Publication costs assisted by the U. S. Energy Research and Development AdminlstrationRate constants for the reactions of H atoms, formed by mercury photosensitization of H2-substrate mixtures at 32 O C , with (CH3),SiH4-, and (C2HS),SiH4-, for n = 0, 1,2,3; with (CH3),SiD4-, for n = 0, 1; and with Si2H6, Si2D6, GeH4, and Ge2H6 have been determined in experiments involving the competitive reaction of H atoms with C2H4 and i-C4HB. Activation energies, estimated from these rate constants, have been combined with thermochemical data by means of a bond-energy-bond-order (BEBO) method of calculation to yield a consistent set of dissociation energies for Si-H bonds in the R,SiH4-, series of silanes for n = 0, 1, 2, 3.
The ion-molecule reactions occurring in ionized monosilane have been studied by high-pressure mass spectrometry up to about 0.5 Torr and by tandem mass spectrometry in both 90 and 180°c onfigurations. Relative cross sections of the second-order primary ion and secondary ion reactions have been determined at relative kinetic energies of reactants near 1 eV. Rate constants of both second-and third-order primary ion reactions have also been measured. It is suggested that SÍ2H74", Si3Hg+, and Si4Hu+, whose abundance reaches 35% of the ions present, are responsible for the large yield of disilane in the radical-scavenged radiolysis.
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