Abstract
Rate constants for the two stages of germane dissociation (GeH4 → GeH2 + H2(I) and GeH2 → Ge + H2(II) have been derived from the studies of the chemiluminescence kinetics during germane dissociation in the presence of nitrous oxide behind shock waves at 1060–1300 K and the full density equal to ∼10−5 mol/cm3. Analysis in terms of the RRKM model gave the following expressions for the rate constants of these reactions in the high and low pressure limits: k 1, ∞ = 2.0 × 1014exp(−208.0/RT) s−1; k 1, 0 = 1.7 × 1018(1000/T)3.85exp(−208.0/RT) cm3/(mol s); and k 2, 0 = 2.8 × 1015(1000/T)1.32exp(−135.0/RT) cm3/(mol s). The results, in combination with the available enthalpies of formation of radical GeH2, show that the back reaction for stage (I) has an energy barrier of about 66 kJ/mol.
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