• Title/Summary/Keyword: Enthalpy and entropy

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The Comparative Study in the Oxygen Atom Transfer Reaction by Ruthenium Mono-Oxo Complexes

  • Seok, Won K.;Son, Yung J.;Moon, Sung W.;Lee, Heung N.
    • Bulletin of the Korean Chemical Society
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    • v.19 no.10
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    • pp.1084-1090
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    • 1998
  • The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

Development of Computer Program for Computation of 12 Refrigerant Properties (12가지 냉매 (R11, R12, R13, R14, R21, R22, R23, R113, R114, R500, R502, C318)의 상태치계산 프로그램)

  • Lee Ki Bang;Chung M. K.
    • The Magazine of the Society of Air-Conditioning and Refrigerating Engineers of Korea
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    • v.16 no.5
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    • pp.477-483
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    • 1987
  • A FORTRAN code has been developed to calculate thermodynamic properties of 12 kinds of refrigerants. Input variables are temperature and pressure or temperature only depending on the saturation. The program output properties are specific volume, saturation pressure, enthalpy, entropy, specific heats and speed of sound. Sample calculations show that output properties are in very good agreements with thermodynamic tables and charts.

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Performance Analysis of a Heat Pump Using Refrigerant Mixtures (II) (혼합냉매를 사용한 열펌프의 성능해석 (II))

  • Kim, M.S.;Kim, T.S.;Won, S.P.;Ro, S.T.
    • Korean Journal of Air-Conditioning and Refrigeration Engineering
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    • v.2 no.3
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    • pp.218-225
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    • 1990
  • Studies on the performance of a heat pump using non-azeotropic refrigerant mixtures are done. In order to estimate the thermodynamic properties for the selected non-azeotropic refrigerant mixtures including R22/R152a, R22/R142b, R22/R114 and R13B1/R152a, Peng-Robinson equation of state is adopted. The pressure-enthalpy diagram and the temperature-entropy diagram are plotted for each refrigerant mixture. Considerations on the capacity modulation for the heat pump system using refrigerant mixtures are taken into. Results show that when the heating load varies, the possibility for the capacity modulation is found in the heat pump system using a compressor with constant volume flow rate. Under a constant heating capacity condition in the heat pump system, the coefficient of performance increases when the refrigerant mixtures are used. The volume flow rate decreases as the mass fraction of lower boiler increases in this case.

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Investigation on the Interaction of Gabapentin with Bovine Serum Albumin by Spectroscopic Techniques

  • Ashoka, S.;Seetharamappa, J.;Kandagal, P.B.;Shaikh, S.M.T.
    • Journal of Photoscience
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    • v.12 no.3
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    • pp.113-117
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    • 2005
  • Spectroscopic investigations on the interaction of gabapentin (GBP) with bovine serum albumin (BSA) were reported. The association constant of GBP-BSA system was determined at different temperatures (298, 302, 306 and 311 K) based on the fluorescence quenching results. The GBP was found to quench the fluorescence of BSA through static mechanism. Thermodynamic parameters, the standard enthalpy change, $({\Delta}H^o)$ and the standard entropy change $({\Delta}S^o)$ were observed to be $-9.61{\pm}0.008\;kJ\;mol^{-1}$ and $3.58{\pm}0.011\;Jmol^{-1}K{-1}$ respectively. These indicated that the hydrophobic and electrostatic forces played a role in the interaction of GBP with BSA. The negative value of ${\Delta}G^o$ revealed that the binding reaction is spontaneous. The circular dichroism studies indicated the conformational changes in BSA upon interaction with GBP. The effect of some metal ions on the binding constant was also investigated.

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Electrochemical Approach in Plasma Display Panel Glass Melts doped with Sulfate and Sulfide II. Square Wave Voltammetry

  • Kim, Ki-Dong
    • Journal of the Korean Ceramic Society
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    • v.45 no.7
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    • pp.375-379
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    • 2008
  • Redox behavior was observed in alkali alkaline earth silicate PDP (Plasma Display Panel) glass melts doped with sulfate and sulfide by square wave voltammetry (SWV). According to voltammograms produced at a temperature range of 1100 to $1400^{\circ}C$ and frequency range of 5 to 1000 Hz, both melts showed the same behavior in which there is one reduction peak at low frequency but another peak at an increase of frequency. Based on the frequency dependence of the peak current, self diffusivity of $S^{4+}$ was determined. Based on the temperature dependence of the peak potential, standard enthalpy (${\Delta}H^0$) and standard entropy (${\Delta}S^0$) for the reduction of $S^{4+}$ to $S^0$ were calculated.

The Thermodynamic Study on the Micellization of Carboxybetaine Derivatives (카르복시베타인유도체(誘導體)의 미셀형성(形成)에 대한 열역학적(熱力學的) 연구(硏究))

  • Kim, Yong-In;Kim, Yu-Ok
    • Journal of the Korean Applied Science and Technology
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    • v.6 no.1
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    • pp.67-73
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    • 1989
  • The adsorptions of 2-(dimethylalkylammonio)propanoates with straight chain alkyl group having from 12 to 16 carbon atoms on the liquid-air interface were decreased while lowering the surface tensions at critical micelle concentrations. In micellization, the standard free energy changes per methylene in alkyl group were found to make same contribution to the micelle formation of corresponding C-alkylcarboxybetaines, and the standard enthalpy and entropy changes were studied within the range of temperature from 30 to $50^{\circ}C$.

Flow Mechanism of Dilatant Systems. (Ⅰ) Starch Suspension in Water

  • Bang, Jeong-Hwang;Kim, Eung-Ryul;Hahn Sang-Joon;Ree, Tai-kyue
    • Bulletin of the Korean Chemical Society
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    • v.4 no.5
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    • pp.212-217
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    • 1983
  • Depending on the range of shear rates, temperatures and concentrations, the potato starch suspension in water behaves as a typical dilatant system. The flow curves of the suspension at various concentrations and temperatures were obtained by using a Couette type rotational viscometer. The flow mechanism of the suspension is explained by a structure model of starch granules in the suspension. Based on the experimental results, a general flow equation for the dilatant system is proposed. By analyzing the temperature dependency of the relaxation time, the activation enthalpy and activation entropy for flow in the starch-water suspension were calculated, the former being about 10 kcal/mol.

A Study on Complex Formation of Heavy Metal Ions with N,N'-Oxalybis(salicylaldehyde hydrazone) (N,N'-Oxalylbis(salicylaldehyde hydrazone)과 중금속이온과의 착물 형성에 관한 연구)

  • Kyu-Seong Choi;Ick-Hee Lee;Yong-Nam Kim
    • Journal of the Korean Chemical Society
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    • v.35 no.2
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    • pp.135-141
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    • 1991
  • The complexation of N,N'-oxalylbis(salicylaldehyde hydrazone) (OBSH) with Zn (II), Cd (II), and Pb(II) ions was studied by polarographic method in DMSO solution. The order of stability constants was Cd(II) < Zn(II) < pb(II), and all heavy metal ions formed stable complex with OBSH ligand. The stability constants of complexation were measured at various temperatures. As the results, enthalpy and entropy changes of the complexation were distributed on the complex stabilities.

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The Effect of Temperature on the Critical Micelle Concentration of Cationic Surfactant for Chemical Dispersants (유처리제용 양이온 계면찰성제의 임계미셀농토에서 온도의 효과)

  • kim, Yeoung-Chan
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.14 no.2
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    • pp.145-148
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    • 2008
  • Cationic surfactant can be used as cosmetics and chemical dispersants. The variation of critical micelle concentration (CMC) with temperature over the range $40^{\circ}C$ to $60^{\circ}C$ for N-octadecyl pyridinium bromide was measured by drop methods. Thermodynamic quantities such as free energy, enthalpy, entropy and heat capacity for micellization of N-octadecyl pyridinium bromide in water were calculated by fourth-degree polynominal equation In the result, free energy change was decreased generally by the increment of temperature.

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Mechanistic Studies of the Solvolyses of Cyclohexanesulfonyl Chloride

  • Kang, Suk Jin;Koh, Han Joong
    • Journal of the Korean Chemical Society
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    • v.63 no.4
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    • pp.233-236
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    • 2019
  • In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.