• 제목/요약/키워드: Excess Gibbs Energy

검색결과 13건 처리시간 0.018초

Dissolution behavior of SrO into molten LiCl for heat reduction in used nuclear fuel

  • Kang, Dokyu;Amphlett, James T.M.;Choi, Eun-Young;Bae, Sang-Eun;Choi, Sungyeol
    • Nuclear Engineering and Technology
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    • 제53권5호
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    • pp.1534-1539
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    • 2021
  • This study reports on the dissolution behavior of SrO in LiCl at varying SrO concentrations from low concentrations to excess. The amount of SrO dissolved in the molten salt and the species present upon cooling were determined. The thermal behavior of LiCl containing various concentrations of SrO was investigated. The experimental results were compared with results from the simulated results using the HSC Chemistry software package. Although the reaction of SrO with LiCl in the standard state at 650 ℃ has a slightly positive Gibbs free energy, SrO was found to be highly soluble in LiCl. Experimentally determined SrO concentrations were found to be considerably higher than those present in used nuclear fuel (<2 g/kg). As Sr-90 is one of the most important heat-generating nuclides in used nuclear fuel, this finding will be impactful in the development of fast, simple, and proliferation-resistant heat reduction processes for used nuclear fuel without the need for separating nuclear materials. Heat reduction is important as it decreases both the volume necessary for final disposal and the worker handling risk.

Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism

  • Park, Yu-Chul;Cho, Young-Je
    • Bulletin of the Korean Chemical Society
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    • 제11권4호
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    • pp.309-313
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    • 1990
  • The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

투과증발에 의한 이소프로판올 수용액의 분리특성 (Separation Characteristics of Aqueous Isopropanol Solution by Pervaporation)

  • 이규일;김현진;김진환
    • 멤브레인
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    • 제6권1호
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    • pp.22-31
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    • 1996
  • 35$^{\circ}$C에서 polydimethytsiloxane(PDMS)막에 의한 이소프로판올수용액의 투과증발실험을 행하여 이소프로판올의 부피분율이 0.5~0.7범위에서 이상적인 투과속도로부터 가장 크게 벗어났다. 이소프로판올의 가소화 영향은 물의 투과를 증가시키는 데 비하여 물의 존재는 이소프로판올의 투과를 감소시키는 경향을 나타내었다. 혼합물에서 농도에 의존하는 확산계수를 Vignes식으로 나타내고, Flory-Huggins열역학과 Maxwell-Stefan식을 이용하여 투과속도와 선택도를 예측하였다. 이소프로판올과 물 사이의 Flory-Huggins상호작용계수는 과잉Gibbs에너지를 이용하여 계산하였으며 각 액체 성분과 고분자 사이의 상호작용계수는 평행팽윤 실험에 의하여 결정하였다. 이론적으로 예측한 투과속도는 35%이내의 오차범위에서 실험값과 일치하였으며, 투과선택도는 전 농도 범위에서 실험값과 이론값이 잘 일치하였다.

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