Emanuel / Zaikov / Maizus Oxidation of Organic Compounds

Medium Effects in Radical Reactions
1. Auflage 2013
ISBN: 978-1-4831-4511-2
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 628 Seiten, Web PDF

Oxidation of Organic Compounds: Medium Effects in Radical Reactions explores the role of solvents and of the composition of phase states in radical-chain processes involved in the oxidation of organic compounds. Organized into 10 chapters, this book begins with a discussion of the basic concepts relating to the mechanism involved in the oxidation of hydrocarbons and other organic compounds in liquid-phase reactions. Subsequent chapters detail some methods for studying the mechanism of oxidation reactions; role of solvation in chemical reaction kinetics; role of the medium in chain-initiation reactions; role of non-specific and specific solvation in chain-propagation and chain-termination reactions; and the role of solvation in chain-termination reactions in inhibitors. The influence of the solvent and the phase state of substances undergoing oxidation on the rates and mechanisms of individual elementary processes are also addressed. The last chapter examines the problem of the influence of the solid state of the polymer on the reactivity of radicals. This monograph will be valuable to scientific research workers, engineers, and engineering technologists specializing in the field of radical reactions and in particular in the oxidation of organic compounds.

Autoren/Hrsg.

Emanuel, N. M.

Zaikov, G. E.

Maizus, Z. K.

Hirschler, M. M.

Inhaltsverzeichnis

1;Front Cover ;1
2;Oxidation of Organic Compounds: Medium Effects in Radical Reactions;4
3;Copyright Page;5
4;Table of Contents;12
5;Preface;6
6;Preface to the English Edition;8
7;Epigraph;11
8;Introduction;18
8.1;LITERATURE REFERENCES;22
9;CHAPTER 1. Mechanism of the Liquid Phase Oxidation of Organic Compounds;23
9.1;1.1 INTRODUCTION;23
9.2;1.2 CHAIN MECHANISM OF OXIDATION REACTIONS;23
9.3;1.3 INITIALLY-FORMED INTERMEDIATE OXIDATION PROCESSES;27
9.4;1.4 KINETIC LAWS AND THE OVERALL OXIDATION REACTION SCHEME;30
9.5;1.5 ELEMENTARY REACTIONS INVOLVED IN THE OXIDATION PROCESSES;34
9.6;LITERATURE REFERENCES;84
10;CHAPTER 2. Some Methods for Studying the Mechanism of Oxidation Reactions;91
10.1;2.1 INTRODUCTION;91
10.2;2.2 METHODS FOR MEASURING THE OXIDATION RATE;91
10.3;2.3 DETERMINATION OF THE RATE CONSTANTS OF ELEMENTARY CHAIN-PROPAGATION AND CHAIN-TERMINATION REACTIONS;94
10.4;2.4 DETERMINATION OF THE RATE CONSTANT OF THE ELEMENTARY REACTIONS INVOLVED IN FREE RADICAL INITIATION;112
10.5;2.5 CHEMILUMINESCENCE METHODS FOR DETERMINING THE RATE CONSTANTS OF CHAIN-TERMINATION REACTIONS BROUGHT ABOUT BY INHIBITORS;124
10.6;LITERATURE REFERENCES;129
11;CHAPTER 3. The Role of Solvation in Chemical Reaction Kinetics;135
11.1;3.1 INTRODUCTION;135
11.2;3.2. NON-SPECIFIC SOLVATION;136
11.3;3.3. SPECIFIC SOLVATION;152
11.4;3.4 EFFECT OF COMPLEX FORMATION ON THE KINETICS AND MECHANISM OF REACTION;171
11.5;3.5 SOME SPECIFIC PHENOMENA RELATING REACTIVITIES TO THE PHYSICAL STATE OF SUBSTANCES;175
11.6;LITERATURE REFERENCES;191
12;CHAPTER 4. The Role of the Medium in Chain-initiation Reactions;204
12.1;4.1 INTRODUCTION;204
12.2;4.2 THE ROLE OF THE MEDIUM IN PROCESSES OF CHAIN-INITIATION. THE INFLUENCE OF THE PHASE COMPOSITION OF THE OXIDANT ON THE MECHANISM OF CHAIN-INITIATION;204
12.3;4.3 THE RÔLE OF THE MEDIUM IN PROCESSES OF DEGENERATE
CHAIN-BRANCHING;210
12.4;4.4 INFLUENCE OF SOLVENTS ON THE RATE OF FORMATION OF RADICALS FOLLOWING THE THERMAL DECOMPOSITION OF INITIATORS.;273
12.5;LITERATURE REFERENCES;283
13;CHAPTER 5. Role of Non-specific Solvation in Chain-propagation and Chain-termination Reactions;295
13.1;5.1 INFLUENCE OF THE POLARITY OF THE MEDIUM ON THE REACTIVITY OF ORGANIC COMPOUNDS;295
13.2;5.2 OXIDATION OF KETONES;306
13.3;5.3 OXIDATION OF ALKENES;323
13.4;5.4 OXIDATION OF NON-POLAR HYDROCARBONS;328
13.5;LITERATURE REFERENCES;335
14;CHAPTER 6. The Role of Specific Solvation in Chain-propagation and Chain-termination Reactions;338
14.1;6.1 INTRODUCTION;338
14.2;6.2 THE INFLUENCE OF HYDROGEN BONDS ON THE OXIDATION OF KETONES;339
14.3;6.3 THE RÔLE
OF HYDROGEN BONDS IN THE OXIDATION OF ALKENES;358
14.4;6.4 THE RÔLE OF HYDROGEN BONDS IN THE OXIDATION OF SATURATED
HYDROCARBONS;365
14.5;6.5 THE INFLUENCE OF HYDROGEN BONDS ON THE RATE OF REACTION OFPHENOXYL AND ALKYL RADICALS;370
14.6;6.6 THE INFLUENCE OF THE FORMATION OF p-COMPLEXES ON THE REACTIVITY OF NITROXYL AND METHYL RADICALS;391
14.7;6.7 THE ROLE OF IONIC REACTIONS IN THE ELEMENTARY PROCESSES OF CHAIN-PROPAGATION AND CHAIN-TERMINATION;401
14.8;LITERATURE REFERENCES;413
15;CHAPTER 7. The Role of Solvation in Chain-termination Reactions in Inhibitors;417
15.1;7.1 INTRODUCTION;417
15.2;7.2 EFFECTIVENESS OF INHIBITORS IN THE OXIDATION OF ORGANIC COMPOUNDS OF DIFFERENT CLASSES;417
15.3;7.3 INFLUENCE OF NON-SPECIFIC SOLVATION ON THE EFFICIENCY OF INHIBITOR ACTIVITY;432
15.4;7.4 INFLUENCE OF SPECIFIC SOLVATION ON THE EFFECTIVENESS OF INHIBITORS;440
15.5;LITERATURE REFERENCES;455
16;CHAPTER 8. The Causes of the Difference Between the Composition of Products Formed in the Oxidation of Organic Substances in the Vapour and Liquid Phases;459
16.1;8.1 INTRODUCTION;459
16.2;8.2 DIFFERENCES BETWEEN LIQUID-PHASE AND VAPOUR-PHASE OXIDATION REACTIONS;460
16.3;8.3 OXIDATION OF ALKANIC HYDROCARBONS;467
16.4;8.4 OXIDATION OF
BUTAN-2-ONE;481
16.5;8.5 OXIDATION OF ETHYL ALCOHOL;490
16.6;8.6 REGION OF CHAIN-OXIDATION BY THE PEROXIDE MECHANISM;500
16.7;LITERATURE REFERENCES;507
17;CHAPTER 9. Influence of Solvents on the Rate and Direction of Oxidation Processes;513
17.1;9.1 INTRODUCTION;513
17.2;9.2 THE INFLUENCE OF SOLVENTS ON THE RATES AND DIRECTION OF THE OXIDATION OF BUTAN-2-ONE AND OF ETHYL ALCOHOL;513
17.3;9.3 INFLUENCE OF NON-SPECIFIC S0LVATI0N ON THE RATE AND DIRECTION OF OXIDATION;519
17.4;9.4 INFLUENCE OF THE MEDIUM ON THE SELECTIVITY OF OXIDATION;530
17.5;9,5 INFLUENCE OF WATER ON THE RATE CONSTANT AND SELECTIVITY OF LIQUID-PHASE OXIDATION OF BUTANE;539
17.6;9.6 CONCLUSIONS;543
17.7;LITERATURE REFERENCES;544
18;CHAPTER 10. Some Special Features of the Kinetic Laws and the Mechanism of Oxidation of Solid Polymers;546
18.1;10.1 INTRODUCTION;546
18.2;10.2 THE INFLUENCE OF THE RATE OF STRUCTURAL REARRANGEMENTS ON THE REACTION RATE;546
18.3;10.3 THE INFLUENCE OF THE INTENSITY OF MOLECULAR MOTIONS ON THE
SPECIFICITY OF REACTIONS IN A SOLID POLYMER;549
18.4;10.4 THE INFLUENCE OF THE ADDITION OF PLASTICISERS ON THE RELATIONSHIPS GOVERNING RADICAL REACTIONS IN THE SOLID PHASE;555
18.5;10.5 ANTI-RADICAL ACTIVITY OF ANTIOXIDANTS IN A SOLID POLYMER;558
18.6;10.6 THE RÔLE
OF SURFACE PHENOMENA IN THE DEGRADATION OF SOLID POLYMERS;560
18.7;10.7 SPECIAL FEATURES OF THE CHAIN-PROPAGATION AND CHAIN TERMINATION
REACTIONS DURING THE OXIDATION OF A SOLID POLYMER;562
18.8;10.8 THE RÔLE PLAYED BY COMPOUNDS OF LOW MOLECULAR WEIGHT IN
THE OXIDATION OF SOLID POLYMERS;568
18.9;10.9 THE INFLUENCE OF INHOMOGENEITIES ON THE RATE OF OXIDATION OF POLYMERS;570
18.10;10.10. SOME EFFECTIVE METHODS FOR THE INVESTIGATION OF PROCESSES TAKING PLACE WITHIN A POLYMER MATRIX;575
18.11;10.11 THE RELATIONSHIP BETWEEN THE KINETIC LAWS GOVERNING DEGRADATION PROCESSES AND THE INTERNAL STRESSES IN POLYMER MOLECULES;578
18.12;10.12 ADDITIONAL DATA ON THE CHARACTERISTIC FEATURES OF CHEMICAL CONVERSIONS IN A POLYMER MATRIX;592
18.13;LITERATURE REFERENCES;602
19;Appendix;611
20;Subject Index;617