Hydrogen evolution reaction （HER） at polycrystalline silver electrode in 0.1 mol/L HClO4 solution is investigated by cyclic voltammetry in the temperature range of 278-333 K. We found that at electrode potential φa...Hydrogen evolution reaction （HER） at polycrystalline silver electrode in 0.1 mol/L HClO4 solution is investigated by cyclic voltammetry in the temperature range of 278-333 K. We found that at electrode potential φa,app decreases with φ, while pre-exponential factor A remains nearly unchanged,which conforms well the prediction from Butler-Volmer equation. In contrast, with φ nega-tive shifts from the onset potential for HER to the potential of zero charge （PZC≈-0.4 V）, both Ea,app and A for HER increase （e.g., Ea,app increases from 24 kJ/mol to 32 kJ/mol）. The increase in Ea,app and A with negative shift in φ from -0.25 V to PZC is explained by the increases of both internal energy change and entropy change from reactants to the transition states, which is correlated with the change in the hydrogen bond network during HER. The positive entropy effects overcompensate the adverse effect from the increase in the activation energy, which leads to a net increase in HER current with the activation energy negative shift from the onset potential of HER to PZC. It is pointed out that entropy change may contribute greatly to the kinetics for electrode reaction which involves the transfer of electron and proton, such as HER.展开更多
A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol....A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) kJ·mol-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, △CHM- (s), was calculated to be (104.160 ± 0.168) kJ · mol-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.展开更多
The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at ...The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at 298 K can be represented by F（kmol·m-2·s-1）=10-5.07 [TiO 2 ＋ ][H＋]-1 [NaHA 2 ]（o）·Analysis of the rate expression reveals that the rate determining step is（TiO）（i）2＋ ＋（HA 2）（i）-[TiO（HA2）]（i）＋.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.展开更多
In（Ⅲ） was quantitatively adsorbed by iminodiacetic acid resin （IDAAR） in the medium of pH = 4.52. The statically saturated sorption capacity of IDAAR is 235.5 mg·g^-1. 1.0 mol·L^-1 HCl can be used as an...In（Ⅲ） was quantitatively adsorbed by iminodiacetic acid resin （IDAAR） in the medium of pH = 4.52. The statically saturated sorption capacity of IDAAR is 235.5 mg·g^-1. 1.0 mol·L^-1 HCl can be used as an eluant. The elution efficiency is 97.9%. The resin can be regenerated and reused without apparent decrease of sorption capacity. The sorption rate constant is k298 = 1.94 × 10-5 s^-1. The apparent sorption activation energy of IDAAR for In（Ⅲ） is 20.1 kJ·mol^-1. The sorption behavior of IDAAR for In（HI） obeys the Freundlich isotherm. The enthalpy change is AH= 17.2 kJ·mol^-1.展开更多
In the present paper cusp catastrophe is used to model the topological property of poten-tial energy profile of elementary reactions, and four typical situations, which can be trans-formed into two types, have been sy...In the present paper cusp catastrophe is used to model the topological property of poten-tial energy profile of elementary reactions, and four typical situations, which can be trans-formed into two types, have been systematically analyzed with 58 independent elementaryreactions. The main results obtained here are (i) the concept of activation energy is brieflydiscussed and extended; (ii) the reaction O+ CO→CO_2 is found to belong to type Ⅳ, not totype Ⅰ;and (iii) there may be some special correlation between α_1 and α_2. Finally the neces-sary discussions are carried out.展开更多
基金ACKNOWLEDGMENTS This work was supported by the One Hundred Talents＇ Program of the Chinese Academy of Science, the National Natural Science Foundation of China （No.21073176）, and the National Basic Research Program of China National Science and Technology （No.2010CB923302）.
文摘Hydrogen evolution reaction （HER） at polycrystalline silver electrode in 0.1 mol/L HClO4 solution is investigated by cyclic voltammetry in the temperature range of 278-333 K. We found that at electrode potential φa,app decreases with φ, while pre-exponential factor A remains nearly unchanged,which conforms well the prediction from Butler-Volmer equation. In contrast, with φ nega-tive shifts from the onset potential for HER to the potential of zero charge （PZC≈-0.4 V）, both Ea,app and A for HER increase （e.g., Ea,app increases from 24 kJ/mol to 32 kJ/mol）. The increase in Ea,app and A with negative shift in φ from -0.25 V to PZC is explained by the increases of both internal energy change and entropy change from reactants to the transition states, which is correlated with the change in the hydrogen bond network during HER. The positive entropy effects overcompensate the adverse effect from the increase in the activation energy, which leads to a net increase in HER current with the activation energy negative shift from the onset potential of HER to PZC. It is pointed out that entropy change may contribute greatly to the kinetics for electrode reaction which involves the transfer of electron and proton, such as HER.
文摘A ternary solid complex Lu(Et2dtc)3(phen) has been obtained from the reaction of hydrated lutetium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1,10-phenanthroline (o-phen·H2O) in absolute ethanol. IR spectrum of the complex indicates that Lu3+ binds with sulfur atom in the Na(Et2dtc)3 and nitrogen atom in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex, △CHM- (l), was determined to be (-32.821 ± 0.147 ) kJ·mol-1 at 298.15 K by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex, △CHM- (s), was calculated to be (104.160 ± 0.168) kJ · mol-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, such as the activation enthalpy (△HM-), the activation entropy (?驻SM-), the activation free energy (△GM-), the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A) and the reaction order (n), were obtained by combination the reaction thermodynamic and kinetic equations with the data of thermokinetic experiments. The molar heat capacity of the complex, cm, was determined to be (82.23 ± 1.47) J·mol-1·K-1 by the same microcalormeter. The constant-volume combustion energy of the complex, ΔcU, was determined as (-17 898.228 ± 8.59) kJ·mol-1 by an RBC-Ⅱtype rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, △CHM-, and standard enthalpy of formation, △CHM-, were calculated to be (-17 917.43 ± 8.11) kJ·mol-1 and (-859.95 ±10.12) kJ·mol-1, respectively.
基金supported by the Key Subject of Shanghai Municipality (S30109)the Opening Project of Key Laboratory of Solid Waste Treatment and Resource Recycle (SWUST),the Ministry of Education (09zxgk02)Research Program of Science and Technology Commission of Shanghai Municipality (09dz1204403)
文摘The kinetics of forward extraction of Ti（IV） from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti（IV）,the rate of forward extraction at 298 K can be represented by F（kmol·m-2·s-1）=10-5.07 [TiO 2 ＋ ][H＋]-1 [NaHA 2 ]（o）·Analysis of the rate expression reveals that the rate determining step is（TiO）（i）2＋ ＋（HA 2）（i）-[TiO（HA2）]（i）＋.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.
文摘In（Ⅲ） was quantitatively adsorbed by iminodiacetic acid resin （IDAAR） in the medium of pH = 4.52. The statically saturated sorption capacity of IDAAR is 235.5 mg·g^-1. 1.0 mol·L^-1 HCl can be used as an eluant. The elution efficiency is 97.9%. The resin can be regenerated and reused without apparent decrease of sorption capacity. The sorption rate constant is k298 = 1.94 × 10-5 s^-1. The apparent sorption activation energy of IDAAR for In（Ⅲ） is 20.1 kJ·mol^-1. The sorption behavior of IDAAR for In（HI） obeys the Freundlich isotherm. The enthalpy change is AH= 17.2 kJ·mol^-1.
基金Project supported by the National Natural Science Foundation of China.
文摘In the present paper cusp catastrophe is used to model the topological property of poten-tial energy profile of elementary reactions, and four typical situations, which can be trans-formed into two types, have been systematically analyzed with 58 independent elementaryreactions. The main results obtained here are (i) the concept of activation energy is brieflydiscussed and extended; (ii) the reaction O+ CO→CO_2 is found to belong to type Ⅳ, not totype Ⅰ;and (iii) there may be some special correlation between α_1 and α_2. Finally the neces-sary discussions are carried out.
