Table 1

TABLE 1: Summary of Rate Constants for the Epoxidation of Alkenes by Peroxyl Radicals in the Gas Phase.

reaction	temp (K)	log10(A/dm3mol-1s-1)	E(kJ/mol)	ref	dEc(kJ/mol)a	dNca	Ialkene-Aperoxyl(eV)a
CH3C(O)O2 + 2-methyl-2-butene	357-410	8.08±0.76	16.3±4.3	6	38.0	0.200	5.94
CH3C(O)O2 + trans-2-penteneb	373	8.10±0.50	22.5±4.10	6	32.9	0.185	6.29
CH3C(O)O2 + cis-2-penteneb	373	8.10±0.50	22.5±4.1	6	32.9	0.185	6.29
CH3C(O)O2 + trans-2-buteneb	373	8.10±0.50	24.6±3.8	8	32.1	0.182	6.38
CH3C(O)O2 + cis-2-buteneb	373	8.10±0.50	22.9±3.8	8	32.9	0.184	6.38
CH3C(O)O2 + 2-methyl-1-buteneb	373	8.10±0.50	22.1±3.8	6	31.7	0.181	6.40
CH3C(O)O2 + 2-methylpropene	370-410	8.29±0.77	25.0±4.4	9	31.5	0.180	6.49
CH3C(O)O2 + 1-hexeneb	373	8.10±0.50	28.3±3.9	6	27.4	0.167	6.73
CH3C(O)O2 + 3-methyl-1-buteneb	373	8.10±0.50	30.4±4.0	6	26.9	0.166	6.78
CH3C(O)O2 + 1-butene	357-410	7.94±0.89	28.9±5.5	9	25.8	0.162	6.88
CH3C(O)O2 + propeneb	373	8.10±0.50	32.5±3.8	6	25.3	0.160	7.00
*
CH3O2 + 2,3-dimethyl-2-butene	373-403	7.95±0.45	36.6±3.4	10	24.0	0.156	7.06
CH3O2 + 2-methyl-2-butene	373-403	7.43±0.44	38.6±3.3	10	20.4	0.142	7.47
CH3O2 + 2-methyl-1-butene	373-403	7.83±0.63	48.6±4.7	10	16.1	0.126	7.94
CH3O2 + 2-methylpropeneb	410	8.10±0.50	57.9±3.9	11	16.1	0.125	8.03
CH3O2 + etheneb	410	9.00±0.50	65.2±4.8	11	7.2	0.082	9.30
*
HO2 + 2,3-dimethyl-2-butene	653-773	8.58±0.35	35.4±5.0	7	23.8	0.152	7.46
HO2 + trans-2-hexene	673-773	8.41±0.35	53.4±5.0	12	17.3	0.128	8.16
HO2 + cis-2-hexene	673-773	8.41±0.35	53.4±5.0	12	17.3	0.128	8.16
HO2 + cis-2-butene	673-773	8.61±0.30	53.4±5.0	13	16.4	0.124	8.31
HO2 + 2-methylpropene	673-793	8.80±0.35	53.1±5.0	14	16.1	0.122	8.43
HO2 + 1-hexene	673-773	8.91±0.34	58.6±5.0	12	13.3	0.111	8.67
HO2 + 1-pentene	673-793	8.80±0.34	59.7±5.0	12	13.0	0.110	8.71
HO2 + propene	673-773	9.01±0.30	62.3±5.0	15	12.0	0.105	8.93
HO2 + ethene	653-773	9.58±0.35	71.6±5.0	16	7.4	0.081	9.70
HO2 + ethene	673-773	9.58±0.35	74.7±5.0	14	7.4	0.081	9.70
HO2 + ethene	637-688	9.10±0.27	56.6±3.4	17	7.4	0.081	9.70
*
i-C3H7O2 + 2,3-dimethyl-2-butene	303-363	7.96±0.50	40.9±1.8	18	24.6	0.159	6.87
i-C3H7O2 + 2-methyl-2-butene	303-408	8.03±0.35	48.2±1.8	19	20.9	0.145	7.28
i-C3H7O2 + 2-methyl-1-butene	303-408	8.30±0.08	54.9±0.9	19	16.5	0.128	7.74
i-C3H7O2 + 2-methylpropene	303-408	8.59±0.19	62.7±2.2	19	16.5	0.127	7.84
i-C3H7O2 + propene	303-408	8.92±0.36	67.7±2.5	19	12.2	0.109	8.34
i-C3H7O2 + 3-flouropropeneb	393	8.10±0.50	8.10±3.8	19	12.9	0.110	8.64
*
t-C4H9O2 + 2,3-dimethyl-2-butene	313-393	7.96±0.62	45.3±4.1	20	24.7	0.160	6.80
t-C4H9O2 + 2-methyl-2-butene	313-393	7.54±0.39	52.9±2.4	20	21.0	0.146	7.21
t-C4H9O2 + 2-methyl-1-buteneb	393	8.10±0.50	57.8±3.8	20	16.6	0.129	7.67
t-C4H9O2 + 2-methylpropeneb	393	8.10±0.50	58.9±3.8	20	16.5	0.128	7.76
t-C4H9O2 + etheneb	393	9.00±0.50	58.0±3.8	20	7.4	0.083	9.04

^a dN_c, dE_c and (I_alkene - A_peroxyl) were determined using ionisation energies and electron affinities from table 2.

^b For rate constants determined at only one temperature, activation energies have been calculated assuming an A factor of 1.28×10⁸ dm³ mol^-1 s^-1.

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