• 제목/요약/키워드: Preferential solvation

검색결과 5건 처리시간 0.016초

Preferential Solvation and Statistical Analysis for Solvent Polarity Parameters in MeOH Binary Mixtures

  • Sakong Yeol;Yoo Seoung-Kyo;Lee Ikchoon
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.636-642
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    • 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.

Using the New Developed Equation to Reproduce the Enthalpies of Transfer of Urea from Water to Aqueous Ethanol, Propan-1-ol and Acetonitrile at 298 K

  • Behbehani, G. Rezaei;Tazikeh, E.;Saboury, A.A.
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.208-210
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    • 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.

Facile Evaluation of Thermodynamic Parameters for Reverse Thermochromism of Indolinobenzospiropyran-6-carboxylates in Aqueous Binary Solvents

  • Keum, Sam-Rok;Ma, So-Young;Lim, Hyun-Woo;Han, Tae-Hwi;Choi, Kyu-Hyun
    • Bulletin of the Korean Chemical Society
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    • 제33권8호
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    • pp.2683-2688
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    • 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.

The Measurement of Tranfer Enthalpy in Mixed Solvent (Part 2) Solvent Effects on Nucleophilic Substitution Reactions of Ethyl and 2-Phenylethyl Benzenesulfonates

  • 허철;이해황;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제16권1호
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    • pp.53-58
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    • 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.

Inverse Gas Chromatography를 이용한 Poly(dimethylsiloxane)-Solvent계의 열역학적 연구 (Thermodynamic Study of Poly(dimethylsiloxane)-Solvents Systems Using Inverse Gas Chromatography)

  • 조정모;강춘형
    • 공업화학
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    • 제10권5호
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    • pp.718-725
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    • 1999
  • Inverse gas chromatography(IGC) 방법은 고분자-용매 계의 열역학적 특성을 신속하고 정확하게 결정할 수 있는 신뢰할 만한 방법 중 하나이다. 본 연구에서는 유한 농도에서의 IGC 방법을 사용하여 poly(dimethylsiloxane)(PDMS)과 물, 에탄올, 그리고 이소프로판올과의 상호작용을 정량적으로 결정하였다. 이를 위하여 고정상 내 용매의 체류시간으로부터 Flory-Huggins의 상호작용 계수를 산출하여 PDMS와 용매간의 소수성 상호작용을 의미하는 큰 양의 값(2$2.0{\times}10^{-3}mol/g$이었다. 또한 선형고분자에 대한 Kirkwood-Buff-Zimm(KBZ) 적분을 행하여 고분자와 용매의 분자분포 구조를 추정하였다. 이로부터 물분자는 PDMS에 대하여 용매화되지 않고 자체 분자끼리 부분적인 클러스트를 형성하며, 에탄올과 이소프로판올에서는 탄소수가 증가함에 따라 균일한 혼합에 가까운 분자분포의 구조적 성질을 추정할 수 있었다.

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