• Title/Summary/Keyword: thermodynamic parameters

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Kinetics and Mechanism of Hydrolysis of Insecticidal 2-chloro-1-(2,4,5-trichlorophenyl) vinyldimethylphosphate (Gardona)$^{\(R)}$ (살충성 2-Chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate (Gardona)$^{\(R)}$의 가수분해 반응메카니즘)

  • Sung, Nack-Do;Yun, Tae-Yong;Kwon, Ki-Sung;Kim, Tae-Rin
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.483-489
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    • 1990
  • The rate of hydrolysis of insecticidal 2-chloro-l-(2,4,5-trichlorophenyl)-vinyldimethylphosphate(Gardona) have been investigated in 25${\%}$ aqueous methanol. Studies at varying pH suggest that the hydrolysis of Gardona proceeds through the bimolecular (Ad$_{N-E}$) mechanism involving the transition state and carbanion intermediate as evidenced by solvent effect (m < 0.4, n < 0.7, [m] ${\ll}$ [l](associative SN$_2$ type)), thermodynamic parameters (${\{Delta}S^{\neq}$ = -27∼-32 e.u. & ${\{Delta}H^{\neq}$ = 13∼18 Kcal/mole), hydrolysis rate equation (k = k$_A+_B$ [OH-]), general base catalysis and hydrolysis product analysis, respectively.

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A Comparative Study on Adsorption Characteristics of PCBs in Transformer Oil Using Various Adsorbents (여러 흡착제를 이용한 변압기 오일 중의 PCBs 흡착특성에 관한 비교연구)

  • Ryoo, Keon Sang;Hong, Yong Pyo;Ahn, Chun Ju
    • Journal of the Korean Chemical Society
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    • v.56 no.6
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    • pp.692-699
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    • 2012
  • The aim of the present study is to explore the possibility of utilizing loess and fly ash as well as activated carbon for the adsorptive removal of PCBs in transformer oil. Here, we investigated the effect of various factors such as temperature (5, 25, 55), contact time (30 min-3 day) and adsorbent does (1, 2.5, 5, 10 g) in detail. It was found that PCBs adsorption rate from transformer oil by activated carbon is more favored than loess at the equilibrium time of 60 minutes. The equilibrium data for both activated carbon and loess is fitted well to the Freundlich isotherm model. The rate constant and activation energy of PCBs adsorption in transformer oil on each adsorbent was analyzed by fitting a kinetic model at 5, 25 and $55^{\circ}C$. From the thermodynamic parameters, the PCBs adsorption process for transformer oil/activated carbon and loess system is spontaneous and endothermic in nature.

Solubilization of 4-Alkylbenzoic Acid Isomers by the Aqueous Solution of Tetradecyltrimethylammonium Bromide (테트라데실트리메틸암모늄 브로마이드의 수용액에서 4-알킬벤조산 이성질체들의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.56 no.2
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    • pp.188-194
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    • 2012
  • The interaction of 4-alkylbenzoic acid isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of 4-alkylbenzoic acid isomers into the TTAB micellar system and the critical micelle concentration (CMC) of TTAB have been measured with the change of temperature. Various thermodynamic parameters have been calculated and analyzed from those measurements. The results show that the values of ${\Delta}G^o{_s}$ for the solubilization of all the isomers are negative and the values of ${\Delta}H^o{_s}$ and ${\Delta}S^o{_s}$ are all positive within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of 4-alkylbenzoic acid isomers have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate that the solubilization sites of 4-alkylbenzoic acids are the core or deep palisade region of the TTAB micelle.

Comparative Study on the Micellization of SDS/Brij 30, DBS/Brij 30, and SDS/DBS Mixed Surfactant Systems in Pure Water (순수 물에서 SDS/Brij 30, DBS/Brij 30 및 SDS/DBS 혼합계면활성제의 미셀화에 대한 비교연구)

  • Lee, Byung-Hwan;Park, In-Jung
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.379-384
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    • 2011
  • The critical micelle concentration (CMC) and the counter ion binding constant (B) for the mixed micellizations of DBS (sodium dodecylbenzenesulfonate), SDS (sodium dodecylsulfate), and Brij 30 (polyoxyethylene(4) lauryl ether) at $25^{\circ}C$ in pure water were determined by the use of electric conductivity and surface tension measuring methods. Various thermodynamic parameters ($X_i,\;{\gamma}i,\;C_i,\;a_i^M,\;{\beta}$, and ${\Delta}H_{mix}$) were calculated and compared with each other mixed surfactant system by means of the equations derived from the nonideal mixed micellar model. The results show that the SDS molecule interacts more strongly with Brij 30 molecule than DBS molecule and that the SDS/Brij 30 mixed surfactant system has the greatest negative deviation from the ideal mixed micellar model and the SDS/DBS mixed system has followed almost the ideal mixed micellar model.

Effects of Butanol Isomers on the Mixed Micellization of TTAB/Brij 35 Mixed Surfactant Systems (TTAB/Brij 35 혼합계면활성제의 미셀화에 미치는 부탄올 이성질체들의 효과)

  • Gil, Han-Nae;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.52 no.2
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    • pp.111-117
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    • 2008
  • critical micelle concentration (CMC) and the counter ion binding constant (B) in a mixed micellar state of the trimethyltetradecylammonium bromide (TTAB) with the polyoxyethylene (23) lauryl ether (Brij 35) at 25oC in water and in aqueous solutions of butanol isomers were determined as a function of 1 (the overall mole fraction of TTAB) by the use of electric conductivity method and surface tensiometer method. Various thermodynamic parameters (Xi, i, Ci, aiM, and Hmix) were calculated by means of the equations derived from the nonideal mixed micellar model. The results say that the effects of butanol isomers on the micellization of TTAB/Brij 35 mixtures have been in the order of n-butanol>iso-butanol>t-butanol> water.

The Inhibition of C-steel Corrosion in H3PO4 Solution by Some Furfural Hydrazone Derivatives

  • Fouda, A.S.;Badr, G.E.;El-Haddad, M.N.
    • Journal of the Korean Chemical Society
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    • v.52 no.2
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    • pp.124-132
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    • 2008
  • effect of some furfural hydrazone derivatives (I -V) as corrosion inhibitors for C-steel in 3M H3PO4 solution in which M indicates mol/l has been studied using weight-loss and galvanostatic polarization techniques. A significant decrease in the corrosion rate of C-steel was observed in the presence of the investigated compounds. This study revealed that, the inhibition efficiency increases with increasing the inhibitor concentration, and the addition of iodide and thiocynate ions enhances it to a considerable extent. The effect of temperature on the corrosion behavior of C-steel was studied in the range from 30-60oC with and without 510-6 M investigated compounds using weight-loss method. Apparent activation corrosion energy (Ea*) and other thermodynamic parameters for the corrosion process were calculated and discussed. The polarization measurements show that the investigated compounds act as mixed-type inhibitors, but the cathode is more polarized when an external current was applied. The adsorption of these compounds on the surface of C-steel in 3M H3PO4 obeys Frumkins adsorption isotherm. The mechanism of inhibition was discussed in the light of the chemical structure of the investigated compounds.

Evaluation of the inhibitive characteristics of 1,4-dihydropyridine derivatives for the corrosion of mild steel in 1M $H_2SO_4$

  • Sounthari, P.;Kiruthika, A.;Sai santhoshi, J.;Chitra, S.;Parameswari, K.;Selvaraj, A.
    • Corrosion Science and Technology
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    • v.12 no.2
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    • pp.65-78
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    • 2013
  • The present investigation deals with the corrosion inhibition of mild steel in 1M $H_2SO_4$ with 1, 4-dihydro pyridine and its derivatives prepared using microwave activation method. The synthesis of inhibitor was confirmed by IR spectra. The effect of 1, 4-dihydropyridine derivatives on the corrosion inhibition of mild steel in 1M $H_2SO_4$ was studied using weight loss and electrochemical polarization techniques. Influence of temperature (303-333K) and synergistic effect of halide ions ($I^-$, $Br^-$ and $Cl^-$) on the inhibition behaviour was also studied. Corrosion products on the metal surface were analyzed by scanning electron microscopy (SEM) and a possible mechanism of inhibition by the compounds is suggested. Thermodynamic parameters were calculated using weight loss data in order to elaborate the mechanism of corrosion inhibition. Polarization measurements revealed that the studied compounds acted as mixed type inhibitor but slightly anodic in nature. Electrochemical impedance measurements revealed that the compounds were adsorbed onto the carbon steel surface and the adsorption obeyed the Langmuir adsorption isotherm. The synergistic effect of halide ions on the IE increases with increase in concentration. The IE obtained from atomic absorption spectrophotometric studies was found to be in good agreement with that obtained from the conventional weight loss method. SEM revealed the information of a smooth, dense protective layer in presence of the inhibitors.

On the Aquation of Dichloro Bis-(Ethylenediamine)-Chromium (III) Cation (Dichloro Bis-(Ethylenediamine)-Chromium (III) 양이온의 수화반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Soung-Oh Bek
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.95-101
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    • 1984
  • Aquation reaction kinetics of $[Cr(en)_2Cl_2]^+$complex was carried by the electric conductivity method. Its temperature range was $15^{\circ}C$ to $30^{\circ}C$ and pressure was varied up to 2,000 bars. The reaction rate was increased with increasing temperature, but was reversed to increasing pressure. The activation volume(${\Delta}V^{\neq}$) was increased with increasing temperature and decreased with increasing pressure. At $25^{\circ}C$ and 1 bar it was fairly small positive value, $1.82cm^2/mole$. Activation entropy change(${\Delta}S^{\neq}$) $was calculated as small negative value,-9.019 eu, at $25^{\circ}C$ and 1bar. Referring to the thermodynamic parameters, it was estimated that aquation reaction was proceeded by the interchange-dissociation(Id) mechanism.

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Study on Governing Equations for Modeling Electrolytic Reduction Cell (전해환원 셀 모델링을 위한 지배 방정식 연구)

  • Kim, Ki-Sub;Park, Byung Heung
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.12 no.3
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    • pp.245-251
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    • 2014
  • Pyroprocess for treating spent nuclear fuels has been developed based on electrochemical principles. Process simulation is one of the important methods for process development and experimental data analysis and it is also a necessary approach for pyroprocessing. To date, process simulation of pyroprocessing has been focused on electrorefining and there have been not so many investigations on electrolytic reduction. Electrolytic reduction, unlike electrorefining, includes specific features of gas evolution and porous electrode and, thus, different equations should be considered for developing a model for the process. This study summarized required concepts and equations for electrolytic reduction model development from thermodynamic, mass transport, and reaction kinetics theories which are necessitated for analyzing an electrochemical cell. An electrolytic reduction cell was divided and equations for each section were listed and, then, boundary conditions for connecting the sections were indicated. It is expected that those equations would be used as a basis to develop a simulation model for the future and applied to determine parameters associated with experimental data.

Characterization and Solution Behavior of Polyethylene-based Ionomer Particles in Water (물에서의 폴리에틸렌계 아이오노머 입자 특성과 용액 거동)

  • Yeo, Sang Ihn;Woo, Kyu Whan
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.512-518
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    • 1998
  • In this study, various thermodynamic and hydrodynamic parameters characterizing the solution properties of polyethylene ionomer particles in water were determined at $30^{\circ}C$ by means of light scattering and viscosity measurements. Based on the experimental data, we investigated the solution behavior of three kinds of polyethylene ionomers, which are different in composition of the pendant ionic groups of COOK, COOH and $CONH_{2}$, and characterized their particle properties. Ionomers containing 7.6 mol% potassium salt only behave as flexible coils in a relatively good solvent state. On the other hand, two ionomers containing 3.8 mol% amide group together with potassium salt form the compact particles. In addition, the concentration dependence of the effective diffusion coefficient $(D_{eff})$ and the reduced viscosity of the latter ionomers showed the opposite trend from the former, indicating that the composition of the pendant ionic groups have a great influence on the interparticle interaction of ionomers formed in water.

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