• 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.4 no.3
• /
• pp.118-124
• /
• 2001

The Langmuir adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic $H_2$ evolution reaction (HER) at the $poly-Au|0.5M\;H_2SO_4$ aqueous electrolyte interface has been studied using cyclic voltammetric and ac impedance techniques. 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 profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, i.e., the phase-shift method, can be used as a new method to estimate the Langmuir adsorption isotherm $(\theta\;vs.\;E)$ of the OPD H for the cathodic HER at the interface. At the poly-$Au|0.5M\;H_2SO_4$ electrolyte interface, the equilibrium constant (K) and standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.3\times10^{-6}\;and\;32.2\;kJ\;mol^{-1}$, respectively.

• Journal of the Korean Electrochemical Society
• /
• v.6 no.2
• /
• pp.119-129
• /
• 2003

The Langmuir adsorption isotherms of the over-potentially deposited hydrogen (OPD H) fur the cathodic $H_2$ evolution reaction (HER) at the poly-Au and $Rh|0.5M\;H_2SO_4$ aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, i.e., the phase-shift method, can be used as a new electrochemical method to determine the Langmuir adsorption isotherm $({\theta}\;vs.\;E)$ of the OPD H for the cathodic HER at the interfaces. At the poly-Au|0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.3\times10^{-6}$ and 32.2kJ/mol, respectively. At the poly-Rh|0.5M $H_2SO_4$ aqueous electrolyte interface, K and ${\Delta}G_{ads}$ of the OPD H are $4.1\times10^4\;or\;1.2\times10^{-2}$ and 19.3 or 11.0kJ/mol depending on E, respectively. In contrast to the poly-Au electrode interface, the two different Langmuir adsorption isotherms of the OPD H are observed at the poly-Rh electrode interface. The two different Langmuir adsorption isotherms of the OPD H correspond to the two different adsorption sites of the OPD H on the poly-Rh electrode surface.

• Korean Chemical Engineering Research
• /
• v.54 no.6
• /
• pp.734-745
• /
• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• Journal of the Korean Electrochemical Society
• /
• v.3 no.2
• /
• pp.109-114
• /
• 2000

The relation between the phase-shift profile fur the intermediate frequencies and the Langmuir adsorption isotherm at the poly-Ir/0.1 M $H_2SO_4$ aqueous electrolyte interface has been studied using ac impedance measurements, i.e., the phase-shift methods. The simplified 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 pseudoca-pacitance $(C_\phi)$. The comparison of the change rates of the $\Delta(-\phi)/{\Delta}E\;and\;\Delta{\theta}/{\Delta}E$ are represented. The delayed phase shift $(\phi)$ depends on both the cathode potential (E) and frequency (f), and is given by $\phi=tan^{-1}[1/2{\pi}f(R_s+R_F)C_P]$. The phase-shift profile $(-\phi\;vs.\;E)$ for the intermediate frequency (ca. 1 Hz) can be used as an experimental method to determine the Langmuir adsorption isotherm $(\theta\;vs.\;E)$. The equilibrium constant (K) for H adsorption and the standard free energy $({\Delta}G_{ads})$ of H adsorption at the poly-Ir/0.1 M $H_2SO_4$ electrolyte interface are $2.0\times10^{-4}$ and 21.1kJ/mol, respectively. The H adsorption is attributed to the over-potentially deposited hydrogen (OPD H).

• Journal of the Korean Electrochemical Society
• /
• v.4 no.1
• /
• pp.14-20
• /
• 2001

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the single crystal Pt(100)/0.5 M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using the phase-shift method. The phase-shift profile $({-\varphi}\;vs.\;E)$ for the optimum intermediate frequency can be used as a useful method to estimate the Langmuir adsorption isotherm $(\theta\;vs.\;E)$ at the interfaces. The equilibrium constant (K) for the OPD H and the standard free energy $({\Delta}G_{ads})$ of the OPD H at the Pt(100)/0.5M $H_2SO_4$ aqueous electrolyte interface are $1.5\times10^{-4}$ and 21.8 kJ/mol, respectively. At the Pt(100)/0.5 LiOH aqueous electrolyte interface, K transits from 1.9(UPD H) to $6.8\times10^{-6}$(OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits -1.6 kJ/mol (UPD H) to 29.5 kJ/mol (OPD H) depending on E and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and OPD H on the Pt(100) surface. The UPD H and the OPD H at the Pt(100) interfaces are the independent processes depending on the H adsorption sites rather than the sequential processes for the cathodic $H_2$ evolution reactions.

• Journal of the Korean Electrochemical Society
• /
• v.2 no.3
• /
• pp.144-149
• /
• 1999

The two distinct adsorption sites and transition between the under and over-potentially deposited hydrogen (UPD H and OPD H) on the polycrystalline iridium (poly-Ir) surface in the 0.2 M LiOH electrolyte have been studied using the phase-shift method. At the forward and backward scans, the UPD H peak occurs on the cyclic voltam-mogram. The transition region on the phase-shift profile or the Langmuir adsorption isotherm occurs at ca. -0.80 to -0.95 V vs. SCE. At the transition region (-0.80 to -0.95 V vs. SCE), the equilibrium constant (K) for H adsorption transits from $7.9\times10^{-2}\;to\;1.5\times10^{-4}$ and vice versa. Similarly, the standard free energy $({\Delta}G_{ads})$ of H adsorption transits from 6.3 to 21.8kJ/mol and vice versa. The UPD H and OPD H on the poly-Ir surface act as two distinguishable electroadsorbed H species. Both the UPD H peak and the transition region are attributed to the two distinct adsorption sites of the UPD H and OPD H on the poly-Ir surface.

• 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.

• Journal of the Korean Electrochemical Society
• /
• v.5 no.3
• /
• pp.131-142
• /
• 2002

The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

• 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).