Understanding reduction of carbon tetrachloride at nickel surfaces

Nickel has been found to be an effective cathode material and catalyst for reductive destruction of chlorinated solvents in contaminated water. This study investigated reductive dechlorination of carbon tetrachloride (CT) at a nickel rotating disk electrode using chronoamperometry and electrochemical impedance spectroscopy. Chronoamperometry experiments were performed to determine rates of CT reduction as a function of the electrode potential, pH, CT concentration, and temperature. The reaction products of CT dechlorination were 95 +/- 4% methane and 4.1 +/- 2.5% chloroform. Only trace levels of methylene chloride and chloromethane were produced, indicating that sequential hydrogenolysis was not the predominant pathway for methane production. Electrochemical impedance spectroscopy showed that the rate-limiting step for methane production was the transfer of the first electron to a physically adsorbed CT molecule. The temperature independence of the electron transfer coefficient and the decreasing activation energy with decreasing electrode potential indicated that the rate-limiting step involved an outer-sphere electron transfer. At neutral pH values, oxides inactivated much of the electrode surface for both CT reduction and hydrogen evolution. At lower pH values, oxide dissolution served to increase the electroactive surface area of the disk electrode. Anson analysis and kinetic modeling showed that CT adsorption to electroactive sites was a nonlinear function of the CT concentration and was in equilibrium with the bulk solution. CT dechlorination rates on nickel electrodes were 16 times slower than those on iron electrodes under similar conditions. However, CT reactions at nickel surfaces produced predominantly methane as the first detectable product, while reduction at iron surfaces produced chloroform. These results suggest that, although nickel is not a catalyst for the rate-limiting step for CT dechlorination, it may serve a catalytic role in subsequent reaction steps.     

Experimental and molecular mechanics and ab initio investigation of activated adsorption and desorption of trichloroethylene in mineral micropores

This research investigated activated adsorption of a hydrophobic organic contaminant(HOC) in mineral micropores using experimental and molecular modeling techniques. Adsorption of trichloroethylene (TCE) on a silica gel adsorbent was measured using a frontal analysis chromatography technique at atmospheric and elevated fluid pressures. Increasing the fluid pressure yielded increased TCE uptake that was not released upon lowering the pressure back to atmospheric conditions. This showed that the increase in pressure was able to rapidly induce the formation of a desorption-resistant fraction that previous investigations have shown requires months to develop at atmospheric pressure. Grand Canonical Monte Carlo (GCMC) modeling was then used to elucidate the nature of water and TCE behavior within silica micropores. The GCMC modeling showed that molecular scale packing restrictions resulted in pore fluid densities that ranged from 0.28 to 0.78 of those in the bulk solution. The modeling also showed that TCE was able to displace water from hydrophilic mineral pores due to molecular scale packing restrictions. Exothermic isosteric heats for TCE adsorption up to -27 kJ/mol were observed and were greatest in pores of 7 and 8 A. This indicated that TCE adsorption was energetically most favorable in pores that were minimally large enough to accommodate a TCE molecule. The pressure-induced uptake appeared to result primarily from an increase in the packing density in the smallest pores. Ab initio calculations showed that small distortions of a TCE molecule from its low energy conformation require high activation energies. Results from this study indicate that activated adsorption requiring bond angle distortions in the adsorbate may be responsible forthe slow attainment of adsorptive equilibrium of HOCs on microporous solids. Likewise, activated desorption from molecular-sized adsorption sites may contribute to the slow release of HOCs from aquifer sediments.     

Remembering Joseph Brozek (1913-2004): Brozek's China connection.

In the pages of a recent issue of this journal, several historians of psychology wrote of their acquaintance with the late Professor Joseph Brozek, the naturalized American polymath born in central Bohemia (today known as the Czech Republic) who worked nearly all of his adult life in the Universities of Pennsylvania, Minnesota, and Lehigh and championed the cause of international collaborations for the furtherance of studies in the history of psychology (Woodward et al., 2004). Apart from a brief biography, these historians mentioned his numerous investigations into the work of several Czech scientists who worked in psychology or related fields and who were either unknown or neglected in the West; they also discussed his numerous book chapters and reviews, some of which were in his specialty field, nutrition. But Brozek is most remembered for his desire to link up people in different parts of the world who had a common interest in the history of psychology. Although several of the contributors addressed this feature of his work, there was no mention of his attempts to bring Chinese psychologists into the international arena. What follows is the author's attempt to redress this omission. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Ab initio study of carbon-chlorine bond cleavage in carbon tetrachloride

Chlorinated solvents in groundwater are known to undergo reductive dechlorination reactions with Fe(ll)-containing minerals and with corroding metals in permeable-barrier treatment systems. This research investigated the effect of the reaction energy on the reaction pathway for C-Cl bond cleavage in carbon tetrachloride (CCl4). Hartree-Fock, density functional theory, and modified complete basis set ab initio methods were used to study adiabatic electron transfer to aqueous-phase CCl4. The potential energies associated with fragmentation of the carbon tetrachloride anion radical (CCl4-) into a trichloromethyl radical (CCl3) and a chloride ion (Cl-) were explored as a function of the carbon-chlorine bond distance during cleavage. The effect of aqueous solvation was investigated using a continuum conductor-like screening model. Solvation significantly lowered the energies of the reaction products, suggesting that dissociative electron transfer was enhanced by solvation. The potential energy curves in an aqueous medium indicate that reductive cleavage undergoes a change from an inner-sphere to an outer-sphere mechanism as the overall energy change for the reaction is increased. The activation energy for the reaction was found to be a linear function of the overall energy change, and the Marcus-Hush model was used to relate experimentally measured activation energies for CCl4 reduction to overall reaction energies. Experimentally measured activation energies for CCl4 reduction by corroding iron correspond to reaction energies that are insufficiently exergonic for promoting the outer-sphere mechanism. This suggests that the different reaction pathways that have been observed for CCl4 reduction by corroding iron arise from different catalytic interactions with the surface, and not from differences in energy of the transferred electrons.     

Evaluation of density functional theory methods for studying chemisorption of arsenite on ferric hydroxides

Understanding adsorption of arsenic on ferric hydroxide surfaces is important for predicting the fate of arsenic in the environment and in designing treatment systems for removing arsenic from potable water. This research investigated the binding of arsenite to ferric hydroxide clusters using several density functional theory methods. Comparison of calculated and experimentally measured As-O and As-Fe bond distances indicated that As(III) forms both bidentate and monodentante corner-sharing complexes with Fe(III) octahedra. Edge-sharing As(III) complexes were less energetically favorable and had As-O and As-Fe distances that deviated more from experimentally measured values than corner-sharing complexes. The hydrated bidentate complex was the most energetically favorable in the vacuum phase, while the monodentate complex was most favored in the aqueous phase. Structures optimized using the Harris and Perdew-Wang local functionals were close to both experimental data and structures optimized using the nonlocal Becke-Lee-Yang-Parr (BLYP) functional. Binding energies calculated with the gradient-corrected BLYP functional were only weakly dependent on the method used for geometry optimization. The approach of using low-level structures coupled with higher level single-point energies was found to reduce computational time by 75% with no loss in accuracy of the computed binding energies.     

Theoretically predicted rate constants for mercury oxidation by hydrogen chloride in coal combustion flue gases

In this work, theoretical rate constants are estimated for mercury oxidation reactions by hydrogen chloride that may occur in the flue gases of coal combustion. Rate constants are calculated using transition state theory at the quadratic configuration interaction (QCI) level of theory with single and double excitations, and are compared to results obtained from density functional theory, both including high level pseudopotentials for mercury. Thermodynamic and kinetic data from the literature are used to assess the accuracy of the theoretical calculations when possible. Validation of the chosen methods and basis sets is based upon previous and current research on mercury reactions involving chlorine. The present research shows that the QCISD method with the 1992 Stevens et al. basis set leads to the most accurate kinetic and thermodynamic results for the oxidation of mercury via chlorine containing molecules. Also, a comparison of the heats of reaction data for a series of mercury oxidation reactions reveals that the density functional method, B3LYP, with the 1997 Stuttgart basis set provides reasonably accurate results for these large systems.     

Chen Li: China's elder psychologist.

Chen Li is one a small group of psychologists in China who trained abroad early in their careers, returned to teach and do research, and continued doing so into later life beyond normal retirement age. His contacts with a number of prominent psychologists in England and Germany in the 1930s, and his inadvertent position of a political row in China in the 1960s, leading to the shutting down of psychology for 10 yrs, make him historically important. Known for his work in organizational psychology and education, he is a distinguished psychologist and educational leader. Although trained as an experimentalist, he now embraces a broader view of psychology but remains emphatic it should be applied to real-life problems. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Learning from others: Japan's role in bringing psychology to China.

Recent research by Chinese and Japanese historians of psychology and education suggests that it was educational reformers' copying of Japan's education system in the 1st decade of the 20th century that provided the context for developing modern psychology in China. Psychology, although not well understood by those reformers, was thought to be useful in teacher training. In 1902 Japanese psychology teachers came to China and some textbooks were translated. Chinese students studying in Japan also brought back psychological knowledge in translations. However, the Chinese attraction to study in Japan declined after 1906. As the United States opened new universities and provided opportunities for Chinese students to study in US schools, it became a more attractive option for later generations of Chinese, who saw psychology become established as a separate discipline. (PsycINFO Database Record (c) 2010 APA, all rights reserved)