Substitution at saturated carbon. Part 26. A complete analysis of solvent effects on initial states and transition states for the solvolysis of the t-butyl halides in terms of G, H, and S using the unified method

Abraham, Michael H.; Grellier, Priscilla L.; Nasehzadeh, Asadollah; Walker, Rosemary A. C.

doi:10.1039/p29880001717

Cited by 49 publications

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“…The data that we have collected on solubility or partition of non-electrolytes is in Table 2 [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30]. We distinguish, for the moment, data that refers to dry benzonitrile and to wet (that is water-saturated) benzonitrile, and include in Table 2 an 'indicator variable', I, for dry or wet benzonitrile.…”

Section: Resultsmentioning

confidence: 99%

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

Abraham

Acree

2011

Thermochimica Acta

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Equations have been constructed for the transfer of 64 neutral solutes from water and from the gas phase to the solvent benzonitrile. The equations contain five descriptors and can be used to predict further values of the water-benzonitrile and gas-benzonitrile partition coefficients for a wide range of solutes. The water-benzonitrile equation has been extended to include ions and ionic species derived from acids by loss of a proton and bases by acceptance of a proton. Only two further descriptors are needed, one for anions and one for cations. A previous equation for transfer of neutral solutes from water to nitrobenzene has also been extended to include ions and ionic species. Comparison of the equations for transfer to benzonitrile and to nitrobenzene shows that the two solvents behave quite similarly, although benzonitrile as a solvent is a stronger hydrogen bond base.

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Section: Resultsmentioning

confidence: 99%

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

Abraham

Acree

2011

Thermochimica Acta

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“…The results of Abraham et al [13] cast doubts by two reasons. First, the DH and DS values in 7 of the 23 solvents studied were only estimated; moreover, in certain cases (THF, AcOEt, PhCl, and C 6 H 6 ) estimated were also the DG values.…”

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confidence: 89%

“…The lack of rate effect of solvent nucleophilicity is explained by a compensation effect: Increase in solvent nucleophilicity increases both DH 0 Tr (rate decrease) and DS 0 Tr (rate increase). In t-BuBr heterolysis, the DH 3DS (R 0.64) and DG 3DS (R 0.08) compensation effects are lacking [13].…”

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Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XXXVIII. Correlation analysis of solvent effects on the activation parameters of heterolysis of t-BuBr and t-BuI

2004

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Heterolysis of t-BuBr and t-BuI in aprotic solvents involves a DH 3DS compensation effect.The DG of t-BuBr heterolysis in aprotic solvents decreases with increasing solvent polarity and cohesion, whereas the respective value for t-BuI heterolysis decreases with increasing solvent polarity, nucleophilicity, and polarizability. In protic solvents, a negative effect of nucleophilic solvation is observed.The correlation analysis of the effects of solvent parameters (ionizing ability, polarity, polarizability, electrophilicity, nucleophilicity, cohesion) on the rates of monomolecular heterolysis reactions (SN1, E1, solvolysis) in terms of many-parameter linear free energy equations has given insight into the nature of solvation effects [237]. Most commonly, solvent effects on log rate constants or, what is the same, activation Gibbs energies are studied. However, these values are strongly temperature-dependent [438]. The activation Gibbs energy is determined by the activation enthalpy and entropy (DG = DH 3 TDS ), which are almost invariable in the experimental temperature range. Studying solvent effects on these activation parameters makes it possible to understand the nature of solvation effects and to reveal the mechanism of transition state solvation [9313]. However, such studies have been few in number.

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“…The authors calculated the activity coefficients of both mixture components from the observed total vapor pressures. Abraham and coworkers [47] published infinite dilution activity coefficient data for 2-chloro-2-methylpropane and 2-bromo-2- …”

Section: Dataset and Computation Methodologymentioning

confidence: 99%

Abraham model correlations for estimating solute transfer of neutral molecules into anhydrous acetic acid from water and from the gas phase

Stovall

Schmidt

Dai

et al. 2015

Journal of Molecular Liquids

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Experimental infinite dilution activity coefficient data, gas-to-liquid partition coefficient data, and solubility data have been combined from the published literature for neutral organic molecules and inert gases dissolved in anhydrous acetic acid. The compiled experimental data were transformed into molar solubility ratios, water-to-acetic acid (P) and gas-to-acetic acid (K) using standard thermodynamic relationships. The derived Abraham model correlations described the observed solubility and partition coefficient data of neutral organic compounds to within 0.18 log units (or less). Our analysis further showed that acetic acid solvent has considerable hydrogen-bond acidity, in agreement with the proposed linear structure for the solvent, and in terms of solubility related properties is not an unusual solvent at all.

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Substitution at saturated carbon. Part 26. A complete analysis of solvent effects on initial states and transition states for the solvolysis of the t-butyl halides in terms of G, H, and S using the unified method

Cited by 49 publications

References 0 publications

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XXXVIII. Correlation analysis of solvent effects on the activation parameters of heterolysis of t-BuBr and t-BuI

Abraham model correlations for estimating solute transfer of neutral molecules into anhydrous acetic acid from water and from the gas phase

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