• Journal of Korean Society on Water Environment
• /
• v.30 no.2
• /
• pp.175-183
• /
• 2014

The influence of temperature on the treatment efficiency of chlorinated organic substances contained in groundwater by permeable reactive barrier which is composed of $Fe^{\circ}$ has been investigated by constructing the Pourbaix diagrams for Fe-$H_2O$ system at different temperatures based on thermodynamic estimation. In aerobic condition, the equilibrium potentials for $Fe^{\circ}/Fe^{2+}$ and $Fe^{2+}/Fe^{3+}$ were observed to increase, therefore, the dechlorination reaction for organic pollutants by $Fe^{\circ}$ was considered to decline with temperature due to the diminished oxidation of reactive barrier. The result for the variations of the ionization fraction of $Fe^{2+}$ and $Fe^{3+}$ ion in the pH range of 0 ~ 2.5 obtained by employing Visual MINTEQ program showed that the ionization fraction of $Fe^{2+}$ increased with pH, however, that of $Fe^{3+}$ decreased symmetrically and the extent of the variation of ionization fraction for both ions was raised as temperature rises. The equilibrium pH for $Fe^{3+}/Fe(OH)_3$ was examined to decrease with temperature so that the treatment efficiency of chlorinated organic substance was expected to decrease with temperature due to the enhanced formation of passivating film in aerobic condition. The change of the reactivity of a specific chemical species with temperature was defined quantitatively based on the area of its stable region in Pourbaix diagram and depending on this the reactivity of $Fe^{3+}$ was shown to decrease with temperature, however, that of $Fe(OH)_3$ was decreased monotonously as temperature is raised for $Fe^{3+}/Fe(OH)_3$ equilibrium system. In anaerobic condition, the equilibrium potential for $Fe^{\circ}/Fe^{2+}$ was observed to rise and the equilibrium pH for $Fe^{2+}/Fe(OH)_2$ were examined to decrease as temperature increases, therefore, similar to that for aerobic condition the efficiency of the dechlorination reaction for organic substances was considered to be diminished when temperature rises because of the reduced oxidation of $Fe^{\circ}$ and increased formation of $Fe(OH)_2$ passivating film.

• 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.