• Journal of the Korean Electrochemical Society
• /
• v.4 no.4
• /
• pp.146-151
• /
• 2001

The Frumkin adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic $H_2$ evolution reaction (HER) at the poly-Ni|0.05M KOH aqueous electrolyte interface has been studied using the phase-shift method. The behavior of the phase shift $(0^{\circ}\leq{\phi}\leq90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1\geq{\theta}\geq0)$ at the interface. The phase-shift method, i.e., the Phase-shift profile $(-{\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new method to estimate the Frumkin adsorption isotherm $(\theta\;vs.\;E)$ of the OPD H for the cathodic HER at the interface. At the poly-Ni|0.05M KOH aqueous electrolyte interface, the rate (r) of change of the standard free energy of the OPD H with $\theta$, the interaction parameter (g) for the Frumkin adsorption isotherm, the equilibrium constant (K) for the OPD H with $\theta$, and the standard free energy $({\Delta}G_{\theta})$ of the OPD H with ${\theta}$ are $24.8kJ mol^{-1},\;10,\;5.9\times10^{-6}{\leq}K{\leq}0.13,\;and\;5.1\leq{\Delta}G_{\theta}\leq29.8kJ\;mol^{-1}$. The electrode kinetic parameters $(r,\;g,\;K,\;{\Delta}G_{\theta})$ depend strongly on ${\theta} (0{\leq}{\theta}{\leq}1)$.

• Journal of the Korean Electrochemical Society
• /
• v.3 no.1
• /
• pp.25-30
• /
• 2000

The relation between the phase-shift profile for the intermediate frequencies and the Langmuir adsorption isotherm at the poly-$Pt/0.1\;M\;H_2SO_4$ aqueous electrolyte interface has been studied using ac impedance measurements, i.e., the phase-shift methods. The suggested interfacial equivalent circuit consists of the serial connection of the electrolyte resistance ($R_S$), the faradaic resistance $(R_F)$ and the equivalent circuit element $(C_P)$ of the adsorption pseudocapacitance $(C_\varphi)$. The delayed phase shift $(\varphi)$ depends on both the cathode potential (E) and frequency (f), and is given by $\varphi=-tan^{-1}[1/2{\pi}f(R_s+R_F)C_p]$. The phase-shift profile $(\varphi\;vs.\;E)$ for the intermediate frequency (ca. 6Hz) can be used as an experimental method to determine the Langmuir adsorption isotherm (9 vs. E). The equilibrium constant (K) for H adsorption and the standard free energy $({\Delta}G_{ads})$ of H adsorption at the poly-$Pt/0.1\;M\;H_2SO_4$ electrolyte interface are $1.8\times10^{-4}\;and\;21.4kJ/mol$, respectively. The H adsorption is attributed to the over-potentially deposited hydrogen (OPD H).

• Journal of the Korean Electrochemical Society
• /
• v.10 no.3
• /
• pp.219-228
• /
• 2007

The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). 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 and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

• Journal of the Korean Electrochemical Society
• /
• v.12 no.1
• /
• pp.26-33
• /
• 2009

The phase-shift method and correlation constants, i.e., the unique electrochemical impedance spectroscopy (EIS) techniques for studying the linear relationship between the behavior ($-{\varphi}$ vs. E) of the phase shift ($90^{\circ}{\geq}-{\varphi}{\geq}0^{\circ}$) for the optimum intermediate frequency and that ($\theta$ vs. E) of the fractional surface coverage ($0{\leq}{\theta}{\leq}1$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at noble metal (alloy)/aqueous solution interfaces. At a Zr/0.2 M ${H_2}{SO_4}$ aqueous solution interface, the Frumkin and Temkin adsorption isotherms ($\theta$ vs. E), equilibrium constants (K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ for the Frumkin and K = $1.401{\times}10^{-16}\exp(8.1{\theta})mol^{-1}$ for the Temkin adsorption isotherm), interaction parameters (g = 3.5 for the Frumkin and g = 8.1 for the Temkin adsorption isotherm), rates of change of the standard free energy (r = $8.7\;kJ\;mol^{-1}$ for g = 3.5 and r = $20\;kJ\;mol^{-1}$ for g = 8.1) of H with $\theta$, and standard free energies ($96.13{\leq}{\Delta}G^0_{\theta}{\leq}104.8\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-17}\exp(-3.5{\theta})mol^{-1}$ and $0{\leq}{\theta}{\leq}1$ and ($94.44<{\Delta}G^0_{\theta}<106.5\;kJ\;mol^{-1}$ for K = $1.401{\times}10^{-16}\exp(-8.1{\theta})mol^{-1}$ and $0.2<{\theta}<0.8$) of H are determined using the phase-shift method and correlation constants. At 0.2 < $\theta$ < 0.8, the Temkin adsorption isotherm correlating with the Frumkin adsorption isotherm, and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are probably the most accurate, useful, and effective ways to determine the adsorption isotherms of H and related electrode kinetic and thermodynamic parameters at highly corrosion-resistant metal/aqueous solution interfaces.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.11a
• /
• pp.111.1-111.1
• /
• 2010

This paper focuses on a systematic configuration of steam reforming fuel processor, particularly designed for small and medium sized hydrogen production application. In a typical integration of the fuel processor, there exist significant temperature gradients over the entire system which has negative effect on both catalyst life-time and system performance. Also, the volumetric inefficiency should be avoided to obtain the possible compactness for the commercial purpose. In the present work, the computational analysis will be performed to gain the fundamental insight on the transport phenomena and chemical reactions in the reformer consisting of preheating, steam reforming (SR), and water gas shift (WGS) reaction beds in the flow direction. Also, the fuel processing system includes a top-fired burner providing necessary thermal energy for endothermic catalytic reactor. A fully two-dimensional numerical modeling for a integrated fuel processing system is introduced for in-depth analysis of the heat and mass transport phenomena based on surface kinetics and catalytic process. In the model, water gas shift reaction and decomposition reaction were assumed to be at equilibrium. A kinetic model was developed and then computational results were compared with the experimental data available in the literature. Finally, the case study was done by considering the key parameters, i.e. steam to carbon (S/C) ratio and temperature. The computer-aided models developed in this study can be greatly utilized for the design of advanced fast-paced compact fuel processors research.

• The Transactions of the Korean Institute of Power Electronics
• /
• v.18 no.6
• /
• pp.530-539
• /
• 2013

In large vessels, proper water level must be maintained with a balance for right and left equilibrium by absorbing or draining sea water in ballast water tank. However, this ship's ballast-water can be drained marine organisms to local sea area by world trade and this can be a source of ecological disturb. In order to solve these problems, marine organisms must be removed in accordance with the international covenant for the emission of microorganisms. By this reason, the seawater electrolysis rectifier of low-voltage high-current rectifiers with excellent ability for microbial treatment is required. In this paper, PSFB converter will be discussed for the seawater electrolysis rectifier. Furthermore, a new output control method with the power limit operation under the limited maximum voltage condition is proposed for this rectifier. The simulation for the proposed current control method for PSFB Converter is shown using MATLAB/SIMULINK. Finally the usefulness of the proposed control method is presented by the experimental results.

• Journal of the Korean Electrochemical Society
• /
• v.7 no.4
• /
• pp.194-200
• /
• 2004

The constant correlation factors between the Temkin and the Langmuir or the Frumkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) for the cathodic H2 evolution reaction (HER) at poly-Pt and Re/0.5M $H_2SO_4$ and poly-Ni/0.05 M KOH aqueous electrolyte interfaces have been experimentally and consistently found using the phase-shift method. At intermediate values of the fractional surface coverage $(\theta),\;i.e.,\;02<{\theta}<0.8$, the Langmuir and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other even though the adsorption conditions or processes are different from each other. At the same range of $\theta$, correspondingly, the Frumkin and Temkin adsorption isotherms of OPD H for the cathodic HER are correlated to each other. The equilibrium constants $(K_o)$ for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ca. 10 times greater than those (K, Ko) for the corresponding Langmuir or Frumkin adsorption isotherms ($({\theta}\;vs.\; E)$. The interaction parameters (g) for the Temkin adsorption isotherms $({\theta}\;vs.\; E)$ are consistently ra. 4.6 greater than those (g) for the corresponding Langmuir or Frumkin adsorption isotherms $({\theta}\;vs.\; E)$. These numbers (10 times and 4.6) can be taken as constant correlation factors between the corresponding adsolftion isotherms (Temkin, Langmuir, Frumkin) at the interfaces. The Temkin adsorption isotherm corresponding to the Langmuir or the Frumkin adsorption isotherm, and vice versa, can be effectively verified or confirmed using the constant correlation factors. Both the phase-shift methodand constant correlation factors are useful and effective for determining or confirming the suitable adsorption isotherms (Temkin, Langmuir, Frumkin) of intermediates for sequential reactions in electrochemical systems.

• Applied Chemistry for Engineering
• /
• v.16 no.2
• /
• pp.282-287
• /
• 2005

Palladium membranes, which are permselective to hydrogen separation, were used for the hydrogen purification and in membrane reactors for improving conversions by shifting the reaction equilibrium. Palladium/ceramic composite membranes were prepared by electroless plating technique and then etched in titanium chloride ($TiCl_4$) as a post treatment to enhance the membrane's durability. These membranes were used for membrane reactors in water gas shift (WGS) reaction. CO conversions for the membrane reactor were obtained according to experimental parameters and compared to the traditional reactor without a palladium/ceramic membrane. As a result, CO conversion using palladium membrane reactor at an appropriate condition was over 20~25% greater than that without the membrane reactor. The stability in the long-term test of up to 120 h for WGS reaction with the membrane reactor was good without the degredation of CO conversion.

• Journal of the Korean Electrochemical Society
• /
• v.9 no.1
• /
• pp.19-28
• /
• 2006

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

• Transactions of the Korean hydrogen and new energy society
• /
• v.24 no.6
• /
• pp.543-549
• /
• 2013

In this study, $La_{0.9}Sr_{0.1}Cr_{0.7}M_{0.3}O_{3{\pm}{\delta}}$ (M=Mn, Ru, Fe, Ni) were prepared by sol-gel method and water gas shift reaction with simulated coal-derived syngas between $400{\sim}650^{\circ}C$ was conducted to evaluate the catalytic activity of prepared catalysts. Physico-chemical properties were characterized by XRD, BET, SEM-EDS and TPR. The formation of perovskite crystallite, $LaCrO_3$ was confirmed and the highest surface area was measured with $La_{0.9}Sr_{0.1}Cr_{0.7}Mn_{0.3}O_{3{\pm}{\delta}}$. Equilibrium conversion of CO above $550^{\circ}C$ was achieved except $La_{0.9}Sr_{0.1}Cr_{0.7}Fe_{0.3}O_{3{\pm}{\delta}}$. and methanation reaction was carried out as side reaction of water gas shift reaction with $La_{0.9}Sr_{0.1}Cr_{0.7}Ni_{0.3}O_{3{\pm}{\delta}}$ and $La_{0.9}Sr_{0.1}Cr_{0.7}Ru_{0.3}O_{3{\pm}{\delta}}$. Conclusively, $La_{0.9}Sr_{0.1}Cr_{0.7}M_n{0.3}O_{3{\pm}{\delta}}$ was the most suitable catalyst of water gas shift reaction above $500^{\circ}C$ for CO conversion and hydrogen production.