Gas-Phase Thermal Reactions

by Come, Guy-Marie

• ISBN13: 9781402000492
• ISBN10: 1402000499
• Format: Hardcover
• Copyright: 2001-10-01
• Publisher: Kluwer Academic Pub

Summary

This book is dedicated to gas-phase thermal reactions which take place in engines, burners, and industrial reactors for the production of mechanical or thermal energy, for the incineration of pollutants, or for the manufacture of chemicals. It also studies their effect on the environment: fires, explosions, tropospheric pollution, the greenhouse effect, and holes in the ozone layer. After a short reminder of the concepts and laws of thermodynamics, and of chemical and physical kinetics, the book suggests a methodology for the kinetic modelling of these reactions: generation and reduction of reaction mechanisms, estimation of kinetic data of elementary reactions, estimation of the thermodynamic data and transport data of molecules and free radicals, and analysis and validation of mechanisms by comparison of calculated results with the experimental results obtained using laboratory reactors. The models thus generated carry all the information necessary to allow them to be incorporated into computer programs for the calculation of reactors or of the fluid dynamics of reacting gases. Tables of numerical data and a list of computer programs and URLs complete the book.

Table of Contents

Preface to the English Edition	xv
Preface to the French Edition	xvii
Introduction	1	(8)
Energy, Processes, Environment
Raw Material and Energy	9	(3)
Energy Production	12	(1)
Chemical Industries	13	(2)
Chemical Safety	15	(3)
Atmospheric Pollution	18	(17)
The atmosphere	18	(2)
Tropospheric pollution	20	(5)
Greenhouse effect	25	(2)
Stratospheric ozone	27	(5)
Conclusion : the concept of ecodevelopment	32	(1)
Further Reading	33	(2)
Fuels, Engines, Burners, Industrial Reactors
Engine and Heating Fuels	35	(12)
Natural gas or NG (Table 1a)	37	(1)
Liquefied petroleum gases or LPGs (Table 1b)	37	(1)
Petrols	37	(4)
Fuels for turbojets, turbines, missiles and rockets	41	(2)
Diesel fuels and diesel fuel oils (Table 1e)	43	(1)
Heavy fuels	43	(1)
Heating fuels	44	(1)
Other characteristics of fuels (Table 3)	44	(1)
Characteristics of combustion mixtures	44	(3)
Thermal Engines	47	(9)
Spark-ignition engines	47	(3)
Diesel engines	50	(3)
Turbojet engines and gas turbine engines	53	(2)
Launchers	55	(1)
Burners	56	(2)
Industrial Chemical Reactors	58	(7)
The steamcracker	58	(2)
Synthesis gas	60	(2)
Further Reading	62	(3)
Macroscopic Description of a Reacting Gas Mixture
The State of a Mixture of Gases	65	(3)
Ideal Gases	65	(3)
The REDLICH and KWONG equation	68	(1)
Conversion, Selectivity, Yield	68	(5)
Continuous chemical unit operation	68	(2)
Stoichiometric equation for the process	70	(1)
Conversion	70	(1)
Selectivity	71	(1)
Yield	72	(1)
Stoichiometric Analysis	73	(5)
Stoichiometric equations	74	(1)
The Brinkley criterion	74	(1)
The Jouguet criterion	75	(1)
The Jouguet - de Donder equations	76	(1)
The Jouguet - de Donder invariants	77	(1)
Reaction Schemes	78	(13)
Development of a reaction scheme	78	(3)
Rate of reaction	81	(2)
Empirical kinetic laws	83	(5)
Conclusion	88	(1)
Further Reading	89	(2)
Thermodynamic Laws
Thermodynamic Properties of Chemical Species	91	(7)
Standard reaction of formation	91	(1)
The standard enthalpy of formation	92	(1)
Standard entropy	93	(1)
Standard free enthalpy of formation	94	(1)
NASA polynomials	95	(1)
Chemical potential	96	(2)
Thermodynamic Properties of Reactions	98	(1)
Equilibria Laws	99	(5)
The law of mass action	99	(3)
The Le Chatelier laws	102	(2)
Calculation of Equilibria	104	(7)
Law of mass action	104	(3)
Minimization of the free enthalpy	107	(2)
Kinetic calculation	109	(1)
Further Reading	110	(1)
Computer Programs	110	(1)
Estimation of Thermodynamic Data
Benson's Method	111	(6)
The additivity of group properties	112	(1)
Corrections	113	(1)
Examples	114	(3)
Statistical Mechanics	117	(9)
Degrees of freedom	117	(1)
Fundamental vibrations	118	(3)
Vibrational analysis	121	(1)
Calculation of the entropy and of the heat capacity of a molecule	122	(4)
Thermodynamic Data for Free Radicals	126	(6)
Standard enthalpy of formation	127	(1)
Entropy and heat capacity	127	(5)
Extrapolation to High Temperature	132	(2)
Calculation of Cop∞	132	(2)
Extrapolation formula	134	(1)
Chetah Safety Criteria	134	(5)
Further Reading	138	(1)
Computer Programs	138	(1)
Elementary Reactions
Generic Elementary Reactions	139	(4)
Initiation and branching	139	(1)
Propagations	140	(2)
Terminations	142	(1)
Molecular reactions	143	(1)
Kinetic Laws	143	(10)
Influence of concentrations	143	(3)
The Arrhenius-Kooij law	146	(1)
Examples	147	(2)
Principle of detailed balancing	149	(2)
Further Reading	151	(2)
Estimation of Kinetic Parameters
Collision Theory	153	(2)
Benson's Method	155	(4)
Transition-state theory	156	(1)
Free radical isomerization	157	(2)
Structure-Reactivity Correlations	159	(4)
Initiations	159	(1)
Unimolecular decompositions of free radicals	160	(1)
Reactions of free radicals with molecular oxygen	161	(1)
Metatheses	161	(1)
Further Reading	162	(1)
Computer Programs	162	(1)
Kinetic Morphology
Quasi-Stationary-State Approximation	163	(3)
Molecular Reactions	166	(2)
Non-Chain Reactions	168	(3)
The pyrolysis of tertiary dibutyl peroxide	168	(1)
The thermal decomposition of ozone	169	(2)
Straight Chain Reactions	171	(11)
The pyrolysis of neopentane: experimental facts	171	(1)
Primary mechanism for the pyrolysis of neopentane	172	(3)
Mechanism of inhibition by isobutene	175	(2)
Kinetic rules β μ Y	177	(5)
Branched Chain Reactions	182	(6)
Explosion limits of the H2-O2 system in a batch reactor	183	(1)
Interpretation of the limits	184	(4)
Chain Reactions With Degenerate Branching	188	(8)
The main experimental facts	188	(5)
Globalized mechanisms for the oxidation of alkanes	193	(3)
Thermal Explosions	196	(7)
Further Reading	198	(3)
Generation of Reaction Mechanisms
Introduction	201	(2)
General Description of the Exgas System	203	(2)
The C0-C1-C2 Basic Set of Reactions	205	(2)
The Generation of Detailed Primary Mechanisms	207	(3)
Algorithm for the generation of an exhaustive primary mechanism	207	(3)
A priori simplification of the primary mechanism	210	(1)
The Generation of Secondary Mechanisms	210	(5)
Lumping of the species	211	(1)
Lumping of the secondary reactions	212	(2)
Estimation of the kinetic parameters of the lumped secondary mechanism	214	(1)
Lumping of the Detailed Primary Mechanisms	215	(10)
Lumped primary mechanism	215	(1)
Estimation of the fractional stoichiometric coefficients and of the kinetic parameters of the lumped primary mechanism	216	(6)
Further Reading	222	(1)
Computer Programs	223	(2)
Molecular Transport Laws
Molecular Transport Phenomena	225	(1)
Molecular Transport of Matter	226	(2)
Fick's law	226	(1)
Soret effect	227	(1)
Barodiffusion	228	(1)
General law	228	(1)
Molecular Transport of Heat	228	(2)
Fourier's law	228	(1)
Diffusional transport	229	(1)
Dufour effect	229	(1)
General law	229	(1)
Molecular Transport of Momentum	230	(1)
Unidimensional case	230	(1)
Three-dimensional case	230	(1)
Analogies Between the Phenomena of Molecular Transport	231	(4)
Further Reading	233	(2)
Estimation of Molecular Transport Data
Diffusion Coefficient	235	(3)
Binary diffusion coefficient	235	(2)
Diffusion coefficient in a mixture	237	(1)
Viscosity	238	(1)
Dynamic viscosity of a pure gas	238	(1)
Dynamic viscosity of a mixture of gases	239	(1)
Thermal Conductivity	239	(3)
Thermal conductivity of a monoatomic gas	239	(1)
Thermal conductivity of a polyatomic gas	240	(2)
Thermal conductivity of a mixture of gases	242	(1)
Lennard-Jones Parameters	242	(2)
Limits of Validity	244	(1)
Further Reading	244	(1)
Computer Programs	244	(1)
Laboratory Reactors
General Characteristics	245	(2)
Batch Reactor	247	(7)
Experimental aspects	247	(4)
Balance equations	251	(3)
Stirred Flow Reactor	254	(6)
Experimental aspects	254	(4)
Balance equations	258	(2)
Plug-Flow Reactor	260	(5)
Experimental aspects	261	(1)
Balance equations	261	(4)
Rapid Compression Machine	265	(3)
Experimental aspects	265	(2)
Balance equations	267	(1)
Flat-Flame Burner	268	(3)
Experimental aspects	268	(2)
Balance equations	270	(1)
Shock Tube	271	(14)
Experimental aspects	271	(3)
Rankine-Hugoniot equations	274	(4)
Balance equations	278	(4)
Further Reading	282	(3)
Analysis and Reduction of Reaction Mechanisms
Analysis of Reaction Mechanisms	285	(6)
Sensitivity Analysis	285	(4)
Analysis of the chemical fluxes	289	(2)
Reduction of Reaction Mechanisms	291	(8)
Quasi-stationary-state and partial equilibria approximations	291	(3)
Analysis using eigenvalues	294	(2)
Other methods	296	(2)
Conclusion	298	(1)
Further Reading	298	(1)
Computer Programs	298	(1)
Tables of Thermodynamic and Kinetic Data and of Molecular Parameters
Thermodynamic Tables	299	(8)
Benson's molecular groups	299	(1)
Benson's corrections	300	(1)
R-H bond dissociation energies at 298.15K	301	(1)
Free internal rotors	302	(1)
Internal rotation barriers	302	(1)
Entropy corrections for the internal rotation barriers	302	(1)
Heat capacity Cop of a hindered internal rotor	303	(1)
Wavenumbers	303	(1)
Standard entropy of a harmonic oscillator	304	(1)
Heat capacity Cop of a harmonic oscillator	304	(1)
Thermodynamic data of elements in the standard state	305	(1)
Thermodynamic data of hydrocarbon species	305	(1)
Thermodynamic data of oxygenated species	305	(1)
Bibliography	306	(1)
Kinetic Tables	307	(4)
Combination of free radicals: values of the steric factors	307	(1)
Covalent radii (in A)	308	(1)
Disproportionation of free radicals: values of the kdi/kco ratio	308	(1)
Isomerization of free radicals by internal transfer of hydrogen atoms	308	(1)
Initiations	308	(1)
Unimolecular decompositions of free radicals	309	(1)
Reactions of free radicals with molecular oxygen	309	(1)
Metathesis	309	(1)
Bibliography	310	(1)
Databases	310	(1)
Tables of Molecular Parameters	311	(2)
COMPUTER PROGRAMS AND DATABASES	313	(8)
URLs	321	(8)
NOTATIONS
Symbols, Fundamental Constants, Units	323	(3)
Linear Chemical Notation	326	(3)
Index	329