Phosphorus: Chemistry, Biochemistry and Technology, Sixth Edition

1426 Pages·2013·23.251 MB·English

by  D.E.C. Corbridge

Chemistry CORBRIDGE
SIXTH EDITION
Praise for Previous Editions
“I feel this volume should be a standard addition to the laboratory of any chemist
S I X TH E D ITI O N
working directly in the field or around the periphery of phosphorus chemistry.
There is probably no faster way to get acquainted with the vast world of
phosphorus chemistry.”
—Journal of the American Chemical Society
“...The frequent inserts and footnotes are bristling with information of all types
and the same is true of the tables and the reaction schemes.”
—Nature
Over two decades have passed since the fifth edition of Phosphorus: Chemistry,
Biochemistry and Technology. Major advances in chemistry, materials science,
electronics, and medicine have expanded and clarified the role of phosphorus
in both our everyday appliances and groundbreaking research. Significantly
expanded, updated, and reorganized, this sixth edition organizes and explains
vital phosphorus research and relevant information available in highly specialized
reviews and references on select related topics.
An authoritative and comprehensive review of phosphorus chemistry and related
technology, Phosphorus: Chemistry, Biochemistry and Technology covers
historical, academic, industrial, agricultural, biological, medical, and military
aspects of phosphorus. Furthermore, it offers a starting point for more extended
studies of the highly specialized branches of phosphorus chemistry.
Although this book deals with a small fraction of the >106 known phosphorus
compounds, it thoroughly covers the simpler derivatives and most key compounds
of economic, sociological, and biological importance. Extensively updated and
expanded with tables, figures, equations, structural formulae, and references, it
is ideal for scientists in related fields seeking a rapid introduction to phosphorus
chemistry.
SIXTH EDITION
ISBN: 978-1-4398-4088-7
90000
9 781439 840887 D.E.C. CORBRIDGE
S I X TH E D ITI O N
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
S I X TH E D ITI O N
D.E.C. CORBRIDGE
Boca Raton London New York
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Version Date: 20121106
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To my early mentors: C.J. Brown, E.G. Cox and B. Raistrick
Without phosphorus, our world could not be.
With phosphorus, our world might not be.
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
Contents
Prefacexxxi
Acknowledgements xxxiii
Chapter 1 Introduction and Historical Background 1
11 General Overview 1
12 Historical Survey 2
121 Importance of Phosphorus Compounds 5
13 Classification and Nomenclature of P Compounds 14
131 Formulae and Graphics 21
14 Literature of Phosphorus Chemistry 21
Bibliography 22
Chapter 2 Distribution and Environment 23
21 General Occurrence 23
22 Phosphate Mineral Deposits 25
221 Apatitic Phosphate Minerals Ca (PO ) (F,OH,Cl) 25
10 4 6 2
222 Non-Apatitic Phosphate Minerals 27
223 Apatite Mining Development 28
224 Production and Reserves 29
225 Alternative Sources of Phosphorus 31
226 Active Biosources of Phosphorus 31
227 Extra-Terrestrial Phosphorus and Reduced Forms 33
23 Environmental Phosphorus 34
231 Natural and Artificial Cycles of Phosphorus 34
232 Ocean Phosphate 35
233 Phosphate in Lakes and Rivers 37
234 Phosphorus Content of Road-Deposited Sediments 37
235 Phosphorus Content of Desert Dusts 37
236 Planetary Distribution of Apatite 37
237 Eutrophication and Pollution 38
238 Sewage Treatment 39
239 Future Ecological Outlook 39
2310 Toxicity of Phosphorus Compounds 40
2311 Possible Radioactivity and Other Hazards 40
References 41
Chapter 3 Atomic and Molecular Properties 45
31 Atomic Properties 45
311 Comparisons with Pnictides 46
312 Electronegativity 47
313 Electron Affinity 48
314 Ionization Potential 49
315 Basic Stereochemistry 49
vii
viii Contents
316 Oxidation States 51
317 Electronic Structure 52
318 Formal Valence Bond Structures 54
319 Bond Orbitals 55
3110 Basic Schemes of σ-Bonding (Single Bonds) 57
3111 dπ–pπ Bonding 59
3112 pπ–pπ Bonding 61
3113 Metal–Phosphorus and dπ–dπ Bonding 62
3114 Mixed Valency Compounds 64
32 Equilibria and Stereochemistry 64
321 Optical Isomers 64
322 Inversion and Pseudorotation 65
323 Fluxional Molecules 66
324 Tautomerism 66
325 Equilibria of Trigonal Bipyramidal Molecules 67
326 Resonance (Mesomerism) 67
327 Sigmatropic Rearrangements: Phospha-Cope 68
328 Reorganisation Reactions69
33 Types of Reaction 70
331 Phosphorylation 74
332 Ester Hydrolysis Involving P–O–P or P–O–C Linkages76
333 Thermal Condensation 77
334 Oxidation 77
335 Reduction 77
336 Michaelis–Arbusov Reaction (Arbusov Reaction) 78
337 Wittig Reaction 78
338 Kirsanov Reaction79
339 Polymerisations 79
34 Bond Strengths and Bond Lengths 80
341 Bond Strengths 80
342 Covalent Bond Lengths and Interatomic Distances 82
343 Long Bonds 87
References 90
Chapter 4 Phosphides of Non-Metals 93
41 The Element 93
411 White Phosphorus 93
412 By-Products from Apatite 95
413 Alternative Processes for Extraction of Phosphorus from Its Ores 95
414 Properties of White Phosphorus 96
415 Black Phosphorus 99
416 Cubic Black Phosphorus and Rhombohedral Black Phosphorus 100
417 Phosphorus Nanotubes 101
418 Red Phosphorus 101
419 Commercial Red Phosphorus 102
4110 Phosphorus Vapour 105
4111 Liquid Phosphorus 105
4112 Phosphohedrane Structures 105
4113 Phosphorus Anions 108
4114 Phosphorus Cations 110
Contents ix
4115 Comparisons of Pnictide Elements 110
4116 Interpnictide Compounds 111
42 Oxides 113
421 Phosphorus Pentoxide (Phosphoric Anhydride) 113
422 Phosphorus Trioxide 118
423 Phosphorus Tetroxide 119
424 Sub-Oxides of Phosphorus120
425 Miscellaneous Oxides 121
426 Pnictide Oxide Comparisons 121
43 Sulphides 122
431 Thermal Stability of Phosphorus Sulphides 127
432 Hydrolytic Stability of Phosphorus Sulphides 127
433 Oxysulphides of Phosphorus 131
44 Hydrides132
441 Pnictide Hydrides, XH 134
3
442 Phosphine, PH 134
3
443 Phosphonium Salts 138
444 Phosphide Anion, PH− ...................................................................138
2
445 Phosphinidene, PH 138
446 Diphosphine 138
447 Polyphosphines 140
448 Triphosphine 140
45 Nitrides 143
451 Phosphazate Anions, [PN]n–17a 145
x y
46 Halides 146
461 Phosphorus Trihalides 146
462 Phosphorus Pentahalides 152
463 Mixed Pentahalides 156
464 Polyhalides of Phosphorus 159
465 Polyphosphorus Halides159
466 Hexahalophosphates (Halophosphorides) 160
467 Addition Complexes 162
468 Pseudo Halides 163
469 Phosphoryl Halides (Phosphorus Oxyhalides) 163
4610 Phosphoryl Halide Complexes 166
47 Borides 167
48 Carbides 169
49 Silicides 170
References 170
Chapter 5 Oxyphosphorus Compounds 177
51 Introduction 177
52 Phosphoric and Polyphosphoric Acids 179
521 The Commercial Wet Process179
522 By-Products from the Wet Process 181
523 Alternative Processes for Phosphoric Acid Manufacture 182
524 Properties of Orthophosphoric Acid (H PO )183
3 4
525 Deuterophosphoric Acid 187
526 Polyphosphoric Acids 187
527 Pyrophosphoric Acid 188