Surface stoichiometry, hydrogen production

Both vanadium and niobium metals form dihydrides only at high pressures(27), and numerous phases with hydrogen compositions less than one(28). Experiments were performed to saturate vanadium clusters with deuterium. Figure 4 is a plot of the number of deuteri urn molecules found in the products. The solid straight lines are for D V ratios of 1 and 2. The corresponding curved dashed lines include corrections for some bulk atoms(2c). The best fit to the data including only surface atoms indicate a stoichiometry of 1.5. It is likely that this high surface stoichiometry is an indication of bulk i ncorporation of deuterium. 

After crystal illumination, spectrophotometric examination of the electrolyte by the pertitanate method (16) showed no dissolved titanium with a sensitivity on the order of 10 monolayers. It appears that no irreversible change in the surface stoichiometry of constituent elements accompanies the slow photogeneration of hydrogen on metal-free crystals in aqueous NaOH. Although a change in stoichiometry occurred in NaClOi, no such change occurs in other electrolytes which are also ineffective for hydrogen production. 

A detailed study of the oxidation of alkenes by O on MgO at 300 K indicated a stoichiometry of one alkene reacted for each O ion (114). With all three alkenes, the initial reaction appears to be the abstraction of a hydrogen atom by the O ion in line with the gas-phase data (100). The reaction of ethylene and propylene with O" gave no gaseous products at 25°C, but heating the sample above 450°C gave mainly methane. Reaction of 1-butene with O gives butadiene as the main product on thermal desorption, and the formation of alkoxide ions was proposed as the intermediate step. The reaction of ethylene is assumed to go through the intermediate H2C=C HO which reacts further with surface oxide ions to form carboxylate ions in Eq. (23),... 

Carbon dioxide and hydrogen also interact with the formation of surface formate. This was documented for ZnO by the IR investigation of Ueno et al. (117) and, less directly, by coadsorption-thermal decomposition study (84). Surface complex was formed from C02 with H2 at temperatures above 180°C, which decomposed at 300°C with the evolution of carbon monoxide and hydrogen at the ratio CO Hs 1 1. When carbon dioxide and hydrogen were adsorbed separately, the C02 and H2 desorption temperatures were different, indicating conclusively that a surface complex was formed from C02 and H2. A complex with the same decomposition temperature was obtained upon adsorption of formaldehyde and methanol. Based upon the observed stoichiometry of decomposition products and upon earlier reported IR spectra of C02 + H2 coadsorbates, this complex was identified as surface formate. Table XVI compares the thermal decomposition peak temperatures and activation energies, product composition, and surface... 

Curves (g), (h) and (i) of Figure 3 show the stability surfaces at pH 3.00. Note that the CLASP-w region for S3 is lower than that for S2. This is the only example of such a trend, in this figure. This is due to the fact that the conditional stability products for the 1 3 complexes are smaller than those for the 1 2 complexes (Table II) because of the enhanced influence of alpha-coefficients (21,22) on reactions of higher stoichiometry. The hydrogen ion concentration at pH 3.00 prevents CLASP-7 conditions from being attained over the range covered in... 

A pressure maximum, instead of minimum, inside the membrane could result from cases where both chemical reaction and surface diffusion are present [Sloot et al., 1992]. Thus the occurrence of a maximum or minimum local pressure inside the membrane depends on the reaction stoichiometry as well as the mobilities of the reaction species. It is assumed that only hydrogen sulfide adsorbs on the pore surface. Due to a higher transport rate of H2S enhanced by surface diffusion, the reaction zone is shifted toward the SO2 side of the membrane. In the reaction zone, larger amounts of the products are formed and higher molar fluxes of the products out of the membrane are expected so that the maxima of the mole fraction profiles of the products at the reaction zone can be sustained. 

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