Rate Constant Calculation for Thermal Reactions

Methods and Applications

Herbert DaCosta, Maohong Fan, Herbert DaCosta, Maohong Fan

• Publisher: Wiley
• Year: 2011
• Print ISBN: 9780470582305
• eBook ISBN: 9781118166116
• Edition: 1
• Topic: Biological Sciences
• Subtopic: Biochemistry
• Index: Biological Sciences

Providing an overview of the latest computational approaches to estimate rate constants for thermal reactions, this book addresses the theories behind various first-principle and approximation methods that have emerged in the last twenty years with validation examples. It presents in-depth applications of those theories to a wide range of basic and applied research areas. When doing modeling and simulation of chemical reactions (as in many other cases), one often has to compromise between higher-accuracy/higher-precision approaches (which are usually time-consuming) and approximate/lower-precision approaches (which often has the advantage of speed in providing results). This book covers both approaches. It is augmented by a wide-range of applications of the above methods to fuel combustion, unimolecular and bimolecular reactions, isomerization, polymerization, and to emission control of nitrogen oxides. An excellent resource for academics and industry members in physical chemistry, chemical engineering, and related fields.

Part I

Methods

Chapter 1

Overview of Thermochemistry and Its Application to Reaction Kinetics

Elke Goos

Institute of Combustion Technology, German Aerospace Center (DLR), Stuttgart, Germany

Alexander Burcat

Faculty of Aerospace Engineering, Technion - Israel Institute of Technology, Haifa, Israel

1.1 History of Thermochemistry

Thermochemistry deals with energy and enthalpy changes accompanying chemical reactions and phase transformations and gives a first estimate of whether a given reaction can occur. To our knowledge, the field of thermochemistry started with the experiments done by Malhard and Le Chatelier 1 with gunpowder and explosives. The first of their two papers of 1883 starts with the sentence: “All combustion is accompanied by the release of heat that increases the temperature of the burned bodies.” In 1897, Berthelot [2], who also experimented with explosives, published his two-volume monograph Thermochimie in which he summed up 40 years of calorimetric studies.

The first textbook, to our knowledge, that clearly explained the principles of thermochemical properties was authored by Lewis and Randall [3] in 1923.

Thermochemical data, actually heats of formation, were gathered, evaluated, and published for the first time in the seven-volume book International Critical Tables of Numerical Data, Physics, Chemistry and Technology [4] during 1926–1930 (and the additional index in 1933).

In 1932, the American Chemical Society (ACS) monograph No. 60 The Free Energy of Some Organic Compounds [5] appeared.

In 1936 was published The Thermochemistry of the Chemical Substances [6] where the authors Bichowsky and Rossini attempted to standardize the available data and published them at a common temperature of 18°C (291K) and pressure of 1 atm.

In 1940, Josef Mayer and Nobel Prize winner Maria Mayer published their monograph Statistical Mechanics [7], in which the method of calculating thermochemical properties from spectroscopic data was explained in detail.

In 1947, Rossini et al. published their Selected Values of Properties of Hydrocarbons [8], which was followed by the famous NBS Circular 500 (1952) [9] that focuses on the thermochemistry of inorganic and organic species and lists not only the enthalpies of formation but also heat capacities (C_p), enthalpies (H_T − H₀), entropies (S), and equilibrium constants (K_c) as a function of temperature. Within the data, thermodynamic relations (e.g., through Hess's Law) between the same property of different substances or between different properties of the same substance were satisfied. During the 1950s, the loose leaf compendium of the Thermodynamic Research Center (TRC) [10] at A&M University in Texas appeared as a continuation of API Project 44. In this compendium, thermochemistry as a function of temperature is only a small part of their data that also include melting and boiling points, vapor pressures, IR spectra, and so on. Although their values are technically reliable, a very serious drawback is the lack of documentation of the data sources and the calculation methods.

In 1960, the first loose leaf edition of the Joint Army–Navy–Air Force (JANAF) thermodynamic tables appeared, but was restricted solely to U.S. government agencies. It is devoted to chemical species involving many elements; however, it contains only a very limited number of organic species. The publication, which became very famous when published as bound second edition in 1971 11, set the standard temperature reference at 298.15K and published the enthalpy increments (also known as integrated heat capacities) as (H_T − H₂₉₈) instead of (H_T − H₀). This edition of the JANAF tables, with Stull as the main editor, for the first time described in detail methods of calculating thermochemical properties mainly based on the monograph of Mayer and Mayer [7]. It also set the upper temperature range limit of the tables up to 6000K in order to assist the needs and requests of the space research institutions and industry. Further editions published afterward 11 kept the many errors and wrong calculation results instead of correcting or improving them to include better available values.

Published in 1960, the report “Thermodynamic Data for Combustion Products” [12] by Gordon focused on high-performance solid rocket propellants.

In 1961, Duff and Bauer wrote a Los Alamos report [13], which was summarized in 1962 in the Journal of Chemical Physics [14], in which for the first time thermochemical properties of organic molecules, that are, enthalpies and free energies, were given as polynomials.

In 1963, McBride et al. published the “Thermodynamic Properties to 6000K for 210 Substances Involving the First 18 Elements,” NASA Report SP-3001 [15]. This publication revealed for the first time to the public world the methods of calculating thermochemical data for monoatomic, diatomic, and polyatomic species. At that time, JANAF tables were accessible to only a very restricted number of people. The NASA publication lists, also for the first time, the thermochemical properties not only in table format but also as seven-coefficient polynomials. The NASA program to calculate thermochemical properties and these seven-term polynomials was published by McBride ...

Table of contents

• Cover
• Title Page
• Copyright
• Preface
• Contributors
• Part I: Methods
• Part II: Minireviews and Applications
• Index