Table Of ContentCHEMISTRY RESEARCH AND APPLICATIONS
A K M
NALYSIS OF INETIC ODELS
C R S .
OF HEMICAL EACTION YSTEMS
VALUE APPROACH
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C R A
HEMISTRY ESEARCH AND PPLICATIONS
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CHEMISTRY RESEARCH AND APPLICATIONS
A K M
NALYSIS OF INETIC ODELS
C R S .
OF HEMICAL EACTION YSTEMS
VALUE APPROACH
L. A. TAVADYAN AND G. A. MARTOYAN
National Academy of Sciences of the Republic of Armenia
A.B. Nalbandyan Institute of Chemical Physics
New York
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Library of Congress Cataloging-in-Publication Data
Tavadian, L. A. (Levon Agasievich)
[Analiz kineticheskikh modelei khimicheskikh reaktsionnykh sistem. English]
Analysis of kinetic models of chemical reaction systems : value approach / Levon Agasi
Tavadyan, Gagik Ashot Martoyan.
pages cm. -- (Chemistry research and applications)
English version of: Analiz kineticheskikh modelei khimicheskikh reaktsionnykh sistem.
Includes bibliographical references and index.
ISBN: (cid:28)(cid:26)(cid:27)(cid:16)(cid:20)(cid:16)(cid:25)(cid:22)(cid:22)(cid:21)(cid:20)(cid:16)(cid:19)(cid:27)(cid:20)(cid:16)(cid:22) (eBook)
1. Reaction mechanisms (Chemistry) 2. Chemical kinetics--Mathematical models. I. Martoian,
G. A. (Gagik Ashotovich) II. Title.
QD502.5.A5313 2014
541'.394--dc23
2014017740
Published by Nova Science Publishers, Inc. † New York
CONTENTS
Preface vii
Chapter 1 Fundamentals of Chemical Chain Reaction Kinetics 1
Chapter 2 Kinetic Significance of Steps in Complex Chemical Transformation 15
Chapter 3 Value Analysis of Kinetic Models for Chemical Reaction Systems 29
Chapter 4 Value Analysis As a Basis to Purposely Influence on Multistep
Chemical Reactions 59
Chapter 5 Kinetics of Multicentered Chain Chemical Reactions.
Value Approach 93
Chapter 6 Illustrative Examples of Value Analysis Application for
Chemical Reaction Control 121
Chapter 7 Efficient Inhibition of Chain Chemical Reactions 133
Chapter 8 Value Approach in the Solution of Problems of Nonlinear
Chemical Dynamics and Synergetics 175
Chapter 9 Valkin: A Software Package for the Kinetic Analysis of
Reaction Systems by the Value Method 189
Summary 209
Glossary of Symbols 211
Index 215
PREFACE
The problem of numerical modeling of complex chemical reactions attracts the increasing
attention of researchers associated with the tendency to control efficiently chemical reactions
in practical applications. The mechanism of the complex (multistep) reaction or, otherwise, its
kinetic model is defined as a set of single-step individual chemical transformations.
Construction of kinetic models conforming to experimental data and having prognostic
capability enables the successful control of one of the major problems of chemical kinetics of
complex reactions. Meanwhile, in solving this problem the broad application of conventional
analytical methods is a challenge.
Computational approaches enable to overcome the “barriers” of high complexity in
chemical transformation. However, the use of numerical methods in their simplest versions
does not possess an ideological content. This book is addressed just to provide a practical
understanding of the calculational methods.
The book was intended and written with an objective to present new kinetic approaches,
which provide insight into the mechanism of the complex chemical reactions using numerical
methods.
In fact, the conceptual and valid basis for these approaches is the creation of the
methodology and tools for rigorous kinetic orientation in complex chemical transformation.
We believe that the solution of the above-mentioned critical problem of chemical kinetics of
complex reactions lies just on this path.
Recent efforts of the authors resulted in development of a numerical method for the
analysis of reaction mechanisms, based on their Hamiltonian systematization with marking
out target characteristics of reactions and with the kinetic comprehension of conjugate
variables. The core factor of this approach is the ability to calculate numerically the dynamics
of value magnitudes, which characterize the systemic kinetic significances of the chemical
species of a reaction and its individual steps. Such information makes it possible to realize
chemically the mechanism of a complex transformation, and particularly, to carry out the
purposeful selection of efficient ways to control the reactions.
Without taking account of the shape of mathematical representations, the basic point that
forms the foundation of the value approach in the study of the reaction mechanisms, may be
specified as follows: different types of matter motion, including chemical transformation, can
be described by similar concepts. In this case the value quantities, as new universal concepts
of chemical kinetics, arise from the physico-chemical and kinetic understanding of the ideas
viii L. A. Tavadyan and G. A. Martoyan
of the classical Hamiltonian formalism for dynamic systems in describing the kinetics of
multistep chemical reactions.
In the book the capabilities and distinctive features of the suggested value analysis
method of the reaction mechanisms are discussed in detail. Besides, a short and contrastive
overview of existing approaches for studying and controlling the complex reactions is
presented. The structure of the book includes a wide range of problems associated with the
numerical value to describe and study the kinetics of complex reactions, such as:
The numerical determination of kinetic significances for the individual steps and
species of a complex chemical reaction;
The reduction of excessive kinetic reaction models; via the identification of the
base(minimal) reaction mechanisms;
The identification and analysis of reaction critical conditions under which the
qualitative and quantitative characteristics of the reaction change drastically;
The identification of priorities that have target-oriented influence on a chemical
reaction via optimal control;
The determination of the molecular design of an efficient stimulators and inhibitors
of a complex reaction among a number of similar compounds on the basis of kinetic
model;
The evaluation and improvement of prognostic capability of the kinetic model of a
multistep reaction.
Chain chemical reactions are the dominant objects of studies in this volume. Historically,
just the chain theory mainly initiates a new philosophy for chemical reactions that is the
system analysis.
Chain reactions belong to the class of chemical processes for which the kinetic laws are
studied extensively. In the book selection of the reactions with the aim to demonstrate the
capabilities of the value approach was mainly based on the scientific interests of the authors.
However, at the same time the examples are provided on the use of the proposed approach to
solve the key problems that are relevant to chain reactions. Among these are the identification
and analysis of critical phenomena, the explosion limits in branching-chain reactions, the
interpretation of the molecular structure of an efficient antioxidants, the identification of
dominant steps responsible for its activity, etc.
In this volume we also considered the self-organizing systems consisting of the
oscillating reactions, of which the Belousov-Zhabotinsky reaction is a well-known example.
Attempt was made to demonstrate a generality of the problem on the identification of critical
phenomena in branching-chain reactions and in the nonlinear reaction systems as a whole.
It is important that the value method of studying complex chemical reactions is easily
compatible with computational methods of calculation. This emphasis is validated by the
kinetic software package VALKIN described here.
The authors hope that in this volume the offered value method for analyzing kinetic
models of multistep reactions will find followers among researchers, who are dealing with the
problems of chemical kinetics, the studies of the reaction mechanisms and their control. The
book also will be useful for students and graduates to extend their knowledge in this field. At
the same time we appreciate to receive the reader’s feedback and suggestion.
