A.V. Ivanov

The temperature dependence of the reactions H2(v = 1) + D, H

Abstract The temperature dependence of the rate constant for the reactions H2(v = 1)+D and H2(v = 1)+H was studied using a flow-tube method combined with EPR and thermometric techniques. The rate constants (in cm3/molecule s) were found to be kuD = (2.3 ± 1.3)×10−10exp[−(3200 ± 600)/RT]. knD = (1 ± 0.5)×10−10exp[−(3100 ± 300)/RT]. krD ⩽ 2.7×10−13 over the range 254–367 K for H2(v = 1)+D and knH+krH = (1.8 ± 0.7)×10−13 at 254 K and (3.9 ± 1.0)×10−13 at 298 K for H2(v = 1)+H.

Heterogeneous reactions of H and O2 with solid alkanes

The paper describes a new source of surface organic radicals whose special feature is a low rate of the initiation of alkyl radicals in reactions of H atoms with the surface of alkanes. A special reactor design was used to accumulate radicals at room temperature and observe alkoxyl radicals RO by the EPR method. For this purpose, alkanes were deposited on aerosil and placed into an EPR cavity. Thanks to the large area of aerosil loads (∼103 cm2), we were able to obtain a stable signal corresponding to a ∼1017 total amount of alkoxyl radicals (the degree of surface coverage ∼0.1%). When O2 was introduced into the reactor in concentrations of 1015–1016 cm−3, a sharp decrease in the signal from surface organic radicals was observed. The process was described as the first-order (RO)s + O2 → HO2 + ketone reaction with a 1.7 × 10−17 cm3 s−1 rate constant.