The Thermal Decomposition of Germane. I. Kinetics.

Kinetics and mechanism of the germane decomposition

“…We have reinvestigated the static system germane pyrolysis reaction in order to obtain more information about the nature of the decomposition reactions under conventional reaction conditions. Our results, along with those of the prior workers ( [2] and [3]), are given in Table I.…”

“…The question remains, then, as to the real nature of the first-order reaction proposed and measured by Tamaru et al [2] and Devyatykh and Frolov under static system studies. The later [3] have suggested that the first-order process may really apply to reactions occurring on the surfaces of germane particulates dispersed uniformly in the container volume.…”

“…Thus in the first such study, Hogness and Johnson [l] using Langmuir adsorption theory, fit their data to a threecenter adsorption of germane on a germanium surface; while Tamaru, Boudart, and Taylor [2] interpreted their data in terms of two parallel reaction pathways: a zero-order reaction occurring on the surface of deposited germanium films, and a first-order reaction occurring in the space of the reaction vessel. The latter interpretation was subsequently reexamined and retained by Devyatykh and Frolov [3].…”

The Heterogeneous and Homogeneous Thermal Decompositions of Nickel Carbonyl

“…After tlie deposition of further layers of 1licl;el (only a few partial deco~npositioils are required), the rate was re-established. Thus oxygen illhibits tlie heterogeneous reaction, contrary to its effect on a germanium surface when germane is thermally deconlposed (13). Its effect also dilTers in tliat the inhibition is eliminated on further depositio~l of nickel, whereas tlie oxygen liad a persistent effect with germnnium films and was therefore considered to diffuse to tlie surface 011 addition of further germanium.…”

In situ surface dynamics in heterogeneous catalysis

“…The observations (3) and (4) demonstrate that the chemisorbed hydrogen during the reaction has much higher fugacity than the ambient hydrogen gas, in other words, the desorption of fully covered hydrogen is the rate-determining step of the overall reaction. In this way this catalytic system still remains as one of the cases of which reaction mechanism is well understood.…”