichorn (1850). The first synthetic aluminum based ion exchanger was prepared by Rumpler in 1903 to purify the beet syrup. According to Lamberg (1870) and Wiegner (1912), the materials responsible for the phenomenon were mainly clays, zeolites, gluconites and humic acids. The first application of synthetic zeolite for collection and separation of ammonia from urine was made by Folin and Bell (1917). Due to the limitations in the applications of neutral and synthetic silicates in various industrial applications and in an attempt to meet the demands of the industries, Adam and Holms (1935) laid the foundation of organic exchangers when they observed that the crushed phonograph records exhibit ion exchange properties. This lead to investigators to develop synthetic ion exchange resins. Farben industries in Germany followed by the manufacturers in U.S.A. and U.K, which proved very effective for separations, recoveries, the ionization catalysis etc. 1.1. Inorganic Ion Exchangers Although inorganic ion exchange materials were first to be recognized, they lost their utility after the discovery of organic resins. However, revival of the interest in these materials took place in the 20th century, because of their use in the field of nuclear research. At that time there was need of some new materials that were stable at high temperatures

- 2 - INTRODUCTION M. Khalil

and in presence of intense radioactive radiations. Kraus et al. (1956) at Oak Ridge national laboratory and Amphlett and Mcdonald (1962) in United Kingdom did the excellent work on these materials in the initial stages. The work up to 1963 has been summarized by Amphlett and Jones (1964) in the classical book ‘Inorganic Ion exchangers’. The later wok up to 1970 has been condensed by Clearfield et al., (1973); Alberti and Allulli (1968); Walton (1976) 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 material and studied their ion exchange behavior during the last 15 years. Other groups that were engaged in the field of research and whose work is significant interest are Anil K. De at Shantinikaten and Tandon at Rorkee. The few important uses of these inorganic ion exchangers are: separation of metal ions, separation of organic compounds, removal of wastes and air pollutants, preparation of ion-selective electrodes, preparation of artificial kidney machines and preparation of fuel cells. Some naturally occurring and/or synthetically prepared inorganic materials have been known for a long time as adsorbents for various radionuclides, mainly alkali and alkaline earth cations [Zakaria and El-Naggar 1998; Ibrahim et al., 2003; Ibrahim et al., 2004]. The analytical importance of the synthetic inorganic ion exchangers is now firmly established. The review of ion exchange in analytical chemistry for the year 1970 includes the significant statement; the obvious advances in the last two years are in the area of inorganic ion exchangers. Even today this statement is almost equally true. Synthetic ion exchanger may be classified in the following categories: 1) Synthetic zeolites 2) Polybasic acid salts 3) Hydrous oxides

- 3 - INTRODUCTION M. Khalil

4) Metal ferrocynides 5) Insoluble ion exchange materials 6) Hetropolyacids 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 studied as per given order of preference. • Ion exchange capacity • Chemical and thermal stability • Composition • pH titration • Structural studies • Selectivity • Analytical applications Besides the applications, inorganic ion exchangers have some limitations as following: • Relatively low exchange capacities • Relatively low mechanical durability • Non-controllable pore size • Clay minerals tend to peptize (i.e. convert to a colloidal form) • Zeolites are difficult to size mechanically • Partial decomposition in acids or alkalis • Limited chemical stability in many solutions • Need for a chemical or thermal pretreatment (especially those with a very low salt content) 1.2. Synthetic Organic Ion Exchangers The resins are made insoluble by cross-linking the various hydrocarbon chains. The degree of cross-linking determines the mesh width of the matrix, swelling ability, movement of mobile ions, hardness and mechanical durability. Highly cross-linked resins are harder, more resistant to mechanical degradation, less porous and swell less in

- 4 - INTRODUCTION M. Khalil solvents. When an organic ion exchange is placed in a solvent or solution it will expand or swell. The degree of swelling depends both on the characteristics of the solution/solvent and the exchanger itself and is influenced by a number of other conditions. The main advantages of synthetic organic ion exchange resins are their high capacity, wide applicability, wide versatility and low cost relative to some synthetic inorganic media. The main limitations are their limited radiation, thermal stabilities and their swelling. The main groups of synthetic organic ion exchange resins are described below. 1.2.1. Polystyrene divinylbenzene The most common form of ion exchange resin is based on a copolymer of styrene and divinylbenzene. The degree of cross-linking is adjusted by varying the divinylbenzene content and is expressed as the percentage of divinylbenzene in the matrix; for example, 5% cross- linking means 5 mol % divinylbenzene in the matrix. Low divinylbenzene content resins are soft and gelatinous and swell strongly in solvents. 1.2.2. Phenolic Phenol-formaldehyde condensation products, with the phenolic –OH groups as the fixed ionic groups, are very weak acid exchangers. Sulphonation of the phenol prior to polymerization can be used to increase the acid strength. Phenolsulphonic acid resins are bifunctional with both strong acid –SO3H and weak acid –OH groups included. The degree of cross-linking is controlled by the amount of formaldehyde. A resorcinol-formaldehyde polycondensate resin was recently developed, characterized and tested extensively in India for the efficient removal of radiocaesium from alkaline reprocessing waste containing a large concentration of competing sodium ions [Samanta et al., 1995]. 1.2.3. Acrylic A weak acid ion exchange resin with weakly ionized carboxylic

- 5 - INTRODUCTION M. Khalil acid groups is prepared by the suspension copolymerization of acrylic or methacrylic acid with divinylbenzene. The –COOH functional groups have very little salt splitting capacity, but under alkaline conditions exhibit a strong affinity for Ca2+ and similar ions (such as strontium). 1.3. Composites Ion Exchangers The main advantages of synthetic organic ion exchange resins are their high capacity, wide applicability, wide versatility and low cost relative to some synthetic inorganic materials. But they also have some limitations. The main limitations are their limited radiation and thermal stabilities. At a total absorbed radiation dose of 109 to 1010 rads most organic resins will exhibit a severe reduction in their ion exchange capacity (a 10 to 100% capacity loss), due to physical degradation at both the molecular and macroscopic level. The conversion of inorganic ion exchange materials has been taking place into composite ion exchange materials is the latest development in this discipline. Sol-gel derived composite materials have found numerous applications in the areas of chemistry, biochemistry, engineering, and material science [Collinson, 1999]. The ‘organic-inorganic’ hybrid materials prepared via the sol-gel technique have attracted significant attention in the literature [Philipp and Schmidt, 1984]. The combination of organic and inorganic precursors yields hybrid materials that have mechanical properties not present in the pure materials. Organic- inorganic composite ion exchange materials show the improvement in its granulometric properties that makes them more suitable for the application in column operations. The binding of organic polymer also introduces the better mechanical properties in the end product, i.e. composite ion exchange materials. More recently, some organic-inorganic composite ion exchange materials have been developed. Khan et al. (2005) have reported

- 6 - INTRODUCTION M. Khalil polypyrrole-Th(IV) phosphate, polyaniline-Sn(IV) arsenophosphate [Khan et al., 1999] and polystyrene-Zr(IV) tungstophosphate [Khan et al., 1998] used for the selective separation of Pb2+, Cd2+, Hg2+ respectively, and ion exchange kinetics of M2+- H+ exchange and adsorption of pesticide, Khan et al. (2002) has also carried out on these materials. Pandit and Chudasma (2001) have synthesized such type of ion exchange materials, i.e. o-chlorophenol Zr(IV) tungstate and p- chlorophenol Zr(IV) tungstate. Styrene supported Zr(IV) phosphate hybrid material [Varshney and Pandith, 1996], and fibrous ion exchange materials such as polymethyl methacrylate, polyacrylonitrile, styrene and pectin based Ce(IV) phosphate, Th(IV) phosphate and Zr(IV) phosphate have been reported by Varshney et al. (2003) have numerous analytical applications. These materials can be used as ion exchange membranes and electrodes. Polyacrylonitrile fibers and zeolite composites have also been reported in literature. Polyaniline-Zr(IV) tungstophosphate has been synthesized by Ikram (2000) that was used 3+ 2+ for the selective separation of La and UO2 . Demarco and Sengupta

(2003) reported polyacrylic acid coated SiO2 as a new ion exchange material. A polymeric/inorganic hybrid sorbent has also been used for arsenic removal. Ion exchangers find applications in a wide variety of industrial, domestic, governmental and laboratory operations. The column operation suitability makes it more convenient in regeneration of exhausted beds also. These hybrid ion exchangers have good ion exchange capacity, high stability, reproducibility and selectivity for heavy metal ions indicating its useful environmental applications. In general these materials have their applications in the following disciplines: · Water softening [Gans, 1906]. · Separation and preconcentration of metal ions [Mulik and Sawicki, 1975]

- 7 - INTRODUCTION M. Khalil

· Nuclear separations [Miller et al., 1997] · Catalysis [Clearfield and Thakur, 1986] · Redox system [La Ginestra et al., 1983] · Electrodialysis [Meyer and Strauss, 1940] · Hydrometallurgy [Mindler and Paulson, 1953] · Effluent treatment [Bolto and Pawlowaski, 1983] · Ion exchange fibers [Bajaj et al., 1994] · Ion-selective electrodes [Khan and Alam, 2003] The main groups of composite ion exchangers are described below: 1.3.1. Amines Khan et al. (1998) introduced organic amines in place of ammonium ion in ammonium hexacynoferrate (II) compounds of cobalt (II) and reported that the organic amine compounds have excellent exchange properties of 137Cs. Amine tin (II) hexacynoferrate (II) [Varshney and Naheed, 1977], amine tin (IV) hexacynoferrate (II) [Varshney et al., 1982], tin (IV) diethanolamine [Rawat and Igbal, 1981] and iron (III) diethanolamine [Singh et al., 1986] have already been reported and utilized for the separations of metal ions. 1.3.2. Nylon-6,6 Nylon-6,6, Zr(IV) phosphate hybrid cation-exchanger have been developed [Inamuddin et al., 2007]. This hybrid cation-exchanger possessed good ion-exchange capacity (IEC) 1.80 meq. g−1 and high selectivity for Hg(II) a toxic metal ion. 1.3.3. Polycarylonitrile Polyacrylonitrile (PAN) based composite inorganic–organic absorbers represent a group of inorganic ion exchangers modified by using PAN binder to produce larger size particles. In the view of stability and treatment for final disposal, the composite absorbers represent a separate group of absorbers similar both to the organic and inorganic ion exchange resins [Mimura et al., 1997]. Their main feature is that the organic

- 8 - INTRODUCTION M. Khalil binding polymer (PAN) is inert and all the radionuclides are bound to inorganic active component (inorganic ion exchanger). As a result, contrary to organic ion exchange resins even in the case of decomposition of organic binding matrix (radiation, chemical, thermal or biological decomposition) no radionuclides are released. Modified polyacrylonitrile has been proposed as a universal binding polymer for practically any inorganic ion exchanger, and the principal scheme for the preparation was proposed [Sebesta, 1997]. Several works on PAN as a binding polymer for granulating hydrous oxides of polyvalent metals, such as titanium oxide [Akyil et al., 1996]. Nakamura et al. (1988) used a commercial PAN-HTO (Asahi Chemical Industry Co. Ltd.) containing hydrous titanium oxide granulated with PAN to study the uptake of uranium from sea water. John et al. (1997) conducted a dynamic leaching tests of 137Cs from cesium loaded cemented NiFC (nickel ferrocyanate)- PAN composite ion exchanger. They proved that the leached fractions were 100 times lower than those from simply cemented samples. Hwang et al. (1998) succeeded in the preparation of a fiber type of PAN-zeolites composite ion exchangers. Moon et al. (2000) preparing the spherical PAN/potassium titanate and PAN/nickel ferrocyanate composite ion exchanger beads and evaluation of their adsorption characteristics for the Ag+ and Sr2+ ions in acidic waste solutions. Nilchi et al. (2006) was prepared the composite, potassium hexacyanocobalt (II) ferrate (II)–polyacrylonitrile (KCFC– PAN) and discus its properties and technological application for Ba2+,Sr2+,Ca2+and Mg2+are evaluated. 1.3.4. Polypyrrole Polypyrrole thorium(IV) phosphate cation-exchanger have been developed by Khan et al. (2005) as a new class of hybrid cation- exchangers with good ion exchange capacity, higher stability, reproducibility and selectivity for for pb(II) ion, it used as a selective

- 9 - INTRODUCTION M. Khalil ion-sensitive membrane electrode. 1.3.5. Polymethyl methacrylate Siddiqui et al. (2007) were synthesized a hybrid type of ion exchanger poly(methyl methacrylate) Zr(1V) phosphate by mixing poly(methyl methacrylate) (PMMA) into inorganic cation-exchange material Zr(IV) phosphate. Sorption studies showed that the composite cation-exchanger has high selectivity to Pb(II) in comparison to other metal ions. Its selectivity was used for some important binary separations like Pb(II)–Mg(II), Pb(II)–Cd(II), Pb(II)–Hg(II), Pb(II)–Cu(II), and Cu(II)–Cd(II). 1.3.6. Polyaniline Examples of studies on the polyaniline based composite ion exchangers are reviewed in several papers, polyaniline _ _ _ _ Sn(IV)tungstoarsenate [(SnO2)(WO3)(As2O5)4 ( C6H5 NH )2 nH2O] was synthesized by incorporating polyaniline into inorganic ion-exchanger material and discussed the ion exchange kinetics and electrical conductivity studies [Khan et.al, 2003]. Khan and Inamuddin (2006) also were prepared Polyaniline Sn(IV) phosphate, an ‘organic–inorganic’ composite material, via sol–gel mixing of an electrically conducting organic polymer polyaniline into the matrices of inorganic precipitate of Sn(IV) phosphate. This material was used as a cation-exchanger, on the basis of distribution studies, the material was found to be highly selective for Pb(II). Its selectivity was examined by achieving some important binary separations like Pb(II)– Mg(II), Pb(II)–Sr(II), Pb(II)–Zn(II), and Pb(II)–Fe(III) on its column. This material possessed DC electrical conductivity in the semi- conducting range, i.e. 10-5–10-3 S cm-1. The DC electrical conductivity of composite material was found stable up to 110 oC under ambient conditions. polyaniline Sn(IV) tungstoarsenate was developed by mixing polyaniline into inorganic precipitate of Sn(IV) tungstoarsenate. the

- 10 - INTRODUCTION M. Khalil material was found to be highly selective for Cd(II) and its selectivity was tested by achieving some important binary separations like Cd(II)– Zn(II), Cd(II)–Pb(II), Cd(II)–Hg(II), Cd(II)–Cu(II) on its column. Using this composite cation exchanger as electroactive material, a new heterogeneous precipitate based selective ion-sensitive membrane electrode was developed for the determination of Cd(II) ions in solutions [Khan et al., 2003]. Khan et al. (1999) was prepared polyaniline Sn(IV)arsenophosphate by mixing polyaniline into inorganic material. On the basis of distribution studies, the material has been found to be highly selective for Pb(II). Now days, efforts and researchers must be an interesting on an inorganic ion exchanger based on organic polymeric matrix material as it should possess the mechanical stability. Due to the presence of organic polymeric species and the basic characteristics of an inorganic ion exchanger regarding its selectivity for some specific metal ions. It was therefore considered to synthesize such an ion exchanger. 1.4. Characterization of Ion Exchangers 1.4.1. Ion exchange capacity Ion exchange capacity is a major characteristic of ion exchange materials. From a practical point of view, an ion exchanger can be considered as a “reservoir” containing exchangeable counterions. The counterion content in a given amount of material is defined essentially by the amount of fixed charges which must be compensated by the counterions, and thus is essentially constant. According to this fact, ion exchangers are quantitatively characterized by their capacity which is defined as the number of counter ion equivalents in a specified amount of the material [Helfferich, 1962]. The above definition gives a good filling about the chemical nature of the capacity. However, it does not reflect either physico-chemical or practical property of any ion exchange material. Scientists and engineers

- 11 - INTRODUCTION M. Khalil use many different definitions of capacity depending on practical need and even individual preferences. As a result, each material can be characterized by several values of capacity. Even more, the conditional capacity (capacity exhibited under certain particular conditions) is often used to describe and compare ion exchangers. Taking the infinite number of possible operating conditions, the number of capacity values for one material can be raised up to infinity. Any practically valuable characteristic of ion exchange capacity can be defined only as a content of the counterion in the ion exchanger, i.e. it is a ratio between the amount of ions and the amount of the substance containing these ions:

m Z Q = ion ion (2) m ion exchange where Zion is the ion charge, mion is the amount of the ion, , and mion exchanger is the amount of the ion exchanger. Breakthrough capacity is a technology concept. If the ion exchange material is used for a column process, the operation is often discontinued at breakthrough, i.e. when the ion or substance that is targeted to be trapped by the column appears at the outlet. As a result of such process, the loading of material is not homogeneous along the longitudinal axis of the column. In case of imperfect performance of the column, a radial in homogeneity can also occur. As a result, the value of breakthrough capacity of the column is always lower than that of an ion exchange capacity characterizing the material loaded in this column. The breakthrough capacity depends on the operating conditions and on the properties (including capacity) of the material; however, the reversed calculation is impossible, i.e. the breakthrough capacity cannot be used to obtain the material’s characteristics. Many sources operate with terms static ion exchange capacity or

- 12 - INTRODUCTION M. Khalil dynamic ion exchange capacity. The words static and dynamic reflect practical methods used for the capacity determination, i.e. refer to the measurement method. As a matter of fact, static ion exchange capacity is a particular case of equilibrium capacity [Helfferich, 1962; Samuelson, 1963; Kokotov and Pasechnik, 1970; Vulikh, 1973; Hubicki and Olszak, 1998]. 1.4.2. Chemical and thermal stability Chemical stability is an additional criterion that emphasizes the basic difference between organic and inorganic ion exchange sorbets. In this concern, the insoluble salts of polyvalent metals are highly stable in very concentrated acids [Amphlett and Jones 1964]. Crystalline antimonic acids are extremely stable to most reagents and are very difficult to dissolve, even by heating with concentrated hydrochloric acid or 1M potassium hydroxide. On the other hand aluminosilicates are generally less resistant to acids than to bases. Some sorbets are dealuminated at pH 7 and a number of sorbets cannot be used at pH's of 1 and 2. Dealumination is accompanied by a decrease in the capacity of the aluminosilicate. On the other hand, most zeolites are stable up to a pH of about 11. Decomposition occurs at high pH values. Compared to organic sorbets, which are incomparably more stable to acids, aluminosilicates sorbets are very unstable. For this reason, inorganic zeolites which were used for all the early work on ion-exchanging materials have become less popular over the years. On the other hand, the resistance of many oxides and hydrous oxides to strong oxidizing reagents and organic solvents constitutes an advantage over organic resins. The polymer matrices of organic resins break down at elevated temperatures, with a concomitants decrease in their exchange capacity. In contrast inorganic sorbets are very stable at elevated temperatures; this is also true of zeolites, especially in the Na+ or K+ forms. For example, mordenite is stable up to 800°C and climoptilolite up to 750°C.

- 13 - INTRODUCTION M. Khalil

1.4.3. Selectivity of ion exchanger The selectivity is a widely used characteristic of ion exchange systems. It indicates the preference of the material to one ion in comparison with another ion, i.e. the selectivity is a comparative value. The simplest description of selectivity can be done on the basis of comparison of equivalent fractions of the ion in two phases. The exchanger is considered as selective towards one ion, if (at the equilibrium state) the equivalent fraction of this ion in the exchanger phase is higher than in the surrounding solution. Selectivity is a characteristic of each ion exchange material and is determined by several factors, such as the nature of the exchanging ion, its charge, size and hydration, the structure and the net charge of the framework of the exchanger, and the concentration of the surrounding solution ( degree of loading ). For binary ion exchange, the selectivity M coefficient k H can be determined as in equation (3):

[][]MHn+ + n K M = (3) H + n n + []H []M

where; [M n+ ] and [H + ]n denote to the concentrations of Mn+ and H+ ions in the cation exchanger respectively and [H+] and [Mn+] are their concentrations in solution, Generally, amorphous materials exhibit selectivity sequences that are similar to those reached with organic ion- exchange resins. This is due to that both materials have relatively open and elastic structures [Inoue and Abe, 1996]. The selectivity of organic ion exchange resins for alkali metal ions increases with decreasing loading of these ions and with increase of their degree of their cross- linking [Clearfield and styne, 1972] with smaller solvated volume (usually smallest solvated volume will have largest ionic diameter) [Kinniburgh and Jackson, 1968] with monovalent alkali metal cations,

- 14 - INTRODUCTION M. Khalil electrostatic interaction, predominate and the general order of selectivity is;

Cs+ > Rb+ > K+ > Na+ > Li+ This order is related to the size of the hydrated radius. The ion in the above group with the smallest hydrated radius, Cs+, can approach the surface and be held the most tightly. However, on some cases, the reveres order is often observed and this has been particularly noted for some hydrous metal oxide. The reason for this selectivity is not well understood, but may be related to the effect of the solid on water that is present on the oxide surface [Kinniburgh and Jackson, 1968] or to variation in the solution matrix [Abe and Ito, 1968]. With divalent ions there is little consistency in the selectivity order. However the selectivity of alkaline earth captions and divalent transition and heavy metal captions on metal oxide surfaces the surface and the pH both appear to have major effects on the selectivity sequence. Differences in the H+/Mn+ could cause reversals in selectivity, since the ions with the higher H+/Mn+ stoichiometry would be favored at higher pH[Kinniburgh and Jackson, 1968]. Divalent transition and heavy metal cations, both of which are often sorbed as inner-sphere complexes, are more strongly adsorbed than alkaline earth cations [Abe and Ito, 1968]. One can say that for a given group of elements from the periodic table with the same valence, ions with the smallest hydrated radius will be preferred, since ions are hydrated in the radioactive waste. Thus, for group I elements the general order of selectivity would be Cs+ > Rb+ > K+ > Na+ > Li+ > H+ If one is dealing with ions of different valence, generally the higher charged ion will be preferred; 3+ 2+ 2+ + + For cation; Al > Ca > Mg > K = NH4 > Na . Ph4+ > Nd3+ > Ca2+ > Na+ 3− 2− − For anion; PO4 > SO4 > Cl

- 15 - INTRODUCTION M. Khalil

In examining the effect of valence on selectivity, polarized ion must be considered. Polarization is the distortion of the electron cloud about an anion by cation. The smaller the hydrated radius of the cation, the greater the polarization, and the greater its valence, the greater it’s polarizing power. With anions, the larger they are, the more easily they can be polarized. − − − − NO3 > Br > NO2 > Cl The counter ion with the greater polarization is usually preferred [Abe and Ito, 1968] and it is also least participation to form complex with other ions [Kinniburgh and Jackson, 1968]. − − − − − Cl > HCO3 > CH3COO > OH > F Helfferich (1962) has given the following selectivity sequence for some of the common cations: Ba3+ > Pb2+ > Sr2+ > Ca2+ > Ni2+ > Cd2+ > Cu2+ > Co2+ > Zn2+ > Mg2+ > + + + + + + + Ag > Cs > Rb > K > NH4 > Na > Li . The selectivity of inorganic ion exchangers can be discussed in terms of an ion sieve effect and steric effect. 1.4.3.1. Ion sieve effect In order to replace protons in the acid form of inorganic ion exchangers, the cation present in the external solution must diffuse through the windows connecting the cavities. The water molecules of the hydrated ions are exchanged frequently with bulk water molecules in the solution. When the size of the window is smaller than the diameter of the hydrated counter ions, a part or all of the water of their hydration shell must be lost to allow the cation to pass through the window. If the cation can pass the inorganic ion exchanger pores after having lost water molecules coordinated to them in solution, the distinct kinetic observed varies with the hydration energies of the various ions. If the counter ions have larger crystal ionic radii than this opening of the window, ion sieve effect can prevail [Abe, 1995].

- 16 - INTRODUCTION M. Khalil

1.4.3.2. Steric Effect If there is not enough available space for ingoing large ions within the cavities in the exchangers, their exchange becomes increasingly difficult in the course of the ion exchange reaction [Abe and Furuki, 1987]. 1.5. Concepts of Ion Exchange The term ion exchange is most commonly applied to interactions including ion exchange materials. Ion exchangers are insoluble materials carrying reversibly fixed ions. These ions can be stoichiometrically exchanged for other ions of the same sign. Ion exchangers are conventionally called cation exchangers if the negatively charged functional groups and carry exchangeable cations. Anion exchangers carry anions due to the positive charge of their fixed groups. The framework of a cation exchanger may be regarded as a macromolecular or crystalline polyanion and that of an anion exchanger as a polycation. If both types of groups are present in the same exchanger, it is called amphoteric ion exchanger. A typical cation exchange and typical anion exchange were presented in Eq. 4 and 5 respectively.

2RNa+ CaCl2 R 2 Ca + 2 NaCl (4)

2RCl+ NaSO2 4 R 2 SO 4 + 2 NaCl (5) The cation exchange process is used in water softening. A solution containing dissolved calcium chloride (hard water) is treated with acation exchanger containing sodium ions. The ion exchanger removes Ca2+ ions from the solution and replaces them with Na+. Of course, hard water contains a mixture of Ca2+ and Mg2+ ions and two parallel processes identical for both the ions take place. Ion exchange resembles sorption because in both the cases a solid takes up a dissolved species. The characteristic difference between these two phenomena is in stoichiometric nature of ion exchange. Every ion removed from the solution is replaced by an equivalent amount of

- 17 - INTRODUCTION M. Khalil another ion of the same sign. In sorption, on the other hand, a solute is usually taken up non-stoichiometrically without being replaced. The competition of two or more ions for functional sites, and thus precisely stoichiometric character of the process, is illustrated in Fig. 1 [Harjula and Lehto 1995; Lehto and Harjula 1996]. 1.5.1. Kinetics of ion exchange 1.5.1.1. Mechanism of ion exchange Ion exchange, like any heterogeneous process, is accomplished by transfer of ions to and from the inter-phase boundary, i.e. the chemical reaction itself, diffusion inside the material, and diffusion in the surrounding solution should be taken into account. Besides the two major phases, the thin film of solution at surface of the exchanger should be accounted separately. The film properties differ from properties of the surrounding bulk solution. Formation of this film is unavoidable. Even a rigorous agitation (an intensive stirring in batch processes or turbulent hydrodynamic flow in flow in column systems) – while being able to reduce the thickness of the inter-phase film – can never take it off completely. Figure 2 shows the simplest illustration of the mass transfer at ion exchange. Ions B diffuse from the solution through the film into the beads and ions A diffuse out of the beads crossing the film into the solution. This inter-phase diffusion of counterions is what is called ion exchange [Helfferich, 1962]. To complete the overall picture of the ion exchange mechanism. Thus, the mechanism of ion exchange can be presented by Fig. 3. The following steps can be listed: • The first step is diffusion of the first ion from bulk of the solution towards the interphase film (process 2 in Fig. 3). This step can be easily manipulated because the diffusion transport in the bulk solution can be assisted with agitation. If a column process is considered, turbulence of the local flows between the exchanger beads can assist the mass transfer

- 18 - INTRODUCTION M. Khalil

Figure 1 Equivalent character of ion exchange, (a) RNa+ K+ = RK + Na + ; 2+ + +2 + (b)2 RNa+ Ca = RCa2 + 2 Na ; (cRCa) 2 +2 Na = 2 RNa + Ca

- 19 - INTRODUCTION M. Khalil

Figure 2 Mass transfer at ion exchange process (stirred batch reactor). The material is initially loaded with counterions A. Solution (grey) initially contains counterions B and co-ions Y. During the process, ions B are transferred inside the exchanger replacing ions A. When transferred between two phases, the ions pass through the Nernst film of the liquid (dark grey) that cannot be removed with agitation.

- 20 - INTRODUCTION M. Khalil

Figure 3 General mechanism of the ion exchange process. (1) dissociation of the dissolved complexes containing first ion; (2) diffusion of the first ion from solution towards the inter-phase film; (3) diffusion of the first ion through the inter-phase film; (4) diffusion of the first ion inside the material phase; (5) association between the first ion and functional group; (6) dissociation of the associates between the second ion and functional group; (7) diffusion of the second ion inside the material phase towards the surface; (8) diffusion of the second ion through the interphase film; (9) diffusion and random distribution of the second ion in the solution; (10) formation of the second ion complexes in the solution.

- 21 - INTRODUCTION M. Khalil

• After the transfer of the ion through the boundary between the film and the solid, the ion diffuses inside the phase of material (process 4). This towards and from the inter-phase boundary. process is defined solely by properties of the material and of the ion. The only driving force is the concentration gradient. In order to fulfil the electroneutrality principle, the above mentioned steps are compensated by the following: • Second counterion diffuses from bulk of the ion exchange material towards the surface (process 7). • After transfer of the second ion, through the boundary, it diffuses through the film towards the bulk solution (process 8). • Finally, the second ion diffuses from the film into bulk of the solution (process 9). There are also few steps which could accomplish the process: • Dissociation of dissolved complexes which incorporate first ion (process 1). • Association between first ion and functional group (process 5). • Dissociation of associates between second ion and functional group (process 6) • Association of second ion in the solution phase (process 10). • The next step is diffusion of the ion through the Nernst film (process 3). No convection can be established here. The mass transfer is defined solely by mobility of the ion. Agitation of the external solution can somehow reduce the thickness of the film but cannot remove it completely. 1.5.1.2. Rate-determining step The mechanism of ion exchange processes defines possible rate- determining steps. Let us continue to consider Fig. 3 and identify the crucial stages. • Mass transfer (diffusion) in the solution or in other external medium

- 22 - INTRODUCTION M. Khalil

(processes 2 and 9 in Fig. 3) is an unavoidable step in any ion exchange interaction. The process is well-known and described by conventional equations of diffusion. It can be easily assisted by hydrodynamic turbulences (for example, by stirring) and thus, is not considered as a possible limiting step for ion exchange. • Mass transfer (diffusion) through the film surrounding the ion exchanger is represented by processes 3 and 8 in Fig. 3. The film is a solution zone of certain thickness with no convection. The mass transfer in the film is defined solely by the diffusion coefficients. The film thickness can be reduced by an agitation of the solution but the zero- thickness is not achievable. • Mass transfer (diffusion) in the exchanger phase (processes 4 and 7) depends on the physico-chemical properties of the system and cannot be enhanced without altering the chemical system itself, i.e. without affecting selectivity and other important characteristics. • Reactions between counterions and fixed groups (ion-pair association/dissociation), presented by processes 5 and 6, are the only chemical interactions that can affect the overall rate of the ion exchange. • Complexes dissociation and formation in solution (processes 1 and 10 in Fig. 3) is no considered as a part of the ion exchange. Nevertheless, the complex formation can be the bottleneck for the overall process. In this case, the description uses well-known mathematical approaches developed for solution chemistry and thus can be left out of this discussion. Two main rate-determining steps are considered in most of the cases: diffusion of ions inside the material or diffusion of ions through the liquid film. Despite the fact that both these cases are diffusion-controlled, the difference is tremendous. In both cases, migration of ions is defined solely by properties of the system. Rate of these steps cannot be enhanced or slowed down with external actions without altering the system itself.

- 23 - INTRODUCTION M. Khalil

Diffusion inside the material is referred to as particle diffusion and diffusion through the Nernst film is referred to as film diffusion. In simple cases, the rate of ion exchange is determined by the slower of these two processes [Helfferich, 1962]. Dominance of one of these mechanisms can be predicted using the following approximate criterion [Helfferich, 1956].

(6)

(7) where Q is the concentration of fixed groups; C is the solution concentration (normality); D is the interdiffusion coefficient in the ion exchanger; D is the interdiffusion coefficient in the film; r0 is the bead B radius; is the film thickness; α A is the separation factor. The following particle diffusion equation can be applied for single exchanger of a pair of ions as follows; 6 ∞ 1 F ( t ) = 1 − − n 2 Bt 2 2 e (8) π n = 1 n

Where; F (t) is the fractional attainment of equilibrium 2 2 B = Di /r

Di is the internal diffusion coefficient, n is an integer number and r is the particle radius. In the case of particle diffusion control, other steps presented in Fig.3 are much faster. Thus, the concentration gradients exist only inside the exchanger beads. The momentary exchange flux is approximately proportional to the concentration of fixed charges and to the interdiffusion coefficient in the beads and is inversely proportional to the bead radius. The flux is independent of the film thickness, solution concentration, and diffusion coefficients in the film [Helfferich, 1962]. - 24 - INTRODUCTION M. Khalil

In the case of film diffusion control, the concentration gradients exist only in the film. The momentary exchange flux is proportional to the solution concentration and to the interdiffusion coefficient in the film, inversely proportional to the film thickness, and independent of the concentration of functional groups, interdiffusion coefficient in the bead, and the bead radius Helfferich, 1962]. So, All factors which tend to increase the rate of interdiffusion in the beads and to reduce the rate in the film, favour the film diffusion control and vice versa. Thus, the film diffusion control may prevail in systems characterized by the following properties [Helfferich, 1962] are high concentration of exchange sites in the material; low degree of cross- linking; small particle size; dilute solution; inefficient agitation. 1.5.2. Equilibrium isotherm A common way to represent the equilibrium in adsorption and ion- exchange systems is the equilibrium isotherm. The equilibrium isotherm represents the distribution of the adsorbed material between the adsorbed phase and the solution phase at equilibrium. This isotherm is characteristic for a specific system at a particular temperature. The basic difference between adsorption and ion exchange is that while there is only one isotherm at a specified temperature for adsorption, more than one isotherm can exist at a specified temperature for different concentrations of the solution in the exchange of ions of different valences due to the concentration–valence effect [Helfferich, 1962]. Thus, a specific ion-exchange system presents one equilibrium curve (isotherm) only under constant temperature and normality. This is why, while the term “isotherms” is used for the equilibrium curves in the case of adsorption, the term “isotherm–isonormal” should be used for ion exchange. The most important isotherm types are Freundlich isotherm in which adsorbents that follow the Freundlich isotherm equation are assumed to have a heterogeneous surface consisting of sites with

- 25 - INTRODUCTION M. Khalil different adsorption potentials, and each type of site is assumed to adsorb molecules and Langmuir isotherm in which adsorbents that exhibit the Langmuir isotherm behavior are supposed to contain fixed individual sites, each of which equally adsorbs only one molecule, forming thus a monolayer. 1.5.2.1. Freundlich isotherm The Freundlich equilibrium isotherm equation [Freundlich, 1906] was used to describe experimental adsorption data. This isotherm is used for the description of multilayer adsorption with interaction between adsorbed molecules. The model predicts that the cesium concentrations on the material will increase as long as there is an increase of the cesium concentration in the solution (this is not restricted to the monolayer in the adsorbent). The model applies to adsorption onto heterogeneous surfaces with a uniform energy distribution and reversible adsorption. The Freundlich isotherm is the earliest known relationship describing the adsorption equation. The application of the Freundlich equation suggests that adsorption energy exponentially decreases on completion of the adsorptional centres of an adsorbent. In the Freundlich model, it is considered that the binding sites affinities on the biomass surface vary with the interactions between the adsorbed molecules. Consequently, the sites with stronger affinity are occupied first [Davis et al., 2003]. 1.5.2.2. Langmuir isotherm The Langmuir model was originally developed to describe gas solid adsorption and was later derived thermodynamically [Everett, 1964], kinetically [Ruthven, 1984] and stoichiometrically [Ruthven, 1984]. All those derivations are based on a few common assumptions, namely, all binding sites are equivalent, distinguishable and independent; each binding site combines with only one solute molecule; and a molecule adsorbed onto one binding site does not influence the adsorption of another molecule on a neighboring binding site. It is essentially one of

- 26 - INTRODUCTION M. Khalil the ‘flat surface’ models and assumes a monolayer deposition of adsorbate on localized sites with negligible interaction between adsorbed molecules. However, despite its origin, the Langmuir model has been applied successfully to describe equilibrium data from porous adsorption and ion exchange systems [Perry and Green, 1997]. Visual inspection of the data also shows that the curves become linear in the regions of very high and very low equilibrium concentrations. Unlike other classical models, such as Fruendlich, the Langmuir equation becomes linear in these concentration regions which also make it an intuitive choice for these data. Finally, the Langmuir model is a convenient choice because it gives the asymptotic maximum solid phase capacity (qo) which can be compared to theoretical capacity as a measure of sorbent efficiency. The Langmuir adsorption isotherm [Langmuir, 1916] is most widely used for the adsorption of a pollutant from a liquid solution given the following hypotheses: • monolayer adsorption (the adsorbed layer is one molecule thick); • adsorption takes place at specific homogeneous sites within the adsorbent; • once a cesium occupies a site, no further adsorption can take place at that site; • adsorptional energy is constant and does not depend on the degree of occupation of an adsorbent’s active centres; • the strength of the intermolecular attractive forces is believed to fall off rapidly with distance; • the adsorbent has a finite capacity for the cesium (at equilibrium, a saturation point is reached where no further adsorption can occur); • all sites are identical and energetically equivalent; • the adsorbent is structurally homogeneous; • there is no interaction between molecules adsorbed on neighboring sites.

- 27 - INTRODUCTION M. Khalil

1.5.3. Thermodynamic of ion exchange Thermodynamic is the only thermodynamically precise characteristic of the ion exchange equilibrium. The value is usually calculated with some theoretical assumptions due to the lack of experimental methods to measure activity inside the ion exchanger phase. Gibbs energy of ion exchange is usually calculated with classic Relationship ∆GRTKo = − ln (9) Entropy of the ion exchange reaction is commonly calculated from the Gibbs energy and enthalpy values:

∆HGo − ∆ o ∆S o = − (10) T

Note that H0 and S0 are integral values, i.e. they correspond to complete transfer of the ion exchanger from one ionic form to another. This makes them non-sensitive to internal structure of the ion exchanger but limits practical value of the information incorporated in these functions [Soldatov et al., 1972].

1.5.4. Distribution coefficient (Kd)

The value of distribution coefficient (kd) was calculated using the following formula :

(IF− )V K = (mL g-1) (11) d F m where I is the initial concentration of metal ion in the aqueous phase (mgL-1), F is the final concentration of metal ion in the aqueous phase (mgL-1), V is the volume of the initial solution in ml and m is the dry mass of the ion exchanger in g. When the simple ion exchange proceeds by the following reaction

+n + n + + (12) nH+ M M + nH - 28 - INTRODUCTION M. Khalil in sufficiently diluted solution, where activity coefficient may be neglected, the selectivity coefficient can be defined by the following equation;

[M n+ ] [H + ]n M K H = ————— (13) [H + ]n [M n+ ] from the above equation kd is given by the relation;

concentration of the cation in exchanger

Kd = ————————————————— concentration of the cation in solution

(14) n + M K = d n + M n (15) H + M (16) KKd= H + n H

n logK= log KM H+ − n log H + (17) d H

n+ + n n+ + M + n when [M ] <<[H ] and [M ] << [H ] , K H [H ] , is considered constant, thus equation (31) can be reduced to: + logKd = C − n log H (18)

Plotting log Kd as a function of log pH generates a straight line with a slope equal the valences of the exchanging ions [Helfferich, 1995; Lehto and Harjula, 1995; Harjula, 2000]. The capacity of an ion exchanger (Q, meq. g-1) is a term which describes the quantity of uptake of exchangeable category ions under specific conditions. The theoretical capacity is often higher than the apparent capacity, which strongly depends on solution concentration and pH. In addition, the framework of the exchanger may create circumstances in which the access of larger ions and hydrated cations is prevented, and therefore the experimentally - 29 - INTRODUCTION M. Khalil obtained maximum uptake may not represent theoretical capacity. An exchanger with a high charge density is more likely to be able to strip the hydration shell of an ion, thus enabling the entrance of the bare ion, than a material of low framework charge. This is a phenomenon well demonstrated in zeolites. 1.5.5. Column processes Column exchange resembles carrying out a large number of successive batch operations in series [Lehto and Harjula, 1995]. The column technique has many advantages in comparison to the batch operations and thus are widely used in practical applications. Most of the ion exchange operations are carried out in columns. A simplest column is a cylinder loaded with beads of an ion exchange material. The whole bulk of the exchanger inside the column including inter-bead voids is called the bed of ion exchanger or simply the bed. One or two sides of the cylinder are supplied with sieve or grid-like manifolds that allow a free pass for solutions but keep the material from washing out. The beads do not move in course of the exploitation, while the flow of solution could be both laminar and turbulent. Such reactors are called packed bed or fixed bed columns. The most conventional direction to pump solutions is up–down. Composition of the solution passing through the bed is changed due to the ion exchange reaction. The changes are not the same during the column process and depend on: • properties of the ion exchanger, • composition of the feed solution, • operating conditions, • shape and dimensions of the column. Plots represent concentration at the outlet of the column. They are called break-through curves. This reflects an ability of the column to accumulate targeted ions. Breakthrough capacity is another important

- 30 - INTRODUCTION M. Khalil concept. The breakthrough capacity of the ion exchange column is the amount of ions that can be removed from the solution by the column prior to the breakthrough. Breakthrough capacity is not a property of the ion exchange material but a characteristic of the column performance under particular conditions. The breakthrough capacity is always less than the total ion exchange capacity of the column. 1.6. Applications of Ion Exchangers Probably, the first extensive investments in the development of ion exchangers and ion exchange processes were done bearing in mind the potential application for isotope separation in nuclear industry. However, the highest amount of commercial ion exchange materials is sold today for use in water-treatment technologies. The main consumers of water are semiconductors manufacturing, electronics, and nuclear industry. The main benefits of ion exchange technologies lie in a possibility of removing highly diluted contaminants and in the insensitivity of ion exchange techniques to variations in flow and concentration. These advantages are also decisive in many other separation applications as in Table 1. The wide application of ion exchange resins in pharmaceutics and in food industry is determined by another advantage of these materials. While being chemically active, they are highly stable in both physical and chemical senses and, as a result, do not contaminate the product. An extensive use of ion exchangers and, most often, chelating materials in hydrometallurgy is determined by the possibility of creating highly selective separation systems for a number of ions. Extraction of uranium or noble metals can be mentioned as most common examples. The list of some conventional and prospective applications is presented in Table 1. The listed references are not comprehensive by any means but could help to find good examples and more details about particular processes.

- 31 - INTRODUCTION M. Khalil

Table 1 Few applications of ion exchange materials including both well- developed and experimental techniques.

• Water preparation for different • Isotope separation: purposes: Eu3+ isotopes [Botros, 1990], preparation of pure and ultrapure deionised water [Lee, 2000], lithium isotopes [Araki, 1998],

water softening [ Perlov, 1990], boron isotopes [Tsukamoto, 1991],

potable water preparation [ Mavrov, 1997]. nitrogen isotopes [Kruglov, 1996],

• Removal of specific constitutes: isotope analysis [Hilton, 1997].

dealkalisation [Kaya, 2002], • Pulp and paper industry:

removal of inorganic salts from liquors [Thompson, fluoride removal [Popat , 1994], ,2000],

removal of organic matter detoxification of by-products transferred for bio- [Reichenberg, 1953], cultivation [Horvath, 2004]. particularly colourants [Heijman , • Purification of sugars and 1999] , polyhydric alcohols:

oxygen removal [Sinha, 2000], purification of cane, corn, and beet sugars [Schick, ,1995], iron [Korngold, 1994] and manganese [

Vaaramaa, 2003] removal, purification of fructose [Shuey, 1990], Cd2+ removal from drinking separation of monosaccharides [Viard, 1992], water [Zhao, 2002], purification of glycerine [Miesiac, 2003], nitrate removal [Lin, 1996], treatment of sorbitol [Caruel, 1992], ammonia removal [Turan, 2003], recovery of xylitol [Gurgel, 1995]. removal of radionuclides from drinking water [Vaaramaa, 2000], • Food industry [Grandison, 1996]: removing off tasters and odours [Dale, removal of other harmful ions from drinking 2000], water [Nakanishi, 1996]. recovery of glutamic-acid [Das, 1995], • Nuclear industry:

separation of uranium isotopes[Harjula, purification of steviosides [Fuh, 1990],

2001], deacidification of fruit juice [Vera, 2003]. • Dairy: separation of cesium [ El-Naggar, 1995] extraction of lactoperoxidase and lactoferrin waste decontamination [Shuey, 1990], [Dionysius, 1991],

final storage of radioactive wastes purification of casein [Cayot, 1992]. [Fernandez, 1983], • Winery: adsorption of wine proteins in the production of condensate polishing [Little, 1996]. wines [Malinovskii, 1992],

stabilisation of wine [Palacios, 2001].

- 32 - INTRODUCTION M. Khalil

Decontamination and recuperation of Solvent purification. waste streams: Reagent purification. recycling of industrial water [Kentish, Preparation of inorganic salts [Vulikh, 1973]. 2001], Catalysis: removal of heavy metal ions [Leinonen, petroleum refining with ,2001], zeolites [Sherman, 1999],

recuperation of metals [Fries, 1993], ethylbenzene synthesis [Tabata, 1995],

ammonia removal [Lahav, 2000], olefin isomerisation [Tabata, 1995],

recovery of calcium aconitate [Hanine, catalytic reduction of nitrogen oxides [Takeda, 1992] , 1996]. • Pharmaceutics and medicine: removal of heavy metals [El-Naggar, 1998] antibiotics [Belter, 1984], removal of radioactive substances [Gula, vitamins [Gu, 1992], 1995].

Recovery and purification of biological and active ingredients [Bellamy, 1996], biochemical substances: taste masking [Bellamy, 1996], amino acids [Shuey, 1990], tablet disintegration [Bellamy, 1996], proteins [Palacios, 2001], controlled and sustained drug release [Kim,

enzymes [Silva, 2000], 1992 ],

DNA [Gunther, 1995], immobilisation of drugs in a carrier function [Sundell, 2001]. antibodies [Dunn, 1991]. • Soil science and technology: Biotechnology: artificial soils [Berkovich, 2003],

separation of lactic acid from fermentative remediation of contaminated soils [Karim, 2001], broth [Wang, 1994],

evaluation of soil properties [Qian, 2002]. production of L-glutamine [Kusumoto, 2001],

production of citric acid [Wang, 2000][, • Buffering.

organic acids [Shuey, 1990]. • Analysis: chromatography, Recovery and purification in hydrometallurgy:

sample preparation: separation, concentrating, uranium [Wang, 2000], purification,

thorium [Eccles, 1984], replacement of analyte.

rare earths [DeVilliers, 1997], • Drying of different media:

tungsten [Martins, 1984], Desiccation of solvents with zeolites [Tsitsishvili, 1999], transition metals [Melling, 1984], Gas drying with polymeric exchangers gold, silver, platinum, palladium [Malinovskii, 1992] and zeolites [Sherman, 1999]. [Warshawsky, 1984].

- 33 - INTRODUCTION M. Khalil

1.7. Ion Exchangers Showing High Selectivity for Cesium A large number of ion-exchange and solvent-extraction systems have been investigated to achieve selective sorption/concentration of cesium from aqueous solutions. 1.7.1. Organic ion exchangers with high selectivity for cesium Separation of alkali metals can be achieved by chromatography on cation-exchange resins [Korkisch, 1969]. The sorption studies for different alkali metal ions on strongly acid cation-exchange resins containing sul-phonic acid groups, e.g., Dowex-50 indicated selectivity for cesium [Sauer and Scheibe, 1962] and other alkali metals in the order Li

- 34 - INTRODUCTION M. Khalil molybdenum and tungsten, such as ammonium 12-molybdophosphate commonly known as AMP and ammonium 12-tungstophosphate commonly known as ATP, and complex cyanides, such as insoluble hexacyanoferrate(II) and hexacyanoferrate(III) salts of transition metals. 1.7.2.1. Heteropolyacid salts Although a large number of insoluble salts of dodecaheteropolyacids are studied for the purpose of selective concentration of cesium from aqueous solutions, ammonium dodecamolybdophosphate (AMP) is the most extensively investigated ion exchanger. Ion-exchange properties of

AMP [(NH4)3MO12O40-H2O] for cesium were discovered by Smit et al., 1959. Since then this exchanger has been widely used for the determination of cesium in environmental samples. The distribution coefficient (Kd) value for cesium on AMP is almost 100 times higher than on Dowex-50 in ammonium form [Smit and Van, 1958]..These results also showed a very large value of separation factor for Cs+/Na+ ion pair at 6000 or greater on AMP. The separation factor for Cs+/Na+ ion pair was only 2.4 on Dowex-50. The large separation factor on AMP suggests that this exchanger can be used for selective concentration of Cs+ ions in the presence of a very large excess of sodium. Due to the small separation factor between Cs+/Na+ ion pair, Dowex-50 ion exchanger could not be used for the preconcentration of cesium in the presence of a large concentration of sodium ions. The salts of various other dodecaheteropolyacids also showed similar sorption properties as AMP. The ones which are most frequently used for the isolation of cesium and other heavy alkali metals, such as rubidium and francium, from acid solutions are the salts of dodecatungstophosphoric acid [Krtil, 1962; Caron and Sugihara, 1962] and dodecatungstosilicic acid [Juznic et al., 1965]. Thallium(I) dodecatungstophosphate was also found to be specifically selective for cesium [Caron and Sugihara, 1962].

- 35 - INTRODUCTION M. Khalil

1.7.2.2. Insoluble hexacyanoferrate(II) salts of transition metals Insoluble salts of transition metals with hexa-cyanoferrate(II) can incorporate alkali metal ions into their crystal lattices. The alkali metals on hexacyanoferrate(II) ion exchangers are generally adsorbed with increasing strength in the order Li< Na

under static conditions. In other studies, freshly prepared Cu2Fe(CN)6 was used for sorption of Cs-134 and Cs-137 [Hoigye, 1991]. The affinities of insoluble ferrocyanides of Fe(III), Cu(II), Zn(II), Ni(II), and Co(II) for alkali metal ions was studied by Dolezal and Kourim (1969). They found that the total amount of the alkali metal ions

- 36 - INTRODUCTION M. Khalil incorporated in the precipitates increased from sodium to cesium. In another paper, Kourim et al. (1964) reported the properties of various transition metal ferrocyanides as ion exchangers for cesium. These authors concluded that zinc(II) and copper(II) compounds were the most promising materials for column operation among the ferrocyanides of zinc(II), copper(II), nickel(II), cobalt(II), iron(III), lead(II), cadmium(II), bismuth(III) and silver(I). The product 'ferrocyanide molybdate' (FeMo) also possessed attractive ion-exchange properties [Baetsle et al., 1966] in regard to selective separation and recovery of cesium from highly radioactive solutions. Equilibration of the exchanger with aqueous solutions containing mono-, bi- and tri-valent cations showed that cesium was preferred to all other cations studied. The preparation and properties of sodium-copper cyanoferrate(II) (NaCuFC) for the removal of cesium from nitric acid solution was reported [Shahbandeh and Streat, 1982]. The properties of this adsorbent depended greatly on the concentration and volume ratio of the reagents used in its preparation. The sorption of cesium from different aqueous solutions was conducted in a series of experiments. In pure water NaCuFC was found to be an effective scavenger for cesium and the distribution coefficient of cesium increased with increasing pH up to 10.5. In the presence of competing ions, such as sodium or magnesium, the distribution coefficients of cesium on NaCuFC were greatly reduced. Optimal sorption under these conditions occurred at a pH of about 2. 1.7.2.3. Insoluble hexacyanoferrate(III) salts of transition metals Sorption behavior of about 50 ions in nitric acid medium on zinc(II) hexacyanoferrate(III) (ZFiC) was studied by Valentini et al. (1973) by batch equilibration. ZFiC was formed by the oxidation of zinc(II) hexacyanoferrate(II) (ZFiC) in nitric acid solutions of molarity greater than 0.1 M. ZFiC, prepared in granular form, was found suitable for

- 37 - INTRODUCTION M. Khalil column separation of cesium from other cations. Jain et al. (1980) reported the preparation and exchange properties of chromium(III) hexacyanofer-rate(III) gel (CFiC). This exchanger showed specific selectivity for monovalent cations. Among the monovalent cations, high selectivity was obtained for Ag+, Cs+, Tl+ and Rb+. Copper(II) hexacyanoferrate(III), which can be converted into granular form suitable for column operation, was also prepared [Jain et al., 1982]. This exchanger showed very high selectivity for cesium over mono-, di-, tri- and tetra-valent metal ions. Separation of cesium from a number of other metal ions was achieved on the column of this exchanger. A comparison of sorption studies of cesium on hexacyanoferrate(III) salts of Cr(III) [Jain et al., 1980], Cu(II) [Jain et al., 1982], Co(II) Jain et al., (1983) and Zr(IV) [Jain et al., 1985], indicated high selectivity for cesium only on chromium and copper compounds [Singh et al., 1990]. These studies [Singh et al., 1990] which were aimed at using the copper (II) hexacyanoferrate(III) ion exchanger for the selective recovery of cesium ions from nuclear waste showed 95% recovery from simulated waste. 1.7.2.4. Zeolites Wingefors et al. (1984) reported the performance and use of mordenite for the sorption of cesium and other fission products from an acidic radioactive waste solution. A complete removal of cesium was achieved by the use of mordenite columns, as no cesium could be detected in the effluent. Very little adsorption of other fission products was observed. In spite of the acidic nature of the feed solution, no signs of degradation of the zeolite structure were noticed. Mordenite columns could thus be used to isolate cesium from acidic radioactive solutions. The selective sorption of cesium and strontium from high-activity-level water was also studied on various other zeolites [Mimura et al., 1988]. The rate of adsorption of cesium and strontium increased with the

- 38 - INTRODUCTION M. Khalil decrease in zeolite particle size. An uptake of close to 100% was observed for cesium and strontium after shaking for 5 and 10 h, respectively. 1.7.2.5. Hydrous oxides Layered vanadium pentoxide gels, analogous to montmorillonite- layered silicate, could be synthesized under hydrothermal conditions at 200°C [Shrivastava et al., 1991]. This ion exchanger exhibited high selectivity for cesium ions in the presence of highly concentrated solutions containing Li +, Na+, K+, Mg2+ and Ca2+. Cesium selectivity of this exchanger could be useful in the separation of Cs-137 from radioactive waste solutions or naturally occurring brines such as seawater. 1.7.2.6. Acid salts of metals Acid salts of zirconium showed high selectivity for heavy alkali metals in acid solutions. Zirconium phosphate [Alberti et al., 1962], zirconium molybdate [Lavrukhina et al., 1963], and zirconium tungstate [Kraus et al., 1956], were used for the isolation of cesium-137 and to separate cesium from rubidium. These separations can be performed on columns or on filter papers impregnated with these materials [Alberti et al., 1962]. Similar ion-exchange properties are also shown by hydrated titanium dioxide in ammonium form [Lavrukhina et al., 1963], stannic phosphate [Inoue and Bull, 1963], and clay minerals [Sawhney, 1965]. Betteridge and Stradling (1967) reported a glassy chromium polyphosphate ion exchanger which showed specific selectivity for monovalent cations. The order of selectivity amongst monovalent ions was Cs>Rb>K>Na>H. The uptake of potassium, rubidium and cesium ions at pH 2 and 3 was not affected by manyfold molar excess of Ni(II), Co(II), Mn(II), Cd(II), Zn(II), Ca(II), Sr(II), Mg(II), Fe(III), Cr(IH) ions. This ion exchanger exhibited no affinity for multivalent ions. Another paper by the same authors reported [Betteridge and Stradling, 1969]

- 39 - INTRODUCTION M. Khalil batch and column ion-exchange reactions of alkali metals with chromium tripolyphosphate exchanger. The exchanger was found suitable for column chromatography due to its good mechanical and chemical stability. 1.8. Recent Developments The organic ion exchangers are well known for their uniformity, chemical stability and control of their ion exchange properties through synthetic method [Devi et al., 2010]. Inorganic ion exchange materials, besides other advantages, are more stable at high temperatures and in radiation fields than the organic [Ali et al., 2008; El-Naggar et al., 1999; Alberti et al., 2001; Zakaria et al., 2002; Varshney et al., 2007]. In order to obtain a combination of these advantages and to increase interlayer distance of layered inorganic ion exchangers many organic- inorganic exchangers have been developed earlier by the incorporation of organic monomers in the inorganic matrix [Alberti et al., 2005; Shpeizer et al., 2010; Ferragina et al., 2010]. Efforts have been made to improve the chemical, thermal and mechanical stabilities of ion exchangers and to make them highly selective for certain metal ions. Mardan et al. (1999) prepared silica potassium cobalt hexacyanoferrate composite ion exchanger which has excellent exchange properties of cesium. polyaniline Sn(IV) tungstoarsenate [Khan et al., 2003] was found to be highly selective for Cd(II). Polypyrrole thorium(IV) phosphate cation-exchanger was found to be highly selective for pb(II) ion [Khan et al., 2005]. Khan and Inamuddin (2006) prepared Polyaniline Sn(IV) phosphate that was found to be highly selective for Pb(II). Siddiqui et al. (2007) synthesized a hybrid type of ion exchanger poly(methyl methacrylate) Zr(1V) phosphate that has high selectivity to Pb(II). Nabi et al. (2009) prepared acrylonitrile stannic(IV) tungstate that has high selectivity to Pb(II). Cobalt ferrocyanide impregnated organic anion

- 40 - INTRODUCTION M. Khalil exchanger was found to be highly selective for cesium [Valsala et al., 2009]. Alam et al. (2010) prepared Polyaniline Ce(IV) molybdate that has high selectivity to Cd(II). Inamuddin and Ismail prepared poly-o- methoxyaniline Zr(1V) molybdate that has high selectivity to Cd(II) [Inamuddin and Ismail, 2010]. In recent years, progress has also been made in the development of methods which can be used for direct determination of very small concentrations of cesium (radioactive and /or non-radioactive). The determination of non-radioactive or total concentration of cesium in most environmental waters, typically reported to be lower than parts per billion (ppb), also require pre-concentration. Polyaniline based composite inorganic–organic absorbers represent a group of inorganic ion exchangers modified by using Polyaniline binder to produce larger size particles. In the view of stability and treatment for final disposal, the composite absorbers represent a separate group of absorbers similar both to the organic and inorganic ion exchange resin [Mimura et al., 1997]. Their main feature is that the organic binding polymer (Polyaniline) is inert and all the radionuclides are bound to inorganic active component (inorganic ion exchanger). As a result, contrary to organic ion exchange resins even in the case of decomposition of organic binding matrix (radiation, chemical, thermal or biological decomposition) no radionuclides are released. Preparation of composite absorbers with organic binding matrices involves dispersing an exchanger in a solution of a matrix/matrix–monomer/matrix- component, followed by coagulation/ polymerization/polycondensation of the dispersion and separation of a product. Several authors published papers on the use of Polyaniline as a binding polymer for granulating polyvalent metals. Khan et al. (2003) prepared A new and novel electrically conducting ‘polymeric_/inorganic’ composite cation-exchange material; polyaniline

- 41 - INTRODUCTION M. Khalil

Sn(IV) tungstoarsenate by incorporating polyaniline into inorganic ion- exchanger material. It possessed improved ionexchange capacity, high chemical and thermal stabilities, reproducibility and It is highly selective for cadmium (a major toxic element), which makes it important for the environmentalists. Kinetic study of exchange for some divalent metal ions of alkaline earths and transition metals are favoring a particle diffusion-controlled. The conductivity values lie in the semiconductor region, i.e. in the range of 10-3 S cm-1 that follows the Arrhenius equation. The energy of activation of electrical conduction for the composite was also calculated. Khan and Inamuddin (2006) synthesized Polyaniline Sn(IV) phosphate, an ‘organic–inorganic’ composite material, via sol–gel mixing of an electrically conducting organic polymer polyaniline into the matrices of inorganic precipitate of Sn(IV) phosphate. This material was used as a cation-exchanger. On the basis of distribution studies, the material was found to be highly selective for Pb(II). Its selectivity was examined by achieving some important binary separations like Pb(II)– Mg(II), Pb(II)–Sr(II), Pb(II)–Zn(II), and Pb(II)–Fe(III) on its column and has enhanced ion-exchange capacity, high chemical, mechanical, and thermal stabilities. This material possessed DC electrical conductivity in the semi-conducting range, i.e. 10-5–10-3 S cm-1. The stability in terms of DC electrical conductivity retention was also studied in an oxidative environment by two slightly different techniques viz. isothermal and cyclic techniques. The DC electrical conductivity of composite material was found stable upto 110 °C under ambient conditions. Alam et al. (2010) supported organic–inorganic composite and strongly acidic cation-exchanger polyaniline Ce(IV) molybdate was chemically synthesized and demonstrated to be an excellent ion-exchange material due to its high selectivity for Cd(II), thermal stability and fast elution of an exchangeable H+ ion. The material was characterized for its

- 42 - INTRODUCTION M. Khalil ion exchange properties to study its cation-exchange behavior. Cd(II) selectivity depends upon the distribution coefficient in several solvent systems. The selectivity of this material varied depending upon its composition and the composition of the eluting solvent. Its selectivity was examined and some important binary separations such as Cd(II)– Pb(II), Cd(II)–Hg(II), Cd(II)–Zn(II) and Cd(II)–Ni(II) were also achieved. The physico-chemical properties of the material were also studied using C, H, N elemental analysis. In the following parts of this contribution, composite absorbers, titanotungstate with Polyaniline binding matrix is prepared and its properties and technological application are evaluated. Column studies for removal cesium from acid and alkaline solutions. Furthermore, it is found high selectivity for cesium from other metal ions from radioactive waste, aqueous solution and applied for removal cesium from milk.

- 43 -

MATERIALS AND METHODS M. Khalil 2. MATERIALS AND METHODS

2.1. Chemicals and Reagents All chemicals and reagents used in this work were of analytical grade purity and used without further purification. Cesium chloride, titanium tetrachloride, TiCl4. H2O, potassium persulphate (K2S2O8) were obtained from Prolabo (England). Sodium tungstate Na2WO2.2H2O, aniline

(C6H5NH2), nitric acid and hydrochloric acid were purchased from Adwic (Egypt). In all experiments, bidistilled water was used for preparation and dilution of solutions. 2.2. Radioactive Materials The radioactive tracer used in the present work 134Cs isotope was locally prepared. In this respect, highly pure spectroscopic material of cesium nitrate used for preparation of 134Cs, which the target warped separately in aluminum foil and packed in aluminum container followed by irradiation for 48 hours in the Egyptian 2MW Research Reactor at Inshas, using neutron flux of 1.3x1013n.cm-2.s-1. After irradiation the target was left for suitable period to cool for the decay of short lived radionuclides of aluminum and its radioactive products. The -activity of 134Cs was measured using a scintillation detector head (NaI) connected to scalar of the type SR-7 obtained by Nuclear Enterprises [USA]. In most cases the counting was at least 10 times greater than of the background. Each result recorded in this thesis is tabulated or graphed is a mean value of three reading obtained under the same geometrical conditions, calculated after correction for background. In all experiments done, measurements of the -activity of the solid took place after washing with acetone to remove fine adherent active solution. Generally, in all experimental the net counting rate has a standard deviation less than ±5%. 2.3. Preparation of the Reagent Solutions

A solution (1M) of titanium chloride, TiCl4. H2O, was prepared in

- 44 - MATERIALS AND METHODS M. Khalil

4 M HCl, while 1 M sodium tungstate, Na2WO2.2H2O solution was prepared in demineralized water (DMW). Solutions of 10% (v/v) aniline

(C6H5NH2) and 0.1M potassium persulphate (K2S2O8) were prepared in 1 M HCl. 2.4. Synthesis of Polyaniline Polyaniline gel was prepared by mixing equal volume of 10% aniline

(C6H5NH2) and 0.1M potassium persulphate with continuous stirring by a magnetic stirrer. Green colored polyaniline gel was obtained by keeping the solution below 10 oC for half an hour. 2.5. Synthesis of Titanotungstate (TiW) A precipitate of titanium tungstate was prepared by adding 1 M titanium chloride solution to an aqueous solution of 1M sodium tungstate in equal volume ratio at 65 ±1 oC [El-Naggar et al., 2012]. The white precipitate was obtained when the pH of the mixture was adjusted to 6.5 by adding aqueous ammonia with constant stirring. The supernatant liquid was decanted and the gel was rewashed with bidistilled water in order to remove fine adherent particles then filtered by using a centrifugation (about 104 rpm). The excess acid was removed by washing with DMW and the material was dried in an air oven at 50 ±1 oC. The dried product was immersed in DMW to obtain small granules. The material was converted to H -form by treating with 0.01 M HNO3 for 24 h with occasional shaking intermittently replacing the supernatant liquid with fresh acid. The excess acid was removed after several washings with DMW and then dried at 50 ±1 oC. Several particles size of material was obtained by sieving and kept in desiccators. 2.6. Synthesis of Polyaniline Titanotungstate (PATiW) The fresh gel of polyaniline was added to the fresh white precipitate of TiW that previously obtained and mixed thoroughly with constant stirring. The resultant green color gel was kept for 24 h at room temperature (25 ±1 oC) for digestion. The supernatant liquid was

- 45 - MATERIALS AND METHODS M. Khalil decanted and the gel was rewashed with bidistilled water in order to remove fine adherent particles and was filtered by using a centrifugation (about 104 rpm). The hybrid material was dried in an air oven at 50 oC. The dried product was immersed in DMW to obtain small granules. It was converted to H -form by treating with 0.01 M HNO3 for 24 h with occasional shaking intermittently replacing the supernatant liquid with fresh acid. The excess acid was removed after several washings with DMW and then dried at 50 oC. Several particles sizes of material were obtained by sieving and kept in desiccators [El-Naggar et al., 2012]. 2.7. Instruments and Characterization of Materials The IR spectra of the materials were measured by IR spectrometer using KBr disc technique. The spectra were scanned over the wave length range 400-4000 cm-1 using BOMEM FTIR model MB 147, Canada. Measurements of powder X-ray diffraction patterns were carried out using Shimadzu X-ray diffractometer, XD- DI Shimadzu, Japan, with a nickel filter and Cu- K radiation tube. Samples were very lightly ground and mounted on a flat sample plate at room temperature. Microphotographs of the prepared materials were obtained by the scanning electron microscope (SEM) at various magnifications, JSM- 6510LA, Jeol, Japan. Measurements of differential thermal analysis (DTA) and thermogravimetric analysis (TGA) were carried out using a Shimadzu DT-60 thermal analyzer, Shimadzu, Japan. The sample heated from ambient temperature up to 1000°C at heating rate of 20°C /min. The Cs+ concentration was measured using atomic absorption spectrophotometer, AA6701F, Shimadzu, Japan, a scintillation detector head (NaI) and the other ions that used are measured using an inductively coupled plasma spectrometer (ICPs), Shimadzu, Japan. All samples and chemicals used in this work were weighted using an analytical balance of Bosch type having maximum sensitivity of 105g and accuracy ±0.001/y.

- 46 - MATERIALS AND METHODS M. Khalil

For the equilibrium experiments, a good mixing for the two phases of solid and solution were achieved using thermostatic shaker water bath of the type Julabo SW-20C, West Germany. All the pH values of different solutions were measured using an Orion digital pH meter research model 610A with microprocessor and have accuracy of ±0.02 units. The pH meter scale was calibrated using two standard buffer solutions within the pH range of the measured solution before each experiment. The deviation in the readings was in the range of ±0.01 at the laboratory temperature 25 ±1 °C. 2.8. Elemental Composition To determine the elemental composition of PATiW, the material was analyzed for Ti and W by X-ray fluorescence. Carbon, hydrogen and nitrogen contents of the material were determined by elemental analysis. 2.9. Chemical Stability The chemical stability also plays an important role in the elucidation of properties of the ion-exchangers. Portions of 50 mg of TiW and PATiW in the H+ form were treated with 50 ml of varying concentration of acids

(HCl, HNO3), NaOH and also with DMW for 3 weeks with occasional shaking. 2.10. pH Titration Topp and Pepper (1949) method was employed for pH titration studies of PATiW in solutions of alkali metal chlorides and their hydroxides. 200 mg was placed in a column that was fitted with glass wool at its bottom. A glass bottle containing 20 mL of 0.001 M HCl was placed below the column, and for determination of pH, a glass electrode was placed in the solution, then 75 mL of 0.1 M of NaOH was poured into the column. Titration was carried out, by passing the NaOH solution at a drop rate of about 1mL/min. The pH of the solution was recorded until equilibrium was attained. 2.11. Ion-Exchange Capacity (IEC)

- 47 - MATERIALS AND METHODS M. Khalil

The IEC of PATiW was determined by the repeated batch technique, by equilibrating 50 mg solid with 5ml of 0.1M cesium chloride solution on a shaker thermostat adjusted at 25 ± 1 oC and to attain equilibrium, then decontamination of solution was took place and saturation process was repeated until no further sorption. The solution was analyzed using atomic absorption in order to determine the amount of Cs+ sorbed. The percent sorption (P) was calculated from the expression:

CC− P= 0 t x 100 (19) C 0 where C0 is the initial concentration and Ct is the concentration at time t of metal ion in solution. The sorption capacity was calculated using the following equation:

% uptake V capacity= xC x xZ meq g-1 (20) 100 0 m

where, C0 is the initial concentration of solution, Z is the charge of adsorbed metal ion, V is the solution volume (ml), and m is the weight of the exchanger (g). 2.12. Distribution Studies The distribution behavior of metal ions plays an important role in the determination of the material's selectivity. In certain practical applications, equilibrium is most conveniently expressed in terms of the distribution coefficients of the counter ions. The distribution coefficients + 2+ 2+ 2+ 2+ 3+ 4+ (Kd) for different metal ions (Cs , Co ,Zn , Cd , Cu , Cr , Zr , As5+, V5+, Mo6+) were determined by batch method as a function of pH. + The Kd values of Cs were determined by shaking 40 mg of each of TiW + and PATiW samples in H form with 20 mL of HNO3 solutions -4 -1 containing 10 mol L cesium ion solutions as chloride, where Kd values of the other metal ions were determined by shaking 50 mg of PATiW in

- 48 - MATERIALS AND METHODS M. Khalil

+ -5 -1 H form with 5mL of HNO3 solutions containing 10 mol L metal ions as chlorides, this low concentration was applied in order to rise the percent sorption of these ions. After 24 h with continuous shaking for 6 h in a shaker adjusted at 25 ±1oC to attain equilibrium, the solutions were then filtered and the ions concentrations were determined using AAS for cesium ion and ICPs for the other ions. The Kd values were calculated by the following equation;

(IF− )V K = mL g-1 (21) d F m where I is the initial concentration of metal ion in the aqueous phase (mgL-1), F is the final concentration of metal ion in the aqueous phase (mgL-1), V is the volume of the initial solution in ml and m is the dry mass of the ion exchanger in g. 2.13. Separation Factor For the preferential uptake of the metal ions, the separation factor is

A determined by the separation of two metal ions. Separation factor α B can be calculated as:

KA( ) α A = d (22) B KB() d where Kd (A) and Kd (B) are the distribution coefficients for the two competing species A and B in the ion-exchange system. 2.14. Kinetic Studies Kinetic measurements were performed, using a batch technique, by equilibrating 0.05 g of each of TiW and PATiW with V/m = 50 ml g-1 at three different concentrations of 660, 1300 and 6600 mg L-1 of Cs+. The experiments were also conducted at different reaction temperatures (25, 45 and 60 ±1 oC), different particle diameters (0.156, 0.318 and 0.46 mm) and different drying temperatures (50, 200 and 400 oC) using an initial

- 49 - MATERIALS AND METHODS M. Khalil ion concentration of 1300 mg L-1. For these investigations 0.05 g of TiW and PATiW was contacted with 2.5 ml of certain concentration of Cs+ (V/m = 50 ml g-1) as a function of the time and the solution was kept stirred in a thermostatic shaker adjusted at the desired temperature. After interval time, the shaker is stopped and the solution is separated at once from the solid. The solution was analyzed using atomic absorption in order to determine the amount of Cs+ sorbed. The amount of metal ion -1 sorbed onto TiW and PATiW at any time, qt (mg g ) was calculated from the expression:

V -1 qt=() c0 − c t mg g (23) m and q F() t = t (24) q e where C0 is the initial concentration and Ct is the concentration at time t (mg L-1) of metal ions in solution, V the volume (L), m is the weight (g) of the adsorbent, F is fractional attainment of equilibrium and qe is the amount of metal ion sorbed when equilibrium is attained (mg g−1). The F (t) equation developed by Boyd et al. (1947) and improved by Reichemberg (1953) was valid as:

6 ∞ 1 − n 2 Bt F ( t ) = 1 − 2 2 e (25) π n = 1 n and

2 2 B = π Di / r (26) where n is an integer number, Di is the effective diffusion coefficient of the exchanging ions inside the exchanger particles, r is the particle radius.

2.15. Sorption Isotherms Sorption isotherm is done by the gradual increase of the concentration - 50 - MATERIALS AND METHODS M. Khalil of the sorbate ion in solution and measuring the amount sorbed at each equilibrium concentration. The degree of sorption should therefore be a function of the concentration of the sorbate only. A series of experiments were carried out by contacting a fixed amount of the wet adsorbent 0.05 g with 2.5 mL of Cs+ solution at the desired initial CsCl concentration. Sorption isotherms for Cs+ were determined over the concentration ranges 13– 13290 mg L-1 at a neutral pH and constant V/m ratio of 50 ml/g. The experiments were carried out in shaker thermostat at 25, 45 and 6o ±1 °C and agitated for a sufficiently time (~24 h) required to reach equilibrium. Cesium ion concentration changes were recorded with Atomic Absorption Spectrometer. The amount of cesium ion sorbed onto the particles at equilibrium (qe, in mg/g of the dried particles) was calculated by a mass-balance relationship:

V -1 q=() c − c mg g (27) e0 e m

where C0 and Ce are the initial and equilibrium concentrations of cesium in aqueous solution and V is the solution volume (ml), and m is the weight of the exchanger (g). Two important isotherm models were selected in this study, which are namely the Freundlich and Langmuir isotherm models. Freundlich and Langmuir isotherm models were applied to establish the relationship between the amount of cesium adsorbed onto TiW and PATiW and its equilibrium concentration in aqueous solution. The adsorption data obtained were then fitted to the Freundlich adsorption isotherm (which the earliest relationship is known describing the adsorption equilibrium) and Langmuir adsorption isotherm (which is applied to equilibrium adsorption assuming monolayer adsorption onto a surface with a finite number of identical sites). 2.16. Column Operations

- 51 - MATERIALS AND METHODS M. Khalil

A glass column of 1 cm diameter was used in this study. The column was packed with 1 g of the composite sorbent and treated with distilled water and then all column studies were performed. The breakthrough + curves (C/C0 vs. volume) were obtained for Cs sorption onto PATiW at different bed depths (3.0 and 4.0 cm) for a constant linear flow rate of 2.5 mL min-1 and at 140 mg L-1 of neutral cesium concentration. Also the breakthrough curves were carried out from acidic simulant

(0.5 M HNO3+0.1 M NaNO3) and alkaline simulant (0.5 M NaOH + 0.1

M NaNO3) solutions. The concentration of cesium in the feed solution was fixed at 13 mg g-1 labeled with radioactive 134Cs that prepared by cesium nitrate. The feed solution was conducted on the composite sorbent packed in a column and the effluent was collected at the flow rate of 0.7 ml min-1. The break-through percentage was calculated as

C Breakthrough = (28) C 0

where C and C0 are the concentrations of cesium in the effluent and feed solution respectively. The sorption capacity (q) of the PATiW was calculated by

V xC q= 50 0 mg g−1 (29) W

where V50 is the effluent volume corresponding to 50% break-through, C0 is the concentration of cesium in the feed solution (mg g-1) and W is the mass of composite absorber (g). 2.17. Recovery of Cesium from Milk Milk with 3% fat solution was prepared with 10-2 M of cesium solution, and was labeled with 134Cs active. Kinetic studies are carried by adding 5 ml of milk solution to 50 mg of PATiW exchanger and shaking in thermostatic shaker water bath at 25 ±1 oC. The shaker was stopped at

- 52 - MATERIALS AND METHODS M. Khalil intervals and 1ml of milk solution was withdrawn for counting using a scintillation detector head (NaI). The Cs -ray activity in the tested milk was larger than background by at least three times.

- 53 -

RESULTS AND DISCUSSION M. Khalil

3. RESULTS AND DISCUSSION Cesium is one of these pollutants that its separation from aqueous solution is mostly needed. The amount control of cesium isotopes, particularly 137Cs, in liquid wastes has become an issue of great concern because of their destructive effects on the environment. They are potentially dangerous to human health and also to the environment, because the high solubility of cesium can cause its migration through groundwater to the biosphere [Cortes-Martinez, et al., 2010]. Composite adsorbents/ion exchangers have been widely studied for treatment of liquid wastes. The composite ion exchangers present improved qualities with respect to those of pure inorganic exchangers, such as; better selectivity for the capture of some ions, increased mechanical and chemical resistance, more regular form of the grains, smaller solubility in water than the respective inorganic compound, and better kinetics of exchange relatively to the pure inorganic exchangers. The composite ion exchangers are generally obtained by implantation of inorganic into the wide range of organic materials during the polymerization process [Kaygun and Akyil, 2007]. In composite ion exchangers, inorganic materials are active components and organic materials are simply inert binders. Titanotungstate as one of heteropolyacid materials is very useful for the removal of Cs+ from water streams. As noted above, titanotungstate supported on polyaniline (PA) as a matrix material is used to separate cesium from liquid wastes. Polyaniline has been proposed as a universal binding polymer for practically any inorganic ion exchanger. The use of PA as based organic binding polymer has a number of advantages provided by the relatively easy modification of its physico-chemical properties (hydrophilicity, porosity, mechanical strength).

Polyaniline gel was prepared by oxidative coupling using K2S2O8 in an acidic aqueous medium at less than 10 oC as given in Scheme 1

- 54 - RESULTS AND DISCUSSION M. Khalil

[Stejskal and Gilbert, 2002]:

2− 4 NH3 + 5SO2 8

Aniline H2O, 0 - 2 oC, 1h

NH NH +2 − 2 + 12HSO+ 10 4

Polyaniline Scheme 1 The effect of temperature on the reaction seems to be very pronounced. Aniline underwent oxidative coupling only below 10 °C very effectively, leading to a good quantity of polyaniline with fairly good yield. The binding of polyaniline into titanotungstate is indicated in Scheme 2:

TiW + NH NH

Polyaniline

NH NH nH O ()()TiO2 WO 3 2

PATiW Scheme 2 A precipitate of titanium tungstate was prepared by adding 1 M titanium chloride solution to an aqueous solution of 1M sodium tungstate

(Na2WO2.2H2O) in equal volume ratio at 65 ±1 °C. The polyaniline gel was added to the white inorganic precipitate of titaotungstate and mixed

- 55 - RESULTS AND DISCUSSION M. Khalil thoroughly with constant stirring [El-Naggar et al., 2012]. The supernatant liquid was decanted and the gel was rewashed with bidistilled water and filtered using a centrifugation. The material was dried in an air oven at 50 ±1 °C. The dried product was immersed in DMW to obtain different particles sizes. It was converted to H -form by treating with 0.01

M HNO3 for 24 h then dried again at 50 ±1 °C. Several particles size of materials were obtained by sieving and kept in desiccators. The formation of inorganic precipitate TiW was significantly affected by the pH of the mixture, and the most favorable pH of the mixture was 6.5. The preparation of the inorganic precipitate at pH lower or higher than 6.5 lead to decrease in yield and in ion-exchange capacity of the material. 3.1. Characterization of Materials 3.1.1. IR spectra Figs. (4-6) show the FTIR spectra of polyaniline, TiW and PATiW, respectivly. In the polyaniline spectrum (Fig.4) the peak; at 1476 cm-1 due to the NH bending vibration appeared. The CN stretching vibration in the region 1299 cm-1, the N-H rocking at 796 cm-1, CC stretching band at 1117 cm-1 and CC at 1562 cm-1 also reported [Alam et al., 2010]. Fig. 5 shows the IR spectrum of TiW in H+-form. This Fig. shows three beaks at 3168 cm-1, 1615 cm-1 and 1400 cm-1 corresponding to presence of external water molecules, –OH groups and metal oxygen of Ti and W–OH bonds respectively. It is evident from the FTIR studies of the ‘organic–inorganic’ composite cation-exchanger PATiW in H+ - form (Fig. 6) that the material shows the presence of external water molecules in addition to –OH groups and the metal oxygen bond. In the spectrum of the material, a strong and broad band around 3134 cm-1 is found which can be ascribed to –OH stretching frequency. A sharp peak around 1600 cm-1 can be attributed to H–O–H bending band, represents the free water molecules [Rao, 1993]. The band appearing at 1400 cm-1 - 56 - RESULTS AND DISCUSSION M. Khalil

Figure 4 FTIR spectrum of a prepared polyaniline.

- 57 - RESULTS AND DISCUSSION M. Khalil

Figure 5 FTIR spectrum of a prepared TiW.

- 58 - RESULTS AND DISCUSSION M. Khalil

Figure 6 FTIR spectrum of a prepared PATiW composite material.

- 59 - RESULTS AND DISCUSSION M. Khalil may correspond to the Ti and W–OH bonds [Rawat et al., 1990; Nabi and Shalla, 2009]. Also in the PATiW spectrum (Fig. 6) it can be detected that peaks at 1493 and 1118 cm-1 corresponding to NH and CC stretching respectively. These characteristic bands of PATiW (Fig. 6) indicating the binding of inorganic precipitate with organic polymer and formation of ‘inorganic –organic’ composite PATiW. This indicates that the PATiW contains considerable amount of aniline. In this study, the IR spectra of PATiW were also stydied at different drying temperatures. Fig. 7 shows the FTIR spectra of PATiW perheated at 50, 200, 400, 600, 700 and 850 °C. The Fig. shows that the characteristic bands of vibrational water which appear at ≈ 3287 cm-1 and ≈ 1615 cm-1 were disappeared with increasing the temperature from 50 to 600 °C and this may be assigned to loss of water molecules with increasing the temperature [El-Naggar et al., 1992]. The characteristic peaks of the organic polyaniline are disappeared by increasing the drying temperature above 400 oC indicating the decomposition the organic part from the compound. 3.1.2. X-ray diffraction patterns X-ray powdered diffraction patterns of PATiW at different drying temperatures (50, 200, 400, 600, 700 and 850 °C) are given in Fig. 8. It was found that the PATiW is amorphous at 50 °C. The crystallinity of PATiW slightly improved with the increase of heating temperature from 50 °C to 850 °C, which may be indicate to the oxide formation 3.1.3. Scanning electron microscopy (SEM) studies A scanning electron microscopy (SEM) study was performed to examine the difference in surface morphology between the parent materials and composite. SEM photographs of the polyaniline, TiW at 50 and 850 °C and PATiW at 50 and 850 °C (Figs. 9 - 13), indicate the binding of inorganic material with organic polymer, i.e. polyaniline. The SEM pictures showed that the surface morphology of composite material

- 60 - RESULTS AND DISCUSSION M. Khalil

Figure 7 FTIR spectra of PATiW composite at different drying temperatures.

- 61 - RESULTS AND DISCUSSION M. Khalil

3 ntensity (KCPS) ntensity I 2

0 0 10 20 30 40 50 2T angle deg. Figure 8 XRD patterns of PATiW at different drying temperatures.

- 62 - RESULTS AND DISCUSSION M. Khalil

Figure 9 Scanning electron microphotograph (SEM) of chemically prepared polyaniline at the magnification of 900×.

- 63 - RESULTS AND DISCUSSION M. Khalil

Figure 10 Scanning electron microphotograph (SEM) of chemically prepared TiW dried at 50 oC at the magnification of 3000×.

- 64 - RESULTS AND DISCUSSION M. Khalil

Figure 11 Scanning electron microphotograph (SEM) of chemically prepared TiW dried at 850 oC at the magnification of 3000×.

- 65 - RESULTS AND DISCUSSION M. Khalil

Figure 12 Scanning electron microphotograph (SEM) of chemically o prepared PATiW dried at 50 C at the magnification of 2000×.

- 66 - RESULTS AND DISCUSSION M. Khalil

Figure 13 Scanning electron microphotograph (SEM) of chemically o prepared PATiW dried at 850 C at the magnification of 3000×.

- 67 - RESULTS AND DISCUSSION M. Khalil is totally different from their individual inorganic and organic components. The morphology of the composite material is essentially different due to the binding of polyaniline with titanotungstate. It has been revealed that PATiW after binding shows a plate like morphology. Figures 11 and 13 show the SEM for TiW and PATiW at 850 oC. These Figs. were approximately similar. This indicates that TiW and PATiW were converted by drying at 850 oC to oxides. This result was agreement with the results of IR and X-ray analysis. 3.1.4. Thermal analysis The DTA–TGA analysis curve (Fig. 14) of the PATiW shows a continuous loss of mass (about 10%) up to 130 °C, which may be due to the removal of the surface water absorbed [Ali et al., 2010]. A further mass loss between 230 and 730 °C may be due to the decomposition of the organic part of the material. Above 730 °C, a smooth horizontal section is seen, which may be represents the formation of the oxide form of the material. This result was confirmed from the XRD data given in Fig. 8. The total loss of weight was 17% up to 1000 °C indicating the material is stable [Ali et al., 2008]. 3.1.5. Elemental composition of PATiW The weight percent composition of the material was found to be Ti, 15.15%; W, 44.6%; C, 19.25%; H, 2.3%; N, 3.7%; and O, 15.0%. The corresponding molar ratio of Ti, W, C, H, N, and O in the material was estimated as 1.34: 1.0: 6.19: 9.1: 1.015: 3.6, which can suggest the following formula:

[(TiO2) (WO3) (-C6H4NH-)]. nH2O.

Assuming that only the external water molecules are lost at 130 oC, the 10% weight loss of mass represented by TGA curve must be due to the loss of nH2O from the above structure. the value of (n) can be calculated using Alberti’s equation [Alberti et al., 1966]:

- 68 - RESULTS AND DISCUSSION M. Khalil

502.85C 130.80C

958.93 C

Figure 14 TGA-DTA thermogram of PATiW.

- 69 - RESULTS AND DISCUSSION M. Khalil 18n= X( M + 18 n ) /100 (30) where X is the percent weight loss ( 10%) of the exchanger by heating up to 130 °C and (M +18n) is the molecular weight of the material. The calculations indicated that ~2.46 per molecule of the cation-exchanger. Based on the literature data [El-Naggar et al., 1995; Ali, 2004] the structural water molecules may play an important rule as exchange sites 3.1.6. Chemical stability The solubility experiments showed that the PATiW and TiW have good chemical stability (Table 2). As the results indicated that the materials were resistant to 4 M HNO3 and 4 M HCl. The solubility in the

HNO3 was higher than in the HCl and very feeble dissolution was observed in the alkaline medium. It was observed that the solubility of composite is slightly increased than the inorganic material, due to the presence of polyaniline which can dissolute into the solution. Despite this increased in solubility of PATiW than TiW, it showed high mechanical and granular properties [Khan and Alam, 2003]. 3.1.7. pH Titration The pH-titration curve of the PATiW shows only one inflexion point indicating that the PATiW behaves as monofunctional. The pH-titration curve (Fig. 15) showed slow increase when NaOH was added 0.30–1.00 mmol and rapid increase when NaOH added 1.00 – 1.95 mmol. This composite exchanger may be a strong acid cation-exchanger because the pH-titration curve usually showed a step edge at 1.95 mmolg-1. This means that the H+ ions on the hybrid cation-exchanger were depleted and replaced with Na+ ions at that point and the number of H+ sites were equivalent to the same amount of NaOH, i.e. the strong acidic groups Na+ form. Thus, theoretical ion-exchange capacity of this hybrid cation- exchanger may be considered as 1.95 mmolg-1. After that point, in the region when more NaOH added, the equilibrium pH further increases but (H+) of the composite cation-exchanger are completely converted to the

- 70 - RESULTS AND DISCUSSION M. Khalil

Table 2 Chemical stability of TiW and PATiW in various solvent systems.

Solvent Amount dissolved (mg/l)

Concentration, HNO3 HCl NaOH H2O M TiW PATiW TiW PATiW TiW PATiW TiW PATiW not not 0.1 12.0 20.0 4.0 6.0 0.2 6.0 detected detected 1.0 30.0 38.0 24.0 34.0 6.0 10.0 - - 2.0 40.0 46.0 30.0 38.0 - - - - 3.0 62.0 96.0 40.0 44.0 - - - - 4.0 86.0 114.0 56.0 82.0 - - - -

- 71 - RESULTS AND DISCUSSION M. Khalil

8 pH 7

3 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

millimoles of 0.1 M NaOH

Figure 15 The pH-titration curve of PATiW with 0.1M NaOH.

- 72 - RESULTS AND DISCUSSION M. Khalil more slowly. This slow increase of pH-titration curve after 1.95 mmolg-1 implies due to surface precipitation other than conventional ion exchange or surface adsorption. 3.1.8. Ion-Exchange Capacity (IEC) PATiW exhibited high granulometric, mechanical and regeneration properties that show a good reproducible behavior. These were evident from the fact that these materials obtained from various batches did not show any appreciable deviation in their ion-exchange capacities. The ability of PATiW composite for exchange of cesium is significantly affected by the elemental ratio of each of titanium and tungstate. The preparation of PATiW with concenration 1M of each of titanium tetrachloride and sodium tungstate gives the percent sorption 99%, 2.6%, 2.6% for Cs+, Co2+ and Eu3+, respectively at 10-4M. Where the preparation of PATiW with concentration 0.1M of each of titanium tetrachloride and sodium tungstate gives the percent sorption 78%, 7%, 17% for Cs+, Co2+ and Eu3+ respectively, as in Table 3. Figure 16 shows the ion exchange capacity of PATiW for Cs+ as a function of pH value. It was found that the capacity increase by increasing the pH value. This may be attributed to the decreasing [H]þ in solution with increasing pH which facilitate the release of H+ from the exchanger to solution. So the %uptake values were increased and thus the capacity was increased. Titanium tungstate was found to be high stable, but have poor capacity for metal ions [Qureshi et al., 1974]. In this work, an attempt to obtain materials with improved ion exchange properties and have high efficiency for the treatment of nuclear waste. So, PATiW has been synthesized to represent this advanced class of inorganic ion-exchanger, which owned high selective and separation performance for cesium ions of nuclear waste. It was fined that the Cs+ ion-exchange capacity of the composite material PATiW is 1.82 meq g-1 which higher as compared to

- 73 - RESULTS AND DISCUSSION M. Khalil

Table 3 Factors affecting on preparation of PATiW and the percent of sorption of Cs+, Co2+ and Eu3+ ions at 10-4 M and at V/m 100.

Mixing volume ratio Mixing Percent of (v/v) volume Sorption ratio Appearance Sample (v/v) of after drying TiCl Na Wo Cs+ Co2+ Eu3+ 4 2 2 10 % aniline PATiW 1(1 M) 1(1 M) 1 Black shiny 99 2.6 2.6 granules

PATiW-1 1(0.1 M) 1(0.1 M) 2 Black shiny 78 7 17 granules

- 74 - RESULTS AND DISCUSSION M. Khalil

3.0

2.5

-1

2.0

1.5

1.0

Ion exchangeapacityIon g meq

0.5

2 3 4 5 6 7 8 9

pH Figure 16 Plots of capacity versus pH for exchangeof Cs+ on PATiW o at 0.1M, V/m 100 and 25 ±1 C.

- 75 - RESULTS AND DISCUSSION M. Khalil other inorganic ion-exchanger [Möller et al., 2002], magneso-silicate (0.57 meq g-1) and magnesium aluminosilicate (0.77 meq g-1) [El- Naggar et al., 2007]. Also, it is higher than the ion-exchange capacities of Cs+ on lithium zirconium silicate [El-Naggar and Abou-Mesalam, 2005], magnesium and cerium titano-antimonates in aqueous (0.7 meq g−1), in 25% methnol (0.74 meq g−1) and in 25% ethanol (0.8 meq g−1) [Zakaria et al., 2009]. Also it is higher than the saturation capacity of Gd3+ (1.63), Eu3+ (1.41), Ce3+ (1.34) meq g−1 on titanium(IV) antimonite [Zakaria et al., 2002]. The mechanism of the exchange of Cs+ on PATiW can be considered as: + + + R− H + C s R − C s + H (31) Exchanger phase Solution phase Exchanger phase Solution phase This proposed mechanism consider that the TiW part in the PATiW ion pair bonding was precipitated as mixed hydrous oxides of Ti and W. Cesium had been exchanged with H+ of OH- in the hydroxyl of Ti-OH and W-OH, This result supported with IR spectra figures. 3.2. Distribution Studies The distribution coefficient is often a proper quantity to express the distribution of an ion between the exchanger and the solution phase. This is especially true when the exchanging ion is present in the trace concentrations, since the ionic composition does not practically change at + macro levels in trace ion exchange. So the Kd values of Cs were determined by shaking 40 mg of each TiW and PATiW samples with 20 -4 -1 ml of HNO3 solutions containing 10 mol L cesium ion at different pH and different reaction temperatures (25, 45 and 60 ± 1 °C). + Figure 17 shows the plots of log Kd for Cs on TiW and PATiW as a function of pH at 25 ±1 °C. This Fig. shows that the Kd values of cesium ions on PATiW was higher than on the inorganic TiW. + The log Kd for Cs on TiW and PATiW were determined at 25, 45 and

- 76 - RESULTS AND DISCUSSION M. Khalil

60 ± 1 °C as afunction of pH using different concentrations of HNO3 as shown in Figs. 18 and 19. The preliminary studies indicated that the time of equilibrium for the exchange of Cs+ with H+ form of TiW and PATiW were attained within 24 h (sufficient to attain the equilibrium). From the results shown in Figs. 18 and 19, it can be found that the distribution coefficients of Cs+ on TiW and PATiW were increased with increasing pH of solutions, this trend is an obvious phenomenon [Clearfield et al., 1968; El-Naggar et al., 1992; El-Naggar et al., 1994; El-Naggar et al., 1996; Zakaria et al., 2002]. A linear relationship with a slope smaller than the valence of the Cs+ was obtained. Analysis the data shown in Figs. 18 and 19 indicated that the ion exchange reaction deviated from the ideal process. In addition, it was found that the Kd values increased with increasing the temperature. The non-ideality may be due to a different mechanism such as physical adsorption, chemical reaction or other effects, which takes place besides the ion exchange process [Ali et al., 2008]. The effect of drying temperatures of PATiW on the separation of Cs+ was reported. Figure 20 shows plots of log Kd versus pH for exchangeof + o Cs on PATiW at 50, 200 and 400 C. It is found that the Kd values decreased with increasing the drying temperature, this is due to that the active sites is destroyed and the water molecules is removed by increasing the drying temperature. The higher amount of the structural water as well as the hydroxyl groups on the surface of the material seem an important factor to promote the exchange process [Ali, 2003]. From the above results it is found that the PATiW is more sorbed for Cs+ than in the TiW. So the work was directed towards the PATiW as a more efficient exchange material for Cs+. In order to find out the potentiality of the composite cation exchanger in the separation of metal ions, distribution studies for 10 metal ions were performed at different

- 77 - RESULTS AND DISCUSSION M. Khalil

3.50

3.25 d 3.00 log K log

2.75

PATiW TiW

2.50 1 2 3 4 5 6 7 8 9 pH

+ Figure 17 Plots of log Kd versus pH for exchangeof Cs on TiW and PATiW at 10-4M, V/m 50 and 25 ±1 °C.

- 78 - RESULTS AND DISCUSSION M. Khalil

4.00

3.75

3.50 d 3.25 log K log

3.00

25 oC 2.75 45 oC 60 oC

2.50 0 1 2 3 4 5 6 7 8 9 pH

+ Figure 18 Plots of log Kd versus pH for exchangeof Cs on TiW at 10-4 M and V/m 50 at different reaction temperatures.

- 79 - RESULTS AND DISCUSSION M. Khalil

4.00

3.75

3.50 d

3.25 log K log

3.00

25 oC 2.75 45 oC 60 oC

2.50 0 1 2 3 4 5 6 7 8 9 pH + Figure 19 Plots of log Kd versus pH for exchangeof Cs on PATiW at 10-4 M and V/m 50 at different reaction temperatures. .

- 80 - RESULTS AND DISCUSSION M. Khalil

3.6

3.4

3.2

3.0

d 2.8 log K log 2.6

2.4

50 oC o 2.2 200 C 400 oC

2.0 1 2 3 4 5 6 7 8 9 pH + Figure 20 Plots of log Kd versus pH for exchangeof Cs on PATiW at 10-4 M and V/m 50 at different drying temperatures.

- 81 - RESULTS AND DISCUSSION M. Khalil pH and the values obtained for distribution coefficients are given in Table + 2+ 4. The distribution coefficients (Kd) for different metal ions (Cs , Co , Zn2+, Cd2+, Cu2+, Cr3+, Zr4+, As5+, Va5+, Mo6+) on PATiW were determined by batch method as a function of pH (Fig. 21). In this process the Kd values were determined by shaking 50 mg of PATiW with 5mL of -5 -1 HNO3 solutions containing 10 mol L metal ions. The distribution studies showed that the PATiW was found to be the highly selective for cesium where the other metal ions (Co2+, Zn2+, Cd2+, Cu2+, Cr3+, Zr4+, As5+, Va5+, Mo6+) were poorly sorption. The high uptake for Cs+ demonstrates not only the ion-exchange properties but also the adsorption and ion-sieve characteristics of the cation-exchanger. [Shrma and Ruis, 1961; Clearfield and Bleasing, 1972; El-Naggar et al., 1994; Zakaria et al., 2004].

According to the data given in Table 4, it can be indicate that the Kd values vary with the concentration of the HNO3. It is clear that the Kd values increase with increasing the pH values where the [H+] in solution is decreased. With increasing the pH values, it is facilitate a release of H+ from the exchanger to the solution so Kd values increase, this is a characteristic behavior of the cationic ion-exchanger [El-Naggar et al., 1996].

The effect of the size and charge of the exchanging ions on Kd values was also observed on PATiW. The Kd values show a decreasing trend in this order Cs+ >>> Zr4+ > Mo6+ > V5+> As5+ > Cr3+ > Co2+ > Cu2+> Zn2+ > Cd2+ as in Fig. 21. This sequence is in accordance with the unhydrated radii of the exchanging ions. Ions with the smaller unhydrated radii easily enter the pores of the exchanger, which results in higher adsorption. According to [Kossel, 1916; Goldschmidt, 1925; Paulling, 1929] the attraction between cations and anions in ionic crystals obey Coulomb's law on the demands for ions of equal charge, a small ion will be attracted either to a greater force or held more tightly than a larger ion. Therefore,

- 82 - RESULTS AND DISCUSSION M. Khalil

Cs+ 1200 Co2+ Zn2+ Cd2+ 1000 Cu2+ Cr3+ Zr4+ 5+ 800 As V5+ Mo6+

600 K d 400

200

-200 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 pH + 2+ 2+ Figure 21 Plots of Kd versus pH for exchangeof Cs , Co , Zn , Cd2+, Cu2+, Cr3+ , Zr4+, As5+, V5+ and Mo6+ at 25 ±1 oC on PATiW

at 10-4M , V/m 50 of Cs+ and at10-5M , V/m 100 for other ions.

- 83 - RESULTS AND DISCUSSION M. Khalil

+ 2+ 2+ 2+ 2+ 3+ 4+ 5+ 5+ Table 4 Kd values of Cs , Co , Zn , Cd , Cu , Cr , Zr , As , V ,

6+ Cs + + Mo and separation factors ()αB of Cs from other metal ions at different o concentrations of HNO3 on PATiW at 25 ±1 C.

Metal ion Cs+ Co2+ Zn2+ Cd2+ Cu2+ Cr3+ Zr4+ As5+ V5+ Mo6+ HNO3, M 1256.2 199.4 91.9 69.9 163.5 199.4 733 201.2 324.1 572 Water 6.3 13.6 17.9 7.68 6.3 1.7 6.2 3.9 2.2

907.65 119.6 35.7 42.3 105.3 91.5 415 190.5 207 312 10-3M 7.5 25.4 21.5 8.6 9.9 2.2 4.76 4.4 2.9

750.31 139.8 10.5 15.9 11.5 7.1 340.5 184.9 74.8 115.5 10-2M 5.4 71.4 47.2 65.2 105.7 2.2 4.05 10.0 6.5 661.17 11.11 3.9 7.6 3.6 4.2 46.4 157.8 7.6 19.9 10-1M 59.5 169.5 86.9 183.7 157.4 14.2 4.2 86.9 33.2

- 84 - RESULTS AND DISCUSSION M. Khalil the Kd value should increase with decreasing unhydrated radii and increase with electric potential. On the basis of distribution studies, the most promising property of the material was found to be the high selective toward Cs+, which is a major polluting metal in the fission products in radioactive wastes. It can be believed that the spacing of the lattice of PATiW corresponds very closely to the ionic radius of unhydrated Cs+ [Dosch et al., 1992] and, thus, is responsible for its selectivity. Ali, (2009) also found the selectivity order; Cs+ > Eu3+> Co2+ onto phosphoric acid activated silico-antimonate, the unhydrated ionic radius was regarded to play a major role affecting on many of these selectivity behavior. The same behavior sequence is similar on resorcinol–formaldehyde (R–F) and zirconyl-molybdopyrophosphate (ZMPP) [Shady, 2009], where the selectivity order on R–F and ZMPP samples is Cs+ > Co2+ > Eu3+ > Zn2+. Analytical data showed that the nuclides they contained were mainly cesium. The distribution coefficient for Cs+ on PATiW is 14000 at pH + 8.5 and is greater than the values of Kd for Cs on stannic molybdophosphate ion exchanger at the same pH [Marageh et al., 1999] and on zirconium vanadate at the same pH [Lahiri et al., 2005]. The Kd 2+ 2+ 2+ values for Co and Zn on PATiW are lower than the Kd values for Co and Zn2+ on polyaniline Sn(IV) arsenophosphate [Khan et al., 1999] and nylon-6,6, Zr(IV) phosphate [Khan et al., 2007]. On the country, the Kd 2+ 2+ values for Cd on PATiW are lower than the Kd values for Cd on polyaniline Ce(IV) molybdate [Alam et al., 2010]. The Kd values for 2+ 2+ Cu on PATiW are lower than the Kd values for Cu on acrylamide stannic silicomolybdate [Khan et al., 2009]. These results confirm the sepration properties of PATiW for Cs+. It must be notice that although the water molecules play an important role as exchange sites in the obtained materials; the sorption affinity trend of PATiW does not depend on the percentage of water molecules only.

- 85 - RESULTS AND DISCUSSION M. Khalil

Other factors may have an affect, such as channel loading, diffusion of ions, pH, pore size, porosity, surface area and ordinal structuring of these materials [Ali et al., 2008]. It is known that cesium is the major radioactive constituents in low level liquid waste (LLLW) solutions. The sorption of cesium from these solutions would substantially reduce their activity, in some cases to a level enabling normal discharge of the residual solution. Therefore low- level liquid wastes taken from storage tank at nuclear research center here, were treated with PATiW ion-exchanger. 3.2.1. Separation factor Similar to the previous results, the studied systems offer very good selectivity for cesium ion. The separation capability of the material has been demonstrated by achieving some important binary separations such as Cs+ – Co2+, Cs+ – Zn2+, Cs+ – Cd2+, Cs+ – Cu2+, Cs+ – Cr3+, Cs+ – Zr4+, Cs+ – AS5+, Cs+ – V5+, and Cs+ – Mo6+ as in Table 4. Since if the breakthrough was studied where the feed solution is a simulated active waste solution containing different elements of various valence states such as: Cs+, Co2+, Zn2+, Cd2+, Cu2+, Cr3+ , Zr4+, As5+, V5+ , Mo6+. So all these elements could be separated in the first few milliliters of the effluent solution while cesium is retained completely on the column beds.

El-Naggar et al. (2007) discussed the distribution coefficients (Kd) and −3 separation factors () for the mentioned cations in 10 M HNO3 medium. The data indicated the same selectivity sequence where as the distribution coefficients have the affinity sequence Cs+ >Co2+ >Cd2+ >Zn2+ >Cu2+ >Fe3+ on magneso-silicate and Co2+ >Cs+ >Cd2+ >Zn2+ >Cu2+ >Fe3+ on −3 magnesium alumino-silicate in 10 M HNO3. The separation factors on magneso-silicate for Cs+ were 5.03, 1.49, 4.32, 2.59 and 2.39 form Fe3+, Co2+, Cu2+, Zn2+ and Cd2+respectively and on magnesium aluminosilicate ion exchanger the separation factors of Cs+ were 2.65, 0.74, 2.27, 1.35 and 1.05 form Fe3+, Co2+, Cu2+, Zn2+ and Cd2+ respectively. It is

- 86 - RESULTS AND DISCUSSION M. Khalil cleare that the separation of Cs+ on magneso-silicate and magnesium alumino-silicate is very smalls compared to in the PATiW. These values indicated that Cs+ can easily separate from radioactive and industrial waste solutions included the above-mentioned cations. The high uptake of specific metal ion demonstrates not only the ion-exchange properties but also the sorption and ion-sieve characteristics of this cation- exchanger material [Alam et al., 2010]. According to the literature, the selectivity of composite polyaniline with inorganic materials was demonstrated and achieved. Alam et al. (2010) synthesized polyaniline Ce(IV) molybdate that has an excellent ion-exchange character due to its high selectivity for Cd(II). Its selectivity was examined and binary separations such as Cd2+ – Pb2+, Cd2+ – Hg2+, Cd2+ – Zn2+ and Cd2+ – Ni2+ were achieved. Also, Khan and Alam (2003) prepared polyaniline Sn(IV) tungstoarsenate and found that this material has high selectivity towards Cd(II), which is a major polluting metal in the environment. The separation capability of the polyaniline Sn(IV) tungstoarsenate has demonstrated for binary separations such as Cd2+ – Zn2+, Cd2+ – Pb2+, Cd2+ – Hg2+, Cd2+–Mg2+, Cd2+ – Cr3+, Cd2+ – Cu2+ and Mg2+ – Ba2+. Also Khan and Inamuddin (2006) synthesized Polyaniline Sn(IV) phosphate that has high selective for Pb2+. 3.3. Kinetic Studies Kinetic specificity of processes taking place inside the material phase is important to determine the sorption rate. Rates of the interactions are highly dependent on the materials internal structure that is in contrary to kinetics in homogeneous media, in systems including fine powders, and to kinetics of most of the surface processes. Ion exchange rates can be controlled by rates of actual chemical reactions; however, control by diffusion processes is a more common case. Moreover, many ion exchange interactions do not involve any direct chemical reactions and, - 87 - RESULTS AND DISCUSSION M. Khalil hence, the overall process is controlled solely by the diffusion which, is defined by the material structure. Besides the microstructure, macroshape of the material (size of sorbent, layers, etc.) also influences apparent rates of ion exchange. This is because larger pieces could require more time for the process to be completed if the rate is limited by diffusion through bulk of the material. Thus, kinetic approaches are very specific for ion exchange materials. This part considered to study the effect of initial concentrations of Cs+, particle sizes, reaction temperature and dried temperatures on the rate of sorption of Cs+ onto TiW and PATiW and represented the corresponding kinetic model of the sorption process. 3.3.1. Effect of initial concentration and contact time The effect of the initial ion concentration on the Cs+ sorption onto TiW and PATiW was performed at concentrations of 660, 1300 and 6600 mg/L at 25 ±1 °C, the results were shown in Figs. 22 and 23. It is clear that the sorption amount of Cs+ increase with increasing the initial ion concentration, and the amount of Cs+ sorbed by composite is greater than that of Cs+ sorbed by inorganic adsorbent. Also, the amount of Cs+ sorbed sharply increased for each adsorbent with time in the initial stage (0–120 min range), and then gradually increased to reach at equilibrium in approximately 240 min. A further increase in contact time had a negligible effect on the amount of ion sorption. According to these results, the agitation time was fixed at 5 h for the rest of the batch experiments to make sure that the equilibrium was reached. The rate of reaction was found to be independent on the initial concentration as shown in Figs. 24 and 25 for plots of F versus initial concentration. The increase in the uptake capacity of the adsorbent material with increasing the initial ion concentration may be due to higher probability of collision between each investigated ion and the adsorbent particles. The variation in the extent of sorption may also be due to the fact that

- 88 - RESULTS AND DISCUSSION M. Khalil

15 ,mg/g t q

600 mg/L 5 1300 mg/L 6600 mg/L

0 0 50 100 150 200 250 300 time, min Figure 22 Effect of initial ion concentration and contact time on the amount sorbed of Cs+ onto TiW at V/m 50 and 25 ±1 °C.

- 89 - RESULTS AND DISCUSSION M. Khalil

21 ,mg/g t q 14

600 mg/L 1300 mg/L 7 6600 mg/L

0 0 50 100 150 200 250 300 time, min

Figure 23 Effect of initial ion concentration and contact time on the amount sorbed of Cs+ onto PATiW at V/m 50 and 25 ±1 °C.

- 90 - RESULTS AND DISCUSSION M. Khalil

1.0

0.8

0.6

0.4

0.2

600 mg/L 1300 mg/L 6600 mg/L

0.0 0 50 100 150 200 250 time, min Figure 24 Plots of F versus time for sorption of Cs+ onto TiW at different initial ion concentration, V/m 50 and 25 ±1 °C.

- 91 - RESULTS AND DISCUSSION M. Khalil

1.0

0.8

0.6

0.4

0.2 600 mg/L 1300 mg/L 6600 mg/L

0.0 0 50 100 150 200 250 time, min Figure 25 Plots of F versus time for sorption of Cs+ onto PATiW at different initial ion concentration, V/m 50 and 25 ±1 °C.

- 92 - RESULTS AND DISCUSSION M. Khalil initially all sites on the surface of adsorbent were vacant and the metal ion concentration gradient was relatively high. Consequently, the extent of cesium ion uptake decreases significantly with the increase of contact time, depending on the decrease in the number of vacant sites on the surface of adsorbent material. 3.3.2. Effect of particle size Figures 26 and 27 show plots of F and Bt for sorption of Cs+ from aqueous solutions on various adsorbent particle sizes. The adsorbent diameters are the averages of the mesh sizes for the consecutive sieves that allowed the particles to pass through and retained the particles. It is clear from the figures that the metal ion removal rate significantly affected by the particle sizes. The rate and extent of sorption, for a constant mass of the adsorbent, is proportional to the specific surface area, which is higher for small particles indicates the sorption process of Cs into adsorbents controls with particle diffusion mechanism [Guibal et al., 1998]. This results agreement with the sorption of Cs+ onto magnesium and cerium titano-antimonates [Zakaria et al., 2009]. In order to prove that the rate of exchange of Cs+ is depending on particle radius, the values of F and Bt at various time intervals on H+- form of TiW and PATiW are drawn as shown in Figs.26 and 27. From the data presented in these figures it is clear that straight lines passing through the origin are obtained in all studied cases. These figures show that the rate of exchange of Cs+ is increasing with decrease in particle size of TiW and PATiW which is in agreement with the fundamental conditions of particle diffusion mechanism [Zakaria, 2003]. A plot of B vs. 1/r2 for Cs+ on PATiW and TiW was given in Fig. 28. Figure 28 shows that the reciprocal proportionality between the rate of exchange and square of the particle size, which a further proof of particle diffusion controls is the main mechanism. This result agrees with work reported [El-Naggar et al., 1991; El-Naggar and Aly, 1992]. - 93 - RESULTS AND DISCUSSION M. Khalil

1.0 4

0.8 3

0.6 Bt F 2

0.4

1 0.2 0.15 mm 0.32 mm 0.46 mm 0.0 0 0 50 100 150 200 250 time, min Figure 26 Plots of F and Bt versus time for sorption of Cs+ onto TiW at different particular sizes, V/m 50 and 25 ±1 °C.

- 94 - RESULTS AND DISCUSSION M. Khalil

1.0 5

0.8 4

0.6 3

F Bt

0.4 2

0.2 1 0.15 mm 0.32 mm 0.46 mm

0.0 0 0 50 100 150 200 250 time, min

Figure 27 Plots of F and Bt versus time for sorption of Cs+ onto PATiW at different particular sizes, V/m 50 and 25 ±1 °C.

- 95 - RESULTS AND DISCUSSION M. Khalil

2.0

1.8

1.6

1.4 -1 s -4

10 1.2 Bx

1.0

0.8 PATiW TiW

0.6 0 1 2 3 4 5 1/r2 x 103 cm-1 Figure 28 Plots of B versus 1/r2 for sorption of Cs+ onto TiW and PATiW.

- 96 - RESULTS AND DISCUSSION M. Khalil

3.3.3. Effect of contact time and reaction temperature Figures 29 and 30 show plots of F and Bt for sorption of Cs+ ion from aqueous solutions onto TiW and PATiW, at initial metal ion concentration 1300 mg L-1 and at temperature 25, 45 and 60 ±1 °C as a function of contact time. The figures show a high initial rate of removal within the first 120 minutes of contact (over 80% removed) followed by a slower subsequent removal rate that gradually approached an equilibrium conditions in 5 h. The effect of varying reaction temperatures 25, 45 and 60 ±1ºC on the rate of exchange of Cs+ onto TiW and PATiW are investigated and showed that, the rate of exchange reactions of Cs+ were increased with increasing the reaction temperatures from 25 to 60 ±1 ºC where the mobility of the counter ions increased with increasing the reaction temperatures. The thermodynamic parameters for the systems were calculated at different temperatures and summarized in Table 5. In order to gain insight into the thermodynamic nature of the sorption process, several thermodynamic parameters for the present systems were calculated. The Gibbs free energy change, Go, is the fundamental criterion of spontaneity. Reactions occur spontaneously at a given temperature if Go is a negative quantity. The free energy of the sorption reaction is given by the following equation:

o (32) ∆G = − RTLnK c

where Kc is the sorption equilibrium constant, R the gas constant, and T is the absolute temperature (K). The sorption equilibrium constant (Kc) can calculated from:

Fe K = (33) c 1− F e where Fe is the fraction attainment of metal ion sorbed at equilibrium. + The values of the equilibrium constant (Kc) for the sorption of Cs onto

- 97 - RESULTS AND DISCUSSION M. Khalil

3 1.0

0.8

0.6 Bt F

0.4 1

0.2 25 oC 45 oC 60 oC

0.0 0 0 50 100 150 200 250 time, min Figure 29 Plots of F and Bt versus time for sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 98 - RESULTS AND DISCUSSION M. Khalil

5 1.0

0.8 4

0.6 3 F Bt

0.4 2

o 1 0.2 25 C 45 oC 60 oC

0.0 0 0 50 100 150 200 250 time, min Figure 30 Plots of F and Bt versus time for sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 99 - RESULTS AND DISCUSSION M. Khalil composite and inorganic adsorpents were calculated at different temperatures and at equilibrium time of 5 h using Eq. (33). The variation of Kc with temperature, as summarized in Table 5 showed that Kc values increase with increased in sorption temperature, thus implying a strengthening of adsorbate–adsorbent interactions at higher temperature. This also indicates that Cs+ dehydrate considerably at higher temperature before sorption and thus their sizes during sorption are smaller yielding higher Kc values [Ho and McKay, 1999 b]. Also, Gibbs free energy change of adsorption (Go) was calculated as in Table 5 at 25, 45, and 60 ±1 ºC onto TiW and PATiW. The obtained negative values of Go confirm the feasibility of the process and the spontaneous nature of the sorption processes with preference towards Cs+. In addition, the decrease in Go value with increase in reaction temperature confirms that the reaction is favored at high temperature which indicates to an entropy- producing process prevails in the Mn+/H+ exchange system. Such mechanism was proposed earlier for the adsorption of Gd3+, Ce3+ and Eu3+ ions on titanium (IV) antimonate [Zakaria et al., 2002]. The Gibbs free change can be represented as follows:

∆GHTSo = ∆ o − ∆ o (34)

The values of enthalpy change (Ho) and entropy change (So) calculated from the slope and intercept of the plot of Go versus T (Fig. 31) are also given in Table 5. The enthalpy values for TiW and PATiW were 22.08 and 26.26 kJ/mol respectivly. The positive enthalpy values for Cs+ indicate that the exchange process is an endothermic process. This is supported by the observation that the adsorption increased at higher temperature [Zakaria and E1-Naggar, 1998]. While El-Naggar et al. (2009) calculated negative values of Ho for the uptake process on polyacylamide cerium titanate which reflects the exothermic nature. The

- 100 - RESULTS AND DISCUSSION M. Khalil

-3.00

-3.75 PATiW TiW

-4.50

-5.25

-6.00 kJ/mol o

G -6.75

-7.50

-8.25

-9.00

295 300 305 310 315 320 325 330 335 T, K

Figure 31 Relationship between Gibbs free energy change and temperature of sorption of Cs+ onto TiW and PATiW at different reaction temperatures.

- 101 - RESULTS AND DISCUSSION M. Khalil

+ Table 5 Thermodynamic parameters for the sorption of Cs on TiW and PATiW at V/m 50 and at different reaction temperatures.

o o o Kc G (kJ/mol) H (kJ/mol) S (J/mol K) Temperature TiW PATiW TiW PATiW TiW PATiW TiW PATiW 25 °C 4.00 7.84 -3.43 -5.103 45 °C 5.66 13.2 -4.51 -6.73 22.08 26.26 85.38 105.3 60 °C 10.11 24.00 -6.40 -8.79

- 102 - RESULTS AND DISCUSSION M. Khalil

Ho values were -18.23, -29.17 and -26.70 kJ/mol for Cs+, Co2+ and Eu3+ respectively [El-Naggar et al., 1996]. The entropy change (So) depends normally on the extent of hydration of exchangeable and exchanging ions along with any change in water structure around the ions that may occur when they pass through the channel of the exchanger particles. The So values for Cs+/TiW and Cs+/PATiW were found 85.38 and 105.3 J/mol K respectivly. The positive values of entropy change shows increased randomness at the solid/solution interface with some structural changes in the adsorbate and adsorbent. 3.3.4. Effect of drying temperature Plots of F and Bt versus time for sorption of Cs+ (1300 mg L-1) onto both TiW and PATiW dried at 50, 200 and 400 °C are shown in figure 32 and 33. The figures show a high rate of removal of Cs+ onto both TiW and PATiW dried at 50 °C. The sorption rate was decreased with increase the drying temperature from 50 up to 400 oC. Where by increasing drying temperature the active sites in TiW and PATiW are removed and destroyed. The water content in TiW and PATiW were decreased and removed with increasing drying temperature. The los of water content at 200 oC was 8% from the original sample and was 10% at 400 oC. These results were confirmed by IR spectra and XRD which show the materials converted to oxide form. 3.3.5. Sorption kinetics modeling The sorption of metal ions onto natural and synthetic sorbents has been described as a complex process, in which the properties of the sorbate and the solvent often play a critical role. The sorption process occurs within the boundary layer around the sorbent and proceeds in the liquid- filled pores or along the walls of the pores of the sorbent. The latter two processes are called the external and internal mass transfer steps, respectively. The sorption of metal ions onto TiW and PATiW, as in the case of

- 103 - RESULTS AND DISCUSSION M. Khalil

1.0 2.0

0.8 1.5

0.6

1.0 F Bt 0.4

0.5 0.2 50 oC 200 oC 400 oC

0.0 0.0 0 50 100 150 200 250 time, min

Figure 32 Plots of F and Bt versus time for sorption of Cs+ onto TiW dried at 50, 200, 400 oC, at V/m 50 and reaction temperature 25 ±1 oC.

- 104 - RESULTS AND DISCUSSION M. Khalil

1.0 4

0.8

0.6 F Bt

0.4

0.2

50 oC 200 oC 400 oC 0.0 0 0 50 100 150 200 250 time, min Figure 33 Plots of F and Bt versus time for sorption of Cs+ onto PATiW dried at 50, 200, 400 oC at V/m 50 and reaction temperature 25 ±1 oC.

- 105 - RESULTS AND DISCUSSION M. Khalil heterogeneous processes between solids and fluids, could be explained through a number of sequential processes that determine the rate of reaction: (a) the diffusion of the solute through the liquid film surrounding the particle (liquid film diffusion control); (b) the diffusion of the solute through the matrix of the TiW and PATiW (particle- diffusion control); (c) the chemical reaction with the functional groups attached to the matrix. One of these steps usually offers much greater resistance than the others and may thus be considered as the rate-limiting step of the process [Liberti and Passino, 1977]. However, the chemical reaction on the non-functionalized sorbent surfaces could be explained as a chemisorptions process, which is usually assumed too fast to affect the overall sorption rate, unless chemical modifications occur during sorption. Conditions for liquid film diffusion control of the overall sorption rate are well known and are mainly comprised of a low degree of agitation, low solution concentration and small particle size. The study of sorption dynamics describes the solute uptake rate and evidently this rate controls the residence time of adsorbate uptake at the solid/solution interface. In this part of study,the data of the kinetics of Cs+ sorbed from aqueous solutions onto prepared TiW and PATiW at different temperatures were analyzed using pseudo first-order, pseudo second-order, homogeneous particle diffusion model, shell progressive model and intraparticle diffusion model. The homogeneous particle diffusion model (HPDM) and the shell progressive model (SPM) [Helfferich, 1962; Liberti and Passino, 1977] are two kinetic models widely used for fitting sorption and ion exchange data. The aim of this kinetic study was to find the diffusion model that describes the experimental data, to determine the rate controlling steps and to determine the kinetic parameters of the mass transfer of the cesium ions. The conformity between experimental data and each model predicted

- 106 - RESULTS AND DISCUSSION M. Khalil values was expressed by the correlation coefficient (R2). A relatively high R2 values indicates that the model successfully describes the kinetics of metal ion sorption removal. 3.3.5.1. Pseudo first-order model The sorption kinetics of metal ions from liquid phase to solid is considered as a reversible reaction with an equilibrium state being established between two phases. A simple pseudo first order model [Ho and McKay, 1999 a,b] was therefore used to correlate the rate of reaction and expressed as follows:

dqt (35) =k1() qe − q t dt where qe and qt are the concentrations of ions in the adsorbent at equilibrium and at time t, respectively (mg/g) and k1 is the pseudo first- order rate constant (h-1 ).

After integration and applying boundary conditions t=0 to t=t and qt =0 to qt =qt, the integrated form of Eq. (35) becomes:

k log(q− q ) = log q − 1 t (36) e t e 2.303

Plots of Eq. (36) were made for Cs+ sorption at different studied reaction temperatures, and shown in Figs. 34 and 35. Approximately linear fits were observed for the two adsorbents, over the entire range of shaking time explored and at all temperatures, with low correlation coefficients, indicating that the pseudo first-order kinetic model is not valid for the present systems. 3.3.5.2. Pseudo second-order model A pseudo second-order rate model [Ho and McKay, 1999 b, c] is also used to describe the kinetics of the sorption of Cs+ onto adsorbent materials. The differential equation for chemisorption kinetic rate reaction is expressed as:

- 107 - RESULTS AND DISCUSSION M. Khalil

1.2 25 oC 45 oC 60 oC 1.0

0.8 ) t -q e 0.6 log(q

0.4

0.2

0.0 0 30 60 90 120 150 180 time, min Figure 34 Pseudo first-order kinetic plots for the sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 108 - RESULTS AND DISCUSSION M. Khalil

25 oC 1.2 45 oC 60 oC

1.0

0.8 ) t -q e 0.6 log(q

0.4

0.2

0.0 0 30 60 90 120 150 180 time, min Figure 35 Pseudo first-order kinetic plots for the sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 109 - RESULTS AND DISCUSSION M. Khalil dqt 2 (37) =k2 () qe − q t dt where k2 is the rate constant of pseudo second-order equation (L/mg h).

For the boundary conditions t=0 to t=t and qt =0 to qt =qt, the integrated form of Eq. (37) becomes:

1 1 = + k t (38) q− q q 2 e t e Eq.(37) can be rearranged to obtain a linear form equation as: (39) t 1 1 =2 + t qt k2 q e q e

If the initial sorption rate h (mg/L h) is: 2 h= k2 qe (40)

Then Eqs. (39) and (40) becomes: t 1 1 (41) = + t qt h q e The kinetic plots of t/qt versus t for Cs+ sorption at different temperatures are presented in Figs.36 and 37. The relationships are linear, and the values of the correlation coefficient (R2), suggest a strong relationship between the parameters and also explain that the process of sorption of each adsorbent follows pseudo second order kinetic model. In similar the sorption kinetics of Cs+ onto polyacylamide cerium titanate sorbent was found to be followed the pseudo-first-order rate equation [El-Naggar et al., 2009]. From Table 6 it can be shown that the values of the initial sorption rate ‘h’ and rate constant ‘k2’ were increased with increase in temperature. The correlation coefficient R2 has an extremely high value (>0.98), and the theoretical qe values agree with the experimental ones. These results suggest that the pseudo second-order

- 110 - RESULTS AND DISCUSSION M. Khalil

8 t t/q 6

o 4 25 C 45 oC 60 oC 2

0 0 50 100 150 200 250 time,min

Figure 36 Pseudo second-order kinetic plots for the sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 111 - RESULTS AND DISCUSSION M. Khalil

t 4 t/q

2 25 oC 45 oC 60 oC

0 0 50 100 150 200 250 time,min

Figure 37 Pseudo second-order kinetic plots for the sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 112 - RESULTS AND DISCUSSION M. Khalil

Table 6 The calculated parameters of the pseudo second-order kinetic model for Cs + onto TiW and PATiW at V/m 50 and at different reaction temperatures.

qe (mg/g) qe (mg/g) 2 h (mg/L h) K2(L/mg h) R Temperature expermintal calculated

TiW PATiW TiW PATiW TiW PATiW TiW PATiW TiW PATiW

25 °C 19.79 32.08 21.46 34.083 31.2 64.8 1.45 1.91 0.983 0.984

45 °C 20.36 32.79 22.10 34.75 34.8 97.2 1.56 2.76 0.988 0.997

60 °C 20.82 33.5 22.58 35.32 41.4 112.8 1.8 3.18 0.993 0.998

- 113 - RESULTS AND DISCUSSION M. Khalil sorption mechanism is predominant and that the over all rate constant of each adsorbent appears to be controlled by the chemisorptions process. 3.3.5.3. The homogeneous particle diffusion model (HPDM) In this model, the sorption mechanism involves the diffusion of Cs+ from the aqueous solution onto the sorbent phase through a number of possible resistances. The rate-determining step of sorption is normally described by either (a) diffusion of ions through the liquid film surrounding the particle, called film diffusion, or (b) diffusion of ions into the sorbent beads, called particle diffusion mechanism. Nernst–Plank equation [Helfferich, 1962] which takes into accounts both concentration and electrical gradients of exchanging ions into the flux equation, was used to establish the HPDM equations. The sorbent phase controlled diffusion of Cs+ from an infinite volume of solution into sorbent particle was described [Boyd et al., 1947]. As the diffusion rate controls sorption on spherical particles, the solution of the simultaneous set of differential and algebraic equations gives:

6∞ 1 −n2π 2 D t F( t )= 1 − exp i 2 2 2 (42) π n =1 n r

where F(t) is the fractional attainment of equilibrium at time t, Di the effective diffusion coefficient of sorbates in the sorbent phase (m2 s−1), r the radius of the sorbent particle assumed to be spherical (m), and n is an integer. F(t) values could be calculated by using the following equation: q F() t = t (43) q e where qt and qe are the amount of metal ion sorbed at time t and when equilibrium is attained (mg g−1), respectively. Reichemberg (1953) solved this equation and in the range F(t) < 0.5 obtaining the following expression: - 114 - RESULTS AND DISCUSSION M. Khalil π2 π F() t 1/2 2π−F ( t ) − 2 π 1 − = Bt (44) 3 3

π D where B = i (45) r 2

Vermeulen (1953) approximation of the Eq. (42) which fits the whole range 0 < F(t) < 1, for sorption on spherical particles. If the diffusion of ions through the adsorbent beads is the slowest step, the particle diffusion will be the rate-determining step and the particle diffusion model could apply to calculate the diffusion coefficients. This approximation could be further simplified to cover most of the data points for calculating effective particle diffusivity by using the following expression [Helfferich, 1962]: − ln(1 − F 2 ( t )) = 2 Kt , (46)

π 2D where K = i (47) r 2 this equations can be written as: 2 2 2Di π (48) −ln(1 −F ( t )) = 2 t r0 If the diffusion of ions from the solution to the sorbent beads is the slowest step, rate-determining step, the liquid film diffusion model control the rate of sorption; the following analogous expression can be used: DC (49) F( t )= 1 − exp − i rC r

− ln(1 − F ( t )) = K li t (50)

3DCi where K li = (51) rC r - 115 - RESULTS AND DISCUSSION M. Khalil this equation can be written as: 3DC (52) −ln(1 −F ) = i t rC r where C and Cr are the equilibrium concentrations of the ion in solution and solid phases, respectively. The two previous equations (Eqs. (48) and (52)) were tested against the kinetic rate data of both TiW and PATiW at different temperatures for Cs+ by plotting the functions of -ln(1-F) and -ln(1-F2 ) versus contact time. The straight lines that are obtained in the case of -ln(1-F) versus time does not pass through the origin as in Figs.38 and 39, indicating that the film diffusion model does not controls the rate of the sorption processes. On the other hand, the straight lines of the plots of –ln (1-F2) versus contact time, as shown in Figs. 40 and 41, pass through the origin point for both adsorbents indicate the particle diffusion model controls the sorption processes at all studied temperatures. 3.3.5.4. The shell progressive model (SPM) The shell progressive or unreacted shrinking core model is a mass transfer model in which the reaction starts at the particle surface, which forms a reacted zone and moves inward at a certain velocity. In this case, the relationship between the sorption time and the degree of sorption is given by the expressions below [Liberti and Passino, 1977; Schmuckler and Golstein, 1977]. (a) When it is controlled by the fluid film:

3CK F() t= mA t (53) arC r where a stoichiometric coefficient for the fluid that accounts was 2.6, −1 KmA mass transfer coefficient of species A through the liquid film (m s ) (a) When it is controlled by the diffusion though the sorption layer: 6DC 2/3 i (54) [3− 3(1 −F ( t )) − 2 F ( t )] = 2 t ar C r - 116 - RESULTS AND DISCUSSION M. Khalil

2.4

2.1

1.8

1.5

-F) 1.2 -ln(1 0.9

0.6

25 oC 0.3 45 oC 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time,min

Figure 38 Plots of -ln(1-F) as a function of time for the diffusion of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 117 - RESULTS AND DISCUSSION M. Khalil

3.0

2.5

2.0

1.5 -ln(1-F)

1.0

25 oC 0.5 45 oC 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time,min Figure 39 Plots of -ln(1-F) as a function of time for the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 118 - RESULTS AND DISCUSSION M. Khalil

1.6

1.4

1.2

1.0 ) 2 F 0.8 -ln(1- 0.6

0.4

25 oC o 0.2 45 C 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time,min Figure 40 Plots of -ln(1-F2) as a function of time for the diffusion of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 119 - RESULTS AND DISCUSSION M. Khalil

2.4

2.1

1.8

1.5 ) 2 1.2 -ln(1-F 0.9

0.6

25 oC o 0.3 45 C 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time,min

Figure 41 Plots of -ln(1-F2) as a function of time for the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 120 - RESULTS AND DISCUSSION M. Khalil

(c) When it is controlled by the chemical reaction: C [(1−F ( t ))1/3 ] = t (55) r The description of the rate of sorption based on the shell progressive model may be valid for species with a high affinity for TiW and PATiW. Figs. 42 - 45 show the results of the cesium sorption kinetics according to Eqs. 54 and 55 for the SPM model. According to Figs. 42 - 45 it can be observed that chemical reaction and film diffusion control can be discarded as the controlling step since the fit did not give a linear dependence. SPM model fit the data satisfactorily in almost the entire range for cesium diffusion. The straight lines that are obtained in Fig. 42 and 43 pass through the origin point with high correlation coefficient values. This result can be explained that the sorption process controlled by particle diffusion mechanism. Where Fig. 44 and 45 don't given straight lines shows the sorption process doesn't controls with chemical reaction [Valderrama et al., 2008]. Both HPDM and SPM fit the data satisfactorily the entire time range for cesium diffusion. For the sorbents tested, functions pass through the origin point, indicating that particle diffusion is the rate controlling step [Reichenberg, 1953]. The linear correlation coefficients indicated a good fit for both models. The slope values of these plots were used to calculate the diffusion coefficient (Di) using Eq. (48). These calculated values together with the correlation coefficients (R2) for both exchangers are presented in Table 7. The magnitude of the diffusion coefficient is dependent upon the nature of the sorption process. For physical adsorption, the value of the effective diffusion coefficient ranges from10-6 to 10-9 m2/s and forchemisorptions, the value ranges from 10-9 to 10-17 m2/s [Walker and Weatherley, 1999]. The difference in the values is due to the fact that in physical

- 121 - RESULTS AND DISCUSSION M. Khalil

0.7

0.6

0.5

0.4 -2F] 2/3 0.3 [3-3(1-F) 0.2 25 oC 45 oC 0.1 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time, min

Figure 42 Plots of [3-3(1-F)2/3-2F] as a function of time for the diffusion of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 122 - RESULTS AND DISCUSSION M. Khalil

0.8

0.6 -2F] 2/3 0.4 [3-3(1-F)

0.2

25 oC 45 oC 60 oC 0.0 0 20 40 60 80 100 120 140 160 180 200 time,min Figure 43 Plots of [3-3(1-F)2/3-2F] as a function of time for the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 123 - RESULTS AND DISCUSSION M. Khalil

0.6

0.5

0.4 ]

1/3 0.3 -F) [1-(1 0.2

0.1 25 oC 45 oC 60 oC 0.0 0 20 40 60 80 100 120 140 160 180 200 time, min Figure 44 Plots of [1-(1-F)1/3] as a function of time for the diffusion + of Cs onto TiW at V/m 50 and at different reaction temperatures.

- 124 - RESULTS AND DISCUSSION M. Khalil

0.6

0.5

0.4 ] 1/3

-F) 0.3 [1-(1

0.2

25 oC 0.1 45 oC 60 oC

0.0 0 20 40 60 80 100 120 140 160 180 200 time, min Figure 45 Plots of [1-(1-F)1/3] as a function of time for the diffusion of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 125 - RESULTS AND DISCUSSION M. Khalil

Table 7 Diffusion coefficients for the sorption of Cs+ onto TiW and PATiW at V/m 50 and at different reaction temperatures.

-12 2 2 Di x 10 (m /s) R Temperature TiW PATiW TiW PATiW 25 °C 3.33 3.93 0.998 0.998 45 °C 3.62 5.26 0.998 0.998 60 °C 4.29 5.98 0.997 0.999

- 126 - RESULTS AND DISCUSSION M. Khalil adsorption the molecules are weakly bound and therefore there is ease of migration, whereas for chemisorptions the molecules are strongly bound and mostly localized. Therefore, from this research, the most likely nature of sorption is chemisorptions since the values of Di were in the order 10-12 m2 /s for both exchangers. This is in agreement with the pseudo second-order kinetic model. Also, based on the values of the correlation coefficient (R2) obtained for all tested models, the pseudo second-order and PHDM models were found to best correlate the rate kinetic data of the sorption of Cs+ ions. It is important to compared this + data with literature data, The Di values for Cs on silico(IV)titanate was -7 2 −1 found to be 4.03x10 cm s [El-Naggar et al., 2007]. The Di values given by El-Naggar and El-Absy (1992) for Na+ and Cs+ exchange on hydrous titanium oxide were 4.5×10−8 and 2.3×10−8 cm2 s−1, respectively. El-Naggar et al. (1992) studied the self-diffusion of Na+ and Cs+ on hydrous zirconia as a function of ion exchange capacity, they found that the mobility of Na+ and Cs+ decrease with increase of the ion exchange −8 −9 −8 capacity. The Di values were found to be 2.63×10 , 2.6×10 , 3.23×10 and 2.82×10−8 cm2 s−1 for Cs+, Na+, Co2+ and Sr2+ exchanges on silico(IV)titanate, respectively [El-Naggar et al., 1998]. Also, the self- + + coefficients (Di) for Cs and Na exchange on hydrous zirconium oxide was found to be 6.7×10−9 and 11.4×10−9 cm2 s−1 [Abou-Mesalam and El-Naggar, 2003; Misak and El-Naggar, 1989]. For hydrous tin(IV)oxide [Qureshi and Ahmed 1988], the Di values for some anionic species such as Cl−, Br− and SCN− were found to be 4.11×10−9, 5.29×10−9 and 32.7×10−8 cm2 s−1 respectively. El-Naggar and Abou-Mesalam + (2007) calculated the values of effective diffusion coefficient (Di) of Cs on zirconium silicate at different reaction temperatures as 2.6, 3.5, 4.8 x -9 2 -1 3+ 2+ 2+ 2+ 10 cm s . The Di values of Eu , Co , Sr and Zn on cerium(IV) antimonate [El-Naggar et al., 1999] were reported as 3.73×10−9, 5.85×10−9, 4.56×10−9 and 1.84×10−9 cm2 s−1 respectively, which was

- 127 - RESULTS AND DISCUSSION M. Khalil

+ nearly similar to that obtained in this work. The values of Di of Cs were observed to be lower on PATiW than in MgTiSb (2.99 x10-9 cm2 s-1) and CeTiSb (8.40 x 10-9 cm2 s-1) [Zakaria, 2009]. With compared to the self- diffusion coefficients in other ion exchangers, for cerium(IV) antimonate + o −12 2 [El-Naggar et al., 1996] of Cs at 25 C Di was 5×10 m /s at a capacity of about 1.21 meq/g. For tin(IV) antimonate [Shabana et al., + o −12 2 1991] of Cs at 25 C Di was 15.7×10 m /s at a capacity of about 0.75 + o meq/g. Di for sorption of Cs onto titanium(IV) antimonate at 25 C was 0.98 ×10−12 m2/s, [Shady and El-Gammal, 2005], these results were similar to that obtained on PATiW with higher capacity of Cs+ (1.82 meq/g).

On the other hand, plotting of ln Di versus 1/T gave a straight line, as shown in Fig.46; this proves the validation of the linear form of Arrhenius equation: Ea (56) lnDDi= ln o − RT where D0 is a pre-exponential constant analogous to Arrhenius frequency factor. The energies of activation of Cs+ on both adsorbents, Ea, were calculated from the slope of the straight lines in Fig.46 and the obtained values were presented in Table 8. Values of Ea below 42 kJ/mol generally indicate diffusion-control processes and higher values represent chemical reaction processes [Scheckel and Sparks, 2001]. Such a low value of the activation energy for the sorption of each adsorbent indicates a physical sorption process involving weak interaction between adsorbents, and sorbed Cs+ and suggests that each sorption process has a low potential energy. The activation energy for all systems studied are given in Table 8 and these values are relatively small compared to the other organic and inorganic exchangers which confirm the particle diffusion mechanism [El-Naggar et al., 1999]. The activation energy of

- 128 - RESULTS AND DISCUSSION M. Khalil

-21.1

PATiW -21.2 TiW

-21.3

-21.4 /s 2 -21.5 , m , i ln D ln -21.6

-21.7

-21.8

0.0030 0.0031 0.0032 0.0033 0.0034 1/T,K-1

Figure 46 Arrhenius plots for the particle diffusion coefficients of Cs+ sorbed onto TiW and PATiW.

- 129 - RESULTS AND DISCUSSION M. Khalil

Table 8 Kinetic parameters for the sorption of Cs+ onto TiW and PATiW.

2 * Adsorbent D0 (m /s) Ea (kJ/mol) S (J/mol K) TiW 3.98 x 10-9 6.17 -134.53 PATiW 0.20 x 10-9 9.66 -120.96

- 130 - RESULTS AND DISCUSSION M. Khalil

Cs+ diffusion process reflects the ease with which cations can be passing through the exchanger particles. This finding agrees with that obtained for tin (IV) antimonate and crystalline antimonic acid [El-Naggar and Aly 1992, El-Naggar et al., 1992].

The Arrhenius equation would be also used to calculate D0, which in turn is used for the calculation of entropy of activation (S*) of the sorption process using [Mohan and Singh, 2002]: 2.72d2 KT ∆ S * (57) D0 = exp h R where K is the Boltzmann constant, h is the Plank constant, d is the distance between two adjacent active sites in the solid matrix, R is the gas constant, and T is the absolute temperature. Assuming that the value of d is equal to 5×10-8 cm [Mohan and Singh, 2002], the values of S* for both adsorbent were calculated and presented in Table 8. The value of entropy of activation (S*) is an indication of whether or not the reaction is an associative or dissociative mechanism. S* values > -10 J/mol K generally imply a dissociative mechanism [Scheckel and Sparks, 2001]. However, the high negative values of S* obtained in this study (Table 8) suggested that Cs+ sorbed on each of TiW and PATiW were an associative mechanism and no significant structural change occurred in exchangers. Within this context, this result supports the fact that the Cs+enter the exchanger in the unhydrated form as well as the higher stability, and hence the least steric difference of the system. This behavior is similar to that obtained for Cs+ onto titanium(IV) antimonate [Shady and El-Gammal, 2005] and for other ion exchangers [El- Naggar et al., 1992]. 3.3.5.5. Intraparticle diffusion model The sorption of cesium onto TiW and PATiW occur through consecutive stages. The first stage is assumed to occur rapidly and does not form a rate-limiting stage in the sorption of cesium ions on PATiW. It

- 131 - RESULTS AND DISCUSSION M. Khalil is proposed that the main resistance to mass transfer occurs solely in the second stage, during the movement or diffusion of the Cs+ in the internal structure of the sorbent. The mass transfer kinetics of cesium onto PATiW is relatively slow. Theoretically, the solute transport inside a macroporous sorbent particle occurs in parallel through both the pore and solid phases. This parallel solute transport mechanism has formed the basis of several intraparticle diffusion models for macroporous particles [Faust and Aly, 1998; Yoshida et al., 1985]. The intraparticle diffusion model developed by Weber and Morris [Weber and Morris, 1963] could be used as a first approach for describing sorption processes on PATiW. The mathematical dependence of uptake q(t) of sorbates (cesium) on t1/2 is obtained if the sorption process is considered to be influenced by diffusion in the spherical sorbent and by convective diffusion in the sorbate solution. This dependence is given by the following equation:

1/2 (58) qt= k ad t + C

−1 −1/2 where kad is the intraparticle diffusion rate constant (mg g min ) and C (mg g−1) is a constant that gives an indication of the thickness of the boundary layer, i.e. the higher the value of C, the greater the boundary layer effect. It is assumed that the external resistance to mass transfer surrounding the particles is significant only in the early stages of sorption. This can be seen in the initially steeper linear. The second linear portion is the gradual sorption stage in which intraparticle diffusion dominates. 1/2 If the Weber–Morris plot of qt versus t gives a straight line, this means that the sorption process is only controlled by intraparticle diffusion. However, if the data exhibit multilinear plots, then two or more steps influence the sorption process. It can be assumed that the involved mechanism is a diffusion of the

- 132 - RESULTS AND DISCUSSION M. Khalil species as shown in Figs. 47 and 48. In this case the slope of the linear plot is the rate constant of intraparticle transport at different temperatures.

The values of Kad were calculated, from the slope of the linear plots obtained, the values of C were calculated from the intercept and the correlation coefficient (R2) were presented in Table 9. 3.4. Sorption Isotherms Sorption equilibrium is normally represented by ‘sorption isotherm’ curves. In general, a sorption process could be preceded by the following mechanisms: (a) Physical sorption: There is no exchange of electrons in physical sorption, rather intermolecular attractions occur between ‘valence happy’ sites and are therefore independent of the electronic properties of the molecules involved. (b) Chemical sorption: Chemisorption, involves an exchange of electrons between specific surface sites and solute molecules, which results in the formation of a chemical bond. Chemisorption is defined by much stronger adsorption energy than physical adsorption. (c) Electrostatic sorption (ion-exchange): This is a term reserved for coulombic attractive forces between ions and charged functional groups and is more commonly classifiedas ion-exchange. (d) Complex formation between the counter ion and the functional group. (e) Hydrate formation at the surface or in the pores of the ion exchanger [Buffle, 1988; Demirbas et al. 2005]. Ion exchange equilibrium can be characterized by the equilibrium isotherm. This isotherm is a graphical representation which, in theory, covers experimental conditions at a given temperature. Any set of experimental conditions (temperature, solution concentration, sorbent concentration, etc.) corresponds to one point on the isotherm surface. Historically, many theoretical models have been proposed to describe equilibrium in solid- fluid systems. Explicit equations that treat the solid

- 133 - RESULTS AND DISCUSSION M. Khalil

12 ,mg/g t q 9

6 25 oC 45 oC 60 oC 3

0 0 2 4 6 8 10 12 14 16 18 t1/2,min Figure 47 Morris–Weber kinetic plots for the sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 134 - RESULTS AND DISCUSSION M. Khalil

20 ,mg/g t q 15

25 oC 5 45 oC 60 oC

0 0 2 4 6 8 10 12 14 16 18 t1/2,min

Figure 48 Morris–Weber kinetic plots for the sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 135 - RESULTS AND DISCUSSION M. Khalil

Table 9 Intraparticle diffusion rate constant for the sorption Cs+ onto TiW and PATiW at V/m 50 and at different reaction temperatures.

1/2 2 kad (mg/g min ) Intercept (C) R Temperature TiW PATiW TiW PATiW TiW PATiW 25 °C 1.04 1.31 3.17 10.63 0.999 0.993 45 °C 1.05 1.49 4.11 11.47 0.999 0.974 60 °C 1.07 1.46 5.38 14.21 0.999 0.957

- 136 - RESULTS AND DISCUSSION M. Khalil as a flat surface or that assume pore filling have been derived [Perry and Green, 1997]. Many early attempts to model ion exchange equilibria involved fitting empirical equations to experimental results. These equations were usually modifications of the mass action law or adsorption isotherms of Langmuir or Freundlich. Although derived from different models and assumptions, most of these equations will provide a reasonable fit to experimental isotherm data by suitable choice of constants [Helfferich, 1962]. Sorption equilibrium is usually described by an isotherm equation whose parameters express the surface properties and affinity of the sorbent, at a fixed temperature and pH [Sohn et al., 2005]. An adsorption isotherm describes the relationship between the amount of adsorbate adsorbed on the adsorbent and the concentration of dissolved adsorbate in the liquid at equilibrium. In order to evaluate the maximum metal sorption capacity of TiW and PATiW, the sorbent was contacted with varying concentrations of Cs+ (13 –13290 mg g-1) until equilibrium was reached. The Cs+ removing on TiW and PATiW was increase with increasing it concentration in solution until it reached the maximum capacity of PATiW and TiW at different reaction temperatures as represents in Figs. 49 and 50. Equations often used to describe the experimental isotherm data are those developed by Freundlich (1906) and Langmuir (1916). 3.4.1. Freundlich isotherm The empirical model can be applied to non-ideal sorption on heterogeneous surfaces as well as multilayer sorption and is expressed by the following equation: 1/n qe= K f C e (59) where qe is the amount of metal ions sorbed per unit weight of TiW and

PATiW in equilibrium (mg/g), Ce is the equilibrium liquid phase concentration (mg/L), KF the Freundlich constant indicative of the

- 137 - RESULTS AND DISCUSSION M. Khalil

250

200

150

,mg/g e q 100

50 25 oC 45 oC 60 oC

0 0 1000 2000 3000 4000 5000 6000 C ,mg/g e

+ Figure 49 Plots qe versus Ce for sorption isotherm of Cs onto TiW at V/m 50 and at different reaction temperatures.

- 138 - RESULTS AND DISCUSSION M. Khalil

300

250

200

150 ,mg/g e

q 100

50 25 oC 45 oC 60 oC

0 0 1000 2000 3000 4000 5000 C ,mg/g e + Figure 50 Plots qe versus Ce for sorption isotherm of Cs onto PATiW at V/m 50 and at different reaction temperatures.

- 139 - RESULTS AND DISCUSSION M. Khalil relative sorption capacity (mg/L) and 1/n is the heterogeneity factor indicative of the intensity of the sorption process. A linear form of the Freundlich expression can be obtained by taking ln of Eq.(59): 1 lnq= lnK + lnC (60) e fn e The Freundlich constants are empirical constants that depend on several environmental factors. The magnitude of the exponent 1/n gives an indication of the adequacy and capacity of the adsorbent/adsorbate system [Bilgili et al., 2006]. In most cases, an exponent between 1 and 10 shows beneficial adsorption. The value of n ranges between 0 and 1, and indicates the degree of non-linearity between solution concentration and adsorption as follows [Treybal, 1987]: if the value of n is equal to unity, the adsorption is linear; if the value is below unity, this implies that the adsorption process is chemical; if the value is above unity, adsorption is a favorable physical process; the more heterogeneous the surface, the closer n value is to 0 [Al-Duri, 1996]. The fit of data to Freundlich isotherm indicates the heterogeneity of the sorbent surface. The linear plot of ln qe versus ln Ce (Figs. 51 and 52) for TiW and PATiW shows that the adsorption obeys to the Freundlich model. Figures 51 and 52 the sorption of Cs+ onto TiW and PATiW showed that obey Freundlich isotherm over the entire range of sorption concentration studied. A similar result is found for sorption of Cs+ obey Freundlich isotherm onto polyacylamide cerium titanate [El-Naggar et al., 2009]. The numerical values of the constants n and Kf are computed from the slope and the intercepts, by means of a linear least square fitting method, and are also given in Table 10. It can be seen from these data that the Freundlich intensity constants (n) are greater than unity for both TiW and PATiW. This has physicochemical significance with reference to the qualitative characteristics of the isotherms, as well as to the interactions between metal ions and both adsorbents. In our - 140 - RESULTS AND DISCUSSION M. Khalil

, mg/L , 3 e ln q ln

2 o 25 C 45 oC 60 oC

1 2 3 4 5 6 7 8 9 ln C , mg/L e Figure 51 Freundlich isotherm plots for sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 141 - RESULTS AND DISCUSSION M. Khalil

4 , , mg/L e 3 ln q ln

25 oC o 1 45 C 60 oC

0 1 2 3 4 5 6 7 8 9 ln C , mg/L e Figure 52 Freundlich isotherm plots for sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 142 - RESULTS AND DISCUSSION M. Khalil case, n>1 for Cs+, the PATiW shows an increase tendency for sorption with increasing solid phase concentration. This should be attributed to the fact that with progressive surface coverage of adsorbent, the attractive forces between the metal ions such as Vander Waals forces, increases more rapidly than the repulsive forces, exemplified by short-range electronic or long range Coulombic dipole repulsion, and consequently, the metal ions manifest a stronger tendency to bind to the adsorbent site

[Mohan and Singh, 2002; Abd El-Rahman et al., 2006]. 3.4.2. Langmuir isotherm Langmuir sorption isotherm models the monolayer coverage of the sorption surfaces and assumes that sorption occurs on a structurally homogeneous adsorbent and all the sorption sites are energetically identical. The Langmuir model is probably the best known and most widely applied sorption isotherm. It may be represented as follows:

qo bC e qe = (61) 1+bC e

+ where qe is the amount of Cs sorbed per unit weight of TiW and PATiW

(mg/g), Ce the equilibrium concentration of the cesium ions in the equilibrium solution (mg/L), qo the maximum adsorption capacity corresponding to complete monolayer coverage on the surface (mg/g), and b is the Langmuir constant (L/mg) related to the (b e - G/RT) free energy of adsorption. Eq. (61) can be rearranged to a linear form:

CC1 e= + e (62) qe q o b q o

+ The linear plot of (Ce/qe) versus Ce give straight lines for Cs sorbed onto both adsorbent, as presented in Figs.53 and 54, confirming that this expression is indeed a reasonable representation of chemisorptions

- 143 - RESULTS AND DISCUSSION M. Khalil isotherm. The numerical value of constants qo and b evaluated from the slopes and intercepts of each plot are given in Table 10. The value of saturation capacity qo corresponds to the monolayer coverage and defines the total capacity of the adsorbent for a specific metal ion. As it can be seen from Table 10, the monolayer sorption capacity (qo) values of composite toward Cs+ ions are relatively higher than that of inorganic. + The Langmuir constants qo and b for Cs sorbed onto both adsorbent, increased with temperature showing that the sorption capacity and intensity of sorption are enhanced at higher temperatures. This increase in sorption capacity with temperature suggested that the active surface available for sorption has increased with temperature. It was observed that the equilibrium adsorption data indicating the favorable Langmuir’s sorption isotherms of Cs+ ions onto adsorbents. Conformation of the experimental data into Langmuir isotherm model indicates the homogeneous nature of TiW and PATiW at surface, i.e. each Cs+/PATiW adsorption has equal adsorption activation energy and demonstrates the formation of monolayer coverage of Cs+ on the outer surface of PATiW. One of the essential characteristics of the Langmuir model could be expressed by dimensionless constant called equilibrium parameters RL [Mohan and Chande, 2006 ]: 1 R L = (63) 1+bC 0 where C0 is the highest initial concentration of adsorbate (mg/L) and b

(L/mg) is Langmuir constant. The parameter RL indicates the nature of shape of the isotherm accordingly:

RL > 1 unfavorable adsorption

RL = 0 irreversible adsorption

RL = 1 linear adsorption

The values of RL were determined at deferent temperatures (25, 45 and - 144 - RESULTS AND DISCUSSION M. Khalil

40 , g/L , e

/q 30 e C

20 25 oC 45 oC o 10 60 C

0 0 2000 4000 6000 8000 10000 C , mg/L e Figure 53 Langmiur isotherm plots for sorption of Cs+ onto TiW at V/m 50 and at different reaction temperatures.

- 145 - RESULTS AND DISCUSSION M. Khalil

25 , g/L , e /q e 20 C

25 oC 10 45 oC 60 oC 5

0 0 2000 4000 6000 8000 10000

Ce, mg/L Figure 54 Langmiur isotherm plots for sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 146 - RESULTS AND DISCUSSION M. Khalil

Table 10 Freundlich and Langmuir isotherm parameters for the sorption of Cs+ onto TiW and PATiW at V/m 50 and at different reaction temperatures.

Freundlish model Langmiur model parameters parameters Adsorbent Temperature 2 2 n Kf R qo b(L/mg) R RL (mg/g) (mg/g) x10-3 o TiW 25 C 1.39 0.4 0.996 181.81 0.50 0.998 0.103 45 oC 1.30 0.55 0.995 257.06 0.53 0.968 0.127 60 oC 1.31 0.85 0.998 286.53 0.55 0.942 0.123 o PATiW 25 C 1.56 0.96 0.993 227.79 1.07 0.992 0.067 45 oC 1.57 1.55 0.997 292.39 1.09 0.968 0.069 60 oC 1.58 2.29 0.997 332.23 1.26 0.953 0.058

- 147 - RESULTS AND DISCUSSION M. Khalil

60 ± 1 °C) over the broad concentration range and the results are shown in Figs. 55 and 56 for TiW and PATiW. All the RL values (Table 10) were found to be less than 1 and greater than 0 indicating the favorable sorption isotherms of adsorbent Cs+ onto TiW and PATiW and the used these adsorbents are optimum for removal of Cs+ ions from waste solutions. The best fit values of the parameters together with the R2 values are listed in Table 10. The detailed analysis of the R2 values showed that the Freundlich model fit the adsorption data better than the Langmuir model at different temperatures. Freundlich sorption isotherm does not predict any saturation of the solid surface thus envisages infinite surface coverage mathematically [Hasany et al., 2002]. Which indicates that Cs+ is sorbed on TiW and PATiW as a monolayer deposition of adsorbate on localized sites followed by a multilayer sorption with interaction between sorbed molecules having heterogeneous energy distribution, accompanied by interaction between the adsorbed molecules. Similar results were also reported for the adsorption of Zn2+, Cu2+, Cd2+ and Ni2+ on polyacrylamide acrylic acid impregnated with silico-titanate ion exchanger [Abou-Mesalam et al., 2005]. The same result was found for physically sorbed Cs + on magneso-silicate and magnesium aluminosilicate [El-Naggar et al., 2007]. The R2 values in respect to sorption of Cs+ on PATiW were noted to be 0.992 and 0.993, respectively, for Langmuir and Freundlich models at 25 ±1 oC, while the corresponding values for Cs+ ions on TiW were 0.998 and 0.996. The + theoretical capacity (qo) of Cs on TiW and PATiW were calculated as 227.8 and 181.8 mgg−1, respectively, against 205.9 and 156.15 mgg−1 found experimentally indicating that this sorption does not completely match with Langmiur isotherm. As may be noted from Table 10, the adsorption capacity of Cs+ onto PATiW was significantly higher than that of TiW at different temperature indicating the adsorption tendency of Cs+

- 148 - RESULTS AND DISCUSSION M. Khalil

1.0

0.8

0.6 R L 25 oC o 0.4 45 C 60 oC

0.2

0.0 0 2000 4000 6000 8000 10000 12000 14000 C (mg/L) e

Figure 55 plots of separation factor, R , versus initial concentration, L C , for sorption of Cs+ onto TiW at V/m 50 and at different reaction o temperatures.

- 149 - RESULTS AND DISCUSSION M. Khalil

1.0

0.8

0.6

0.4 25 oC 45 oC 60 oC

0.2

0.0 0 2000 4000 6000 8000 10000 12000 14000

Ce (mg/L)

Figure 56 plots of separation factor, RL, versus initial concentration, Co, for sorption of Cs+ onto PATiW at V/m 50 and at different reaction temperatures.

- 150 - RESULTS AND DISCUSSION M. Khalil onto PATiW is higher. It is clear from Table 10 that adsorption capacity (qo) increases with the increase in temperature, this indicating that the process was endothermic in nature. It is hard to compare the maximum capacity with many reported studies due to differences in experimental conditions and models used to fit the data in each study. However, under similar conditions, the maximum adsorption capacity of PATiW is high compared with other adsorbents (Table 10). The adsorption capacity, qm, which is a measure of the maximum sorption capacity corresponding to complete monolayer coverage showed a mass capacity of Cs+ onto TiW and PATiW are 227.8 and 181.8 mg g−1 respectively compaered to the −1 + adsorption capacity, qm, 108.6 and 70.8 mg g of Cs onto iron ferrite and natural magnetite, respectively [Sheha and Metwally, 2007]. Generally, analysis of the experimental results by equilibrium sorption isotherms is important in developing accurate data that could be used for sorption design purposes. The sorption equation parameters and the underlying thermodynamic assumptions of these equilibrium models often provide some insight into both the sorption mechanism and the surface properties and affinity of the adsorbent. 3.5. Column Operations Breakthrough curves of PATiW for the conditions stated previously are shown in Figs. 57 and 58. Batch experimental data are often difficult to apply directly to the fixed bed sorption column because isotherms are unable to give accurate data for scale up since a flow in the column is not at equilibrium. Fixed bed column sorption experiments were carried out to study the sorption dynamics. The fixed bed column operation allows more efficient utilization of the sorption capacity than the batch process. The shape of the breakthrough curve and the time for the breakthrough appearance are the predominant factors for determining the operation and

- 151 - RESULTS AND DISCUSSION M. Khalil the dynamic response of the sorption column. The general position of the breakthrough curve along the volume/time axis depends on the capacity of the column with respect to bed height, the feed concentration and flow rate [Bohart and Adams, 1920; Netpradit et al., 2004; Singh and Pant, 2006; Kumar and Bandyopadhyay, 2006; Malkoc and Nuhoglu, 2006]. + The breakthrough curves (C/C0 vs. volume) obtained for Cs sorption onto PATiW at different bed depths (3.0, and 4.0 cm) for a constant linear flow rate of 2.5 mL/min and at 140 mg/L of neutral cesium concentration are shown in Fig. 57. It can be observed a similar behavior in each curve and a tendency to follow an S shape which is characteristic of an ideal sorption. The results indicate that the volume of breakthrough varies with bed depth. The bed capacity and the percent removal (column performance) for Cs+ increased with increasing bed height, as more binding sites were available for sorption. The increase in the ion sorption with bed depth was due to the increase in the sorbent doses in larger beds, which provided greater sorption sites for Cs+. It was found that the breakthrough capacities for Cs+ onto PATiW at different bed depths 3.0 and 4.0 cm are 5.1 and 6.5 mg g-1, respectively, which are more than the breakthrough capacity 0.67 mg g-1 for Cs+ onto phosphoric acid-activated silico-antimonate [Ali, 2009]. The rate-determining step can be inferred from a stop-flow test, in which the flow is halted and restarted during column loading. The behavior of C/C0 after the column is restarted provides information about the mass transfer mechanism. If the exchange rate is controlled by diffusion in the particle phase, diffusion of Cs+ within the particles continues even after flow is stopped. Highly concentrated cesium on the outer layers of the particles will diffuse toward particle centers, thereby leveling the concentration gradient in the particle and reducing the C/C0 on the surface. The result is a decrease in C/C0 when the column is

- 152 - RESULTS AND DISCUSSION M. Khalil

1.2

1.0

0.8

0.6

0.4 Breakthrough

0.2 3 Cm 4 Cm 0.0

0 50 100 150 200 250 300 350 400 Efluent Vol./ml Figure 57 Performance of PATiW column for cesium removal from neutral -1 -1 solutions at different bed depth, 140 mg L and flow rate 2.5 ml min .

- 153 - RESULTS AND DISCUSSION M. Khalil restarted. As the run continues, the concentration gradients in the particles are reestablished and the breakthrough curve will slowly approach the shape it would have had without interruption [Trantera et al., 2002]. For PATiW column test where flow was interrupted (Fig. 57) there was a significant decrease in C/C0 when the operation was restarted and it took approximately 50- 150 bed volumes for the curve shape to be reestablished. This phenomenon is indicative of a particle diffusion controlled system. This stop-flow test is also analogous to the batch interruption test reported by [Helfferich, 1962] in which the sorbent particles are removed from the solution for a brief period of time and then re-immersed. The interruption gives time for concentration gradients in the solid phase to level out. Then, when the particles are reimmersed, the exchange rate is temporarily faster. This can be seen as a momentary increase in the fractional attainment of equilibrium in the time following re-immersion. The breakthrough curves for the removal of cesium from acid solution

(0.5 M HNO3 + 0.1 M NaNO3) and from alkaline simulant solution (0.5

M NaOH + 0.1 M NaNO3) using PATiW columns at bed depth 1 cm, flow rate of 0.7 ml min-1 and 13 mg g-1 of cesium are represented in Fig. 58. In this figure the breakthrough of cesium begins at 22 ml with acid simulant solution and begin earlier at 10 ml with alkaline solution . The sorption capacity was found to be 2.32 and 0.66 mg g-1 for acid and alkaline columns, respectively. This means that PATiW can be applied to remove radiocesium from acidic solutions where most of the inorganic ion exchangers such as lithium titanate, tin silicate and titanium- ferrocyanides [El-Naggar et al., 2004; Zakaria et al., 2004; Ali et al., 2004;]. This exhibit very low ion exchange efficiency in the high acidic media. Where for alkaline solution the breakthrough begins very early with very less capacity.

- 154 - RESULTS AND DISCUSSION M. Khalil

100

40 Breakthrough

20 0.5M NaOH+0.1MNaNo 3 0.5M HNO +0.1MNaNo 3 3 0

0 50 100 150 200 250 300 350 Efluent Vol./ml

Figure 58 Performance of PATiW column for cesium removal from alkaline and acidic simulant solutions at bed depth 1cm,13 mg L-1 of Cs+ and flow rate 0.7 ml min-1.

- 155 - RESULTS AND DISCUSSION M. Khalil

We can studied the breakthrough of a simulated active waste solution containing different elements of various valence states such as Cs+, Co2+, Zn2+, Cd2+, Cu2+, Cr3+, Zr4+, As5+, V5+, Mo6+. So all these elements could be separated in the first few milliliters of the effluent solution while cesium is retained completely on the column beds. The separation capability of the material has been demonstrated by achieving some important binary separations such as Cs –Co, Cs –Zn , Cs –Cd , Cs –Cu, Cs –Cr, Cs –AS, Cs –Zr, Cs –V, and Cs –Mo as in Table 4 Differences between batch and operating capacities have also been observed in the case of adsorption, an operation similar to ion exchange where the dynamic capacity for phenol adsorption on activated carbon in some cases was lower by 17% than the values for the batch one [Hashimoto et al., 1977] and in this study the dynamic capacity for Cs+ sorption on PATiW was lower than the values for the batch one. The saturation in the column is generally expected to be strongly dependent on the flow rate and be favored by low flow rates [Helfferich, 1995]. Similar situations have been pointed out in the related literature for ammonia removal using natural and modified clinoptilolites where the operating capacity was higher for lower flow rates [McLaren and Farquhar, 1973; Jorgensen, 1976; Hlavay et al., 1982; Inglezakis et al., 2002]. According to the column data it was observed that the obtained breakthrough capacities are less than those obtained from batch experiments. This behavior could be attributed to the insufficient time required for equilibrium in case of column operation. Similar results have been pointed out for Na+, Co2+ and Eu3+ removal on zirconium molybdate and zirconium silicate. The breakthrough capacities of Na+, Co2+ and Eu3+ on zirconium molybdate and zirconium silicate were 0.019, 0.073 0.066 and 0.091, 0.230, 0.452 meq g-1 respectivly are similar as for sorption of cesium onto PATiW [El-Gammal and Shady, 2006].

- 156 - RESULTS AND DISCUSSION M. Khalil

These observations are extended not only to the capacity but also to the equilibrium isotherms [Weber and Wang et al., 1087]. The values of the isotherm constants obtained for the Cr6+ uptake in a packed column of chitosan were considerably lower than those obtained in a batch stirred vessel, and they were clearly flow dependent (decreasing volumetric flow rates led to increased capacities obtained in fixed beds) [Sag and Actay, 2001]. Finally, adsorption capacities of Cr6+ and Zn2+ on goethite calculated from the application of models on fixed bed data were found to be substantially lower than those obtained by batch-mode data [Lehmann et al., 2001]. Under the dynamic conditions typical of adsorption columns, there is the possibility of continuous uptake and slow diffusion of solute into the solid phase. Thus, the difference in equilibrium state between the two types of operation may be related to the slightly less than complete equilibrium conditions obtained in the fixed bed. Furthermore, the difference in the state of equilibrium between the two experimental settings may also be related in part to the existence of the different concentration [Weber and Smith, 1987]. The approach to a given residual solution concentration from higher values (in batch operation the solution-phase concentration is continuously decreasing) may result in an overshoot condition with respect to the uptake process. If the process is not rapid and totally irreversible, this may yield to higher apparent loadings for a given residual concentration compared to the loading achieved when the same residual concentration is approached from lower values (in the fixed bed operation solution-phase the concentration is continuously increasing) [Vassilis et al., 2003]. 3.6. Recover Cesium from Milk The measurement of gamma emission lines due to radioactivity in the environment and in food is of fundamental importance for controlling the radiation levels which human are exposed to directly or indirectly.

- 157 - RESULTS AND DISCUSSION M. Khalil

This work deals with the measurement of gamma lines in powdered milk, using a scintillation detector head (NaI) connected to scalar of the type SR-7 obtained by Nuclear Enterprises. This material can be used not only for treating liquid radioactive waste but also it has been used to remove cesium from contaminated milk. The milk cesium-134 activity was measured over a 3-h period to determine the equilibrium time. Fat separation was not observed except for long mixing time (>3h) [Kaminski et al., 2000]. The uptake of cesium-134 and the decaying of cesium activity are shown as a function of mixing time in Fig. 59. The reaction half-life was 30 min, and by 60 min the reaction was 80% complete. The reaction reached at equilibrium at 2h. This experiment is important for removal of Cs-134 from the milk media. So we can use PATiW column for milk treatment which give a promise application in Cs+ removal from different media.

- 158 - RESULTS AND DISCUSSION M. Khalil

800

50 700 Percent %

600 40

500

(cpm) cpm 30 400

300 20 CS-134 CS-134 activity 200 PercentCs-134 removed from solution 10 100

0 0 0 20 40 60 80 100 120 140 160 180 200 mixing time,min Figure 59 Redaction of cesium-134 on PATiW as a function of o mixing time at V/m 50 and 25 ±1 C. o

- 159 -

SUMMERY M. Khalil

SUMMARY The management of radioactive wastes has become an issue of great concern. This type of wastes could be treated using solid adsorbents such as ion exchanger. 137Cs is the main fission products in radioactive wastes from industrial and research applications. The objectives of this thesis are the removal of cesium -134 from aqueous media, radioactive waste and milk by the preparation of PATiW as anew composite ion exchanger. The thesis is divided into three main chapters, introduction, experimental and the results and discussion. 1. Introduction This first chapter, introduction, includes brief account on history, classification, chemical, thermal and radiation stabilities of ion exchangers, ion exchange theory, characterization of ion exchanger, concepts of ion exchange, applications of ion exchangers, and recent developments. A literature survey related to different ion exchangers showing high selectivity for separation of cesium and different ions up to 2010 is reviewed. 2. Materials and Methods This chapter, deals with the different materials employed and their chemical purity, as well as the methods utilized for the preparation of the radioactive materials was given. Detailed descriptions of the instrumentations, the analytical techniques and procedures used in this thesis were also detailed. A detailed description of the method of preparation of PATiW and TiW at different operative conditions and set up used in this work were presented. Column chromatographic technique and recovery of cesium from milk was also described. 3. Results and Discussion This chapter deals with the results and discussion and is divided into six main sections:

- 160 - SUMMERY M. Khalil

3.1. Preparation and Characterization of TiW and PATiW Polyaniline gel was prepared by mixing equal volumes of of 10% aniline (C6H5NH2) and 0.1M potassium persulphate. A precipitate of titanium tungstate was prepared at (65 ±2 °C) by adding 1 M titanium chloride solution to an aqueous solution of 1M sodium tungstate

(Na2WO2.2H2O). The gel of polyaniline was added to the white inorganic precipitate of titanium and mixed thoroughly with constant stirring. Physicochemical properties of the prepared materials were identified by using different techniques, such as, elemental composition, stability, pH-titration curve, IR-spectra, X-Ray diffraction patterns, SEM as well as thermal analysis (DTA and TGA). The spectrum of prepared polyaniline, PATiW and TiW were displayed in the IR technique. There are characteristic bands of PATiW indicating the binding of inorganic precipitate with organic polymer and formation of PATiW. The characteristic peaks of PATiW are disappeared by increasing drying temperatures indicating the decomposition of the organic materials. According to the X-ray powdered diffraction patterns, the crystallinity of PATiW slightly improved with the increase of heating temperature from 50 °C to 850 °C. The SEM pictures showed that the surface morphology of composite material is totally different from their individual inorganic and organic components. From the DTA/TGA analysis of PATiW, the material shows high thermal stability up to studied temperature. The solubility experiments showed that the composite and inorganic ion exchangers have good chemical stability in acids and alkali solvents. The solubility of composite material is slightly increased than the inorganic material. Elemental analysis determines the formula of PATiW as:

[(TiO2)(WO3) (-C6H4NH-)]. 2.46 H2O.

- 161 - SUMMERY M. Khalil

The pH-titration curve of PATiW showed only one inflexion point indicating that behaves as monofunctional and may be acts a strong acid cation-exchanger. The ion exchange capacity of Cs+ on PATiW as a function of pH is investigated. It was found that the capacity increase by increasing the pH. The Cs+ ion-exchange capacity of the PATiW material is 1.82 meq g-1. 3.2. Distribution Studies In order to find out the potentiality of the new composite PATiW compared to the non-modified TiW in separation of metal ions, distribution coefficient studies were performed. + The distribution coefficient (Kd) of Cs on PATiW showed was found to be the higher than that of TiW at different reaction temperatures. The selectivity performance of PATiW as a new adsorbent was studied for separation of Cs+, Co2+, Zn2+, Cu2+, Cd2+ , Cr3+, Zr4+, V5+, As5+ and Mo6+ were carried out on PATiW at different pH. It is found that the composite showed high selectivity towards Cs+ and the selectivity trend in order of Cs+ > Zr4+ > Mo6+ > V5+> As5+ > Cr3+ > Co2+ > Cu2+> Zn2+ > Cd2+. The separation capability of the material has been demonstrated by achieving some important binary separations such as Cs – Co, Cs – Zn, Cs – Cd, Cs – Cu, Cs – Cr, Cs – AS, Cs – Zr, Cs – V, and Cs – Mo. 3.3. Kinetic Studies The kinetic studies was performed at cesium concentrations (660, 1300 and 6600 mg/L), different particle size, different reaction temperature and different drying temperatures for the sorption of Cs+ onto PATiW and TiW. It is clear that the removal rate significantly affected by particle size. The rate and extent of sorption is higher for small particles, which confirmed the particle diffusion control is the main mechanism. The thermodynamics parameters for the studied systems were

- 162 - SUMMERY M. Khalil calculated, the negative values of Go confirm the feasibility of the process and the spontaneous nature of the sorption processes. The positive value of Ho indicates the reaction is endothermic. The positive values So reveal the increased randomness at the solid/solution interface with some structural changes in the Cs+ sorbed on PATiW and TiW. The data of the kinetics of Cs+ sorbed from aqueous solution onto PATiW and TiW were found to be obeyed the pseudo second-order, homogeneous particle diffusion model, shell progressive model and intraparticle diffusion. This indicates that the rate determining step is diffusion through the exchanger particles and this observation agreed with the fundamental theory of particle diffusion mechanism. -12 2 The Di values of the studied system were found in the range of 10 m /s which indicate to the chemisorptions process. The energies of activation of Cs+ on both adsorbent, Ea, were below 42 kJ/mol which generally indicate diffusion-control processes. 3.4. Sorption Isotherms Sorption equilibrium is usually described by an isotherm equation whose parameters express the surface properties and affinity of the sorbent, at a fixed temperature and pH. Removing Cs+ on PATiW and TiW was increase with increaseing Cs+ concentration in solution until it reached the maximum capacity at different reaction temperatures. The best fit values of the parameters together with the R2 values showed that the Freundlich model fit the adsorption data better than the Langmuir model. This indicates that Cs+ adsorb on PATiW and TiW as monolayer deposition of Cs+ on localized sites followed by a multilayer sorption with interaction between adsorbed molecules that having heterogeneous energy distribution, accompanied by interaction between the adsorbed molecules. In addition, the sorption capacity (qo) increase with increasing temperature, this indicates that the process was endothermic in nature.

- 163 - SUMMERY M. Khalil

Also, it was found that, the maximum adsorption capacity of Cs+ onto PATiW was significantly higher than that of TiW at different temperatures. This indicates that the sorption tendency of Cs+ towards onto PATiW was higher. 3.5. Column Operations + The breakthrough curves (C/C0 vs. volume) obtained for Cs sorption onto PATiW at different bed depths ( 3.0, and 4.0 cm) for a constant linear flow rate of 2.5 ml min-1 and at 140 mg/L of neutral cesium concentration were studies. The bed capacity and the percent removal of Cs+ was increase with increasing bed height, as more binding sites were available for sorption. The rate determining step can be inferred from a stop-flow test, in which the flow is halted and restarted during column loading. There was a significant decrease in C/C0 when the operation was restarted. This phenomenon is indicative of a particle diffusion controlled system. The break-through curves for separation of cesium from acid solution

(0.5 M HNO3+0.1 M NaNO3) and from alkaline simulant solution (0.5 M - NaOH+0.1 M NaNO3) using PATiW columns at flow rate of 0.7 ml min 1, bed depth 1cm and 13 mg g-1 of cesium chloride. It is found that the PATiW can be applied to separate radiocesium from acidic solutionwhere for alkaline solution the break-through begins very early with capacity very small. 3.6. Recover Cesium from Milk The milk cesium-134 activity was measured over a 3-h period to determine the equilibrium time. As well as the removal efficiency of cesium-134 and the decaying of cesium activity were studied. The reaction half-life was 30 min, and by 60 min the reaction was 80% complete. The reaction reached equilibrium at 2h.

- 164 -

REFERENCES M. Khalil

REFERENCES Abd El-Rahman, K.M., El-Kamash, A.M., El-Sourougy, M.R., Abdel- Moniem, N.M., J. Radioanl. Nucl. Chem., 268, 221 (2006). Abe, M., Furuki, N., Solvent. Extr. Ion. Exc., 4, 547 (1987). Abe, M., Ito, T., Bull. Chem. Soc. Jpn., 41, 333 (1968). Abe, M.: Ion Exchange and Solvent Extraction, edited by J.A. Marinsky and Y. Marcus, Marcl Dekker, Inc., Vol. 12, p.381, New York (1995). Abou-Mesalam, M.M., El-Naggar, I.M., Colloid. Surf. A, 215 (2003). Abou-Mesalam, M.M., Moustafa, M.M., Abdel-Aziz, M.M., El-Naggar, I.M., Arab. J. Nucl. Sci. Appl., 38, 53 (2005). Adams, B.A., Holmes, E.L., J. Chem. Soc. Ind., 54, 1 (1935). Akyil, S., Aslani, M.A.A., Olmez, S., Eral, M., J. Radioanal. Nucl. Chem. Letts., 213, 441 (1996). Alam, Z., Inamuddin, Nabi, S.A., Desalination, 250, 515 (2010). Alberti, G., Allulli, S., J. Chromatogr., 32, 379 (1968). Alberti, G., Casciola, M., Donnadio, A., Piaggio, P., Pica, M., Sisani, M., Solid State Ionics, 176, 2893 (2005). Alberti, G., Cavalaglio, S., Marmottini, F., Matusek, K., Megyeri, J., Szirtes, L., Appl. Catal., 218, 219 (2001). Alberti, G., Dobici, F., Grassini, G., J. Chromatogr., 8, 103 (1962). Alberti, G., Torracca, E., Conte, A., J. Inorg. Nucl. Chem., 28, 607 (1966). Al-Duri, B., in: G. McKay (Ed.), Use of Adsorbents for the Removal of Pollutants from Wastewaters, CRC Press, pp.133 (chapter 7) (1996). Ali, I.M., J. Radioanal. Nucl. Chem., 260, 149 (2003). Ali, I.M., Zakaria, E.S., El-Naggar, I.M., Arab. J. Nucl. Sci., 37, 31 (2004). Ali, I.M., Chem .Eng. J., 155, 580 (2009).

- 165 - REFERENCES M. Khalil

Ali, I.M., J. Radioanal. Nucl. Chem., 260, 149 (2004). Ali, I.M., Kotp, Y.H., El-Naggar, I.M., Desalination, 259, 228 (2010). Ali, I.M., Zakaria, E.S., Ibrahim, M.M., El-Naggar, I.M., Polyhedron, 27, 429 (2008). Amphlett, C.B., Jones, P.J., J. Inorg. Nucl. Chem., 26 , 1759 (1964). Amphlett, C.B., Mcdonald, L.A., Proc. Chem. Soc., 276 (1962). Araki, H., Umeda, M., Enokida, Y., Yamamoto, I., Fusion. Eng. Des., 39, 1009 (1998). Baetsle, L.H., Huys, D., Van Deyck, D., J. Inorg. Nucl. Chem., 28, 2385 (1966). Bajaj, P., Goyal, M., Chavan, R.V., J. Appl. Polym. Sci., 51, 423 (1994). Bellamy, S.A. In Ion Exchange Developments and Applications (J. A. Greig, ed.), 494, The Royal Society of Chemistry, Cambridge (UK) (1996). Belter, P.A. AIChE Symposium Series, 233, 110 (1984). Benes, J., Anal. Chim. Acta, 32, 85 (1965). Berkovich, Y.A., Krivobok, N.M., Krivobok, S.M., Matusevich, V.V., Soldatov, V.S., Habitation, 9, 59 (2003). Betteridge, D., Stradling, G.N., J. Inorg. Nucl. Chem., 29, 2652 (1967). Betteridge, D., Stradling, G.N., J. Inorg. Nucl. Chem., 31, 1507 (1969). Bilgili, M.S., J. Hazard. Mater., 137, 157 (2006). Bohart, G.S., Adams, E.Q., J. Am. Chem. Soc., 42, 523 (1920). Bolto, B.A., Pawlowaski, L., Effluent Water Treat., J., 23, 371 (1983). Botros, N., Elbayoumy, S., Elgarhy, M., Marei, S.A., Isotopenpraxis, 26, 399 (1990). Boyd, G.E., Adamson, A.W., Meyers, L.S., J. Am. Chem. Soc., 69, 2849 (1947). Buffle, J., Complexation Reactions in Aquatic Systems: An Analytical Approach, Ellis Horwood Ltd., Chichester, UK, pp. 306 (1988). Caron, H.J., Sugihara, T.T., Anal. Chem., 34, 1082 (1962).

- 166 - REFERENCES M. Khalil

Caruel, H., Phemius, P., Rigal, L., Gaset, A., J. Chromatogr., 594, 125 (1992). Cayot, P., Courthaudon, J. L., Lorient, D., J. Dairy. Res., 59, 551 (1992). Clearfield, A., Bleasing, R.H., J. Inorg. Nucl. Chem., 34, 2634 (1972). Clearfield, A., Nancollas G.H., Blessing, R.H., in J.A. Marinsky, and Y. Marcus (Editors), Ion Exchange and Solvent Extraction, Vol. 5, Marcel Dekker Inc., New York, 1 (1973). Clearfield, A., Smith, G. D., Hammond, B. J. Inorg. Nucl. Chem., 30, 277 (1968). Clearfield, A., Styne, J.A., J. Inorg. Nucl. Chem., 26, 117 (1972). Clearfield, A., Thakur, D.S., Appl. Catal., 26, 1 (1986). Collinson, M.M, Crit. Rev. Anal. Chem., 29, 289 (1999). Cortes-Martinez, R., Olguin,M.T., Solache-Rios, M., Desalination 258, 164 (2010). Dale, J. A., Nikitin, N. V., Moore, R., Opperman, D., Crooks, G., Naden, D., Belsten, E., Jenkins, P., In Ion Exchange at the Millennium (J. A. Greig, ed.), 261, Imperial College Press, London (2000). Das, K., Anis, M., Azemi, B. M. N. M., Ismail, N., Biotechnol. Bioeng., 48, 551 (1995). Davis, T.A., Volesky, B., Mucci, A., Water Res., 37, 4311 (2003). Demarco, M.J., Sengupta, A.K., Greenleaf, J.E., Water Res., 37, 164 (2003). Demirbas, A., Pehlivan, E., Gode, F., Altun, T., Arslan, G., J. Colloid. Interf. Sci., 282, 20 (2005). Devi, P.S.R., Joshi, S., Verma, R., Lali, A.M., Gantayet, L.M., Radiat. Phys. Chem., 79, 41 (2010). DeVilliers, P.G.R., VanDeventer, J.S.J., Lorenzen, L., Miner. Eng., 10, 929 (1997). Dionysius, D. A., Herse, J. B., Grieve, P. A., Aust. J. Dairy. Technol., 46, 72 (1991).

- 167 - REFERENCES M. Khalil

Dolezal, J., Kourim, V., Radiochem. Radioanal. Letts., 1, 295 (1969). Dosch, R.G., Brown, N.E., Stephens, H.P., Anthony, R.G., Sandia National Laboratories Report SAND-92-2737C (1992) Dunn, L., Abouelezz, M., Cummings, L., Navvab, M., Ordunez, C., Siebert, C.J., Talmadge, K.W., J. Chromatogr., 548, 165 (1991). Eccles, H., In Ion Exchange Technology (D. Naden, M. Streat, eds.), 700, Ellis Horwood, Chichester (1984). El-Gammal, B., Shady, S.A., Colloid. Surface. A, 287, 132 (2006). El-Naggar, I.M., Abdel-Hamid, M., Shady, S., Aly, H., Radioactive Waste Managements Environmental Remediation, ASME, (1995). El-Naggar, I.M., Zakaria, E.S., Ali, I.M., Sep. Sci. Technol., 39, 959 (2004). El-Naggar, I.M., Abdel-Hamid, M.M., Aly, H.F., Solvent. Extr. Ion. Exc., 12, 651 (1994). El-Naggar, I.M., Abdel-Hamid, M.M., Zakaria, E.S., Shady, S. A., Aly, H.F., 6th Int. Cof. on Nucl. Sc. Appl., Cairo (1996). El-Naggar, I.M., Abou-Mesalam, M.M., Arab J. Nucl. Sci. Appl., 38, (2005). El-Naggar, I.M., Abou-Mesalam, M.M., J. Hazard. Mater., 149, 686 (2007). El-Naggar, I.M., El-Absy, M.A., J. Radioanal. Nucl. Chem., 157, 313 (1992). El-Naggar, I.M., Aly, H.F., Solvent. Extr. Ion. Exc., 10, 145 (1992). El-Naggar, I.M., Belacy, N., Zakaria, E.S., Mohamed, D.A., Aly, H.F., in: International Conference on HAZARDOUSWASTE: Sources, Effects and Management, Cairo, Egypt, December 12–16, 963 (1998). El-Naggar, I.M., El- Absy, M.A., Aly, H. F., Colloid. Surface. A, 66, 281, (1992).

- 168 - REFERENCES M. Khalil

El-Naggar, I.M., El-Absy M.A., and S.I. Aly, Solid State Ionics, 50,241(1991). El-Naggar, I.M., El-Dessouky, M.E., Aly, H.F., React. Funct. Polym., 28, 209 (1996). El-Naggar, I.M., El-Dessouky, M.I., Aly, H.F., Solid State Ionics, 57, 339 (1992). El-Naggar, I.M., Ibrahim, G.M., El-Kady, E.A., Hegazy, E.A., Desalination, 237, 147 (2009). El-Naggar, I.M., Mowafy, E.A., Abdel-Galil, E.A., Colloid. Surface. A, 307, 77 (2007). El-Naggar, I.M., Mowafy, E.A., El-Aryan, Y.F., Abd El-Wahed, M.G., Solid State Ionics, 178, 741 (2007). El-Naggar, I.M., Shabana, E.I., El-Dessouky, M.I., Talanta, 39, 653 (1992). El-Naggar, I.M., Zakaria, E.S., Ali, I.M., Khalil, M., El-Shahat, M.F., Arabian J. Chem., 5, 109 (2012). El-Naggar, I.M., Zakaria, E.S., Aly, H.F., React. Funct. Polym., 28, 215 (1996). El-Naggar, I.M., Zakaria, E.S., Shady, S.A., Aly, H.F., Solid State Ionics, 122, 65 (1999). Everett, D.H., Thermodynamics of adsorption from solution. Part 1. Perfect systems, Trans. Faraday Soc. 60, 1803 (1964). Faust, S.D., Aly, O.M., Chemistry of Water Treatment, second ed., Ann Arabor Press, MI, (1998). Fernandez, L., Marinsky, J., Muhammed, M., Swelling of Ion Exchange Resins. A Literature Survey, KTH, Stockholm, (1983). Ferragina, C., Rocco, R.D., Giannoccaro, P., Petrilli, L., Mater. Res. Bull., 45, 34 (2010). Folin, O., Bell, R., J. Biol. Chem., 29, 329 (1917).

- 169 - REFERENCES M. Khalil

Freundlich, H.M.F., Uber die adsorption in losungen, Z. Phys. Chem., 57A, 385 (1906). Fries, W., Chew, D., Chemtech, 23, 32 (1993). Fuh, W. S., Chiang, B. H., J. Food Sci., 55, 1454 (1990). Gans, R., Jahrb. Preuss. Geol. Landesanstalt (Berlin), 26, 179 (1905) 27, 63 (1906). Goldschmidt, V.M., Trans. Faraday Soc., 25, 320 (1925). Grandison, A. S., In Separation Processes in the Food and Biotechnology Industries.Principles and Applications (A. S. Grandison, M. J. Lewis, eds.), 155, Woodhead Publishing Limited, Cambridge (UK) (1996). Gu, J., Lizi Jiaohuan Yu Xifu, 8, 458 (1992). Guibal, E., Milot, C., Tobin, J.M., Ind. Eng. Chem. Res., 37, 1454 (1998). Gula, M.J., Totura, G.T., Jassin, L., JOM – J. Min. Metals Mater. Soc., 47, 54 (1995). Gunther, S., Herold, J., Patzelt, D., Int. J. Legal Med., 108, 154 (1995). Gurgel, P. V., Mancilha, I. M., Pecanha, R. P., Siqueira, J. F. M., Bioresource Technol., 52, 219 (1995). Hanine, H., Mourgues, J., Conte, T., Malmary, G., Molinier, J., Bioresource Technol., 39, 221 (1992). Harjula, R., Enc. Sepa. Sci., 4, 1651 (2000). Harjula, R., Lehto, J., Paajanen, A., Brodkin, L., Tusa, E., Nucl. Sci. Eng., 137, 206 (2001). Harjula, R., Lehto, J., React. Funct. Polym., 27, 147 (1995). Hasany, S.M., Saeed, M.M., Ahmed, M., J. Radioanal. Nucl. Chem., 252 477 (2002). Hashimoto, K., Miura, K., Tsukano, M., J. Chem. Eng. Jpn., 10, 27 (1977). Heijman, S. G. J., van Paassen, A. M., van der Meer, W. G. J., Hopman, R., Water Sci. Technol., 40, 183 (1999).

- 170 - REFERENCES M. Khalil

Helfferich, F., Angew. Chem., 68, 693 (1956). Helfferich, F., in: Ion Exchange, Dover Publications Inc., New York, 421 (1995). Helfferich, F., Ion Exchange, McGraw-Hill, New York, (1962). Hilton, J., Nolan, L., Jarvis, K.E. Geochim. Cosmochim. Ac., 61, 1115 (1997). Hlavay, J., Vigh, G., Olasi, V., Inczedy, J., Water Res., 16, 417 (1982). Ho, Y.S., McKay, G., Process Biochem., 34, 451 (1999c). Ho, Y.S., McKay, G., Resour. Conserv. Recy., 25, 171 (1999a). Ho, Y.S., McKay, G., Water Res., 33, 578 (1999b). Hoigye, Z., Fresenius. Z. Anal. Chem., 340, 59 (1991). Horvath, S., Sjöde, A., Nilvebrant, N.O., Zagorodni, A.A., Jönsson, L.J., Appl. Biochem. Biotech., 113, 525 (2004). Hubicki, Z., Olszak, M., Adsorpt. Sci. Technol., 16, 521 (1998). Huys, D., Baetsle, L., J. Inorg. Nucl. Chem., 26, 1329 (1964). Hwang, D. K., Jung, K. T., Shul, Y. G., Lee, W. S., Moon, J. K., Oh, W. Z., J. Kor. Inst. Chem. Eng., 36, 627 (1998). Ibrahim, G.M., El-Gammal, B., El-Naggar, I.M., Curr. Topics Colloid. Interf. Sci., 6, 159 (2003). Ibrahim, G.M., El-Gammal, B., Mowafy, E. A., Arab J. Nucl. Sci. Appl., 37, 93(2004). Ikram Saiqa, “Ph.D Thesis”, D.C.E., Delhi (India), 84 (2000). Inamuddin, Ismail, Y.A., Desalination, 250, 523 (2010). Inamuddin, Khan, S.A., Siddiqui, W.A., Khan, A.A., Talanta, 71, 841 (2007). Inglezakis, V.J., Loizidou, M.D., Grigoropoulou, H.P. Water Res., 36, 2784 (2002). Inoue, Y., Abe, M., Mater. Res. Bull., 31, 691 (1996). Inoue, Y., Bull. Chem. Soc. Jpn., 36, 1316 (1963). Jain, A.K., Agrawal S., and Singh, R.E., Anal. Chem., 52, 1364 (1980).

- 171 - REFERENCES M. Khalil

Jain, A.K., Singh R.P., Bala, C., Bull. Chem. Soc. Jpn., 56, 1269 (1983). Jain, A.K., Singh R.P., Bala, C., J. Radioanal. Nucl. Chem., 75, 85 (1982). Jain, A.K., Singh, R.E., Bala, C., J. Radioanal. Nucl. Chem., 89, 3 (1985). John, J., Sebesta, F., Motl, A., Radiochim. Acta, 78, 131 (1997). Jorgensen, S.E., Libor, O., Graber, K.L., Barkacs, K., Water Res., 10, 213 (1976). Juznic, K., Senegacnik M., Milavec, Z.Z., Anal. Chem., 207, 193 (1965). Kaminski, M.D., Nunez, L., Pourfarzaneh, M., Negri, C., Sep. purif. Technol., 21, 1 (2000). Karim, M.A.; Khan, L.I., J. Hazard. Mater., 81, 83 (2001). Kaya, Y., Vergili, I., Acarbabacan, S., Barlas, H., Fresenius Environ. Bull., 11, 885, (2002). Kentish, S.E., Stevens, G.W., Chem .Eng. J., 84, 149 (2001). Khan, A.A. Inamuddin, Alam, M.M., Mater. Res. Bull., 40, 289 (2005) Khan, A.A., Alam, M.M., Mohammad, F., Electrochimica Acta, 48, 2463 (2003). Khan, A.A., Alam, M.M., React. Funct. Polym., 55, 277 (2003). Khan, A.A., Inamuddin, Alam, M. M., React. Funct. Polym., 63, 119 (2005). Khan, A.A., Inamuddin, React. Funct. Polym., 66, 1649 (2006). Khan, A.A., Niwas, R., Alam, M.M., Indian J. Chem. Technol. 9, 256 (2002). Khan, A.A., Niwas, R., Vershney, K.G., Colloid. Surface. A, 150, 7 (1999). Khan, A.A., Niwas, R., Vershney, K.G., Ind. J. Chem. 37A, 469 (1998). Khan, A.M., Ganai, S.A., Nabi, S.A., Colloid. Surface. A, 337, 141 (2009). Khan, Sh.A.I., Siddiqui, W.A., Khan, A.A., Talanta, 71, 841 (2007). Kaygun, A. K., Akyil, S., J. Hazard. Mater. 147, 357 (2007).

- 172 - REFERENCES M. Khalil

Kim, C.J., Lee, P.I., Pharm. Res., 9, 1268 (1992). Kinniburgh, D.G., Jackson, M.L., Bull. Chem. Soc. Jpn., 41, 333 (1968). Kokotov, Y.A., Pasechnik, V.A., Equilibrium and Kinetics of Ion Exchange (Ravnovesie kinetika ionnogo obmena), Khimiya, Leningrad (1970). Korkisch, J., Modem Methods for the Separation of Rarer Metal Ions, Pergamon Press Ltd., New York, (1969). Korngold, E., Desalination, 94, 243 (1994). Kossel, W., Am. Phys., 49, 222 (1916). Kourim, V., Rais J., Stejskal, J., J. Inorg. Nucl. Chem., 26, 1761 (1964). Kraus, K.A., Carlson, T.A., Johnson, J.S., Nature, 177, 1128 (1956). Krtil, J., J. Chromatogr., 20, 384 (1965). Krtil, J., J. Inorg. Nucl. Chem., 24, 1139 (1962). Krtil, J., J. Inorg. Nucl. Chem., 27, 233 (1965). Kruglov, A., Andreev, B., Pojidaev, Y., Separ. Sci. Technol., 31, 471 (1996). Kumar, U., Bandyopadhyay, M., J. Hazard. Mater., 129, 253 (2006). Kusumoto, I., J. Nutr., 131, 2552 (2001). La Ginestra, A., Ferragina, C., Massucci, M.A., Patrono, P., DiRocco, R., Tomoilson, A.A.G., Gazz. Chim. Ital., 113, 357 (1983). Lahav, O., Green, M., Water Sci. Technol., 42, 179(2000). Lahiri, S., Roy, K., Bhattacharya, S., Maji, S., Basu, S., Appl. Radiat. Isotopes, 63, 293 (2005). Lamberg, J., Z. Dent. Geal. Gos., 22, 355 (1870). Langmuir, I, J. Am. Chem. Soc., 38, 2221 (1916). Lavrukhina, A.K., Malyshev, V.V., Rodin, S.S., Zhur. Vses. Khim., Obshch. in D.I. Mendeleev, 8, 227 (1963). Lee, J., Hussey, D. F., Foutch, G. L., In Ion exchange at the Millennium (J. A. Greig, ed.), 61, Imperial College Press, London. (2000).

- 173 - REFERENCES M. Khalil

Lehmann, M., Zouboulis, A.I., Matis, K.A., Environ. Pollut., 113, 121 (2001). Lehto, J., Harjula, R., In Ion Exchange Developments and Applications (J. A. Greig, ed.), 234, The Royal Society of Chemistry, Cambridge (UK). (1996). Lehto, J., Harjula, R., React. Funct. Polym., 27, 121, (1995). Lehto, J., Paajanen, A., Harjula, R., J. Radioanal. Nucl. Chem. Lett., 164, 39 (1992). Leinonen, H., Lehto, J., Waste Manage. Res., 19, 45 (2001). Liberti, L., Passino, R., in: J.A. Marinsky, Y. Marcus (Eds.), Ion Exchange and Solvent Extraction, vol. 7, Marcel Dekker, Inc., NewYork, Chapter3, (1977). Lin, S. H., Wu, C. L., Water Res., 30, 1851 (1996). Little, T., In Ion Exchange Developments and Applications (J. A. Greig, ed.), 90, The Royal Society of Chemistry, Cambridge (UK) (1996). Marageh, M.G., Husaina, S.W., Khanchi, A.R., Appl. Radiat. Isotopes, 50, 459 (1999). Malinovskii, E.K.; Sivalov, E.G., J. Appl. Chem- USSR+, 65, 2267 (1992). Malkoc, E., Nuhoglu, Y., J. Hazard. Mater., 135, 328 (2006). Mardan, A., Ajaz, R., Mehmood, A., Raza, S.M., Ghaffar, Abdul, Sep. purif. Technol., 16, 147 (1999). Martins, J. Costa, C. Loureiro, J. Rodrigues, A. In Ion Exchange Technology (D. Naden, M. Streat, eds.), 715, Ellis Horwood, Chichester (1984). Maruyama, Y., Jpn. Anal., 13, 956 (1964). Mavrov, V., Chmiel, H., Heitele, B., Rogener, F., Desalination, 108, 159 (1997). McLaren, J., Farquhar, G.J., J. Environ. Eng. Div., 4, 429 (1973).

- 174 - REFERENCES M. Khalil

Melling, J., West, D.W. In Ion Exchange Technology (D. Naden, M. Streat, eds.), 724, Ellis Horwood, Chichester (1984). Merritt, W.F., Can. J. Chem., 36, 425 (1958). Meyer, K.H., Strauss, W., Helv. Chim. Acta, 23, 795 (1940). Miesiac, I., Przemysl Chemiczny, 82, 1045 (2003). Miller H.S., Kline, G.E., J. Am. Chem. Soc., 73, 2741 (1951). Miller, J.E., Brown, N.E., Krumkans, J.L., Trudell, D.E., Anthony, R.G., Mimura, H., Lehto, J., Harjula, R., J. Nucl. Sci. Technol., 34, 484 (1997). Mimura, H., Yamagishi I., Akiha, K., Tohoku Daigaku Senko Seiren Kenkyusho Iho, 44, 1 (1988). Mindler, A.B., Paulson, C., National Meeting of the American Institute of Mining and Metallurgical Engineers, Los Angeles, Calif, (1953). Misak, N.Z., El-Naggar, I.M., React. Polym., 10, 67 (1989). Mishio, N., Kamoshida, A., Kadoya S., Ishihra, T., J. Atom. Energ. Soc. Jpn., 6, 1 (1964). Mohan, D., Chander, S., J. Colloid Interface Sci., 299, 57 (2006). Mohan, D., Singh, K.P., Water Res., 36, 2304 (2002). Möller, T., Clearfield, A., Harjula, R., Micropor. Mesopor. Mat., 54, 187 (2002). Moon, Jei-Kwon, Kim, Ki-Wook, Jung, Chong-Hun, Shul, Yong-Gun, Lee, Eil-Hee, J. Radioanal. Nucl. Chem., 246, 299 (2000). Mulik, J.D., Sawicki, E., Environ. Sci. Technol., 13, 804 (1975) Nabi, S.A., Naushad, Mu., Bushra, R., Chem .Eng. J., 152, 80 (2009). Nabi, S.A., Shalla, A.H., J. Hazard. Mater., 163, 657 (2009). Nakamura, S., Mori, S., Yoshimuta, H., Ito, Y., Kanno, M., Sep. Sci. Technol., 23, 731 (1988). Nakanishi, T., Higuchi, N., Nomura, M., Aida, M., Fujii, Y., J. Nucl. Sci. Technol., 33, 341 (1996). Netpradit, S., Thiravetyan, P., Towprayoon, S., Water Res., 38, 71 (2004).

- 175 - REFERENCES M. Khalil

Niday, J.B., Phys. Rev., 98, 42 (1955). Nilchi, A., Khanchi, A., Atashi, H., Bagheri, A., Nematollahi, L., J. Hazard. Mater., 137, 1271 (2006). Palacios, V. M., Caro, I., Perez, L., Adsorption, 7, 131 (2001). Pandit, B., Chudasma, U., Bull. Mater. Sci., 24, 265 (2001) Paulling, L., J. Am. Chem. Soc., 51, 1010 (1929). Perlov, A. V., Legenchenko, I. A., J. Appl. Chem-USSR+, 63, 662, (1990). Perry, R.H., Green, D.W., Perry’s Chemical Engineer’s Handbook, 7th ed. McGraw-Hill, New York, pp. 16.12 (1997). Philipp, G., Schmidt, H., J. Non-Cryst. Solids, 63, 283 (1984). Popat, K. M., Anand, P. S., Dasare, B. D., React. Polym., 23, 23 (1994). Prout, W.E., E.R. Russell and H.J. Groh, J. Inorg. Nucl. Chem., 27, 473 (1965). Qian, P., Schoenau, J.J., Can. J. Soil Sci., 82, 9 (2002). Qureshi, M., Ahmed, A., Solv. Extr. Ion Exch., 4, 823 (1988). Qureshi, M., Gupta, J. P., Sharma, V., Talanta, 21, 102 (1974). Rao, C.N.R., J. Mol. Struct., 292, 229 (1993). Rawat, J.P., Ansari, A.A., Singh, R.P., Colloid. Surface. A, 50, 207 (1990). Rawat, J.P., Igbal, M., Ann. Chim., 431 (1981). Reichenberg, D., J. Am. Chem. Soc., 75, 589 (1953). Rumpler, A., Inttern. Kongr. f. angrew Chem., Berlin 59 (1903). Ruthven, D.M,. Principles of Adsorption and Desorption Processes, Wiley, New York, (1984). Sag, Y., Actay, Y., Proc. Biochem., 36, 1187 (2001). Samanta, S.K., Theyyunni, T.K., Misra, B.M., J. Nucl. Sci. Technol., 32, 425 (1995). Samuelson, O., Ion Exchange Separations in Analytical Chemistry, Almqvist & Wiksell Wiley, New York (1963). Sauer R., Scheibe, F., Z. Chem., 2, 312 (1962).

- 176 - REFERENCES M. Khalil

Sawhney, B.L., Proc. Soil Sci. Soc. Am., 29, 25 (1965). Scheckel, K.G., Sparks, D.L., Soil Sci. Soc. Am. J., 65, 719 (2001). Schick, R., Reiche, G., Zuckerindustrie, 120, 1037 (1995). Schmuckler, G., Golstein, S., in: J.A. Marinsky, Y. Marcus (Eds.), Ion Exchange and Solvent Extraction, vol. 7, Marcel Dekker, Inc., New York, Chapter 1, (1977). Sebesta, F., J. Radioanal. Nucl. Chem., 220, 77 (1997). Shabana, E.I., Misak, N.Z., Abe, M., Kataoka, I., Suzuki T., New Development in Ion Exchange, Kodansha/Elsevier, (Eds.), Tokyo/Amsterdam, 211 (1991). Shady, S.A., El-Gammal, B., Colloid. Surface. A, 268, 7 (2005). Shady, S.A., J. Hazard. Mater., 167, 947 (2009). Shahbandeh, M.R., Streat, M., J. Chem. Tech. Biotechnol., 32, 580 (1982). Sheha, R.R., Metwally, E., J. Hazard. Mater., 143, 354 (2007). Sherman, J.D., Proceedings of the National Academy of Sciences of the United States of America, 96, 3471 (1999). Shpeizer, B.G., Bakhmoutov, V.I., Zhang, P., Prosvirin, A.V., Dunbar, K.R., Thommes, M., Clearfield, A., Colloid. Surface. A, 357, 105 (2010). Shrivastava, O.E, Komarneni S., Malla, E., Mat. Res. Bull., 26, 357 (1991). Shrma, H.D., Ruis, R.E., J. Phys. Chem., 74, 696 (1961). Shuey, C.D., In Separation Processes in Biotechnology (J. A. Asenjo, ed.), 263, Marcel Dekker, New York (1990). Siddiqui, W.A., Khana, S.A., Inamuddin, J. Colloid. Surface. A, 295, 193 (2007). Silva, F. R. C., Santana, C. C., Appl. Biochem. Biotechnol., 84, 1063 (2000).

- 177 - REFERENCES M. Khalil

Singh, D.K., Bhatnagar, R.R., Darbari, A., Indian J. Technol., 24, 25 (1986). Singh, R.E., Pambid, E.R., Abbas, N.M., Proceedings of the First Saudi Symposium on Energy Utilization and Conservation, Jeddah, Saudi Arabia, 4, 483 (1990). Singh, T.S., Pant, K.K., Sep. Purif. Technol., 48, 288 (2006). Sinha, V., Li, K. Desalination, 127, 155 (2000). Smit, J. van, R., Nature, 181, 1530 (1958). Smit, J. van R., Robb W., Jacobs, J.J., J. Inorg. Nucl. Chem., 12, 104 (1959). Sohn, S., Kim, D., Chemosphere, 58, 115 (2005). Soldatov, V. S., Peryshkina, N. G., Khoroshko, R. P., Vasileva, V. F., Zenchik, L. V., Agrokhimiya, 1, 85 (1972). Stejskal, J., Gilbert, R.J., Pure Appl. Chem., 74, 857 (2002). Sugihara, T.T., James, H.I., Troianello E.J., Bowen, V.T., Anal. Chem., 31, 44 (1959). Sundell, A.M.; Stenlund, B., Journal of Control. Release, 72, 300 (2001). Tabata, T., Ohtsuka, H., Kokitsu, M., Okada, O., Bull. Chem. Soc. Jpn., 68, 1905 (1995). Takeda, H.. Iwamoto, M., Bull. Chm. Soc. Jpn., 69, 2735 (1996). Thompson, H.S., Roy, J., Agr. Soc. Eng., 11, 68 (1850). Thompson, R., Paleologou, M., Jemaa, N., Berry, R., Brown, C., Sheedy, M., Pulp Pap. Canada, 101, 63 (2000). Topp, N. E., Pepper, K. W., J. Am. Chem. Soc., 3299 (1949). Trantera, T.J., Herbsta, R.S., Todda, T.A., Olsona, A.L., Eldredge, H.B., Adv. Environ. Res., 6, 107 (2002). Treybal, R.E., Mass Transfer Operations, McGraw-Hill, New York, (1987). Tsitsishvili, G.V., Skhirtladze, N.S., Andronikashvili, T.G., Tsitsishvili, V.G., Dolidze, A.V., 125, 715. (1999).

- 178 - REFERENCES M. Khalil

Tsubota, H., Bull. Chem. Soc. Jpn., 36, 1038 (1963). Tsukamoto, T., Oi, T., Hosoe, M., Kakihana, H., Isotopenpraxis, 27, 90 (1991). Turan, M., Celik, M. S., J. Water Supply Res. T., 52, 59 (2003). Vaaramaa, K., Lehto, J., Desalination, 155, 157 (2003). Vaaramaa, K., Lehto, J., Jaakkola, T., Radiochim. Acta, 88, 361 (2000). Valderrama C., Gamisans, X., de las Heras, X., Farran, A., Cortina, J.L., J. Hazard. Mater., 157, 386 (2008). Valentini, M.T.G., Maxia, V., Meloni, S., Rollier, A., Gazz. Chim. Ital., 103, 205 (1973). Valsala, T.P., Roy, S.C., Shah, J.G., Gabriel, J., Raj, K., Venugopal, V., J. Hazard. Mater., 166, 1148 (2009). Varshney, K.G., Gupta, P., Agrawal, A., 22nd National Conference in Chemistry, Indian Council of Chemists, I.I.T., Roorkee, (2003). Varshney, K.G., Khan, A.A., Varshney, S.S., Indian J. Chem., 21, 398 (1982). Varshney, K.G., Naheed, S., J. Inorg. Nucl. Chem., 39, 2075 (1977). Varshney, K.G., Pandith, A.H., Chem. Environ. Res., 5, 1 (1996) Varshney, K.G., Rafiquee, M.Z.A., Somya, A., Colloid. Surface. A, 301, 224 (2007). Vassilis J. Inglezakis, Helen P. Grigoropoulou, Micropor. Mesopor. Mat., 61, 273 (2003). Vera, E., Ruales, J., Dornier, M., Sandeaux, J., Persin, F., Pourcelly, G., Vaillant, F., Reynes, M., J. Food Eng., 59, 361 (2003). Vermeulen, T., Ind. Eng. Chem., 45, 1664 (1953). Viard, V., Lameloise, M. L., J. Food Eng., 17, 29 (1992). Vulikh, A.I., Ion-Exchange Synthesis, Khimiya, Moscow (1973). Walker, G.M., Weatherley, L.R., Water Res., 33, 1895 (1999). Walton, H.F., Anal. Chem., 48, 52 (1976) Wang, J.L., Liu, P., Zhou, D., Biotechnol. Tech., 8, 905 (1994).

- 179 - REFERENCES M. Khalil

Wang, J.L., Wen, X.H., Zhou, D., Bioresource Technol., 75, 231 (2000). Warshawsky, A., In Ion Exchange Technology (D. Naden, M. Streat, eds.), 604, Ellis Horwood, Chichester (1984). Way, J.T., Agr. Soc. Eng., 11, 313 (1850). Weber, W.J., Morris, J.M., J. Sanitary Eng. Division –ASCE 89, 31 (1963). Weber, W.J., Smith, E.H., Environ. Sci. Technol., 21, 1040 (1987). Wiegner, G., J. Land Wirisch, 60, 111(1912). Wingefors, S., Persson G., Liljenzin, J.O., Radioact. Waste Manag. Nucl. Fuel Cycle, 5, 327 (1984). Yoshida, H., Kataoka, T., Ikeda, S., Can. J. Chem. Eng., 63, 422 (1985). Zakaria E.S., El-Naggar, I.M., Colloid. Surface. A, 131, 33 (1998). Zakaria, E.S., Ali, I.M., Aly, H.F., Adsorption, 10, 45 (2004). Zakaria, E.S., Ali, I.M., Aly, H.F., J. Colloid. Interf. Sci., 338, 346 (2009). Zakaria, E.S., Ali, I.M., Aly, H.F., J. Radianal. Nucl. Chem., 260, 389 (2004). Zakaria, E.S., Ali, I.M., El-Naggar, I.M., Colloid. Surface. A, 210, 33 (2002). Zakaria, E.S., Arab J. of Nucl. Sci. Appl., 36, 137 (2003). Zhao, X., Höll, W. H., Yun, G. H., Water Res., 36, 851, (2002).

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ﺍﻝﺘﺒﺎﺩل ﻓﻰ ﺍﻝﻭﺴﻁ ﺍﻝﺤﺎﻤﻀﻰ ﺍﻋﻠﻰ ﻤﻨﻬﺎ ﻓﻰ ﺍﻝﻭﺴﻁ ﺍﻝﻘﻠﻭﻯ، ﻤﻤﺎ ﻴﺩل ﻋﻠﻰ ﺍﻨﻪ ﻤﻥ ﺍﻝﻤﻤﻜﻥ ﺍﺴﺘﺨﺩﺍﻡ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻓﻰ ﺍﻝﻭﺴﻁ ﺍﻝﺤﺎﻤﻀﻰ ﻝﻔﺼل ﺍﻝﺴﻴﺯﻴﻭﻡ . . ﺍﻝﺠﺯﺀ ﺍﻝﺴﺎﺩﺱ: ﻓﻰ ﻫﺫﻩ ﺍﻝﺩﺭﺍﺴﺔ ﺘﻡ ﺘﺤﻀﻴﺭ ٠.٠١ ﻤﻭﻝﺭ ﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻓﻰ ﺍﻝﺤﻠﻴﺏ، ﺜﻡ ﺤﻘﻨﻪ ﺒﺎﻝﺴﻴﺯﻴﻭﻡ-١٣٤ ﺍﻝﻤﺸﻊ ﻭﺩﺭﺍﺴﺔ ﻜﻴﻨﺎﺘﻴﻜﻴﺔ ﺍﻝﺘﻔﺎﻋل ﻋﻠﻴﻪ ﻝﻤﺩﺓ ٢ ﺴﺎﻋﺎﺕ، ﻭﺠﺩ ﻋﻨﺩ ٦٠ ﺩﻗﻴﻘﺔ ﻜﺎﻥ ﺍﻤﺘﺼﺎﺹ ﺍﻝﺴﻴﺯﻴﻭﻡ ٨٠%، ﺜﻡ ﺘﻡ ﺍﻻﺘﺯﺍﻥ ﻋﻨﺩ ﺴﺎﻋﺎﺘﺎﻥ. ﻫﺫﺍ ﻤﻤﺎ ﻴﻌﺩ ﺒﻤﺴﺘﻘﺒل ﻫﺎﻡ ﻝﻠﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻓﻰ ﻤﺠﺎﻻﺕ ﻤﺘﻌﺩﺩﺓ ﺫﺍﺕ ﺃﻫﻤﻴﻪ ﺘﻁﺒﻴﻘﻴﻪ . .

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ﻭﻗﺩ ﺘﻡ ﺩﺭﺍﺴﺔ ﺍﻤﺘﺼﺎﺹ ﺃﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻋﻠﻰ ﻜﻼ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ o ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻋﻨﺩ ﺩﺭﺠﺎﺕ ﺤﺭﺍﺭﻩ ٢٥، ٤٥، ٦٠ ﻡ ﻋﻨﺩ ﺘﺭﻜﻴﺯﺍﺕ ﻤﺨﺘﻠﻔﻪ، ﻭﺘﻡ ﺘﻁﺒﻴﻑ ﻜﻼ ﻤﻥ ﻤﻌﺎﺩﻻﺕ ﻻﻨﺠﻤﺒﺭ ﻭﻓﺭﻨﺩﻝﻴﺵ ﻭﻭﺠﺩ ﺃﻨﻬﺎ ﺠﻤﻴﻌﻬﺎ ﺨﺎﻀﻌﺔ ﻝﻤﻌﺎﺩﻝﺔ ﻓﺭﻨﺩﻝﻴﺵ ﻋﻨﻬﺎ ﻝﻤﻌﺎﺩﻝﺔ ﻻﻨﺠﻤﻴﺭ . . ﻭﺒﺭﺴﻡ ﺍﻝﻌﻼﻗﻪ ﺒﻴﻥ ﺘﺭﻜﻴﺯﺍﻝﺴﻴﺯﻴﻭﻡﹺ ﻋﻨﺩ ﺍﻻﺘﺯﺍﻥ ﻤﻊ ﻜﻤﻴﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺍﻝﻤﻤﺘﺯ ﻋﻠﻰ ﻜﻼ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻓﺄﻋﻁﺕ ﻋﻼﻗﺎﺕﹶ ﺨﻁﻴﺔﹶ. ﻤﻥ ﻫﺫﻩ ﺍﻝﻨﹶﺘﺎﺌِﺞﹺ ﻴﺘﺄﻜﺩ ﻝﻨﺎ ﺃﻥ ﺍﻤﺘﺼﺎﺹ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻴﻜﻭﻥ ﺍﻭﻻ ﺒﺘﻜﻭﻴﻥ ﻁﺒﻘﺔ ﻭﺍﺤﺩﺓ ﻤﻥ ﺍﻴﻭﻨﺎﺕ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺍﻝﻐﻴﺭ ﻤﺭﺘﺒﻁﺔ ﻴﻠﻴﻪ ﻁﺒﻘﺎﺕ ﻤﺘﻌﺩﺩﺓ ﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺍﻝﻤﺭﺘﺒﻁﺔ ﺴﻭﻴﺎ ﺫﺍﺕ ﺍﻝﻁﺎﻗﺔ ﺍﻝﻤﺘﺒﺎﻴﻨﺔ، ﻤﺼﺤﻭﺒﺎ ﺒﺎﻝﺘﻔﺎﻋل ﺒﻴﻥ ﺍﻝﺠﺯﻴﺌﺎﺕ ﺍﻝﻤﻤﺘﺼﺔ. ﻭﻭﺠﺩ ﺍﻥ ﺴﻌﺔ ﻜﻼ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺘﺯﺩﺍﺩ ﺒﺯﻴﺎﺩﺓ ﺤﺭﺍﺭﺓ ﺍﻝﺘﻔﺎﻋل ﻤﻤﺎ ﻴﺩل ﻋﻠﻰ ﺍﻥ ﺍﻝﺘﻔﺎﻋل ﻤﺎﺹ ﻝﻠﺤﺭﺍﺭﺓ. ﻭﻜﺎﻨﺕ ﺴﻌﺔ ﺘﺒﺎﺩل ﺍﻝﺴﻴﺯﻴﻭﻡ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺍﻋﻠﻰ ﻤﻥ ﺴﻌﺘﻪ ﻋﻠﻰ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ . . ﺍﻝﺠﺯﺀ ﺍﻝﺨﺎﻤﺱ: ﺘﻡ ﺩﺭﺍﺴﻪ ﺍﺴﺘﺨﺩﺍﻡ ﺃﻋﻤﺩﻩ ﻜﺭﻭﻤﺎﺘﻭﺠﺭﺍﻓﻴﻪ ﻤﻤﺘﻠﺌﻪ ﺒﺄﺤﺠﺎﻡ ﻤﺨﺘﻠﻔﺔ ٣ ﻭ ٤ ﺠﺭﺍﻡ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﻤﻭﻀﻪ ﻤﺘﻌﺎﺩﻝﻪ ﻭﺒﺎﺴﺘﺨﺩﺍﻡ ١٤٠ ﻤﻴﻠﺠﺭﺍﻡ/ﻝﺘﺭ ﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ، ﻤﻊ ﻤﻌﺩل ﺴﺭﻴﺎﻥ ٢.٥ ﻤﻴل/ﺩﻗﻴﻘﺔ، ﻭﺘﻡ ﺤﺴﺎﺏ ﺍﻝﺴﻌﺔ ﻝﻜل ﻋﻤﻭﺩ ، ﻭﻗﺩ ﺘﺒﻴﻥ ﻤﻥ ﻫﺫﻩ ﺍﻝﺩﺭﺍﺴﻪ، ﺃﻥ ﺴﻌﺔ ﺍﻝﻌﻤﻭﺩ ﺘﺯﺩﺍﺩ ﺒﺯﻴﺎﺩﺓ ﺍﻝﺤﺠﻡ ﺍﻝﻤﺴﺘﺨﺩﻡ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ، ﻭﺫﻝﻙ ﻨﺘﻴﺠﺔ ﻝﺯﻴﺎﺩﺓ ﺍﻝﻤﻭﺍﻗﻊ ﺍﻝﻔﻌﺎﻝﺔ ﻝﺘﺒﺎﺩل ﺍﻝﺴﻴﺯﻴﻭﻡ، ﻜﻤﺎ ﺍﻨﻪ ﺍﻤﻜﻥ ﺘﺤﺩﻴﺩ ﻨﻭﻋﻴﺔ ﺍﻝﺘﻔﺎﻋل ﺒﺎﺴﺘﺨﺩﺍﻡ ﺍﻝﻌﻤﻭﺩ، ﻭﺫﻝﻙ ﻋﺩ ﺘﻭﻗﻑ ﺍﻝﻌﻤﻭﺩ ﺜﻡ ﺍﻋﺎﺩﺓ ﺘﺸﻐﻴﻠﻪ ﻝﺘﺤﻤﻴل ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﺭﺓ ﺍﺨﺭﻯ . . ﺍﻴﻀﺎ ﺘﻡ ﺤﺴﺎﺏ ﺴﻌﺔ ﺍﻝﺘﺒﺎﺩل ﻻﻴﻭﻨﺎ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺒﺎﺴﺘﺨﺩﺍﻡ ﺍﻝﻌﻤﻭﺩ ﻓﻰ ﺍﻷﻭﺴﺎﻁ ﺍﻝﺤﺎﻤﻀﻴﺔ ﻭﺍﻝﻘﻠﻭﻴﺔ، ﺤﻴﺙ ﺍﺴﺘﺨﺩﻡ ﻤﺤﺎﻝﻴل ﻤﻥ ﺍﻝﻭﺴﻁ ﺍﻝﺤﺎﻤﻀﻰ ﻓﻰ ﻭﺠﻭﺩ ﻤﻠﺢ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻨﻴﺘﺭﺍﺕ ﻤﺜل (١٣ ﻤﻴﻠﺠﺭﺍﻡ /ﻝﻴﺘﺭﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ + ٠.٥ ﻤﻭﻝﺭ ﻤﻥ ﺤﻤﺽ ﺍﻝﻨﻴﺘﺭﻴﻙ +٠.١ ﻤﻭﻝﺭ ﻤﻥ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻨﻴﺘﺭﺍﺕ) ﻭﺃﻴﻀﺎ ﻤﻥ ﺍﻝﻭﺴﻁ ﺍﻝﻘﻠﻭﻯ ﺍﺴﺘﺨﺩﻡ ﻤﺤﻠﻭل ﻤﻥ (١٣ ﻤﻴﻠﺠﺭﺍﻡ/ﻝﻴﺘﺭﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ + ٠.٥ ﻤﻭﻝﺭ ﻤﻥ ﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ +٠.١ ﻤﻭﻝﺭ ﻤﻥ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻨﻴﺘﺭﺍﺕ) ﻭﺍﺴﺘﺨﺩﺍﻡ ١ ﺠﺭﺍﻡ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ، ﻭﻤﻌﺩل ﺍﻝﺴﺭﻴﺎﻥ ٠.٧ ﻤﻴل/ﺩﻗﻴﻘﺔ، ﻭﻭﺠﺩ ﻤﻥ ﻫﺫﻩ ﺍﻝﺩﺭﺍﺴﺔ ﺃﻥ ﺴﻌﺔ

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ﺍﻝﺘﹶﺠﻔﻴﻑ ﻭﻓﺴﺭ ﺫﻝﻙ ﺒﺘﻜﺴﻴﺭ ﺍﻷﻴﻭﻨﺎﺕ ﺍﻝﻤﺴﺘﺒﺩﻝﺔ ﻭﺍﺯﺍﻝﺔ ﻤﻜﻭﻨﺎﺕ ﺍﻝﻬﻴﺩﺭﻭﻜﺴﻴﺩ ﺒﺯﻴﺎﹾﺩﺓ ﺩﺭﺠﺎﺕ ﺤﺭﺍﺭﺓ ﺍﻝﺘﹶﺠﻔﻴﻑ . .

ﻭ ﻗﺩ ﺘﻡ ﺭﺴﻡ ﺍﻝﻌﻼﻗﻪ ﺒﻴﻥ pH ﻝﻠﻤﺤﻠﻭل ﻤﻊ ﻝﻭﻏﺎﺭﺘﻡ ﻤﻌﺎﻤل ﺍﻝﺘﻭﺯﻴﻊ Kd) ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ، ﻭﺍﻷﻴﻭﻨﺎﺕ ﺍﻷﺨﺭﻯ، ﻭ ﻜﺎﻨﺕ ﻋﻼﻗﺔ ﺨﻁﻴﺔ ﻨﺎﺘﺠﺔ ﻋﻥ ﺇﻨﺘﻘﺎﺌﻴﺔ ﻋﺎﻝﻴﺔ ﺠﺩﺍ ﻝﻠﺴﻴﺯﻴﻭﻡ ﺍﺫﺍ ﻤﺎ ﻗﺭﻥ ﺒﺎﻷﻴﻭﻨﺎﺕ ﺍﻷﺨﺭﻯ ﻭﻜﺎﻨﺕ ﺍﻹﻨﺘﻘﺎﺌﻴﺔ ﻓﻰ ﻫﺫﺍ ﺍﻝﺘﺭﺘﻴﺏ : : + 4+ 6+ 5+ 5+ 3+ 2+ 2+ 2+ 2+ Cs > Zr > Mo > V > As > Cr > Co > Cu > Zn > Cd ﻭﻝﺫﺍﻝﻙ ﻤﻥ ﺍﻝﺴﻬﻭﻝﺔ ﻝﺩﻴﻨﺎ ﺍﻥ ﻴﺘﻡ ﺍﻝﻔﺼل ﺍﻝﺜﻨﺎﺌﻰ ﻝﻜل ﻤﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻊ ﺃﻯ ﺍﻴﻭﻥ ﺍﺨﺭ ﻤﺜل Cs –Co, Cs –Zn , Cs –Cd , Cs –Cu, Cs –Cr, Cs –AS, Cs –Zr, Cs –V, Cs – Mo. ﺍﻝﺠﺯﺀ ﺍﻝﺜﺎﻝﺙ: ﻭ ﻗﺩ ﺘﻡ ﺩﺭﺍﺴﺔ ﻜﻴﻨﺎﺘﻴﻜﻴﻪ ﺍﻝﺘﺒﺎﺩل ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻋﻠﻰ ﻜﹸﻼ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺒﻌﺩ ﺘﻬﻴﺌﺔ ﺍﻝﻅﺭﻭﻑ ﺍﻝﻤﻼﺌﻤﺔ ﻝﺩﺭﺍﺴﺔ ﺁﻝﻴﺔ ﺍﻹﻨﺘﺸﺎﺭ ﺩﺍﺨل ﺍﻝﺤﺒﻴﺒﺎﺕ ﻜﻭﺴﻴﻠﺔ ﺘﺠﺎﺭﺏ ﻤﻨﻔﺼﻠﻪ ﻤﺤﺩﺩﻩ ﻭ ﻗﺩ ﺘﻤﺕ ﻫﻨﺎ ﺩﺭﺍﺴﺔ ﺘﺄﺜﻴﺭ ﺤﺠﻡ ﺍﻝﺤﺒﻴﺒﺎﺕ ﻋﻠﻰ ﺴﺭﻋﺔ ﺍﻝﺘﻔﺎﻋل ﻭ ﺘﺄﺜﻴﺭ ﺘﺭﻜﻴﺯﺍﺕ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﺘﻰ ﺘﺤﺘﻭﻯ ﻋﻠﻰ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺍﻝﻤﺴﺘﺒﺩل ﻋﻠﻰ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺘﺄﺜﻴﺭ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﺘﻔﺎﻋل ﻭ ﺃﻴﻀﺎ ﺘﺄﺜﻴﺭ ﺤﺭﺍﺭﺓ ﺍﻝﺘﺠﻔﻴﻑ. ﻭﻗﺩ ﺘﻡ ﺍﻝﺘﻭﺼل ﺍﻝﻰ ﺍﻥ ﺍﻝﺘﻘﻠﻴﺏ ﻭ ﺍﺨﺘﻼﻑ ﺘﺭﻜﻴﺯ ﺍﻷﻴﻭﻥ ﻓﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺨﺎﺭﺠﻰ ﻻ ﺘﺅﺜﺭ ﻋﻠﻰ ﺴﺭﻋﺔ ﺍﻝﺘﻔﺎﻋل، ﻭﻜﻠﻤﺎ ﻗل ﺤﺠﻡ ﺍﻝﺤﺒﻴﺒﺎﺕ ﻝﻠﻤﺘﺒﺎﺩل ﻜﻠﻤﺎ ﺯﺍﺩﺕ ﺴﺭﻋﺔ ﺍﻝﺘﻔﺎﻋل، ﻭﺍﺘﻀﺢ ﻤﻥ ﺘﻠﻙ ﺍﻝﺩﺭﺍﺴﻪ ﺍﻥ ﻤﻌﺩل ﺍﻝﺘﻔﺎﻋل ﻴﺯﺩﺍﺩ ﺒﺯﻴﺎﺩﺓ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﺘﻔﺎﻋل ﻭﻴﻘل ﺒﺯﻴﺎﺩﺓ ﺤﺭﺍﺭﺓ ﺍﻝﺘﺠﻔﻴﻑ. ﻭ

ﻗﺩ ﺘﻡ ﺤﺴﺎﺏ ﻁﺎﻗﺔ ﺍﻝﺘﻨﺸﻴﻁ Ea) ﻭ ﺍﻷﻨﺘﺭﻭﺒﻰ S∆) ﻭ ﺍﻻﻨﺘﺸﺎﺭDo) ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻋﻠﻰ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ . ﻭﻗﺩ ﺘﻡ ﺩﺭﺍﺴﺔ ﺒﻌﺽ ﺍﻷﻨﻅﻤﺔ ﺍﻝﺘﻰ ﺘﻔﺴﺭ ﻤﻴﻜﺎﻨﻴﻜﻴﺔ ﺘﻔﺎﻋل ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻊ ﺍﻝﻤﺒﺎﺩل ﺍﻷﻴﻭﻨﻰ ﻭﻭﺠﺩ ﺍﻥ ﺍﻝﺘﻔﺎﻋل ﻴﺘﺒﻊ ﻨﻅﺎﻡ ﺍﻹﻨﺘﺸﺎﺭ ﺩﺍﺨل ﺍﻝﺤﺒﻴﺒﺎﺕ ﻭﻨﻅﺎﻡ ﺍﻹﻨﺘﺸﺎﺭ ﺍﻝﻤﺘﺠﺎﻨﺱ، ﻤﻤﺎ ﻴﻔﺴﺭ ﺍﻥ ﺃﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻴﻤﺘﺹ ﺨﻼل ﺠﺯﻴﺌﺎﺕ ﻜﻼ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﻝﻴﺱ ﻋﻠﻰ ﺍﻝﺴﻁﺢ ﺍﻝﻬﻼﻤﻰ ﻝﻠﻤﺒﺎﺩﻻﺕ. ﺍﻝﺠﺯﺀ ﺍﻝﺭﺍﺒﻊ:

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ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ، ﻓﻲ ﺩﺭﺠﺎﺕ ﺤﺭﺍﺭﺓ ﺍﻝﺘﹶﺠﻔﻴﻑ ﺍﻝﻤﺨﺘﻠﻔﺔ، ﻭﻭﺠﺩ ﺃﻥ ﺍﻝﻘﻤﻡ ﺍﻝﻤﻤﻴﺯﺓ ﺘﺨﺘﻔﻰ ﺒﺯﻴﺎﺩﺓ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﺘﺠﻔﻴﻑ ﻴﺩل ﻋﻠﻰ ﺘﺤﻠل ﺍﻝﻤﻭﺍﺩ ﺍﻝﻌﻀﻭﻴﺔ ﻤﻥ ﺍﻝﻤﺭﻜﺒﺎﺕ. ﻭﺘﻡ ﺩﺭﺍﺴﺔ ﺤﻴﻭﺩ ﺍﻷﺸﻌﺔ ﺍﻝﺴﻴﻨﻴﺔ ﻋﻠﻰ ﻤﺴﺤﻭﻕ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻋﻨﺩ ﺩﺭﺠﺎﺕ ﺤﺭﺍﺭﺓ ﺘﺠﻔﻴﻑ ﻤﺨﺘﻠﻔﺔ، ﻭﻗﺩ ﻭﺠﺩ ﺘﺒﻠﻭﺭ ﻁﻔﻴﻑ ﻤﻊ ﺍﺭﺘﻔﺎﻉ ﺍﻝﺤﺭﺍﺭﺓ . . ﻭﺒﺎﺴﺘﺨﺩﺍﻡ SEM ﻭﺠﺩ ﺍﻥ ﺼﻭﺭﺓ ﺍﻝﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺘﺨﺘﻠﻑ ﻋﻥ ﺼﻭﺭﺓ ﻜﻼ ﻤﻥ ﺍﻷﻨﻴﻠﻴﻥ ﻭﺍﻝﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺒﺩﺭﺍﺴﺔ ﺍﻝﺘﺤﻠﻴل ﺍﻝﺤﺭﺍﺭﻯ DTATGA ﻭﺠﺩ ﺃﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻝﻬﺎ ﺜﺒﺎﺕ ﺤﺭﺭﺍﺭﻯ. ﻭﻭﺠﺩ ﺍﻥ ﻫﺫﻩ ﺍﻝﻤﻭﺍﺩ ﻝﻬﺎ ﺜﺒﺎﺕ ﻜﻴﻤﻴﺎﺌﻰ ﻤﺭﺘﻔﻊ ﻓﻲ ﻜﻼ ﻤﻥ ﺍﻝﻤﺎﺀ، ﻭ ﺃﺤﻤﺎﺽ ﺍﻝﻨﻴﺘﺭﻴﻙ ﻭﺍﻝﻬﻴﺩﺭﻭﻜﻠﻭﺭﻴﻙ ﻭﻫﻴﺩﺭﻭﻜﺴﻴﺩ ﺍﻝﺼﻭﺩﻴﻭﻡ ، ﻭﺍﻴﻀﺎ ﺩﺭﺠﺔ ﺫﻭﺍﺒﺎﻨﻬﺎ ﻓﻰ ﺍﻝﻨﻴﺘﺭﻴﻙ ﺃﻋﻠﻰ ﻤﻥ ﺍﻝﻬﻴﺩﺭﻭﻜﻠﻭﺭﻴﻙ، ﻭﻀﻌﻴﻑ ﺠﺩﺍ ﻓﻲ ﺍﻝﻘﻠﻭﻴﺎﺕ، ﻭﻝﻴﺱ ﻫﻨﺎﻙ ﺫﻭﺒﺎﻥ ﻓﻰ ﺍﻝﻤﺎﺀ. ﻭﻤﻨﺤﻨﻰ ﺍﻝﻤﻌﺎﻴﺭﺓ ﻝﻠﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺍﻋﻁﻰ ﻗﻤﺔ ﻭﺍﺤﺩﺓ ﻭﻫﺫﺍ ﻴﺩل ﻋﻠﻰ ﺃﻨﻪ ﻤﺒﺎﺩل ﻜﺘﻴﻭﻨﻰ ﺃﺤﺎﺩﻱ ﺍﻝﺤﺎﻤﻀﻴﺔ . ﻭﺠﺩ ﺍﻥ ﺴﻌﺔ ﺍﻝﺘﺒﺎﺩل ﺍﻵﻴﻭﻨﻲ ﻝﻠﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻴﺯﺩﺍﺩ ﺒﺯﺒﺎﺩﺓ pH ﻓﻰ ﺍﻝﻤﺤﻠﻭل ﺍﻝﺘﻰ ﺘﺴﺎﻋﺩ ﻋﻠﻰ ﺴﻬﻭﻝﺔ ﺨﺭﻭﺝ ﺍﻴﻭﻥ ﺍﻝﻬﻴﺩﻭﺭﺠﻴﻥ ﻤﻥ ﺍﻝﻤﺒﺎﺩل ﺍﻷﻴﻭﻨﻰ، ﻭﻜﺎﻨﺕ ﺴﻌﺔ ﺃﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻝﻠﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻫﻰ ١.٨٢ ﻭﺯﻥ ﻤﻜﺎﻓﻰﺀ ﻝﻜل ﺠﺭﺍﻡ. ﻭﻗﺩ ﺘﻡ ﺘﺤﺩﻴﺩ ﺍﻝﺘﺤﻠﻴل ﺍﻝﻌﻨﺼﺭﻯ ﻝﻠﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﻭﺠﺩ ﺃﻨﻪ

[(TiO2)(WO3) (C6H4NH)]. 2.46 H2O ﺍﻝﺠﺯﺀ ﺍﻝﺜﺎﻨﻰ : :

2+ + ﻭﻫﻨﺎ ﻗﺩ ﺘﻡ ﺘﻘﻴﻴﻡ ﺍﻝﺘﺒﺎﺩل ﻝﻠﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻝﻌﺸﺭﺓ ﺃﻴﻭﻨﺎﺕ Co , Cs, 6+ 5+ 5+ 4+ 3+ 2+ 2+ 2+ Mo ,Va ,As ,Zr ,Cr ,Cu ,Cd ,Zn) ﻝﻤﻌﺭﻓﺔ ﻗﺩﺭ ﺘﻪ ﻝﻔﺼل ﻫﺫﻩ ﺍﻷﻴﻭﻨﺎﺕ ﻤﻊ ﺍﺨﺘﻼﻑ pH . ﻭﺃﻭﻀﺤﺕ ﺩﺭﺍﺴﺔ ﻤﻌﺎﻤل ﺍﻝﺘﻭﺯﻴﻊ ﺃﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻝﻪ ﻗﺩﺭﺓ ﻋﺎﻝﻴﺔ ﻷﻨﺘﻘﺎﺌﻴﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﺩﻭﻥ ﺒﺎﻗﻰ ﺍﻷﻴﻭﻨﺎﺕ. ﻭﻭﺠﺩ ﺃﻥ ﻤﻌﺎﻤﻼﺕ ﺍﻝﺘﻭﺯﻴﻊ ﺘﺯﺩﺍﺩ ﺒﺯﻴﺎﹾﺩﺓ pH ﻓﻰ ﺍﻝﻤﺤﻠﻭلِ. ﻭ ﻜﺎﻨﺕ ﻋﻤﻠﻴﺔ o ﺍﻝﺘﺒﺎﺩل ﺘﺯﺩﺍﺩ ﺒﺯﻴﺎﺩﺓ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻝﺘﻔﺎﻋل ﻤﻥ ٢٥ ﺍﻝﻰ ٦٠ ± ١ ﻡ ﻤﻤﺎ ﻴﻌﻨﻰ ﺃﻥ ﻋﻤﻠﻴﺔ ﺍﻝﺘﺒﺎﺩل ﺍﻷﻴﻭﻨﻰ ﻫﻰ ﻋﻤﻠﻴﻪ ﻤﺎﺼﻪ ﻝﻠﺤﺭﺍﺭﻩ، ﻭﻭﺠﺩ ﺃﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺃﻓﻀل ﻤﻥ

ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻓﻰ ﺇﻨﺘﻘﺎﺌﻴﺘﻪ ﻝﻠﺴﻴﺯﻴﻭﻡ ، ﻭﻭﺠﺩ ﺃﻥ ﻗﻴﻡ Kd ﺍﻨﺨﻔﻀﺕ ﺒﺯﻴﺎﹾﺩﺓ ﺩﺭﺠﺎﺕ ﺤﺭﺍﺭﺓ

٣ ا ا ى

ﻓﻰ ﻫﺫﻩ ﺍﻝﺭﺴﺎﻝﺔ ﻭﺍﺴﺘﺨﺩﺍﻤﺔ ﻓﻰ ﺍﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ، ﻭﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﻤﺸﻌﺔ، ﻭﺃﻴﻀﺎ ﻤﻥ ﺍﻝﺤﻠﻴﺏ ﻭ ﻜﺫﻝﻙ ﺍﻴﻀﺎﺡ ﻓﻜﺭﻩ ﺸﺎﻤﻠﻪ ﻋﻥ ﺍﻝﻐﺭﺽ ﻤﻥ ﺍﻝﺒﺤﺙ. ﺍﻝﻔﺼل ﺍﻝﺜﺎﻨﻲ ﺍﻝﻌﻤﻠﻰ : :

ﻭﻗﺩ ﺍﺸﺘﻤل ﻫﺫﺍ ﺍﻝﺠﺯﺀ ﻋﻠﻰ ﻭﺼﻑ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﻪ ﺍﻝﻤﺴﺘﺨﺩﻤﻪ ﻭﺩﺭﺠﻪ ﻨﻘﺎﻭﺘﻬﺎﹸ، ﺒﺎﻹﻀﺎﻓﺔ ﺇﻝﻰ ﺍﻝﻁﺭﻕ ﺍﻝﻤﺴﺘﺨﺩﻤﻪ ﻝﺘﺤﻀﻴﺭﹺ ﺍﻝﻤﻭﺍﺩ ﺍﻝﻤﺸﻌﺔ. ﻭﻜﺫﻝﻙ ﻭﺼﻑ ﺍﻷﺠﻬﺯﻩ ﺍﻝﻤﺴﺘﺨﺩﻤﻪ ﻭﻁﺭﻕ ﺍﻝﺘﺤﻠﻴل ﺍﻝﻜﻴﻤﻴﺎﺌﻴﻪ ﺍﻝﻤﺴﺘﺨﺩﻤﻪ ﻓﻲ ﻫﺫﺍ ﺍﻝﻌﻤل. ﺃﻴﻀﺎ ﺍﺸﺘﻤل ﻫﺫﺍ ﺍﻝﺠﺯﺀ ﻋﻠﻰ ﻭﺼﻑ ﺩﻗﻴﻕ ﻝﺘﺤﻀﻴﺭ ﻜل ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻋﻨﺩ ﺍﻝﻅﺭﻭﻑ ﺍﻝﻤﺨﺘﻠﻔﺔ. ﻭﻜﻴﻔﻴﺔ ﺤﺴﺎﺏ ﺴﻌﺔ ﻫﺫﻩ ﺍﻝﻤﺎﺩﺓ ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻭﺃﺨﻴﺭﺍ ﺘﻀﻤﻥ ﻫﺫﺍ ﺍﻝﺒﺎﺏ ﻭﺼﻑ ﺍﻝﻌﻤﻭﺩ ﺍﻝﻜﺭﻭﻤﻭﺘﻭﺠﺭﺍﻓﻰ ﺍﻝﻤﺴﺘﺨﺩﻡ ﻭﺍﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺍﻝﺤﻠﻴﺏ ﺍﻝﻤﻠﻭﺙ . . ﺍﻝﻔﺼل ﺍﻝﺜﺎﻝﺙ ﺍﻝﻨﺘﺎﺌﺞ ﻭ ﻤﻨﺎﻗﺸﺘﻬﺎ : :

ﻭﻓﻴﻪ ﺘﻡ ﺍﺴﺘﻌﺭﺍﺽ ﺍﻝﻨﺘﺎﺌﺞ ﺍﻝﺘﻰ ﺘﻡ ﺍﻝﺤﺼﻭل ﻋﻠﻴﻬﺎ ﻭ ﻤﻨﺎﻗﺸﺘﻬﺎ، ﻭﻴﺤﺘﻭﻯ ﻫﺫﺍ ﺍﻝﻔﺼل ﻋﻠﻰ ﺴﺘﺔ ﺃﺠﺯﺍﺀ ﺭﺌﻴﺴﻴﺔ ﻭﻫﻲ : : ﺍﻝﺠﺯﺀ ﺍﻷﻭل : :

ﺘﻡ ﺃﻭﻻ ﺘﺤﻀﻴﺭ ﺍﻝﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﻜﻤﺎﺩﺓ ﻫﻼﻤﻴﺔ ﺨﻀﺭﺍﺀ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ. ﻭ ﺜﺎﻨﻴﺎ ﺘﻡ ﺘﺤﻀﻴﺭ ﺭﺍﺴﺏ ﺃﺒﻴﺽ ﻤﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺫﻝﻙ ﺒﺈﻀﺎﻓﺔ ١ ﻤﻭﻝﺭ ﻤﻥ ﻜﻠﻭﺭﻴﺩ ﺍﻝﺘﻴﺘﺎﻨﻴﻭﻡ ﺍﻝﻰ ١ ﻤﻭﻝﺭ ﻤﻥ ﺘﻨﺠﺴﺘﺎﺕ ﺍﻝﺼﻭﺩﻴﻭﻡ ﻋﻨﺩ ٦٥ ± ١ ﺩﺭﺠﺔ ﻤﺌﻭﻴﺔ، ﺜﻡ ﺍﻀﺎﻓﺔ ﺍﻝﻤﺎﺩﺓ ﺍﻝﻬﻼﻤﻴﺔ ﻤﻥ ﺍﻝﺒﻭﻝﻲ ﺃﻨﻴﻠﻴﻥ ﺍﻝﻰ ﺍﻝﺭﺍﺴﺏ ﺍﻷﺒﻴﺽ ﻤﻥ ﺍﻝﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻭﺨﻠﻁﻬﺎ ﺒﺸﻜل ﺘﺎﻡ ﺜﻡ ﺘﺭﺸﻴﺤﻬﺎ ﻭﻭﻀﻌﻬﺎ ﻓﻰ ﺍﻝﻔﺭﻥ ﻋﻨﺩ o ٦٠ ﻡ ﻝﺘﺠﻑ، ﺜﻡ ﻏﺴﻠﻬﺎ ﺒﺎﻝﻤﺎﺀ ﺍﻝﻤﻘﻁﺭ ﻋﺩﺓ ﻤﺭﺍﺕ ﻝﺘﺨﻠﺹ ﻤﻥ ﺍﻝﺸﻭﺍﺌﺏ ﺜﻡ ﻏﺴﻠﻬﺎ ﺏ٠.٠١ ﻤﻭﻝﺭ ﻤﻥ ﺤﻤﺽ ﺍﻝﻨﻴﺘﺭﻴﻙ ﻝﺘﺤﻭﻴﻠﻬﺎ ﺍﻝﻰ ﺼﻭﺭﺘﻬﺎ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻨ .ﻪ ﻭﺍﻝﻌﻤل ﺒﺎﻝﻤﺜل ﻤﻊ ﺍﻝﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺎﺩﺓ ﻏﻴﺭ ﻋﻀﻭﻴﺔ . . ﺜﻡ ﺘﻡ ﺩﺭﺍﺴﺔ ﺍﻝﺨﻭﺍﺹ ﺍﻝﻜﻴﻤﻴﺎﺌﻴﻪ ﻭﺍﻝﻔﻴﺯﻴﺎﺌﻴﻪ ﻝﻠﻤﻭﺍﺩ ﺍﻝﻤﺤﻀﺭﺓ ﻭﺫﻝﻙ ﺒﺎﺴﺘﺨﺩﺍﻡ ﺍﻷﺸﻌﻪ ﺘﺤﺕ ﺍﻝﺤﻤﺭﺍﺀ ﻭﺍﻝﺴﻴﻨﻴﻪ ، ﺍﻝﺘﺼﻭﺒﺭ ﺍﻝﻤﻴﻜﺭﺴﻜﻭﺒﻰ (SEM ،) ﻁﺭﻕ ﺍﻝﺘﺤﻠﻴل ﺍﻝﺤﺭﺍﺭﻯ DTA TGA ﻭ ﺍﻝﻤﻌﺎﻴﺭﺓ ﺍﻝﻬﻴﺩﺭﻭﺠﻴﻨﻴ ﺔ ﻭ ﺍﻝﺴﻌﺔ ﻭﺃﻴﻀﺎ ﺍﻝﺜﺒﺎﺕ ﺍﻝﻜﻴﻤﻴﺎﺌﻲ . . ﻭﻗﺩ ﻭﺠﺩ ﺃﻥ ﺃﻁﻴﺎﻑ ﺍﻝﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺘﺤﺘﻭﻯ ﻋﻠﻰ ﺍﻷﻨﻴﻠﻴﻥ ﻤﻤﺎ ﻴﺩل ﻋﻠﻰ ﺃﻥ ﺍﻝﺒﻭﻝﻴﻤﺭ ﺍﺭﺘﺒﻁ ﺒﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ. ﻭﻗﺩ ﺘﻡ ﺩﺭﺍﺴﺔ ﻁﻴﻑ ﺍﻻﺸﻌﻪ ﺘﺤﺕ ﺍﻝﺤﻤﺭﺍﺀ ﻝﻠﺒﻭﻝﻲ ﺁﻨﻠﻴﻥ ٢ ا ا ى

ﺍﻝﻤﻠﺨﺹ ﺍﻝﻌﺭﺒﻰ

ﺃَﺼﺒﺤﺕ ﺇﺩﺍﺭﺓ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﻤﺸﻌﺔ ﻗﻀﻴﺔ ﻋﻅﻴﻤﺔ ﺍﻷﻫﻤﻴﺔ، ﺨﺼﻭﺼﺎﹰ ﻓﻴﻤﺎ ﻴﺘﻌﻠﻕ ﺒﺎﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﺴﺎﺌﻠﺔ ﻓﻲ ﺍﻝﺒﻴﺌﺔ. ﻫﺫﺍ ﺍﻝﻨﻭﻉ ﻤﻥ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﺴﺎﺌﻠﺔ ﻴﻤﻜﻥ ﺃَﻥ ﻴﻌﺎﻝﺞ ﺒﺎﺴﺘﻌﻤﺎل ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﺍﻝﺼﻠﺒﺔ، ﺤﻴﺙ ﺃﻥ ﻫﺫﻩ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﺘﹸﺭﻜﹼﺯ ﺍﻷﻨﻭﻴﺔ ﺍﻝﻤﺸﻌﺔ ﻓﻲ ﺤﺠﻭﻡ ﺼﻐﻴﺭﺓ ﻤﻥ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﺼﻠﺒﺔ . ﻴﻌﺘﺒﺭ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﺭﺌﻴﺴﻴﺔ ﺍﻝﻤﺸﻌﺔ ﺍﻝﻨﺎﺘﺠﺔ ﻋﻥ ﺍﻝﺘﺠﺎﺭﺏ ﺍﻝﻨﻭﻭﻴﺔ ﻭﺍﻝﻤﻔﺎﻋﻼﺕ ﺍﻝﺫﺭﻴﺔ ﻭﺇﻨﺘﺎﺝ ﺍﻝﻨﻅﺎﺌﺭ ﺍﻝﻤﺸﻌﺔ ﺍﻝﺘﻰ ﺘﺴﺘﺨﺩﻡ ﻓﻰ ﺍﻝﺘﻁﺒﻴﻘﺎﺕ ﺍﻝﻤﺨﺘﻠﻔﺔ ﺤﻴﺙ ﺃﻨﻪ ﻤﻭﺠﻭﺩ ﻓﻲ ﺤﺠﻭﻡ ﻋﺎﻝﻴﺔ ﻤﻥ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﻤﺸﻌﺔ ﺍﻝﺴﺎﺌﻠﺔ . ﻭﻝﺫﻝﻙ ﺘﻡ ﺘﻭﺠﻴﻪ ﺍﻹﻫﺘﻤﺎﻡ ﻝﻤﻌﺎﻝﺠﺔ ﻤﺜل ﺘﻠﻙ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺸﺩﻴﺩﺓ ﺍﻝﺨﻁﻭﺭﺓ ﻋﻠﻰ ﺍﻝﺒﻴﺌﺔ ﻭﺍﻝﺘﺨﻠﺹ ﻤﻨﻬﺎ ﻭﺍﻝﺘﺤﻔﻅ ﻋﻠﻴﻬﺎ ﻓﻰ ﺃﻓﻀل ﺼﻭﺭﺓ ﺁﻤﻨﺔ ﺒﺤﻴﺙ ﻻ ﻴﺘﻌﺩﻯ ﻀﺭﺭﻫﺎ ﺇﻝﻰ ﺍﻝﺒﻴﺌﺔ ﺍﻝﻤﺤﻴﻁﺔ. ﻝﺫﻝﻙ ﺘﻬﺩﻑ ﺍﻝﺭﺴﺎﻝﺔ ﺇﻝﻰ ﺇﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺍﻝﻤﺤﺎﻝﻴل ﺍﻝﻤﺎﺌﻴﺔ ﻭﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﻤﺸﻌﺔ ﻭ ﺍﻝﺤﻠﻴﺏ ﻋﻥ ﻁﺭﻴﻕ ﺘﻁﻭﻴﺭ ﺨﺼﺎﺌﺹ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻤﺩﻤﺠﺔ ﻤﻊ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﻋﻨﺩ ﺍﻝﻅﺭﻭﻑ ﺍﻝﻤﺨﺘﻠﻔﺔ ﻝﺘﺤﺘﻭﻯ ﻋﻠﻰ ﻤﻤﻴﺯﺍﺕ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﺍﻝﻌﻀﻭﻴﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ. ﺤﻴﺙ ﺃﻥ ﻝﻪ ﺍﻨﺘﻘﺎﺌﻴﺔ ﻋﺎﻝﻴﺔ ﻝﻺﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺍﻷﻭﺴﺎﻁ ﺍﻝﻤﺨﺘﻠﻔﺔ. ﻭﻗﺩ ﺘﻡ ﺩﺭﺍﺴﺔ ﺍﻝﻴﺔ ﺍﺴﺘﺨﺩﺍﻤﻬﺎ ﻓﻰ ﻤﻌﺎﻝﺠﺔ ﺒﻌﺽ ﻨﻭﺍﺘﺞ ﺍﻹﻨﺸﻁﺎﺭ ﺍﻝﻨﻭﻭﻱ ﻭﻗﺩ ﺘﻤﺕ ﺩﺭﺍﺴﺔ ﺨﻭﺍﺹ ﻫﺫﻩ ﺍﻝﻤﻭﺍﺩ ﻭﻁﺭﻴﻘﺔ ﺘﻜﻭﻴﻨﻬﺎ ﻜﻤﺎ ﺘﻡ ﺘﻌﻴﻴﻥ ﺴﻌﺔ ﺍﻝﺘﺒﺎﺩل ﺍﻷﻴﻭﻨﻰ ﻝﻬﺎ ﻭﻤﻌﺎﻤﻼﺕ ﺍﻝﺘﻭﺯﻴﻊ ﻷﻴﻭﻥ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻓﻰ ﻅﺭﻭﻑ ﻤﺨﺘﻠﻔﻪ. ﻭﺘﻨﻘﺴﻡ ﻫﺫﻩ ﺍﻝﺭﺴﺎﻝﺔ ﺍﻝﻰ ﺜﻼﺜﺔ ﻓﺼﻭل ﺭﺌﻴﺴﻴﺔ ﻭﻫﻰ ﺍﻝﻤﻘﺩﻤﺔ ﻭﺍﻝﻌﻤﻠﻰ ﺜﻡ ﺍﻝﻨﺘﺎﺌﺞ ﻭﻤﻨﺎﻗﺸﺘﻬﺎ. ﻭﻓﻴﻤﺎ ﻴﻠﻰ ﻤﻭﺠﺯ ﻝﻤﺤﺘﻭﻴﺎﺕ ﻜل ﻓﺼل . . ﺍﻝﻔﺼل ﺍﻷﻭل ﺍﻝﻤﻘﺩﻤﺔ : :

ﻭ ﻴﺘﻀﻤﻥ، ﻤﻭﺠﺯ ﻋﻥ ﺘﺎﺭﻴﺦﹺ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﻪ، ﻭﺘﺼﻨﻴﻔﻬﺎ، ﺜﻡ ﺍﻝﺘﺭﻜﻴﺯ ﻋﻠﻰ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﻜﻨﻭﻉ ﺠﺩﻴﺩ ﻤﻥ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﺜﻡ ﺍﺴﺘﻌﺭﺍﺽ ﺨﺼﺎﺌﺼﻬﺎ ﻤﻥ ﺴﻌﺘﻬﺎ، ﻭﺜﺒﺎﺘﻬﺎ ﺍﻝﻜﻴﻤﻴﺎﺌﻰ ، ﻭﺍﻨﺘﻘﺎﻴﺘﻬﺎ، ﻭﻤﻴﻜﺎﻨﻴﻜﻴﺘﻬﺎ، ﻭﺘﻁﺒﻴﻘﺎﺘﻬﺎ، ﻭﺍﺴﺘﺨﺩﺍﻡ ﻫﺫﻩ ﺍﻝﻤﺒﺎﺩﻻﺕ ﻓﻰ ﻤﻌﺎﻝﺠﺔ ﺍﻝﻨﻔﺎﻴﺎﺕ ﺍﻝﻤﺸﻌﺔ ﻭﻜﻴﻔﻴﺔ ﺘﻘﺩﻴﺭ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻓﻰ ﻫﺫﻩ ﺍﻝﻨﻔﺎﻴﺎﺕ ﻭﺇﺯﻝﺘﻪ ﺒﺎﻝﻤﺒﺎﺩﻻﺕ ﺍﻷﻴﻭﻨﻴﺔ ﻭﺍﻝﺘﻌﺭﻴﺽ ﻋﻥ ﺍﻷﺒﺤﺎﺙ ﺍﻝﻤﻨﺸﻭﺭﺓ ﻓﻰ ﺫﻝﻙ ﻭﻓﻰ ﻨﻬﺎﻴﺔ ﻫﺫﺍ ﺍﻝﺠﺯﺀ ﺒﻴﺎﻥ ﺍﻤﻜﺎﻨﻴﺔ ﺘﻁﻭﻴﺭ ﻫﺫﻩ ﺍﻝﻤﺒﺎﺩﻻﺕ ﻝﺘﺅﺩﻯ ﺍﻝﻐﺭﺽ ﺍﻝﻤﻨﻭﻁ ﻝﻬﺎ ﺒﺎﻨﺘﺎﺝ ﺍﻝﻤﺒﺎﺩﻻﺕ ﺍﻝﻤﺘﺭﺍﻜﺒﺔ ﻤﺜل ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﺍﻝﺫﻯ ﺘﻡ ﺩﺭﺍﺴﺔ

ﺇﻝﻰ ﻤﻥ ﻜﺎﻨﻭﺍ ﻴﻀﻴﺌﻭﻥ ﻝﻲ ﺍﻝﻁﺭﻴﻕ ﻭﻴﺴﺎﻨﺩﻭﻨﻲ ﻭﻴﺘﻨﺎﺯﻝﻭﻥ ﻋﻥ ﺤﻘﻭﻗﻬﻡ ﻹﺭﻀﺎﺌﻲ ﻭﺍﻝﻌﻴﺵ ﻓﻲ ﻫﻨﺎﺀ ﺇﺨﻭﺘﻲ ﺒﻜل ﺍﻝﻭﻓﺎﺀ.. ﺇﻝﻰ ﺭﻓﻴﻘﺔ ﺩﺭﺒﻲ ﺯﻭﺠﺘﻲ ﻭﺸﺭﻴﻜﺔ ﻋﻤﺭﻱ ﻭﺴﻜﻨﻲ ﺇﻝﻰ ﻤﻥ ﺴﺎﺭﺕ ﻤﻌﻲ ﻨﺤﻭ ﺍﻝﺤﻠﻡ.. ﺨﻁﻭﺓ ﺒﺨﻁﻭﺓ ﺒﺫﺭﻨﺎﻩ ﻤﻌﺎﹰ.. ﻭﺤﺼﺩﻨﺎﻩ ﻤﻌﺎﹰ ﻭﺴﻨﺒﻘﻰ ﻤﻌﺎﹰ.. ﺒﺈﺫﻥ ﺍﷲ ﺠﺯﺍﻙ ﺍﷲ ﺨﻴﺭﺍﹰ ﺯﻭﺠﺘـ ﻲ ﺇﻝﻰ ﺍﺒﻨﺎﺌﻲ ﺍﻻﻋﺯﺍﺀ ﻋﺎﺌﺸﺔ ﻭﻋﺒﺩﺍﷲ ﻓﻠﺫﺓ ﻜﺒﺩﻯ ﺍﻝﺫﻴﻥ ﺃﻀﺤﻰ ﺒﻨﻔﺴﻰ ﻤﻥ ﺃﺠﻠﻬﻡ ﺇﻝﻰ ﺃﺼﺩﻗﺎﺌﻰ ﻭﺯﻤﻼﺌﻰ .. ﺇﻝﻰ ﻤﻥ ﺘﺤﻠﻭ ﺒﺎﻹﺨﺎﺀ ﻭﺘﻤﻴﺯﻭﺍ ﺒﺎﻝﻭﻓﺎﺀ ﻭﺍﻝﻌﻁﺎﺀ ﺇﻝﻰ ﻴﻨﺎﺒﻴﻊ ﺍﻝﺼﺩﻕ ﺍﻝﺼﺎﻓﻲ ﺇﻝﻰ ﻤﻥ ﻤﻌﻬﻡ ﺴﻌﺩﺕ ، ﻭﺒﺭﻓﻘﺘﻬﻡ ﻓﻲ ﺩﺭﻭﺏ ﺍﻝﺤﻴﺎﺓ ﺍﻝﺤﻠﻭﺓ ﻭﺍﻝﺤﺯﻴﻨﺔ ﺴﺭﺕ ﺇﻝﻰ ﻤﻥ ﻜﺎﻨﻭﺍ ﻤﻌﻲ ﻋﻠﻰ ﻁﺭﻴﻕ ﺍﻝﻨﺠﺎﺡ ﻭﺍﻝﺨﻴﺭ

ا اه وار

ا آ و

ا آ هء اهي ة ي اا

ﺍﺩﻋﻭ ﺍﷲ ﻝﻜﻡ ﺠﻤﻴﻌﺎ ﺒﺩﻭﺍﻡ ﺍﻝﺼﺤﺔ ﻭﺍﻝﻌﺎﻓﻴﺔ ﻭﺍﻥ ﻴﺒﺎﺭﻙ ﻝﻜﻡ ﻓﻲ ﺍﻋﻤﺎﻝﻜﻡ ( ﻭﺁﺨﺭ ﺩﻋﻭﺍﻫﻡ ﺍﻥ ﺍﻝﺤﻤﺩ ﷲ ﺭﺏ ﺍﻝﻌﺎﻝﻤﻴﻥ) ﻭﺍﻝﺼﻼﺓ ﻭﺍﻝﺴﻼﻡ ﻋﻠﻰ ﺴﻴﺩ ﺍﻝﻤﺭﺴﻠﻴﻥ ﺴﻴﺩﻨﺎ ﻤﺤﻤﺩ ﻭﻋﻠﻰ ﺁﻝﻪ ﻭﺼﺤﺒﻪ ﺍﺠﻤﻌﻴﻥ ﻭﻤﻥ ﺴﺎﺭ ﻋﻠﻰ ﻨﻬﺠﻬﻡ ﺍﻝﻰ ﻴﻭﻡ ﺍﻝﺩﻴﻥ

ﺇﻫــﺩﺍﺀ ﺒﺴﻡ ﺍﷲ ﺍﻝﺭﺤﻤﻥ ﺍﻝﺭﺤﻴﻡ ( ﻭﻗل ﺇﻋﻤﻠﻭﺍ ﻓﺴﻴﺭﻯ ﺍﷲ ﻋﻤﻠﻜﻡ ﻭﺭﺴﻭﻝﻪ ﻭﺍﻝﻤﺅﻤﻨﻭﻥ )

ﺇﻝﻬﻲ ﻻﻴﻁﻴﺏ ﺍﻝﻠﻴل ﺇﻻ ﺒﺸﻜﺭﻙ ﻭﻻﻴﻁﻴﺏ ﺍﻝﻨﻬﺎﺭ ﺇﻝﻰ ﺒﻁﺎﻋﺘﻙ .. ﻭﻻﺘﻁﻴﺏ ﺍﻝﻠﺤﻅﺎﺕ ﺇﻻ ﺒﺫﻜﺭﻙ .. ﻭﻻ ﺘﻁﻴﺏ ﺍﻵﺨﺭﺓ ﺇﻻ ﺒﻌﻔﻭﻙ .. ﻭﻻ ﺘﻁﻴﺏ ﺍﻝﺠﻨﺔ ﺇﻻ ﺒﺭﺅﻴﺘﻙ ﺍﷲ ﺠل ﺠﻼﻝﻪ ﺇﻝﻰ ﻤﻥ ﺒﻠﻎ ﺍﻝﺭﺴﺎﻝﺔ ﻭﺃﺩﻯ ﺍﻷﻤﺎﻨﺔ .. ﻭﻨﺼﺢ ﺍﻷﻤﺔ .. ﺇﻝﻰ ﻨﺒﻲ ﺍﻝﺭﺤﻤﺔ ﻭﻨﻭﺭ ﺍﻝﻌﺎﻝﻤﻴﻥ .. ﺴﻴﺩﻨﺎ ﻤﺤﻤﺩ ﺼﻠﻰ ﺍﷲ ﻋﻠﻴﻪ ﻭﺴﻠﻡ ﺇﻝﻰ ﻤﻥ ﻜﻠﻠﻪ ﺍﷲ ﺒﺎﻝﻬﻴﺒﺔ ﻭﺍﻝﻭﻗﺎﺭ .. ﺇﻝﻰ ﻤﻥ ﻋﻠﻤﻨﻲ ﺍﻝﻌﻁﺎﺀ ﺒﺩﻭﻥ ﺍﻨﺘﻅﺎﺭ .. ﺇﻝﻰ ﻤﻥ ﺃﺤﻤل ﺃﺴﻤﻪ ﺒﻜل ﺍﻓﺘﺨﺎﺭ .. ﺃﺭﺠﻭ ﻤﻥ ﺍﷲ ﺃﻥ ﻴﻤﺩ ﻓﻲ ﻋﻤﺭﻙ ﻝﺘﺭﻯ ﺜﻤﺎﺭﺍﹰ ﻗﺩ ﺤﺎﻥ ﻗﻁﺎﻓﻬﺎ ﺒﻌﺩ ﻁﻭل ﺍﻨﺘﻅﺎﺭ ﻭﺴﺘﺒﻘﻰ ﻜﻠﻤﺎﺘﻙ ﻨﺠﻭﻡ ﺃﻫﺘﺩﻱ ﺒﻬﺎ ﺍﻝﻴﻭﻡ ﻭﻓﻲ ﺍﻝﻐﺩ ﻭﺇﻝﻰ ﺍﻷﺒﺩ.. ﻭﺍﻝﺩﻱ ﺍﻝﻌﺯﻴﺯ ﺇﻝﻰ ﻤﻼﻜﻲ ﻓﻲ ﺍﻝﺤﻴﺎﺓ .. ﺇﻝﻰ ﻤﻌﻨﻰ ﺍﻝﺤﺏ ﻭﺇﻝﻰ ﻤﻌﻨﻰ ﺍﻝﺤﻨﺎﻥ ﻭﺍﻝﺘﻔﺎﻨﻲ .. ﺇﻝﻰ ﺒﺴﻤﺔ ﺍﻝﺤﻴﺎﺓ ﻭﺴﺭ ﺍﻝﻭﺠﻭﺩ ﺇﻝﻰ ﻤﻥ ﻜﺎﻥ ﺩﻋﺎﺌﻬﺎ ﺴﺭ ﻨﺠﺎﺤﻲ ﻭﺤﻨﺎﻨﻬﺎ ﺒﻠﺴﻡ ﺠﺭﺍﺤﻲ ﺇﻝﻰ ﺃﻏﻠﻰ ﺍﻝﺤﺒﺎﻴﺏ ﺃﻤﻲ ﺍﻝﺤﺒﻴﺒﺔ ﺇﻝﻲ ﻜل ﻤﻥ ﺃﻀﺎﺀ ﺒﻌﻠﻤﻪ ﻋﻘل ﻏﻴﺭﻩ ﻭﺃﻫﺩﻯ ﺒﺎﻝﺠﻭﺍﺏ ﺍﻝﺼﺤﻴﺢ ﺤﻴﺭﺓ ﺴﺎﺌﻠﻴﻪ ﻓﺄﻅﻬﺭ ﺒﺴﻤﺎﺤﺘﻪ ﺘﻭﺍﻀﻊ ﺍﻝﻌﻠﻤﺎﺀ ﻭﺒﺭﺤﺎﺒﺘﻪ ﺴﻤﺎﺤﺔ ﺍﻝﻌﺎﺭﻓﻴﻥ ﺃﺴﺎﺘﺫﺘﻰ

آ ام ﺼﻔﺤﺔ ﺍﻝﻌﻨﻭﺍﻥ

ﻋﻨﻭﺍﻥ ﺍﻝﺭﺴﺎﻝﺔ: ﺩﺭﺍﺴﺎﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺒﺎﺩل ﻜﺎﺘﻴﻭﻨﻰ ﺠﺩﻴﺩ ﻭﺘﻁﺒﻴﻘﺎﺘﻪ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻹﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ ﺇﺴﻡ ﺍﻝﻁﺎﻝــﺏ: ﻤﺠﺩﻱ ﺨﻠﻴل ﻤﺤﻤﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﻜﺎﻥ ﺍﻝﻌﻤــل: ﻤﺭﻜﺯ ﺍﻝﻤﻌﺎﻤل ﺍﻝﺤﺎﺭﺓ – ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍﻝﺩﺭﺠﺔ ﺍﻝﻌﻠﻤـﻴﺔ: ﺩﻜﺘﻭﺭﺍﻩ ﺍﻝﻔﻠﺴﻔﺔ ﻓﻰ ﺍﻝﻌﻠﻭﻡ (ﻜﻴﻤﻴﺎﺀ) ﺍﻝﻘﺴﻡ ﺍﻝﺘﺎﺒﻊ ﻝﻪ: ﻗﺴﻡ ﺘﻜﻨﻭﻝﻭﺠﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺍﻝﻨﻭﻭﻯ ﺇﺴﻡ ﺍﻝﻜﻠــﻴﺔ: ﻜﻠﻴﺔ ﺍﻝﻌﻠﻭﻡ ﺍﻝﺠﺎﻤﻌـــﺔ: ﺠﺎﻤﻌﺔ ﻋﻴﻥ ﺸﻤﺱ ﺴﻨﺔ ﺍﻝﺘﺨـﺭﺝ: ٢٠٠٠ﻡ ﺴﻨﺔ ﺍﻝﻤــﻨﺢ: ٢٠١٢ﻡ

ﺸﻜﺭ ﻭﺘﻘﺩﻴﺭ

ﻭﷲ ﺍﻝﺤﻤﺩ ﻭﺍﻝﺸﻜﺭ ﻤﻥ ﻗﺒل ﻭﻤﻥ ﺒﻌﺩ ﺍﻝﺫﻯ ﺒﺘﻭﻓﻴﻘﻪ ﺘﻡ ﻫﺫﺍ ﺍﻝﻌﻤل

ﺃﺘﻘﺩﻡ ﺒﺄﺴﻤﻰ ﺁﻴﺎﺕ ﺍﻝﺸﻜﺭ ﻭﺍﻝﺘﻘﺩﻴﺭ ﺇﻝﻰ ﺃﺴﺎﺘﺫﺘﻰ ﺍﻷﻓﺎﻀل ﺍﻝﺫﻴﻥ ﻗﺎﻤﻭ ﺍ ﺒﺎﻹﺸﺭﺍﻑ ﻋﻠﻰ

ﺭﺴﺎﻝﺘﻰ ﻭﻫﻡ : :

ﺍ.ﺩ. ﻤﺤﻤﺩ ﻓﺘﺤﻰ ﺍﻝﺸﺤﺎﺕ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﻋﻴﻥ ﺸﻤﺱ ﺍ.ﺩ. ﺇﺒﺭﺍﻫﻴﻡ ﻤﺤﻤﺩ ﺍﻝﻨﺠﺎﺭ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍ.ﺩ. ﻋﺼﺎﻡ ﺼﺎﻝﺢ ﺯﻜﺭﻴﺎ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍ.ﺩ. ﺇﺴﻤﺎﻋﻴل ﻤﺤﻤﺩ ﻋﻠﻰ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ

ﻜﻤﺎ ﺃﺘﻘﺩﻡ ﺒﺨﺎﻝﺹ ﺍﻝﺸﻜﺭ ﺇﻝﻰ ﺠﻤﻴﻊ ﺃﻋﻀﺎﺀ ﻗﺴﻡ ﺘﻜﻨﻭﻝﻭﺠﻴﺎ ﺍﻝﻭﻗﻭﺩ ﺍﻝﻨـﻭﻭﻯ ﺒﻤﺭﻜـﺯ ﺍﻝﻤﻌﺎﻤل ﺍﻝﺤﺎﺭﺓ - ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﻭﻜل ﻤﻥ ﻗﺎﻡ ﺒﻤﺴﺎﻋﺩﺘﻰ ﻓﻰ ﺇﺘﻤﺎﻡ ﻫﺫﻩ ﺍﻝﺭﺴﺎﻝﺔ ، ، ﻭﻜﺫﻝﻙ ﺃﺘﻘﺩﻡ ﺒﺎﻝﺸﻜﺭ ﺇﻝﻰ ﺠﻤﻴﻊ ﺃﻓﺭﺍﺩ ﻋﺎﺌﻠﺘﻰ . .

ﺭﺴﺎﻝﺔ ﺩﻜﺘﻭﺭﺍﻩ ﺍﺴﻡ ﺍﻝﻁﺎﻝﺏ: ﻤﺠﺩﻱ ﺨﻠﻴل ﻤﺤﻤﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻋﻨﻭﺍﻥ ﺍﻝﺭﺴﺎﻝﺔ: ﺩﺭﺍﺴﺎﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭ ﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺒﺎﺩل ﻜﺎﺘﻴﻭﻨﻰ ﺠﺩﻴﺩ ﻭﺘﻁﺒﻴﻘﺎﺘﻪ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻹﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ ﺍﺴﻡ ﺍﻝﺩﺭﺠﺔ: ﺩﺭﺠﺔ ﺩﻜﺘﻭﺭﺍﻩ ﺍﻝﻔﻠﺴﻔﺔ ﻓﻰ ﺍﻝﻌﻠﻭﻡ (ﺍﻝﻜﻴﻤﻴﺎﺀ ) )

ﻝﺠﻨﺔ ﺍﻹﺸﺭﺍﻑ : : ﺍﺩ ﻤﺤﻤﺩ ﻓﺘﺤﻰ ﺍﻝﺸﺤﺎﺕ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﻋﻴﻥ ﺸﻤﺱ ﺍﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺤﻤﺩ ﺍﻝﻨﺠﺎﺭ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍﺩ ﻋﺼﺎﻡ ﺼﺎﻝﺢ ﺯﻜﺭﻴﺎ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍﺩ ﺇﺴﻤﺎﻋﻴل ﻤﺤﻤﺩ ﻋﻠﻰ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ

ﻝﺠﻨﺔ ﺍﻝﺘﺤﻜﻴﻡ ﻭﺍﻝﻤﻨﺎﻗﺸﺔ: ﺍﺩ ﻤﺤﻤﺩ ﻤﺤﻤﺩ ﺸﻜﺭﻯ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﺍﻝﻘﺎﻫﺭﺓ ﺍﺩ ﻋﺒﺩ ﺍﻝﻌﺯﻴﺯ ﺍﻝﺴﻴﺩ ﻓﻭﺩﺓ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ - ﻋﻠﻭﻡ ﺍﻝﻤﻨﺼﻭﺭﺓ ﺍﺩ ﻤﺤﻤﺩ ﻓﺘﺤﻰ ﺍﻝﺸﺤﺎﺕ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﻋﻴﻥ ﺸﻤﺱ ﺍﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺤﻤﺩ ﺍﻝﻨﺠﺎﺭ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ

ﺘﺎﺭﻴﺦ ﺍﻝﺒﺤﺙ 10/ 3 / 2008 ﺍﻝﺩﺭﺍﺴﺎﺕ ﺍﻝﻌﻠﻴﺎ

ﺨﺘﻡ ﺍﻹﺠﺎﺯﺓ ﺃﺠﻴﺯﺕ ﺍﻝﺭﺴﺎﻝﺔ ﺒﺘﺎﺭﻴﺦ / / ٢٠١٢

ﻤﻭﺍﻓﻘﺔ ﻤﺠﻠﺱ ﺍﻝﻜﻠﻴﺔ / / ٢٠١٢ ﻤﻭﺍﻓﻘﺔ ﻤﺠﺎﺱ ﺍﻝﺠﺎﻤﻌﺔ / / ٢٠١٢

ﺩﺭﺍﺴﺎﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭ ﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺒﺎﺩل ﻜﺎﺘﻴﻭﻨﻰ ﺠﺩﻴﺩ ﻭﺘﻁﺒﻴﻘﺎﺘﻪ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻹﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ

ﻤﺠﺩﻱ ﺨﻠﻴل ﻤﺤﻤﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺎﺠﺴﺘﻴﺭ ﻓﻰ ﺍﻝﻌﻠﻭﻡ – ﻜﻴﻤﻴﺎﺀ ﺍﻝﺴﺎﺩﺓ ﺍﻝﻤﺸﺭﻓﻭﻥ: ﺍﻝﺘﻭﻗﻴﻊ ﺍ.ﺩ. ﻤﺤﻤﺩ ﻓﺘﺤﻰ ﺍﻝﺸﺤﺎﺕ ...... ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﻋﻴﻥ ﺸﻤﺱ ﺍ.ﺩ. ﺇﺒﺭﺍﻫﻴﻡ ﻤﺤﻤﺩ ﺍﻝﻨﺠﺎﺭ ...... ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍ.ﺩ. ﻋﺼﺎﻡ ﺼﺎﻝﺢ ﺯﻜﺭﻴﺎ ...... ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍ.ﺩ. ﺇﺴﻤﺎﻋﻴل ﻤﺤﻤﺩ ﻋﻠﻰ ...... ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ

ﺭﺌﻴﺱ ﻗﺴﻡ ﺍﻝﻜﻴﻤﻴﺎﺀ

د.ا / اس

ﺩﺭﺍﺴﺎﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺒﺎﺩل ﻜﺎﺘﻴﻭﻨﻰ ﺠﺩﻴﺩ ﻭﺘﻁﺒﻴﻘﺎﺘﻪ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻹﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ ﺭﺴﺎﻝﺔ ﻤﻘﺩﻤﺔ ﻤﻥ ﻤﺠﺩﻱ ﺨﻠﻴل ﻤﺤﻤﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺎﺠﺴﺘﻴﺭ ﻓﻰ ﺍﻝﻌﻠﻭﻡ – ﻜﻴﻤﻴﺎﺀ ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺇﻝﻰ ﻗﺴﻡ ﺍﻝﻜﻴﻤﻴﺎﺀ - ﻜﻠﻴﺔ ﺍﻝﻌﻠﻭﻡ - ﺠﺎﻤﻌﺔ ﻋﻴﻥ ﺸﻤﺱ ﻝﻠﺤﺼﻭل ﻋﻠﻰ ﺩﺭﺠﺔ ﺩﻜﺘﻭﺭﺍﻩ ﺍﻝﻔﻠﺴﻔﺔ ﻓﻰ ﺍﻝﻌﻠﻭﻡ (ﺍﻝﻜﻴﻤﻴﺎﺀ) ﺘﺤﺕ ﺇﺸﺭﺍﻑ

ﺍﺩ ﻤﺤﻤﺩ ﻓﺘﺤﻰ ﺍﻝﺸﺤﺎﺕ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﺘﺤﻠﻴﻠﺔ ﻭﻏﻴﺭ ﺍﻝﻌﻀﻭﻴﺔ - ﻋﻠﻭﻡ ﻋﻴﻥ ﺸﻤﺱ ﺍﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺤﻤﺩ ﺍﻝﻨﺠﺎﺭ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍﺩ ﻋﺼﺎﻡ ﺼﺎﻝﺢ ﺯﻜﺭﻴﺎ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺍﺩ ﺇﺴﻤﺎﻋﻴل ﻤﺤﻤﺩ ﻋﻠﻰ ﺃﺴﺘﺎﺫ ﺍﻝﻜﻴﻤﻴﺎﺀ ﺍﻝﻔﻴﺯﻴﺎﺌﻴﺔ -ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ

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ﺩﺭﺍﺴﺎﺕ ﻜﻴﻤﻴﺎﺌﻴﺔ ﻋﻠﻰ ﺍﻝﺒﻭﻝﻰ ﺃﻨﻴﻠﻴﻥ ﺘﻴﺘﺎﻨﻭﺘﻨﺠﺴﺘﺎﺕ ﻜﻤﺒﺎﺩل ﻜﺎﺘﻴﻭﻨﻰ ﺠﺩﻴﺩ ﻭﺘﻁﺒﻴﻘﺎﺘﻪ ﺍﻝﺘﺤﻠﻴﻠﻴﺔ ﻹﺯﺍﻝﺔ ﺍﻝﺴﻴﺯﻴﻭﻡ ﻤﻥ ﺃﻭﺴﺎﻁ ﻤﺎﺌﻴﺔ

ﺭﺴﺎﻝﺔ ﻤﻘﺩﻤﺔ ﻤﻥ

ﻤﺠﺩﻱ ﺨﻠﻴل ﻤﺤﻤﺩ ﺇﺒﺭﺍﻫﻴﻡ ﻤﺎﺠﺴﺘﻴﺭ ﻓﻰ ﺍﻝﻌﻠﻭﻡ – ﻜﻴﻤﻴﺎﺀ ﻫﻴﺌﺔ ﺍﻝﻁﺎﻗﺔ ﺍﻝﺫﺭﻴﺔ ﺇﻝﻰ ﻗﺴﻡ ﺍﻝﻜﻴﻤﻴﺎﺀ ﻜﻠﻴﺔ ﺍﻝﻌﻠﻭﻡ - ﺠﺎﻤﻌﺔ ﻋﻴﻥ ﺸﻤﺱ

ﻝﻠﺤﺼﻭل ﻋﻠﻰ ﺩﺭﺠﺔ ﺩﻜﺘﻭﺭﺍﻩ ﺍﻝﻔﻠﺴﻔﺔ ﻓﻰ ﺍﻝﻌﻠﻭﻡ (ﺍﻝﻜﻴﻤﻴﺎﺀ)

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