• Title/Summary/Keyword: Enthalpy and entropy

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Redox Behavior of Sn and S in Alkaline Earth Borosilicate Glass Melts with 1 mol% Na2O

  • Kim, Ki-Dong;Kim, Hyo-Kwang
    • Journal of the Korean Ceramic Society
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    • v.46 no.3
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    • pp.271-274
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    • 2009
  • Redox investigation of Sn and S ion was attempted in alkaline earth borosilicate glass melts with only 1 mol% $Na_2O$ by means of Square Wave Voltammetry (SWV). According to voltammograms, there was only one peak due to $Sn^{4+}/Sn^{2+}$ in melt doped with $SnO_2$. The calculated standard enthalpy and entropy of the reduction of $Sn^{4+}$ to $Sn^{2+}$ were 116kJ/mole and 62 J/mol K, respectively. The determined redox ratio, [$Sn^{2+}$] / [$Sn^{4+}$] in the temperature range of $1300{\sim}1600^{\circ}C$ was in $0.4{\sim}2.1$. On the contrary, in the voltammogram of melt doped with $BaSO_4$ there was no peak due to $S^{4+}/S^o$ but shoulder that might be attributed to the adsorption of sulfur at the electrode. The absence of the peak related with $S^{4+}/S^o$ was discussed from the view-point of the thermal decomposition behavior of $BaSO_4$ in the glass batch.

A Study on the Organic Rankine Cycle Using R245fa (냉매(R245fa)를 이용한 유기랭킨 사이클에 관한 연구)

  • Cho, Soo-Yong;Cho, Chong-Hyun;Kim, Jinhan
    • The KSFM Journal of Fluid Machinery
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    • v.16 no.3
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    • pp.10-17
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    • 2013
  • The organic Rankine cycle has been widely used to convert the renewable energy such as the solar energy, the geothermal energy, or the waste energy etc., to the electric power. Some previous studies focused to find what kind of refrigerant would be a best working fluid for the organic Rankine cycle. In this study, R245fa was chosen to the working fluid, and the cycle analysis was conducted for the output power of 30kW or less. In addition, properties (temperature, pressure, entropy, and enthalpy etc.) of the working fluid on the cycle were predicted when the turbine output power was controlled by adjusting the mass flowrate. The configuration of the turbine was a radial-type and the supersonic nozzles were applied as the stator. So, the turbine was operated in partial admission. The turbine efficiency and the optimum velocity ratio were considered in the cycle analysis for the low partial admission rate. The computed results show that the system efficiency is affected by the partial admission rate more than the temperature of the evaporator.

Thermal Inactivation of Lipase from Geotrichum candidum (Geotrichum candidum Lipase의 열불활성(熱不活性)에 관(關)하여)

  • Park, K.H.
    • Applied Biological Chemistry
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    • v.20 no.1
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    • pp.101-104
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    • 1977
  • Lipase from Geotrichum candidum was heat inactivated in 0.1M phosphate buffer solution. The thermal inactivation followed first order kinetics for the range of temperatures $50^{\circ}-80^{\circ}C$ except at $50^{\circ}C$. The changes in enthalpy, entropy and Gibbs free energy at $60^{\circ}C$ were 120.4 kJ/mol, 73.0 J/mol K and 96.9 kJ/mol respectively a value of $19^{\circ}C$(Geotrichum candidum lipase) is greater than that of lipases from milk and pancreas. The effect of detergents, lecithin and linoleic acid or the thermal inactivation of lipase was found to be negligible.

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Kinetics of the Bromine-Exchange Reaction of Gallium Bromide with Isopropyl Bromide in Nitrobenzene (니트로벤젠 용액내에서의 브롬화갈륨과 브롬화이소프로필의 브롬 교환 반응)

  • Choi, Sang-Up
    • Journal of the Korean Chemical Society
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    • v.14 no.1
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    • pp.85-89
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    • 1970
  • The rate of the bromine-exchange reaction between gallium bromide and isopropyl bromide in nitrobenzene was measured at 19$^{\circ},\;25^{\circ}$ and 40$^{\circ}C$., using isopropyl bromide labelled with Br-82. The results indicated that the exchange reaction was second order with respect to gallium bromide and first order with respect to isopropyl bromide. The third-order rate constant determined at 19$^{\circ}C$. was 3.2 ${\times}10^{-2}l^2{\cdot}mole^{-2}sec^{-1}$. The activation energy, the enthalpy of activation and the entropy of activation for the exchange reaction were also determined.

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Activity Measurement of Zn in Liquid Zn-Cd Alloy Using EMF Method (기전력법을 이용한 용융 Zn-Cd 합금중 Zn의 활동도 측정)

  • Jeong, Seong-Yeop;Jeong, U-Gwang;Park, Jong-Jin
    • Korean Journal of Materials Research
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    • v.12 no.4
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    • pp.283-289
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    • 2002
  • The E.M.F of the galvanic cell with fused salt was measured to determine the activities of zinc at 700-820K over the entire composition range of liquid Zn-Cd alloys. The cell used was as follows: (-) W | Zn(pure) $Zn^{2+}(KCI-LiCl)$ | Zn(in Zn-Cd alloy) | W (+) The activities of zinc in the alloys showed positive deviation from Raoult's law over the entire composition range. The activity of cadmium and some thermodynamic functions such as Gibbs free energy, enthalpy, entropy were derived from the results by the thermodynamic relationship. The comparison of the results and the literature data was made. The liquid Zn-Cd alloy is found to be close to the regular solution. The concentration fluctuations in long wavelength limit, $S_{cc}(o)$, in the liquid alloy was calculated from the results.

A Study on the Adsorption Kinetics of 133Cs by Different Impregnations of Prussian Blue (프러시안 블루 고정화에 따른 133Cs의 흡착거동 모델링)

  • Choi, S.S.;Lee, Y.J.;Yun, K.J.;Cho, Y.J.;Lee, J.H.;Lee, S.H.
    • Journal of the Korean Society of Safety
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    • v.36 no.1
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    • pp.80-85
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    • 2021
  • Radionuclides, particularly radioactive cesium (Cs), are a concern of human health in some nuclear power accidents. It could lead to a high level of intracellular accumulation due to its high radioactivity and long half-life. Therefore, it is imperative to develop a method to remove Cs from wastewater. Herein, we synthesized activated carbon fibers (ACFs) doped with Prussian blue (PB) via in situ methods. We classified samples by their preparation method as either physical (PB-ACF-A) or physicochemical (PB-ACF-B) syntheses for comparison. The PB-ACF-B sample showed a significant surface loss compared to PB-ACF-A but a better 133Cs adsorption capacity. All samples fit well to Langmuir isotherms and the values of qmax were directly correlated to the amount of PB on the surface of the ACFs. Adsorption characteristics were further confirmed by the calculated free energy, enthalpy, and entropy.

A Thermodynamic Investigation into the Stabilization of Poly(dA).[poly(dT)]2 Triple Helical DNA by Various Divalent Metal Ions

  • Choi, Byung-Hoon;Yeo, Ga-Young;Jung, Jin-Ah;Lee, Bae-Wook;Han, Sung-Wook;Cho, Tae-Sub
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2691-2696
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    • 2009
  • Effects of representative group II and transition metal ions on the stability of the $poly(dA){\cdot}[poly(dT)]_2$ triplex were investigated by the van’t Hoff plot constructed from a thermal melting curve. The transition, $poly(dA){\cdot}[poly(dT)]_2\;{\rightarrow}\;poly(dA){\cdot}poly(dT)\;+\;poly(dT)$, was non-spontaneous with a positive Gibb’s free energy, endothermic (${\Delta}H^{\circ}$ > 0), and had a favorable entropy change (${\Delta}S^{\circ}$ > 0), as seen from the negative slope and positive y-intercept in the van’t Hoff plot. Therefore, the transition is driven by entropy change. The $Mg^{2+}$ ion was the most effective at stabilization of the triplex, with the effect decreasing in the order of $Mg^{2+}\;>\;Ca^{2+}\;>\;Sr^{2+}\;>\;Ba^{2+}$. A similar stabilization effect was found for the duplex to single strand transition: $poly(dA){\cdot}poly(dT)\;+\;poly(dT)\;→\;poly(dA)\;+\;2poly(dT)$, with a larger positive free energy. The transition metal ions, namely $Ni_{2+},\;Cu_{2+},\;and\;Zn_{2+}$, did not exhibit any effect on triplex stabilization, while showing little effect on duplex stabilization. The different effects on triplex stabilization between group II metal ions and the transition metal ions may be attributed to their difference in binding to DNA; transition metals are known to coordinate with DNA components, including phosphate groups, while group II metal ions conceivably bind DNA via electrostatic interactions. The $Cd_{2+}$ ion was an exception, effectively stabilizing the triplex and melting temperature of the third strand dissociation was higher than that observed in the presence of $Mg_{2+}$, even though it is in the same group with $Zn_{2+}$. The detailed behavior of the $Cd_{2+}$ ion is currently under investigation.

Adsorption Equilibrium, Kinetics and Thermodynamic Parameters Studies of Bismarck Brown R Dye Adsorption on Granular Activated Carbon (입상 활성탄에 대한 비스마르크 브라운 R 염료의 흡착평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.24 no.3
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    • pp.327-332
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    • 2013
  • Batch experiments were carried out for adsorption equilibrium, kinetics and thermodynamic parameters of the brilliant brown R onto granular activated carbon. The operating variables studied were the initial dye concentration, contact time and temperature. Experimental equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption isotherm by linear regression method. The equilibrium process was well described by Freundlich isotherm model and from the determined separation factor (1/n), granular activated carbon could be employed as an effective treatment for the removal of bismarck brown R. From kinetic experiments, the adsorption processes were found to confirm the pseudo second order model with a good correlation and the adsorption rate constant ($k_2$) increased with increasing adsorption temperature. Thermodynamic parameters like the activation energy, change of Gibbs free energy, enthalpy, and entropy were also calculated to predict the nature of adsorption in the temperature range of 298~318 K. The activation energy was determined as 8.73 kJ/mol for 100 mg/L. It was found that the adsorption of bismarck brown R on the granular activated carbon was physical process. The negative Gibbs free energy change (${\Delta}G$ = -2.59~-4.92 kJ/mol) and the positive enthalpy change (${\Delta}H$ = +26.34 kJ/mol) are indicative of the spontaneous and endothermic nature of the adsorption process.

Study on Equillibrium, Kinetic, Thermodynamic Parameters for Adsorption of Brilliant Green by Zeolite (제올라이트에 의한 Brilliant Green의 흡착에 대한 평형, 동역학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.56 no.1
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    • pp.112-118
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    • 2018
  • Adsorption equilibrium, kinetic and thermodynamic parameters of a brilliant green from aqueous solutions at various initial dye concentration (10~30 mg/L), contact time (1~24 h) and temperature (298~318 K) on zeolite were studied in a batch mode operation. The equilibrium adsorption values were analyzed by Langmuir, Freundlich and Dubinin-Radushkevich model. The results indicate that Langmuir and Freundlich model provides the best correlation of the experimental data. Base on the estimated values of Langmuir dimensionless separation factor ($R_L=0.041{\sim}0.057$) and Freundlich constant (1/n=0.30~0.47), this process could be employed as effective treatment method. calculated values of adsorption energy by Dubinin-Radushkevich model were 1.564~1.857 kJ/mol corresponding to physical adsorption. The adsorption kinetics of brilliant green were best described by the pseudo second-order rate model and followed by intraparticle diffusion model. Thermodynamic parameters such as activation energy, free energy, enthalpy and entropy were calculated to estimate nature of adsorption. negative Gibbs free energy (-10.3~-11.4 kJ/mol), positive enthalpy change (49.48 kJ/mol) and Arrehenius activation energy (27.05 kJ/mol) indicates that the adsorption is spontaneous, endothermic and physical adsorption process, respectively.

Analysis for Adsorption Equilibrium, Kinetic and Thermodynamic Parameters of Aniline Blue Using Activated Carbon (활성탄을 이용한 아닐린 블루의 흡착평형, 동역학 및 열역학 파라미터에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.57 no.5
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    • pp.679-686
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    • 2019
  • Characteristics of adsorption equilibrium, kinetic and thermodynamic of aniline blue onto activated carbon from aqueous solution were investigated as function of initial concentration, contact time and temperature. Adsorption isotherm of aniline blue was analyzed by Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich models. Langmuir isotherm model fit better with isothermal data than other isotherm models. Estmated Langmuir separation factors ($R_L=0.036{\sim}0.068$) indicated that adsorption process of aniline blue by activated carbon could be an effective treatment method. Adsorption kinetic data were fitted to pseudo first order model, pseudo second order model and intraparticle diffusion models. The kinetic results showed that the adsorption of aniline blue onto activated carbon well followed pseudo second-order model. Adsorption mechanism was evaluated in two steps, film diffusion and intraparticle diffusion, by intraparticle diffusion model. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy for adsorption process were estimated. Enthalpy change (48.49 kJ/mol) indicated that this adsorption process was physical adsorption and endothermic. Since Gibbs free energy decreased with increasing temperature, the adsorption reaction became more spontaneously with increasing temperature. The isosteric heat of adsorption indicated that there is interaction between the adsorbent and the adsorbate because the energy heterogeneity of the adsorbent surface.