Isolation of the initial step in the thermal decomposition of di-<i>tert</i>-butyl peroxide

Yip, Carol; Pritchard, H. O.

doi:10.1139/v69-781

Cited by 12 publications

(23 citation statements)

References 6 publications

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“…The preparation and/or purification of di-rerr-butyl peroxide, carbon dioxide, and propane have been described previously (1,2). Cyclopropane was supplied by Matheson of Canada Ltd: the principal impurities were stated to be air and cyclopropyl chloride; the latter would be expected to have a marked catalytic effect on the peroxide decomposition (I).…”

Section: Methodsmentioning

confidence: 99%

“…The remainder of the experimental procedures have been described in detail (1,2): in each of the main series of experiments, a total of mol of peroxide was used, together with a propane o r cyclopropane concentration of 3.1 +_ 0.5 mol I-'; departures from these standard conditions are noted below as they arise.…”

Section: Methodsmentioning

confidence: 99%

“…atm of pressurizing gas (I). Improvements in our analytical procedures (2) now enable us to use ten times as much of certain pressurizing gases, in particular propane, cyclopropane, and carbon dioxide. Much of the preliminary work was done using propane, but for reasons explained below, the most extensive series of experiments was performed with cyclopropane as the pressurizing gas.…”

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confidence: 99%

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Thermal Decomposition of di-tert-Butyl Peroxide in Binary Mixtures near the Critical Point

Yip¹,

Pritchard²

1971

Can. J. Chem.

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The thermal decomposition of di-tert-butyl peroxide has been studied in the presence of high pressures of cyclopropane; the rate constant for the decomposition was determined from the sum of the rates of formation of tert-butanol and acetone. In the temperature range 125-160 OC, i.e. above the critical point of cyclopropane, concentrations of cyclopropane of between 2.6 and 3.6 mol/l (60-80 amagats) were used; in the temperature range 100-124 "C, i.e. below the critical point of cyclopropane, an equivalent mean (liquid + gas) cyclopropane concentration was used. An Arrhenius plot of the rate constants for the peroxide decomposition is continuous through the critical point of the cyclopropane, and is indistinguishable from the best Arrhenius line representing all previous work on the reaction.However, an Arrhenius plot of the ratio of the rates of formation of tert-butanol and acetone shows a marked discontinuity at the critical point, but further investigation shows that this results from the unequal distribution of the reactant peroxide between the two phases which are present below the critical point of the cyclopropane.Less extensive series of experiments using propane, isobutane, cyanogen, and carbon dioxide as pressurizing gases confirm the pressure-independence of the rate of decomposition of di-tert-butyl peroxide: the experiments with propane and isobutane confirm the phase-independence of the rate; the propane experiments also exhibit the same apparent kinetic discontinuity at the critical point. Finally, rate-constant data are obtained for the reactions of the tert-butoxy radical with cyclopropane and isobutane, and for the addition of methyl radicals to cyanogen.La dCcomposition thermique du pCroxyde di-tert-butylique a Ct C CtudiCe en prCsence de fortes pressions de cyclopropane; la constante de vitesse de dCcomposition a Ct C dCterminCe a partir de la somme des vitesses de formation du tert-butanol et de I'acetone. Dans un intervalle de ternpkrature de 125-160 "C, i.e. au-dessus du point critique du cyclopropane, des concentrations de cyclopropane entre 2.6 et 3.6 mol/l (60-80 amagate) ont Ctt utilisCes; dans I'intervalle de temperature 100-124 "C, i.e. en-dessous du point critique du cyclopropane, une moyenne Cquivalente (liquide + gaz) de concentration de cyclopropane a Ct C utilisCe. Un graphe d'ArrhCnius des constantes de vitesse pour la dicomposition du pCroxyde est continu en passant par le point critique du cyclopropane, et est indiscernable de la meilleure ligne dYArrhCnius reprksentant tous les travaux antickdents sur la riaction.Cependant, un graphe d'ArrhCnius du rapport des vitesses deformation du tert-butanol et de l'acCtone montre une discontinuitt marquee au point critique, mais des recherches ultkrieures montrent que ceci rCsulte d'une distribution inkgale du rCactif pCroxyde entre les deux phases qui sont prisentes au-dessous du point critique du cyclopropane.Des sCries d'experiences moins Ctendues utilisant le propane, I'isobutane, le cyanogene et le dioxyde de carbone comme gas po...

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Thermal Decomposition of di-tert-Butyl Peroxide in Binary Mixtures near the Critical Point

Yip¹,

Pritchard²

1971

Can. J. Chem.

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“…The thermal decomposition of di-tert-butyl peroxide (DTBP) proceeds, in the presence of high pressures of hydrocarbon (RH), according to (3) [I]…”

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“…The results presented below are taken from our previous studies of this reaction with R H = propane or cyclopropane (3)(4)(5), and the experimental techniques used have been adequately described elsewhere (3)(4)(5)(6). Figure 1 shows an attempt to deduce the ratio of lc3/k2 from the rates of formation of t-BuOH and acetone at three temperatures, using R H = propane: the diagram is remarkably like vessels.…”

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confidence: 99%

On the Unimolecular Decomposition of the tert-Butoxy Radical

Yip¹,

Pritchard²

1973

Can. J. Chem.

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It is argued that a large apparent pressure dependence in the rate of decomposition of the tert-butoxy radical should not be interpreted in terms ofunimolecular reaction theory; the effect is probabIy heterogeneous in origin.La dependance trks grande du taux de dCcomposition des radicaux tert-butoxy sur la pression ne devrait pas etre interpret6 en termes d'une reaction unimol6culaire; un effet de nature hetkrogkne en e s t probablement l'origine.[Traduit par le journal]Can.

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Pyrolysis of peroxides in the gas phase

Batt

Liu

1983

PATAI'S Chemistry of Functional Groups

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

Cited by 12 publications

References 6 publications

Thermal Decomposition of di-tert-Butyl Peroxide in Binary Mixtures near the Critical Point

Thermal Decomposition of di-tert-Butyl Peroxide in Binary Mixtures near the Critical Point

On the Unimolecular Decomposition of the tert-Butoxy Radical

Pyrolysis of peroxides in the gas phase

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