Effect of pressure on the rates of decomposition of gaseous free-radicals: The kinetics of decomposition of the t-butoxy radical

Mulcahy, Mfr; Williams, DJ

doi:10.1071/ch9641291

Cited by 6 publications

(4 citation statements)

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“…1 are simply k2/k,, from which we find that when T = 100.4, 112.0, 124.0 "C, k2/k, = 0.51, 0.89, 1.23 mole I-', respectively, corresponding roughly to E2 -E, = 11.0 kcal/mole. It is generally agreed that the activation energy E, for the dissociation of the 2-BuO radical is pressure dependent (6,(11)(12)(13), but there is little consistency amongst the actual values of E, that have so far been determined. At low pressures, usually in the fall-off region, values from 11 to 17 kcal have been quoted (3,11), and at infinite pressure, values of 15.5 and 22.8 kcal have been suggested (6,11).…”

Section: Resultsmentioning

confidence: 99%

Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

Yip¹,

Pritchard²

1969

Can. J. Chem.

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The thermal decomposition of di-tert-butyl peroxide in the presence of propane has been studied at total pressures up to 100 atm. At the highest propane concentrations, the major product of the decomposition is tert-butyl alcohol, and extrapolation to infinite propane pressure indicates that the initial step in the peroxide decomposition is exclusively the formation of two tert-butoxy radicals. The activation energy for the abstraction of hydrogen from propane by t-BuO radicals is discussed.

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Section: Resultsmentioning

confidence: 99%

Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

Yip¹,

Pritchard²

1969

Can. J. Chem.

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“…(1) CHaCO (+M) -> CH3 + CO (+M) (2) CH3 + CHsCOCOCHs -±>-CH4 + CH2COCOCH3 (3) CH2COCOCH8 (+M) -> CH2CO + CH3CO (+M) (4) CHa + CH2COCOCH3 -> C2H5COCOCH3 (5) CH3 + CH3 (+M) -> C2H6 (+M) (6) ch3 + CH3CO -CH8COCH3…”

Section: Resultsmentioning

confidence: 99%

Pyrolysis of biacetyl and the third-body effect on the combination of methyl radicals

Hole¹,

Mulcahy²

1969

J. Phys. Chem.

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“…Examples of such behavior are numerous. [32][33][34][35] Assuming a strong-collision (Lindemann) mechanism for the collisional activation of CF3O, reactions 2 is the pseudounimolecular rate constant in the usual sense for the forward dissociation CF3O -* COF2 4-F, and the replacement of ks by kbi, where…”

Section: °2 °2 [Btmp]mentioning

confidence: 99%

Kinetics of the thermal decomposition of bis(trifluoromethyl) peroxide

Descamps¹,

Forst²

1976

J. Phys. Chem.

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The pyrolysis of CF3OOCF3 (BTMP) was studied in the gas phase from 1 to 200 Torr pressure and between 236 and 272 °C in a nickel reactor by the static method. Decomposition was limited to 5% to avoid complications. The reaction proceeds according to the overall stoichiometry BTMP CF3OF + COF2, as determined by analysis of the products. The reaction is self-inhibited by COF2 and accelerated by the addition of inert gases N2, CO2, and C2F6. Addition of 1-400 Torr of C2F6 was studied at 232 and 260 °C. A mechanism is proposed that accounts for the initial rate. Its main features are: (1) steady-state concentration of CF3O radicals maintained by the equilibrium BTMP 2CF3O;(2) the rate-determining step is the unimolecular decomposition of the CF3O radical which is pressure dependent and reversible: CF3O (+M) 4n COF2 + F (+M); this also accounts for the inhibition by COF2. The expression for initial rate is = 2! (A 1 /A 5) [BTMP])1/2, with ko pressure dependent. The observed experimental activation energy of 49.7 kcal/mol therefore corresponds to E2 + %(Ei -E5).

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Effect of pressure on the rates of decomposition of gaseous free-radicals: The kinetics of decomposition of the t-butoxy radical

Cited by 6 publications

References 0 publications

Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

Pyrolysis of biacetyl and the third-body effect on the combination of methyl radicals

Kinetics of the thermal decomposition of bis(trifluoromethyl) peroxide

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