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CHEMICAL KINETICS

Edited by Vivek Patel

Chemical Kinetics

Edited by Vivek Patel

Published by InTech

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Copyright © 2012 InTech

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First published February, 2012

Printed in Croatia

A free online edition of this book is available at www.intechopen.com

Additional hard copies can be obtained from [email protected]

Chemical Kinetics, Edited by Vivek Patel

p. cm.

ISBN 978-953-51-0132-1

Contents

Preface IX

Part 1 Introduction to Chemical Kinetics 1

Chapter 1 Chemical Kinetics, an Historical Introduction 3

Stefano Zambelli

Part 2 Chemical Kinetics and Mechanism 29

Chapter 2 On the Interrelations Between

Kinetics and Thermodynamics as

the Theories of Trajectories and States 31

Boris M. Kaganovich, Alexandre V. Keiko,

Vitaly A. Shamansky and Maxim S. Zarodnyuk

Chapter 3 Chemical Kinetics and Inverse Modelling Problems 61

Victor Martinez-Luaces

Chapter 4 Model Reduction

Techniques for Chemical Mechanisms 79

Terese Løvås

Chapter 5 Vibrational and Chemical

Kinetics in Non-Equilibrium Gas Flows 115

E. V. Kustova and E. A. Nagnibeda

Chapter 6 Numerical Analysis of the Effect

of Inhomogeneous Pre-Mixture on

Pressure Rise Rate in HCCI Engine by

Using Multi-Zone Chemical Kinetics 141

Ock Taeck Lim and Norimasa Iida

Chapter 7 Ignition Process in a

Non-Homogeneous Mixture 155

Hiroshi Kawanabe

VI Contents

Part 3 Chemical Kinetics and Phases 167

Chapter 8 Chemical Kinetics in Cold Plasmas 169

Ruggero Barni and Claudia Riccardi

Chapter 9 Chemical Kinetics in Air

Plasmas at Atmospheric Pressure 185

Claudia Riccardi and Ruggero Barni

Chapter 10 The Chemical Kinetics of

Shape Determination in Plants 203

David M. Holloway

Chapter 11 Plasma-Chemical Kinetics of Film

Deposition in Argon-Methane and Argon-Acetylene

Mixtures Under Atmospheric Pressure Conditions 227

Ramasamy Pothiraja, Nikita Bibinov and Peter Awakowicz

Part 4 Recent Developments 167

Chapter 12 Recent Developments on the

Mechanism and Kinetics of Esterification

Reaction Promoted by Various Catalysts 255

Zuoxiang Zeng, Li Cui, Weilan Xue, Jing Chen and Yu Che

Chapter 13 Progresses in Experimental Study of N2 Plasma

Diagnostics by Optical Emission Spectroscopy 283

Hiroshi Akatsuka

Chapter 14 Nanoscale Liquid is Second Liquid 309

Boris A. Mosienko

Part 5 Application of Chemical Kinetics 323

Chapter 15 Application of Catalysts to Metal Microreactor Systems 325

Pfeifer Peter

Preface

Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical

processes and mechanism of chemical reactions as well, effect of various variables,

including from re-arrangement of atoms, formation of intermediates, etc. Students,

researchers, research scholars, scientists, chemists and industry fraternity needs to

understand chemical kinetics so that industrial reactions can be controlled, and their

mechanisms understood. Chemical kinetics also provide an idea to make predictions

about important reactions such as those that occur between gases in the atmosphere. It

is a huge field that encompasses many aspects of physical chemistry.

The book is designed to help the reader, particularly students, researchers, research

scholars, scientists, chemists and industry fraternity of chemistry and allied fields;

understand the mechanics and reactions rates. The selection of topics addressed and

the examples, tables and graphs used to illustrate them are governed, to a large extent,

by the fact that this book is aimed primarily at chemistry and allied science and

engineering technologist.

The objective of this book is to give academia, research scientists, research scholars,

science and engineering students and industry professionals an overview of the

kinetics quantities such as rates, rate constants, enthalpies, entropies, and volume of

activation. This book also emphasizes how these factors are used in interpretation of

the mechanism of a reaction.

This book is based on the series of chapters written by different authors and divided

into 15 chapters, each one succinctly dealing with a specific chemical kinetics and

reaction mechanisms. The contents are widely encompassing as possible for chemical

kinetic research field.

The book critically compares the chemical kinetics and reaction mechanisms so that

the most attractive options for chemistry (physical, organic and inorganic) research

can be identified for academia, research scientists, research scholars, science and

engineering students and industry professionals.

Dr. Vivek Patel, SKO

Centre for Knowledge Management of Nanoscience & Technology (CKMNT),

Vijayapuri Colony, Tarnaka, Secunderabad,

India

Part 1

Introduction to Chemical Kinetics

1

Chemical Kinetics, an Historical Introduction

Stefano Zambelli

University of Padova,

Italy

1. Introduction

This Chapter would provide a methodological analysis of the historical developments of

chemical kinetics from the beginnings to the achievements of Transition state theory and

Kramers-Christiansen approach. Chemical kinetics is often treated as a side issue of the

most important disciplines of chemical science. Students in most of the cases gain

knowledge of Kinetics as part of Physical Chemistry introductory courses and find it again

applied in many other contests.

Despite that, it would necessitate a fundamental and main teaching course as we will see in

the course of this chapter. This didactical and academic approach could have many reasons.

A general one may be the philosophical and psychological disposition to put our attention

more on objects rather than concepts, matter over processes.

In Science History there are many examples of this tendency: the transmission of heat and

electromagnetic waves are good examples. Phlogiston and Luminiferous Aether represents

a materialization of processes that processes themselves do not need to be studied, however

our mind need this primitive objectivization to grasp the concept in a simpler way.

This represents a fundamental issue of scientific method: to do Science we need to go

beyond banality and perception. The development of Chemical Kinetics is deeply involved

in the counterfactual approach that brought from Alchemy to Chemistry as for Physics form

Aristotelic Natural Philosophy to Galilean Science.

2. Origins of chemical kinetics: The declinations of affinity

The chemical affinity principle, developed during the seventeenth century, derives from the

alchemical concept of chemical wedding: similar substances will interact so we can

categorize them. The real innovation at the end of 17th and during the 18th centuries was the

application of that concept not only as a taxonomic principle but also for the comprehension

of chemical reactivity.

The interaction of bodies is simpler when there is a similitude between them, this is the base

idea of Chemical Affinities and come from ancient and medieval alchemy and naturalism

doctrine. At the end of 17th century this intuitive principle become a theory, although

qualitative, that justify and classify interactions between different substances.

In the same period also the observation of time become important for the determination of

the nature of chemical reactions. Time of decurrence was clearly contemplated for the

4 Chemical Kinetics

preparation of substances with long reactions but it was seen as an ordinary technical factor.

The Opera of Alchemy, for example in the transmutations of metals, was considered as a

means for the acceleration of the millenary gestation of precious metals in the bowels of

Earth Mother. The underestimate of real times in the alchemists conceptions resulted so

natural in an activity that already theoretically reduced geological times. The paradox was

that time, a fundamental principle for alchemic theory, resulted of little importance in the

alchemical praxis.

Probably the first scholar that introduced a dynamical vision of the chemical phenomena

was Wilhelm Homberg (1652-1715). Homberg, a German scholar, worked in Magdeburg

with Von Guericke, in Italy and later in England with Boyle. He introduced the first

principles of quantitative measurement for chemical action: the strength of an acid towards

a series of alkali depends on the time of neutralization of the various alkali.

2.1 Tabulae affinitatum

The lists of strength of alkali and the concept of chemical affinity brought Etienne Francois

Geoffroy (1672-1731), a French scholar initiated to chemistry by Homberg himself, to the

compilation of the Tables of Affinity, (or Tables of Rapports) that could be considered as the

first ancestor of the periodic table. The first one was done by Geffroy (Geoffroy, 1718). You

can see the Encyclopédie version in the following figure.

Fig. 1. Recueil de Planches, sur les Sciences, les Arts Libéraux, et les Arts Méchaniques, 1772

Chemical Kinetics, an Historical Introduction 5

In the first row you can see the primary substances then going down along the columns the

similar substances in order of affinity with the first one.

The development of Affinity tables was inevitably considered in the light of the main

scientific discussion of the 18th century: the debate between plenistic Cartesian vision and

the Newtonian distance action principle. Important chemisters of this period took parts in

that debate: Boerhaave and later Buffon among Newtonian side identified affinities as a

special form of gravitational attraction, Stahl on the other side negated the distance action

invoking the medium of Phlogiston.

Guyton de Morveau (1737-1816), a French scholar, sustained initially phlogiston theory, but

leaved it after in favor of a distance action between the different elementary particles of

substances bringing the chemical affinities to a microscopic level, a similar position was

taken by Berthollet and Lavoisier. De Morveau classified the kind of affinities: simple or by

aggregation, composed, decomposed, double, reciprocal, intermediate, dispositional. He

listed also the laws of affinity:

- Molecules have to be in fluid state to respond to affinities influence.

- Affinities acts between the elementary particles of bodies.

- Affinities between two different substances may be different from that between their

composites.

- Affinity of substances acts only if it is bigger than the aggregation affinity of

themselves.

- Two or more bodies united by affinity form a new body with different properties from

precursors.

- Affinities action and velocity depends on temperature.

Basilar principles of Chemical Kinetics and Chemistry are going to take form. Of particular

importance the last law: temperature and so ambient conditions have influence on chemical

reactivity.

The position of Torben Olof Bergman (1735-1784), a Swedish scholar, about the influence of

temperature is particularly interesting. He assumed the affinity constant at constant

temperature and suggested to compile different affinity tables depending on conditions: the

affinities of dry phase is different from that in liquid phase.

Bergman closed elegantly the debate on the nature of the affinities assuming a very wise

position: it is not useful debating about the last nature of interacting forces between

chemical particles because it will remain unknown until quantitative experiments will be

done on affinities. Bergman so is the first scholar that made some hypothesis about a

measure of the affinities, but their mathematical expressions and measures will be a duty for

future researchers. Bergman compiled also affinity diagrams in his major opera, the

Opuscula. They are an interesting representation of chemical reactions done with alchemical

symbols: the ancestors of stoichiometric equations (although the very first one appeared

even in 1615, but not systematically, in the famous Tyrocinium Chymicum, the first

Textbook of Chemistry written by Jean Beguin). You can see an example in the figure 2. The

diagram represents the reactions of sulfuric and hydrochloric acid with calcium carbonate

and potassium hydroxide (Vitriolic and Marine for acids, Pure calcareous earth and Pure

fixed vegetable alkali for the basis).