Reaction Mechanisms in Sulphuric Acid and other Strong Acid Solutions - 1st Edition - ISBN: 9780124500501, 9780323154031

Reaction Mechanisms in Sulphuric Acid and other Strong Acid Solutions

1st Edition

Authors: M Liler
eBook ISBN: 9780323154031
Imprint: Academic Press
Published Date: 1st January 1971
Page Count: 364
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Reaction Mechanisms in Sulfuric Acid and other Strong Acid Solutions covers the reactivity in sulfuric acid and other strongly acid solutions. This book is composed of five chapters that emphasize the measure of acidity of sulfuric acid and other acid solutions. Chapters 1 and 2 discuss the physical, thermodynamic, spectroscopic properties, and acidity functions of sulfuric acid/water mixtures. Chapters 3 and 4 examine the protonation and more complex modes of ionization of compounds in these acidic media. Chapter 5 outlines first the possible mechanisms of reactions in acid solutions followed by a discussion of mechanistic criteria that have been developed in order to distinguish between kinetically indistinguishable alternatives. This chapter also presents some methods of kinetic investigation, which are specific to concentrated sulfuric acid solutions. Inorganic chemists and researchers, teachers, and students will find this book invaluable.

Table of Contents


General Introduction

Chapter 1 Properties of Sulphuric Acid/Water Mixtures as Solvents

1.1. Introduction

1.1.1. Concentration Units

1.1.2. Preparation and Analysis of Solutions

1.2. Physical Properties

1.2.1. Mechanical Properties

1.2.2. Electrical Properties

1.3. Thermodynamic Properties

1.3.1. Phase Changes

1.3.2. Thermochemical Quantities

1.4. Spectroscopic Properties

1.4.1. Rayleigh Scattering

1.4.2. Raman and Infrared Spectra

1.4.3. Ultraviolet Absorption Spectra

1.4.4. X-Ray Diffraction

1.4.5. Proton Magnetic Resonance Spectra

1.5. Isotopically Substituted Sulphuric Acids

1.5.1. Dideuterosulphuric Acid

1.5.2. 35S-Labeled Sulphuric Acid

Chapter 2 Acidity Functions

2.1. Introduction

2.2. Definitions

2.2.1. Acidity Functions for Simple Protonation

2.2.2. Acidity Function for Complex Ionizations

2.2.3. Acidity Function for Olefin Protonation

2.3. Evaluation of Acidity Functions

2.3.1. Indicator Measurements

2.3.2. Electrochemical Measurements

2.4. Various Acidity Function Scales

2.4.1. The HO or HO Acidity Function

2.4.2. The H''''0 Acidity Function

2.4.3. The HA Acidity Function

2.4.4. The HI Acidity Function

2.4.5. The H+ Acidity Function

2.4.6. The H- Acidity Function

2.4.7. The H'R and HR Acidity Function

2.5. Verification of the Activity Coefficient Postulate

2.5.1. Measurements of Activity Coefficients of Neutral Indicator Bases

2.5.2. Relative Activity Coefficients of Some Indicator Conjugate Acids

2.5.3. Relative Activity Coefficient Ratios

2.6. Physical Significance of Acidity Functions

2.6.1. A Chemical Hydration Treatment of Acidity Functions

2.6.2. The Acidity Function HO in the Vicinity of 100 per Cent Sulphuric Acid

Chapter 3 Protonation of Very Weak Bases

3.1. Introduction

3.2. Methods of Determination of Basicities in Sulphuric Acid Media

3.2.1. The Spectrophotometric Method

3.2.2 The N.M.R. Spectroscopic Method

3.2.3 The Raman Spectrometric Method

3.2.4 The Distribution or Extraction Method

3.2.5 The Cryoscopic Method

3.2.6 The Conductometric Method

3.2.7The Conductometric Titration Method

3.2.8 Correlation of Basicity Determinations in Pure Sulphuric Acid with HO

3.3 Basicities of Very Weak Bases

3.3.1. Introduction

3.3.2 Bases Involving NIII and PIII as the Basic Center

3.3.3 Bases Involving More Complex Groups Containing N,P As

3.3.4 Bases Involving O and S as the Basic Center

3.3.5 Hydrocarbon Bases

3.3.6 Inorganic Bases

Chapter 4 Complex Ionizations

4.1. Introduction

4.2. Methods of Study of Complex Ionizations

4.2.1. The Cryoscopic Method

4.2.2 The Conductometric Method

4.2.3. The Conductometric Titration Method

4.2.4. The Spectrophotometric Method

4.3. Survey of Complex Ionizations

4.3.1. Organic Solutes

4.3.2. Inorganic Solutes

4.3.3. Organometallic Solutes

Chapter 5 Reaction Mechanisms in Sulphuric Acid Solutions

5.1. Introduction

5.2. Mechanisms and Mechanistic Criteria in Strong Acid Solutions

5.2.1. Main Types of Reaction Mechanism in Strong Acid Solutions

5.2.2. Mechanistic Criteria

5.3. Methods of Kinetic Investigation

5.4. Mechanisms of Reactions in Sulphuric Acid Solutions

5.4.1. Hydrolyses

5.4.2. Hydration and Dehydration Reactions

5.4.3. Isomerizations and Rearrangements

5.4.4. Decarbonylations and Decarboxylations

5.4.5. Electrophilic Aromatic Substitutions by the Hydrogen Ion

5.4.6. Electrophilic Aromatic Substitutions by Other Electrophiles

5.4.7. Miscellaneous Reactions Involving Carbonium Ions


Author Index

Subject Index


No. of pages:
© Academic Press 1971
Academic Press
eBook ISBN:

About the Author

M Liler