KINETICS OF OXIDATION OF SOME REDUCING SUGARS BY POTASSIUM PERMANGANATE IN ACIDIC MEDIUM BY VISIBLE SPECTROPHOTOMETRY _ By RAHEELA NAZ M.Sc. DEPARTMENT OF CHEMISTRY JINNAH UNIVERSITY FOR WOMEN KARACHI-74600 PAKISTAN 2008 KINETICS OF OXIDATION OF SOME REDUCING SUGARS BY POTASSIUM PERMANGANATE IN ACIDIC MEDIUM BY VISIBLE SPECTROPHOTOMETRY A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY OF THE JINNAH UNIVERSITY FOR WOMEN KARACHI By RAHEELA NAZ M.Sc. DEPARTMENT OF CHEMISTRY JINNAH UNIVERSITY FOR WOMEN KARACHI-74600. PAKISTAN 2008 DEDICATION I DEDICATE MY EFFORTS IN THE LOVE OF MY DEAR PARENTS MR. MANZOOR HUSSAIN AND MRS. REHANA SHAHNAZ, ESPECIALLY HUSBAND MR. SYED MUDASSIR HASAN AND MY SWEET DAUGHTER SYEDA HANI WHO HAVE LISTENED AND SHARED MY FEELINGS, GIVEN COMFORTS, STRENGTH AND HAVE REALLY CARED FOR ME ALL THE TIME. Table of Contents Table of Contents Table of Contents. i Acknowledgements .vi Abstract .vii Chapter 1 INTRODUCTION 1 1.1 SUGARS. 1 1.2 EQUILIBRIA AND MUTAROTATION OF SUGARS.2 1.3 OXIDATION PRODUCTS OF SUGARS 4 1.4 REDUCING AND NON-REDUCING SUGARS .6 1.5 OXIDATION WITH SOME IMPORTANT OXIDIZING AGENTS .7 1.5.1 Bromine water: the synthesis of aldonic acids 7 1.5.2 Nitric acid oxidation: Aldaric Acids .7 1.5.3 Periodate oxidations: oxidative cleavage of polyhydroxy compounds ..8 1.5.4 Other Sugar Oxidation Products .9 Chapter 2 LITERATURE SURVEY . . 10 2.1 OXIDATION OF REDUCING SUGAR BY HALOGENS . .. 10 2.1.1 Bromine as an oxidant .11 2.1.2 Use of Iodine for oxidation of Sugars .. .11 2.2 OXIDATION THROUGH HALO COMPOUNDS .12 2.2.1 Hypobromous Acid .12 2.2.2 Oxidation with Potassium bromate . 12 2.2.3 Oxidation by Periodic acid .13 2.2.4 Periodate . 14 2.2.5 Electron transfer reaction involving Perchlorate as an oxidant 17 2.2.6 Hypochlorite .17 2.2.7 Chloroamine-T ..17 2.3 N-HALO COMPOUNDS 18 i Table of Contents 2.4 OXIDATION THROUGH TRANSITION METALS .21 2.4.1 Manganese (Mn) .21 2.4.2 Cerium (Ce) ..22 2.4.3 Vanadium (V) .23 2.4.4 Chromium (Cr) ..24 2.4.5 Osmium (Os) .26 2.4.6 Copper (Cu) ..26 2.5 TRANSITION METALS AS CATALYST IN OXIDATION REACTIONS .. .26 2.5.1 Bismuth (Bi) .26 2.5.2 Rhodium (Rh) .27 2.5.3 Ruthenium (Ru) .27 2.5.4 Platinum (Pt) .28 2.5.5 Palladium (Pd) ..28 2.5.6 Mercury (Hg) .. ..28 2.6 AIR OXIDATION .29 2.7 HYDROGEN PEROXIDE (H2O2) . .30 2.8 OXIDATION INVOLVING TRANSITION METAL COMPLEXES AS OXIDANTS .. . 30 2.9 INORGANIC OXIDANTS ..31 2.10 OTHER OXIDATION REACTIONS .32 2.11 REACTIVE FORMS OF SUGARS IN ALKALINE MEDIUM ..37 2.12 PERMANGANATE AS AN OXIDIZING AGENT .38 2.13 AIMS AND OBJECTIVE OF CURRENT RESEARCH ..43 Chapter 3 EXPERIMENTAL ASPECTS . . 45 3.1 LABORATORY PREPARATION .. 45 3.1.1 Glass Wares ..45 3.1.2 Thermostatic Bath .45 3.1.3 Stop Watch 46 3.1.4 Digital Balance ..46 3.1.5 Spectrophotometer 46
