Solvent effects in the hydrogenation of 2-butanone

In liquid-phase reaction systems, the role of the solvent is often limited to the simple requirement of dissolving and/or diluting substrates. However, the correct choice, either pure or mixed, can significantly influence both reaction rate and selectivity. For multi-phase heterogeneously catalysed reactions observed variations may be due to changes in mass transfer rates, reaction mechanism, reaction kinetics, adsorption properties and combinations thereof. The liquid-phase hydrogenation of 2-butanone to 2-butanol over a Ru/SiO catalyst, for example, shows such complex rate behaviour when varying water/isopropyl alcohol (IPA) solvent ratios. In this paper, we outline a strategy which combines measured rate data with physical property measurements and molecular simulation in order to gain a more fundamental understanding of mixed solvent effects for this heterogeneously catalysed reaction. By combining these techniques, the observed complex behaviour of rate against water fraction is shown to be a combination of both mass transfer and chemical effects. © 2012 Elsevier Inc. All rights reserved.

Configuration-interaction effects in and intensity dependence of F- multiphoton detachment

Two- and three-photon detachment rates have been obtained for F- using several expansions in the R-matrix Floquet approach. These rates are compared with other theoretical and experimental results. The use of Hartree-Fock wavefunctions for the ground state of F with addition of continuum electrons does not lead to agreement with experiment for two- and three-photon detachment. By adding correlation terms, agreement with experiment and other theoretical results is improved considerably, demonstrating the importance of electron correlation effects. However, convergence with respect to the wavefunction expansion cannot be established, we also study the intensity dependence of multiphoton detachment rates for F- at the Nd-YAG frequency. Due to the ponderomotive shift the three-photon detachment channel closes at an intensity of 8.5 x 10(11) W cm(-2) and the influence of this channel closure on the multiphoton detachment peaks is illustrated by determining the heights of the excess-photon peaks obtained using a Gaussian laser pulse.

Utility in Willingness to Pay Space: A Tool to Address Confounding Random Scale Effects in Destination Choice to the Alps

We compare two approaches for estimating the distribution of consumers' willingness to pay (WTP) in discrete choice models. The usual procedure is to estimate the distribution of the utility coefficients and then derive the distribution of WTP, which is the ratio of coefficients. The alternative is to estimate the distribution of WTP directly. We apply both approaches to data on site choice in the Alps. We find that the alternative approach fits the data better, reduces the incidence of exceedingly large estimated WTP values, and provides the analyst with greater control in specifying and testing the distribution of WTP. © 2008 Agricultural and Applied Economics Association.

The legacy of past manuring practices on soil contamination in remote rural areas

This paper demonstrates that there can be a legacy of contamination on former arable land in remote rural areas as a result of past manuring practices. In the first part of the study four farms abandoned in the late 19th to mid-20th century were investigated with samples collected from residual material in domestic hearths, the midden heaps, kailyards (walled garden for vegetables), infields (intensively managed arable land) and outfields (less intensively managed land for cropping or grazing). Consistent sequences in concentration values were found for such elements as Pb, Zn, Cu and P in the order hearth>midden>kailyard>infield>outfield. Such patterns can in part be explained in terms of atmospheric deposition on peat and turf which were subsequently burnt in hearths to result in enhanced elemental concentrations. The ash then was deposited in midden heaps and subsequently on kailyards or infields. In the second part, microanalytical results from St. Kilda are discussed. Enhanced loadings of Pb and Zn were found in the old arable land. The highest levels of Zn were found in small fragments of carbonised and humified material and bone fragments; in contrast Pb tended to be more uniformly distributed. Seabird waste was extensively applied to the arable land and some of the Zn may have accumulated in the soil by this pathway. The retention of Zn in bone is likely to have been very minor given the rarity of bone fragments as evident in thin sections (0.3%); this compares with 6.8% for black carbonised particles which are likely to provide the main storage sites for Zn.