Introduction to Chemical Kinetics [Other digital carrier]

Preface. List of Symbols.
1. Introduction.
2. Experimental Procedures.
2.1 Detection, Identification and Estimation of Concentration of Species
Present. 2.1.1 Chromatographic techniques: liquid-liquid and gas-liquid
chromatography. 2.1.2 Mass spectrometry (MS). 2.1.3 Spectroscopic techniques.
2.1.4 Lasers. 2.1.5 Fluorescence. 2.1.6 Spin resonance methods: nuclear
magnetic resonance (NMR). 2.1.7 Spin resonance methods: electron spin
resonance (ESR). 2.1.8 Photoelectron spectroscopy and X-ray photoelectron
spectroscopy. 2.2 Measuring the Rate of a Reaction. 2.2.1 Classification of
reaction rates. 2.2.2 Factors affecting the rate of reaction. 2.2.3 Common
experimental features for all reactions. 2.2.4 Methods of initiation. 2.3
Conventional Methods of Following a Reaction. 2.3.1 Chemical methods. 2.3.2
Physical methods. 2.4 Fast Reactions. 2.4.1 Continuous flow. 2.4.2 Stopped
flow. 2.4.3 Accelerated flow. 2.4.4 Some features of flow methods. 2.5
Relaxation Methods. 2.5.1 Large perturbations. 2.5.2 Flash photolysis. 2.5.3
Laser photolysis. 2.5.4 Pulsed radiolysis. 2.5.5 Shock tubes. 2.5.6 Small
perturbations: temperature, pressure and electric field jumps. 2.6 Periodic
Relaxation Techniques: Ultrasonics. 2.7 Line Broadening in NMR and ESR
Spectra. Further Reading. Further Problems.
3. The Kinetic Analysis of
Experimental Data. 3.1 The Experimental Data. 3.2 Dependence of Rate on
Concentration. 3.3 Meaning of the Rate Expression. 3.4 Units of the Rate
Constant, k. 3.5 The Significance of the Rate Constant as Opposed to the
Rate. 3.6 Determining the Order and Rate Constant from Experimental Data. 3.7
Systematic Ways of Finding the Order and Rate Constant from
Rate/Concentration Data. 3.7.1 A straightforward graphical method. 3.7.2
log/log Graphical procedures. 3.7.3 A systematic numerical procedure. 3.8
Drawbacks of the Rate/Concentration Methods of Analysis. 3.9 Integrated Rate
Expressions. 3.9.1 Half-lives. 3.10 First Order Reactions. 3.10.1 The
half-life for a first order reaction. 3.10.2 An extra point about first order
reactions. 3.11 Second Order Reactions. 3.11.1 The half-life for a second
order reaction. 3.11.2 An extra point about second order reactions. 3.12 Zero
Order Reaction. 3.12.1 The half-life for a zero order reaction. 3.13
Integrated Rate Expressions for Other Orders. 3.14 Main Features of
Integrated Rate Equations. 3.15 Pseudo-order Reactions. 3.15.1 Application of
pseudo-order techniques to rate/concentration data. 3.16 Determination of the
Product Concentration at Various Times. 3.17 Expressing the Rate in Terms of
Reactants or Products for Non-simple Stoichiometry. 3.18 The Kinetic Analysis
for Complex Reactions. 3.18.1 Relatively simple reactions that are
mathematically complex. 3.18.2 Analysis of the simple scheme A-! 3.18.3 Two
conceivable situations. 3.19 The Steady State Assumption. 3.19.1 Using this
assumption. 3.20 General Treatment for Solving Steady States. 3.21 Reversible
Reactions. 3.21.1 Extension to other equilibria. 3.22 Pre-equilibria. 3.23
Dependence of Rate on Temperature. Further Reading. Further Problems.
4.
Theories of Chemical Reactions. 4.1 Collision Theory. 4.1.1 Definition of a
collision in simple collision theory. 4.1.2 Formulation of the total
collision rate. 4.1.3 The p factor. 4.1.4 Reaction between like molecules.
4.2 Modified Collision Theory. 4.2.1 A new definition of a collision. 4.2.2
Reactive collisions. 4.2.3 Contour diagrams for scattering of products of a
reaction. 4.2.4 Forward scattering: the stripping or grazing mechanism. 4.2.5
Backward scattering: the rebound mechanism. 4.2.6 Scattering diagrams for
long-lived complexes. 4.3 Transition State Theory. 4.3.1 Transition state
theory, configuration and potential energy. 4.3.2 Properties of the potential
energy surface relevant to transition state theory. 4.3.3 An outline of
arguments involved in the derivation of the rate equation. 4.3.4 Use of the
statistical mechanical form of transition state theory. 4.3.5 Comparisons
with collision theory and experimental data. 4.4 Thermodynamic Formulations
of Transition State Theory. 4.4.1 Determination of thermodynamic functions
for activation. 4.4.2 Comparison of collision theory, the partition function
form and the thermodynamic form of transition state theory. 4.4.3 Typical
approximate values of contributions entering the sign and magnitude of
-S61/4-. 4.5 Unimolecular Theory. 4.5.1 Manipulation of experimental results.
4.5.2 Physical significance of the constancy or otherwise of k1, k-1 and k2.
4.5.3 Physical significance of the critical energy in unimolecular reactions.
4.5.4 Physical significance of the rate constants k1, k-1 and k2. 4.5.5 The
simple model: that of Lindemann. 4.5.6 Quantifying the simple model. 4.5.7 A
more complex model: that of Hinshelwood. 4.5.8 Quantifying Hinshelwood's
theory. 4.5.9 Critique of Hinshelwood's theory. 4.5.10 An even more complex
model: that of Kassel. 4.5.11 Critique of the Kassel theory. 4.5.12 Energy
transfer in the activation step. 4.6 The Slater Theory. Further Reading.
Further Problems.
5. Potential Energy Surfaces. 5.1 The Symmetrical Potential
Energy Barrier. 5.2 The Early Barrier. 5.3 The Late Barrier. 5.4 Types of
Elementary Reaction Studied. 5.5 General Features of Early Potential Energy
Barriers for Exothermic Reactions. 5.6 General Features of Late Potential
Energy Surfaces for Exothermic Reactions. 5.6.1 General features of late
potential energy surfaces where the attacking atom is light. 5.6.2 General
features of late potential energy surfaces for exothermic reactions where the
attacking atom is heavy. 5.7 Endothermic Reactions. 5.8 Reactions with a
Collision Complex and a Potential Energy Well Further Reading. Further
Problems.
6. Complex Reactions in the Gas Phase. 6.1 Elementary and Complex
Reactions. 6.2 Intermediates in Complex Reactions. 6.3 Experimental Data. 6.4
Mechanistic Analysis of Complex Non-chain Reactions. 6.5 Kinetic Analysis of
a Postulated Mechanism: Use of the Steady State Treatment. 6.5.1 A further
example where disentangling of the kinetic data is necessary. 6.6 Kinetically
Equivalent Mechanisms. 6.7 A Comparison of Steady State Procedures and
Equilibrium Conditions in the Reversible Reaction. 6.8 The Use of
Photochemistry in Disentangling Complex Mechanisms. 6.8.1 Kinetic features of
photochemistry. 6.8.2 The reaction of H2 with I2. 6.9 Chain Reactions. 6.9.1
Characteristic experimental features of chain reactions. 6.9.2 Identification
of a chain reaction. 6.9.3 Deduction of a mechanism from experimental data.
6.9.4 The final stage: the steady state analysis. 6.10 Inorganic Chain
Mechanisms. 6.10.1 The H2/Br2 reaction. 6.10.2 The steady state treatment for
the H2/Br2 reaction. 6.10.3 Reaction without inhibition. 6.10.4 Determination
of the individual rate constants. 6.11 Steady State Treatments and
Possibility of Determination of All the Rate Constants. 6.11.1 Important
points to note. 6.12 Stylized Mechanisms: A Typical Rice-Herzfeld Mechanism.
6.12.1 Dominant termination steps. 6.12.2 Relative rate constants for
termination steps. 6.12.3 Relative rates of the termination steps. 6.12.4
Necessity for third bodies in termination. 6.12.5 The steady state treatment
for chain reactions, illustrating the use of the long chain approximation.
6.12.6 Further problems on steady states and the Rice-Herzfeld mechanism.
6.13 Special Features of the Termination Reactions: Termination at the
Surface. 6.13.1 A general mechanism based on the Rice-Herzfeld mechanism used
previously. 6.14 Explosions. 6.14.1 Autocatalysis and autocatalytic
explosions. 6.14.2 Thermal explosions. 6.14.3 Branched chain explosions.
6.14.4 A highly schematic and simplified mechanism for a branched chain
reaction. 6.14.5 Kinetic criteria for non-explosive and explosive reaction.
6.14.6 A typical branched chain reaction showing explosion limits. 6.14.7 The
dependence of rate on pressure and temperature. 6.15 Degenerate Branching or
Cool Flames. 6.15.1 A schematic mechanism for hydrocarbon combustion. 6.15.2
Chemical interpretation of 'cool' flame behaviour. Further Reading. Further
Problems.
7. Reactions in Solution. 7.1 The Solvent and its Effect on
Reactions in Solution. 7.2 Collision Theory for Reactions in Solution. 7.2.1
The concepts of ideality and non-ideality. 7.3 Transition State Theory for
Reactions in Solution. 7.3.1 Effect of non-ideality: the primary salt effect.
7.3.2 Dependence of -S61/4- and -H61/4- on ionic strength. 7.3.3 The effect
of the solvent. 7.3.4 Extension to include the effect of non-ideality. 7.3.5
Deviations from predicted behaviour. 7.4 -S61/4- and Pre-exponential A
Factors. 7.4.1 A typical problem in graphical analysis. 7.4.2 Effect of the
molecularity of the step for which -S61/4- is found. 7.4.3 Effect of
complexity of structure. 7.4.4 Effect of charges on reactions in solution.
7.4.5 Effect of charge and solvent on -S61/4- for ion-ion reactions. 7.4.6
Effect of charge and solvent on -S61/4- for ion-molecule reactions. 7.4.7
Effect of charge and solvent on -S61/4- for molecule-molecule reactions.
7.4.8 Effects of changes in solvent on -S61/4-. 7.4.9 Changes in solvation
pattern on activation, and the effect on A factors for reactions involving
charges and charge-separated species in solution. 7.4.10 Reactions between
ions in solution. 7.4.11 Reaction between an ion and a molecule. 7.4.12
Reactions between uncharged polar molecules. 7.5 -H61/4- Values. 7.5.1 Effect
of the molecularity of the step for which the -H61/4- value is found. 7.5.2
Effect of complexity of structure. 7.5.3 Effect of charge and solvent on
-H61/4- for ion-ion and ion-molecule reactions. 7.5.4 Effect of the solvent
on -H61/4- for ion-ion and ion-molecule reactions. 7.5.5 Changes in solvation
pattern on activation and the effect on -H61/4-. 7.6 Change in Volume on
Activation, -V61/4-. 7.6.1 Effect of the molecularity of the step for which
-V61/4- is found. 7.6.2 Effect of complexity of structure. 7.6.3 Effect of
charge on -V61/4- for reactions between ions. 7.6.4 Reactions between an ion
and an uncharged molecule. 7.6.5 Effect of solvent on -V61/4-. 7.6.6 Effect
of change of solvation pattern on activation and its effect on -V61/4-. 7.7
Terms Contributing to Activation Parameters. 7.7.1 -S61/4-. 7.7.2 -V61/4-.
7.7.3 -H61/4-. Further Reading. Further Problems.
8. Examples of Reactions in
Solution. 8.1 Reactions Where More than One Reaction Contributes to the Rate
of Removal of Reactant. 8.1.1 A simple case. 8.1.2 A slightly more complex
reaction where reaction occurs by two concurrent routes, and where both
reactants are in equilibrium with each other. 8.1.3 Further disentangling of
equilibria and rates, and the possibility of kinetically equivalent
mechanisms. 8.1.4 Distinction between acid and base hydrolyses of esters. 8.2
More Complex Kinetic Situations Involving Reactants in Equilibrium with Each
Other and Undergoing Reaction. 8.2.1 A further look at the base hydrolysis of
glycine ethyl ester as an illustration of possible problems. 8.2.2
Decarboxylations of --keto-monocarboxylic acids. 8.2.3 The decarboxylation of
--keto-dicarboxylic acids. 8.3 Metal Ion Catalysis. 8.4 Other Common
Mechanisms. 8.4.1 The simplest mechanism. 8.4.2 Kinetic analysis of the
simplest mechanism. 8.4.3 A slightly more complex scheme. 8.4.4 Standard
procedure for determining the expression for kobs for the given mechanism.
8.5 Steady States in Solution Reactions. 8.5.1 Types of reaction for which a
steady state treatment could be relevant. 8.5.2 A more detailed analysis of
Worked Problem 6.5. 8.6 Enzyme Kinetics. Further Reading. Further Problems.
Answers to Problems. List of Specific Reactions. Index.