Hydrogen adsorbed tungsten

Elkowitz A B, McCreery J H and Wolken G 1976 Dynamics of atom-adsorbed atom collisions Hydrogen on tungsten Chem. Phys. 17 423... 

Barker RA, Estrup PJ (1978) Hydrogen on tungsten(lOO) - adsorbate-induced surface reconstruction. Phys Rev Lett 41 1307... 

R.A. Barker and P.J. Estrup. Hydrogen on Tungsten (100) Adsorbate Induced Surface Reconstruction. Phys. Rev. Lett. 41 1307 (1978). 

Unlike the cathodic reaction, anodic oxidation (ionization) of molecular hydrogen can be studied for only a few electrode materials, which include the platinum group metals, tungsten carbide, and in alkaline solutions nickel. Other metals either are not sufficiently stable in the appropriate range of potentials or prove to be inactive toward this reaction. For the materials mentioned, it can be realized only over a relatively narrow range of potentials. Adsorbed or phase oxide layers interfering with the reaction form on the surface at positive potentials. Hence, as the polarization is raised, the anodic current will first increase, then decrease (i.e., the electrode becomes passive see Fig. 16.3 in Chapter 16). In the case of nickel and tungsten... 

Equation (89) shows that the allowance for the variation of the charge of the adsorbed atom in the activation-deactivation process in the Anderson model leads to the appearance of a new parameter 2EJ U in the theory. If U — 2Er, the dependence of amn on AFnm becomes very weak as compared to that for the basic model [see Eq. (79)]. In the first papers on chemisorption theory, a U value of 13eV was usually accepted for the process of hydrogen adsorption on tungsten. However, a more refined theory gave values of 6 eV.57 For the adsorption of hydrogen from solution we may expect even smaller values for this quantity due to screening by the dielectric medium. 

Field electron emission coupled with flash-filament studies have been employed by Condon and Hansen to study benzene chemisorption on tungsten (21). Evidence was obtained for the chemisorption of benzene by a single bond (probably of -character) to the surface. This form of asso-ciatively adsorbed benzene [(I), Scheme 1] appeared to exist in equilibrium with cr-adsorbed-CeHs (II) and adsorbed atomic hydrogen. 

The substrate in these studies was restricted to be rigid, and Morse functions were used for the hydrogen-surface and two-body interactions. The parameters in the Morse functions were determined for single hydrogen atoms adsorbed on the tungsten surface by fitting to extended Huckel molecular orbital (EHMO) results, and the H2 Morse parameters were fit to gas-phase data. The Sato parameter, which enters the many-body LEPS prescription, was varied to produce a potential barrier for the desorption of H2 from the surface which matched experimental results. 

In this section a method for the direct calorimetric determination of heats of adsorption on evaporated metal films is described and results for the heals of adsorption of hydrogen on nickel, iron, and tungsten are reported. In all cases the heats of adsorption decrease with the fraction of surface covered in a mode that can satisfactorily be explained by interaction of adsorbed atoms. A criterion for mobility of the adsorbed atoms is developed... 

Not only the hydrogen adsorption but also the nitrogen adsorption as observed by Davis (17a), as well as by Beeck and coworkers fits well into this picture. It was observed by Beeck et al. that 60 % of the surface of evaporated tungsten films could be covered by nitrogen at room temperature, 50% being adsorbed instantaneously with a constant heat... 

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