Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates

The reactivity of the species formed at the surface of a Au/Ce(La)O2 catalyst during the water������¢���¯���¿���½���¯���¿���½gas shift (WGS) reaction were investigated by operando diffuse reflectance Fourier transform spectroscopy (DRIFTS) at the chemical steady state during isotopic transient kinetic analyses (SSITKA). The exchanges of the reaction product CO2 and of formate and carbonate surface species were followed during an isotopic exchange of the reactant CO using a DRIFTS cell as a single reactor. The DRIFTS cell was a modified commercial cell that yielded identical reaction rates to that measured over a quartz plug-flow reactor. The DRIFTS signal was used to quantify the relative oncentrations of the surface species and CO2. The analysis of the formate exchange curves between 428 and 493 K showed that at least two levels of reactivity were present. ������¢���¯���¿���½���¯���¿���½Slow formates������¢���¯���¿���½���¯���¿���½ displayed an exchange rate constant 10- to 20-fold slower than that of the reaction product CO2. ������¢���¯���¿���½���¯���¿���½Fast formates������¢���¯���¿���½���¯���¿���½ were exchanged on a time scale similar to that of CO2. Multiple nonreactive readsorption of CO2 took place, accounting for the kinetics of the exchange of CO2(g) and making it impossible to determine the number of active sites through the SSITKA technique. The concentration (in mol g������¢���¯���¿���½���¯���¿���½1) of formates on the catalyst was determined through a calibration curve and allowed calculation of the specific rate of formate decomposition. The rate of CO2 formation was more than an order of magnitude higher than the rate of decomposition of formates (slow + fast species), indicating that all of the formates detected by DRIFTS could not be the main reaction intermediates in the production of CO2. This work stresses the importance of full quantitative analyses (measuring both rate constants and adsorbate concentrations) when investigating the role of adsorbates as potential reaction intermediates, and illustrates how even reactive species seen by DRIFTS may be unimportant in the overall reaction scheme.

Absolute single and multiple charge exchange cross sections for highly charged C, O, and Ne ions on H2O, CO, and CO2

Reported herein are measured absolute single, double, and triple charge exchange (CE) cross sections for the highly charged ions (HCIs) Cq+ (q=5,6), Oq+ (q=6,7,8), and Neq+ (q=7,8) colliding with the molecular species H2O, CO, and CO2. Present data can be applied to interpreting observations of x-ray emissions from comets as they interact with the solar wind. As such, the ion impact energies of 7.0q keV (1.62–3.06 keV/amu) are representative of the fast solar wind, and data at 1.5q keV for O6+ (0.56 keV/amu) on CO and CO2 and 3.5q keV for O5+ (1.09 keV/amu) on CO provide checks of the energy dependence of the cross sections at intermediate and typical slow solar wind velocities. The HCIs are generated within a 14 GHz electron cyclotron resonance ion source. Absolute CE measurements are made using a retarding potential energy analyzer, with measurement of the target gas cell pressure and incident and final ion currents. Trends in the cross sections are discussed in light of the classical overbarrier model (OBM), extended OBM, and with recent results of the classical trajectory Monte Carlo theory.

Measurement of charge exchange and X-ray emission cross sections for solar wind-comet interactions

X-ray emission from a comet was observed for the first time in 1996. One of the mechanisms believed to be contributing to this surprisingly strong emission is the interaction of highly charged solar wind ions with cometary gases. Reported herein are total absolute charge-exchange and normalized line-emission (X-ray) cross sections for collisions of high-charge state (+3 to +10) C, N, O, and Ne ions with the cometary species H2O and CO2. It is found that in several cases the double charge-exchange cross sections can be large, and in the case of C3+ they are equal to those for single charge exchange. Present results are compared to cross section values used in recent comet models. The importance of applying accurate cross sections, including double charge exchange, to obtain absolute line-emission intensities is emphasized.

Fractionation of Corynebacterium pekinense AS 1.299 phage subtypes by anion-exchange chromatography

A novel method to fractionate phage into its subtypes while fully retaining biological function is reported. Corynebacterium pekinense AS 1.299 phage samples, purified by either conventional ultracentrifugation or gel chromatography on a Superose® 6 Prep column (0.78×30 cm), were fractionated further into four fractions by anion-exchange chromatography on a Toyopearl SuperQ 650C column (0.5×20 cm) with a linear gradient of NaCl concentration from 0.2 to 1.0 M in 0.02 M carbonate–biocarbonate buffer, pH 10.0. Two peaks were identified to be C. pekinense AS 1.299 phages by their ability to infect the host bacteria when inoculated into the culture media, and when examined by electron microscopy. These two types of the phage were found to be morphologically the same except for the difference in the length of their non-contractile tails. Both possessed an isometric head with a diameter of 50±3 nm, while their tails were 170±10 and 210±10 nm, respectively. This simple technique provides a convenient method for phage isolation not only to its species homogeneity, but also to determine its subtype or variant homogeneity.

Behavior of the heterogeneous electron-transfer rate constants of arenes and substituted anthracenes in room-temperature ionic liquids

We report the anodic oxidation of several arenes and anthracenes within room-temperature ionic liquids (RTILs). In particular, the heterogeneous electron-transfer rates (k(0)) for substituted anthracenes and arenes are also investigated in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and found not to obey the outer-sphere Marcus-type behavior of these compounds in contrast to the behavior in traditional organic solvents,in particular the predictions for k(0) with molecular size and solvent static dielectric constant. To obtain the electron-transfer rate for 9-phenylanthracene, the dimerization and heterogeneous electron-transfer kinetics of its electrogenerated radical cations is studied in [C(2)mim][NTf2] and eight other RTILs and are both found to be largely independent of the solution viscosity.

Measurements of absolute, single charge-exchange cross sections of H+, He+ and He2+ with H2O and CO2

Absolute measurements have been made of single-electron charge-exchange cross sections of H+, He+, and He2+ in H2O and CO2 in the energy range 0.3-7.5 keV amu(-1). Collisions of this type occur in the interaction of solar wind ions with cometary gases and have been observed by the Giotto spacecraft using the Ion Mass Spectrometer/High Energy Range Spectrometer (IMS/HERS) during a close encounter with comet Halley in 1986. Increases in the He+ ion density, and in the He2+ to H+ density ratio were reported by Shelley et al, and Fuselier et al. and were explained by charge exchange. However, the lack of reliable cross sections for this process made interpretation of the data difficult. New cross sections are presented and discussed in relation to the Giotto observations.

International order flows: Explaining equity and exchange rate returns

Macroeconomic models of equity and exchange rate returns perform poorly at high frequencies. The proportion of daily returns that these models explain is essentially zero. Instead of relying on macroeconomic determinants, we model equity price and exchange rate behavior based on a concept from microstructure – order flow. The international order flows are derived from belief changes of different investor groups in a two-country setting. We obtain a structural relationship between equity returns, exchange rate returns and their relationship to home and foreign equity market order flow. To test the model we construct daily aggregate order flow data from 800 million equity trades in the U.S. and France from 1999 to 2003. Almost 60% of the daily returns in the S&P100 index are explained jointly by exchange rate returns and aggregate order flows in both markets. As predicted by the model, daily exchange rate returns and order flow into the French market have significant incremental explanatory power for the daily S&P returns. The model implications are also validated for intraday returns.

Volatile and persistent real exchange rates with or without sticky prices

The flexible-price two-country monetary model is extended to include a consumption externality with habit persistence. Two methodologies are employed to explore this model's ability to generate volatile and persistent exchange rates. In the first, actual data is used for the exogenous driving processes. In the second, the model is simulated using estimated forcing processes. The theory, in both cases, is capable of explaining the high volatility and persistence of real and nominal exchange rates as well as the high correlation between real and nominal rates. © 2007 Elsevier B.V. All rights reserved.