List of Abbreviations Abbreviations and Recommended Values of Some Fundamental Constants and NA Avogadro constant 6.0221.1023mol-1 speed of light in vacuum 2.9979.108ms- absolute permittivity of vacuum 8.8542.10-12 [=1/(Hoco2):Ho =permeability of C2.J-1.m-1 vacuum] elementary charge 1.6022.10-19C h Planck constant 6.6261.10-34J.s R gas constant 8.3145J.K-1.mol-l (or0.08206 L.atm.K-1.mol-) Boltzmann constant (R/NA) 1.3807.10-23J.K- standard molar volume of an ideal 227111.m0l- gas (att=0C and p=100 kPa) ero of the Celsius scale 273.15K ratio of the circumference to the 3.1416 diameter of a circle e 27183 In 10 natural logarithm of ten(In x=In 2.303 10.lg x:lg decadic logarithm) Abbreviations and Symbols for Unitsb) bar bar(=105Pa=105N.m-2 pressure Cg/g centigram/gram weight percent cL/L,cl/ centilitre/litre volume percen cmol/mol centimol/mol mole percent cm centimetre(10-2m) length Cm3 cubic centimetre volume (millilitre mL;10-6 m3) c coulomb electric charge SI C nical Daig a ed Wiley,Chichester,1999: Datensammlung Chemie in SI-Einheiten.3d ed.,Wiley-VCH,Weinheim/Germany,1999
List of Abbreviations Abbreviations and Recommended Values of Some Fundamental Constants and Numbersa,b) NA Avogadro constant 6:0221 1023 mol1 c0 speed of light in vacuum 2:9979 108 m s1 e0 absolute permittivity of vacuum [¼ 1=ðm0 c0 2Þ; m0 ¼ permeability of vacuum] 8:8542 1012 C2 J1 m1 e elementary charge 1:6022 1019 C h Planck constant 6:6261 1034 J s R gas constant 8.3145 J K1 mol1 (or 0.08206 L atm K1 mol1) kB Boltzmann constant (¼ R=NA) 1:3807 1023 J K1 Vm standard molar volume of an ideal gas (at t ¼ 0 C and p ¼ 100 kPa) 22.711 L mol1 T0 zero of the Celsius scale 273.15 K p ratio of the circumference to the diameter of a circle 3.1416 e exponential number and base of natural logarithms (ln) 2.7183 ln 10 natural logarithm of ten (ln x ¼ ln 10 lg x; lg ¼ decadic logarithm) 2.303 Abbreviations and Symbols for Unitsa,b) bar bar (¼ 105 Pa ¼ 105 N m2) pressure cg/g centigram/gram weight percent cL/L, cl/l centilitre/litre volume percent cmol/mol centimol/mol mole percent cm centimetre (102 m) length cm3 cubic centimetre (millilitre mL; 106 m3) volume C coulomb electric charge a) I. Mills, T. Cvitasˇ, K. Homann, N. Kallay, and K. Kuchitsu: Quantities, Units and Symbols in Physical Chemistry. 2nd ed., Blackwell Scientific Publications, London, 1993. b) G. H. Aylward and T. J. V. Tristan: SI Chemical Data. 4th ed., Wiley, Chichester, 1999; Datensammlung Chemie in SI-Einheiten. 3rd ed., Wiley-VCH, Weinheim/Germany, 1999.
XVIII List of Abbreviations oC degrees centigrade(Celsius) temperature dm> cubic decimetre(litre L:10-m) joule energy kJ kiloioule (103 J) energy K kelvin temperature L,1 litre (1 dm3;10-3 m3) volume m metre length min minute time mol mole amount of substance megapascal(106 Pa) pressure mT millitesla (10-3 T) magnetic flux density (magnetic field) m nanometre(10-9m) length pascal (1 N.m-2 =10-5 bar) pressure percent(%) part per hundred (10-2) dimensionless fraction Ppm part per million(10-) dimensionless fraction second time Abbreviations and Symbols for Properties activity of solute i a('H) mT(=10-3T) the solvent's anion-solvating tendency or 'acity'(Swain) AN mber based or (Gutmann and Meyer) electric polarizability of a molecule, C2.m2.J-lor4r0·cm3 polarizability volume empirical parameter of solvent hydrogen-bond donor acidity(Taft and Kamlet) empirica of solvent Lewis basicity (Palm and Koppel) IR based empirical parameter of solvent Lewis basicity(Palm and Koppel)
C degrees centigrade (Celsius) temperature dm3 cubic decimetre (litre L; 103 m3) volume J joule energy kJ kilojoule (103 J ) energy K kelvin temperature L, l litre (1 dm3; 103 m3) volume m metre length min minute time mol mole amount of substance MPa megapascal (106 Pa) pressure mT millitesla (103 T ) magnetic flux density (magnetic field) nm nanometre (109 m) length Pa pascal (1 N m2 ¼ 105 bar) pressure percent (%) part per hundred (102) dimensionless fraction ppm part per million (106) dimensionless fraction s second time Abbreviations and Symbols for Propertiesc) ai activity of solute i að1HÞ ESR hyperfine coupling constant (coupling with 1H) mT (¼ 103 T ) Aj the solvent’s anion-solvating tendency or ‘acity’ (Swain) AN solvent acceptor number, based on 31P NMR chemical shift of Et3PO (Gutmann and Meyer) a electric polarizability of a molecule, polarizability volume C2 m2 J1 or 4pe0 cm3 a empirical parameter of solvent hydrogen-bond donor acidity (Taft and Kamlet) B empirical parameter of solvent Lewis basicity (Palm and Koppel) BMeOD IR based empirical parameter of solvent Lewis basicity (Palm and Koppel) c) P. Mu¨ller: Glossary of Terms used in Physical Organic Chemistry – IUPAC Recommendations 1994. Pure Appl. Chem. 66, 1077 (1994). XVIII List of Abbreviations
List of Abbreriations XIX IR based empirical parameter of solvent Lewis basicity (Koppel and Paju;Makitra) the solvent's cation-solvating tendency or'basity'(Swain) empirical parameter of solvent hydrogen-bond acceptor basicity (Taft and Kamlet) MPa(=105 Pa) G,c() molar conc entration of solute i mol.L-1 CA.CB Lewis acidity and Lewis basicity parameter (Drago) 772 critical micelle concentration mol.I-I molar bond-dissociation energy of the kJ.mol-1 bond between H and A vent Lewis cycloa ion reaction (Nagai et al.) DN solvent donor number(Gutmann) kcal.mol- =-△HD-SbC1s DNN normalized solvent donor number (Marcus) Hildebrand's solubility paran ter MPa2 chemical shift of NMR signals ppm solvent polarizability correction term (Taft and Kamlet) E energy,molar energy kJ.mol-1 E electric field strength V.m enol constant(K.H.Meyer) E empirical parameter of solvent Lewis acidity (Palm and Koppel) EA.E awoaay kJ.mol-1 EA:EB Lewis acidit EA electron affinity kJ.mol-1 E empirical solvent Lewis basicit sed on the orptic of an empirical solvent polarity parameter, kcal.mol-1 based on the d→π'absorption of a molybdenum complex(Walther)
BPhOH IR based empirical parameter of solvent Lewis basicity (Koppel and Paju; Makitra) Bj the solvent’s cation-solvating tendency or ‘basity’ (Swain) b empirical parameter of solvent hydrogen-bond acceptor basicity (Taft and Kamlet) c cohesive pressure (cohesive energy density) of a solvent MPa (¼ 106 Pa) ci; cðiÞ molar concentration of solute i mol L1 CA; CB Lewis acidity and Lewis basicity parameter (Drago) cmc critical micelle concentration mol L1 DHA molar bond-dissociation energy of the bond between H and A kJ mol1 Dp empirical parameter of solvent Lewis basicity, based on a 1,3-dipolar cycloaddition reaction (Nagai et al.) DN solvent donor number (Gutmann) [¼ DH(DaaSbCl5)] kcal mol1 DN N normalized solvent donor number (Marcus) d; dH Hildebrand’s solubility parameter MPa1=2 d chemical shift of NMR signals ppm d solvent polarizability correction term (Taft and Kamlet) E energy, molar energy kJ mol1 E electric field strength V m1 E enol constant (K. H. Meyer) E empirical parameter of solvent Lewis acidity (Palm and Koppel) EA; Ea Arrhenius activation energy kJ mol1 EA; EB Lewis acidity and Lewis basicity parameter (Drago) EA electron a‰nity kJ mol1 E N B empirical solvent Lewis basicity parameter, based on the n ! p absorption of an aminyloxide radical (Mukerjee; Wrona) EK empirical solvent polarity parameter, based on the d ! p absorption of a molybdenum complex (Walther) kcal mol1 List of Abbreviations XIX
XX List of Abbreviations empirical solvent polarity parameter based on the d-absorption of a tungsten complex(Lees) kJ·mol-!or kcal.mol-l Er(30) empirical solvent polarity parameter, kcal mol- based on the intramolecular CT absorption of a pyridinium-N- phenolate betaine dye(Dimroth and Reichardt) E normalized Er(30)solvent polarity parameter(Reichardt) empirical solvent polarity parameter, kcal.mol- based on the n一π*absorption of an S-oxide (Walter) EPA electron-pair acceptor EPD electron-pair donor relative permittivity (=/Eo) ("dielectric constant") 元'absorptiono G IR based empirical solvent polarity parameter(Schleyer and Allerhand) G standard molar Gibbs energy change kI.mol-! AG standard molar Gibbs energy of kJ.mol- activation △Go standard molar Gibbs energy of kI.mol- solvation △Gt standard molar Gibbs energy of kJ.mol-1 hydration △G(X,0→S), standard molar Gibbs energy of kJ.mol-1 △GX,W-S) transfer of solute X from a reference solvent(O)or water(W)to another solvent(S) activity coefficient of solute i AH standard molar enthalpy change kI.mol- AH standard molar enthalpy of activation kJmol- △H molar enthalpy (heat)of kJ:mol vapourization Ho acidity function(Hammett) A hydrogen-bond acceptor
E MLCT empirical solvent polarity parameter, based on the d ! p absorption of a tungsten complex (Lees) ET molar electronic transition energy, molar electronic excitation energy kJ mol1 or kcal mol1 ETð30Þ empirical solvent polarity parameter, based on the intramolecular CT absorption of a pyridinium-Nphenolate betaine dye (Dimroth and Reichardt) kcal mol1 E N T normalized ETð30Þ solvent polarity parameter (Reichardt) ESO T empirical solvent polarity parameter, based on the n ! p absorption of an S-oxide (Walter) kcal mol1 EPA electron-pair acceptor EPD electron-pair donor er relative permittivity (¼e=e0) (‘‘dielectric constant’’) F empirical solvent polarity parameter, based on the n ! p absorption of ketones (Dubois) G IR based empirical solvent polarity parameter (Schleyer and Allerhand) DG standard molar Gibbs energy change kJ mol1 DG0 standard molar Gibbs energy of activation kJ mol1 DG solv standard molar Gibbs energy of solvation kJ mol1 DG hydr standard molar Gibbs energy of hydration kJ mol1 DG t ðX; O!SÞ, DG t ðX; W!SÞ standard molar Gibbs energy of transfer of solute X from a reference solvent (O) or water (W) to another solvent (S) kJ mol1 gi activity coe‰cient of solute i DH standard molar enthalpy change kJ mol1 DH0 standard molar enthalpy of activation kJ mol1 DHv molar enthalpy (heat) of vapourization kJ mol1 H0 acidity function (Hammett) HBA hydrogen-bond acceptor XX List of Abbreviations
List of Abbreriations XXI HBD hydrogen-bond donor HOMO highest occupied molecular orbital E,I IP ionization energy kJ.mol-1 gas-chromatographic retention index (Kovats) NMR spin-spin coupling constant Hz rate c for monom olecula (L·mol-1s-l (n=1)and bimolecular (n =2) reactions rate constant in a reference solvent or (L.mol-1)-1.s-1 in the gas phase for monomolecular (=1)and bimolecular reactions n=2) ko the rate (Lmo-s1wit constant of unsub n=lor2 K,Ks equilibrium constant(concentration (mol.L-)24 basis:o=stoichiometric number) Ka:Kb acid and base ionization constants (mol L-1)z Kauto autoionization ion product, mol2.L-2 autoprotolysis constant equilibrium constants of association, (mol.L-1) dissociation,ionization,resp tautomerization reactions Kolw 1-octanol/water partition constant (Hansch and Leo) KB kauri-butanol number L desmotropic constant(K.H.Meyer) LUMO lowest unoccupied molecular orbital wavelength nm(∈10-9m) m mass of a particle g relative molecular mass of a substance ("molecular weight) M miscibility number(Godfrey MH microscopic hydrophobicity parameter of substituents(Menger) permanent electric dipole moment of C.m(or D) a molecule induced electric dipole moment of a C.m(or D) molecule
HBD hydrogen-bond donor HOMO highest occupied molecular orbital Ei;I;IP ionization energy kJ mol1 I gas-chromatographic retention index (Kova´ts) J NMR spin-spin coupling constant Hz k rate constant for monomolecular (n ¼ 1) and bimolecular (n ¼ 2) reactions (L mol1)n1 s1 k0 rate constant in a reference solvent or in the gas phase for monomolecular (n ¼ 1) and bimolecular reactions (n ¼ 2) (L mol1)n1 s1 k0 in Hammett equations the rate constant of unsubstituted substrates (L mol1)n1 s1 with n ¼ 1 or 2 K; Kc equilibrium constant (concentration basis; v ¼ stoichiometric number) (mol L1)Sv Ka; Kb acid and base ionization constants (mol L1)Sv Kauto autoionization ion product, autoprotolysis constant mol2 L2 KAssoc; KDissoc, Kion; KT equilibrium constants of association, dissociation, ionization, resp. tautomerization reactions (mol L1)Sv Ko=w 1-octanol/water partition constant (Hansch and Leo) KB kauri-butanol number L desmotropic constant (K. H. Meyer) LUMO lowest unoccupied molecular orbital l wavelength nm (¼ 109 m) m mass of a particle g Mr relative molecular mass of a substance (‘‘molecular weight’’) M miscibility number (Godfrey) MH microscopic hydrophobicity parameter of substituents (Menger) m empirical solvent softness parameter (Marcus) m permanent electric dipole moment of a molecule C m (or D) mind induced electric dipole moment of a molecule C m (or D) List of Abbreviations XXI