• Journal of the Korean Electrochemical Society
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• v.10 no.2
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• pp.132-140
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• 2007

The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

• Applied Chemistry for Engineering
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• v.2 no.2
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• pp.165-174
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• 1991

The kinetics and the mechanism for the selective oxidation of ethylene on the supported monolithic silver catalyst were experimentally investigated in a fixed bed tubular reactor. The formation rates of ethylene oxide and carbon dioxide were measured at the atmospheric pressure with various combinations of partial pressures of ethylene and oxygen at temperature range of $225-300^{\circ}C$, conversion with 1.2-7.5 %, and then the mechanism of the selective oxidation of ethylene was verified. Their formation rates fitted with the Langmuir-Hinshelwood mechnism. The ethylene oxide and carbon dioxide are produced by reation of adsorbed ethylene with monoatomic oxygen adsorbed on the active sites of Ag-surface, and their formation rate equation are expressed as : $R_{EO}={\frac{k_1K_0{^{1/2}}K_EK_SP_{02}{^{3/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^2(1+{\sqrt{K_SP_{02}})^2}}$ $R_C={\frac{k_2K_0{^3}K_EK_S{^{7/2}}P_{02}{^{13/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^7(1+{\sqrt{K_SP_{02}})^7}}$ The activation energies of ethylene oxide and dioxide and carbon dioxide formations can be estimated to be 12.25 and 17.85 Kcal/mol, respectively.

• Applied Chemistry for Engineering
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• v.5 no.5
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• pp.825-835
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• 1994

Synthesis of ETBE as an octane number enhancer from ethanol and isobutene in a flow reactor under atmospheric pressure was studied. Amberlyst-15 and Amberlyst XN-1010 were used as catalysts within the temperature range of $70-140^{\circ}C$. The activity of Amberlyst 15 was higher than that of Amberlyst XN-1010. The reaction rate data obtained under differential reactor condition were tested by a linear regression method to determine the reaction mechanism and kinetic parameters. The ETBE synthesis reaction seems to be proceeded via the LHHW(Langmuir-Hinshelwood-Hougen-Watson) machanism. The activation energy of the surface reaction was estimated by the reaction rate constants as well as the adsorption equilibrium constants. Apparent activation energies are 18.64 and 24.19kcal/mol for Amberlyst-15 and Amberlyst XN-1010, respectively.

• Applied Chemistry for Engineering
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• v.2 no.2
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• pp.108-118
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• 1991

Interactions between pyridine hydrodenitrogenation (HDN) and m-cresol hydrodeoxygenation(HDO), and the kinetic analysis were studied over sulfided $CoMo/{\gamma}-Al_2O_3$ catalyst at the range of temperatures between 473 K and 723 K, the total pressures between $10{\times}10^5Pa$ and $50{\times}10^5Pa$, and the contact times between 0.0125 g-cat. hr/ml-feed and 0.03g-cat. hr/ml-feed. HDN of pyridine and HDO of m-cresol were inhibited by each other and the inhibition effect of HDO by pyridine is higher than that of HDN by m-cresol. But reactivity of m-cresol is higher than that of pyridine. The rate equations of pyridine and m-cresol were given to be ${\gamma}_{HDN}=k_{HDN}{\cdot}K_pC_p/(1+K_cC_c+K_pC_p)$ and ${\gamma}_{HDO}=k_{HDO}{\cdot}K_cC_c/(1+K_cC_c+K_pC_p)$ in terms of Langmuir-Hinshellwood-Hougen-Watson model. At each temperature, reaction rate constants and adsorption equilibrium constants were determined and activation energies of pyridine HDN and m-cresol HDO are 13.83kcal/mol, respectively and the heat of adsorption are -6.458 and -5.045kcal/mol, respectively.

• Korean Journal of Food Science and Technology
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• v.19 no.3
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• pp.231-238
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• 1987

Two kinds of soy pastes with different colors (reddish brown and yellowish white) were dehydrated by freeze drying in powder form. Hygroscopic behaviors of powdered soy pastes were investigated under the conditions of various water acitivities (0.11-0.88) and three different temperatures (25,40 and $50^{\circ}C$), and presented a kinetic and thermodynamic interpretatons in the view point of qualities and storage stability. Moisture absorption isotherms of powdered soy pastes were of type II according with BET classification and can be described by the Henderson's empirical equation. The safe storage moisture levels calculated by the Laurie's equation were ranging from 5.5 to 3.98% dry basis with oaring temperatures. The moisture absorption process for powdered soy paste followed the Ist order kinetic in the difference of equilibrium moisture content and arbitrary moisture content and the initial step was characterized by very fast absorption of moisture. The change of, dispersion capacity and color difference for powdered soy paste were extremely dependent upon water activity under the storage and the maximum stability was found at safe storage moisture levels. Also, the variation of thermodynamic parameters with moisture content was significant at safe storage moisture content levels and suggested d the considerable correspondence to storage stability of powdered soy paste.

• Journal of Soil and Groundwater Environment
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• v.8 no.2
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• pp.55-61
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• 2003

The objective of this study was to investigate the characteristics of nitrate removal by conducting the column test in order to see the performance of surfactant modified zeolite (SMZ) as a permeable reactive barrier material. The prediction of nitrate removal was tested using the one-dimensional advective-dispersive model fitted to the experimental breakthrough curve. A methodology for scaling up to in-situ permeable reactive barrier was also proposed. The breakthrough of nitrate in the column packed with SMZ was well predicted using linear equilibrium adsorption model. The breakthrough time and half-life obtained by breakthrough experiment with variation of flowrates were decreased with the increase of flowrates. When 10㎥/day of groundwater containing the 50 mg/l of nitrate is to be treated to satisfy the potable water quality criteria (10 mg/l) by SMZ reactive barrier, 300 tons of SMZ and about 6 years of breakthrough time will be required, suggesting that 165 million wons are needed as barrier material expenses in each 6 years besides the initial design and construction expenses and the minimal monitoring and maintenance expenses.