E-Book Overview
This book covers the results of investigations into the mechanisms and kinetics of thermal decompositions of solid and liquid substances on the basis of thermochemical analyses of the processes. In the framework of the proposed ideas, the main features of these reactions are explained and many problems and unusual phenomena, which have accumulated in this field are interpreted. New methods of TA measurement and calculation have been developed, which permit the precision and accuracy of determination of kinetic parameters to be increased substantially. Reliable kinetic characteristics have been obtained and the decomposition mechanisms for several tens of substances have been interpreted. These include different classes of compounds: crystalline hydrates, oxides, hydroxides, nitrides, azides, nitrates, sulfates, carbonates and oxalates.
E-Book Content
Thermal Decomposition of Solids and Melts Hot Topics in Thermal Analysis and Calorimetry Volume 7 Series Editor: Judit Simon, Budapest University of Technology and Economics, Hungary The titles published in this series are listed at the end of this volume. S Thermal Decomposition of Solids and Melts New Thermochemical Approach to the Mechanism, Kinetics and Methodology by , Boris V. L vov St. Petersburg State Polytechnic University St. Petersburg, Russian Federation ABC , Boris V. L vov St. Petersburg State Polytechnic University St. Petersburg Russian Federation Series Editor: Judit Simon Budapest University of Technology and Economics Hungary Library of Congress Control Number: 2007932972 ISBN 978-1-4020-5671-0 e-ISBN 978-1-4020-5672-7 Printed on acid-free paper. © 2007 Springer No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. 9 8 7 6 5 4 3 2 1 springer.com To Anna, my Wife with love Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Foreword xi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii Preface (Original Russian Edition) . . . . . . . . . . . . . . . . . . xv Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvii Part I Thermal Decomposition: Basic Concepts 1 Historical Overview . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Decomposition Mechanism . . . . . . . . . . . . . . . 2.1 Preliminary Remarks . . . . . . . . . . . . . . . . . 2.2 Basics of the Congruent Dissociative Vaporization (CDV) Mechanism . . . . . . . . . . . . . . . . . . 2.3 Direct Observation of the Primary Decomposition Products . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Induction and Acceleratory Periods and the Localization Effect . . . . . . . . . . . . . 2.5 Shape and Position of the Nucleus . . . . . . . . . 2.6 Structure and Composition of the Solid Product . 2.7 Thermal Stability of Complex Gaseous Molecules . 2.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Decomposition Kinetics . . . . . . . . . . . . . . 3.1 Preliminary Remarks . . . . . . . . . . . . . . 3.2 The Arrhenius Equation . . . . . . . . . . . . 3.3 The Hertz–Langmuir Equation and Langmuir Diffusion Equations . . . . . . 3.4 Modification of the Hertz–Langmuir Equation as Applied to Decomposition Reactions . .