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Modification of Resins for Their Use in the Separation, Preconcentration and Determination of Metal Ions

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Modification of Resins for Their Use in the Separation, Preconcentration and Determination of Metal Ions MODIFICATION OF RESINS FOR THEIR USE IN THE SEPARATION, PRECONCENTRATION AND DETERMINATION OF METAL IONS BY AKIL AHMAD Under the supervision of Dr. Aminul Islam Department of Chemistry Submitted in fulfillment of the requirement of the degree of Doctor of Philosophy DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY ALIGARH (INDIA) 2011 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY AMINUL ISLAM ALIGARH– 202002, INDIA PhD E-mail: [email protected] Assistant Professor Ph: (Off) 91-571-2703515 Analytical Chemistry Mob.: 91- 9358979659 DATE- 18th May, 2011 Certificate This is to certify that the thesis entitled “Modification of resins for their use in the separation, preconcentration and determination of metal ions ” being submitted by Mr. Akil Ahmad, for the award of Doctor of Philosophy in Chemistry, is a bonafide research work carried out by him under my supervision. The thesis, to my knowledge, fulfills the requirements for submission for the award of the degree of Doctor of Philosophy in Chemistry. Dr. Aminul Islam Dedicated in the memory of my Abba Acknowledgement At the outset, I wish to pay my most humble obeisance to the almighty Allah for giving me the wisdom and inspiration to take up this task. It has been Thy guiding hand that has brought this task to a successful completion. I express my deepest respect and the most sincere gratitude to my esteemed supervisor Dr. Aminul Islam for his scholastic guidance and ungrudged encouragement throughout the course of research work. His systematic and analytical approach blended with constructive criticism and innovative ideas helped me to understand the basics of research and to overcome many experimental hurdles. I am also grateful to him for the freedom he has given to me. I am thankful to the Chairman, Department of Chemistry, AMU, Aligarh, for providing the necessary research facilities during my research work. Financial assistance from U.G.C., New Delhi is gratefully acknowledged. My deep sense of gratitude for the guiding hand of my father late Mr. Jamil Ahmad and the humble and loving care of my mother Mrs. Sajada Begum, who allowed me to study in Ph.D cheerfully putting up with inconvenience and difficulties. I am also thankful to my brother Mr. Shakil Ahmad, Mr. Haider Khan, Mr. Shabbir Khan, Mr. Shakib Khan, Fuzail, Sharique, Jahandad, Zeeshan, Tufail, Humail, Tarique, Ahsan, Saheb, Zubi and my affectionate sisters Kehkasha, Seema, Firoza, Enayat and benign support of Shama Nahid and Asma. My neice Shawaiz deserves a special mention for making the task easier for me. I greatly acknowledge the moral and sympathetic support of all my relatives and well wishers. I must express a very special appreciation to Md Asaduddin Laskar for his constant encouragement through out my ups and downs and often of great help in difficult times. I also thank to my lab colleague Hilal and Noushi being there for me always whenever their help was needed. I am indebted to my friends particularly Mr. Shadab, Mr. Shahadat, Mr. Ahmad, Mr. Rehan, Mr. Qamar, Mr. Fazil, Mr. Afzal, Mr. Mannan, Mr. Shahab for their support and wishes at every phase of my life and study. This acknowledgement will be incomplete without the name ‘Dr. Naheed’ for caring and constant encouragement and her loving sons Muaaz and Zaidu. I am obliged to Prof. Masood Alam (Jamia Milia Islamia, New Delhi) and the Chairman, Department of Botany, AMU for their kind permission to avail the atomic absorption spectrophotometer facility. The help rendered by Mr. Misbah (Instrumentation Centre) and seminar library staff of the department is also duly appreciated. Akil Ahmad Dedication Certificate Acknowledgement List of publications CONTENTS List of figures i List of tables iv Chapter 1: Introduction 1.1 Role of geocycle in the introduction of metals into our environment 1 1.2 Significance and characteristics of preconcentration 10 1.3 Solid-phase extraction (SPE) as a preconcentration method 12 1.4 Types of analytical techniques coupled with preconcentration method 26 1.5 Statistical Treatment of Data 35 1.6 Present work and its scope 39 1.7 Merits of the present work 47 REFERENCES 50 Chapter 2: Experimental 2.1 Instrumentation 75 2.2 Reagents and solutions 77 2.3 Pretreatment of samples 79 2.4 Preparation of chelating resin 82 2.5 Characterization of chelating resins 85 2.6 Recommended procedure for sorption studies of metal ions 86 2.7 Procedures for method validation 90 REFERENCES 91 Chapter 3: Characterization of a chelating resin functionalized via azo spacer and its analytical applicability for the determination of trace metal ions in real matrices 3.1 Introduction 93 3.2 Experimental 94 3.3 Results and discussion 96 3.4 Method validation 107 3.5 Applications 108 3.6 Conclusion 110 REFERENCES 111 Chapter 4: Preparation, Characterization of a Novel Chelating Resin Functionalized with o-Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions 4.1 Introduction 114 4.2 Experimental 115 4.3 Results and discussion 116 4.4 Method validation 127 4.5 Applications 129 4.6 Conclusions 131 REFERENCES 134 Chapter 5: A newly developed salicylanilide functionalized Amberlite XAD-16 chelating resin for its use in preconcentration and determination of trace metal ions from environmental and biological samples 5.1 Introduction 137 5.2 Experimental 138 5.3 Results and discussion 140 5.4 Analytical figures of merit 153 5.5 Applications 155 5.6 Conclusions 158 REFERENCES 159 Chapter 6: Flame atomic absorption spectrometric determination of trace metal ions in environmental and biological samples after preconcentration on a new chelating resin containing p-Aminobenzene Sulfonic Acid 6.1 Introduction 164 6.2 Experimental 165 6.3 Results and discussion 167 6.4 Analytical figures of merit 181 6.5 Applications 183 6.6 Conclusions 186 REFERENCES 187 LIST OF FIGURES Page No. Figure 1.1 Interaction of human with the environment 1 Figure 1.2 SPE operation steps 14 Figure 1.3 Interactions occurring at the surface of the solid sorbent 19 Figure 1.4 Atomic absorption spectrometer block diagram 32 Figure 1.5 Typical representation of the breakthrough curve 45 (i.e. concentration of the analyte at the outlet of the SPE system vs. sample volume percolated through the system) Figure 2.1 Diagram depicting a preconcentration system 78 Figure 2.1 Synthesis of chelating resins by incorporating reagents through azo spacer 84 Figure 3.1 Structure of a monomeric unit of AXAD-4 modified with 94 Salicylic acid (SA); ‘a’ is the probable chelating sites Figure 3.2 FT-IR spectrum of a) AXAD-4-SA and 97 b) AXAD-4-SA saturated with Cu(II) Figure 3.3 TGA/DTA curves of AXAD-4-SA 97 Figure 3.4 Dependence of sorption capacity on the pH of the solution 98 Figure 3.5 Kinetics of sorption of metal ions on AXAD-4-SA 99 Figure 3.6 Regenerability of AXAD-4-SA for different metals 102 Figure 3.7 Langmuir sorption isotherms depicting the sorption behaviors 105 of metal ions onto AXAD-4-SA Figure 3.8 Breakthrough curves for sorption of metal ions: C/Co is the 106 concentration ratio of the effluent to influent Figure 4.1 Structure of a monomeric unit of AXAD-4 modified with 115 o-Hydroxybenzamide (HBAM); ‘a’ is the probable chelating sites Figure 4.2 FT-IR spectrum of a) AXAD-4-HBAM and 117 b) AXAD-4- HBAM saturated with Cu(II) Figure 4.3 TGA/DTA curves of AXAD-4-HBAM 118 i Figure 4.4 Dependence of sorption capacity on the pH of the solution 119 Figure 4.5 Kinetics of sorption of metal ions on AXAD-4- HBAM 120 Figure 4.6 Langmuir sorption isotherms depicting the sorption behaviors 124 of metal ions onto AXAD-4-HBAM Figure 4.7 Freundlich sorption isotherms depicting the sorption behaviors 125 of metal ions onto AXAD-4-HBAM Figure 4.8 Breakthrough curves for sorption of metal ions: C/Co is 126 the concentration ratio of the effluent to influent Figure 5.1 Structure of a monomeric unit of AXAD-16 modified with Salicylanilide; 138 (a) and (b) are the probable chelating sites Figure 5.2 TGA/DTA curves of AXAD-16-SALD 141 Figure 5.3 FT-IR spectrum of a) AXAD-16-SALD and 142 b) AXAD-16-SALD saturated with Cu(II) Figure 5.4 Dependence of sorption capacity on the pH of the solution 143 Figure 5.5 Kinetics of sorption of metal ions on AXAD-4-SALD 144 Figure 5.6 Influence of temperature on the distribution ratio of metal ions 145 Figure 5.7a, b Pseudo first and second-order kinetic plots for removal of metal ions 147 Figure 5.8 Langmuir sorption isotherms depicting the sorption behaviors 148 of metal ions onto AXAD-16-SALD Figure 5.9 Breakthrough curves for sorption of metal ions: C/Co is 153 the concentration ratio of the effluent to influent Figure 6.1 Structure of a monomeric unit of AXAD-16 modified with 165 p-Aminobenzene sulfonic acid; (a) is the probable chelating site and (b) is the hydrophilic and ion exchange group that enhances the hydrophilicity and sorption capacity of the resin Figure 6.2 TGA/DTA curves of AXAD-16-ABSA 168 Figure 6.3 FT-IR spectrum of a) AXAD-16-ABSA and 169 b) AXAD-16-ABSA saturated with Cu(II) ii Figure 6.4 Dependence of sorption capacity on the pH of the solution 170 Figure 6.5 Kinetics of sorption of metal ions on AXAD-16-ABSA 171 Figure 6.6 Influence of temperature on the distribution ratio of metal ions 172 Figure 6.7a Pseudo first-order kinetic plots for removal of metal ions 174 Figure 6.7b Pseudo second-order kinetic plots for removal of metal ions 174 Figure 6.8 Langmuir sorption isotherms depicting the sorption behaviors 176 of metal ions onto AXAD-16-ABSA Figure 6.9 Breakthrough curves for sorption of metal ions: C/Co is 181 the concentration ratio of the effluent to influent iii Abstract The thesis comprises of six chapters.
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