Ab initio modeling of organophosphorus combustion chemistryElectronic supplementary information (ESI) available: Optimized geometric parameters for transition states. See http://www.rsc.org/suppdata/cp/b4/b402742f/

Degradation mechanisms of SOFC anodes in coal gas containing phosphorus

“…In previous studies, it has been concluded that the predominant phosphorus-containing gas species in coal gas is HPO 2 (g) [12]. Inclusion of parameters for HPO 2 (g) and HPO 3 (g) [41,42] in the calculations indeed led to predictions that HPO 2 (g) should be predominant, but also that the critical concentration of phosphorus needed to form Ni 2 P is more than two orders of magnitude higher than shown in Fig. 16, is also inconsistent with experimental observations.…”

The decisive role of pericyclic reactions in the thermal decomposition of organophosphorus compounds

“…Quantum chemical calculations have been used to determine mainly thermochemical properties [17,18], but also rate constants of molecular systems containing trivalent or pentavalent phosphorus [19]. Sullivan et al [20] investigated the combustion of methylphosphonic acid (MPA) at the CBS-Q level of theory and evaluated several elementary reactions, such as the unimolecular decomposition of MPA and the hydrogen abstraction from MPA by OH radicals. Comparison with literature showed significant discrepancies especially for reactions involving P-O bonds and highlighted the fact that reaction rates based on analogous C-O bond chemistry are unreliable.…”

Elementary reaction rate model for MPA oxidation in supercritical waterElectronic supplementary information (ESI) available: Full MPA SCWO reaction mechanisms. See http://www.rsc.org/suppdata/cp/b4/b402743d/

“…Possible reaction intermediates were identified and the thermochemical values for these intermediates were accurately calculated from CBS-Q ab initio calculations in Gaussian 98, as discussed in separate documentation. 13 By examining different possible reaction types, pathways between the different organophosphorus intermediates were proposed and rates were estimated. In addition to developing a new organophosphorus reaction set, an updated C-1 SCWO submechanism was added to the model.…”

“…The first paper presented ab initio calculations of organophosphorus thermochemistry and reaction rates. 13 As discussed in the introduction of that paper, few elementary reaction rate models for organophosphorus combustion are available. The two most detailed combustion mechanisms by Korobeinichev et al 14 and Glaude et al 15 are for the model compound, dimethylmethylphosphonate (DMMP or PO(OCH 3 ) 2 CH 3 ).…”

“…In the first paper in this series, the thermochemistry and key reaction rates for MPA oxidation were computed from ab initio calculations. 13 Thermochemical values for 17 phosphorus-containing compounds, including 10 new phosphorus-containing species, were determined at the CBS-Q level. Additionally, 14 reaction rates were calculated that could be important in the MPA SCWO mechanism.…”