• Title/Summary/Keyword: Themodynamics

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Non-equilibrium Monte Carlo Simulations for Critical Flux of Hard Sphere Suspensions in Crossflow Filtration

  • Kim, Albert S.
    • Proceedings of the Membrane Society of Korea Conference
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    • 2008.05a
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    • pp.33-47
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    • 2008
  • Non-equilibrium (irreversible) themodynamics is used to investigate colloidal back-diffusion during crossflow membrane filtration. The chemical potential is generalized as a superposition of equilibrium and irreversible contributions, originating from Brownian and shear-induced diffusion, respectively. As a result, an effective drag force is derived using the irreversible thermodynamics for a particle undergoing both Brownian and shear-induced diffusion in a sheared concentrated suspension. Using the drag force, a hydrodynamic force bias Monte Carlo method is developed for crossflow membrane filtration to determine the critical flux of hard sphere suspensions. Effects of shear rate and particle size on the critical flux are studied, and results show a good agreement with experimental observations reported in the literature.

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Effect of Number and Location of Amine Groups on the Thermodynamic Parameters on the Acridine Derivatives to DNA

  • Kwon, Ji Hye;Park, Hee-Jin;Chitrapriya, Nataraj;Han, Sung Wook;Lee, Gil Jun;Lee, Dong Jin;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.810-814
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    • 2013
  • The thermodynamic parameters for the intercalative interaction of structurally related well known intercalators, 9-aminoacridine (9AA) and proflavine (PF) were determined by means of fluorescence quenching study. The fluorescence intensity of 9AA decreased upon intercalation to DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$]. A van't Hoff plot was constructed from the temperature-dependence of slope of the ratio of the fluorophore in the absence and presence of a quencher molecule with respect to the quencher concentration, which is known as a Stern-Volmer plot. Consequently, the thermodynamic parameters, enthalpy and entropy change, for complex formation was calculated from the slope and y-intercept of the van't Hoff plot. The detailed thermodynamic profile has been elucidated the exothermic nature of complex formation. The complex formation of 9AA with DNA, poly[$d(A-T)_2$] and poly[$d(G-C)_2$] was energetically favorable with a similar negative Gibb's free energy. On the other hand, the entropy change appeared to be unfavorable for 9AA-poly[$d(G-C)_2$] complex formation, which was in contrast to that observed with native DNA and poly[$d(A-T)_2$] cases. The equilibrium constant for the intercalation of PF to poly[$d(G-C)_2$] was larger than that to DNA, and was the largest among sets tested despite the most unfavorable entropy change, which was compensated for by the largest favorable enthalpy. The favorable hydrogen bond contribution to the formation of the complexes was revealed from the analyzed thermodynamic data.

Spectrophotometric Investigation of Oxidation of Cefpodoxime Proxetil by Permanganate in Alkaline Medium: A Kinetic Study (알칼리성 용매에서 과망간에 의한 세프포독심 프록세틸의 산화의 분광광도법적 조사: 속도론적 연구)

  • Khan, Aftab Aslam Parwaz;Mohd, Ayaz;Bano, Shaista;Siddiqi, K. S.
    • Journal of the Korean Chemical Society
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    • v.53 no.6
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    • pp.709-716
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    • 2009
  • A Kinetics pathway of oxidation of Cefpodoxime Proxetil by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in cefpodoxime acid and alkali concentrations. Increasing ionic strength of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with cefpodoxime acid. The latter decomposes slowly, followed by a fast reaction between a free radical of cefpodoxime acid and another molecule of permanganate to give the products. Investigations of the reaction at different temperatures allowed the determination of activation parameters with respect to the slow step of proposed mechanism and fallows first order kinetics. The proposed mechanism and the derived rate laws are consistent with the observed kinetics.