NIST Chemical Kinetics Database

Author(s):   Sullivan, P.A.; Sumathi, R.; Green, W.H.; Tester, E.W.
Title:   Ab initio modeling of organophosphorus combustion chemistry
Journal:   Phys. Chem. Chem. Phys.
Volume:   6
Page(s):   4296 - 4309
Year:   2004
Reference type:   Journal article
Squib:   2004SUL/SUM4296-4309

Reaction:   O=P(OH)2CH₃ → HOPO + CH₃OH
Reaction order:   1
Temperature:   300 - 1500 K
Rate expression:   3.26x10¹³ [s^-1] (T/298 K)^0.73 e^{-439738 [J/mole]/RT}
Category: Theory
Data type:   Ab initio
Pressure dependence:   Rate constant is high pressure limit
Comments:   Reactions involved in organophosprous combustion chemistry were studied via ab initio molecular orbital theory calculations. Energies of the reactants, products and transition states were calculated using the CBS-Q method and transition-state-theory calculations were performed to evaluate the rate constants.

Geometries, frequencies, rotational constants, and energies are reported, along with bond dissociation energies and thermochemistry, including enthalpies, entropies, and heat capacities.

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Rate constant values calculated from the Arrhenius expression:

T (K)	k(T) [s^-1]
300	8.96E-64
400	1.53E-44
500	5.49E-33
600	2.84E-25
700	9.36E-20
800	1.30E-15
900	2.20E-12
1000	8.48E-10
1100	1.11E-7
1200	6.52E-6
1300	2.05E-4
1400	3.96E-3
1500	5.17E-2