Ionization constants of weak acids and bases in organic solvents

被引:144
作者
Sarmini, K [1 ]
Kenndler, E [1 ]
机构
[1] Univ Vienna, Inst Analyt Chem, A-1090 Vienna, Austria
来源
JOURNAL OF BIOCHEMICAL AND BIOPHYSICAL METHODS | 1999年 / 38卷 / 02期
关键词
organic solvents; pK(a); values; enthalpy/entropy; ionization; electrostatic effects; solute-solvent interactions;
D O I
10.1016/S0165-022X(98)00033-5
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
A discussion of the influence of organic solvents on pK(a) values is presented. Enthalpy and entropy of ionization in organic solvents are compared with aqueous systems. The impact of the solvent on the ionization constants is interpreted based on the free energy of transfer applied to all particles involved in the ionization reaction of acids and bases, and the concept of the 'medium effect' on these species. The limitation of Born's approach (which takes into account only electrostatic effects on the ionization equilibrium) is demonstrated and the importance of solute-solvent interactions on the change of the pK(a) values emphasized. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:123 / 137
页数:15
相关论文
共 56 条
[11]   SOLUTE-SOLVENT INTERACTIONS .2. RELATIVE ACTIVITIES OF ANIONS IN ACETONITRILE AND WATER [J].
COETZEE, JF ;
CAMPION, JJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (11) :2517-&
[12]  
Conway B., 1981, ION HYDRATION CHEM B
[13]  
COURTOTCOUPEZ J, 1968, CR ACAD SCI C CHIM, V267, P1475
[14]  
Covington A.K., 1973, Physical Chemistry of Organic Solvent Systems, P1, DOI [10.1007/978-1-4684-1959-7_1, DOI 10.1007/978-1-4684-1959-7_1]
[15]  
CRIIS CM, 1973, PHYSICAL CHEM ORGANI, P253
[16]   STANDARD POTENTIALS OF POTASSIUM ELECTRODES AND ACTIVITY COEFFICIENTS AND MEDIUM EFFECTS OF POTASSIUM CHLORIDE IN ETHANOL-WATER SOLVENTS [J].
DILL, AJ ;
ITZKOWIT.LM ;
POPOVYCH, O .
JOURNAL OF PHYSICAL CHEMISTRY, 1968, 72 (13) :4580-&
[18]   THE MEASUREMENT AND CORRELATION OF ACID DISSOCIATION CONSTANTS FOR CARBOXYLIC ACIDS IN THE SYSTEM ETHANOL WATER - ACTIVITY COEFFICIENTS AND EMPIRICAL ACTIVITY FUNCTIONS [J].
GRUNWALD, E ;
BERKOWITZ, BJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1951, 73 (10) :4939-4944
[19]   THE ACIDITY AND BASICITY SCALE IN THE SYSTEM ETHANOL WATER - THE EVALUATION OF DEGENERATE ACTIVITY COEFFICIENTS FOR SINGLE IONS [J].
GUTBEZAHL, B ;
GRUNWALD, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1953, 75 (03) :565-574