The effect of hydroxylic solvents on the solvolysis of t-butyl chloride; calculation of the cavity terms

Solvolysis rates of diarylmethyl p-nitrobenzoates in aqueous ethanol. The question of solvent assistance and the validity of selectivity probes

“…Abraham and his co-workers have most cogently pointed out that the act of substrate ionization in solu-tion must be accompanied by creation of a solvent cavity, necessarily different in size and shape from the cavity accommodating the initial state, before the solvent can electrostatically stabilize the polar TS. [30][31][32] Thus in calculating free energies of transfer of transition states from a standard solvent to a solvent system of interest by considering 8AGX, the solvent effect on the observed free energy of activation, and AGto, the free energy of transfer of the initial state solute, via equation (3), one must be certain to correct for the cavity or size…”

Determination of partition coefficients of halobenzenes in heptane/water and 1-octanol/water systems and comparison with the scaled particle calculation

“…The SPT has the advantage of calculating microscopic cavity formation energy without any ambiguous fitting parameter for any kind of solution systems including an aqueous solution. Some applications of the SPT have been reported on the various solution processes, e.g., the gas solubility (9), the salt effect {.10), the hydrophobic interaction {11), the solvation of electrolyte ( 12), and the solvolysis (13). Thus far, no systematic application of the SPT has appeared in the field of the solvent extraction chemistry.…”

Um Curso Prático de Cinética Química — 4. Funções termodinâmicas de transferência: efeito de solvente

“…Na Tabela 4 apresentam-se valores de energia de Gibbs de transferência de vários solutos alguns dos quais, face às suas dimensões de separação de carga, se prevê serem modelos adequados para o estado inicial ou de transição da reacção de solvólise de t-BuCl [13,14]. As Figuras 3 e 4 mostram a correlação que se obtém entre a energia de Gibbs de transferência do reagente t-BuCl (V = 111 cm' moi'; = 2 D) e a do soluto modelo pentano (V = 116 cm' mol-'; 1.1 0 D) e a energia de Gibbs de transferência do correspondente complexo activado e do soluto modelo tetrametilamónio (V = 107 cm' moi-'; par-iónico).…”