Atmospheric Oxidation and Antioxidants, Vol. 1

246 Pages·1993·6.44 MB·English

Atmospheric Oxidation
and Antioxidants
VOLUME I
This page intentionally left blank
Atmospheric
Oxidation and
Antioxidants
VOLUME I
G. Scott, editor
Green Ridge
Newby Nr. Middlesbrough
Cleveland TS8 OAH
U.K.
ELSEVIER
AMSTERDAM - LONDON - NEW YORK - TOKYO 1993
ELSEVIER SCIENCE PUBLISHERS B.V.
Sara Burgerhartstraat 25
P.O. Box 211,1000 AE Amsterdam, The Netherlands
ISBN: 0-444-89615-5 (volume I)
0-444-89616-3 (volume II)
0-444-89617-1 (volume III)
0-444-89618-x (set)
© 1993 Elsevier Science Publishers B.V. All rights reserved.
No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any
means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the
publishers, Elsevier Science Publishers B.V., Copyright & Permissions Department, P.O. Box 521, 1000 AM
Amsterdam, The Netherlands.
Special regulations for readers in the U.S.A. This publication has been registered with the Copyright Clearance
Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about conditions under
which photocopies of parts of this publication may be made in the U.S.A.. All other copyright questions,
including photocopying outside of the U.S.A., should be referred to the copyright owner, Elsevier Science
Publishers B.V., unless otherwise specified.
No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of
products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions
or ideas contained in the material herein.
This book is printed on acid-free paper.
Printed in The Netherlands.
V
CONTENTS
Preface vii
List of authors ix
CHAPTER 1. AUTOXIDATION AND ANTIOXIDANTS:
HISTORICAL PERSPECTIVE, by Gerald Scott 1
1. The Ageing of Rubber 1
2. Hydroperoxides and the Autoxidation Chain Reaction 2
3. Antioxidants 4
4. Synergism 23
5. The Effect of the Reaction Environment upon Oxidation and
Antioxidant Mechanisms 24
6. Biological Oxidation 30
7. The Present Position 36
References 38
CHAPTER 2. AUTOXIDATION, by S. Al-Malaika 45
1. Introduction 45
2. Mechanism and Kinetics of Autoxidation 46
3. Technological Effects of Oxidation 68
4. Other Techniques used for Oxidation Studies 78
References 78
CHAPTER 3. INITIATORS, PROOXIDANTS AND SENSITISERS,
by Gerald Scott 83
1. Reactions of Oxygen 83
2. Peroxides 102
References 116
CHAPTER 4. ANTIOXIDANTS: CHAIN-BREAKING
MECHANISMS, by Gerald Scott 121
1. The Chain-Breaking Donor Mechanism 121
2. Chain-Breaking Hydrogen (Electron) Acceptor Mechanism . . . 140
3. Catalytic Antioxidants 142
References 157
VI
CHAPTER 5. ANTIOXIDANTS — PREVENTIVE MECHANISMS,
by S. Al-Malaika 161
1. Catalytic Peroxidolytic Mechanisms and the Role of Sulphur-
Containing Compounds 164
2. Stoichiometric Peroxidolytic Mechanisms (PD-S) and the Role
of Phosphite Esters 208
3. Metal Ion Deactivation 211
4. Ultra-Violet Light Deactivation 218
References 221
Subject Index 225
vii
PREFACE
Oxidation by molecular oxygen is one of the most practically important of
all chemical processes. It is the basis of energy production in animals and,
at the same time, a major cause of irreversible deterioration and ultimate
death. Man uses oxygen positively in the production of energy by combus­
tion, and many important industrial processes in the petrochemical in­
dustry are based on the controlled oxidation of hydrocarbons. At the same
time, oxidation is the main cause of deterioration of foodstuffs and of many
industrial polymers.
It is clearly of great practical importance that the mechanisms of oxida­
tion and its prevention should be understood in order to utilise the reactions
of oxygen more effectively but, equally importantly, to control the adverse
effects of oxygen on man-made products and in biological systems. The three
volumes of this work are directed toward these objectives. Volume I reviews
current understanding of autoxidation, largely on the basis of the reactions
of oxygen with characterised chemicals. From this flows the modern mech­
anisms of antioxidant action and their application in stabilisation technol­
ogy. Volume II examines the oxidation chemistry of carbon-based materials
in more detail with emphasis on the technological phenomena that result
from the attack of oxygen and the practical procedures developed to prevent
them. Volume III addresses our present understanding of how oxidation is
involved both positively and negatively in life processes. This is a more
recent and rapidly developing aspect of oxidation chemistry and many of the
concepts still have to be proved by rigorous scientific investigation. Never­
theless, the mechanistic principles developed as a result of studies in vitro
over the years now provide the basis for understanding the complex oxida­
tion chemistry of life processes and its control by biological antioxidants.
The three volumes, although complementary to one another, form a single
whole and it is hoped that, by frequent cross-reference, the reader will be
enabled to utilise ideas and experience from other disciplines to enlighten
his own. The first edition of this work was published a quarter of a century
ago in a single volume. The increase in size of the second edition reflects the
growth of interest in the subject in the intervening period. Nevertheless, the
mechanisms outlined in the first edition still form the basis of our present
understanding of oxidation chemistry and there will therefore be frequent
reference to it in this edition.
GERALD SCOTT
This page intentionally left blank
IX
LIST OF AUTHORS
S. AL-MALAIKA (Volume I)
Department of Chemical Engineering and Applied Chemistry, Aston
University, Aston Triangle, Birmingham B4 7ET, U.K.
N.C. BILLINGHAM (Volume II)
School of Chemistry and Molecular Sciences, University of Sussex,
Brighton BN1 9QJ, U.K.
JOHN A. BLAIR (Volume III)
Pharmaceutical Sciences Institute, Aston University, Aston Triangle,
Birmingham B4 7ET, U.K.
E.B. BURLAKOVA (Volume III)
The Institute of Chemical Physics, Kosygin-str. 4, Moscow 117334,
Russia
G. CAMINO (Volume II)
Dipartimento di Chimica Inorganica, Università Degli Studi di Torino,
Via Pietro Giuria, 10125 Torino, Italy
D.J. CARLSSON (Volume II)
Division of Chemistry, National Research Council of Canada, Ottawa,
K1A 0R9, Canada
T. COLCLOUGH (Volume II)
Exxon Chemical Technology Centre, Abingdon, Oxon. 0X13 6BB, U.K.
NANCY E. DAVIDSON (Volume III)
Oncology Center, Johns Hopkins Medical Institutions, 615 N. Wolfe
Street, Baltimore, MD 21205, U.S.A.
H.H. DRAPER (Volume III)
Department of Nutritional Sciences, University of Guelph, Ontario,
Canada NIG 2W1