Greg Fridman
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Plasma Chemistry
new book by Alexander Fridman
Plasma Chemistry
Alexander Fridman
Drexel University, Philadelphia

Hardback
(ISBN-13: 9780521847353)
* Published May 2008

Plasma Chemistry

This unique book provides a fundamental introduction to all aspects of modern plasma chemistry. The book describes mechanisms and kinetics of chemical processes in plasma, plasma statistics, thermodynamics, fluid mechanics, and electrodynamics, as well as all major electric discharges applied in plasma chemistry. The book considers most of the major applications of plasma chemistry, from electronics to thermal coatings, from treatment of polymers to fuel conversion and hydrogen production, and from plasma metallurgy to plasma medicine. The book can be helpful to engineers, scientists, and students interested in plasma physics, plasma chemistry, plasma engineering, and combustion, as well as in chemical physics, lasers, energy systems, and environmental control. The book contains an extensive database on plasma kinetics and thermodynamics, as well as many convenient numerical formulas for practical calculations related to specific plasma–chemical processes and applications. The book contains a large number of problems and concept questions that are helpful in university courses related to plasma, lasers, combustion, chemical kinetics, statistics and thermodynamics, and high-temperature and high-energy fluid mechanics.

Alexander Fridman is Nyheim Chair Professor of Drexel University and Director of Drexel Plasma Institute. His research focuses on plasma approaches to material treatment, fuel conversion, hydrogen production, biology, medicine, and environmental control. Professor Fridman has more than 35 years of plasma research experience in national laboratories and universities in Russia, France, and the United States. He has published 6 books and 450 papers, chaired several international plasma conferences, and received numerous awards, including the Stanley Kaplan Distinguished Professorship in Chemical Kinetics and Energy Systems, the George Soros Distinguished Professorship in Physics, and the State Prize of the USSR for discovery of selective stimulation of chemical processes in non-thermal plasma.

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© Alexander Fridman 2008

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the written permission of Cambridge University Press.

First published 2008

Printed in the United States of America.

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ISBN-13 978-0-521-84735-3 hardback

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Contents

  Foreword page xxxix
  Preface xli
1   Introduction to Theoretical and Applied Plasma Chemistry 1
1.1.   Plasma as the Fourth State of Matter 1
1.2.   Plasma in Nature and in the Laboratory 2
1.3.   Plasma Temperatures: Thermal and Non-Thermal Plasmas 4
1.4.   Plasma Sources for Plasma Chemistry: Gas Discharges 5
1.5.   Fundamentals of Plasma Chemistry: Major Components of Chemically Active Plasma and Mechanisms of Plasma-Chemical Processes 8
1.6.   Applied Plasma Chemistry 9
1.7.   Plasma as a High-Tech Magic Wand of Modern Technology 10
2   Elementary Plasma-Chemical Reactions 12
2.1.   Ionization Processes 12
2.1.1.   Elementary Charged Particles in Plasma 12
2.1.2.   Elastic and Inelastic Collisions and Their Fundamental Parameters 13
2.1.3.   Classification of Ionization Processes 14
2.1.4.   Elastic Scattering and Energy Transfer in Collisions of Charged Particles: Coulomb Collisions 15
2.1.5.   Direct Ionization by Electron Impact: Thomson Formula 16
2.1.6.   Specific Features of Ionization of Molecules by Electron Impact: Frank-Condon Principle and Dissociative Ionization 17
2.1.7.   Stepwise Ionization by Electron Impact 18
2.1.8.   Ionization by High-Energy Electrons and Electron Beams: Bethe-Bloch Formula 20
2.1.9.   Photo-Ionization Processes 20
2.1.10.   Ionization in Collisions of Heavy Particles: Adiabatic Principle and Massey Parameter 21
2.1.11.   Penning Ionization Effect and Associative Ionization 21
2.2   Elementary Plasma-Chemical Reactions of Positive Ions 22
2.2.1.   Different Mechanisms of Electron–Ion Recombination in Plasma 22
2.2.2.   Dissociative Electron–Ion Recombination and Possible Preliminary Stage of Ion Conversion 23
2.2.3.   Three-Body and Radiative Electron–Ion Recombination Mechanisms 25
2.2.4.   Ion–Molecular Reactions, Ion–Molecular Polarization Collisions, and the Langevin Rate Coefficient 26
2.2.5.   Ion–Atomic Charge Transfer Processes and Resonant Charge Transfer 28
2.2.6.   Non-Resonant Charge Transfer Processes and Ion–Molecular Chemical Reactions of Positive and Negative Ions 29
2.3.   Elementary Plasma-Chemical Reactions Involving Negative Ions 31
2.3.1.   Dissociative Electron Attachment to Molecules as a Major Mechanism of Negative Ion Formation in Electronegative Molecular Gases 31
2.3.2.   Three-Body Electron Attachment and Other Mechanisms of Formation of Negative Ions 33
2.3.3.   Destruction of Negative Ions: Associative Detachment, Electron Impact Detachment, and Detachment in Collisions with Excited Particles 35
2.3.4.   Recombination of Negative and Positive Ions 37
2.3.5.   Ion–Ion Recombination in Binary Collisions 38
2.3.6.   Three-Body Ion–Ion Recombination: Thomson’s Theory and Langevin Model 39
2.4.   Electron Emission and Heterogeneous Ionization Processes 42
2.4.1.   Thermionic Emission: Sommerfeld Formula and Schottky Effect 42
2.4.2.   Field Emission of Electrons in Strong Electric Fields: Fowler-Nordheim Formula and Thermionic Field Emission 43
2.4.3.   Secondary Electron Emission 45
2.4.4.   Photo-Ionization of Aerosols: Monochromatic Radiation 46
2.4.5.   Photo-Ionization of Aerosols: Continuous-Spectrum Radiation 49
2.4.6.   Thermal Ionization of Aerosols: Einbinder Formula 51
2.4.7.   Space Distribution of Electrons and Electric Field Around a Thermally Ionized Macro-Particle 52
2.4.8.   Electric Conductivity of Thermally Ionized Aerosols 53
2.5.   Excitation and Dissociation of Neutral Particles in Ionized Gases 54
2.5.1.   Vibrational Excitation of Molecules by Electron Impact 54
2.5.2.   Rate Coefficients of Vibrational Excitation by Electron Impact: Semi-Empirical Fridman Approximation 56
2.5.3.   Rotational Excitation of Molecules by Electron Impact 58
2.5.4.   Electronic Excitation of Atoms and Molecules by Electron Impact 59
2.5.5.   Dissociation of Molecules by Direct Electron Impact 61
2.5.6.   Distribution of Electron Energy in Non-Thermal Discharges Between Different Channels of Excitation and Ionization 63
2.6.   Elementary Relaxation Processes of Energy Transfer Involving Vibrationally, Rotationally, and Electronically Excited Molecules 67
2.6.1.   Vibrational–Translational (VT) Relaxation: Slow Adiabatic Elementary Process 67
2.6.2.   Landau–Teller Formula for VT-Relaxation Rate Coefficients 69
2.6.3.   Fast Non-Adiabatic Mechanisms of VT Relaxation 71
2.6.4.   Vibrational Energy Transfer Between Molecules: Resonant VV Relaxation 72
2.6.5.   Non-Resonant VV Exchange: Relaxation of Anharmonic Oscillators and Intermolecular VV Relaxation 74
2.6.6.   Rotational Relaxation Processes: Parker Formula 76
2.6.7.   Relaxation of Electronically Excited Atoms and Molecules 76
2.7.   Elementary Chemical Reactions of Excited Molecules: Fridman-Macheret α-Model 79
2.7.1.   Rate Coefficient of Reactions of Excited Molecules 79
2.7.2.   Efficiency α of Vibrational Energy in Overcoming Activation Energy of Chemical Reactions: Numerical Values and Classification Table 81
2.7.3.   Fridman-Macheret α-Model 81
2.7.4.   Efficiency of Vibrational Energy in Elementary Reactions Proceeding Through Intermediate Complexes: Synthesis of Lithium Hydride 83
2.7.5.   Dissociation of Molecules in Non-Equilibrium Conditions with Essential Contribution of Translational Energy: Non-Equilibrium Dissociation Factor Z 86
2.7.6.   Semi-Empirical Models of Non-Equilibrium Dissociation of Molecules Determined by Vibrational and Translational Temperatures 87
  Problems and Concept Questions 89
3   Plasma-Chemical Kinetics, Thermodynamics, and Electrodynamics 92
3.1.   Plasma Statistics and Thermodynamics, Chemical and Ionization Equilibrium, and the Saha Equation 92
3.1.1.   Statistical Distributions: Boltzmann Distribution Function 92
3.1.2.   Equilibrium Statistical Distribution of Diatomic Molecules over Vibrational–Rotational States 93
3.1.3.   Saha Equation for Ionization Equilibrium in Thermal Plasma 94
3.1.4.   Dissociation Equilibrium in Molecular Gases 94
3.1.5.   Complete Thermodynamic Equilibrium (CTE) and Local Thermodynamic Equilibrium (LTE) in Plasma 95
3.1.6.   Thermodynamic Functions of Quasi-Equilibrium Thermal Plasma Systems 95
3.1.7.   Non-Equilibrium Statistics of Thermal and Non-Thermal Plasmas 97
3.1.8.   Non-Equilibrium Statistics of Vibrationally Excited Molecules: Treanor Distribution 99
3.2.   Electron Energy Distribution Functions (EEDFs) in Non-Thermal Plasma 100
3.2.1.   Fokker-Planck Kinetic Equation for Determination of EEDF 100
3.2.2.   Druyvesteyn Distribution, Margenau Distributions, and Other Specific EEDF 101
3.2.3.   Effect of Electron–Molecular and Electron–Electron Collisions on EEDF 103
3.2.4.   Relation Between Electron Temperature and the Reduced Electric Field 104
3.2.5.   Isotropic and Anisotropic Parts of the Electron Distribution Functions: EEDF and Plasma Conductivity 104
3.3.   Diffusion, Electric/Thermal Conductivity, and Radiation in Plasma 106
3.3.1.   Electron Mobility, Plasma Conductivity, and Joule Heating 106
3.3.2.   Plasma Conductivity in Crossed Electric and Magnetic Fields 107
3.3.3.   Ion Energy and Ion Drift in Electric Field 109
3.3.4.   Free Diffusion of Electrons and Ions; Continuity Equation; and Einstein Relation Between Diffusion Coefficient, Mobility, and Mean Energy 109
3.3.5.   Ambipolar Diffusion and Debye Radius 110
3.3.6.   Thermal Conductivity in Plasma 111
3.3.7.   Non-Equilibrium Thermal Conductivity and Treanor Effect in Vibrational Energy Transfer 112
3.3.8.   Plasma Emission and Absorption of Radiation in Continuous Spectrum and Unsold-Kramers Formula 112
3.3.9.   Radiation Transfer in Plasma: Optically Thin and Optically Thick Plasmas 113
3.4.   Kinetics of Vibrationally and Electronically Excited Molecules in Plasma: Effect of Hot Atoms 114
3.4.1.   Fokker-Plank Kinetic Equation for Non-Equilibrium Vibrational Distribution Functions 114
3.4.2.   VT and VV Fluxes of Excited Molecules in Energy Space 115
3.4.3.   Non-Equilibrium Vibrational Distribution Functions: Regime of Strong Excitation 117
3.4.4.   Non-Equilibrium Vibrational Distribution Functions: Regime of Weak Excitation 119
3.4.5.   Kinetics of Population of Electronically Excited States in Plasma 120
3.4.6.   Non-Equilibrium Translational Energy Distribution Functions of Heavy Neutrals: Effect of “Hot” Atoms in Fast VT-Relaxation Processes 122
3.4.7.   Generation of “Hot” Atoms in Chemical Reactions 123
3.5.   Vibrational Kinetics of Gas Mixtures, Chemical Reactions, and Relaxation Processes 124
3.5.1.   Kinetic Equation and Vibrational Distributions in Gas Mixtures: Treanor Isotopic Effect in Vibrational Kinetics 124
3.5.2.   Reverse Isotopic Effect in Plasma-Chemical Kinetics 126
3.5.3.   Macrokinetics of Chemical Reactions of Vibrationally Excited Molecules 129
3.5.4.   Vibrational Energy Losses Due to VT Relaxation 131
3.5.5.   Vibrational Energy Losses Due to Non-Resonance VV Exchange 132
3.6.   Energy Balance and Energy Efficiency of Plasma-Chemical Processes 132
3.6.1   Energy Efficiency of Quasi-Equilibrium and Non-Equilibrium Plasma-Chemical Processes 132
3.6.2.   Energy Efficiency of Plasma-Chemical Processes Stimulated by Vibrational Excitation of Molecules 133
3.6.3.   Energy Efficiency of Plasma-Chemical Processes Stimulated by Electronic Excitation and Dissociative Attachment 134
3.6.4.   Energy Balance and Energy Efficiency of Plasma-Chemical Processes Stimulated by Vibrational Excitation of Molecules 134
3.6.5.   Components of Total Energy Efficiency: Excitation, Relaxation, and Chemical Factors 136
3.6.6.   Energy Efficiency of Quasi-Equilibrium Plasma-Chemical Systems: Absolute, Ideal, and Super-Ideal Quenching 137
3.6.7.   Mass and Energy Transfer Equations in Multi-Component Quasi-Equilibrium Plasma-Chemical Systems 137
3.6.8.   Transfer Phenomena Influence on Energy Efficiency of Plasma-Chemical Processes 139
3.7.   Elements of Plasma Electrodynamics 140
3.7.1.   Ideal and Non-Ideal Plasmas 140
3.7.2.   Plasma Polarization: Debye Shielding of Electric Field in Plasma 141
3.7.3.   Plasmas and Sheaths: Physics of DC Sheaths 142
3.7.4.   High-Voltage Sheaths: Matrix and Child Law Sheath Models 144
3.7.5.   Electrostatic Plasma Oscillations: Langmuir or Plasma Frequency 145
3.7.6.   Penetration of Slow-Changing Fields into Plasma: Skin Effect in Plasma 146
3.7.7.   Magneto-Hydrodynamics: “Diffusion” of Magnetic Field and Magnetic Field Frozen in Plasma 146
3.7.8.   Magnetic Pressure: Plasma Equilibrium in Magnetic Field and Pinch Effect 147
3.7.9.   Two-Fluid Magneto-Hydrodynamics: Generalized Ohm’s Law 149
3.7.10.   Plasma Diffusion Across Magnetic Field 149
3.7.11.   Magneto-Hydrodynamic Behavior of Plasma: Alfven Velocity and Magnetic Reynolds Number 150
3.7.12.   High-Frequency Plasma Conductivity and Dielectric Permittivity 151
3.7.13.   Propagation of Electromagnetic Waves in Plasma 153
3.7.14.   Plasma Absorption and Reflection of Electromagnetic Waves: Bouguer Law: Critical Electron Density 154
  Problems and Concept Questions 155
4   Electric Discharges in Plasma Chemistry 157
4.1.   Fundamentals of Electric Breakdown, Streamer Processes, and Steady-State Regimes of Non-Equilibrium Electrical Discharges 157
4.1.1   Townsend Mechanism of Electric Breakdown and Paschen Curves 157
4.1.2.   Spark Breakdown Mechanism: Streamer Concept 159
4.1.3.   Meek Criterion of Streamer Formation: Streamer Propagation Models 163
4.1.4.   Streamers and Microdischarges 164
4.1.5.   Interaction of Streamers and Microdischarges 166
4.1.6.   Monte Carlo Modeling of Interaction of Streamers and Microdischarges 167
4.1.7.   Self-Organized Pattern of DBD Microdischarges due to Streamer Interaction 168
4.1.8.   Steady-State Regimes of Non-Equilibrium Electric Discharges and General Regimes Controlled by Volume and Surface Recombination Processes 170
4.1.9.   Discharge Regime Controlled by Electron–Ion Recombination 171
4.1.10.   Discharge Regime Controlled by Electron Attachment 172
4.1.11.   Non-Thermal Discharge Regime Controlled by Charged-Particle Diffusion to the Walls: The Engel-Steenbeck Relation 172
4.2.   Glow Discharges 175
4.2.1.   General Structure and Configurations of Glow Discharges 175
4.2.2.   Current-Voltage Characteristics of DC Discharges 177
4.2.3.   Dark Discharge and Transition from Townsend Dark to Glow Discharge 178
4.2.4.   Current-Voltage Characteristics of Cathode Layer: Normal Glow Discharge 179
4.2.5.   Abnormal, Subnormal, and Obstructed Regimes of Glow Discharges 181
4.2.6.   Positive Column of Glow Discharge 182
4.2.7.   Hollow Cathode Glow Discharge 183
4.2.8.   Other Specific Glow Discharge Plasma Sources 184
4.2.9.   Energy Efficiency Peculiarities of Glow Discharge Application for Plasma-Chemical Processes 186
4.3.   Arc Discharges 187
4.3.1.   Classification and Current-Voltage Characteristics of Arc Discharges 187
4.3.2.   Cathode and Anode Layers of Arc Discharges 189
4.3.3.   Cathode Spots in Arc Discharges 191
4.3.4.   Positive Column of High-Pressure Arcs: Elenbaas-Heller Equation 193
4.3.5.   Steenbeck-Raizer “Channel” Model of Positive Column 194
4.3.6.   Steenbeck-Raizer Arc “Channel” Modeling of Plasma Temperature, Specific Power, and Electric Field in Positive Column 196
4.3.7.   Configurations of Arc Discharges Applied in Plasma Chemistry and Plasma Processing 197
4.3.8.   Gliding Arc Discharge 200
4.3.9.   Equilibrium Phase of Gliding Arc, Its Critical Parameters, and Fast Equilibrium-to-Non-Equilibrium Transition 204
4.3.10.   Gliding Arc Stability Analysis and Transitional and Non-Equilibrium Phases of the Discharge 205
4.3.11.   Special Configurations of Gliding Arc Discharges: Gliding Arc Stabilized in Reverse Vortex (Tornado) Flow 207
4.4.   Radiofrequency and Microwave Discharges in Plasma Chemistry 209
4.4.1.   Generation of Thermal Plasma in Radiofrequency Discharges 209
4.4.2.   Thermal Plasma Generation in Microwave and Optical Discharges 211
4.4.3.   Non-Thermal Radiofrequency Discharges: Capacitive and Inductive Coupling of Plasma 215
4.4.4.   Non-Thermal RF-CCP Discharges in Moderate Pressure Regimes 216
4.4.5.   Low-Pressure Capacitively Coupled RF Discharges 219
4.4.6.   RF Magnetron Discharges 222
4.4.7.   Non-Thermal Inductively Coupled RF Discharges in Cylindrical Coil 224
4.4.8.   Planar-Coil and Other Configurations of Non-Thermal Inductively Coupled RF Discharges 226
4.4.9.   Non-Thermal Low-Pressure Microwave and Other Wave-Heated Discharges 229
4.4.10.   Non-Equilibrium Plasma-Chemical Microwave Discharges of Moderate Pressure 231
4.5.   Non-Thermal Atmospheric Pressure Discharges 233
4.5.1.   Corona Discharges 233
4.5.2.   Pulsed Corona Discharges 234
4.5.3.   Dielectric Barrier Discharges 237
4.5.4.   Special Modifications of DBD: Surface, Packed-Bed, and Ferroelectric Discharges 239
4.5.5.   Spark Discharges 240
4.5.6.   Atmospheric Pressure Glow Mode of DBD 241
4.5.7.   APGs: Resistive Barrier Discharge 242
4.5.8.   One-Atmosphere Uniform Glow Discharge Plasma as Another Modification of APG 243
4.5.9.   Electronically Stabilized APG Discharges 244
4.5.10.   Atmospheric-Pressure Plasma Jets 245
4.6.   Microdischarges 247
4.6.1.   General Features of Microdischarges 247
4.6.2.   Micro-Glow Discharge 248
4.6.3.   Micro-Hollow-Cathode Discharge 251
4.6.4.   Arrays of Microdischarges: Microdischarge Self-Organization and Structures 252
4.6.5.   Kilohertz-Frequency-Range Microdischarges 254
4.6.6.   RF Microdischarges 255
4.6.7.   Microwave Microdischarges 257
  Problems and Concept Questions 257
5   Inorganic Gas-Phase Plasma Decomposition Processes 259
5.1.   CO2: Dissociation in Plasma, Thermal, and Non-Thermal Mechanisms 259
5.1.1.   Fundamental and Applied Aspects of the CO2 Plasma Chemistry 259
5.1.2.   Major Experimental Results on CO2: Dissociation in Different Plasma Systems and Energy Efficiency of the Process 260
5.1.3.   Mechanisms of CO2 Decomposition in Quasi-Equilibrium Thermal Plasma 262
5.1.4.   CO2 Dissociation in Plasma, Stimulated by Vibrational Excitation of Molecules 263
5.1.5.   CO2 Dissociation in Plasma by Means of Electronic Excitation of Molecules 265
5.1.6.   CO2 Dissociation in Plasma by Means of Dissociative Attachment of Electrons 267
5.2.   Physical Kinetics of CO2 Dissociation, Stimulated by Vibrational Excitation of the Molecules in Non-Equilibrium Plasma 268
5.2.1.   Asymmetric and Symmetric CO2 Vibrational Modes 268
5.2.2.   Contribution of Asymmetric and Symmetric CO2 Vibrational Modes into Plasma-Chemical Dissociation Process 269
5.2.3.   Transition of Highly Vibrationally Excited CO2 Molecules into the Vibrational Quasi Continuum 271
5.2.4.   One-Temperature Approximation of CO2 Dissociation Kinetics in Non-Thermal Plasma 273
5.2.5.   Two-Temperature Approximation of CO2 Dissociation Kinetics in Non-Thermal Plasma 274
5.2.6.   Elementary Reaction Rates of CO2 Decomposition, Stimulated in Plasma by Vibrational Excitation of the Molecules 275
5.3.   Vibrational Kinetics and Energy Balance of Plasma-Chemical CO2 Dissociation 276
5.3.1.   Two-Temperature Approach to Vibrational Kinetics and Energy Balance of CO2 Dissociation in Non-Equilibrium Plasma: Major Energy Balance and Dynamic Equations 276
5.3.2.   Two-Temperature Approach to Vibrational Kinetics and Energy Balance of CO2 Dissociation in Non-Equilibrium Plasma: Additional Vibrational Kinetic Relations 277
5.3.3.   Results of CO2 Dissociation Modeling in the Two-Temperature Approach to Vibrational Kinetics 279
5.3.4.   One-Temperature Approach to Vibrational Kinetics and Energy Balance of CO2 Dissociation in Non-Equilibrium Plasma: Major Equations 280
5.3.5.   Threshold Values of Vibrational Temperature, Specific Energy Input, and Ionization Degree for Effective Stimulation of CO2 Dissociation by Vibrational Excitation of the Molecules 281
5.3.6.   Characteristic Time Scales of CO2 Dissociation in Plasma Stimulated by Vibrational Excitation of the Molecules: VT-Relaxation Time 282
5.3.7.   Flow Velocity and Compressibility Effects on Vibrational Relaxation Kinetics During Plasma-Chemical CO2 Dissociation: Maximum Linear Preheating Temperature 283
5.3.8.   CO2 Dissociation in Active and Passive Discharge Zones: Discharge (τev) and After-Glow (τp) Residence Time 284
5.3.9.   Ionization Degree Regimes of the CO2 Dissociation Process in Non-Thermal Plasma 285
5.3.10.   Energy Losses Related to Excitation of CO2 Dissociation Products: Hyperbolic Behavior of Energy Efficiency Dependence on Specific Energy Input 286
5.4.   Energy Efficiency of CO2 Dissociation in Quasi-Equilibrium Plasma, and Non-Equilibrium Effects of Quenching Products of Thermal Dissociation 288
5.4.1.   Ideal and Super-Ideal Modes of Quenching Products of CO2 Dissociation in Thermal Plasma 288
5.4.2.   Kinetic Evolution of Thermal CO2 Dissociation Products During Quenching Phase 288
5.4.3.   Energy Efficiency of CO2 Dissociation in Thermal Plasma Under Conditions of Ideal Quenching of Products 289
5.4.4.   Vibrational–Translational Non-Equilibrium Effects of Quenching Products of Thermal CO2 Dissociation in Plasma: Super-Ideal Quenching Mode 290
5.4.5.   Maximum Value of Energy Efficiency of CO2 Dissociation in Thermal Plasma with Super-Ideal Quenching of the Dissociation Products 291
5.4.6.   Kinetic Calculations of Energy Efficiency of CO2 Dissociation in Thermal Plasma with Super-Ideal Quenching 291
5.4.7.   Comparison of Thermal and Non-Thermal Plasma Approaches to CO2 Dissociation: Comments on Products (CO-O2) Oxidation and Explosion 292
5.5.   Experimental Investigations of CO2 Dissociation in Different Discharge Systems 293
5.5.1.   Experiments with Non-Equilibrium Microwave Discharges of Moderate Pressure, Discharges in Waveguide Perpendicular to Gas Flow Direction, and Microwave Plasma Parameters in CO2 293
5.5.2.   Plasma-Chemical Experiments with Dissociation of CO2 in Non-Equilibrium Microwave Discharges of Moderate Pressure 295
5.5.3.   Experimental Diagnostics of Plasma-Chemical Non-Equilibrium Microwave Discharges in Moderate-Pressure CO2: Plasma Measurements 296
5.5.4.   Experimental Diagnostics of Plasma-Chemical Non-Equilibrium Microwave Discharges in Moderate-Pressure CO2: Temperature Measurements 297
5.5.5.   CO2 Dissociation in Non-Equilibrium Radiofrequency Discharges: Experiments with Inductively Coupled Plasma 299
5.5.6.   CO2 Dissociation in Non-Equilibrium Radiofrequency Discharges: Experiments with Capacitively Coupled Plasma 300
5.5.7.   CO2 Dissociation in Non-Self-Sustained Atmospheric-Pressure Discharges Supported by High-Energy Electron Beams or UV Radiation 302
5.5.8.   CO2 Dissociation in Different Types of Glow Discharges 302
5.5.9.   CO2 Dissociation in Other Non-Thermal and Thermal Discharges: Contribution of Vibrational and Electronic Excitation Mechanisms 304
5.6.   CO2 Dissociation in Special Experimental Systems, Including Supersonic Stimulation and Plasma Radiolysis 304
5.6.1.   Dissociation of CO2 in Supersonic Non-Equilibrium Discharges: Advantages and Gasdynamic Characteristics 304
5.6.2.   Kinetics and Energy Balance of Non-Equilibrium Plasma-Chemical CO2 Dissociation in Supersonic Flow 306
5.6.3.   Limitations of Specific Energy Input and CO2 Conversion Degree in Supersonic Plasma Related to Critical Heat Release and Choking the Flow 308
5.6.4.   Experiments with Dissociation of CO2 in Non-Equilibrium Supersonic Microwave Discharges 308
5.6.5.   Gasdynamic Stimulation of CO2 Dissociation in Supersonic Flow: “Plasma Chemistry Without Electricity” 309
5.6.6.   Plasma Radiolysis of CO2 Provided by High-Current Relativistic Electron Beams 310
5.6.7.   Plasma Radiolysis of CO2 in Tracks of Nuclear Fission Fragments 311
5.6.8.   Ionization Degree in Tracks of Nuclear Fission Fragments, Energy Efficiency of Plasma Radiolysis of CO2, and Plasma-Assisted Chemonuclear Reactors 313
5.7.   Complete CO2 Dissociation in Plasma with Production of Carbon and Oxygen 314
5.7.1.   Complete Plasma-Chemical Dissociation of CO2: Specifics of the Process and Elementary Reaction Mechanism 314
5.7.2.   Kinetics of CO Disproportioning Stimulated in Non-Equilibrium Plasma by Vibrational Excitation of Molecules 314
5.7.3.   Experiments with Complete CO2 Dissociation in Microwave Discharges Operating in Conditions of Electron Cyclotron Resonance 316
5.7.4.   Experiments with Complete CO2 Dissociation in Stationary Plasma-Beam Discharge 317
5.8.   Dissociation of Water Vapor and Hydrogen Production in Plasma-Chemical Systems 318
5.8.1.   Fundamental and Applied Aspects of H2O Plasma Chemistry 318
5.8.2.   Kinetics of Dissociation of Water Vapor Stimulated in Non-Thermal Plasma by Vibrational Excitation of Water Molecules 319
5.8.3.   Energy Efficiency of Dissociation of Water Vapor Stimulated in Non-Thermal Plasma by Vibrational Excitation 320
5.8.4.   Contribution of Dissociative Attachment of Electrons into Decomposition of Water Vapor in Non-Thermal Plasma 322
5.8.5.   Kinetic Analysis of the Chain Reaction of H2O Dissociation via Dissociative Attachment/Detachment Mechanism 324
5.8.6.   H2O Dissociation in Thermal Plasma and Quenching of the Dissociation Products: Absolute and Ideal Quenching Modes 325
5.8.7.   Cooling Rate Influence on Kinetics of H2O Dissociation Products in Thermal Plasma: Super-Ideal Quenching Effect 326
5.8.8.   Water Dissociation and H2 Production in Plasma-Chemical System CO2–H2O 328
5.8.9.   CO-to-H2 Shift Reaction: Plasma Chemistry of CO–O2–H2O Mixture 330
5.9.   Experimental Investigations of H2O Dissociation in Different Discharge Systems 331
5.9.1.   Microwave Discharge in Water Vapor 331
5.9.2.   Plasma-Chemical Experiments with Microwave Discharge in Water Vapor 332
5.9.3.   Dissociation of Water Vapor in Glow Discharges 332
5.9.4.   Dissociation of H2O with Production of H2 and H2O2 in Supersonic Microwave Discharges 334
5.9.5.   Plasma Radiolysis of Water Vapor in Tracks of Nuclear Fission Fragments 335
5.9.6.   Effect of Plasma Radiolysis on Radiation Yield of Hydrogen Production in Tracks of Nuclear Fission Fragments 336
5.10.   Inorganic Gas-Phase Plasma-Chemical Processes of Decomposition of Triatomic Molecules: NH3, SO2, and N2O 336
5.10.1.   Gas-Phase Plasma Decomposition Reactions in Multi-Phase Technologies 336
5.10.2.   Dissociation of Ammonia in Non-Equilibrium Plasma: Mechanism of the Process in Glow Discharge 337
5.10.3.   Mechanism of Formation of Molecular Nitrogen and Hydrogen in Non-Equilibrium Plasma-Chemical Process of Ammonia Dissociation 338
5.10.4.   Plasma Dissociation of Sulfur Dioxide 338
5.10.5.   Destruction and Conversion of Nitrous Oxide in Non-Equilibrium Plasma 340
5.11.   Non-Thermal and Thermal Plasma Dissociation of Diatomic Molecules 341
5.11.1.   Plasma-Chemical Decomposition of Hydrogen Halides: Example of HBr Dissociation with Formation of Hydrogen and Bromine 341
5.11.2.   Dissociation of HF, HCl, and HI in Plasma 343
5.11.3.   Non-Thermal and Thermal Dissociation of Molecular Fluorine 344
5.11.4.   Dissociation of Molecular Hydrogen in Non-Thermal and Thermal Plasma Systems 345
5.11.5.   Dissociation of Molecular Nitrogen in Non-Thermal and Thermal Plasma Systems 347
5.11.6.   Thermal Plasma Dissociation of Other Diatomic Molecules (O2, Cl2, Br2) 347
  Problems and Concept Questions 351
6   Gas-Phase Inorganic Synthesis in Plasma 355
6.1.   Plasma-Chemical Synthesis of Nitrogen Oxides from Air and Nitrogen–Oxygen Mixtures: Thermal and Non-Thermal Mechanisms 355
6.1.1.   Fundamental and Applied Aspects of NO Synthesis in Air Plasma 355
6.1.2.   Mechanisms of NO Synthesis Provided in Non-Thermal Plasma by Excitation of Neutral Molecules: Zeldovich Mechanism 356
6.1.3.   Mechanisms of NO Synthesis Provided in Non-Thermal Plasma by Charged Particles 358
6.1.4.   NO Synthesis in Thermal Plasma Systems 358
6.1.5.   Energy Efficiency of Different Mechanisms of NO Synthesis in Thermal and Non-Thermal Discharge Systems 359
6.2.   Elementary Reaction of NO Synthesis Stimulated by Vibrational Excitation of Molecular Nitrogen 361
6.2.1.   Limiting Elementary Reaction of Zeldovich Mechanism: Adiabatic and Non-Adiabatic Channels of NO Synthesis 361
6.2.2.   Electronically Adiabatic Channel of NO Synthesis O+N2⃗NO+N Stimulated by Vibrational Excitation of Molecular Nitrogen 361
6.2.3.   Electronically Non-Adiabatic Channel of NO Synthesis (O+N2⃗NO+N): Stages of the Elementary Process and Method of Vibronic Terms 363
6.2.4.   Transition Probability Between Vibronic Terms Corresponding to Formation of Intermediate N2O*(|Σ) Complex 364
6.2.5.   Probability of Formation of Intermediate N2O*(|Σ) Complex in Electronically Non-Adiabatic Channel of NO Synthesis 365
6.2.6.   Decay of Intermediate Complex N2O*(|Σ): Second Stage of Electronically Non-Adiabatic Channel of NO Synthesis 366
6.2.7.   Total Probability of Electronically Non-Adiabatic Channel of NO Synthesis (O+N+2⃗NO+N) 367
6.3.   Kinetics and Energy Balance of Plasma-Chemical NO Synthesis Stimulated in Air and O2–N2 Mixtures by Vibrational Excitation 367
6.3.1.   Rate Coefficient of Reaction O+N+2⃗NO+N Stimulated in Non-Equilibrium Plasma by Vibrational Excitation of Nitrogen Molecules 367
6.3.2.   Energy Balance of Plasma-Chemical NO Synthesis: Zeldovich Mechanism Stimulated by Vibrational Excitation 368
6.3.3.   Macro-Kinetics of Plasma-Chemical NO Synthesis: Time Evolution of Vibrational Temperature 369
6.3.4.   Energy Efficiency of Plasma-Chemical NO Synthesis: Excitation and Relaxation Factors 370
6.3.5.   Energy Efficiency of Plasma-Chemical NO Synthesis: Chemical Factor 371
6.3.6.   Stability of Products of Plasma-Chemical Synthesis to Reverse Reactions in Active Zone of Non-Thermal Plasma 371
6.3.7.   Effect of “Hot Nitrogen Atoms” on Yield of NO Synthesis in Non-Equilibrium Plasma in Air and Nitrogen–Oxygen Mixtures 372
6.3.8.   Stability of Products of Plasma-Chemical NO Synthesis to Reverse Reactions Outside of the Discharge Zone 373
6.4.   Experimental Investigations of NO Synthesis from Air and N2–O2 Mixtures in Different Discharges 374
6.4.1.   Non-Equilibrium Microwave Discharge in Magnetic Field Operating in Conditions of Electron Cyclotron Resonance 374
6.4.2.   Evolution of Vibrational Temperature of Nitrogen Molecules in Non-Equilibrium ECR: Microwave Discharge During Plasma-Chemical NO Synthesis 376
6.4.3.   NO Synthesis in the Non-Equilibrium ECR Microwave Discharge 377
6.4.4.   NO Synthesis in Non-Self-Sustained Discharges Supported by Relativistic Electron Beams 378
6.4.5.   Experiments with NO Synthesis from Air in Stationary Non-Equilibrium Plasma-Beam Discharge 379
6.4.6.   Experiments with NO Synthesis from N2 and O2 in Thermal Plasma of Arc Discharges 380
6.4.7.   General Schematic and Parameters of Industrial Plasma-Chemical Technology of NO Synthesis from Air 381
6.5.   Plasma-Chemical Ozone Generation: Mechanisms and Kinetics 382
6.5.1.   Ozone Production as a Large-Scale Industrial Application of Non-Thermal Atmospheric-Pressure Plasma 382
6.5.2.   Energy Cost and Energy Efficiency of Plasma-Chemical Production of Ozone in Some Experimental and Industrial Systems 383
6.5.3.   Plasma-Chemical Ozone Formation in Oxygen 383
6.5.4.   Optimum DBD Microdischarge Strength and Maximization of Energy Efficiency of Ozone Production in Oxygen Plasma 385