14457-64-8Relevant articles and documents
Gas-Phase Reaction between Hydrocarbons and Metal Oxides: The AlO + CH4 Reaction from 590 to 1380 K
Belyung, David P.,Fontijn, Arthur,Marshall, Paul
, p. 3456 - 3459 (1993)
A recent ab initio study suggested that gaseous metal oxides can directly abstract H atoms from hydrocarbons, but with considerable barriers.To try to confirm the occurrence of such reactions, the title reaction has been studied in a high-temperature fast-flow reactor.The data are well described by a fitting expression k(590-1380 K) = 9.6 * 10-39(T/K)7.96 exp(2468 K/T) cm3 molecule-1 s-1, with 2? precision limits varying with temperature from +/- 4percent to +/- 12percent.The corresponding 2? accuracy limits are about +/- 25percent.Comparison of this result to further ab initio and conventional transition-state theory calculations suggests that direct abstraction indeed can occur at the higher temperatures but that one or more other channels, possibly involving AlO insertion into a C-H bond, dominate in the initial attack step.The potential implications of this work for catalytic conversion of methane to higher hydrocarbons are considered.
Electron spin resonance matrix isolation studies of 27Al16,17O, 69,71Ga16,17O and 115In16,17O: Observed hyperfine interactions compared with ab initio theoretical results
Knight Jr., Lon B.,Kirk, Thomas J.,Herlong, John,Kaup, John G.,Davidson
, p. 7011 - 7019 (2007/10/03)
Electron spin resonance (ESR) studies are reported for Al16,17O, Ga16,17O, and In16,17O isolated in neon matrices at 4 K. Except for Al16O, no previous ESR measurements have been reported for these X 2Σ diatomic radicals. The pulsed laser vaporization of the metals in the presence of 16O2 and 17O2 produced high quality ESR spectra of these metal oxide radicals whose nuclear hyperfine interactions (A tensors) were fully resolved for both the metal and oxygen nuclei. An analysis of the experimental spin densities in combination with different types of theoretical calculations provided detailed information concerning the electronic structure trends going down this metal oxide group. Increased p-orbital spin density on oxygen was observed for the heavier metal oxide radicals. Nonrelativistic ab initio calculations with an extended basis set and the UB3LYP method reproduced the trends in the isotropic and dipolar hyperfine interactions. All-electron CI calculations, restricted open-shell Hartree-Fock (ROHF) wave functions, and unrestricted Hartree-Fock wave functions gave results very different from experiment and from each other for the isotropic interaction. All calculations were in fair agreement with each other for the dipolar interaction and provided an assignment of the sign for that term.
Reactivities of spin-orbit states in Al((2)P(1/2,3/2))+O2(X(3)Σ(-)(g))AlO(X(2)Σ(+))+O((3)P(0,1,2)). A fluorescence imaging study
Chen, Kuo-mei,Sung, Chun-hwa,Chang, Jia-lin,Chung, Teng-hui,Lee, Kuo-huei
, p. 17 - 24 (2008/10/08)
A crossed beam chemical reaction, Al((2)P(1/2,3/2))+O2(X(3)Σ(-)(g)) AlO(X(2)Σ(+))+O((3)P(0,1,2)) was investigated by fluorescence imaging techniques. Multiplex detection of speeds and quantum states of both reactants and products has been implemented. The
