• Title/Summary/Keyword: Enthalpy and entropy

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Evaluation of Loess Capability for Adsorption of Total Nitrogen (T-N) and Total Phosphorous (T-P) in Aqueous Solution

  • Kim, Daeik;Ryoo, Keon Sang;Hong, Yong Pyo;Choi, Jong-Ha
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2471-2476
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    • 2014
  • The aim of the present study is to explore the possibility of utilizing loess for the adsorption of total phosphorous (T-P) and total nitrogen (T-N) in water. Batch adsorption studies were performed to evaluate the influences of various factors like initial concentration, contact time and temperature on the adsorption of T-P and T-N. The adsorption data showed that loess is not effective for the adsorption of T-N. However, loess exhibited much higher adsorption capacity for T-P. At concentration of $1.0mgL^{-1}$, approximately 97% of T-P adsorption was achieved by loess. The equilibrium data were fitted well to the Langmuir isotherm model. The pseudo-second-order kinetic model appeared to be the better-fitting model because it has higher $R^2$ compared with the pseudo-first-order and intra-particle kinetic model. The theoretical adsorption equilibrium $q_{e,cal}$ from pseudo-second-order kinetic model was relatively similar to the experimental adsorption equilibrium $q_{e,exp}$. The thermodynamic parameters such as free energy ${\Delta}G$, the enthalpy ${\Delta}H$ and the entropy ${\Delta}S$ were also calculated.

Entropy, enthalpy, and gibbs free energy variations of 133Cs via CO2-activated carbon filter and ferric ferrocyanide hybrid composites

  • Lee, Joon Hyuk;Suh, Dong Hack
    • Nuclear Engineering and Technology
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    • v.53 no.11
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    • pp.3711-3716
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    • 2021
  • The addition of ferric ferrocyanide (Prussian blue; PB) to adsorbents could enhance the adsorption performance of 133Cs. Toward this goal, we present a heterogeneously integrated carbonaceous material platform consisting of PB in direct contact with CO2-activated carbon filters (PB-CACF). The resulted sample retains 24.39% more PB than vice versa probed by the ultraviolet-visible spectrometer. We leverage this effect to capture 133Cs in the aqueous environment via the increase in ionic strength and micropores. We note that the amount of PB was likely to be the key factor for 133Cs adsorption compared with specific surface characteristics. The revealed adsorption capacity of PB-CACF was 21.69% higher than the bare support. The adsorption characteristics were feasible and spontaneous. Positive values of 𝜟Ho and 𝜟So show the endothermic nature and increased randomness. Based on the concept of capturing hazardous materials via hazardous materials, our work will be of interest within the relevant academia for collecting radionuclides in a sufficient manner.

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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    • v.11 no.4
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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.

Comparative Study on Adsorptive Characteristics of Diazinon in Water by Various Adsorbents

  • Ryoo, Keon Sang;Jung, Sun Young;Sim, Hun;Choi, Jong-Ha
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2753-2759
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    • 2013
  • The aim of the present study is to explore the possibility of utilizing fly ash and loess, as alternative to activated carbon, for the adsorption of diazinon in water. Batch adsorption experiment was performed to evaluate the influences of various factors like initial concentration, contact time and temperature on the adsorption of diazinon. The adsorption data shows that fly ash is not effective for the adsorption of diazinon. The equilibrium data for both activated carbon and loess were fitted well to the Freundlich isotherm model. The pseudo-second-order kinetic model appeared to be the better-fitting model because it has higher $R^2$ compared to the pseudo-first-order kinetic model. The thermodynamic parameters such as free energy (${\Delta}G$), the enthalpy (${\Delta}H$) and the entropy (${\Delta}S$) were calculated. Contrary to loess, the ${\Delta}G$ values of activated carbon were negative at the studied temperatures. It indicates that the adsorption of diazinon by activated carbon is a favorable and spontaneous process. The positive ${\Delta}H$ values of activated carbon and loess suggest that the diazinon adsorption process is endothermic in nature. In addition, the positive ${\Delta}S$ values show that increased randomness occurs at the solid/solution surface during the adsorption of diazinon.

Kinetic Study using Ultrasonic Technique on the Dissociation-Recombination Reaction between Micelle and Counter-ion in Dodecyl Pyridinium Chloride Solution (超音波를 利用한 Dodecyl Pyridinium Chloride 水溶液中의 미셀과 반대이온 사이의 解離-再結合反應의 反應速度論的 硏究)

  • Kun Moo Lee
    • Journal of the Korean Chemical Society
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    • v.20 no.3
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    • pp.193-197
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    • 1976
  • The ultrasonic absorption has been measured in aqueous solution of dodecyl pyridinium chloride (DPC) at $20^{\circ}C$ over the frequency range of 0.1${\sim}$90 Mc.The excess absorption was observed only in solutions in which the concentration was higher than the critical micellar concentration(cmc). The mechanism for this feature was attributed to the reaction $M_2\;{\rightleftharpoons}\;M_1\;+\;1.2Cl^-$ Where $M_2$ and $M_1$ and M1 are two types of micelle. The rate constants of the forward and the reverse reactions were $6.6{\times}10^5 sec^{-1}\;and\;2.7{\times}10^11sec^{-1}mol^{-1.2}$respectively. Some kinetic charateristics including the free energy, enthalpy and entropy were calculated.

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The Physicochemical Properties on the Organic, Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구. 사염화탄소 용액내에서의 헥사메틸벤젠과 1,3,5-트리니트로벤젠과의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Oh Cheun Kwun;Myong Ja Kim
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.513-519
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    • 1988
  • The effect of pressure and temperature on the stabilities of hexamethylbenzene-1,3,5-trinitrobenzene charge transfer complex in carbon tetrachloride has been investigated by spectrophotometric measurements. The absorption spectra of charge transfer complexes were measured at 25, 40, $50^{\circ}C$ under 1, 200, 500, 1000, 1400 bar in this experiments. The equilibrium constants of the complex were increased with pressure and decreased with temperature rising. The absorption coefficients were increased with pressure and temperature. Change of volume, enthalpy, free energy and entropy for the formation of complexes were calculated from the equilibrium constants. The red-shift observed at a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic fuctions.

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The Effect of Pressures on the Formation of Charge Transfer Complexes of Toluene with Iodine (I) (톨루엔과 요오드 사이의 전하이동착물에 대한 압력의 영향 (I))

  • Kwun Oh Cheun
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.73-84
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    • 1975
  • The effect of pressures and temperatures on the stabilities of the toluene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at $25~60{\circ}C$ under 1~1,200 bars. The equilibrium constant of the complex was increased with pressure and decreased with temperature raising. The absorption coefficient was increased with both pressure and temperature. Changes of volume, enthalpy, free energy and entropy for the formation of complexes were obtained from the equilibrium constants. The red-shift observed a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions.

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Modelling of noise-added saturated steam table using the neural networks (신경회로망을 사용한 노이즈가 첨가된 포화증기표의 모델링)

  • Lee, Tae-Hwan;Park, Jin-Hyun
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2008.05a
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    • pp.205-208
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    • 2008
  • In numerical analysis numerical values of thermodynamic properties such as temperature, pressure, specific volume, enthalpy and entropy are required. But most of the thermodynamic properties of the steam table are determined by experiment. Therefore they are supposed to have measurement errors. In order to make noised thermodynamic properties corresponding to errors, random numbers are generated, adjusted to appropriate magnitudes and added to original thermodynamic properties. the neural networks and quadratic spline interpolation method are introduced for function approximation of these modified thermodynamic properties in the saturated water based on pressure. It was proved that the neural networks give smaller percentage error compared with quadratic spline interpolation. From this fact it was confirmed that the neural networks trace the original values of thermodynamic properties better than the quadratic interpolation method.

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Optical properties and thermodynamic function properties of undoped and Co-doped $Zn_{0.5}Cd_{0.5}Al_{2}Se_{4}$ Single Crystals ($Zn_{0.5}Cd_{0.5}Al_{2}Se_{4}$$Zn_{0.5}Cd_{0.5}Al_{2}Se_{4}:Co^{2+}$ 단결정의 광학적 특성과 열역학 함수 추정)

  • Hyun, Seung-Cheol;Kim, Hyung-Gon;Kim, Duck-Tae;Park, Kwang-Ho;Park, Hyun;Oh, Seok-Kyun
    • Proceedings of the KIEE Conference
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    • 2002.06a
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    • pp.88-93
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    • 2002
  • $Zn_{0.5}Cd_{0.5}Al_{2}Se_{4}$ and $Zn_{0.5}Cd_{0.5}Al_{2}Se_{4}:Co^{2+}$ + single crystals were grown by CTR method. The grown single crystals have defect chalcopyrite structure with lattice constant a= 5.5966A. c= 10.8042${{\AA}}$ for the pure. a= 5.6543${{\AA}}$. c= 10.8205${{\AA}}$ for the Co-doped single crystal. respectively. The optical energy band gap was given as indirect band gap. The optical energy band gap was decreased according to add of Co-impurity. Temperature dependence of optical energy band gap was fitted well to the Varshni equation. From this relation. we can deduced the entropy. enthalpy and heat capacity. Also. we can observed the Co-impurity optical absorption peaks assigned to the $Co^{2+}$ ion sited at the $T_d$ symmetry lattice and we consider that they were attributed to the electron transitions between energy levels of ions.

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Kinetic Studies on Bromine-Exchange Reactions of Antimony Tribromide with $\alpha$-Phenyl-n-butyl and $\alpha$-Phenyl-i-butyl Bromides in Nitrobenzene$^\dag$

  • Rhyu, Sok-Hwan;Choi, Sang-Up
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.408-414
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    • 1987
  • The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.