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 SUGARS4 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 acids7 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 oxidant17 2.2.6 Hypochlorite.17 2.2.7 Chloroamine-T..17 2.3 N-HALO COMPOUNDS18

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 Watch46 3.1.4 Digital Balance..46 3.1.5 Spectrophotometer46

ii

Table of Contents 3.1.6 Mass Spectrometer46 3.1.7 NMR Spectrometers..46 3.1.8 TLC...46 3.1.9 Chemicals..47 3.2 PREPARATION OF STOCK SOLUTIONS..47 3.2.1 Stock Solution of KMnO4.47 3.2.2 Stock Solution of Galactose..47 3.2.3 Stock Solution of Fructose48 3.2.4 Stock Solution of Maltose....48 3.2.5 Stock Solution of Lactose.48 3.2.6 Stock Solution of Potassium Nitrate.48 3.2.7 Sulphuric Acid..48 3.3 KINETIC EXPERIMENTS.48 3.3.1 Effect of Substrate Concentration on kobs..49 3.3.2 Effect of Oxidant Concentration on kobs....49 3.3.3 Effect of [H+] Concentration on kobs.....49 3.3.4 Effect of Salt on kobs .....49 3.3.5 Effect of Temperature on kobs ...49 3.4 DATA ANALYSIS..50 3.5 STOICHIOMETRY AND PRODUCTANALYSIS ...50 3.6 ANALYSIS OF REACTION MIXTURE..51 3.7 PREPARATION OF REACTION MIXTURES.52 3.7.1 For Galactose52 3.7.2 For Fructose..52 3.7.3 For Maltose...53 3.7.4 For Lactose53 3.8 ANALYSIS OF OXIDATION PRODUCTS..54

Chapter 4 RESULTS..55
4.1 EFFECT OF CONCENTRATION OF KMnO4 ON THE RATE OF OXIDATION OF SUGARS WITH KMnO4......56 4.2 EFFECT OF CONCENTRATION OF SUGARS ON THE RATE OF OXIDATION OF SUGARS WITH KMnO4..65

iii

Table of Contents 4.3 EFFECT OF CONCENTRATION OF H2SO4 ON THE RATE OF OXIDATION OF SUGAR WITH KMnO4.74 4.4 EFFECT OF IONIC STRENGTH ON RATE OF OXIDATION OF SUGARS WITH KMnO4.........83 4.5 EFFECT OF TEMPERATURE ON RATE OF OXIDATION OF SUGARS WITH KMnO4.....92

Chapter 5 DISCUSSION......101
5.1 INFLUENCE OF VARIATION OF CONCENTRATION OF KMnO4 ON THE OXIDATION OF REDUCING SUGARS.102 5.2 INFLUENCE OF VARIAITION OF CONCENTRATION OF SUGARS ON THE OXIDATION BY KMnO4.115 5.3 INFLUENCE OF VARIATION OF CONCENTRATION OF H+ IONS ON THE OXIDATION OF SUGARS BY KMnO4..128 5.4 NFLUENCE OF THE IONIC STRENGTH ON THE OXIDATION OF SUGARS BY KMnO4...141 5.5 EFFECT OF TEMPERATURE ON RATE OF OXIDATION OF SUGARS BY KMnO4...................................................................................151 5.6 REACTIVE SPECIES OF MnO4-.156 5.7 REACTIVE SPECIES OF Hg (II) CHLORIDE IN ACIDIC MEDIUM......156 5.8 SPECTRAL EVIDENCE FOR THE FORMATION OF COMPLEXES DURING COURSE OF REACTION...157 5.9 REACTIONS FOR OXIDATION OF SUGARS INTO ALDONIC ACIDS...162 5.9.1 Reaction Pathway of the Oxidation of Galactose and Fructose.162 5.9.2 Mechanism of Catalytic Oxidation of Maltose and Lactose...163 5.10 REACTIONS FOR OXIDATION OF SUGARS INTO OTHER ACID....166 5.10.1 Reaction Pathway for Oxidation of Galactose and Fructose168 5.10.2 Mechanism for Oxidation of Maltose and Lactose...170 5.11 CHARACTERIZATION OF ACID OF D-GALACTOSE.173 5.12 CHARACTERIZATION OF ACID OF D-FRUCTOSE176

iv

Table of Contents 5.13 CHARACTERIZATION OF ACID OF D-MALTOSE..179 5.14 CHARACTERIZATION OF ACID OF D-LACTOSE...183 5.15 PROPOSED MECHANISM OF KINETICS OF OXIDATION AGAINST KMnO4.187 5.16 COMPARATIVE STUDIES...190 5.17 CONCLUSIONS.193 5.18 FUTURE PERSPECTIVES.195 5.19 RESEARCH IMPORTANCE, APPLICATION AND USE...196

Chapter 6 REFERENCES...198
PUBLISHED PAPER

Acknowledgements

ACKNOWLEDGEMENTS
I am very much grateful to Allah who bestowed upon me the blessing of accomplishing this work.

I am thankful to my respected supervisor Dr. Rafia Azmat, Department of Chemistry, Jinnah University for Women, Karachi, who has provided me the research facilities of lab. I am grateful for her help, cooperation, suggestions and kind guidance throughout my work.

I am also thankful to Prof. Dr. Fahim Uddin (Former Chairman), Deparment of Chemistry and Former Dean Faculty of Science for his kind suggestions regarding thesis.

I am grateful to my respected Vice Chancellor Prof. Dr. Riaz Ahmed Hashmi for providing me research facilities.

I am thankful to Chairperson of Chemistry Department, Colleagues and Dean Faculty of Science for their cooperation.

My special thanks to Mr. Imran Malik, Dr. Qaiser Fatimi, H.E.J. Research Institute of Chemistry, University of Karachi, and Mr. Khalid Ahmed of University of Karachi, who were always ready to helped me whenever I needed.

I am thankful to Ms. Zubaida, Ms. Bina and Mr. Shan for their help in providing me reagents and support at the time of experimental work.

I am also grateful to my brothers Mr. Zahid Hussain and Mr. Syed Hamid Hasan, my husband Mr. Syed Mudassir Hasan who helped me at the time of compiling thesis.

RAHEELA NAZ
M. Sc.

vi

Abstract

ABSTRACT
Sugars containing either aldehyde (aldose), ketone (ketose ) or hemiacetal groups can be oxidized and are classified as reducing sugars. As oxidation of carbohydrates is widely studied under the field of organic chemistry, the present research has been conducted to study the oxidation of reducing sugars (galactose, fructose, maltose and lactose) with potassium permanganate as an oxidizing agent in sulphuric acid medium. The rate of oxidation of sugars was monitored by recording the change in optical density of MnO4- ion at max 545nm. The reactions exhibit first order with respect to [H+], [Sugar] & [MnO4-]. Plots of kobs vs [substrate] were found to be linear for the oxidation of galactose, fructose, maltose and lactose. A plot of log[sugar] vs logk gave straight line with slope of the order of unity (0.81, 0.84, 0.48 and 1.20 in galactose, fructose, maltose and lactose respectively). The oxidation showed that configuration of sugars has some bearing on rate of oxidation. At lower concentration of oxidants, the linear dependence of reaction rate tends towards new order at their higher concentration. Poor dependence on ionic strength suggests the presence of molecular species in the rate determining step. The rate of reaction was affected at elevated temperature where thermodynamic activation parameters like activation energy (Ea), enthalpy change of activation (H#), free energy change of activation (G#) and entropy change of activation (S#) were determined by Arrhenius and Erying equations. The negative value of entropy of activation suggests the existence of highly solvated transition intermediate state and the value of energy of activation suggests the slow kinetics. Hg catalyst was used to increase the rate of reaction in case of maltose and lactose where reactions proceed very slowly with respect to time as compared to other sugars used.
OH [Hg(H2O)6]+2 + MnO4-+ H3O+ O
Mn
+2

Hg(H2O)5

+ 2 H2O

vii

Abstract

The positive value for the free energy of activation indicated high electrostatic interaction between solute and solvent which was supported by the negative value of

S# indicating the solvated intermediate state. By considering the first order kinetics
with respect to sugars concentration a mechanism consistent with above findings has been proposed in the relevant section of this thesis. TLC and conventional (spot test) methods were used for the verification of oxidation products of sugars. The main products were formic acid and arabinonic acids which were detected in the oxidation of all sugars (Galactose, Fructose, Maltose and Lactose). The other respective acids of each sugar were identified as galacturonic, fructuronic, malturic and lacturic acid by Fab mass, spectroscopy.

H-NMR and

13

C-NMR

C 6 H12O6 + 2 MnO4
Galactose / Fructose

H C5 H10O6 + HCOOH + 2 MnO3

Arabinonic acid Formic acid

Hg C 12 H 22O11 + 4 MnO4 + H 2O H / 2C5 H10O6 + 2 HCOOH + 4 MnO3

+2

Maltose / Lactose

Arabinonic acid

Formic acid

C 6 H12O6 + 2 MnO4
Galactose / Fructose

H C6 H10O7 + H 2O + 2 MnO3
galacturonic / fructuronic acid

C12 H 22O11 + 4 MnO4

Maltose / Lactose

Hg H / 2C12 H18O13 + 2 H 2O + 4 MnO3

+2

malturic/ lacturic acid

The reactions pathways leading to the formation of above acids have been proposed by presenting four schemes in relevant section.

viii

Abstract

ix

CHAPTER # 1

INTRODUCTION

Chapter 1

Introduction

1. INTRODUCTION
1.1 SUGARS
Sugars are a class of organic compounds containing several hydroxyl functional groups and a carbonyl group (aldehyde or ketone) with the capability of forming an intramolecular hemiacetal or hemiketal. The nomenclature suffix "ose" is used to denote a sugar. The common usage of the word "sugar" signifies table sugar, which is a disaccharide (sucrose) containing one monosaccharide each of Dglucose and D-fructose. The monosaccharides also known as simple sugars possess the general formula CnH2nOn. The name carbohydrate originates falsely from "carbon hydrate" [C(H2O)]n in which one water molecule was said to be bound to carbon.
1 1

Despite this initial structural description, the name

carbohydrate has been adapted in literature. The monosaccharides are classified according to the number of carbon atoms they contain: triose (n = 3), tetrose (n = 4), pentose (n = 5), hexose (n = 6), heptose (n = 7) etc. The simple basic building block is glyceraldehyde possessing only one asymmetric centre and therefore two enantiomers. Another type of classification of sugar compounds is by the nature of the carbonyl groups in their free, open chain form. A sugar containing an aldehyde is denoted by "aldose" and one containing a ketone is denoted by "ketose". Based on the fundamental works of van't Hoff and Fischer, an aldopentose has eight isomers and an aldohexose has sixteen isomers i.e. eight sets of enantiomeric pairs.
3,4 2

Two diastereomers, which differ at only one inverted

asymmetric centre, are called epimers.

Chapter 1

Introduction

The epimeric relations starting from allequatorial D-glucose and all axial D-idose are outlined as follows:

Fig:1.1 Epimeric relations of - and -D-glucopyranose and - and -D-idopyranose. It is evident that there are a large number of sugars exhibiting increasing structural complexity. The structural complexity increases further when consideration is given to combinations of monosaccharides leading to disaccharides, oligosaccharides and polysaccharides.
2,5

The most abundant monosaccharide is (+)-D-glucose, also commonly known as grape sugar, followed by (+)-D-mannose and (+)-D-galactose.1 The least available monosaccharides are L-altrose, L- and D-idose as well as L- and D-gulose, all of which are hexoses.

1.2 EQUILIBRIA AND MUTAROTATION OF SUGARS

-/-D-Glucopyranose is very stable as a solid. However, isomerization occurs rapidly in aqueous solution through mutarotation as shown in the following scheme.
2,6

In aqueous solution seven equilibria exist within the D-glucose

system. All products of these equilibria are isomers of D-glucose with the exception of 7, which is a hydrated form. The transformations pathways to all products occur via the open chain form of D-glucose.

Chapter 1

Introduction

The most predominant form is -D-glucopyranose (1) followed by -Dglucopyranose (2). The two five membered ring forms are the -Dglucopyranoses 3 with configuration and 4 with respectively. The least stable seven membered forms 5, 6 play only a very minor role in the equilibria network. The hydrated specie 7 is acyclic similar to D-glucose.

(1)

(2)

(3)

(7)

(4)

(6)

(5)

Fig: 1.2 Equilibria of glucose in aqueous solution.

Chapter 1

Introduction

1.3 OXIDATION PRODUCTS OF SUGARS

Aldopyranonses and -furanoses possess three different alcohol functionalities: a primary alcohol, three secondary alcohol groups and one hemiacetal hydroxylgroup. These hydroxyl functionalities are identified in figure 1.3 with D-glucopyranose as an example.

Figure 1.3 Different hydroxyl groups of -D-glucopyranose.

Each of these OH groups can be oxidized to corresponding sugar derivatives as shown in Figure 1.4. Aldonic acids can be generated by the oxidation at the C1 terminus. These are generally found in lactone form. Three possible keto-sugars can be generated by oxidation of any of the secondary alcohol function. By oxidation of the primary alcohol an aldehydo-sugar is formed.

Chapter 1

Introduction

Fig:1.4 First oxidation products of glucopyranose.

An aldonic acid is any of a family of sugar acids obtained by oxidation of the aldehyde functional group of an aldoses to form a carboxylic acid functional group. Thus, their general chemical formula is HOOC-(CHOH)n-CH2OH. Oxidation of the terminal hydroxyl group instead of the terminal aldehyde yields a uronic acid, while oxidation of both terminal ends yields an aldaric acid. Aldonic acids are typically prepared by oxidation of the sugar with bromine. They are generally found in their lactone form, with the ring structure essentially the same as in the original sugar's cyclic hemiacetal form, which is the form the sugar is usually found in. However, unlike hemiacetals, lactones do not have a chiral anomeric carbon, and they cannot form glycosidic linkages. Aldonic acids are found in many biological systems, and are the products of the oxidation of aldoses by Benedict's or Fehling's reagents. Their lactones are key intermediates in the Kiliani-Fischer synthesis of sugars.

Chapter 1

Introduction

1.4 REDUCING AND NON-REDUCING SUGARS

Sugars may be classified as reducing or non reducing based on their reactivity with Tollens, Benedicts or Fehlings reagent. If a sugar is oxidized by these reagents it is called reducing, since the oxidant (Ag+ or Cu+2) is reduced in the reaction
CHO

Cu+2

(CHOH)n CH2OH

Cu2O

+ Oxidation Products

All carbohydrates that contain a hemiacetal group give positive tests (Fig 1.5). In aqueous solution these hemiacetals exist in equilibrium with relatively small concentrations of non cyclic aldehydes or -hydroxy ketones that undergo the oxidation.
C O OH

C
C

R/

Fig 1.5 Hemiacetal (R' = H or =CH2OH) Reducing sugar

Carbohydrates that contain only acetal groups do not give positive tests with
Benedicts Tollens solution, and they are called non reducing sugars (Fig 1.6).

Acetals do not exist in equilibrium with aldehydes or -hydroxy ketones in the basic aqueous media of the test reagents.

O C C

R/

Fig 1.6 Acetal (R = Alkyl group or another sugar, R' = H or = CH2OH) Non-reducing sugar

Chapter 1

Introduction

1.5 OXIDATION WITH SOME IMPORTANT OXIDIZING AGENTS 1.5.1 Bromine Water: The Synthesis of Aldonic Acids
The free sugar acids can be obtained by oxidation with aqueous bromine solutions or electrochemically from their corresponding free monosaccharides.7,8,9 Bromine water is a general reagent that selectively oxidizes the CHO group to a CO2H group.

CHO (CHOH)n (CH2OH)

Br2 H2O

COOH (CHOH)n CH2OH

Another access to aldonic acids is possible through the Kiliani method, in which the aldose sugar is reacted with cyanide and the resulting epimeric cyanohydrins are then hydrolyzed to the homologous aldonic acids.10,11 In this case the carbon chain is of course lengthened by one atom, i.e. a hexose would yield a heptonic acid.

CHO R

HCN

CN
OH

H3O+

COOH
OH

1.5.2 Nitric Acid Oxidation: Aldaric Acids

Dilute nitric acid, a stronger oxidizing agent than bromine water, oxidizes both the CHO group and the terminal CH2OH group of an aldose to CO2H groups. These dicarboxylic acids are known as aldaric acids.
CHO COOH

HNO3
(CHOH)n

(CHOH)n

CH2OH

COOH

Chapter 1

Introduction

1.5.3 Periodate Oxidations: Oxidative Cleavage of Polyhydroxy Compounds

Compounds that have hydroxyl groups on adjacent atoms undergo oxidative cleavage when they are treated with aqueous periodic acid (HIO4). The reaction breaks carbon-carbon bonds and produces carbonyl compounds (aldehydes, ketones or acids). The stoichiometry of the reaction is

OH

+
C OH

HIO4

+ HIO3 + H2O

Periodate oxidations are thought to take place through a cyclic intermediate:

OH

+
C OH

IO4-

-H2O

C C

O O

+ IO3-

In these periodate oxidation that for every CC bond broken, a CO bond is formed at each carbon.

Chapter 1

Introduction

1.5.4 Other Sugar Oxidation Products

The oxidation of sugar compounds has been widely studied as there is a general interest to produce value-added chemical building blocks from feedstock other than petroleum based sources such as cellulose and starch.12-16 e.g. the modification of cellulose is being studied as part of material science to create new compounds with improved physical properties such as high water absorption.

CHAPTER # 2

LITERATURE S U R V EY

Chapter 2

Literature Survey

2. LITERATURE SURVEY
The study of carbohydrates is one of the most exciting fields of organic chemistry. Vast literature is available on the kinetics of oxidation of carbohydrates by various organic and inorganic oxidants.

2.1 OXIDATION OF REDUCING SUGAR BY HALOGENS

The oxidation of aldoses by chlorine, bromine and iodine has been reported in alkaline media.17-19 Patel and co-workers20 worked on oxidation of starch and its derivatives with chlorine and sodium hypochlorite. The oxidation rate of starch with NaOCl in buffered systems was highest at pH 7. The OH groups of starch take an active part in the oxidation rate which decreased when C-2 and C-3 OH groups were blocked. Zienius and purves21 studied the oxidation of DGalacturonic acid with some delignifying and bleaching agents. It was observed that D-galacturonic acid was oxidized with decreasing ease, and in the approximate order shown, by excess of the following agents; Sodium chlorite near pH 2.8 and 75o; sodium hypochlorite at pH 10-11 and 25o; chlorine dioxide, pH 1.3 of 5 at 75o; chlorine 0o and pH 5 (slight); and hydrogen peroxide at pH 10 11 and 25o (negligible). Some uronic acid was always recovered uncharged, even from conditions that would have oxidized glucose quantitatively to gluconic acid. The only other products were mucic acid, together with DL-tartaric acid and tartronic acid presumably derived there from. Chlorine dioxide, however, never produced tartronic acid. Methyl--D-galacturonic side methyl ester yielded some galacturonic acid when exposed to alkaline hypochlorite or peroxide, and this cleavage of the glycosidic group was tentatively attributed to the oxidants rather than to the alkalinity of the systems, Anhydrous bromine degraded the silver salt of Methyl--D-galacturonoside in poor yield to a syrup which was probably
L-arabotrihydroxyglutartic dialdehyde.

10

Chapter 2

Literature Survey

2.1.1 Bromine as an Oxidant

The aldonic acids as primary products of oxidation of aldoses by bromine have been extensively studied by Isbell and co-workers.22-25 It was suggested that differences in the rates of oxidation of the and anomers are largely determined by differences in the free energy required by the reactants for passing from the ground state to the complex in the transition state. The relative rates of oxidation are in accordance with the hypothesis that each of the aldoses in the ground state has the conformation predicted by Reeves, and in the plane formed by the ring oxygen atom, C-1, C-2 and C-5. Presumably, this conformation is stabilized by resonance involving the oxygen atom of the ring. For aldoses having high stability in one chair conformation, the rates of oxidation of the anomers differ widely; in each instance, the anomer in which the C-l hydroxyl group is axial is oxidized more slowly than the anomer in which this group is equatorial.

2.1.2 Use of Iodine for Oxidation of Sugars

Prasad et al 26 gave the kinetics of oxidation of arabinose and xylose by iodine in alkaline solution. The order of reaction with respect to iodide ion is unity. Nizami et al27 studied that kinetics of the oxidation of maltose and lactose by alkaline iodine solution. The reactions of different concentrations of sugars and iodine at different pH and temperature were studied. The findings revealed that iodine followed zero kinetics and the different sugars concentrations followed first order kinetics. The rate of oxidation of sugars in iodine was independent of different iodine concentrations. Iodine reacted with sodium hydroxide and then was converted to triiodide (I3-), Hypoiodate (OI-) and hypoiodous acid (HOI). The most effective oxidizing agent was HOI.

11

Chapter 2

Literature Survey

The rate of oxidation reaction was followed first order kinetics with respect to disaccharide concentration. The rate of reaction was affected by change in pH. The maximum rates of oxidation of maltose and lactose occurred at pH 11.0. Salt electrolyte did not affect the reactions. The activation energy for maltose was 60.29 KJ/mol. Singh et al28 investigated the kinetics of oxidation of mellibiose and cellobiose by alkaline aqueous iodine at different pH. The results indicated that the active oxidizing species is hypoiodous acid. A first order dependence in hypoiodous acid, melibiose and cellobiose has been observed.

2.2 OXIDATION THROUGH HALO COMPOUNDS 2.2.1 Hypobromous Acid

Yang et al29 studied that the kinetics of the oxidation of glucose with hypobromous acid in a nearly neutral medium by using spectrometry technique. The reaction was of first order with respect to glucose and to hypobromous acid and had a negligible salt effect.

2.2.2 Oxidation with Potassium Bromate

Potassium Bromate has been widely used in the oxidation of various compounds.
30-38

Kalyan et al39 described the kinetics of oxidation of some aldoses and amino

sugars by potassium bromate in hydrochloric acid medium. The reactions appear to proceed through the intermediate formation of bromate esters followed by the decomposition of the esters to give products. Hydrogen ion accelerates the rate of each reaction.

12

Chapter 2

Literature Survey

Shukla and Bajpai40 studied the kinetics of oxidation of D-(+)-glucose by potassium bromate in acidic medium. The order with respect to KBrO3 was determined by Vant Hoff's differential method where as in case of D-(+)-glucose and H+ it was determined by Vant Hoff's differential method. The reaction is of first order with respect to substrate and oxidant. A combination of sulphuric acid and potassium bromate in the presence of SiO2 were used as an effective oxidizing agent for the oxidation of alchohols to their corresponding aldehyde or ketone derivatives in dichloromethane, acetonitrile or toluene with good yields.41 Ru (III) catalyzed oxidation of maltose by bromate in acidic as well as alkaline medium was also studied by Srivastava and co-workers.42,43 They observed first order kinetics in the lower KBrO3 concentration which become zero order at higher concentration. The order of reaction with respect to Ru(III) is one. Srivastava and co-workers44 also studied the Ru(III) catalyzed oxidation of xylose by an acidified solution KBrO3 in presence of mercuric acetate as a scavenger for Br- ion. First order kinetics in the lower KBrO3 concentration range tended to zero order at higher concentration. The order of reaction with respect to substrate is zero but the order with respect to Ru(III) is one.

2.2.3 Oxidation by Periodic Acid

Xiong et al45 showed the oxidation of cellulose with periodic acid by using the additives under heterogeneous method. The results showed the degree of oxidation was 100%, when the reaction temperature was increased about 30-40 and the reaction was shortened to 4 hours.

13

Chapter 2

Literature Survey

2.2.4 Periodate
Reports regarding the use of periodate in the uncatalyzed oxidized oxidation of carbohydrates and polymeric substrate and Ru(III) and ruthenate ion catalyzed oxidation of reducing sugars in alkaline medium are also available. 46-48 Singh et al48 studied the kinetics and mechanism of oxidation of D-glucose and Dfructose by alkaline solution of potassium iodate in the presence of Ru (III) as homogenous catalyst. Their results show that the order with respect to [Ru (III)] is unity and the order wit respect to [reducing sugar] is zero in the oxidation of both glucose and fructose. Variation in [Cl-] and ionic strength used of the medium does not affect the oxidation rate. Varma and Kulkarni49 gave the detailed studies on the sodium metaperiodate oxidation of cellulose to yield 2,3-dialdehyde cellulose. It has been carried out to ascertain the effects of concentration of periodate relative to cellulose, temperature of reaction, pH of the medium. Microcrystal, cellulose had slightly higher reactivity than cellulose because of its greater purity and lower molecular weight, which gave rise to more reactive end groups. Tripathi and Upadhyay50 investigated the kinetics of oxidation of some reducing sugars viz. glucose, galactose, fructose, maltose and lactose by Os (VIII) in presence of sodium metaperiodate in alkaline medium. The reactions are zero order in periodate. The order of reaction in substrate and OH- decreases from unity to zero at higher [substrate] and [OH-] respectively. Rate of oxidation is proportional to [Os (VIII)]. Os (VIII) serves as an effective oxidant which oxidizes reducing sugars and itself reduces to Os (VI). Role of IO4- is to regenerate Os (VIII) from Os (VI). An evidence for the complex formation between Os (VIII) and reducing sugar has also been obtained.

14

Chapter 2

Literature Survey

Singh et al51 gave a general mechanism for Ru (III) catalyzed oxidation of

L(+)arabinose (Ara) and D(+)galactose (Gal) with periodate in aqueous alkaline

medium.

The most reactive species of the catalyst was found to be

[RuCl3 (OH)2 H2O]2-. The reactions exhibit pseudo-first order kinetics with respect to Ru (III) and are first order with respect to lower [IO4-] and [OH-] but tend towards zeroth order to both higher [IO4 -] and [OH-]. The reactions are zero order with respect to each aldose. Positive effect of Cl- on the rate of reaction is also evident in the oxidation of both reducing sugars. The kinetics of oxidation of maltose by periodate in alkaline medium have also been investigated.52 The reaction rate is zero order dependent in [IO-4] while the order with respect to [maltose] and [OH-] is unity. Oxidation of some reducing sugars by sodium metaperiodate in alkaline medium was also studied in presence of Ru (III) as a catalyst.53 The kinetic results may be represented by the following rate law:
[Catalyst] k OH [Substrate] IO4 d IO4 = I dt k + k 0 OH + k III [Substrate] IO4

[ ] [

] [

[ ]

[ ]

Shenai and Wagh54 reported that the rates of oxidation by sodium periodate of cellulose and cellulose dyed with reactive dyes at 32oC was markedly increased by the addition of alkali metal chlorides or sulfates. The extent of oxidative degradation of cellulose was assessed in terms of oxygen consumption during oxidation. Srivastava and Singh55 investigated the kinetics of Rh (III) catalyzed oxidation of sucrose by sodium periodate in acidic medium in the temperature range 30-50oC. The reaction is carried out in the presence of mercuric acetate as a scavenger for bromide ion. The rate shows first order kinetics with respect to the oxidant i.e, sodium periodate and Rh (III) for sucrose.

15

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Negligible effect of mercuric acetate and ionic strength of the medium was observed and the reaction showed no effect of [Cl-] and [H+] on the reaction rate for sucrose. Srivastava et al56 also studied the kinetics of oxidation of dextrose and maltose under same conditions. The rate shows first order kinetics with respect to the oxidant, sodium periodate and Ru (III) for the dextrose and maltose. Singh et al57 worked on the Ir (III) catalysis of the iodate oxidation of xylose and maltose in aqueous alkaline medium. The reactions show first order kinetics with respect to lower [IO-3 ] and [OH-] and show zero order kinetics at their higher concentrations. Unity order at low concentration of maltose becomes zero order at its higher concentration whereas zero order kinetics with respect to [xylose] was observed throughout its variation. The reaction rate is found to be directly proportional to [Ir (III)]. It is reported that KIO3 has also been used as an oxidant in the oxidation of acetophenones,
58

ferrocyanide,

59

thiocynate

60

and 1.3-dihydroxybenzene

61

in
, 62

acidic medium. In each case IO3- has been regarded as the reactive species of KIO3 in acidic medium. Kinetic studies for Os (VIII)-59 and Ru (III) catalyzed 59

oxidation of organic compounds by an acidic solution of iodate are also reported. In these cases either HIO3 or IO3- has also been concluded to be the reactive species of KIO3 in acidic medium. A few reports are available where NaIO4 has been as an oxidant in Ru (III) and ruthenate ion-catalyzed oxidation of reducing sugars in alkaline medium. On the basis of equivalence and kinetic studies for both the redox processes, IO4- is reported to be finally converted into IO3-, which very well supports the existence of IO3- in alkaline medium. In view of the reported kinetic data and spectral evidence, it can very easily be concluded that the species IO3- is the reactive species of KIO3 in oxidation of xylose and maltose in alkaline medium.

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2.2.5 Electron Transfer Reactions Involving Perchlorate as an Oxidant

Fadnis and Arzare63 determined the kinetics of electron transfer reactions of aquothallium (III) perchlorate with aldo-pentoses (D-xylose, D-arabinose and D-ribose) under the pseudo-first order conditions. The fractional order with respect to aldopentoses concentrations suggests Michaelis-Menten type of kinetics. The rate decreases with acid concentration, and is strongly inhibited by the complex chloride, acetate ions and acetic acid. A free radical mechanism involving aldopentoses derived free radical has been proposed for these reactions.

2.2.6 Hypochlorite
Singh64 discussed the rate of uncatalyzed, Mn (II)-catalyzed, and Co (II)-catalyzed hypochlorite oxidation of cellulose:
dc = k [HOCl ] OCl dt

1 2

The reaction proceeds by a free-radical mechanism. The maximum rate occurred of cellulose is

dc = k / [HOCl ] OCl dt

The maximum rate occurs at pH 7.5.

2.2.7 Chloroamine-T
Kambo and Upadhay65 studied the kinetics of the Ru (III) catalyzed oxidation of reducing sugars, viz, arabinose, xylose, galactose, glucose, fructose, lactose and maltose by chloramines-T in alkaline medium. The reactions exhibit a first order rate dependence with respect to: [substrate], [chloramine-T] and [OH-]. The rate is proportional to {k'+k" [Ru (III)]}, where k' and k" are rate constants for uncatalyzed and catalyzed way respectively.

17

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Kambo and Upadhay66 also investigated the kinetics of Pt (IV) catalyzed chloroamine-T oxidation of glucose, galactose and fructose in alkaline medium. The reactions are first order in oxidant, while the order reaction in substrate and OH- decreases from unity at higher [substrate] and [OH-] respectively.

2.3 N-HALO COMPOUNDS

The catalyzed and uncatalyzed oxidation sugars have been studied in detail by using N-halo compounds.67-75 Rangappa et al76 proposed the kinetics and mechanism of oxidation of three methyl pentoses, namely D-fructose, L-fructose and L-rhamnose with sodium-N-chloro benzene sulfonamide in alkaline medium at 313K. Benzene sulfonamide and chloride ion, the reduced product of oxidant has no effect on the reaction rate. Kanchugarakoppal et al77 studied the kinetics and mechanism of oxidation of D-glucose, D-mannose, D-fructose, D-arabinose and D-ribose with N chloro-p-toluene-sulfonamide in alkaline medium. The rate of reaction was influenced by change in ionic strength of the medium and the dielectric effect was found to be negative. N-Bromo-arylsulfonamides of different oxidizing strengths are used for studying the kinetics of oxidation of D-fructose and D-glactose in aqueous alkaline medium.78 The results are analysed and compared with those from the sodium salts of N-bromo-benzenesulfonamide and N-bromo-4-methylbenzenesulfonamide. The reactions show zero order kinetics in [oxidant], fractional order in [Fructose/Glucose] and nearly first order in [OH-]. Gowada et al79 also employed nine sodium salts of mono and di-substituted NChloroarylsulfonamides as an oxidant for studying the kinetics of oxidation of
D-fructose and D-glucose in aqueous alkaline medium. The reactions show first

order kinetics each in [oxidant], [Fructose/Glucose] and [OH-]. The rates slightly increase with increase in ionic strength of the medium.

18

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Rahmani et al80 studied the kinetics of Ir (III)-catalyzed and Hg (II)-co-catalyzed oxidation of D-glucose (Glu) and D-fructose (Fru) by N-bromoacetamide (NBA) in acidic medium. The reactions follow identical kinetics, being zero order in each sugar concentration. The experimental results show a first-order dependence on NBA and Ir (III) at low concentrations, but tending towards zeroth order at higher concentrations. A negative effect of variation of [H+], [Cl-] and [NBsA] was observed whereas the ionic strength (I) of the medium has no influence on oxidation rate. The important feature of the reaction is that it follows a secondorder dependence on mercury (II) ion concentration at low concentrations, but it tends towards first order at higher concentrations. The corresponding acids were identified as the main oxidation products of the reaction. Kumar et al81 gave the kinetics of oxidation of reducing sugars D-galactose and
D-ribose by N-bromoacetamide (NBA) in the presence of Ru (III) chloride as a

homogenous catalyst and in perchloric acid medium, using mercuric acetate as a scavenger for Br- ions, as well as a co-catalyst. Singh et al82, 83 studied the kinetics of Pd (II) catalyzed and Hg (II) co-catalyzed oxidation of D-glucose D-fructose, D-mannose and D-maltose by Nbromoacetamide (NBA) in the presence of perchloric acid using mercury (II) acetate as a scavenger for Br- ions. The results showed first-order kinetics with respect to NBA at low concentrations, tending to zero order at high concentrations. First order kinetics with respect to Pd (II) and inverse fractional order in Cl- ions throughout their variation have also been noted. The observed direct proportionality between the first order rate constant (k1) and the reducing sugar concentration shows departure from the straight line only at very higher concentration of sugar. Addition of acetaminde (NBA) decreases the first order rate constant while the oxidation rate is not influenced by the change in the ionic strength () of the medium.

19

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Variation of [Hg(OAc)2] shows a positive effect on the rate of reaction. The observed negative effect in H+ at lower concentrations tends to an insignificant effect at its higher concentrations. Kinetic studies have also been made for the oxidation of reducing sugars by acidic solution of N-bromosuccinimide (NBS) in presence of Ir (III) as the homogenous catalyst.84 Moreover, the role of Pd (Il) chloride as a catalyst in NBS oxidation of arabinose, xylose and galactose by N-bromosuccinimde (NBS) in acidic medium using Hg (OAc)2 as a scavenger for the Br- ion has also been reported.85 The reaction data showed the first order kinetics in each pentose and hexoses at low concentration tend to zero order at high concentration. First order kinetics with respect to NBS and Pd (II) and inverse fractional order, i.e, decreasing effect of [H+] and [Cl-], were observed, whereas ionic strength Hg (OAc)2 and succinimde did not influence the oxidation rate. Various activation parameters have been calculated and recorded. The corresponding acids, arabinonic, xylonic and galactonic were identified as the main oxidation products of the reactions. Several researchers
93

worked

upon

oxidation

kinetics

involving

N-

bromosucccinimide (NBS) and esters86, alcohols 87 and 88, ketones 89-91, polyhydric alcohols 92 and glycol as oxidizing agents. It is also known that NBS oxidation of organic compound is complicated by parallel bromine oxidation. However, bromine oxidation is obviated by using Hg (II).86 The repeating sequences of elastin, glycylglycylalanylproline (GGAP) glycylglycylisoleucylproline (GGIP) and more hydrophobic glycylglycylphenylalanylproline (GGPP), were synthesized by classical solution phase methods and characterized.94 The kinetics of oxidation of tetrapeptides (TPs) and their constituent amino acids (AAs) by Nbromosuccinimide (NBS) was studied in the presence of perchlorate ions in acidic medium at 28 C. The reaction was followed spectrophotometrically at max 240 nm.

20

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Literature Survey

The reactions follow identical kinetics, being first order each in [NBS], [AA] and [TP]. No effect on the rate of [H+], reduction product [succinimide] and ionic strength was observed. Effects of dielectric constant of the medium and the added anions such as chloride and perchlorate were studied. Activation parameters have been computed. The oxidation products of the reaction were isolated and characterized. An apparent correlation was noted between the rate of oxidation and the hydrophobicity of AAs and TPs.

2.4 OXIDATION THROUGH TRANSITION METALS 2.4.1 Manganese (Mn)

Khan and Kumar95 describe the oxidative degradation of gum Arabic by colloidal manganese dioxide (MnO2). Monitoring the disappearance of the MnO2 spectrophotometrically at 375 nm was used to follow the kinetics. The oxidation obeyed fractional-order kinetics with respect to the [gum Arabic]. Effects of various experimental parameters such as the initial colloidal [MnO2], [HClO4], temperature, and complexing agents (P2O74-, F-, and Mn2+) for the oxidation of gum arabic were studied. The reaction was acid catalyzed. Addition of P2O74-, F-, and Mn2+ ions enhances the rate of oxidation significantly. Gum arabic adsorbs on to the surface of the colloidal MnO2 through the equatorial OH groups of the rhamnose moiety, and the complex breaks down into products. The reducing nature of gum arabic is found be due to the presence of OH group in the skeleton. Gupta and Begum96 studied the kinetics of oxidation of some aldoses, amino sugars and methylated sugars by tris- (pyridine-2-carboxylato) manganese (III) spectrophotometrically in sodium picolinate-picolinic acid buffer medium.

21

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Sricar et al97 determined the glucose, fructose, xylose, arabinose, and sucrose titrimetrically using Mn (III) sulfate as an oxidant. On reaction in the dark, glucose consumes 5, fructose 7, xylose and arabinose 6 each, and sucrose after hydrolysis 12 equivalent of Mn (III)/mol, respectively.

2.4.2 Cerium (Ce)

Pottenger and Johnson98 examined that Ce (IV) oxidations of model compounds for the hydroxylic functional groups of cellulose in 1.0 mol dm-3 perchloric acid. Glucose, the model selected for the reducing end group was oxidized 360 times faster than Schardinger -dextrin, the model for anhydro-D-glucose repeating units. In the presence of a fourfold excess of glucose, stoichiometry indicated specific conversion to arabinose; the competitive oxidation of arabinose produced is insignificant. Kinetic studies showed that chelate complexes were involved in the oxidations of glucose, methyl -D-glucopyranoside, 1, 5-anhydro-D-glucitol and Schardinger-dextrin. Agarwal99 studied the kinetics of oxidation of mannitol by Ce (IV) in sulphuric acid medium. The spectral analysis of hydrazone derivative of the product indicates the product to be an aldehyde. The substrate forms an intermediate complex with the oxidant as observed both kinetically and spectrophotometrically. Ce (SO4)2 has been considered to be the reactive species. The rate of bromide catalyzed oxidation of fructose by Ce (IV) has been measured by Sah100 in aqueous sulphuric acid medium at constant ionic strength. The reaction is first order dependent each in fructose and Ce (IV). The rate of reaction decreases on increasing the concentration of hydrogen ion. The bromide ion shows positive catalytic effect on the reaction rate. Sharma and Sah101 discussed the kinetics of bromide catalyzed oxidation of dextrose by Ce (IV) in aqueous sulphuric acid medium which showed first order dependence each in dextrose and Ce (IV). The reaction rate decreases on increasing the concentration of hydrogen ion. The bromide ion shows positive 22

Chapter 2

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catalytic effect on the reaction rate. The kinetics and mechanism of cerium (IV) oxidation of hexitols i.e. D-sorbitol and D-mannitol in aqueous sulfuric acid media have been studied in the presence and absence of surfactants.102 The over all process shows first order dependence on [Ce (IV)]T and [S]T and is acid catalyzed and inhibited by [HSO4-]. Singh et al103 examined the Ce (IV) oxidation of dextrose and sorbose in aqueous sulphuric acid medium. This reaction shows first order kinetics with respect to both Ce (IV) as well as the substrate. The reaction rate decreases on increasing the concentration of hydrogen ion. The variation of sulphate ions shows retarding effect on the reaction rate. Din et al104 observed the effect of surfactant micelles on the kinetics of oxidation of D-fructose by cerium (IV) in sulphuric acid medium. Kinetics of the oxidation of D-fructose by cerium (IV) has been investigated both in the absence and presence of surfactants (cetyltrimethylammonium bromide, CTAB, and sodium dodecyl sulphate, SDS) in sulphuric acid medium. The reaction exhibits first order kinetics each in [Ce (IV)] and [D-Fructose] and inverse first order in [H2SO4]. The Arrhenius equation is found to be valid for the reaction between 3050oC. While SDS has no effect, CTAB increases the reaction rate with the same kinetic behavior in its presence. The catalytic role of CTAB micelles is discussed in terms of the pseudo phase model proposed by Menger and Portony. The association constant Ks that equals to 286 mol-1 dm3 is found for the association of Ce (IV) with the positive head group of CTAB miscelles.

2.4.3 Vanadium (V)

Khan et al105 proposed the oxidative degradation of D-fructose by V (V) in the presence of H2SO4 as an induction period followed by auto acceleration. The kinetics and mechanism of the induction period has been studied at constant ionic strength. The reaction was followed spectrophotometrically by measuring the change in absorbance at 350nm. V (V) is only reduced to V (IV).

23

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The reaction is first and fractional order in [V (V)] and [D-fructose], respectively; but dependence on [H+] is complex. At constant [H2SO4] sodium hydrogensulfate accelerates the reaction. The effect of added sodium sulfate on the H2SO4 and HSO4 catalyzed reaction is also reported. Reaction products are also examined and it is concluded that oxidation of D-fructose by V (V) involves consecutive one-electron abstraction process. Rizvi and Singh106 reported the reaction of some monosaccharides with ammonium metavanadate in sulphuric acid. It has been followed potentiometrically and kinetically. The results are consistent with the mechanisms proposed by Water and Soffyn. Bhattnagar and Fadnis107 discussed the rate of oxidation of D-ribose with quinquevalent vanadium. The reaction involving C-C bond fission and via free radical has been proposed. The kinetics of oxidation of lactose by vanadium (V) in sulfuric acid perchloric acid and hydrochloric acid media was studied.108 The reaction was of first order with respect to oxidant and substrate. The reaction was catalyzed by acids but the dependence on acidity is complex. Kumar and co-workers109 studied the kinetics of oxidation of D-maltose by quinquevalent vanadium in aqueous sulphuric acid. The order of reaction with respect to the oxidant and substrate has been found to be one.

2.4.4 Chromium (Cr)

Sala et al110 studied the oxidation of D-lactose, D-maltose, D-melibiose and
D -cellobiose by Cr (VI) yield the corresponding aldobionic acid and Cr (III) as the

final products, when an excess of reducing disaccharides over Cr (VI) is used. The rate law for the Cr (VI) oxidation reaction is expressed by

d [Cr (VI )] = k H [disaccharide] [Cr (VI )] dt

where the second order rate constant kH depends on [H+]. The relative reactivity of the disaccharides with Cr (VI) is expressed as Mel.> Lac.> Cel.> Mal.

24

Chapter 2

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At 33C in acidic medium, intermediate Cr (V) forms and reacts with the substrate faster than Cr (VI). The EPR spectra show that five- and six- coordinate oxo-Cr (V) intermediates are formed, with the disaccharide acting as a bidentate ligand. Fivecoordinate oxo-Cr(V) species are present at any [H+], where as six- coordinate ones are observed only at pH<2 where they rapidly decompose to the redox products. Sala et al111 also discussed the kinetics of oxidation of L-rhamnose and Dmannose by Cr (VI) in perchloric acid leading to L-1,4-rhamnonelactone and D1,4-mannonelactone. Relative values of kinetic constants are interpreted in terms of primary hydroxyl group participation in the chromic ester formed in the first reaction step. The free radicals formed during the reaction react with Cr (VI) to yield Cr (V). Sharma and Rai112 showed the oxidation of D-galactose, D-xylose and D-arabinose by chromium peroxydichromate in very dilute sulphuric acid. The reaction is of first order each in substrate, oxidant and sulphuric acid. HCrO4appears to be the predominant oxidant. The kinetics of the reduction of Cr (VI) to Cr (III) by D-fructose in HClO4 was studied by Garcia et al.113 The redox reaction involves the formation of intermediate Cr (V) and Cr (V) species. Cr (IV) reacts with fructose much faster than Cr (V) and Cr (VI) do. The kinetics and mechanism of Cr (VI) oxidation of fructose in the presence and absence of 2,2-bipyridyl (bipy) and 1,10phenanthroline (phen) in aqueous media have been studied.114 The monomeric species of Cr (VI) has been found to be kinetically alkaline in the absence of bipy and phen whereas in the heteroaroms.

25

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2.4.5 Osmium (Os)

Singh et al115 proposed the general mechanism for oxidizing reducing sugars (pentoses, hexoses and disaccharides) by OsO4 in alkaline medium. The reactions exhibit pseudounimolecular kinetics with respect to OsO4, are first order with respect to lower [sugar] and [OH-], but tend towards zero order with respect to both higher [sugar] and [OH-].

2.4.6 Copper (Cu)

Singh116 reported the oxidation of maltose and lactose by Cu (II) in the presence of ammonium hydroxide. The reactions are zero order in Cu (II) and first order in substrate and hydroxide ion concentration. It was suggested that the rate determining step involves the reaction between hydroxyl ion and reducing sugar, leading to an intermediate active product which is rapidly oxidized by Cu (II) complex through an electron transfer process. Cu (II) oxidation of D-xylose, Larabinose, D-glucose, D-fructose, D-mannose, D-galactose, L-sorbose, lactose, maltose, cellobiose and melibiose in alkaline medium was studied by Singh and co-workers.117 The reaction showed a first order dependence with reducing sugar and alkalis concentration and the oxidation process was independent of Cu (II) concentration for all the reducing sugars.

2.5 TRANSITION METALS AS CATALYST IN OXIDATION REACTIONS 2.5.1 Bismuth (Bi)

Karshi and Witonska
118

determined the effect of Bi on the catalytic properties

used for oxidation with oxygen of glucose to gluconic acid in liquid phase at 1 atm pressure, 333K temperature and pH 9. Addition of Bi resulted in an increased activity and selectivity of the Pd/SiO2 catalyst.

26

Chapter 2

Literature Survey

Wenkin et al119 showed that Bi is a well-established promoter of noble metal based catalysts for the selective liquid phase oxidation of alcohols, aldehydes and carbohydrates with molecular oxygen. Experiments were carried out to improve the understanding of the promoting role of bismuth in bimetallic Pd-Bi catalysts used for the selective oxidation of glucose to gluconate. These catalysts undergo substantial bismuth bleaching under the reaction conditions. The bleaching process and the promoting effect itself are discussed in line with formation of Bi-glucose and the Bi-gluconate complexes present in solution but also as adsorbed species at the catalyst surface.

2.5.2 Rhodium (Rh)

The use of Rh (III) chloride as catalyst has been reported by several workers. 120, 21 Srivastava and Singh55 investigated the kinetics of Rh (III) catalyzed oxidation of sucrose by sodium periodate in acidic medium in the temperature range 30-50oC. The reaction is carried out in the presence of mercuric acetate as a scavenger for bromide ion. The rate shows first order kinetics with respect to the oxidant i.e, sodium periodate and Rh (III) for sucrose.

2.5.3 Ruthenium (Ru)

Ru (III) catalyzed oxidation of maltose by bromate in acidic as well as in alkaline medium was also studied by Srivastava and co-workers.42,43 Singh et al48 studied the kinetics and mechanism of oxidation of D-glucose and D-fructose by alkaline solution of potassium iodate in the presence of Ru (III) as homogenous catalyst. Kinetic studies for Os (VIII)59 and Ru (III) catalyzed
59, 62

oxidation of organic

compounds by an acidic solution of iodate are also reported. Kumar et al81 gave the kinetics of oxidation of reducing sugars D-galactose and D-ribose by Nbromoacetamide (NBA) in the presence of Ru (III) chloride as a homogenous catalyst and in perchloric acid medium, using mercuric acetate as a scavenger for Br- ions, as well as a co-catalyst.

27

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2.5.4 Platinum (Pt)

Basson et al122 showed that the glucose and the gluconate aqueous solutions were oxidized with air (atmospheric pressure, 333K, pH 7) on active charcoalsupported, platinum catalysts. The activity of unpromoted Pt/C catalysts for glucose oxidation was comparable with that of Pd-Bi/C catalysts and there was no deactivation. The oxidation of gluconate on very well dispersed Pt catalysts prepared by cationic exchange or anionic adsorption leads to higher glucarate selectivities. Van Dam et al123 showed that the factors affecting the activity of the Pt catalyzed oxidation of glucose 1-phosphate I glucuronic acid 1-phosphate II. A partial loss of starting material occurs through side reactions starting with the oxidation of secondary hydroxyl groups, followed by C-C bond cleavage.

2.5.5 Palladium (Pd)

Basson et al124 investigated the influence of the size of Pd particle and of their location supports on the activity of glucose oxidation. Abbadi et al125 showed the effect of pH on the palladium catalyzed oxidation of glucose to gluconic acid. The oxidation reactions were performed in the pH range 2 to 9 in a batch reactor using Pd/C or Pd black as the catalysts. It is concluded that gluconic acid in its free form reversibly inhibits the oxidation process in acidic media.

2.5.6 Mercury (Hg)

Mercury has been widely used as a catalyst or a co-catalyst by many researchers for the oxidation of sugars. Rahmani et al80 studied the kinetics of Ir (III)-catalyzed and Hg (II)-co-catalyzed oxidation of D-glucose (Glu) and D-fructose (Fru) by Nbromoacetamide (NBA) in acidic medium. Kumar et al81 gave the kinetics of oxidation of reducing sugars D-galactose and D-ribose by N-bromoacetamide (NBA) in the presence of Ru (III) chloride as a homogenous catalyst and in perchloric acid medium, using mercuric acetate as a scavenger for Br- ions, as well as a co-catalyst.

28

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Singh et al82-83 studied the kinetics of Pd (II) catalyzed and Hg (II) co-catalyzed oxidation of D-glucose D-fructose, D-mannose and D-maltose by Nbromoacetamide (NBA) in the presence of perchloric acid using mercury (II) acetate as a scavenger for Br- ions.

2.6 AIR OXIDATION

Heinen et al126 discussed the oxidation of D-fructose with molecular oxygen on Pt/C catalysts. Two major products are formed: 2-keto-D-gluconic acid
D-threohexo-2, 5-diulose. Deactivation of the catalyst was observed, caused both

by over-oxidation of the active surface and inhibition of the reaction by 2-keto gluconic acid. Bao et al127 discussed the air oxidation of glucose catalyzed by free and immobilized glucose oxidase. It was carried out in the gluconate buffer solution prepared to develop an efficient production of calcium gluconate crystals. The optimal pH, temperature and gluconate concentration as well as the kinetic parameters in the Michaelis-Menten rate expression were determined for the free enzyme reaction in an airtight batch reactor. The fine manganese dioxide particles were entrapped together with glucose oxidase within the calcium alginate gel beads to decompose hydrogen peroxide produce in the oxidation. Shalaby et al128 discussed the chromatographic method for the separation, identification and estimation of the products formed when saccharides are oxidized in alkaline solution with oxygen. The technique was then used to quantitate the acids produced when glucose is subjected to such an oxidation. Gleason and Barker129 studied the oxidation of pentoses ( D-xylose, D-ribose and L-arabinose and D-lyxose) with oxygen in alkaline solution. The reaction of pentoses with oxygen in dilute aqueous sodium hydroxide at 25.00 + 0.05o has been studied by determining the initial rate of oxygen uptake and the rate of disappearance of reducing sugar. Pentoses reactivity decreased through the series: D-ribose, D-lyxose, D-xylose and L-arabinose.

29

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2.7 HYDROGEN PEROXIDE (H2O2)

Nogues et al130 studied the structure changes, i.e. crystallinity, induced in cellulose fibers by oxidation during mercerization, laundering, etc. using FTIR Spectroscopy and measurements of total crystallinity index and lateral order index. The treatment with H2O2 of ramie and flax fibers resulted in an increase in the ratio of crystallinity in cellulose due to oxidative hydrolysis. At high H2O2 concentration, partial transformation of cellulose 1 to cellulose 2 occurred. Velarde et al131 determined the oxidation of D-glucose with hydrogen peroxide as an oxidant over several titanium-containing zeolites and Titania as catalysts. The oxidation of D-glucose occurred mainly to gluconic acid, glucuronic acid, tartaric acid, glycolic acid and glyceric acid.

2.8 OXIDATION INVOLVING TRANSITION METAL COMPLEXES AS OXIDANTS

Bajpai et al132 observed an inhibited effect of PdCl2 on the rate of oxidation of sugars by alkaline hexacyanoferrate (III). The order of reactions in hexacyanoferrate (III) and OH- is zero and unity respectively, while that in sugars decreases from unity at higher sugar concentration. The kinetic data and spectrophotometric evidence support the formation of {Pdll (sugar)} and {Pdll (sugar)2} complexes and their resistance to react with Fe(CN)63-. Hexacyanoferate (III) was also used by Srivastava and co-workers133 for the oxidation of some disaccharides in alkaline medium. The order of reaction is zero with respect to ferricyanide and first with respect to reducing sugar. Krishna and Rao134 investigated the kinetics of oxidation of D-glucose,
D-galactose, D-fructose, D-ribose, D-arabinose, D-xylose and 2-deoxy-D-glucose

by diperiodatoargentate (III) (DPA) in an alkaline medium. The order of the reaction with respect to [DPA] is unity while the order with respect to [sugar] is < 1 over the concentration range studied. The rate increases with an increase in [OH-] and there is a marginal decrease in rate with an increase in [IO4-]. No 30

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significant dependence on ionic strength was found, but the rate increases with a decreasing dielectric constant. Formic acid and the corresponding aldonic acids were detected as the products of oxidation. Srivastava et al135 worked on oxidation of D-maltose by aquasulfate cerium (IV) complex. The rate determining step is the formation of free radicals from the hydrolyzed substrate molecule. Gupta et al136 investigated the kinetics and mechanism of oxidation of lactose and maltose by tetraaminecopper (II) in ammonical and buffered medium. The rate of the reaction is dependent of [Cu(II)] and directly proportional to [dissacharide] and square root of [NH3]. On addition of NH4Cl the reaction rate decreases due to common ion effect.

2.9 INORGANIC OXIDANTS

Inorganic oxidants such as Cu (II), ammonical Ag (I) and Nesselers reagent have been used in the uncatalyzed oxidation of sugars in aqueous alkaline medium.137139

Nessler's reagent was used to oxidize maltose and cellobiose. The reaction rate

is completely independent of initial [Hg(II)] and is first order with respect to reducing [Sugar]. The reaction rate followed first order kinetics at low [OH-] and retarded with increasing iodide ion concentration. Modi and Ghosh140 gave the kinetic studies of oxidation of fructose by ammonical silver nitrate. The rate of reaction is of first order with respect to silver nitrate but has a tendency to increase at a lower temperature or decreasing ammonia concentration. The mechanism of the oxidation of fructose by ammonical silver nitrate is suggested through the enolic transformation of the carbonyl group. The determination of the number of equivalents of silver consumed per mole of monosaccharide shows that the molecule undergoes a fission reaction to yield glycolic and oxalic acid as oxidized products. Cerchiaro et al141 described an interesting Isatin-Schiff base copper (II) complex, [Cu(isapn)](ClO4)2 where (isapn)=N,Nt [bis-(3,3t-indolin-2-one)]-1,3-diaminepropane, was prepared and characterized by different techniques, both in the solid state and in solution, and its reactivity toward carbohydrate oxidation was

31

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verified. This compound was shown to catalyze the oxidation of hexoses (glucose, fructose and galactose), in alkaline media, via reactive oxygen species, which were detected by using specified enzymes, and by E.P.R. spin trapping. The reaction was monitored at (25.0 0.1) C by the consumption of oxygen, and showed first-order dependence on catalyst, followed by a saturation effect. Firstorder kinetics with respect to [OH-] concentration was also observed, indicating that enolization of the substrate as well as the metal-catalyzed enediol oxidation are the rate-determining steps. Abualreish142 worked on the mechanism of oxidation of arabinose, fructose and lactose by peroxydisulphate. The reactions are first order in peroxydisulphate and of fractional order in substrate concentrations. Tomar and Kumar143 studied the oxidation of
D-fructose

by

tetraethyl

ammonium

chlorochromate

[(C2H5)4NCrO3Cl] in aqueous acetic acid. The reaction has been found to be first order with respect to each of the oxidant and substrate under pseudo first order conditions. The reaction follows a first order dependence on H+ ion concentration while variation of ionic strength has no effect on the reaction rate. The kinetics and mechanism of oxidation of D-ribose, D-glucose and D-fructose by dichloroisocynauric acid (DCICA) in aqueous acetic acid-pechloric acid mixtures catalyzed by Ru (III) have been investigated.144 The oxidation has the following kinetic order: first order in oxidant and Ru (III) and zero order in substrate and H+.

2.10 OTHER OXIDATION REACTIONS

Tronchet and Bourgeoes145 discussed the treatment of the 1,2,5,6-di-Oisopropylidene--D-ribo- and xylo-hexofuranos-3-uloses with cyanomethylene triphenylphosphorane led in each case, and in almost quantitative yields, to a pair of geometrical isomers of C-cyanomethylenic sugars having respectively the ribo and the xylo configurations. Permanganate oxidation of these branched-chain unsaturated sugars yielded the corresponding gemhydroxyformyl compounds bearing the formyl group on the more hindered face of the molecule. The formyl

32

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group of these sugars is easily reduced to a hydroxymethyl group. Tildom et al146 observed the rates of [6-14C]-glucose oxidation by reconstituted systems of cytosol and mitochondria or cytosol and synaptosomes were essentially the same as the rate of oxidation of [3-14C]-3-hyroxybutyrate. However, the rate of [U-14C]glutamine oxidation by mitochondria was 2.5 times that by synaptosomes. The addition of glutamine (5 mM) caused a reduction in the rates of oxidation of [614

C]-glucose of 20% and 40% by mitochondria and synaptosomes respectively.

Singh et al147 discussed the kinetic study of oxidation of D-glucose, D-fructose,

D-mannose and D-galactose by quinolinium chlorochromate C9H7NH [CrO3Cl] in

the presence of perchloric acid in aqueous acetic acid medium. The reaction exhibits first order dependence in oxidant and substrate both under pseudo-first order conditions. The reaction is catalyzed by acid and a medium of low dielectric constant favors the oxidation process. Lu et al148 gave the synthesis of sorbitol and gluconic acid by electro-reduction and electro-oxidation of glucose. The optimum conditions of sorbitol synthesis and gluconic synthesis include Cc.d.0.18 A.cm-2,temperature of reaction: 30, initial concentration of glucose: 0.11 mol L-1, concentration of supporting electrolyte: 0.15 mol L-1 and c.d.0.18 A.cm-2, temperature of reaction: 50, initial concentration of glucose: 0.04 mol L-1, concentration of supporting electrolyte: 0.2 mol L-1 respectively. Under these conditions the current efficiency was 86.84% and 76.50% respectively. King et al149 studied that cellulose web was fabricated by electrospinning process under high voltage. Also, oxidized cellulose web was made by oxidation process, which involved the reaction of cellulose web with a mixture of nitrogen dioxide and perfluorocarbon. It was developed to prevent the adhesion of human body. Biella et al150 described the selective oxidation of D-glucose to D-gluconic acid. It was performed at both controlled (7-9.5) and free pH values in an aqueous solution in the presence of gold on carbon catalyst using dioxygen. No isomerisation of glucose to fructose was observed during the reaction, and total

33

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Literature Survey

selectivity to D-gluconate was obtained. Ibert et al151 gave the side products formed in the TEMPO-mediated oxidation of glucose to glucaric acid. Next to gluaric acid, gluconic acid, the intermediate in the oxidation and the degrading products, oxalic acid, tartonic acid, meso-(erytharic) and DL-threaric (tartaric) acid were detected. The DL-tartaric acid to be non-racemic mixtures of L-and Dtartaric acid, with inverse D/L ratios depending on the oxidation of the D- of Lglucose. Lundt et al152 showed the references on the chemoenzymic oxidation, reduction and deoxygenation reactions at the anomeric carbon of unprotected and protected carbohydrates and glycosides in preparation of lactose and alditols. Reactions on metal catalysts using oxygen and hydrogen peroxides, as well as microbial oxidation of carbohydrates, are emphasized. Wang et al153 reported that the starch adhesive was prepared from cassava starch by mixing it with water, oxidizing with KMnO4 in the presence of moderator. The effects of added concentration of oxidizing agent and oxidation time on the quality of the adhesive were studied. Cassiano and Almeida154 proposed the anodic oxidation of 0.80 mol L-1glucose (I) in the presence of fructose, from HCl hydrolysis of sucrose (II) in the presence of 0.050 mol L-1 bromide as catalyst and 0.80 mol L-1 as supporting electrolyte. Preliminary electrolytic studies with I allowed the best working conditions with II hydrolyzates to be established. The sodium gluconate solution obtained was precipitated with a stoichiometric concentration of CaCl2 in order to obtain Ca gluconate. Pao et al155 discussed a method of analysis where the sample was treated with oxidase to produce H2O2, and H2O2 reacts with a color reagent in the presence of peroxidase and is detected through Raman spectroscopy. Delobeau and Moine156 showed that the lactose solutions are hydrolyzed, the resulting glucose-galactose mixture is oxidized to give mixtures of D-arabinose and D-xylose, and this mixture is hydrogenated to give D-arabitol.

34

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Literature Survey

Agarwal and Tiwari157 gave the kinetics of oxidation of D-mannose with pyridinium chlorochromate, C5H5NHCrO3Cl, in aqueous perchloric acid medium. The ionic strength of the medium was maintained constant by adding sodium perchlorate solution. The oxidation process exhibits unit dependence in each of the reactants, namely D-mannose and pyridinium chlorochromate. The reaction is acid catalyzed. A 3:2 stoichiometry is observed in the oxidation and the reaction did not induce polymerization of acrylonitrile. Miljkovic et al158 determined the oxidation of D-glucose (I) with 36 % H2O2 in presence of CaCO3 and I2 in 1:5:3:0:1 ratio gave 18.8 % Ca D-gluconate (II) after 4 hours at 60. Oxidation of (I) with I2 in H2O containing CaCO3 in 1:1:2 ratios at 90 for 3 hours gave 59.5% II. D-fructose was inert to these conditions, and did not affect I oxidation to II. Blazicek and Langr159 discussed that the oxidation of cotton cellulose with N2O4 gave monocarboxycellulose with less ordered structure than that of the initial material. Glattfeld and Hanke160 used hydrogen peroxide and air to oxidize maltose in alkaline solution. They explained the formation of oxidation products by assuming that the free glucose unit of maltose is first enolized and the enols, after breaking, either become oxidized at once or undergo certain rearrangements with subsequent oxidation. Ross and McCarl161 observed the rates of uptake and oxidation of glucose, lactate, pyruvate, and palmitate were measured for "mixed" cultures of rat heart cells that exhibit a myocyte-to-fibroblast ratio similar to that observed in vivo. Glucose uptake and conversion to lactate were also measured using enriched cultures of myocytes and fibroblasts. The metabolism of mixed cultures, which contain 7080% myocytes, closely resembles that of enriched myocyte cultures. The energy production and substrate oxidation rates of cultured neonatal heart cells, adult myocytes, and perfused hearts are compared. It appears that the energy requirements of cultured heart cells are much lower than that of whole tissue.

35

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Literature Survey

Kuptsan et al162 showed that CoSO4-catalyzed oxidative degradation of cellulose in alkaline medium is a free radical process. The presence of catalyst increases the rate and extent of the degradation. Giffhorn et al163 and Freimund et al164-165 reported that the enzyme 2-glucoseoxidase catalyzed the oxidation of sugar substrates to 2-oxo-sugars as illustrated in Fig.2.1. The enzyme had been harvested from fungi. The proposed actual oxidant used by the enzyme was oxygen from the air generating hydrogen peroxidase by-product. The generated hydrogen peroxide was disproportionated to water and oxygen by a peroxidase in order to avoid undesired side reactions of hydrogen peroxide with the sugar products and enzyme present in the reaction solution.

-D-glucopyranose

2-oxo-- D-glucopyranose

Fig: 2.1 Synthesis of 2-oxo-- D-glucopyranose from - D-glucopyranose with an enzymatic process.

36

Chapter 2

Literature Survey

2.11 REACTIVE FORMS OF SUGARS IN ALKALINE MEDIUM

It is reported that in the presence of alkali reducing sugars undergo a tautomeric change resulting in the formation of an enediol anion and enediol.
O166

H H

C C

C R

OH + OH-

OH

+ H2O

R enediol anion

C C

OOH

C C

OH
OH

+ H2O

H2O

R enediol anion

R (1,2-endiol)

C
C

OH

C C R

OH

OH-

O-

+ H2O

R C C R

OH

C C

OH
OH

O-

+ H2O

OH-

enediol anion

(1,2-endiol)

The formation of the enediol anion and the enediol in the presence of alkali is also supported by the work of Isbell and co-workers. 167
37

Chapter 2

Literature Survey

2.12 PERMANGANATE AS AN OXIDIZING AGENT

Rao et al168 discussed the kinetics of oxidation of some monosaccharide viz., Dribose,
D-xylose, D-arabinose, D-glucose, D-fructose,
-

D-galactose,

2-

deoxyglucose, and -methyl glucopyranoside by MnO4 in aqueous alkaline medium. The rate of oxidation has been found to be first-order both with respect to [oxidant] and [sugar]. The rate is independent of [OH-] under experimental conditions of [OH-] > 0.5 M where the oxidant is stable. The effect of ionic strength is negligible on the rate. A mechanism involving the formation of a 5membered cyclic intermediate complex between MnO4- and 1,2enediol form of the sugar is proposed. Ahmed et al169 observed the kinetics of oxidation of chitosan as polysaccharide by permanganate in aqueous perchlorate media at a constant ionic strength. The reaction was found to have second-order overall kinetics and to be first-order in the concentration of both reactants, the results obtained show that the reaction is acid catalysed. It has been discovered that potassium permanganate is an effective heterogeneous oxidant, even without resorting to the use of a solid support, if acetonitrile is employed as the solvent.170 Primary benzylic and secondary alcohols are converted to the corresponding aldehydes and ketones, alkyl arenes are oxidized to the corresponding -ketones in good yields using this procedure, and both alkyl and aryl sulfides are smoothly converted to the corresponding sulfones, also in excellent yields. When methylene chloride is used as the solvent, instead of acetonitile, the yields of aldehydes, ketones, -ketones, and sulfones are reduced. However, the oxidation of thiols to disulfides proceeds satisfactorily when methylene chloride is the solvent.

38

Chapter 2

Literature Survey

Huang et al171 studied the oxidation of chlorinated ethenes by potassium permanganate. It has been observed that several materials can be used as KMnO4 carriers for scrubbing ethylene; rice hull ash, lahar (volcanic ejecta) ash and coconut coir dust have been evaluated. The ethylene scrubbing efficiency and stability of rice hull ash, lahar ash and coconut coir dust were studied. The oxidation of C2H4 by KMnO4 was found to be approximately first order for the three carriers. Based on the calculated values of the reaction rate coefficients, the most efficient KMnO4 carrier for KMnO4 oxidation was rice hull ash per gram of scrubber followed by lahar ash and then coconut coir dust. Calculated values of the intrinsic rate coefficient indicate that, at the same KMnO4 loading, lahar ash scrubs ethylene more efficiently, followed by rice hull ash and then coconut coir dust. However, in practical terms, the most efficient scrubber is that based on rice hull ash. This material was also found to be the most stable among three carriers based on the color intensity (chromacity) of the reflected light from the scrubber. The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 was studied by Panari et al172 spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde has no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism.

39

Chapter 2

Literature Survey

Desai et al172 studied the kinetics of oxidation of (R)-(+)-pantothenic acid (PA) by permanganate in aqueous alkaline medium at constant ionic strength 0.20 mol dm3 spectrophotometrically. The reaction showed first-order kinetics in (MnO4) and an apparent less than unit order dependence each in (pantothenic acid) and (alkali). Initial addition of products had no significant effect on the rate of the reaction. An increase in ionic strength and decrease in dielectric constant of the medium increases the rate. The results suggest that first the alkali reacts with pantothenic acid to form its anionic species with deprotonation catalysis which reacts with one molecule of oxidant species i.e., permanganate species to form the free radical of pantothenic acid in a slow step. The oxidation of As (III) with potassium permanganate was studied under conditions including pH, initial As (III) concentration and dosage of Mn (VII). 174 The results have shown that potassium permanganate was an effective agent for oxidation of As (III) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As (III) by Mn (VII). Although theoretical redox analysis suggests that Mn (IV) should have better performance in oxidation of As (III)within lower pH ranges, the experimental results show that the oxidation efficiencies of As (III) under basic and acidic conditions were similar, which may be due to the adsorption of As (III) on the Mn (OH)2 and MnO2 resulting from the oxidation of As (III). Kolb175 studied the permanganate oxidation of cyclohexane, cyclohexene, and cyclohexanol. Alkaline potassium permanganate is treated with cyclohexane, cyclohexene, and cyclohexanol. The cyclohexene reacts more rapidly than cyclohexanol. Cyclohexane does not react. The secondary alcohol cyclohexanol is oxidized by permanganate to give the ketone cyclohexanone. The alkene cyclohexene reacts to give cis-1, 2-cyclohenanediol. The permanganate ion is reduced to the green manganate ion.

40

Chapter 2

Literature Survey

Selective oxidation of alkylarenes in dry media with potassium permanganate is reported on Montmorillonite K10.176 The solvent-free oxidation of alkylarenes with KMnO4 supported on Montmorillonite K10 is reported. The beneficial effects of microwave and ultrasound irradiation on the reactions are described.

KMnO4/K10 /MW/>>>

Berka and Zavesky177 used potassium permanganate as oxidizing agent to determine organic substances. The questions of performance of blank determinations of organic substances, when excess potassium permanganate is used in weekly acid solutions, were studied.

41

Chapter 2

Literature Survey

Igov et al178 studied the catalytic effect of traces of Al (III) ion on oxidation of 4-hydroxycoumarin by potassium permanganate. Oxidation of 4-hydroxycoumarin by potassium permanganate in acid media of acetate buffer is catalyzed by Al (III) ions, which is the proposed new homogeno-catalytic method for determination of Al (III)in solutions. Under the optimum conditions, Al(III) has been determined at 525 min solutions containing analyte at 50-1000 ng/ml with probable relative error of 15.6 5 &nbsp;% and detection limit of 20 ng/ml). Appropriate kinetic questions for both catalytic and noncatalytic processes have been derived and the mechanism of catalytic effect of Al(III) investigated. Interferences studies show that most of the common cations and anions do not interfere. Latona179 studied the kinetics of oxidation of sugar in alkaline potassium permanganate and chromic acid media. The reactions were monitored under pseudo-first order condition. The effects of ionic strength, pH, sugar concentration and temperature were kinetically investigated. Kinetics of oxidation of fructose, sucrose and maltose by potassium permanganate in NaHCO3/NaOH buffer and of fructose and sucrose by hexachloro-iridate (IV) in acidic buffer have been measured spectrophotometrically under pseudo-first order condition.180 The rate of oxidation of sugars follow the order maltose>fructose>sucrose, and increase with pH in both acidic and alkaline media.

42

Chapter 2

Literature Survey

2.13 AIMS AND OBJECTIVES OF CURRENT RESEARCH

The study of carbohydrates is one of the most exciting fields of Organic/ Biochemistry. Vast literature is available on the kinetics of oxidation of carbohydrates by various organic and inorganic oxidants. The oxidations of aldoses by, chlorine, bromine and iodine have been reported in alkaline media.1719

The catalyzed and uncatalyzed oxidation of sugars have been reported in by using N-halocompounds.67-75 N-Bromoacetamide181-183 ,N-

detail

Bromosuccinamide184-186 and Potassium bromate30-38 ,Sodium Periodate187-190 have been earlier used in oxidation of various compounds. In organic oxidants such as Cu(II), ammonical Ag(I) and Nesslers reagent have been used in the uncatalyzed oxidation of sugars in aqueous alkaline medium.137-139 The uncatalyzed oxidation of oxalic acid, benzaldehydes and Ru(III)-catalyzed oxidation of -hydroxy acids by iodate in acidic medium have been reported.191193

The mechanism for the oxidation of some aldoses by Cr(VI), V(V), Ce(II), Ir(IV),

Au(III) and periodic acid have been investigated in acidic media.194 In the light of the biological importance of reducing sugars and also in a view of the fact that the KMnO4 based reactions have been found relatively rare application in the oxidation of sugars leads to corresponding acids through further oxidation of aldehyde formed by alcohols especially for the oxidation of hydroxyl group of substrates and a few investigations have been reported on the kinetics of oxidation of reducing sugars with potassium permanganate in acidic medium to drawn a mechanism of oxidation by using advanced techniques. This research covers the following aspects: i. ii. To study the kinetics of reducing sugars by potassium permanganate spectrophotometrically. Determination of rate of reaction by the change in optical density of KMnO4 in acidic medium.

43

Chapter 2

Literature Survey

iii. iv. v. vi. vii.

To study the reaction kinetics in acidic medium at different parameters like concentration of sugar, oxidant, pH and temperature. Determination of order of reaction with respect to concentration of sugar, oxidant and pH of the medium. Evaluation of thermodynamics activation parameters (Ea, H #, G #, S# ) were determined by using Arrhenius & Erying equations. Establishment of reaction mechanism of oxidation of sugars. Isolation of the product formed by establishing equilibrium in heterogeneous solvent system. TLC was checked and product subjected to ve & +ve Fab mass spectrophotometery,
13

C-NMR, 1H-NMR and

establishment of the reaction mechanism and stoichiometric equations.

44

CHAPTER # 3

EXPERIMENTAL ASPECTS

Chapter 3

Experimental Aspects

3. EXPERIMENTAL ASPECTS
The oxidations of sugars have been investigated by various researchers by using various oxidizing agents.17-60 Several workers used classical methods to study reaction kinetics. A scant attention has been paid to spectrophotometric method. Therefore the spectrophotometric method has been adapted to study the reaction kinetics of oxidation of sugars with potassium permanganate in acidic medium. The experiment was planned for 2-3 hrs laboratory sessions. This includes time for: 1) Laboratory preparation 2) Preparation of solutions 3) Kinetic Experiments 4) Data Analysis Effect of different experimental parameters such as concentration of oxidant, reductant, hydrogen ion, ionic strength and temperature was studied.

3.1 LABORATORY PREPARATION 3.1.1 Glass Wares

All the volumetric apparatus used were of Pyrex. All the glass wares used were washed with detergent solution and tap water, washing with double distilled and deionized water and ultimate drying in an oven (W.T.C binder, 7200, Tuttlinger / Germany Type E 28 No. 89248) at temperature 150 C for 2 hrs. before starting reaction kinetics.

3.1.2 Thermostatic Bath

Thermostatic bath model # FJPS0 (Made in England) was used throughout the experiment which maintained a constant temperature within + 0.1 C.

45

Chapter 3

Experimental Aspects

3.1.3 Stop Watch

AVICON AVTN Stopwatch having a least count + 0.1 was used for the determination of time elapsed.

3.1.4 Digital Balance

For weighing purpose the digital balance model # Mettler College 150 was used having least count + 0.0001.

3.1.5 Spectrophotometer
The present kinetic study was followed by the change in optical density of KMnO4 as a function of time. In all the reactions the optical density or change in optical density was in visible region and for monitoring change in optical density a digital spectrophotometer S 104 D (Cambridge UK) No. 1229 was used. A spectrum of potassium permanganate was recorded on Schimadzu

spectrophotometer to obtain wavelength maximum of KMnO4. All other spectra were also recorded on the same instrument.

3.1.6 Mass Spectrometer

The electron impact (EI) mass spectra were recorded on Finnigem Mat 112 Spectrometer coupled with PDP 11\34 Computer System.

3.1.7 NMR Spectrometers

The 1H NMR were recorded at 300 and 400 MHz on Bruker AM 300 and AM 400 Spectrometers with aspects. 300 date system.

3.1.8 TLC
The TLC was performed on DC. Micro cards SiF 5 10 cm (Silica gel with fluorescent indicator 254 nm and for reversible TLC was performed on RP18F252 S.

46

Chapter 3

Experimental Aspects

3.1.9 CHEMICALS (i) Sugars

Sugars i.e. Galactose, Fructose, Lactose, and Maltose were of A R grades and were used without further purification.

(ii) Potassium Permanganate

Potassium Permanganate used in present investigation was of Fluka (Switzerland).

(iii) Salt
Potassium nitrate (KNO3) of E. Merck was used throughout the experiment to investigate the salt effect.

(iv) Sulphuric Acid

H2SO4 used to provide H+ ions in the reaction mixture was of E. Merck.

(v) Water
Double distilled and deionized water was used throughout the experimental work.

3.2 PREPARATION OF STOCK SOLUTIONS 3.2.1 Stock Solution of KMnO4

A 0.01 M stock solution of KMnO4 was prepared by dissolving 0.157g/100ml of KMnO4 in water.

3.2.2 Stock Solution of Galactose

A 0.1 M stock solution of galactose (C6H12O6) was prepared by dissolving known weight of galactose in 100 ml of water.

3.2.3 Stock solution of fructose

A 0.1 M stock solution of fructose (C6H12O6) was prepared by dissolving known weight of fructose in 100 ml of water.

47

Chapter 3

Experimental Aspects

3.2.4 Stock Solution of Maltose

A 0.1 M stock solution of maltose (C12H22O11) was prepared by dissolving known weight of maltose in 100 ml of water.

3.2.5 Stock Solution of Lactose

A 0.1 M stock solution of lactose (C12H22O11) was prepared by dissolving known weight of maltose in 100 ml of water.

3.2.6 Stock Solution of Potassium Nitrate

A 1 M stock solution of potassium nitrate (KNO3) was prepared by dissolving known weight of KNO3 in 100 ml of water.

3.2.7 Sulphuric Acid

A 1 M stock solution of sulphuric acid (H2SO4) was prepared by diluting known volume of concentrated H2SO4 (18 M) in 100ml of water.

3.3 KINETIC EXPERIMENTS

Initially, the spectrum of KMnO4 solution was scanned to determine the wavelength of maximum absorption. All stock solutions of various sets of experiments were immersed in water bath for at least 10-15 minutes before directly drawn in the cuvet placed in the cell holder of spectrophotometer. The change in optical density of KMnO4 was recorded after 60 s at max 545 nm. The requisite ionic strength of the medium was maintained by adding appropriate volumes of 0.3M KNO3 solution. The reaction was initiated by adding sugar solution. At least five kinetic runs were performed for each individual experiment designed for every parameter studied.

48

Chapter 3

Experimental Aspects

3.3.1 Effect of Substrate Concentration on kobs

Dilutions of the required concentrations were made from the various stock solutions of substrates. The change in optical density was monitored by keeping oxidant, [H+] and salt concentration constant at a wavelength of 545 nm at a temperature of 32C + 1C. The influences of various parameters were studied on reaction kinetics of oxidation of sugars by KMnO4 in acidic medium.

3.3.2 Effect of Oxidant Concentration on kobs

Dilutions of the required concentrations were made from the stock solution of KMnO4. The change in optical density was monitored by keeping substrate, [H+] and salt concentration constant at a wavelength of 545 nm at a temperature of 32C + 1C.

3.3.3 Effect of [H+] Concentration on kobs

For finding out the dependence of k on [H+], appropriate dilutions of H2SO4 stock solution were prepared. The change in optical density was at a temperature of 32C + 1C. monitored at a wavelength of 545 nm by keeping oxidant, substrate and salt concentration constant

3.3.4 Effect of Salt on kobs

To investigate the dependence of k on salt, different dilutions of KNO3 were prepared from the KNO3 stock solution. The change in optical density was recorded by keeping the [H+], oxidant and substrate concentration constant at a max 545 nm at a temperature of 32C + 1C.

3.3.5 Effect of Temperature on kobs

To study the effect of different temperatures viz 30C, 35C, 40C, 45C and 50C fresh dilutions were made for each kinetic run. Arrhenius and Erying equations were used to calculate the thermodynamic activation parameters like Ea, H#, S# and G#.

49

Chapter 3

Experimental Aspects

3.4 DATA ANALYSIS

Beer Lambert law was used to analyze the experimental data. According to the Beer-Lambert law, the absorbance (A) of a dilute solution is proportional to its concentration, c and path length, l: A = cl where is molar absorptivity. Change in optical density of MnO4- was used as reaction monitoring tool at different optimum conditions. Rates of reaction were determined from plots of optical density vs time (t) where as a plot of ln Ao -A/ At -A was used to determine pseudo-first-order rate constant (k). ln Ao -A/ At -A = kt where Ao , At , and A represents optical density at beginning, at time t and at infinity respectively.

3.5 STOICHIOMETRY AND PRODUCT ANALYSIS

Varying [MnO4-]: [sugar] ratios were equilibrated at room temperature for 72 h with condition [MnO4-] >> [sugar].Estimation of residual [MnO4-] in different sets showed that 1mol of sugar consumed 2 (for galactose and fructose) and 4 (for maltose and lactose) mol of MnO4-. Accordingly, the following stoichiometric equations could be formulated:

C 6 H12O6 + 2 MnO4
Galactose / Fructose

H C5 H10O6 + HCOOH + 2 MnO3

Arabinonic acid Formic acid

C12 H 22O11 + 4 MnO4

Maltose / Lactose

Hg + H 2O H / 2C5 H10O6 + 2 HCOOH + 4 MnO3

+2

Arabinonic acid

Formic acid

50

Chapter 3

Experimental Aspects

C 6 H12O6 + 2 MnO4
Galactose / Fructose

H C6 H10O7 + H 2O + 2 MnO3
galacturonic acid/ fructuronic acid

C12 H 22O11 + 4 MnO4

Maltose / Lactose

Hg H / 2C12 H18O13 + 2 H 2O + 4 MnO3

+2

malturic acid/ lacturic acid

The main products of the oxidation formic acid and arabinonic acids were detected
17

by TLC and by conventional (spot test) methods18, 19. Surprisingly, the products

formed from all sugars (Galactose, Fructose, Maltose and Lactose) were same. The other oxidation products i.e galacturonic acid, fructuronic acid, malturic acid and lacturic acid were identified by Fab mass, 1H-NMR and 13C-NMR spectroscopy.

3.6 ANALYSIS OF REACTION MIXTURE

Analysis of reaction mixture was carried out by taking 0.2g of KMnO4, 1g of reducing sugars viz. galactose, fructose, maltose and lactose which were mixed in 50 ml of deionised water and 50ml of hexane. The mixture was allowed to stand to complete the reaction for 2hrs then 5ml of conc. H2SO4 was added. The complete decolorization took place within 30 minutes. After 5 days solution was shacked and two layers were separated by using separating funnel. Then hexane was evaporated by rotary evaporator. Crystals obtained were dissolved in methanol. TLC was taken which did not show any promising spot. Therefore the polarity of solvent was increased as follows: 20ml H2O + 80ml CH3OH, 40ml H2O + 60ml CH3OH, 60ml H2O + 40ml CH3OH, 80ml H2O+20ml CH3OH. Then B.A.W was taken and TLC was checked but no promising spot appeared but only streaking was present on the plate. Analysis of reaction mixture was then performed with Chloroform instead of hexane, again only streaking was observed on the TLC plate. The mole method was used for the preparation of reaction mixtures for the oxidation of sugars.

51

Chapter 3

Experimental Aspects

3.7 PREPARATION OF REACTION MIXTURES

3.7.1 For Galactose
Molecular wt. of Galactose Molecular wt. of KMnO4 1 mole of Galactose Mole Mole
= = = =

180 g

163 g

180 g of Galactose.

Mass Mol.wt. 1 180

Mole = 5.55 x 10-3 mole of Galactose used for oxidation. 1 mole of Galactose = 2 moles of KMnO4 5.55 x 10-3 mole of Galactose = 2 5.55 x 10-3 mole of KMnO4 5.55 x 10-3 mole of Galactose = 1.11 x 10-2 mole of KMnO4 Mass = mole mol.wt. = 1.11 x 10-2 163 g Mass = 1.8093 g of KMnO4 used to oxidize 1 g of Galactose.

3.7.2 For Fructose

Molecular wt. of fructose 1 mole of fructose Mole Mole
= =

180 g

Molecular wt. of KMnO4 = 163 g

=

180 g of fructose

Mass Mol.wt. 1 180

Mole = 5.55 x 10-3 mole of fructose used for oxidation. 1 mole of fructose = 2 moles of KMnO4 5.55 x 10-3 mole of fructose = 2 5.55 x 10-3 mole of KMnO4 5.55 x 10-3 mole of fructose = 1.11 x 10-2 mole of KMnO4

52

Chapter 3

Experimental Aspects

Mass = mole mol.wt. = 1.11 x 10-2 163 g Mass = 1.8093 g of KMnO4 used to oxidize 1 g of fructose.

3.7.3 For Maltose

1 mole of maltose Mole Mole
= =

342 g of maltose.

Mass Mol.wt. 1 342

Mole = 2.9x 10-3 mole of maltose used for oxidation. 1 mole of Maltose = 4 moles of KMnO4 2.9x 10-3mole of Maltose = 2 2.9x 10-3 mole of KMnO4 2.9x 10-3 mole of Maltose = 1.16 x 10-2 mole of KMnO4 Mass = mole mol.wt. = 1.16 x10-2 163 gm Mass = 1.89 g of KMnO4 used to oxidize 1 g of Maltose.

3.7.4 For Lactose

1 mole of lactose = 342 g lactose Mole = Mass Mol.wt. Mole
=

1 342

Mole = 2.9x 10-3 mole of lactose used for oxidation. 1 mole of lactose = 4 moles of KMnO4 2.9x 10-3mole of lactose = 2 2.9x 10-3 mole of KMnO4 2.9x 10-3 mole of lactose = 1.16 x 10-2 mole of KMnO4

53

Chapter 3

Experimental Aspects

Mass = mole mol.wt. = 1.16 x10-2 163 gm Mass = 1.89 g of KMnO4 used to oxidize 1 g of lactose.

3.8 ANALYSIS OF OXIDATION PRODUCTS

In reagent bottle 1g galactose with 1.8093 g of KMnO4, 1 g fructose with 1.8093 g KMnO4, 1 g maltose with 1.89 g KMnO4 and 1 g lactose with 1.89 g KMnO4 were mixed in 20 ml deionized water. 0.5ml conc. H2SO4 was also added in each solution. The bottles were covered with stop cork and kept overnight. The water was evaporated under reduced pressure to set product in bottom. The obtained product in each case dissolved in DMSO and checked on reversible TLC plate in the solvent (1:1 water and MeOH). It was observed that product is uv.active. Ceric sulphate was sprayed to check the compound which gave brown spot. Therefore it was confirmed that compound belongs to COOH group. Finally the isolated product was submitted for Fab, mass and other spectroscopic techniques.

54

CHAPTER # 4

RESULTS

Chapter 4

Results

4. RESULTS
The present research has been conducted by monitoring change in absorbance of MnO4- with respect to time. The absorption spectrum of MnO4- was recorded in aqueous solution (Fig 4.1) to obtain maximum wavelength of absorption. The spectrum shows two maxima at 525nm and 545nm respectively. Magnesedioxide (MnO2), a reduction product of MnO4- also absorbs at 525nm therefore, 545nm was considered as max.

Fig 4.1 Absorption spectrum of KMnO4

55

Chapter 4

Results

4.1 EFFECT OF CONCENTRATION OF KMnO4 ON THE RATE OF OXIDATION OF SUGARS WITH KMnO4
The oxidation of sugar with potassium permanganate in acidic medium has been investigated spectrophotometrically. In order to evaluate the effect of concentration of KMnO4 on rate of oxidation, the reaction was studied at various initial concentrations of KMnO4 ranging from 1-5x10-3 mol dm-3. The concentration of sugars was maintained constant at 2x10-3 mol dm-3 galactose, 4x10-2 mol dm-3 fructose, 4x10-2 mol dm-3 maltose, 3x10-2 mol dm-3 lactose while KNO3 concentration at 0.3 mol dm-3. The temperature was kept constant at 305 K. The reaction was followed by change in optical density of KMnO4 in reaction mixture at max 545 nm. The values of optical density were plotted against time to evaluate rate of reaction. It clearly indicates the rate increases as the concentration increases. The values of rate constants were obtained from the slope plot of ln Ao-A/At- A vs time (Figs 4.2 to 4.9). These values are tabulated in Tables 4.1 to 4.4 showing first order kinetics with respect to KMnO4.

56

Chapter 4

Results

Table: 4.1 Effect of Concentration of KMnO4 on the Rate of Oxidation of Galactose with KMnO4
[Galactose] = 210-2 mol dm-3 [KNO3 ] = 0.3 mol dm-3 max = 545 nm [H2SO4 ] = 110-1 mol dm-3 T = 305 K.

[KMnO4] x 103 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 2.6 0.53 5.3 0.53 3.5 0.53 5.2 0.53 4.9 0.53 1.48

k x 103 (s-1) 3.2 1.23 8.7 1.23 9.1 1.23 9.3 1.23 10.0 1.23 3.42

57

Chapter 4

Results

2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 100 200 time (s) 300 400

O.D

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

Fig 4.2 : Plots of O.D vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

2.50

ln [(Ao-A)/ (At-A)]

2.00 1.50 1.00 0.50 0.00 0 50 100 150 200

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

time (s)

Fig 4.3 : Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

58

Chapter 4

Results

Table: 4.2 Effect of Concentration of KMnO4 on the Rate of Oxidation of Fructose with KMnO4
[Fructose] = 410-2 mol dm-3 [ KNO3 ] = 0.3 mol dm-3 max = 545 nm [H2SO4 ] = 110-1 mol dm-3 T = 305 K.

[KMnO4] x 103 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 4.7 1.1 3.7 1.1 8.5 1.1 9.5 1.1 6.8 1.1 3.04

k x 103 (s-1) 4.5 2.8 7.5 2.8 11.9 2.8 15.4 2.8 20.3 2.8 7.77

59

Chapter 4

Results

3 2.5
O.D

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

2 1.5 1 0.5 0 0 100 200 300 400 time (s)

Fig 4.4 : Plots of O.D vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

6 ln [(Ao-A)/(At-A)] 5 4 3 2 1 0 0 50 100 150

time(s)

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

200

250

300

350

Fig 4.5 : Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

60

Chapter 4

Results

Table: 4.3 Effect of Concentration of KMnO4 on the Rate of Oxidation of Maltose with KMnO4.
[Maltose] = 410-2 mol dm-3 [KNO3 ] = 0.3 mol dm-3 max = 545 nm [ H2SO4 ] = 110-1 mol dm-3 T = 305 K

[KMnO4] x 103 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 0.7 0.38 2.2 0.38 2.6 0.38 2.8 0.38 2.7 0.38 1.07

k x 103 (s-1) 1.5 0.78 5.9 0.78 5.4 0.78 4.4 0.78 5.3 0.78 2.18

61

Chapter 4

Results

1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 200 400 time (s) 600

O.D

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

Fig 4.6: Plots of O.D vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

2.50

2.00 ln [(Ao-A)/(At-A)]

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

1.50

1.00

0.50

0.00 0 200 400

time (s)

600

800

Fig 4.7: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

62

Chapter 4

Results

Table: 4.4 Effect of Concentration of KMnO4 on Rate of Oxidation of Lactose with KMnO4
[Lactose] = 310-2 mol dm-3 [KNO3] = 0.3 mol dm-3 max = 545 nm [KMnO4 ] = 110-3 mol dm-3 T = 305 K.

[KMnO4] x 103 (mol dm-3) 1.0

x 103 (mol dm-3 s-1) 0.3 1.27

k x 103 (s-1) 1.4 1.54

2.0 3.0 4.0 5.0 Confidence Interval (95%)

0.3 1.27 0.4 1.27 5.5 1.27 5.6 1.27 3.54

1.6 1.54 2.8 1.54 7.2 1.54 8.9 1.54 4.27

63

Chapter 4

Results

2 1.5 O.D 1

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

0.5 0 0 200 Time (s) 400

Fig 4.8: Plots of O.D vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

4.500 4.000 3.500

ln [(Ao-A)/(At-A)]

110-3 mol dm-3 210-3 mol dm-3 310-3 mol dm-3 410-3 mol dm-3 510-3 mol dm-3

3.000 2.500 2.000 1.500 1.000 0.500 0.000 0 2 4 6 8

time (s) Fig 4.9: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-3 mol dm-3 of KMnO4

64

Chapter 4

Results

4.2 EFFECT OF CONCENTRATION OF SUGARS ON THE RATE OF OXIDATION OF SUGARS WITH KMnO4
The oxidation of sugars by potassium permanganate in acidic medium has been studied spectrophotometrically at various initial concentrations of sugars keeping potassium permanganate, sulphuric acid, salt concentration and temperature constant. The Effect of concentration of sugars was investigated at different concentrations ranging from 1-5x10-2 mol dm-3. The concentration of KMnO4, H2SO4 and KNO3 was maintained at 1x10-3 mol dm-3, 1x10-1 mol dm-3 and 0.3 mol dm-3 respectively. The temperature was kept constant at 305 K. The reaction was followed by change in optical density of KMnO4 in reaction mixture at max 545 nm,. The absorbance was obtained after each 60sec. Plots of optical density vs time were obtained from which rate of reaction was calculated (Tables 4.5 to 4.8 and Figs 4.10, 4.12, 4.14 and 4.16). It is obvious from the table that rate of reaction increase as the concentration of sugar increases. It means that rate of reaction depend upon the sugar concentration. Plots of ln Ao-A/At- A Vs time were also obtained. (Figs 4.11, 4.13, 4.15 and 4.17) to evaluate the values of rate constant. The plots gave straight line whose slopes provided the values of rate constant, tabulated in Tables 4.5 to 4.8. The values indicate that it is first order reaction with respect to sugar.

65

Chapter 4

Results

Table: 4.5 Effect of Concentration of Galactose on the Rate of Oxidation of Galactose with KMnO4.
[KMnO4 ] = 110-3 mol dm-3 [KNO3 ] = 0.3 mol dm-3 max = 545 nm [H2SO4 ] = 110-1 mol dm-3 T = 305 K.

[Galactose] x 102 (mol dm-3)

x 103 (mol dm-3 s-1)

k x 103 (s-1)

1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

3.9 0.79 3.3 0.79 5.3 0.79 3.6 0.79 3.6 0.79 0.98

4.3 2.23 8.8 2.23 10 2.23 12 2.23 18 2.23 6.20

66

Chapter 4

Results

1.4 1.2 1 0.8 0.6 0.4 0.2 0 0

110-2 mol dm-3 210-2 mol dm-3 310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

O.D

100

200 300 400 time (s)

Fig 4.10 : Plots of O.D vs time for concentrations (1-5)x10-2 mol dm-3 of Galactose

6 5
ln [(Ao-A)/(At-A)]

110-2 mol dm-3 210-2 mol dm310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

4 3 2 1 0 0 100 200
time (S)

300

400

Fig 4.11 : Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-2 mol dm-3 of Galactose

67

Chapter 4

Results

Table: 4.6 Effect of Concentration of Fructose on the Rate of Oxidation of Fructose with KMnO4.
[KMnO4] = 110-3 mol dm-3 [KNO3 ] = 0.3 mol dm-3 max = 545 nm [H2SO4] = 110-1 mol dm-3 T = 305 K.

[Fructose] x 102 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 1.6 0.97 3.0 0.97 5.6 0.97 6.3 0.97 6.5 0.97 2.71

k x 103 (s-1) 2.3 1.12 3.4 1.12 5.9 1.12 7.2 1.12 8.3 1.12 3.13

68

Chapter 4

Results

2 1.5

110-2 mol dm-3 210-2 mol dm-3 -2 310 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

O.D

0.5 0 0 200 400

time (s)

Fig 4.12 : Plots of O.D vs time for concentrations (1-5)x10-2 mol dm-3 of Fructose

4.00 3.50 3.00 ln [(Ao-A)/(At-A)] 2.50 2.00 1.50 1.00 0.50 0.00 0 100 200
time (s)

110-2 mol dm-3 210-2 mol dm-3 310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

300

400

Fig 4.13: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-2 mol dm-3 of Fructose

69

Chapter 4

Results

Table: 4.7 Effect of Concentration of Maltose on the Rate of Oxidation of Maltose with KMnO4.
[KMnO4 ] = 110-3 mol dm-3 [KNO3 ] = 0.3 mol dm-3 max = 545 nm [H2SO4] = 110-1 mol dm-3 T = 305 K.

[Maltose] x 102 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 0.3 0.21 1.6 0.21 0.9 0.21 1.3 0.21 1.1 0.21 0.60

k x 103 (s-1) 1.2 0.28 1.3 0.28 1.4 0.28 2.4 0.28 2.5 0.28 0.78

70

Chapter 4
110-2 mol dm-3 210-2 mol dm-3 -2 310 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

Results

2 1.5

O.D

1 0.5 0 0 200 400 600

time (s)
Fig 4.14: Plots of O.D vs time for concentrations (1-5)x10-2 mol dm-3 of Maltose

2.50 2.00 ln [(Ao-A)/(At-A)] 1.50

110-2 mol dm-3 210-2 mol dm-3 310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

1.00 0.50 0.00 0 200 400

time (s)

600

800

Fig 4.15: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-2 mol dm-3 of Maltose

71

Chapter 4

Results

Table: 4.8 Effect of Concentration of Lactose on the Rate of Oxidation of Lactose with KMnO4.
[Lactose] = 310-2 mol dm-3 [KNO3] = 0.3 mol dm-3 max = 545 nm [H2SO4] = 110-1 mol dm-3 T = 305 K.

[Lactose] x 102 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 2.0 0.58 2.0 0.58 3.0 0.58 4.0 0.58 5.0 0.58 1.61

k x 103 (s-1) 1.4 1.54 1.6 1.54 2.8 1.54 7.2 1.54 8.9 1.54 4.27

72

Chapter 4

Results

0.2 0.15 O.D 0.1 0.05 0 0 200 time (s) 400

110-2 mol dm-3 210-2 mol dm-3 310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

Fig 4.16: Plots of O.D vs time for concentrations (1-5)x10-2 mol dm-3 of Lactose

2.000 1.800 1.600

ln [(Ao-A)/(At-A)]

1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000 0 100 200 300 400

110-2 mol dm-3 210-2 mol dm-3 310-2 mol dm-3 410-2 mol dm-3 510-2 mol dm-3

time (s)

Fig 4.17: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-2 mol dm-3 of Lactose

73

Chapter 4

Results

4.3 EFFECT OF CONCENTRATION OF H2SO4 ON THE RATE OF OXIDATION OF SUGAR WITH KMnO4
The influence of hydrogen ion concentration has been studied by changing sulphuric acid concentration (1-5)x10-1 mol dm-3 at constant sugars, 2x10-2 mol dm-3 galactose, 4x10-2 mol dm-3 fructose, 4x10-2 mol dm-3 maltose, 3x10-2 mol dm-3 lactose, KMnO4 concentration 1x10-3 mol dm-3, KNO3 concentration 0.3 mol dm-3 and temperature 305 K. The reaction was followed by change in optical density of KMnO4 in reaction mixture at max 545 nm. The absorbance was obtained after each 60 seconds. The absorbance values are plotted against time to obtain rate of reaction which clearly indicates that rate increases as the concentration of acid increases as shown in the Figs 4.18, 4.20, 4.22 and 4.24. Plots of ln Ao-A/At- A Vs time were also obtained as straight lines (Figs 4.19, 4.21, 4.23 and 4.25) which indicates that it is first order reaction with respect to sulphuric acid. The values of rate constant obtained from the slope of above plots are tabulated in (Tables 4.9 to 4.12). These values are also in a good agreement with first order kinetics.

74

Chapter 4

Results

Table: 4.9 Effect of Concentration of H2SO4 on the Rate of Oxidation of Galactose with KMnO4
[Galactose] = 210-2 mol dm-3 [KNO3] = 0.3 mol dm-3 max = 545 nm [KMnO4 ] = 110-3 mol dm-3 T = 305 K.

[H2SO4 ] x 101 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 3.0 0.94 6.7 0.94 6.9 0.94 8.8 0.94 5.8 0.94 2.62

k x 102 (s-1) 1.40 0.06 1.47 0.06 1.26 0.06 1.65 0.06 1.56 0.06 0.18

75

Chapter 4

Results

2 1.5 O.D 1

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

0.5 0 0 100 200 300

time (s)

Fig 4.18: Plots of O.D vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

3.000 2.500 2.000 ln [(A-A)/ (A-A)] 1.500 1.000 0.500 0.000 0 200 400 time (s) 600 800

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

Fig 4.19: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

76

Chapter 4

Results

Table: 4.10 Effect of Concentration of H2SO4 on the Rate of Oxidation of Fructose with KMnO4
[Galactose] = 210-2 mol dm-3 [H2SO4] = 110-1 mol dm-3 max = 545 nm [ KMnO4 ] = 110-3 mol dm-3 T = 305 K.

[H2SO4 ] x 101 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 6.2 0.22 6.8 0.22 5.8 0.22 5.8 0.22 6.8 0.22 0.62

k x 102 (s-1) 1.73 0.19 1.73 0.19 2.43 0.19 2.43 0.19 2.70 0.19 0.55

77

Chapter 4

Results

1.4 1.2 1 0.8 0.6 0.4 0.2 0

O.D

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

200 time (s)

400

Fig 4.20: Plots of O.D vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

5
ln [(Ao-A)/(At-A)]

4 3 2 1 0 0 50 100 150
time (s)

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

200

250

300

350

Fig 4.21: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

78

Chapter 4

Results

Table: 4.11 Effect of Concentration of H2SO4 on the Rate of Oxidation of Maltose with KMnO4
[Maltose] = 410-2 mol dm-3 [KNO3] = 0.3 mol dm-3 max = 545 nm [KMnO4 ] = 110-3 mol dm-3 T = 305 K.

[H2SO4 ] x 101 (mol dm-3) 1.0 2.0 3.0 4.0

x 103 (mol dm-3 s-1) 4.4 0.83 1.5 0.83 4.8 0.83 4.3 0.83

k x 102 (s-1) 5.9 1.53 2.8 1.53 8.6 1.53 9.4 1.53

5.0 Confidence Interval (95%)

0.8 0.83 2.31

1.6 1.53 4.27

79

Chapter 4

Results

2 1.5

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

O.D

1 0.5 0 0 200 400

time (s) Fig 4.22: Plots of O.D vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

3.50 3.00 2.50

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

ln [(Ao-A)/(At-A)]

2.00 1.50 1.00 0.50 0.00 0 100 200

Time (s)

300

400

Fig 4.23: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

80

Chapter 4

Results

Table: 4.12 Effect of Concentration of H2SO4 on the Rate of Oxidation of Lactose with KMnO4
[Lactose] = 310-2 mol dm-3 [KNO3] = 0.3 mol dm-3 max = 545 nm [KMnO4] = 1 10-3 mol dm-3 T = 302 K.

[H2SO4 ] x 101 (mol dm-3) 1.0 2.0 3.0 4.0 5.0 Confidence Interval (95%)

x 103 (mol dm-3 s-1) 5.0 0.58 6.0 0.58 7.0 0.58 8.0 0.58 8.0 0.58 1.61

k x 102 (s-1) 1.4 0.20 2.1 0.20 2.2 0.20 2.5 0.20 2.5 0.20 0.55

81

Chapter 4

Results

0.6 0.5
O.D

0.4 0.3 0.2 0.1 0 0 200 400 600

time (s)

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

Fig 4.24: Plots of O.D vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

3 2.5
ln [(Ao-A)/(At-A)]

110-1 mol dm-3 210-1 mol dm-3 310-1 mol dm-3 410-1 mol dm-3 510-1 mol dm-3

2 1.5 1 0.5 0 0 5
time (s)

10

15

Fig 4.25: Plots of ln Ao-A/At-A vs time for concentrations (1-5)x10-1 mol dm-3 of H2SO4

82

Chapter 4

Results

4.4 EFFECT OF IONIC STRENGTH ON RATE OF OXIDATION OF SUGARS WITH KMnO4

The effect of ionic strength on the rate of oxidation of galactose by KMnO4 in acidic medium has been investigated by varying KNO3 concentration (0.3 mol dm-3, 0.5 mol dm-3, 0.7 mol dm-3, 0.9 mol dm-3, 1.1 mol dm-3) by keeping sugar and KMnO4 concentration and temperature constant at 210-2 mol dm-3 galactose, 410-2 mol dm-3 fructose, 410-2 mol dm-3 maltose and 310-2 mol dm-3 lactose, 110-3 mol dm-3 and 305 K respectively. The reaction was followed by change in optical density of KMnO4 in the reaction mixture at
max

545 nm. The

absorbance was obtained after each 60 sec. It was observed that KMnO4 was decolorized after a certain time. Results are tabulated in Tables 4.13 to 4.16. Plots of ln Ao-A/At- A Vs time were also obtained as straight lines (Figs 4.26 to 4.29).The values of rate constant were calculated from the slope of these plots which indicated no salt effect on the reaction.

83

Chapter 4

Results

Table: 4.13 Effect of Ionic Strength on Rate of Oxidation of Galactose

[Galactose] = 210-2 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 max = 545 nm

[KMnO4] =110-3 mol dm-3 T = 305 K.

[KNO3] (mol dm-3) 0.3 0.5 0.7 0.9 1.1 Confidence Interval (95%)

k x 103 (s-1) 9.5 0.06 9.3 0.06 9.6 0.06 9.3 0.06 9.5 0.06 0.16

84

Chapter 4

Results

4.5 4 3.5 ln [(Ao-A)/(At-A)] 3 2.5 2 1.5 1 0.5 0 0 100 time (s) 200 300

0.3 mol dm-3 0.5 mol dm-3 0.7 mol dm-3 0.9 mol dm-3 1.1 mol dm-3

Fig 4.26: Plots of ln Ao-A/At-A vs time for concentrations (0.3- 1.1 mol dm-3) of KNO3

85

Chapter 4

Results

Table: 4.14 Effect on Ionic Strength on Rate of Oxidation of Fructose:

[Fructose] = 410-2 mol dm-3 [H2SO4 ] = 110-1 mol dm-3 max = 545 nm [KMnO4] = 110-3 mol dm-3 T = 305 K

[KNO3] (mol dm-3) 0.3 0.5 0.7 0.9 1.1 Confidence Interval (95%)

k x 103 (s-1) 7.4 0.08 7.7 0.08 7.2 0.08 7.6 0.08 7.5 0.08 0.23

86

Chapter 4

Results

4
ln [(Ao-A)/(At-A)]

3 2 1 0 0 50 100 150 200

time (S)

0.3 mol dm-3 0.5 mol dm-3 0.7 mol dm-3 0.9 mol dm-3 1.1 mol dm-3

250

300

350

Fig 4.27: Plots of ln Ao-A/At-A vs time for concentrations (0.3- 1.1 mol dm-3) of KNO3

87

Chapter 4

Results

Table: 4.15 Effect of Ionic Strength on Rate of Oxidation of Maltose

[Maltose] = 410-2 mol dm-3 [H2SO4] = 110-1 mol dm-3 max = 545 nm [KMnO4] = 110-3 mol dm-3 T = 305 K

[KNO3] (mol dm-3) 0.3 0.5 0.7 0.9 1.1 Confidence Interval (95%)

k x 103 (s-1) 6.3 0.04 6.5 0.04 6.4 0.04 6.5 0.04 6.3 0.04 0.12

88

Chapter 4

Results

5 4.5 4
ln [(Ao-A)/(At-A)]

0.3 mol dm-3 0.5 mol dm-3 0.7 mol dm-3 0.9 mol dm-3 1.1 mol dm-3

3.5 3 2.5 2 1.5 1 0.5 0 0 100 200

time (s)

300

400

Fig 4.28: Plots of ln Ao-A/At-A vs time for concentrations (0.3- 1.1 mol dm-3) of KNO3

89

Chapter 4

Results

Table: 4.16 Effect of Ionic Strength on Rate of Oxidation of Lactose

[Lactose ] = 310-2 mol dm-3 [H2SO4 ] = 110-1 mol dm-3 max = 545 nm [KMnO4] = 110-3 mol dm-3 T = 305 K

[KNO3] (mol dm-3) 0.3 0.5 0.7 0.9 1.1 Confidence Interval (95%)

k x 103 (s-1) 3.5 0.06 3.7 0.06 3.7 0.06 3.9 0.06 3.7 0.06 0.17

90

Chapter 4

Results

3.50 3.00
ln [(Ao-A)/ (At-A)]

0.3 mol dm-3 0.5 mol dm-3 0.7 mol dm-3 0.9 mol dm-3 1.1 mol dm-3

2.50 2.00 1.50 1.00 0.50 0.00 0 200 400

time (s)

600

800

Fig 4.29: Plots of ln Ao-A/At-A vs time for concentrations (0.3- 1.1 mol dm-3) of KNO3

91

Chapter 4

Results

4.5 EFFECT OF TEMPERATURE ON RATE OF OXIDATION OF SUGARS WITH KMnO4

Dependence of k rate constant for oxidation of sugars by KMnO4 on temperature has been studied at constant substrate, oxidant and acid concentration 210-2 mol dm -3 galactose, 410-2 mol dm -3 fructose, 410-2 mol dm -3 maltose, 310-2 mol dm -3 lactose, 110-3 mol dm -3 KMnO4 and 110-1 mol dm -3 H2SO4 respectively. The rate data was collected at different temperatures (30-50oC) by using KNO3 to vary ionic strength. The values of rate constants at different temperature was obtained by plotting ln Ao-A/At-A vs time. Values are tabulated in Tables 4.17 to 4.20. It was observed that rate constant increases with increasing temperature. The reaction has also been studied by varying initial concentrations of KNO3 at different temperatures. As ionic strength has no effect on rate constant, it remains unchanged at one temperature. Plots between log k Vs 1/T were obtained with negative slopes to calculate the values of activation energy (Ea). The corresponding plots are shown in Figs 4.30 to 4.33.

92

Chapter 4

Results

Table: 4.17 Effect of Temperature on Rate of Oxidation of Galactose with KMnO4

[Galactose] = 210-2 mol dm-3 [H2SO4] = 110-1 mol dm-3 [KMnO4] =110-3 mol dm-3 max = 545 nm

RATE CONSTANT x 103

(mol dm-3)0.5 30 0.775 0.894 1.000 1.095 1.183 Confidence Interval (95%) 9.0 0.06 9.2 0.06 8.9 0.06 9.0 0.06 8.8 0.06 0.18

TEMPERATURE C 35 11.2 0.09 10.9 0.09 10.8 0.09 11.0 0.09 11.3 0.09 0.25 40 15.0 0.06 14.9 0.06 15.2 0.06 15.0 0.06 14.8 0.06 0.18 45 23.1 0.07 22.9 0.07 23.2 0.07 22.8 0.07 23.0 0.07 0.19 50 24.3 0.16 24.9 0.16 24.8 0.16 24.6 0.16 24.0 0.16 0.45

93

Chapter 4

Results

-6 -5 -4 -3 -2 -1 0 3.05 3.1 3.15 3.2 3.25 3.3 3.35

1/Tx103(K-1)

lnk

Fig: 4.30 A plot of lnk vs 1/T of Galactose against KMnO4 at 0.775 (mol dm-3)0.5

94

Chapter 4

Results

Table: 4.18 Effect of Temperature on Rate of Oxidation of Fructose with KMnO4

[Fructose] = 410-2 mol dm-3 [H2SO4] = 110-1 mol dm-3 [KMnO4] = 110-3 mol dm-3 max = 545 nm

RATE CONSTANT x 103

(mol dm-3)0.5 30 0.775 0.894 1.000 1.095 1.183 Confidence Interval (95%) 4.4 0.07 4.1 0.07 4.0 0.07 4.3 0.07 4.3 0.07 0.20 35 5.8 0.09 5.5 0.09 5.3 0.09 5.4 0.09 5.3 0.09 0.25

TEMPERATURE C 40 7.6 0.05 7.4 0.05 7.5 0.05 7.3 0.05 7.4 0.05 0.14 45 11.3 0.07 11.0 0.07 11.4 0.07 11.3 0.07 11.1 0.07 0.20 50 14.7 0.07 14.6 0.07 14.8 0.07 14.5 0.07 14.9 0.07 0.19

95

Chapter 4

Results

-6 -5 -4 -3 -2 -1 0 3.05

lnk

3.1

3.15

3.2

3.25

3.3

3.35

1/Tx103(K-1)
Fig: 4.31 A plot of lnk vs 1/T of Fructose against KMnO4 at 0.775 (mol dm-3)0.5

96

Chapter 4

Results

Table: 4.19 Effect of Temperature on Rate of Oxidation of Maltose with KMnO4

[Maltose] = 410-2 mol dm-3 [H2SO4] = 110-1 mol dm-3 [KMnO4 ] =110-3 mol dm-3 max = 545 nm

RATE CONSTANT x 103

(mol dm-3)0.5 30 0.775 0.894 1.000 1.095 1.183 Confidence Interval (95%) 6.3 0.10 6.0 0.10 6.2 0.10 5.8 0.10 6.4 0.10 0.29

TEMPERATURE C 35 6.9 0.05 7.0 0.05 7.1 0.05 6.9 0.05 7.2 0.05 0.16 40 7.7 0.10 7.5 0.10 7.9 0.10 7.4 0.10 7.3 0.10 0.29 45 8.8 0.06 8.5 0.06 8.7 0.06 8.5 0.06 8.8 0.06 0.18 50 12.3 0.12 12.1 0.12 11.6 0.12 11.7 0.12 12.0 0.12 0.35

97

Chapter 4

Results

-5.2 -5 lnk -4.8 -4.6 -4.4 -4.2 3.05 3.1 3.15 3.2 3.25 3.3 3.35

1/Tx103(K-1)
Fig: 4.32 A plot of lnk vs 1/T of Maltose against KMnO4 at 0.775 (mol dm-3)0.5

98

Chapter 4

Results

Table: 4.20 Effect of Temperature on Rate of Oxidation of Lactose with KMnO4

[Lactose] = 310-2 mol dm-3 [H2SO4 ] = 110-1 mol dm-3 [KMnO4] =110-3 mol dm-3 max = 545 nm

RATE CONSTANT x 103

(mol dm-3)0.5 30 0.775 0.894 1.0 1.095 1.183 Confidence Interval (95%) 3.6 0.11 3.6 0.11 3.1 0.11 3.3 0.11 3.1 0.11 0.31

TEMPERATURE C 35 4.1 0.06 4.3 0.06 4.2 0.06 4.3 0.06 4.5 0.06 0.18 40 6.0 0.21 5.8 0.21 6.0 0.21 6.8 0.21 6.8 0.21 0.59 45 9.6 0.29 9.1 0.29 9.9 0.29 8.2 0.29 9.6 0.29 0.83 50 11.6 0.12 11.1 0.12 11.7 0.12 11.5 0.12 11.8 0.12 0.33

99

Chapter 4

Results

-8 -6 ln k -4 -2 0 3.05 3.1 3.15 3.2 3.25 3.3 3.35

1/Tx103(K-1)
Fig: 4.33 A plot of lnk vs 1/T of Lactose against KMnO4 at 0.775(mol dm-3)0.5

100

CHAPTER # 5

DISCUSSION

Chapter 5

Discussion

5. DISCUSSION
Carbohydrates are a major source of energy for living organisms and the understanding of the mechanisms of oxidation of sugars is therefore of immense importance. The kinetics of oxidation of sugars by a variety of oxidants has been reported
17-50

in both acidic and alkaline media. Several different mechanisms

showing the importance of enediols, cyclic forms of sugars, etc have been proposed and there do not seem to appear any common features even in a single medium. Studies involving the oxidation of sugars by metal ions or their complexes in alkaline medium are limited.
198, 199

. The present study involves the

kinetics of D-galactose, D-fructose, D-maltose and D-lactose by KMnO4 in acidic medium at constant ionic strength maintained by KNO3. The reaction was followed by change in optical density of KMnO4 in reaction mixture at max 545nm. The rate constants were calculated from the slope of the plot of ln Ao-A / Ao-A Vs time. The rate data was obtained in the form of pseudo-first order rate constant (kobs) under varying kinetics conditions. Considering MnO4-, reducing sugars, H+ ions as the main reactants, the general form of rate equation for the reaction can be written as

rate = k MnO4

] [Sugar ] [H ]

or
d MnO4 = k MnO4 dt

] [

] [Sugar ] [H ]

(1)

For the determination of the experimental rate law, first of all a series of experiments with varying initial concentrations of MnO4- were performed at constant concentration of all other reactants and at constant temperature 308 K. In the light of Ostwald's isolation method the concentration of reducing sugars and H+ ions were fixed in large excess with respect to MnO4- throughout its variation.

101

Chapter 5

Discussion

Since the concentration of those in excess will not change very much during the course of reaction and Hg (II) being a catalyst is reproduced in the reaction, the rate law (Eq-1) under this condition becomes
rate = kobs MnO4

Where kobs the apparent rate constant

kobs = [Sugar ] H +

[ ]

5.1 INFLUENCE OF VARIATION OF CONCENTRATION OF KMnO4 ON THE OXIDATION OF REDUCING SUGARS

The oxidation of fructose, galactose, maltose and lactose with KMnO4 has been studied at various initial concentrations (1-5x10-3 mol dm-3) of oxidant keeping the substrates as well as sulphuric acid and temperature constant at 308 K respectively. Ionic strength was maintained constant by using KNO3 of 0.3M. Kinetic results obtained with the variation of MnO-4 with aforesaid sugars are presented in Tables 4.1 to 4.4. The plots of kobs Vs [MnO4-] were obtained (Figs 5.1, 5.4, 5.7 and 5.10). It is clear from figures that in oxidation of all sugars, there is direct proportionality between the rate and [MnO4-] throughout its variation. This shows that the order of reaction with respect to [MnO4-] is unity. The plot of log [MnO-4] Vs log kobs was also linear as shown in Figs 5.3, 5.6, 5.9 and 5.12 with slopes equal to 0.68 with galactose 0.94 with fructose 0.67 with maltose and 1.2 with lactose. These values are nearly equal to unity suggesting first order dependence with respect to KMnO4. The oxidation of reducing sugars showed that configuration of disaccharides and monosaccharide is bearing some effect on rate of reaction.

102

Chapter 5

Discussion

TABLE: 5.1 Influence of Variation of Concentration of KMnO4 on the Oxidation of Galactose

[Galactose] = 2 x 10-2 mol dm-3 [KNO3] = 0.3 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K

[MnO4-] x 103 1/[MnO4-]x10-2 (mol dm-3) (mol-1dm3) 1 2 3 4 5 10.00 5.00 3.33 2.50 2.00

log [MnO4-] -3.00 -2.69 -2.52 -2.39 -2.30

k x 103 (s-1) 3.00 8.70 9.10 9.30 1.00

1/k x10-2 (s) 1.42 1.14 1.09 1.07 1.00

log k -2.50 -2.06 -2.00 -2.03 -2.00

103

Chapter 5

Discussion

0.012 0.01 0.008 0.006 0.004 0.002 0 0 0.002 0.004 0.006 [MnO 4-]mol dm-3 Fig: 5.1 A plot of k Vs [MnO4-] for the oxidation of Galactose

k (s-1) 1/k (s)

200 150 100 50 0 0 200 400 600 800 1000 1200 1/[MnO 4-]mol -1dm 3 Fig: 5.2 A plot of 1/k Vs 1/ [MnO4-] for the oxidation of Galactose

104

Chapter 5

Discussion

-3 -2.5 -2 logk -1.5 -1 -0.5 0 -2.2 -2.4 -2.6 -2.8 -3 -3.2

log[MnO4-]

Fig: 5.3 A plot of log k Vs log [MnO4-] for the oxidation of Galactose

105

Chapter 5

Discussion

TABLE: 5.2 Influence of Variation of Concentration of KMnO4 on the Oxidation of Fructose

[Fructose] = 4 x 10-2 mol dm-3 [KNO3] = 0.3 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K

[MnO4-] x 103 (mol dm-3) 1 2 3 4 5

1/[MnO4-]x10-2 (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [MnO4-] -3.00 -2.69 -2.52 -2.39 -2.30

k x 103 (s-1) 4.50 7.50 11.90 15.40 20.30

1/k x10-2 (s) 1.58 1.33 0.84 0.64 0.49

log k -2.35 -2.12 -1.92 -1.81 -1.69

106

Chapter 5

Discussion

0.025 0.02 k (s-1) 0.015 0.01 0.005 0 0 0.001 0.002 0.003 0.004 0.005 0.006 [MnO 4-] mol dm -3 Fig: 5.4 A plot of k Vs [MnO4-] for the oxidation of Fructose

250 200 1/k (s) 150 100 50 0 0 200 400 600 800 1000 1200 1/[MnO 4-] mol -1dm 3 Fig: 5.5 A plot of 1/k Vs 1/ [MnO4-] for the oxidation of Fructose

107

Chapter 5

Discussion

-2.5 -2 -1.5 logk -1 -0.5 0 -2.2 -2.4 -2.6 -2.8 log[MnO4-] -3 -3.2

Fig: 5.6 A plot of log k Vs log [MnO4-] for the oxidation of Fructose

108

Chapter 5

Discussion

TABLE: 5.3 Influence of Variation of Concentration of KMnO4 on the Oxidation of Maltose

[Maltose] = 4 x 10-2 mol dm-3 [KNO3] = 0.3 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K

[MnO4-] x 103 (mol dm-3) 1 2 3 4 5

1/[MnO4-]x10-2 (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [MnO4-] -3.00 -2.69 -2.52 -2.39 -2.30

k x 103 (s-1) 1.50 5.90 5.40 4.40 5.30

1/k x10-2 (s) 6.66 1.69 1.85 2.27 1.88

log k -2.82 -2.23 -2.27 -2.36 -2.28

109

Chapter 5

Discussion

0.008 k (s-1) 0.006 0.004 0.002 0 0 0.001 0.002 0.003 0.004 0.005 0.006 [MnO 4-] mol dm -3 Fig: 5.7 A plot of k Vs [MnO4-] for the oxidation of Maltose

700 600 500 400 300 200 100 0 0 200 400 600 800 1000 1200 1/[MnO 4-] mol -1dm 3 Fig: 5.8 A plot of 1/k Vs 1/ [MnO4-] for the oxidation of Maltose

1/k (s)

110

Chapter 5

Discussion

-3 -2.5 logk -2 -1.5 -1 -0.5 0 -2.2 -2.4 -2.6 -2.8 -3 -3.2

log[MnO4-]

Fig: 5.9 A plot of log k Vs log [MnO4-] for the oxidation of Maltose

111

Chapter 5

Discussion

TABLE: 5.4 Influence of Variation of Concentration of KMnO4 on the Oxidation of Lactose

[Lactose] = 3 x 10-2 mol dm-3 [KNO3] = 0.3 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K

[MnO4-] x 103 (mol dm-3) 1 2 3 4 5

1/[MnO4-]x10-2 (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [MnO4-] -3.00 -2.69 -2.52 -2.39 -2.30

k x 103 (s-1) 1.40 1.60 2.80 7.20 8.90

1/k x10-2 (s) 7.14 6.25 3.57 1.38 1.12

log k -2.85 -2.79 -2.55 -2.14 -2.05

112

Chapter 5

Discussion

0.01 0.008 k (s-1) 0.006 0.004 0.002 0 0 0.001 0.002 0.003 0.004 0.005 0.006 [MnO 4-] mol dm -3 Fig: 5.10 A plot of k Vs [MnO4-] for the oxidation of Lactose

1000 800 1/k (s) 600 400 200 0 0 200 400 600 800 1000 1200 1/[MnO 4-] mol dm -3 Fig: 5.11 A plot of 1/k Vs 1/ [MnO4-] for the oxidation of Lactose

113

Chapter 5

Discussion

-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 -2.2

logk

-2.4

-2.6

-2.8

-3

-3.2

log[MnO4-] Fig: 5.12 A plot of log k Vs log [MnO4-] for the oxidation of Lactose

114

Chapter 5

Discussion

5.2 INFLUENCE OF VARIAITION OF CONCENTRATION OF SUGARS ON THE OXIDATION BY KMnO4

After establishing the first order kinetics with respect to [MnO-4] nearly ten-fold variations in the concentration of sugars were made under pseudo-first order conditions. The effect of changing sugars (maltose, lactose, galactose and fructose) concentration has been investigated at constant oxidant (1x10-3 mol dm-3) and acid concentration (1x10-1 mol dm-3) at 308 K. The values of rate constants are summarized in Tables 4.5 to 4.8. It is obvious from the Tables that an increase in sugar concentration enhances the rate of oxidation. The values of rate constants for the oxidation of sugars are in the order fructose>galactose>maltose>lactose. This indicates faster kinetics with monosaccharide as compared with disaccharides which may be attributed with structural difference of studied sugars or may be related with the hydrolysis of disaccharides. Maltose and lactose exhibited slower rates of oxidation which were enhanced by the addition of catalyst mercuric chloride. Figs 5.13, 5.16, 5.19 and 5.22 represent the plots of kobs against [sugar] concentration. A straight line is obtained passing through origin which confirms that the order of reaction with respect to sugar is also unity. The second order rate constant (k1) evaluated by the slope of the plot between kobs and [sugar] has been found to be 3.45 x 10-1 in case of galactose, 1.76 x 10-1 of fructose, 5.4 x 10-2 of maltose and 1.56 x 10-1 of lactose and comparable with the work reported earlier. 121. The plots of 1/k vs 1 / [sugars] were found to be linear (Figs 5.14, 5.17, 5.20 and 5.23) showing first order kinetics with respect to sugars. These indicate a direct influence of concentration of substrate over the rate constant. A plot of logk vs log [sugar] gives a straight line with a slope near unity (0.81, 0.84, 0.48 and 1.20 in galactose, fructose, maltose and lactose respectively) which confirms first order dependence of the reaction on sugars.

115

Chapter 5

Discussion

TABLE: 5.5 Influence of Variation of Concentration of Galactose on the Oxidation by KMnO4

[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Galactose] x 102 (mol dm-3) 1 2 3 4 5 1/[Galactose]x10-2 (mol-1dm3) 10.00 5.00 3.33 2.50 2.00 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K log [Galactose] -2.00 -1.69 -1.52 -1.39 -1.30 k x 103 (s-1) 4.30 8.80 10.00 12.00 18.00 1/kx10-2 (s) 2.32 1.13 1.00 0.83 0.55

log k -2.37 -2.05 -2.00 -1.92 -1.74

116

Chapter 5

Discussion

0.02 0.015 k (s-1) 0.01 0.005 0 0 0.02 0.04 0.06 [Galactose] mol dm-3 Fig: 5.13 A plot of k Vs [Galactose] for the oxidation by KMnO4

300 250 1/k (s) 200 150 100 50 0 0 20 40 60 80 100 120 1/[Galactose]mol -1 dm 3

Fig: 5.14 A plot of 1/k Vs 1/ [Galactose] for the oxidation by KMnO4

117

Chapter 5

Discussion

-2.5 -2 -1.5 logk -1 -0.5 0 0 -0.5 -1 -1.5 -2 -2.5 log [Galactose] Fig: 5.15 A plot of log k Vs log [Galactose] for the oxidation by KMnO4

118

Chapter 5

Discussion

TABLE: 5.6 Influence of Variation of Concentration of Fructose on the Oxidation by KMnO4

[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K

[Fructose] x 102 (mol dm-3) 1 2 3 4 5

1/[Fructose] x10-2 (mol-1dm3) 1.00 0.50 0.33 0.25 0.20

log [Fructose] -2.00 -1.69 -1.52 -1.39 -1.30

k x 103 (s-1) 2.30 3.40 5.90 7.20 8.30

1/kx10-2 (s) 4.34 2.94 1.69 1.38 1.20

log k -2.64 -2.47 -2.23 -2.14 -2.08

119

Chapter 5

Discussion

0.01 0.008 k (s-1) 0.006 0.004 0.002 0 0 0.01 0.02 0.03 0.04 0.05 0.06 [Fructose] mol dm -3

Fig: 5.16 A plot of k Vs [Fructose] for the oxidation by KMnO4

600 500 1/k (s) 400 300 200 100 0 0 20 40 60

-1

80

100

120

1/[Fructose] mol dm 3 Fig: 5.17 A plot of 1/ k Vs 1/ [Fructose] for the oxidation by KMnO4

120

Chapter 5

Discussion

-3 -2.5 log k -2 -1.5 -1 -0.5 0 0 -0.5 -1 -1.5 -2 -2.5 log [Fructose] Fig: 5.18 A plot of log k Vs log [Fructose] for the oxidation by KMnO4

121

Chapter 5

Discussion

TABEL: 5.7 Influence of Variation of Concentration of Maltose on the Oxidation by KMnO4

[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Maltose] x 102 (mol dm-3) 1 2 3 4 5 1/[Maltose]x10-2 (mol-1dm3) 1.00 0.50 0.33 0.25 0.20 log [Maltose] -2.00 -1.69 -1.52 -1.39 -1.30 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K k x 103 (s-1) 1.20 1.30 1.40 2.40 2.50 1/k x10-2 (s) 8.33 7.69 7.14 4.16 4.00

log k -2.92 -2.89 -2.85 -2.62 -2.60

122

Chapter 5

Discussion

0.003 0.0025 k (s-1) 0.002 0.0015 0.001 0.0005 0 0 0.01 0.02 0.03 0.04 0.05 0.06 [Maltose] mol dm-3 Fig: 5.19 A plot of k Vs [Maltose] for the oxidation by KMnO4

1200 1000 800 600 400 200 0 0 20 40 60

-1

1/k (s)

80

100

120

1/[Maltose] mol dm 3 Fig: 5.20 A plot of 1/k Vs 1/ [Maltose] for the oxidation by KMnO4

123

Chapter 5

Discussion

-3 -2.9 log k -2.8 -2.7 -2.6 -2.5 0 -0.5 -1 -1.5 -2 -2.5 log [Maltose] Fig: 5.21 A plot of log k Vs log [Maltose] for the oxidation by KMnO4

124

Chapter 5

Discussion

TABLE: 5.8 Influence Of Variation of Concentration of Lactose on the Oxidation by KMnO4

[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Lactose] x 102 (mol dm-3) 1 2 3 4 5 1/[Lactose]x10-2 (mol-1dm3) 1.00 0.50 0.33 0.25 0.20 log [Lactose] -2.00 -1.69 -1.52 -1.39 -1.30 [H2SO4] = 1 x 10-1 mol dm-3 T = 305 K k x 103 (s-1) 1.40 1.60 2.80 7.20 8.90 1/k x10-2 (s) 7.14 6.25 3.57 1.38 1.12

log k -2.85 -2.79 -2.55 -2.14 -2.05

125

Chapter 5

Discussion

0.01 0.008 k (s-1) 0.006 0.004 0.002 0 0 0.01 0.02 0.03 0.04
-3

0.05

0.06

[Lactose] mol dm

Fig: 5.22 A plot of k Vs [Lactose] for the oxidation by KMnO4

1000 800 1/k (s) 600 400 200 0 0 20 40 60 80 100 120

1/[Lactose] mol-1 dm3 Fig: 5.23 A plot of 1/k Vs 1/ [Lactose] for the oxidation by KMnO4

126

Chapter 5

Discussion

-3.5 -3 -2.5 log k -2 -1.5 -1 -0.5 0 0 -0.5 -1 -1.5 -2 -2.5

log [Lactose] Fig: 5.24 A plot of log k Vs log [Lactose] for the oxidation by KMnO4

127

Chapter 5

Discussion

5.3 INFLUENCE OF VARIATION OF CONCENTRATION OF H+ IONS ON THE OXIDATION OF SUGARS BY KMnO4

The oxidation of sugars by various oxidizing agents in acidic medium was studied earlier
39, 103, 85, 55

. The reactions have been investigated at different [H+]

39

concentration varied by hydrochloric acid

or dilute sulphuric acid

112

. Both

reactions exhibited a uniform increase in Pseudo-first order rate constant with increasing concentration of an acid. The slopes of plot of logk vs log [Acid] were equal to the unity showing first order dependence in acid. The present study involves the oxidation of galactose, fructose, maltose and lactose by KMnO4 in dilute sulphuric acid medium. The reactions have been studied at different hydrogen ion concentrations varied by the addition of sulphuric acid but at constant ionic strength i.e. 0.3 moldm-3, oxidant and substrate concentrations. It was observed that the reactions were accelerated by an increase in acidity of the medium (Tables 4.9 to 4.12). This can be shown by the plots of 1/k vs 1/ [H+] (Figs 5.26, 5.29, 5.32 and 5.35) .The plots of kobs against [H+] for all the substrates are linear with positive intercept on yaxis (Figs 5.25, 5.28, 5.31 and 5.34) indicating that the redox reactions have aciddependent as well as acid-independent paths.200 The values of n were determined from the slope of the plot of log kobs vs log [H+] at constant temperature. The values of n were found to be 0.06 for galactose, 0.57 for fructose, -0.24 for maltose and 0.36 for lactose. The values for the galactose and maltose may be explained on basis of their configuration which plays a significant role in oxidation of sugars. The corresponding plots are shown in Figs 5.27, 5.30, 5.33 and 5.36.

128

Chapter 5

Discussion

TABLE: 5.9 Influence Of Variation of Concentration of H+ Ions on the Oxidation of Galactose by KMnO4
[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Galactose] = 2 x 10-2 mol dm-3 T = 305 K

[H2SO4] x 101 (moldm-3) 1 2 3 4 5

1/[H2SO4] (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [H2SO4] -1.00 -0.69 -0.52 -0.39 -0.30

k x 103 (s-1) 14.00 14.70 12.60 16.50 15.60

1/k (s) 71.43 68.03 79.36 60.60 64.10

log k -1.85 -1.83 -1.89 -1.78 -1.81

129

Chapter 5

Discussion

0.02 k (s-1) 0.015 0.01 0.005 0 0 0.2 0.4 0.6 [H2SO 4]mol dm-3 Fig: 5.25 A plot of k Vs [H2SO4] for the oxidation of Galactose by KMnO4

100 80 1/k (s) 60 40 20 0 0 2 4 6 8 10 12

1/[H2SO4]mol-1dm3

Fig: 5.26 A plot of 1/k Vs 1/ [H2SO4] for the oxidation of Galactose by KMnO4

130

Chapter 5

Discussion

-1.9 -1.88 -1.86 -1.84 -1.82 -1.8 -1.78 -1.76 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2 log [H2SO4] Fig: 5.27 A plot of log k Vs log [H2SO4] for the oxidation of Galactose by KMnO4

logk

131

Chapter 5

Discussion

TABLE: 5.10 Influence of Variation of Concentration of H+ ions on the Oxidation of Fructose by KMnO4
[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Fructose] = 4 x 10-2 mol dm-3 T = 305 K

[H2SO4] x 101 (mol dm-3) 1 2 3 4 5

1/[H2SO4] (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [H2SO4] -1.00 -0.69 -0.52 -0.39 -0.30

k x 103 (s-1) 17.30 17.30 24.30 24.30 27.00

1/k (s) 57.80 57.80 41.15 41.15 37.03

log k -1.76 -1.76 -1.61 -1.16 -1.57

132

Chapter 5

Discussion

0.03 0.025 k (s-1) 0.02 0.015 0.01 0.005 0 0 0.1 0.2 0.3 0.4 0.5 0.6 [H2SO 4]mol dm-3

Fig: 5.28 A plot of k Vs [H2SO4] for the oxidation of Fructose by KMnO4

70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 1/[ H 2SO 4]mol -1dm 3

1/k (s)

Fig: 5.29 A plot of 1/k Vs 1/ [H2SO4] for the oxidation of Fructose by KMnO4

133

Chapter 5

Discussion

-2 -1.5 log k -1 -0.5 0 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2 log [H2SO4]

Fig: 5.30 A plot of log k Vs log [H2SO4] for the oxidation of Fructose by KMnO4

134

Chapter 5

Discussion

TABLE: 5.11 Influence of Variation of Concentration of H+ Ions on the Oxidation of Maltose by KMnO4

[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3

[Maltose] = 4 x 10-2 mol dm-3 T = 305 K

[H2SO4] x 101 (mol dm-3) 1 2 3 4 5

1/[H2SO4] (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [H2SO4] -1.00 -0.69 -0.52 -0.39 -0.30

k x 103 (s-1) 5.90 2.80 8.60 9.40 1.60

1/k x 10-2 (s) 1.69 3.57 1.16 1.06 6.25

log k -4.07 -4.40 -3.91 -3.87 -4.64

135

Chapter 5

Discussion

0.01 0.008 k (s-1) 0.006 0.004 0.002 0 0 0.1 0.2 0.3 0.4 0.5 0.6 [H 2SO 4]mol dm-3

Fig: 5.31 A plot of k Vs [H2SO4] for the oxidation of Maltose by KMnO4

700 600 500 400 300 200 100 0 0 2 4 6 8 10 12 1/[ H 2SO 4]mol -1dm 3

1/k (s)

Fig: 5.32 A plot of 1/ k Vs 1/ [H2SO4] for the oxidation of Maltose by KMnO4

136

Chapter 5

Discussion

-4.8 -4.6 log k -4.4 -4.2 -4 -3.8 0 -0.2 -0.4 -0.6 -0.8 log [H2SO4] -1 -1.2

Fig: 5.33 A plot of log k Vs log [H2SO4] for the oxidation of Maltose by KMnO4

137

Chapter 5

Discussion

TABLE: 5.12 Influence of Variation of Concentration of H+ Ions on the Oxidation of Lactose by KMnO4
[KMnO4] = 1 x 10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Lactose] = 3 x 10-2 mol dm-3 T = 305 K

[H2SO4] x 101 (mol dm-3) 1 2 3 4 5

1/[H2SO4] (mol-1dm3) 10.00 5.00 3.33 2.50 2.00

log [H2SO4] -1.00 -0.69 -0.52 -0.39 -0.30

k x 103 (s-1) 1.40 2.10 2.20 2.50 2.50

1/kx10-2 (s) 7.14 4.76 4.54 4.00 4.00

log k -2.85 -2.67 -2.65 -2.60 -2.60

138

Chapter 5

Discussion

0.003 k (s-1) 0.0025 0.002 0.0015 0.001 0.0005 0 0 0.1 0.2 0.3 0.4 0.5 0.6 [H 2SO 4]mol dm-3 Fig: 5.34 A plot of k Vs [H2SO4] for the oxidation of Lactose by KMnO4

800 1/k (s) 600 400 200 0 0 2 4 6 8 10 12 1/[ H2SO 4]mol -1dm 3 Fig: 5.35 A plot of 1/k Vs 1/ [H2SO4] for the oxidation of Lactose by KMnO4

139

Chapter 5

Discussion

-2.9 -2.85 -2.8 -2.75 -2.7 -2.65 -2.6 -2.55 -0.2

log k

-0.4

-0.6

-0.8

-1

-1.2

log [H2SO4]
Fig: 5.36 A plot of log k Vs log [H2SO4] for the oxidation of Lactose by KMnO4

140

Chapter 5

Discussion

5.4 INFLUENCE OF THE IONIC STRENGTH ON THE OXIDATION OF SUGARS BY KMnO4

In aqueous solutions, ionic strength plays an important role in theories of reaction rates. It can be studied by varying the concentration of an inert electrolyte. The Bronsted equation (5.1) predicts the influence of ionic concentration and charges on the reaction rate in dilute solutions.
k = k0 A B / i (5.1)

where k0 is the limiting value of the rate constant as ionic strength tends to zero and A. B and i# are the activity coefficients for A, B, and activated complex, respectively. The Debye-Hckel limiting (eq 5.2) presents the relationship between the ionic strength () and the activity coefficients () of the reacting ions in the solutions.

log i = A zi2 0.5

(5.2)

where z is the ionic charge and A is a constant that depends on the dielectric constant and temperature of the solution. By substituting eq 5.2 in eq 5.1 a relationship between the rate constant and ionic strength () is derived. For the reactions in dilute aqueous solutions, the equation may be given as
log k = log k0 + 1.02 z A z B 0.5 (5.3)

Therefore, a plot of log k versus 0.5 should be linear, with the slope and intercept equal to 1.02 zAzB and log k0, respectively. The slope represents the product of charges, on the species involved in the rate-limiting step. If the rate-limiting step is between the species of like charges, a positive slope is expected. When the reaction is between opposite charges, it results in a negative slope.201

141

Chapter 5

Discussion

In present study effect of ionic strength was studied by varying the concentration of KNO3 while other parameters were kept constant. It was observed that change in ionic strength of the medium does not alter the rate constant. (Tables 4.13 to 4.16). The absence of salt effect indicates that the reaction does not take place between ionic substances. Hence, at least one of the reactants must be non-ionic. These findings were confirmed by the plot of logk vs (Figs 5.36 to 5.39). The values of slopes in case of galactose, fructose, maltose and lactose were found to be zero. Therefore, it was concluded that the rate determining step must involve at least one neutral molecule as mentioned earlier. 26, 28

142

Chapter 5

Discussion

Table: 5.13 Effect of Ionic Strength on the Oxidation of Galactose by KMnO4

[Galactose] = 2x10-2 mol dm-3 [H2SO4] = 1x10-1 mol dm-3 [KMnO4] = 1x10-3 mol dm-3 T = 305 K

(mol dm-3)0.5

logk

0.775 0.894 1.000 1.095 1.183

-2.02 -2.03 -2.00 -2.03 -2.02

143

Chapter 5

Discussion

-2.032 -2.03 -2.028 -2.026 -2.024 -2.022 -2.02 -2.018 -2.016 0 0.5

logk

(mol dm-3) 0.5

1.5

Fig: 5.36 A plot of vs logk for the oxidation of Galactose by KMnO4

144

Chapter 5

Discussion

Table: 5.14 Effect of Ionic Strength on the Oxidation of Fructose by KMnO4

[Fructose] = 4x10-2 mol dm-3 [H2SO4] = 1x10-1 mol dm-3 [KMnO4] = 1x10-3 mol dm-3 T = 305 K

(mol dm-3) 0.5

logk

0.775 0.894 1.000 1.095 1.183

-2.13 -2.11 -2.14 -2.11 -2.12

145

Chapter 5

Discussion

-2.145 -2.14 -2.135 -2.13 logk -2.125 -2.12 -2.115 -2.11 -2.105 0 0.5 1 1.5

(mol dm-3) 0.5

Fig: 5.37 A plot of vs logk for the oxidation of Fructose by KMnO4

146

Chapter 5

Discussion

Table: 5.15 Effect of Ionic Strength on the Oxidation of Maltose by KMnO4

[Maltose] = 4x10-2 moldm-3 [H2SO4] = 1x10-1 moldm-3 [KMnO4] = 1x10-3 moldm-3 T = 305 K

(mol dm-3) 0.5

logk

0.775 0.894 1.000 1.095 1.183

-2.20 -2.18 -2.19 -2.18 -2.20

147

Chapter 5

Discussion

-2.205 -2.2 logk -2.195 -2.19 -2.185 0 0.5

1 (mol dm-3) 0.5

1.5

Fig: 5.38 A plot of vs logk for the oxidation of Maltose by KMnO4

148

Chapter 5

Discussion

Table: 5.16 Effect of Ionic Strength on the Oxidation of Lactose by KMnO4

[Lactose] = 4x10-2 mol dm-3 [H2SO4] = 1x10-1 mol dm-3 [KMnO4] = 1x10-3 mol dm-3 T = 305 K

(mol dm-3) 0.5

logk

0.775 0.894 1.000 1.095 1.183

-2.45 -2.43 -2.43 -2.41 -2.43

149

Chapter 5

Discussion

-2.46 -2.45 -2.44 logk -2.43 -2.42 -2.41 -2.4 0 0.5 1 1.5

(mol dm-3) 0.5

Fig: 5.39 A plot of vs logk of for the oxidation of Lactose by KMnO4

150

Chapter 5

Discussion

5.5 EFFECT OF TEMPERATURE ON RATE OF OXIDATION OF SUGARS BY KMnO4

Effect of temperature on rate of oxidation of sugars by KMnO4 was studied at five different temperatures i.e. 30, 35, 40, 45 and 50 oC. The reactions were found to be affected by the increase in temperature. The results are tabulated in Table 4.17 to 4.20. The activation parameters were determined. Arrhenius equation was used to evaluate the energy of activation (Ea).
k = A e RT
Ea

Or
log k = log A Ea 2.303RT

The slope of the plot of log k vs 1/T gave the value of Ea (Figs. 4.30 to 4.33). Other thermodynamic parameters such as change in enthalpy of activation (H#) and entropy of activation (S#) were calculated by using theory of absolute reaction rate.
H RT S RT

kT k= e h

Dividing by T and taking ln we get,

ln

k k H # 1 S # = ln + + . h T R T R k k S # H # 1 = ln + . h T R R T

ln

ln k/ T was plotted against 1/T (Fig 5.40 to 5.43) to obtain H# from slope and S# from the intercept. Free energy of activation (G#) was determined by using the following relation.

G # = H # TS #

151

Chapter 5

Discussion

These thermodynamic values are tabulated in Table 5.17. The values of activation energy for the reactions of galactose, Fructose, Maltose and lactose were found to be 43.5, 50, 25.4 and 50.2 KJ mol-1 respectively. The low values of Ea indicate that at least one of the reacting substances of rate determining reaction may be a neutral molecule. The value of Ea for maltose is 25.4 KJ mol-1 is due to the addition of mercuric chloride as a catalyst which reduced Ea. The values of enthalpy change of activation (H#) and entropy change of activation (S#) for galactose, fructose, maltose and lactose were calculated as 40.9, 47.6, 23, 47.9 KJmol-1 and -149.8, -133.8, -212, -134 JK-1mol-1. The high negative value of entropy of activation indicates highly solvated state of transition complex that showed a great degree of freedom of molecules in the transition state as compared to that in the reactive specie as supported by the earlier work53. The values of free energy change of activation (G#) were found to be 86.6, 88.4, 87.6 and 89.0 KJ mol-1 in the oxidation of galactose, fructose, maltose and lactose respectively. These high values of free energy of activation suggest that transition state is highly solvated as mentioned earlier 26, 85.

152

Chapter 5

Discussion

Table 5.17 Values of Activation Parameters

[Galactose] = 2x10-2 mol dm-3 [Maltose] = 4x10-2 mol dm-3 [KMnO4] = 1x10-3 mol dm-3 [KNO3] = 0.3 mol dm-3 [Fructose] = 4x10-2 mol dm-3 [Lactose] = 3x10-2 mol dm-3 [H2SO4] = 1x10-1 mol dm-3 T = 305 K

Sugars

Ea KJmol-1

H#
KJmol-1

S#
JK-1mol-1

G#
KJmol-1

Galactose

43.5

40.9

-149.8

86.6

Fructose

50.0

47.6

-133.8

88.4

Maltose

25.4

23.0

-212.0

87.6

Lactose

50.2

47.9

-134.6

89.0

153

Chapter 5

Discussion

-10.6 -10.4 -10.2 lnk /T -10 -9.8 -9.6 -9.4 3.05 3.1 3.15 3.2 3.25 3.3 3.35

1/Tx103(K-1)

Fig: 5.40 plot of lnk/T vs 1/T of Galactose against KMnO4 at 0.775 (mol dm-3)0.5

-11.4 -11.2 -11 lnk/T -10.8 -10.6 -10.4 -10.2 -10 -9.8 3.05 3.1 3.15 3.2 3.25 3 -1 1/Tx10 (K ) 3.3 3.35

Fig: 5.41 plot of lnk/T vs 1/T of Fructose against KMnO4 at 0.775 (mol dm-3)0.5

154

Chapter 5

Discussion

-11 -10.8 -10.6 -10.4 -10.2 -10 3.05

ln k / T

3.1

3.15 3.2 3.25 1/Tx103(K-1)

3.3

3.35

Fig: 5.42 plot of lnk/T vs 1/T of Maltose against KMnO4 at 0.775 (mol dm-3)0.5

-12 -11.5 ln k /T -11 -10.5 -10 3.05

3.1

3.15 3.2 3.25 1/Tx103(K-1)

3.3

3.35

Fig: 5.43 plot of lnk/T vs 1/T of Lactose against KMnO4 at 0.775 (mol dm-3)0.5

155

Chapter 5

Discussion

5.6 REACTIVE SPECIES OF MnO4On the basis of stoichiometric studies it can be easily concluded that MnO-4 is the active reactive oxidizing specie in acidic medium which forms permanganic acid when combine with H+ ion. This permanganic acid is highly oxidative unstable inorganic acid which with catalyst or lonely oxidizes the sugar via the formation of unstable intermediate complex which leads to the formation of aldehyde hydrate. This aldehyde hydrate frequently reacts with MnO-3 species and converted into respective carboxylic acid

H+ + MnO4-

HMnO4

5.7 REACTIVE SPECIES OF Hg (II) CHLORIDE IN ACIDIC MEDIUM

Aqueous HgCl2 solution was subjected to spectrophotometric studies which suggest rate constant and equilibrium constant K for the reversible reaction.
k1 k-1

HgCl2 +6H2O

[Hg(H2O)6]+2 + 2Cl-

The above equation is comparable with the work reported earlier

84 and 71

where

kinetic studies have been made for the oxidation of reducing sugars by acidic solution of N-bromosuccinimide and NBA in presence of Ir (III) as a homogeneous catalyst. In this case existence of following equilibrium was suggested.
[Ir Cl6]3- + H2O [IrCl5(H2O)]-2 + Cl-

In catalyzed oxidation of maltose and lactose in acidic medium, since the solution of catalyst is prepared in water therefore it is reasonable to assume that the reactive specie of catalyst is [Hg(H2O)6]+2 .

156

Chapter 5

Discussion

5.8 SPECTRAL EVIDENCE FOR THE FORMATION OF COMPLEXES DURING COURSE OF REACTION
In the kinetic studies of reducing sugars, it has been observed that metal ions such as Ru (III)22 & Pd(II)67 form complexes with the reducing sugars in acidic medium. It is also reported 67,68 that the complex thus formed have tendencies to react with the reacting species of NBA & also with Hg(II), whose function in the reaction was as a Br- ion scavenger and as co-catalyst. In the oxidation of maltose & lactose with permanganate ion in acidic medium, order with respect to sugars concentration was first throughout its 10-fold variation. This shows that OH group of sugar involves in the oxidation before the rate determining step although it will combine with the most reactive complex to form the reaction products along with the regeneration of Hg catalyst. In order to probe the possible formation of complex MnO4- and [Hg(H2O)6]+2 spectra for the solution of MnO4-, H+ and for the solution of MnO4- , H+ and [Hg(H2O)6]+2 have been collected (Fig.5.44 and 5.45). From the spectra, it is clear that the addition of [Hg(H2O)6]+2 solution there is an increase of absorbance from 1.79 to 2.00 (max 545 nm). This increase in absorbance can be considered as an indication of increased formation of the complex between reactive species of [Hg(H2O)6]+2 in acidic medium according to the following equilibrium:

OH [Hg(H2O)6]+2 + MnO4-+ H3O+ O

Mn

+2

Hg(H2O)5

+ 2 H2O

When maltose and lactose solutions were added to the solutions of MnO4- , H+ and [Hg(H2O)6]+2 a decrease in absorbance from 2.00 to 1.631 & 1.99 (max 545 nm) for maltose & lactose was noted (Fig.5.48 and5.49 ).

157

Chapter 5

Discussion

This shows that the complex formed subsequently combines with maltose to give a highly solvated activated complex of the type
H O H C R H
+2

O+
O

Mn O H

Hg(H 2 O) 5

according to the following equilibrium

H OH H C R O + O H Mn O
+2

H O H C R H

+2

Hg(H 2O) 5

O+
O

Mn

O
O H

Hg(H 2O) 5

Conclusions for the formation of complexes in the reactions of galactose and fructose have been drawn on the basis of the spectra collected for MnO4- , H+ solutions and MnO4- , H+ with galactose and fructose solutions. From the observed spectra it is apparent that absorbance was decreased as the solutions of galactose and maltose were added.(Fig.5.46 and 5.47).This decrease in absorbance with MnO4- can be considered as an indication of increased formation of the complex between reacting species of MnO4- and sugar in acidic medium.
H H C R H O + MnO4- + H3O+ H C R H

H O

O+
O

Mn

OO H

+ H2O

158

Chapter 5

Discussion

Fig: 5.44 Absorption Spectra of MnO4 and H+ solutions.

Fig: 5.45 Absorption Spectra of MnO4 , H+ and [Hg(H2O)6]+2 solutions.

159

Chapter 5

Discussion

Fig: 5.46 Absorption Spectra of MnO4 , H+ and galactose solutions.

Fig: 5.47 Absorption Spectra of MnO4 , H+ and fructose solutions.

160

Chapter 5

Discussion

Fig: 5.48 Absorption Spectra of MnO4 , H+,[Hg(H2O)6]+2 and maltose solutions.

Fig: 5.49 Absorption Spectra of MnO4 , H+,[Hg(H2O)6]+2 and lactose solutions.

161

Chapter 5

Discussion

5.9 REACTIONS FOR OXIDATION OF SUGARS INTO ALDONIC ACIDS

C 6 H12O6 + 2 MnO4
Galactose / Fructose

H C5 H10O6 + HCOOH + 2 MnO3

Arabinonic acid Formic acid

C12 H 22O11 + 4 MnO4

Maltose / Lactose

Hg + H 2O H / 2C5 H10O6 + 2 HCOOH + 4MnO3

+2

Arabinonic acid

Formic acid

5.9.1 Reaction Pathway for the Oxidation of Galactose and Fructose

MnO4- + H3+O
k1 k2

HMnO4+ H2O

H C6H12O6 + HMnO4 + H2O

k3 slow

H C O Mn O O O + H3O

C OH O

Where R = C4H9O5

162

Chapter 5

Discussion

H R H C O

H C O O Mn O O O +H
fast

C O

H +H

C O

OH+ HMnO3

OH R C O O H
MnO4-/ H3O

C O Mn O

OH R C O O Mn O O H
fast

C O

OH + HMnO3

Scheme 5.1 Formation of Formic and Arabinonic Acid as a result of Oxidation of Galactose and Fructose

163

Chapter 5

Discussion

5.9.2 Reaction Pathway for Catalytic Oxidation of Maltose and Lactose

k1 k2

MnO4- + H3+O

HMnO4+ H2O

OH [Hg(H2O)6]+2 + HMnO 4
fast

+2

Mn

Hg(H 2O)5

+ H2O

OH O
Mn

+2

H C O Mn O O Hg(H2O)5 O

Hg(H2O)5 + C6H12O6 + H2O

k3 slow

C OH O

+ H3O

H R H C O

H C O O Mn O O Hg(H 2O)5 O + H3O

fast

C O

H +H

C O

OH+ HMnO3
+2 + Hg(H 2O)6

164

Chapter 5

Discussion

OH R C O O H
MnO4-/ H3O Hg(H2O)+2

C O Mn O

OH R C O O Mn O O H
fast

C O

OH + HMnO3

Scheme 5.2 Formation of Formic and Arabinonic Acid as a result of Oxidation of Maltose and Lactose

165

Chapter 5

Discussion

5.10 REACTIONS FOR OXIDATION OF SUGARS INTO OTHER CARBOXYLIC ACID

C 6 H12O6 + 2MnO4
Galactose / Fructose

H C6 H10O7 + H 2O + 2MnO3
galacturonic acid/ fructuronic acid

C 12 H 22 O11 + 4MnO4
Maltose / Lactose

Hg H / C12 H 18 O13 + 2 H 2 O + 4MnO3

+2

malturic acid/ lacturic acid

These reactions can be shown as follows:

HOH2C OH HO O OH OH

OH HO MnO4/ H3O OH

OH

OH

Galactose
OH O OH OH OH OH MnO4/ H3O OH OH

Galacturonic acid

O
OH OH

OH

Fructose

Fructuronic acid

166

Chapter 5

Discussion

OH OH OH OH OH MnO4/H3O Hg+2

OH OH O OHO

O
OH OH OH

OH

O
OH OH

O
OH

OH

Maltose

Malturic Acid

OH OH O OH OH OH O MnO4/H3O Hg
+2

OH OH O O OH OH OH

O
O

OH

O
O

OH

OH OH OH

OH

Lactose

Lacturic Acid

167

Chapter 5

Discussion

5.10.1 Reaction Pathway for Oxidation of Galactose and Fructose in absence of Catalyst

H H H C O O O H

O
H O

Mn
O

Fast R

H C

K
O O H

Mn
O

Sugar

O H

Permanganate ion (A)

H H

O H

Solvated activated complex (B)

O H C O O H H

O O O H

Mn

Fast R

H C H

Mn
O

Fast

Intermediate transition complex (C)

O
H H

Manganate ester (D)

168

Chapter 5

Discussion

C
R

+ Mn
O

O
H H

Solvated aldehyde

C
R O H H

k1 k2

C
R O H

MnO4- ,H+

Aldehyde hydrate (E)

OH

O O

C
H O Mn O

k3 slow R
C OH

_
+
Mn

Carboxylic acid

O
H H

where R = C5H9O5

Scheme 5.3 Formation of Galacturonic and Fructuronic Acid as a result of Oxidation of Galactose and Fructose

169

Chapter 5

Discussion

5.10.2 Reaction Pathway for Oxidation of Maltose and Lactose in presence of Catalyst

H O H H C O O

+3
O O H H O H

+O
H

Mn
O

O + Hg(H2O)6+2

Fast R

H C

O O H

Mn

Hg(H 2O) 5

Sugar

H O Permanganate ion
H

(A) +2
O H C O O H H

Solvated activated complexH (B)

O O O H

Mn

Hg(H 2O) 5
_

Fast Hg(H2O)6+2 R

H C H

Mn
O

Fast

Intermediate transition complex (C)

O
H H

Manganate ester (D)

170

Chapter 5

Discussion

C
R

+ Mn
O

O
H H

Solvated aldehyde

C
R O H H

k1 k2

C
R O H

MnO4- ,H+

Aldehyde hydrate (E)

OH

O O

C
H O Mn O

k3 slow R
C OH

_
+
Mn

Carboxylic acid

O
H H

where R = C11H17O11

Scheme 5.4 Formation of Malturic and Lacturic Acid as a result of Oxidation of Maltose and Lactose

171

Chapter 5

Discussion

Reaction Pathway which showed the catalytic oxidation of maltose and lactose into respective carboxylic acid by potassium permanganate in acidic medium is interesting because it involves the change in oxidation state of permanganate, an inorganic compound and between the organic compounds. Permanganate ion, active reactive species (A) in acidic medium is highly oxidative and reacts with the alcoholic group of sugars rapidly. Reaction is initiated when alcohol donates an electron pair to the manganese atom as one of the oxygen extracts a proton. At this stage Hg (II) accepts electron pair from oxygen forming a highly unstable solvated activated intermediate (B). The equilibrium is established into two possible activated intermediates (B) and (C) which later on converted into Manganate ester (D) through (C). A manganate ester is formed when a water molecule departs as a leaving group. In this step Hg (II) catalyst is recovered by donating electron pair to oxygen as a result double bond formed in between manganese and oxygen. Manganese atom then departs from the ester (D) with a pair of electron that formerly belonged to the alcoholic group. The alcoholic group is there by oxidized and reduction of manganese takes place with the formation of solvated aldehyde or aldehyde hydrate. This aldehyde hydrate reacts with MnO4- in presence of H+ ion and slowly converts into respective carboxylic acid. This is the rate determining step which is represented by k3.

172

Chapter 5

Discussion

5.11 CHARACTERIZATION OF ACID FORMED THROUGH THE OXIDATION OF D-GALACTOSE

The acid formed as a result of oxidation of D-Galactose Fab(+) mass spectrometry, the M+1 peak was at 195.
202,203

was identified by

Table: 5.18

13

C-NMR Chemical Shifts () values

1 7 0 .3 1

OH

OH
7 3 .1 9

7 7 .8 6

O OH
9 9 .1 7

OH
7 1 .8 7

7 2 .0 1

OH
Fig: 5.50 Galacturonic Acid

173

Chapter 5

Discussion

Carbons

(ppm)
99.17

71.87

72.01

73.19

77.86

170.31

The

13

C-NMR chemical shift value of anomeric carbon is 99.17 while that of

carboxylic carbon of acid of galactose is found to be 170.31 ppm.

174

Chapter 5

Discussion

Table: 5.19 1H-NMR Chemical Shifts () values of acid of

D-Galactose
6.09

O
6.09

OH
6.09

OH

O
H OH
3.92 3.35 6.09

OH

4.32

2.81

3.35

6.09

OH

Node
OH OH OH OH H H H H H

(ppm)
6.09 6.09 6.09 6.09 2.81 3.35 3.35 4.32 3.92

The 1H-NMR chemical shift value of anomeric hydrogen of acid of galactose is found to be 2.81ppm.

175

Chapter 5

Discussion

5.12 CHARACTERIZATION OF ACID FORMED THROUGH THE OXIDATION OF D-FRUCTOSE

The acid formed as a result of oxidation of D-Fructose (+) mass spectrometry; the M+1 peak was at 195.
204

was identified by Fab

Table: 5.20

13

C-NMR Chemical Shifts () values of acid of DFructose

O
100.78

O
OH

166

OH

71.90

102

OH

72.38 78.08

OH

OH
Fig: 5.51 Fructuronic acid

176

Chapter 5

Discussion

Carbon

(ppm)
100.78

71.90

72.38

78.08

102

166.00

The 13C-NMR chemical shift value of anomeric carbon is 100.78 while that of carboxylic carbon of acid of fructose is found to be 166.00 ppm.

177

Chapter 5

Discussion

Table: 5.21 1H-NMR Chemical Shifts () values

H
4.20 3.49

OH

5.17

O
H3.54 H 4.14 OH OH OH
4.38 5.17

OH
5.17

5.17

5.17

Node
OH OH OH OH H H H H H

(ppm)
5.17 5.17 5.17 5.17 3.49 3.54 4.02 4.14 4.38

The 1H-NMR chemical shift value of anomeric hydrogens of acid of fructose is found to be 3.49 and 3.54 ppm.

178

Chapter 5

Discussion

5.13 CHARACTERIZATION OF ACID FORMED AS A RESULT OF OXIDATION OF D-MALTOSE

The acid formed as a result of oxidation of D-Maltose was identified by Fab(+) mass spectrometry, the M+1 peak was at 371.

Table: 5.22

13

C-NMR Chemical Shifts () values

OH OH O
172.97 79.52

170.01 78.92

O OH
98.47

O
O
102.3

79.32

OH

72.64

OH

76.70

77.26

OH

73.99

75.38

OH

OH
Fig: 5.52 Malturic acid

179

Chapter 5

Discussion

Carbon
C C C C C C C C C C C C

(ppm)
102.30 75.38 73.99 72.64 78.92 79.32 79.52 98.47 77.26 76.70 170.01 172.97

The 13C-NMR chemical shift values of anomeric carbons are 102.30 and 98.47ppm while that of carboxylic carbons of acid of maltose are found to be 170.01 and 172.97 ppm.

180

Chapter 5

Discussion

Table: 5.23 1H-NMR Chemical Shifts () values

6.50

OH

6.50

OH O
4.44

H 4.17 H O OH OH
6.50 3.5 6.50

O
4.34

H 3.50 H

O
OH
6.50 4.00

O
4.99

OH

6.50

H
4.72 4.30

4.48

OH
6.50

OH

6.50

181

Chapter 5

Discussion

Node
OH OH OH OH OH OH OH OH H H H H H H H H H H

(ppm)
6.50 6.50 6.50 6.50 6.50 6.50 6.50 6.50 4.72 4.00 4.30 4.34 3.50 4.99 3.50 4.48 4.44 4.17

The 1H-NMR chemical shift values of anomeric hydrogens of acid of maltose are found to be 4.72 and 4.99 ppm.

182

Chapter 5

Discussion

5.14 CHARACTERIZATION OF ACID FORMED AS A RESULT OF OXIDATION OF D-LACTOSE

The acid of D-Lactose was identified by Fab (+) mass spectrometry, the M+1 peak was at 371.

Table: 5.24

13

C-NMR Chemical Shifts () values

OH OH O
172.97 79.52

170.01

O OH
98.47

OH
72.64

78.92

O
O
102.3

79.32

OH

OH

76.70 73.99 75.38

77.26

OH

OH

Fig: 5.53 Lacturic acid

183

Chapter 5

Discussion

Carbon
C C C C C C C C C C C C

(ppm)
102.30 75.38 73.99 72.64 78.92 79.32 79.52 98.47 77.26 76.70 170.01 172.97

The 13C-NMR chemical shift values of anomeric carbons are 102.30 and 98.47ppm while that of carboxylic carbons of acid of lactose are found to be 170.01 and 172.97 ppm.

184

Chapter 5

Discussion

Table: 5.25 1H-NMR Chemical Shifts () values of acid of D-Lactose

6.50

OH

6.50

OH O
4.44

H4.17 H O OH OH
6.50 3.5 6.50

O
OH
6.50

H 3.50

O
6.50 4.00

OH H

O
4.99

4.34

H
4.72 4.30

4.48

OH
6.50

OH
6.50

185

Chapter 5

Discussion

Node
OH OH OH OH OH OH OH OH H H H H H H H H H H

(ppm)
6.50 6.50 6.50 6.50 6.50 6.50 6.50 6.50 4.72 4.00 4.30 4.34 3.50 4.99 3.50 4.48 4.44 4.17

The 1H-NMR chemical shift values of anomeric hydrogens of acid of lactose are found to be 4.72 and 4.99 ppm.

186

Chapter 5

Discussion

5.15 PROPOSED MECHANISM OF KINETICS OF OXIDATION AGAINST KMnO4

Thus based on above experimental facts the proposed reaction mechanism involves the formation [O] by the action of H2SO4 on KMnO4.

2KMnO 4 + 3H 2SO 4 RCHO +[O]

K 2SO 4 + 2MnSO 4 + 8[O] + 3H 2O RCOOH

The permanganate ion reacts with galactose to form complex [C6H11O6---MnO4-] .This complex finally gives the aldonic acid in presence of nucleophile. The probable rate law might be proposed.
d MnO4 = k [RCHO ] MnO4 dt

Where RCHO represents the concentration of galactose or maltose and MnO4 - is of Oxidant. The following mechanism is proposed to explain the path of oxidation of sugars :

RCHO + MnO4 + H

k1 k2
k [Complex] [Pr oduct ]
3

[ RCHO----MnO4 ] Complex

slow

187

Chapter 5

Discussion

where k1 and k2 represent the rate constant in the forward and reverse direction and k3 is the rate constant of the formation of product. Rate of formation of complex will be given as:

d [Complex] = k1 [RCHO] MnO4 [k2 k3 ] [Complex] dt

(1)

At steady state,

d [Complex ] =0 dt

(2)

From equation no.(1) and (2) concentration of complex comes out to be:

[Complex] = k1[RCHO][MnO4 ]

k 2 + k3

(3)

At steady state rate of disappearance of MnO4- may be:

d MnO4 = k3 [Complex] dt

(4)

d MnO4 k k [RCHO ] MnO4 = 1 3 (k2 + k3 ) dt

(5)

Now the total [MnO4-] may be considered as:

[MnO ] = [MnO ] + [Complex]

4 T 4

(6)

Now put the value of Complex:

[MnO ] [
4 T

k [RCHO ] MnO4 = MnO + 3 (k2 + k3 )

4

(7)

188

Chapter 5

Discussion

from equation (7) the value of [MnO4-] comes out :

[MnO

(k2 + k3 )[MnO4 ]T ] = (k + k ) + k [RCHO] 2 3 1

(8)

The final rate law from 5 to 8 :

k 1 k 3{ } [RCHO ][k 2 + k 3 ] MnO 4 T d MnO 4 = {(k 2 + k 3 ) + k 1 [RCHO ]}[k 2 + k 3 ] dt
k1k3 [RCHO ] MnO4 [k1 + k3 ] + k1[RCHO]

(9)

(10)

In present experimental conditions,

k2 + k3 > k1 [RCHO ]

Hence above equation reduces to,

d MnO dt

]=

k 1 k 3 [RCHO ] MnO k2 + k3

4 T

= k [RCHO

][MnO

4 T

(11)

where,
k= k1k 3 k 2 + k3

The above equation indicates first order kinetics with respect to sugar and permanganate ion concentration.

189

Chapter 5

Discussion

5.16 COMPARATIVE STUDIES

The results of the present study of the oxidation of galactose, fructose, maltose and lactose by potassium permanganate in acidic medium were compared with the results supported for the oxidation of some
112

aldoses

by

chromium

peroxydichromate in very dilute sulphuric acid medium. 39

and the reactivities of some

aldoses and aldoseamines towards potassium bromate in hydrochloric acid

When the present study in respect of the role of MnO4- was compared, it is found that the MnO4- is the reactive species of potassium permanganate in acidic as well as in alkaline medium, as far as the kinetic order with respect to MnO4- is concerned, it is first order throughout the variation of [MnO4-]. When the present study has been made for the effect of [sugar] on the rate of oxidant, it is found that the reactions are first order with respect to all the sugars. The reported
39, 103

first order kinetics in [sugar] seems to be similar with the

present study. The reducing sugar molecules participate in the reactions as such in present study as well as in the previous work. The effect of H+ ion concentration have the same effect as in the oxidation of some aldoses by peroxydichromate in dilute sulphuric acid
112

and reactivities of some aldoses and aldoseamines

towards potassium bromate in hydrochloric acid medium. 39 The reported results in these studies are quite similar i.e. these reactions exhibited a uniform increase in pseudo_first order rate constant with increasing concentration of an acid. The reported influence of H+ ion concentration also seems to be similar with present study i.e. the reaction was accelerated by an increase in the acidic of the medium kobs vs [H2SO4] plot shows a linear relationship with positive intercept on the Y-axis.

190

Chapter 5

Discussion

Table: 5.26 Comparison of Rate Constants with reported Data

Oxidant

[Oxidant] (mol dm-3)

Sugar

[Sugar] (mol dm-3)

k (s-1)

Reference

Mannose NBAa 8 x 10-4 Maltose

2 x 10-2 4 x 10-2 2 x 10-2 4 x 10-2 2 x 10-2 2 x 10-2 1 x 10-4 1 x 10-4 1 x 10-4 1 x 10-1 1 x 10-1 1 x 10-1 1 x 10-1 2 x 10-2 4 x 10-2 4 x 10-2 3 x 10-2

2.0 x 10-5 3.2 x 10-5 1.6 x 10-5 3.1 x 10-5 6.0 x 10-4 2.0 x 10-4 3.6 x 10-4 2.5 x 10-4 8.1 x 10-4 6.0 x 10-4 7.2 x 10-4 8.4 x 10-4 9.4 x 10-4 8.8 x 10-3 7.2 x 10-3 2.4 x 10-3 2.8 x 10-3

83

Potassium Iodate

1 x 10-3

Xylose Maltose Glucose Galactose Fructose Glucose Mannose Galactose Xylose Galactose Fructose Maltose Lactose

57

DPAb

9 x 10-5

134

Potassium Bromate

1 x 10-2

39

Potassium Permanganate

1 x 10-3

Present Study

a b

N-Bromoacetamide Diperiodatoargentate (III)

191

Chapter 5

Discussion

Table: 5.27 Comparison of Activation Parameters

Sugar

Ea (KJmol-1)

H# (KJmol-1)

S # (JK mol-1)
-1

G# (KJmol-1)

Reference

Sucrose Glucose Mannose Galactose Xylose Arabinose Xylose Glucose Galactose Fructose Mannose Maltose Galactose Fructose Maltose Lactose

63.7

72.4 40.0 37.0 35.0 32.0 43.3 40.8 67.6 48.1 63.5 73.6 80.1 40.9 47.6 23.0 47.9

-8.84 -170 -178 -185 -194 -83.6 -85.4 -66.7 -140.0 -75.3 8.4 29.0 -149.8 -133.8 -212.0 -134.6

75.1

55

39

45.4 42.3

68.12 66.32

53

134

76.2 82.8 43.5 50.0 25.4 50.2

70.9 71.1 86.6 88.4 87.6 89.0

83

Present Study

192

Chapter 5

Discussion

5.17 CONCLUSIONS
The following conclusions were drawn from the observed kinetic data and from the spectral information collected for the oxidation of galactose, fructose, maltose and lactose by potassium permanganate in acidic medium while Hg was used in the oxidation of maltose and lactose. 1. MnO4- and [Hg (H2O)6]+2 have been assumed as the reactive species of potassium permanganate and Hg(II) in acidic medium.

H R C OH O

H C O Mn O O O

2.
H R C

The
H C O Mn O

complex,
+

and

the

complex,

O Hg(H2O)5 O

OH O

has been proposed as the most unstable activated

complex in the oxidation of galactose, fructose and maltose, lactose respectively. 3. The formation of highly solvated activated complex (scheme 1, 2, 3 & 4) is supported by observed negative value of entropy of activation. 4. First order kinetics has been observed with respect to oxidant and sugar.

193

Chapter 5

Discussion

5. Linear dependence of rate is observed when acidity of medium increased. 6. The rate of oxidation of galactose, fructose, maltose and lactose is unaffected by the change in ionic strength of the medium. 7. Formic acid and arabinonic acid are identified as main oxidation products along with the other acids such as galacturonic, fructuronic, malturic and lacturic acid.

194

Chapter 5

Discussion

5.18 FUTURE PERSPECTIVES

Oxidation of carbohydrates including reducing and non reducing sugars with different inorganic and organic oxidizing agents have been studied very widely. A lot of literature has been reported on the oxidation of aldoses and ketoses, oligosaccharides and polysaccharides. This project of oxidation of carbohydrates (monosaccharides and disaccharides) can be extended in many ways like:

Oxidation of reducing and non reducing sugars with KMnO4 can be studied by recording the time of decoloration of KMnO4 visually. Pb and Cd can be used as a catalyst in presence of KMnO4. A comparative study can be carried out to study the oxidation of pentose with hexoses, dextroses and other group of carbohydrates. KMnO4 with base should be tested to oxidize the sugar into respective acid. Effect of pH with temperature can be studied in oxidation of sugars with KMnO4. KMnO4 with different buffer in alkaline and acidic medium should be checked for the oxidation of carbohydrates. Compound may be analyzed by using Gas Chromatography, HPLC, Mass Spectrum, negative and positive fab. New organic and inorganic oxidants should be searched with different catalyst using alkaline and acidic medium to extend the oxidation of carbohydrates.

New mechanism should be developed to establish the reaction kinetics of oxidation of sugars.

195

Chapter 5

Discussion

5.19 RESEARCH IMPORTANCE, APPLICATION AND USE

Carbohydrates are the structural backbone of the DNA, RNA and nucleic acids and play major role in nutrition. The biochemical importance of the carbohydrates lies in the fact that they form the direct link between the radiant energy emitted by the sun and the demand of living tissues, plant and animal, for supplies of energy required for the purpose of metabolism. They are further important due to their wide occurrence and multihydroxy functionality that allows coordination and chelation to many metal ions. Besides acting simply as effective chelators, many cases they are also reducing agents.
17-50 205

in

Potassium permanganate (KMnO4) is used primarily to control taste and odors, remove colour, control biological growth in treatment plants and remove iron and manganese, where as secondary role of it, may be useful in controlling the formation of THMS and DBPS. 206 Potassium permanganate is highly reactive under conditions found in the water industry. It will oxidize a wide variety of inorganic and organic substances. Potassium permanganate (Mn+7) is reduced to (MnO2) (Mn+4).206 Under acidic conditions the following reaction has been established:

MnO 4 + 4 H + + 3e MnO2 + H 2 O MnO 4 + 8 H + + 5e Mn +2 + 4 H 2 O

Current research based on the oxidative property of KMnO4 with organic reducing sugars in acidic medium where HMnO4 specie was reported as an oxidizing agent.

196

Chapter 5

Discussion

The importance of this investigation lies in the fact that there is no pertinent work related with the oxidation of sugars in acidic medium has been reported in which the compound formed during oxidation is isolated and subjected to advanced techniques in elucidation of mechanism and structure of compound formed. All the steps involve in the kinetics measurement including the value of Ea, H#, G# & S# were used to establish the complex formed between permanganate ion and sugar lead to the formation of acid derivative. This project will be helpful in understanding the mechanism of oxidation of sugars with KMnO4 as an oxidizing agent for the research scholars and other students of learning process.

197

CHAPTER # 6

REFERENCES

Chapter 6

References

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200

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