• Journal of the Korean Electrochemical Society
• /
• v.2 no.1
• /
• pp.23-26
• /
• 1999

The Langmuir adsorption isotherm at the $(Pt)/0.1M\;H_2SO_4$ electrolyte interface has been qualitatively analyzed using the ac impedance measurement and phase-shift method. The phase shift $(\phi)$ depends on both the cathode potential (E<0) and frequency (f) and is inversely proportional to the factional surface coverage $(\theta)$. At an intermediate frequency band (ca. $1\~100$ Hz), the phase-shift profile $(\phi\;vs.\;E)$ can be related to the fractional surface coverage $(\theta\;vs.\;E)$. The phase-shift profile $(\phi\;vs.\;E)$ can be used as an experimental method to estimate and analyze the Langmuir adsorption isotherm $(\theta\;vs.\;E)$. The equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the adsorbed hydrogen atom $(H_{ads})\;and\;3\times10^{-4}$ and 20.1 kJ/mol, respectively.

• Journal of Electrochemical Science and Technology
• /
• v.4 no.2
• /
• pp.81-87
• /
• 2013

Inhibition of corrosion of mild steel in sulphuric acid by acidic extract of Jatropha Curcas leaves has been studied using weight loss and thermometric measurements. It was found that the leaves extract act as a good corrosion inhibitor for mild steel in all concentrations of the extract. The inhibition action depends on the concentration of the Jatropha Curcas leaves extract in the acid solution. Results for weight loss and thermometric measurements indicate that inhibition efficiency increase with increasing inhibitor concentration. The adsorption of Jatropha curcas leaves extract on the surface of the mild steel specimens obeys Langmuir adsorption isotherm. Based on the results, Jatropha curcas leaves extract is recommended for use in industries as a replacement for toxic chemical inhibitors.

• 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.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.

• 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.4
• /
• pp.311-316
• /
• 2009

Inhibition effects of alanine and methionine on the corrosion of aluminum were investigated in artificial sea water. Based on the low coverage of alanine and methionine we suggested that alanine and methionine adsorption process in aluminum surface is Langmuir isotherm and the carboxyl ion of amino acids seems to be adsorbed on Al.

• Applied Chemistry for Engineering
• /
• v.30 no.2
• /
• pp.190-197
• /
• 2019

The adsorption of methyl green dye using an activated carbon from an aqueous solution was investigated. Adsorption experiments were carried out as a function of the adsorbent dose, initial concentration, contact time and temperature. The Langmuir isotherm model showed a good fit to the equilibrium adsorption data. Based on the estimated Langmuir separation factor, ($R_L=0.02{\sim}0.106$), this process could be employed as the effective treatment (0 < $R_L$ < 1). It was found that the adsorption was a physical process with the adsorption energy (E) value range between 316.869 and 340.049 J/mol obtained using Dubinin-Radushkevich equation. The isothermal saturation capacity obtained from brunauer emmett teller (BET) model increased with increasing the temperature. The kinetics of adsorption followed a pseudo second order model. The free energy and enthalphy values of -5.421~-7.889 and 31.915 kJ/mol, respectively indicated that the adsorption process follows spontaneous endothermic reaction. The isosteric heat of adsorption increased with the increase of equilibrium adsorption amounts, and the total interaction of the adsorbent - adsorbate increased as the surface coverage increased.

• Applied Chemistry for Engineering
• /
• v.30 no.5
• /
• pp.562-568
• /
• 2019

Cylindrical shape extrudates of calcium silicate hydrate (CSH) were prepared using different percentages of polyvinyl alcohol (PVA) / sodium alginate (SA) mixtures as binders and an aqueous solution containing 6% $H_3BO_3$ and 3% $CaCl_2$ was used as a cross linking agent. As the quantity of alginate increases, the phosphate removal efficiency and capacity were decreased. Among four different extrudate samples, the sample prepared by 8% PVA + 2% SA showed the highest phosphate removal efficiency (59.59%) and capacity (29.97 mg/g) at an initial phosphate concentration of 100 ppm and 2.0 g/L adsorbent dosage. Effects of the adsorbent dosage, contact time and initial phosphate concentration on the sample were further studied. The removal efficiency and capacity obtained by a 4.0 g/L adsorbent dose at an initial phosphate concentration of 100 ppm in 3 h were 79.38% and 19.96 mg/g, respectively. The experimental data of kinetic and isotherm measurements followed the pseudo-second-order kinetic equation and Langmuir isotherm model, respectively. These results suggested that the phosphate removal was processed via a chemisorption and a monolayer coverage of phosphate anions was on the CSH surface. The maximum adsorption capacity ($q_{max}$) was calculated as 23.87 mg/g from Langmuir isotherm model.

• Applied Chemistry for Engineering
• /
• v.28 no.2
• /
• pp.206-213
• /
• 2017

The adsorption of crystal violet dyes from aqueous solution using the granular activated carbon was investigated. Adsorption experiments were carried out as a function of the adsorbent dose, initial concentration, contact time and temperature. The adsorption characteristic of crystal violet followed Langmuir isotherm. Based on the estimated Langmuir separation factor ($R_L=0.02{\sim}0.106$), this process could be employed as an effective treatment (0 < $R_L$ < 1). The adsorption kinetics followed the pseudo second order model. The values of Gibbs free energy (-1.61~-11.66 kJ/mol) and positive enthalpy (147.209 kJ/mol) indicated that the adsorption process is a spontaneous and endothermic reaction. The isosteric heat of adsorption decreased with increasing of surface loading by the limited adsorbent-adsorbate interaction due to increased surface coverage.

• Journal of the Korean Chemical Society
• /
• v.56 no.4
• /
• pp.401-405
• /
• 2012

Corrosion inhibition efficiencies of holy basil on Al in HCl solution were studied by weight loss and thermometric methods in presence and in absence of stem extract of three different varieties of holy basil viz. ocimum basilicum ($E_B$), ocimum canum ($E_C$) and ocimum sanctum ($E_S$). Inhibition efficiency increases with the increasing concentration of stem extract and decreases with increases in acid strength. Results show that all varieties under study are good corrosion inhibitors, among which, $E_B$ is most effective. Maximum inhibition efficiency was found 97.09% in 0.5N HCl solution with 0.6% stem extract. The Langmuir adsorption isotherm indicates that surface coverage also increases with increasing in the concentration of extract of stem in HCl solution.