Table Of ContentThermitic Thermodynamics
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Thermitic Thermodynamics
A Computational Survey and Comprehensive
Interpretation of Over 800 Combinations of
Metals, Metalloids, and Oxides
Anthony Peter Gordon Shaw
CRC Press
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Library of Congress Cataloging‑in‑Publication Data
Names: Shaw, Anthony Peter Gordon, author.
Title: Thermitic thermodynamics : a computational survey and comprehensive
interpretation of over 800 combinations of metals, metalloids, and
oxides / by Anthony Peter Gordon Shaw.
Description: Boca Raton : CRC Press, [2020] | Includes bibliographical
references and index.
Identifiers: LCCN 2019058129 (print) | LCCN 2019058130 (ebook) | ISBN
9781138482821 (hardback) | ISBN 9781351056625 (ebook)
Subjects: LCSH: Thermochemistry. | Thermit. | Metallic oxides. |
Pyrometallurgy. | Powder metallurgy. | Oxidizing agents.
Classification: LCC QD511 .S53 2020 (print) | LCC QD511 (ebook) | DDC
546/.3—dc23
LC record available at https://lccn.loc.gov/2019058129
LC ebook record available at https://lccn.loc.gov/2019058130
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Contents
Preface..........................................................................................................................................xxiii
Author ............................................................................................................................................xxv
Part 1 thermitic thermodynamics
Chapter 1 An Introduction to Thermitic Reactivity......................................................................3
1.1 Origins, Applications, and Examples ................................................................3
1.2 Enthalpic Relationships and the Properties of the Elements ...........................11
1.3 Thermodynamic Formalisms and Computational Methods ...........................21
1.4 A dditional Clarifications .................................................................................27
Data Sources ...............................................................................................................28
References ..................................................................................................................29
Chapter 2 Characteristics of the Metal–Metal Oxide Reaction Matrix ......................................31
2.1 An Adiabatic Survey of 800 Metal–Metal Oxide Systems .............................31
2.2 Trends Involving Adiabatic Temperature and Product Phase .........................34
2.3 Adiabatic Temperature and Gas Production Maxima .....................................42
2.4 Complexity in Unrestricted Reactive Systems ................................................47
2.5 Characteristics of Selected Metals and Metal Oxides .....................................49
2.5.1 Magnesium .........................................................................................50
2.5.2 Titanium, Zirconium, and Hafnium ...................................................50
2.5.3 Vanadium, Niobium, and Tantalum ...................................................51
2.5.4 Chromium, Molybdenum, and Tungsten ............................................52
2.5.5 Manganese, Iron, Cobalt, and Nickel .................................................52
2.5.6 Copper and Silver ...............................................................................53
2.5.7 Zinc, Cadmium, and Mercury ............................................................53
2.5.8 Boron and Aluminum .........................................................................54
2.5.9 Silicon, Tin, and Lead ........................................................................55
2.5.10 Antimony and Bismuth ......................................................................56
2.5.11 O xygen ...............................................................................................56
2.6 Other Elements and Compounds .....................................................................56
2.6.1 The Alkali and Alkaline Earth Elements ..........................................57
2.6.2 The Rare Earth Elements and the Actinides ......................................57
2.6.3 T he Chalcogens ..................................................................................58
2.6.4 T he Halogens ......................................................................................59
2.7 S ummary Tables ..............................................................................................59
2.7.1 T emperature-Based Tables .................................................................60
2.7.2 G as-Based Tables ...............................................................................66
Data Sources ...............................................................................................................72
References ..................................................................................................................72
Chapter 3 Some Thermodynamic Concepts and Considerations ...............................................75
3.1 Essential Elements of Classical Thermodynamics ..........................................75
vii
viii Contents
3.2 Chemical Reactions as Thermodynamic Processes ........................................81
3.3 Conventions Concerning Pure Substances ......................................................90
3.4 Chemical Decomposition Equilibria ...............................................................95
3.5 Constituents, Components, and Phases in Equilibrium ................................104
3.6 Our Approach to Equilibrium .......................................................................124
Data Sources .............................................................................................................124
References ................................................................................................................124
Chapter 4 Applying Thermodynamic Concepts .......................................................................127
4.1 Periodic Trends in the Stabilities of Metal Oxides........................................127
4.2 Assessing the Stabilities of Metal Oxides at Various Temperatures .............132
4.3 Assorted Ellingham Diagrams ......................................................................142
4.3.1 Common Oxides of Titanium, Zirconium, Hafnium,
Aluminum, and Magnesium .............................................................143
4.3.2 Common Manganese and Iron Oxides .............................................146
4.3.3 Oxides and Suboxides of Boron and Aluminum..............................149
4.3.4 Oxides and Suboxides of Silicon, Tin, Antimony, and Bismuth ......150
4.3.5 Some Oxides of Silver, Mercury, and Lead .....................................150
4.4 Reconciling Gibbs Energy, Enthalpy, and Entropy .......................................153
4.4.1 Premises, Assumptions, and Simplifications ...................................157
4.4.2 E nthalpy Changes .............................................................................157
4.4.3 E ntropy Changes ..............................................................................158
4.4.4 Gibbs Energy Changes .....................................................................158
4.5 F eatures in Adiabatic Temperature and Gas Production Profiles .................158
4.6 Consequences of Database Deficiencies ........................................................166
Data Sources .............................................................................................................170
References ................................................................................................................170
Chapter 5 Additional Topics .....................................................................................................171
5.1 A luminum ......................................................................................................171
5.2 Borides, Silicides, and Intermetallics ............................................................187
5.3 Metals as Fuels in Combustion Reactions .....................................................194
5.4 Sulfur and Metal Sulfides ..............................................................................217
5.5 Thermodynamics, Combustion, and Technology ..........................................233
Data Sources .............................................................................................................233
References ................................................................................................................233
Part 2 adiabatic Descriptions of Binary thermitic Systems
Chapter 6 Magnesium–Oxidizer Systems ................................................................................241
6.1 O verview .......................................................................................................241
6.2 M agnesium + O ............................................................................................242
2
6.3 Magnesium + TiO ........................................................................................244
2
6.4 M agnesium + VO ........................................................................................246
2 5
6.5 Magnesium + NbO ......................................................................................248
2 5
6.6 M agnesium + Ta O .......................................................................................250
2 5
6.7 M agnesium + Cr O .......................................................................................251
2 3
Contents ix
6.8 M agnesium + MoO ......................................................................................253
3
6.9 Magnesium + WO ........................................................................................255
3
6.10 M agnesium + MnO ........................................................................................257
6.11 Magnesium + Mn O .....................................................................................258
3 4
6.12 Magnesium + Mn O .....................................................................................260
2 3
6.13 M agnesium + MnO ......................................................................................262
2
6.14 M agnesium + FeO .........................................................................................264
6.15 M agnesium + FeO .......................................................................................265
3 4
6.16 M agnesium + FeO .......................................................................................267
2 3
6.17 M agnesium + CoO ........................................................................................269
6.18 M agnesium + CoO ......................................................................................270
3 4
6.19 Magnesium + NiO .........................................................................................272
6.20 M agnesium + Cu O .......................................................................................274
2
6.21 M agnesium + CuO ........................................................................................276
6.22 M agnesium + Ag O .......................................................................................278
2
6.23 M agnesium + ZnO .........................................................................................279
6.24 M agnesium + CdO ........................................................................................280
6.25 M agnesium + HgO ........................................................................................282
6.26 M agnesium + BO ........................................................................................284
2 3
6.27 M agnesium + SiO .........................................................................................286
2
6.28 M agnesium + SnO .........................................................................................288
6.29 Magnesium + SnO ........................................................................................290
2
6.30 M agnesium + PbO .........................................................................................292
6.31 M agnesium + PbO ......................................................................................294
3 4
6.32 M agnesium + PbO ........................................................................................296
2
6.33 M agnesium + SbO .......................................................................................298
2 3
6.34 Magnesium + Bi O .......................................................................................300
2 3
Chapter 7 Titanium–Oxidizer Systems ....................................................................................303
7.1 O verview .......................................................................................................303
7.2 Titanium + O ................................................................................................304
2
7.3 Titanium + TiO .............................................................................................306
2
7.4 T itanium + VO ............................................................................................307
2 5
7.5 Titanium + NbO ..........................................................................................309
2 5
7.6 T itanium + Ta O ...........................................................................................311
2 5
7.7 T itanium + Cr O ...........................................................................................312
2 3
7.8 T itanium + MoO ...........................................................................................313
3
7.9 T itanium + WO.............................................................................................315
3
7.10 T itanium + MnO ............................................................................................317
7.11 T itanium + Mn O .........................................................................................318
3 4
7.12 Titanium + Mn O .........................................................................................320
2 3
7.13 T itanium + MnO ..........................................................................................322
2
7.14 T itanium + FeO .............................................................................................324
7.15 T itanium + FeO ...........................................................................................326
3 4
7.16 T itanium + FeO ...........................................................................................328
2 3
7.17 T itanium + CoO .............................................................................................330
7.18 T itanium + CoO ..........................................................................................332
3 4
7.19 T itanium + NiO .............................................................................................334
7.20 T itanium + Cu O ...........................................................................................336
2
7.21 Titanium + CuO .............................................................................................338
