NIST Chemical Kinetics Database

Author(s):   Chang, J.G.; Chen, H.T.; Xu, S.C.; Lin, M.C.
Title:   Computational study on the kinetics and mechanisms for the unimolecular decomposition of formic and oxalic Acids
Journal:   J. Phys. Chem. A
Volume:   111
Page(s):   6789 - 6797
Year:   2007
Reference type:   Journal article
Squib:   2007CHA/CHE6789-6797

Reaction:   HOOCCOOH → dihydroxycarbene + CO₂
Reaction order:   2
Temperature:   300 - 2000 K
Rate expression:   3.47x10^-2 [cm³/molecule s] (T/298 K)^-0.01 e^{-149160 [J/mole]/RT}
Category: Theory
Data type:   Transition state theory
Pressure dependence:   Rate constant is low pressure limit
Comments:   Reaction potential energy surface was studied using quantum chemistry and rate constants were calculated using RRKM. This channel is one of two producing dihydroxycarbene and CO₂; rate constants for the two channels were calculated separately.

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Rate constant values calculated from the Arrhenius expression:

T (K)	k(T) [cm³/molecule s]
300	3.71E-28
400	1.15E-21
500	9.04E-18
600	3.57E-15
700	2.55E-13
800	6.28E-12
900	7.57E-11
1000	5.55E-10
1100	2.83E-9
1200	1.10E-8
1300	3.48E-8
1400	9.32E-8
1500	2.19E-7
1600	4.62E-7
1700	8.92E-7
1800	1.60E-6
1900	2.71E-6
2000	4.34E-6