Christopher L. Wilson

Bio: Christopher L. Wilson is an academic researcher from University College London. The author has contributed to research in topics: Deuterium & Ketone. The author has an hindex of 11, co-authored 37 publications receiving 328 citations.

Direct Introduction of Deuterium into Benzene without Heterogeneous Catalysis

Abstract: The transference of deuterium to benzene from hydrogen gas or from water at the surface of finely divided metal catalysts has been realised by Horiuti, Polanyi and Ogden1, and unsuccessful attempts to achieve a similar object have recently been recorded by Farkas, Farkas and Rideal2 and Murray, Squire and Andrews3.

Applying Stable Isotope Fractionation Theory to New Systems

Abstract: A basic theoretical understanding of stable isotope fractionations can help researczzzhers plan and interpret both laboratory experiments and measurements on natural samples. The goal of this chapter is to provide an introduction to stable isotope fractionation theory, particularly as it applies to mass-dependent fractionations of non-traditional elements and materials. Concepts are illustrated using a number of worked examples. For most elements, and typical terrestrial temperature and pressure conditions, equilibrium isotopic fractionations are caused by the sensitivities of molecular and condensed-phase vibrational frequencies to isotopic substitution. This is explained using the concepts of vibrational zero-point energy and the partition function, leading to Urey’s (1947) simplified equation for calculating isotopic partition function ratios for molecules, and Kieffer’s (1982) extension to condensed phases. Discussion will focus on methods of obtaining the necessary input data (vibrational frequencies) for partition function calculations. Vibrational spectra have not been measured or are incomplete for most of the substances that Earth scientists are interested in studying, making it necessary to estimate unknown frequencies, or to measure them directly. Techniques for estimating unknown frequencies range from simple analogies to well-studied materials to more complex empirical force-field calculations and ab initio quantum chemistry. Mossbauer spectroscopy has also been used to obtain the vibrational properties of some elements, particularly iron, in a variety of compounds. Some kinetic isotopic fractionations are controlled by molecular or atomic translational velocities; this class includes many diffusive and evaporative fractionations. These fractionations can be modeled using classical statistical mechanics. Other kinetic fractionations may result from the isotopic sensitivity of the activation energy required to achieve a transition state, a process that (in its simplest form) can be modeled using a modification of Urey’s equation (Bigeleisen 1949). Theoretical estimates of isotopic fractionations are particularly powerful in systems that are difficult to characterize experimentally, or when empirical …

Organic Catalysis over Crystalline Aluminosilicates

Abstract: Publisher Summary This chapter focuses on organic catalysis over crystalline alumiosilicates. Zeolites are crystalline aluminosilicates composed of SiO4 and AlO4 tetrahedra arranged in various geometric patterns. The chapter discusses reactions over a wide variety of crystalline aluminosilicates and emphasizes on catalysis over X- and Y-type faujasites. Unusual opportunities for organic catalysis were found to exist when these were base exchanged to substantially eliminate their alkali metal content. It is shown that catalytic activity in ion-exchanged faujasites is influenced by cation type, cation location in the lattice, zeolite Si/Al ratio, and the presence of proton donors. The existence of several crystallographically distinct cation locations provides the basis for a potential heterogeneity of sites in catalytic reactions. The Linde workers made calculations for the electrostatic field strengths of surface cations near SII and SIII in an X-type zeolite of Si/Al ratio 1.0 and in a Y-type zeolite of Si/Al ratio 2.0. In both cases, the fields has been significantly larger near SIII than SII at a distance of 2 Ǻ from the center of the cation for the univalent cation-exchanged systems, provided both sites are occupied.