• Bulletin of the Korean Chemical Society
• /
• v.13 no.6
• /
• pp.636-642
• /
• 1992

Preferential solvation (PS) phenomena of solutes based on solvent polarity, $E_T$ and AN, were studied by UV/vis. and NMR spectra in MeOH binary mixtures. According to the extent of solvent-solvent interaction, different solvation phenomena were found. PS concept was applied to explain the reactivity of tert-butyl halides solvolysis. The findings of solvation phenomena have been related to the rate of solvolysis and PS suggested as a reason for the solvent dependence of the rates of reaction. Moreover, we found that the results of principal components analysis using six parameters are in good accordance with the results of PS phenomena in mixed methanol systems.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.2
• /
• pp.208-210
• /
• 2006

The enthalpies of transfer, $\Delta H_t^\theta$, of urea from water to aqueous ethanol, EtOH, propan-1-ol, PrOH, and acetonitrile, MeCN, are reported and analysed in terms of the new solvation theory. The analyses show that the solvation of urea is random in the considered solvent mixtures. It is also found that urea interact more strongly with EtOH or PrOH than water.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.8
• /
• pp.2683-2688
• /
• 2012

The position of the thermodynamic equilibrium for reverse thermochromic spiropyran 6-carboxylates (SP-COOHs) was easily determined in aqueous binary mixtures, such as water-methanol, water-acetonitrile and water-dimethyl sulfoxide. The existence of more than one type of interconvertible species of the ring-opened form of SP-COOH in aqueous binary solvents enables us to evaluate the molar extinction coefficients of the ring-opened species of SP-COOH and to obtain the thermodynamic parameters.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.1
• /
• pp.53-58
• /
• 1995

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

• Applied Chemistry for Engineering
• /
• v.10 no.5
• /
• pp.718-725
• /
• 1999

In order to investigate the interaction characteristics of poly(dimethylsiloxane) (PDMS) with various solvents such as water, ethanol, and iso-propanol, Inverse Gas Chromatography(IGC) at finite concentration, which is a very fast, accurate, and thus promising technique in thermodynamic study of polymer systems, is employed. By measuring the specific retention volumes of the probes, the interaction parameters are calculated by means of the Flory-Huggins equation. From the results, the interaction parameters of the probes are, as expected due to the hydrophobicity of the polymer, found to be of large positive values (2$2.0{\times}10^{-3}mol/g$. For the linear PDMS, interpretation of the space distribution of molecules is performed by the Kirkwood-Buff-Zimm(KBZ) integrals, which give intuitive information about physical properties. From the KBZ integrals, water does not show the tendency of preferential solvation with the PDMS but formed self-cluster. The larger solvent molecules show a stronger tendency to distribute more randomly in the mixture.