Thermal Decomposition of Solids and Melts: New Thermochemical Approach to the Mechanism, Kinetics and Methodology

ISBN-13: 9789048174218 / Angielski / Miękka / 2010 / 247 str.

Boris V. L'Vov;Michael E. Brown

Opis

The appearance of this English edition of my book, ?rst published in Russian in mid-2006, is related to the help and support of two prominent scientists: Professor Michael Brown (Rhodes University Grahamstown, South Africa) and Dr. Judit Simon (Budapest University of Technology and Economics, Hungary). The story is as follows. In the winter of 2006, in the process of exchange of views by email with Michael on some problems of decomposition kinetics, I asked him about the possibility of publishing my book in English. He s- gestedthatIshouldcontactJudit, theSeriesEditorof"HotTopicsinThermal Analysis and Calorimetry." My application was kindly accepted, considered, and approved. As a result, Judit strongly recommended this book to Springer for publication, and Michael kindly agreed to help me with linguistic impro- ments of my hurriedly translated book. In the process of editing, he made some critical comments and questions, which stimulated me to improve and clarify the text, but we did have to agree to put our di?erences of scienti?c opinions aside so as not to delay the process. Without this invaluable help, this book would not be as "readable" as I hope it is now. The author uses this opportunity to express his sincere thanks to Michael and Judit for their signi?cant help and support. Although only about a year has gone after the preparation of the original edition of the book (in Russian), this English version of the manuscript has undergone considerable revision. These changes refer to Sections2. 2, 2.

Recenzje

Aus den Rezensionen:

"Das Buch ist eine Übersetzung aus dem Russischen mit Zusätzen und Verbesserungen. ... Es beschäftigt sich mit der thermischen Zersetzung von Festkörpern und Schmelzen. ... Ulgolkov beschreibt die instrumentellen Parameter thermodynamisch und erläutert sie an Beispielen. Das Buch schließt mit einem Index, Massekonstanten und Gasdruckdaten. Das Fachbuch wendet sich an Anwender der Thermischen Analysetechniken. Die thermodynamischen Effekte werden gut beschrieben ..." (Robert Fuchs, in: Mitteilungsblatt der GDCh -Gesellschaft Deutscher Chemiker-, 2008, Issue 4, S. 12)

Spis treści

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.

O autorze

Professor and Head of the Analytical Chemistry department at St. Petersburg State University, Russia.

Blurb

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.