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Correlations between empirical lewis acid–base solvent parameters and the thermodynamic parameters of ion solvation. Part II. Acidity parameters of cations and basicity parameters of anions
Author(s) -
Wrona Piotr K.,
Krygowski Tadeusz M.,
Galus Zbigniew
Publication year - 1991
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610040706
Subject(s) - chemistry , solvation , solvent , lewis acids and bases , acid–base reaction , base (topology) , inorganic chemistry , ion , acidity function , computational chemistry , organic chemistry , aqueous solution , catalysis , mathematical analysis , mathematics
The parameters α, β and γ of the equation W Δ s G f (MX) = α B KT + β E T + γ were calculated and analysed for different salts (MX) in pure solvents and in non‐aqueous solvent–water mixtures (S). Among 109 different equations, only 64 were taken for the final analysis since in the case of 38 equations the parameters B KT and E T were highly correlated. After a statistical analysis and normalization, on the basis of the coefficients α and β obtained, it was found that the ions analysed may be divided into three classes characterized by the different dependences of α on β: class I, H + , Li + , Na + , Rb + , Cs + , Me 4 N + , Cl − , Br − and I − , where α N = 1.074β N + 1.639; class II, Ag + , Cl − , Br − , I − , OAc − , SCN − and N 3 −where α N = 2.057β N + 2.147; and class III, Ph 4 As + , BPh 4 − , Ph 4 C and Ph 4 Ge, where α N is variable and β N is almost constant. Two main conclusions can be drawn out from the results obtained: the behaviour of ions considered as Lewis acids and bases reflects different hard–soft properties of the ions, and the behaviour of the Ph 4 As + ion is different from that of BPh 4 − .