ReactionMechanismGenerator / ReactionMechanismGenerator/RMG-database
Ea in ROOH_sec;C_rad/H/NonDeC - Amrit Jalan's Thesis - Is the entry in the database correct?
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Description
The reaction ROOH + R. = ROO. + RH has an exact match in the RMG database, indicated with '[AJ]'.
It was suggested that this was calculated by Amrit Jalan - however reading his thesis, unless I am making a mistake, a positive activation energy is suggested while the database contains a negative activation energy? (Thesis link: https://dspace.mit.edu/handle/1721.1/91059 - page 195)
Entry in the database (same applies for the entry above with ROOH_pri):
entry(
index = 551,
label = "ROOH_sec;C_rad/H/NonDeC",
kinetics = ArrheniusEP(
A = (2.51e-11, 'cm^3/(mol*s)'),
n = 6.77,
alpha = 0,
E0 = (-8.6, 'kcal/mol'),
Tmin = (500, 'K'),
Tmax = (1000, 'K'),
),
rank = 3,
shortDesc = u"""[AJ]CBS-QB3 calculations with 1DHR corrections, reverse rates computed using DFT_QCI_thermo""",
)
And in Jalan's Thesis (page 195) I find:
Table 6.1: Predicted Arrhenius parameters (Units: mol, cm 3 , sec, kcal/mol) for
CH3OO* + RH* H-abstraction reactions with R=CH3CH2CH2_, CH3C_(OOH)CH3,
CH3COCH2_, CH3CH2C_O.Reaction A n Ea
CH3CH2CH3 -> CH300H + CH3CH_CH3 1.3 x10-8 6.2 8.5
CH3CH(OOH)CH 3 -> CH3C(O)CH3 + *OH + CH300H 1.1 x10-13 7.2 2.9
CH3C(O)CH3 -> CH300H + *CH2C(O)CH3 4.4 x10-12 7.1 8.9
CH3CH2CHO -> CH300H + CH3CH2C_O 1.9 x10-3 4.5 4.4The units for A are sec- 1 for unimolecular reactions and in cm 3 mol-1 sec-1 for
bimolecular reactions, with Ea in kcal/mol. The rate coefficient is
k = A(T/1[K])" exp(-Ea/RT).
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Research direction
Inspect the database entry for index 551, labeled "ROOH_sec;C_rad/H/NonDeC", and compare its Arrhenius parameters with page 195 of Amrit Jalan's thesis. Verify whether the negative E0 and associated A and n values are correct for the stated reaction, then document and correct the entry if the comparison confirms an error.
Written by the indexing model from the issue text.
Assessment
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- Issue type
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