CORBRIDGE Chemistry SIXTH E DITION Praise for Previous Editions “I feel this volume should be a standard addition to the laboratory of any chemist 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 SIXTH E DITION “ 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 ISBN: 978-1-4398-4088-7 S I X TH E D ITI O N 90000 781439 840887 D.E.C CORBRIDGE Uploaded by: Ebooks Chemical Engineering https://www.facebook.com/pages/Ebooks-Chemical-Engineering/238197077030 For More Books, softwares & tutorials Related to Chemical Engineering Join Us @facebook: https://www.facebook.com/pages/Ebooks-ChemicalEngineering/238197077030 @facebook: https://www.facebook.com/AllAboutChemcalEngineering @facebook: https://www.facebook.com/groups/10436265147/ ADMIN: I.W > SIXTH E DITION This page intentionally left blank SIXTH E DITION D.E.C CORBRIDGE Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2013 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20121106 International Standard Book Number-13: 978-1-4398-4089-4 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright.com (http:// www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com 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 This page intentionally left blank Contents Preface������������������������������������������������������������������������������������������������������������������������������������������xxxi Acknowledgementsỉ‰¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ï·¿ xxxiii Chapter 1)>> Introduction and Historical Background 1.1)>> 1.2)>> General Overview .1 Historical Survey 1.2.1)>> Importance of Phosphorus Compounds 1.3)>> Classification and Nomenclature of P Compounds 14 1.3.1)>> Formulae and Graphics 21 1.4)>> Literature of Phosphorus Chemistry 21 Bibliography 22 Chapter 2)>> Distribution and Environment 23 2.1)>> 2.2)>> General Occurrence 23 Phosphate Mineral Deposits 25 2.2.1)>> Apatitic Phosphate Minerals Ca10(PO4)6(F,OH,Cl)2 .25 2.2.2)>> Non-Apatitic Phosphate Minerals 27 2.2.3)>> Apatite Mining Development 28 2.2.4)>> Production and Reserves 29 2.2.5)>> Alternative Sources of Phosphorus 31 2.2.6)>> Active Biosources of Phosphorus 31 2.2.7)>> Extra-Terrestrial Phosphorus and Reduced Forms 33 2.3)>> Environmental Phosphorus 34 2.3.1)>> Natural and Artificial Cycles of Phosphorus 34 2.3.2)>> Ocean Phosphate 35 2.3.3)>> Phosphate in Lakes and Rivers 37 2.3.4)>> Phosphorus Content of Road-Deposited Sediments 37 2.3.5)>> Phosphorus Content of Desert Dusts 37 2.3.6)>> Planetary Distribution of Apatite 37 2.3.7)>> Eutrophication and Pollution 38 2.3.8)>> Sewage Treatment 39 2.3.9)>> Future Ecological Outlook 39 2.3.10)>> Toxicity of Phosphorus Compounds .40 2.3.11)>> Possible Radioactivity and Other Hazards .40 References 41 Chapter 3)>> Atomic and Molecular Properties 45 3.1)>> Atomic Properties 45 3.1.1)>> Comparisons with Pnictides 46 3.1.2)>> Electronegativity 47 Electron Affinity .48 3.1.3)>> Ionization Potential 49 3.1.4)>> Basic Stereochemistry 49 3.1.5)>> vii viii Contents 3.1.6)>> Oxidation States 51 3.1.7)>> Electronic Structure 52 3.1.8)>> Formal Valence Bond Structures 54 3.1.9)>> Bond Orbitals 55 3.1.10)>> Basic Schemes of σ-Bonding (Single Bonds) 57 3.1.11)>> dπ–pπ Bonding 59 3.1.12)>> pπ–pπ Bonding 61 3.1.13)>> Metal–Phosphorus and dπ–dπ Bonding 62 3.1.14)>> Mixed Valency Compounds 64 3.2)>> Equilibria and Stereochemistry 64 3.2.1)>> Optical Isomers .64 3.2.2)>> Inversion and Pseudorotation 65 3.2.3)>> Fluxional Molecules .66 3.2.4)>> Tautomerism 66 3.2.5)>> Equilibria of Trigonal Bipyramidal Molecules 67 3.2.6)>> Resonance (Mesomerism) 67 3.2.7)>> Sigmatropic Rearrangements: Phospha-Cope 68 3.2.8)>> Reorganisation Reactions 69 3.3)>> Types of Reaction 70 3.3.1)>> Phosphorylation 74 3.3.2)>> Ester Hydrolysis Involving P–O–P or P–O–C Linkages 76 3.3.3)>> Thermal Condensation 77 3.3.4)>> Oxidation 77 3.3.5)>> Reduction 77 3.3.6)>> Michaelis–Arbusov Reaction (Arbusov Reaction) 78 3.3.7)>> Wittig Reaction 78 3.3.8)>> Kirsanov Reaction 79 3.3.9)>> Polymerisations 79 3.4)>> Bond Strengths and Bond Lengths 80 3.4.1)>> Bond Strengths 80 3.4.2)>> Covalent Bond Lengths and Interatomic Distances 82 3.4.3)>> Long Bonds 87 References 90 Chapter 4)>> Phosphides of Non-Metals 93 4.1)>> The Element 93 4.1.1)>> White Phosphorus 93 4.1.2)>> By-Products from Apatite 95 4.1.3)>> Alternative Processes for Extraction of Phosphorus from Its Ores 95 4.1.4)>> Properties of White Phosphorus 96 4.1.5)>> Black Phosphorus 99 4.1.6)>> Cubic Black Phosphorus and Rhombohedral Black Phosphorus 100 4.1.7)>> Phosphorus Nanotubes 101 4.1.8)>> Red Phosphorus 101 4.1.9)>> Commercial Red Phosphorus 102 4.1.10)>> Phosphorus Vapour 105 4.1.11)>> Liquid Phosphorus 105 4.1.12)>> Phosphohedrane Structures 105 4.1.13)>> Phosphorus Anions 108 4.1.14)>> Phosphorus Cations 110 Appendix 5: Properties of Phosphine, PH3 Form at NTP:╇ Colourless gas, MWâ•–=â•–33.998 Freezing point:╇ −133.8°C (under own vapour pressure of 27.3â•–mm) Boiling point:╇ –87.8°C Transition points (solid):╇ −184.5, −223.6, −242.7°C Heat of fusion:╇ 0.270â•–kcal/mol Heat of vaporisation:╇ 3.493â•–kcal/mol Heat of formation:╇ (at 25°C) 2.29â•–kcal Interatomic distance:╇ P–Hâ•–=â•–1.421 A Interbond angle:╇ H/P/Hâ•–=â•–93.5° Dipole moment:╇ μâ•–=â•–0.55 D Density:╇ (0°C, 760â•–mm) ρâ•–=â•–1.5307↜g/L Solubility (20°C, 760â•–mm) in: Water Nitrobenzene Carbon tetrachloride Acetone Benzene Carbon disulphide 26â•–cm3 PH3/100â•–cm3 solvent 306â•–cm3 PH3/100â•–cm3 solvent 419â•–cm3 PH3/100â•–cm3 solvent 445â•–cm3 PH3/100â•–cm3 solvent 726â•–cm3 PH3/100â•–cm3 solvent 1025â•–cm3 PH3/100â•–cm3 solvent Toxicity:╇ very high (Appendix 1) Note: There exists an anthracene-based orange dyestuff, ‘Crysaniline’, which has also been known in some quarters as ‘phosphine’ The word ‘phosphene’ has been used to describe an impression of light on the retina, when it is caused by stimulation other than rays of light 1377 This page intentionally left blank Appendix 6: Properties of Orthophosphoric Acid, H3PO4 Form at NTP:╇ Colourless solid and aqueous solutions Molecular weight:╇ 98.00 Crystal system:╇ Monoclinic Unit cell:╇ â•–=â•–5.78, bâ•–=â•–4.84, câ•–=â•–11.65 A; βâ•–=â•–95.5°: P21/c, 4H3PO4 units/cell Density:╇ ρâ•–=â•–1.864â•–g/cm3 Melting point:╇ 42.3°C Boiling point:╇ 261°C at 760â•–mm Heat of formation:╇ −303â•–kcal/mol at 25°C Heat capacity:╇ 25.3â•–cal/°C/mol Toxicity:╇ Non-toxic when pure, but concentrated solutions are caustic and are potentially toxic Solution properties: H3PO4 (%) P2O5 (%) Density (g/ cm3) bp (°C) fp (°C) Viscosity cps (25°C) Vapour Pressure mm (25°C) 10 20 30 50 75 85 100 105 3.62 7.24 14.49 21.73 36.22 54.32 61.57 72.42 76.10 0.997 1.025 1.053 1.113 1.182 1.333 1.573 1.685 1.864 1.925 100.0 100.1 100.2 100.8 101.8 108 135 158 261 300 −0.8 −2.1 −6.0 11.8 −44.0 −17.5 21.1 42.3 16.0 1.0 1.1 1.3 1.8 2.3 5.7 24.0 47.0 177.5 600.0 23.8 23.5 23.2 22.4 21.3 16.7 10.7 2.24 0.022 — Conductivity (W−1â•–cm−1) 0.0102 0.0334 0.0617 0.1236 0.1836 0.2324 0.1373 0.0907 0.0467 1379 1380 Appendix 6: Properties of Orthophosphoric Acid, H3PO Composition of Strong Phosphoric Acid Solutions P2O5 % P2 O nâ•–=â•– H2 O 67.4 68.7 70.4 71.7 0.263 0.279 0.302 0.321 100 99.7 96.2 91.0 0.3 3.8 8.9 tr 73.5 75.7 77.5 80.5 81.2 82.4 85.0 86.1 87.9 89.4 0.352 0.394 0.438 0.523 0.549 0.594 0.717 0.787 0.920 1.066 77.1 53.9 33.5 13.8 10.9 7.3 2.3 1.5 0.5 1.9 22.1 40.7 50.6 35.0 32.9 23.0 6.4 2.8 0.8 1.5 0.8 4.9 11.5 24,9 22.3 19.3 7.3 3.7 1.6 0.8 nH3PO 0.5 2.7 14.0 15.0 15.9 8.0 4.4 1.8 0.6 0.7 6.6 9.4 12.3 8.2 4.5 1.7 0.6 10 11 12 >12 tr 0.9 5.3 4.7 2.0 1.0 0.1 4.7 4.6 2.2 1.2 10.8 52.0 80.7 89.4 H n + Pn O3n+1 + (n − 1)H O tr 3.1 5.4 8.2 7.7 4.8 2.0 0.7 2.8 2.8 5.7 7.2 4.8 2.1 0.5 1.0 1.7 3.9 6.9 4.9 2.3 0.7 0.2 1.0 2.5 6.4 4.7 2.1 0.9 0.4 1.4 5.9 4.5 2.2 1.0 Note:)>> Substantially the same results (by chromatography) are obtained by dehydration of H3PO4 solutions or by adding P2O5 to H3PO4 solutions Theoretically 100% H3PO4â•–=â•–72.4% P2O5, but this solution contains about 12.7% H4P2O7 Above about 86% P2O5, small amounts of cyclic metaphosphate are also present At 92.3% P2O5 an azeotropic mixture bpâ•–=â•–864°C at 760â•–mm is obtained Composition of Phosphate Buffer Solutions Required pH (25°C) 5.8 6.0 6.2 6.4 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 0.2 M Na2HPO4 (mL) 4.0 6.15 9.25 13.25 18.75 24.50 30.50 36.00 40.50 43.50 45.75 47.35 0.2â•–M NaH2PO4 (mL) 46.0 43.85 40.75 36.75 31.25 25.50 19.50 14.00 9.50 6.50 4.25 2.65 Note:)>> 0.2â•–M contains 35.598â•–g/L of Na2HPO4â•–·â•–2H2O; 31.202â•–g/L of NaH2PO4â•–·â•–2H2O Appendix 7: Abbreviations and Symbols Listed below are miscellaneous examples used in this work and found elsewhere See also Table 1.3 for P-containing compounds, Table 10.7 for amino acids, Table 10.15 for bases, nucleosides and nucleotides and Table 14.4 for symbols in use for analytical techniques Symbols in commercial use for branded products are mostly excluded from all these tables Symbols for the elements are also excluded While some symbols and abbreviations appear to be here to stay, it should be remembered that the use of some of them can be very subject to fashion or personal choice In the case of some single-letter symbols, ambiguity can be avoided by using three letters, and this is favored by the present author An example is to replace s by sol for soluble, sub for sublimes, and sec for seconds A A)>> Å (or A))>> Ac)>> AChE)>> ACP)>> ACS)>> Ad)>> ADA)>> ADP)>> AEP)>> AIDS)>> AlPO)>> AMP)>> APA)>> aq)>> Ar)>> ASTM)>> atm)>> ATP)>> av)>> AZT)>> adenine (base) Angstrom units acetyl CH3,CO– acetylcholinesterase acyl carrier protein American Chemical Society adamantyl American Dental Association adenosine diphosphate aminoethyl phosphonic acid acquired immune deficiency syndrome AlPO4 network adenosine monophosphate available phosphoric acid (in fertilisers) water or aqueous phase aromatic (aryl) American Society for Testing Materials atmosphere(s) unit of pressure adenosine triphosphate average azido thymidine B bar)>> bcc)>> bipy)>> BO)>> BOD)>> bp (or BP))>> unit of pressure body-centred cubic unit cell bipyridyl bond order biological oxygen demand boiling point (usually °C) 1381 1382 BPL)>> BPR)>> BSE)>> Bu, nBu or Bun)>> t Bu)>> Bz)>> Appendix 7: Abbreviations and Symbols bone phosphate of lime, Ca3(PO4)2 Berry pseudorotation mad cow diseasê•– butyl CH3â•–⋅â•–CH2,CH2â•–⋅â•–CH3 – tertiary butyl –C(CH3)3 benzyl –CH2 –Ph C C)>> °C)>> CA)>> cal(s))>> c-AMP)>> CAPP)>> CDP)>> CMP)>> Co-A)>> COD)>> COT or cot)>> CP)>> Cp)>> Cp*)>> CS)>> CTP)>> CVD)>> Cy)>> Cyclam)>> CZP)>> cytidine (base) temperature, degrees Celsius Chemical Abstracts (Chem Abs.) calorie(s) unit of heat quantity cyclic adenosine monophosphate CaH2P2O7 cytidine diphosphate cytidine monophosphate co-enzyme A 1,5 cyclo octadiene 1-cyclo octatetraene C8H8 creatine phosphate (phosphocreatine) cyclopentadienyl pentamethylcyclopentadienyl crystal structure cytidine triphosphate chemical vapour deposition cyclohexyl tetra azacyclotetradecane Ca0.5Zr2(PO4)3 D d or dec)>> D)>> d)>> D)>> DABCO)>> DAP)>> DBP)>> DBU )>> DDT)>> D2EHPA)>> DFP )>> Diglyme)>> DMAP)>> DMF )>> DMSO)>> DNA)>> DPG)>> dppe)>> dppm )>> decomposes, or interatomic distance (in Å) Debye units dextro, right handed (see L) dissociation energy (of a diatomic molecule) 1,4 diazabicyclo(2,2,2) octane (NH4)2HPO4 (nBuO)2P(O)(OH) dibutyl phosphate 1,8 diazabicyclo(5,4,0)undecane-7 p-Clâ•–⋅â•–C6H4â•–⋅â•–CH(CCl3)â•–⋅â•–C6H4 p-Cl as HDEP (PriO)2P(O)F CH3OCH2CH2OCH2CH2OCH3 4-dimethylaminopyridine dimethyl formamide dimethyl sulphoxide deoxyribonucleic acid 2,3 diphospho glucose Ph2Pâ•–⋅â•–CH2CH2â•–⋅â•–PPh2 Ph2Pâ•–⋅â•–CH2â•–⋅â•–PPh2 Appendix 7: Abbreviations and Symbols DSP)>> DTA)>> Na2HPO4 differential thermal analysis E E )>> E )>> E)>> EBPR)>> EDTA)>> EEC)>> EHDP)>> ESR (or esr))>> Et)>> element (usually p-block) (see Z) a symmetry configuration heat of formation (of a bond in a polyatomic molecule) enhanced biophosphorus removal ethylene diamine tetraacetic acid European Economic Community ethane-1-hydroxy-1,1-diphosphonate electron spin resonance spectroscopy ethyl CH3â•–⋅â•–CH2 – F F)>> °F)>> FAD)>> FAO)>> Fc )>> fcc)>> FDA)>> FIA)>> FID)>> FP or fp)>> FRS)>> face-centred cubic unit cell temperature in degrees Fahrenheit flavin adenine dinucleotide Food and Agricultural Organisation (UN) ferrocenyl face-centred cubic unit cell Food and Drug Authority (USA) flow injection analysis flame ionised detector freezing point Fellow of the Royal Society G G)>> g (or gm))>> GA)>> GABA)>> gal)>> GB)>> GB)>> GDP)>> GLC)>> GM)>> gm (or g))>> GMP)>> GTP)>> Guanine base gram (weight) Tabun nerve gas γ-amino butyric acid gallon Great Britain (as UK) Sarin nerve gas guanosine diphosphate gas-liquid chromatography genetically modified grams weight guanosine monophosphate guanosine triphosphate H h or hrs)>> HA)>> hcp)>> HDEP )>> hours of time hydroxy apatite hexagonal close-packed unit cell bis-222 ethylhexylphosphate 1383 1384 HDL)>> HIV)>> HMPA)>> HPLC)>> HSV)>> HUP)>> Hz)>> Appendix 7: Abbreviations and Symbols high-density lipoprotein human immunodeficiency virus hexamethyl phosphoramide high-performance liquid chromatography herpes simplex virus UO2HPO4â•–⋅â•–4H2O Hertz – cycles/s frequency units I I)>> I)>> IMP)>> IR)>> Is)>> IUPAC)>> body-centred cubic unit cell inosine inosine monophosphate infra red 2,4,6 tri isopropylphenyl International Union of Pure and Applied Chemistry J J)>> J)>> coupling constant in NMR Joule, unit of energy K °K)>> Ka)>> kcal)>> KDP)>> kg)>> KMP)>> KTP)>> KZP)>> temperature in degrees Kelvin acid dissociation constant kilocalories KH2PO4 kilogram K2(HPO4) K(TiO)PO4 KZr2(PO4)3 L L)>> l)>> L)>> lb)>> LC50)>> LD50)>> LDL)>> LED)>> liq)>> LNA)>> ligand leuvo, left handed (see D) litre, unit of volume pounds, unit of weight minimum lethal dose (by inhalation) to kill 50% of species exposed minimum lethal dose (by injection) to kill 50% of species exposed low-density lipoproteins light-emitting diode liquid locked DNA M m)>> m-)>> MAP)>> MAPO)>> mirror plane of symmetry meta substitution position (on ring) NH4H2PO4 metal-substituted AlPO Appendix 7: Abbreviations and Symbols MCPA)>> MDA)>> MDF)>> Me)>> Mes)>> Mes*)>> mg)>> min)>> mm)>> MP (or mp))>> MRI)>> m-RNA)>> MRS)>> MRSA)>> MS)>> MSG)>> MSP)>> mw (or MW))>> Ca(H2PO4)2 multiple displacement amplification macro defect-free (cements) methyl –CH3 2,4,6 tri-terbutylphenyl 2,4,6 tri-methylphenyl milligram minute millimetre melting point (usually °C) magnetic resonance imaging messenger ribonucleic acid magnetic resonance spectroscopy methicillin-resistant Staphylococcus aureus molecular spectroscopy monosodium glutamate monosodium phosphate NaH2PO4 molecular weight N NAD+)>> NADH)>> NADP)>> NADPH)>> NATO)>> NHS)>> NLO)>> NMR)>> NPD)>> NPK)>> NTA )>> NTP)>> NZP)>> nicotinamide adenine dinucleotide (oxidised) reduced form of NAD phosphorylated nicotinamide adenine dinucleotide reduced form of NADP North Atlantic Treaty Organisation National Health Service (UK) non-linear optical materials nuclear magnetic resonance nitrogen phosphorus detector N, K2O, P2O5 content (fertilisers) nitrilotriacetic acid normal temperatures and pressures NaZr2(PO4)3 O O)>> OA)>> OCP)>> Oct)>> OMPA)>> OP)>> OPEC)>> OPIDN)>> Ox)>> ortho-substitution position (on ring) optically active octacalcium phosphate octyl octamethylpyrophosphoramide organophosphorus pesticides Organisation of Oil-Producing Countries OP-induced neuropathy oxalate P P)>> p)>> Phosphorus para-substitution position (on ring) 1385 1386 P)>> Pa)>> PAA)>> PAFC)>> PAM)>> PAPS)>> PBA )>> PCR)>> PEP)>> PEO)>> PFA)>> Ph)>> pH)>> Pi (Pi or Pi ))>> pI)>> pKa)>> PNA)>> PNP)>> PPi)>> ppm)>> PPN)>> Pr or Prn)>> i Pr or Pr i )>> PRPP)>> psi)>> PTFE)>> PVA)>> PVC)>> py)>> Appendix 7: Abbreviations and Symbols primitive cubic unit cell Pascalâ•–=â•–unit of pressure phosphonoacetic acid phosphoric acid fuel cell pyridine aldoxime methiodide 3′-phosphoadenosine-5′-phosphosulphate phospho-bioassembly polymerase chain reaction phosphoenol pyruvate polyethylene oxide phosphonoformic acid phenyl radical degree of acidity =log10 [H+] inorganic phosphate isoelectric point (amino acids) acid dissociation constant (strength) a variety of DNA [Ph2P-N-PPh2]− inorganic pyrophosphate parts per million [Ph3P-N-PPh3]+ propyl isopropyl –C3H7 α-5-phosphoribosyl-1-pyrophosphate pounds per square inch pressure polytetrafluoroethylene polyvinyl alcohol polyvinyl chloride pyridine R R)>> R)>> rc)>> RNA)>> rpm)>> r-RNA)>> RSC)>> RT)>> RUBISCO)>> rv or rvw)>> aliphatic (alkyl) (see S) enantiomer covalent radius (in Å) ribonucleic acid revolutions per minute ribosomal RNA Royal Society of Chemistry room temperature ribulose-bis-phosphate carboxylate van der Waal radius (in Å) S s or sec)>> SAMA)>> SAPO)>> SCR or scr)>> SDMA)>> SFM)>> seconds of time scanning auger electron microscopic analysis Si-substituted AlPO sum of covalent radii Na AlH2(OCH2CH2OCH3)2 scanning force spectroscopy Appendix 7: Abbreviations and Symbols SN1)>> SN2)>> Sol or s)>> STM)>> STP)>> STPP)>> Sub)>> SVR or svr)>> SZP)>> unimolecular nucleophilic substitution reaction bimolecular nucleophilic substitution reaction soluble scanning tunneling microscopy standard temperature and pressure sodium tripolyphosphate, Na5P3O10 sublimes sum of van der Waal radii Sr0.5 Zr2(PO4)3 T T)>> TB)>> TBP)>> TEPO)>> TEPP)>> Tg)>> THF or thf)>> THPC)>> TKD)>> TLC)>> Tm)>> TMEDA)>> TMV)>> TNA)>> TOP)>> TOPO)>> TPP)>> TPPO)>> t-RNA)>> TR)>> tripy (or terpy))>> TSP)>> TVA)>> thymine tuberculosis (BuO)3PO triethyl phosphine oxide tetraethyl pyrophosphate glass transition temperature (flexibility point) tetrahydrofuran tetraxis(hydroxymethyl)phosphonium chloride tetrakaidecahedral 9-fold coordination thin layer chromatography melting temperature tetramethylethylene diamine tobacco mosaic virus a variety of DNA trioctyl phosphine trioctylphosphine oxide (C8H18)3P(O) triphenyl phosphine triphenylphosphine oxide transferâ•–=â•–R NA turnstile rotation tripyridyl (terpyridyl) Na3PO4 Tenessee Valley Authority U U)>> UK)>> UN)>> UNESCO)>> US or USA)>> USSR)>> UTP)>> UV)>> uridine United Kingdom (as GB) United Nations United Nations Educational, Scientific and Cultural Organization United States of America Union of Soviet Social Republics uridine triphosphate ultra-violet radiation V vp)>> VX)>> vapour pressure a variety of nerve gas 1387 1388 Appendix 7: Abbreviations and Symbols W WGA)>> WHO)>> whole genome amplification World Health Organisation X X)>> xe)>> any element but often halogen electronegativity value Z Z (see E))>> a symmetry configuration Other symbols in use ∙)>> –)>> ∙)>> ≡)>> )>> — )>> – l )>> λ)>> λ )>> σ )>> σ )>> µ)>> µD)>> η)>> ρ)>> ν)>> Δ)>> δ)>> Ω)>> a vacant site single bond double bond triple bond partial (shared) double bond character a hydrogen bond, a very weak bond, or an unspecified type of covalent bond a centre of symmetry valency state wavelength single bond P-coordination number a coordination mode around an atom dipole moment a coordination mode around an atom density (g/cm3) frequency heat NMR chemical shift downfield (ppm) ohmsâ•–=â•–unit of electrical resistance Appendix 8: Conversion Factors % Põã=õã% P2O5õãìõã0.4364 % Põã=õã% BPLõãìõã0.1997 (BPLõã=õãCa3(PO4)2, bone phosphate of lime) % P2O5õã=õã% Põãìõã2.2914 % P2O5õã=õã% BPLõãìõã0.4576 % BPLõã=õã% Põãìõã5.0073 % BPLõã=õã% P2O5õãìõã2.1853 1õã=õã104õãcmõã=õã1õãm 1õã=õã108õãcmõã=õã100õãpm 1õãp.m.õã=õã102 A (pmõã=õãpico meter) 1õãmõã=õã1õãnmõã=õã10 A (nmõã=õãnanometer) 1õãcalõã=õã103õãkcalõã=õã4.184õãJõã=õã4.184õãìõã107 ergs 1õãkcal/molõã=õã4.184õãìõã103õãJ/molõã=õã4.33634õãìõã102õãeV/mol 1õãeVõã=õã96.485õãk J/molõã=õã23.061õãkcal/mol 1õãatmõã=õã760õãTorrõã=õã101.325õãk Paõã=õã760õãmmHgõã=õã1.0132 bars barâ•–=â•–105â•–Pa 1â•–Pâ•–=â•–10−5 bar pKâ•–=â•––log ka pHâ•–=â•–log10 [H+] 1389 This page intentionally left blank Appendix 9: Shortened Journal Nomenclature Shortened AC AWC BSCF CB CSR HCA IC JACS JCS JCSCC JCSDT JES JINC JMC JOC JSStC MBS MRB NJC Nw OBC Orgmets PCCP PSSi SC SSI T T.Lett TCC ZAC ZK Z.Nat B Other Acta Cryst Angew Chem Bull Soc Chim France Chem Ber Chem Soc Revs Helv Chem Acta Inorg Chem J Am Chem Soc J Chem Soc Chem Commun Dalton Trans J Electrochem Soc J Inorg Nucl Chem J Mater Chem J Org Chem J Solid St Chem Mol Biosystems Mater Res Bull New J Chem Naturwiss Org Biomol Chem Organometallics Phys Chem Chem Phys Phos Sulph Silicon Supramol Chem Sol St Ionics Tetrahedron Tetrahedron Lett Topics Curr Chem Zeit Anorg Chem Z Krist Zeit Naturforsch Chem 1391 ... 1943 Hill and Meyerhof Gross and Mehmel Jansen and Donath Sumner Hall Eggleton Fiske and Subarrow Hall Mehmel and Naray-Szabo ———– ———– Morgan Embden and Meyerhof Lange and Kruger Krebs and Hensleit... Smith Temin and Baltimore Khorana Ashe Sutherland Braye Woodward and Eschenmoser Ginsberg and Lindsell Franz Fleming et al and Marganof et al Sutherland Boyer, Berg and Cohen Niecke and Flick Green... Gier Hall and Spiegelman Horner Marmur and Doty 1963 Cairns Wagner Weil and Vinograd Denney and Relles Dimroth and Hoffmann Ramirez Bangham and Horne Wilkinson Markl Nirenberg, Ochoa and Khorana