ChemInform Abstract: HYDROGEN-WATER DEUTERIUM EXCHANGE OVER UNSUPPORTED GROUP VIII NOBLE METALS

1974 ◽  
Vol 5 (45) ◽  
pp. no-no
Author(s):  
NORMAN H. SAGERT ◽  
RITA M. L. POUTEAU
1973 ◽  
Vol 51 (24) ◽  
pp. 4031-4037 ◽  
Author(s):  
Norman Henry Sagert ◽  
Rita Mary Louise Pouteau

Specific activities of Group VIII noble metals supported on Graphon have been determined for hydrogen–water deuterium exchange. Metal surface areas, which are required to calculate specific activities, were measured by hydrogen chemisorption, and by reaction of hydrogen with chemisorbed oxygen. For the second triad metals, ruthenium, rhodium, and palladium, and in the temperature range 140 to 225 °C, the variation of activity was Ru < Rh > Pd. For the third triad metals, osmium, iridium, and platinum, the variation of activities was Os < Ir < Pt in the same range of temperature. Apparent activation energies were measured over this temperature range, and orders of reaction with respect to hydrogen and water were measured at 160 °C (200 °C for Pt). From these data, activation energies for the surface exchange reaction were calculated. In the second triad the activation energies decrease slightly with increasing atomic number, but in the third triad they decrease quite markedly with increasing atomic number. A good correlation was obtained between the activation energy for surface exchange and the thermionic work function of the metal. This supports our earlier suggestion that Graphon is able to donate electrons to the metal and thus lower the activation energy for the surface exchange.


1974 ◽  
Vol 52 (16) ◽  
pp. 2960-2967 ◽  
Author(s):  
Norman H. Sagert ◽  
Rita M. L. Pouteau

Specific activities of unsupported powders of all six Group VIII noble metals have been determined for hydrogen – water deuterium isotope exchange. The metal surface areas, which are required to calculate the specific activities were measured by hydrogen chemisorption and were checked by electron microscopy. Specific activities were measured as a function of temperature in the range 353 to 573 K and also as a function of the partial pressure of hydrogen and water at suitable temperatures and over a tenfold range of partial pressures.The variation in the specific activities was Pd < Ir ≤ Ru < Rh < Os < Pt, and these specific activities varied over a range of about 1000. The observed orders with respect to hydrogen and water are shown to be consistent with a mechanism in which chemisorbed hydrogen atoms exchange with physically adsorbed water.From the orders and the apparent activation energies, the chemical activation energies (E0) were calculated. These varied randomly within the range 61 ± 6 kJ mol−1 for all the metals studied. Previously we showed that there was a correlation of E0 with the work function of the metal when metals were supported on a highly graphitized carbon black, and suggested that electron donation from the carbon to the metal was responsible for the correlation. This suggestion is supported by the present results which show that E0 is relatively constant for all six metals in the absence of a support.


Author(s):  
O. V. Bragin ◽  
E. G. Khelkovskaya-Sergeeva ◽  
S. V. Zotova ◽  
�. I. Vostokova ◽  
A. L. Liberman
Keyword(s):  

1971 ◽  
Vol 49 (21) ◽  
pp. 3411-3417 ◽  
Author(s):  
N. H. Sagert ◽  
R. M. L. Pouteau

Some rate data are reported for deuterium exchange between water and hydrogen using series of platinum–silica catalysts. Three different methods of preparing catalysts were used to give different series of metal particle sizes. Within each series, the particle size was increased by sintering batches in air, at temperatures up to 700 °C. These methods produced platinum particles ranging from 5 to 250 Å in diameter. Metal surface areas and particle sizes were measured by hydrogen chemisorption, X-ray diffraction, and electron microscopy.The specific rates, i.e., rates per unit surface area of platinum varied by a factor of three within each series, reaching a maximum for sintering temperatures of about 500 °C. These maximum rates, measured at 127 °C with a water-to-hydrogen ratio of 0.31, varied from 1.9 × 10−8 to 5 × 10−8 mol D2 cm−2 s−1. Thus no effect of particle size on rate was observed, and the differences noted are ascribed to other effects of the methods of preparing the catalysts.


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