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Chemistry - Physical Chemistry | Thermal Decomposition of Solids and Melts - New Thermochemical Approach to the Mechanism, Kinetics

Thermal Decomposition of Solids and Melts

New Thermochemical Approach to the Mechanism, Kinetics and Methodology

L'vov, Boris V.

Brown, Michael E. (Ed.)

2007, XIX, 247 p.

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  • Collects results together in a unified scheme
  • Highlights recent successes and new perspectives
  • Provides in-depth analysis of several different classes of compounds

Thermal Decomposition of Solids and Melts describes the results of investigations into the mechanisms and kinetics involved in the thermal decomposition of solid and liquid substances via thermochemical analysis (TA). The main features of these thermal decomposition reactions are explained within and the observed anomalies 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 substances have been interpreted. These include different classes of compounds:

  • crystalline hydrates
  • oxides
  • hydroxides
  • nitrides
  • azides
  • nitrates
  • sulfates
  • carbonates
  • oxalates

This book is intended for advanced undergraduates, researchers, and technologists working in the fields of engineering, metallurgy, chemistry, and material science.

Content Level » Research

Keywords » Congruent Dissociative Vaporisation - Decomposition Mechanism and Kinetics - Enthalpy - Langmuir Vaporisation Equations - Thermochemical Approach - Third-law Method - crystal - liquid - modeling

Related subjects » Analytical Chemistry - Characterization & Evaluation of Materials - Materials - Nanotechnology - Physical Chemistry - Special types of Materials

Table of contents / Preface 

Preface.-Abbreviations.-Introduction.-Part I. Thermal Decomposition: Primary Concepts: Mechanism: Congruent Dissociative Vaporization.- Direct Observation of Primary Products of Decomposition by Mass Spectrometric Methods.- Induction, Acceleration and Process Localization.- Nucleus Shape and Position.-Peculiarities of Structure and Composition of Solid Product.-Thermal Stability of Complex Gaseous Molecules.- Kinetics: The Arrhenius Equation.- The Hertz–Langmuir Equation and Langmuir Diffusion Equations.- Modification of the Hertz–Langmuir Equation as Applied to Decomposition Reactions.- Equilibrium Pressure of Products in the Equimolar and Isobaric Modes.- Equations for Calculation of the Absolute Rates of Decomposition.- Interpretation of the Arrhenius Parameters by the Use of the Langmuir Evaporation Equations.- Methodology: The Arrhenius-plots Method.- The Second-law Method.-The Third-law Method.- Approximate Evaluation of the Molar Enthalpies.- Reproducibility of Measurements.- Accuracy.- Measurement Time.- Part II. Interpretation and Quantitative Analysis of the Effects, Phenomena and Regularities Accompanying the Decomposition: Decomposition Conditions and the Molar Enthalpy: Ratio of Initial Decomposition Temperature to the Molar Enthalpy.- Thermal Desorption and Criteria for its Identification.- Impact of the Decomposition Mode and Reaction Stoichiometry on the Molar Enthalpy.- Decomposition of Carbonates in the Presence of CO2.- Decomposition of Crystalline Hydrates in the Presence of H2O.- The Self-cooling Effect: The Model of Temperature Calculation.- The Temperature Distribution in Powder Reactants.- Corrections to the Kinetic Parameters.- Experimental Evaluation of Self-cooling.- The Topley–Smith Effect: Experimental Observations.- Modeling of the Topley–Smith Effect for Li2SO4 .H2O.- Modeling of the Topley–Smith Effect for CaCO3.- Impact of Vapour Condensation on the Enthalpy Change: The Contribution of the Condensation Energy to the Enthalpy Change.- Increase of the Enthalpy Change with Temperature.- Reactant Melting and the Decomposition Enthalpy.- Thermochemical Analysis of the Composition of the Primary Decomposition Products.- Effect of the Crystalline Structure of a Substance on the Composition of the Primary Decomposition Products: Oxides.- Nitrides.- Phosphorous, Arsenic and Antimony.- Evaporation Coefficients.- The Kinetic Compensation Effect.- Conclusions.- Part III. Thermal Decomposition of Individual Substances: Instruments for Thermogravimetric Measurements.- Measurement Conditions and Procedures for Thermogravimetric Studies: Evaluation of the Absolute Rate of Decomposition.- Choice of the Decomposition Temperature.- Choice of the Residual Pressure of Air in the Reactor (equimolar mode).- Decomposition in the Presence of the Gaseous Product (isobaric mode).- Decomposition of Hydrates in Air and Carbonates in Argon and Air.- Evaporation and Decomposition of Some Substances: Non-metals (phosphorus).- Metalloids (arsenic, antimony).- Oxides.- Higher Oxides for IV Group of Metals.- Sulfides, Selenides and Tellurides.- Nitrides.- Azides.- Hydroxides.- Clays.- Hydrates.- Nitrates.- Sulfates.- Carbonates.- Oxalates.- Final conclusions.- Appendices: Fundamental Physical Constants.- Atomic Masses of Elements.- Coefficients of Mutual Diffusion of Gases.- Spectral and Integrated Emittance of Some Metals and Oxides.- Composition of Dry Atmospheric Air.- Saturation Pressure of Water Vapour.- Subject Index.

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