<b>Excited Alkoxy Radicals in the Photolysis of Dialkyl Peroxides</b>

McMillan, G. R.

doi:10.1021/ja00872a013

Cited by 12 publications

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“…I n the decomposition of methanol (2), CH3 radicals apparently resulted from the decomposition of energy-rich MeOH, in the reaction analogous to [12]. In that case, where the amount of back reaction was less than in the present system (because of the high rate of abstraction from the substrate) the atomic cracking reaction amounted to ca.…”

Section: Resultsmentioning

confidence: 67%

“…The results of the series of runs with added CF4, shown in Fig. 6, also indicate that isobutane and neopentane result from (~e ) a C radicals formed in step [12] in that, as the partial pressure of CF4 is increased, there is evidently increased collisional deactivation of R4e3COH*, thereby reducing the rates of [12], [13], and [14]. T h e Can.…”

Section: Resultsmentioning

confidence: 84%

“…5% of the total decomposition a t 50 mm methanol pressure (2) and 18yo a t 8 mm (1). With 35 mm t-butyl alcohol, the t-butyl radicals produced in reaction [12] account for ca. 10% of the total decomposition.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, however, McMillan (12) has found evidence for the formation of excited t-butoxy radicals in the photolytic system, thereby rendering uncertain the activation energy calculations previously reported. This author has also reported (13) the presence of vibrationally excited h1e3C0 radicals in the photolysis of t-butyl nitrite, and has shown that such species can be collisionally deactivated by the addition of inert gas.…”

Section: Introductionmentioning

confidence: 94%

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THE REACTION OF t-BUTYL ALCOHOL VAPOR WITH Hg 6(³P₁) ATOMS

Knight¹,

Gunning²

1963

Can. J. Chem.

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The nature of the decomposition of t-butyl alcohol vapor, photosensitized by Hg 6(3P1) atoms in a static system a t room temperature, has been examined under a variety of conditions of continuous and intermittent illumination. The inhibiting effect of nitric oxide has also been studied, as well as the influence of added inert gas.In the decomposition of pure substrate, the reaction products, with the initial quantum yields, W, under continuous illumination in parenthesis, were: Hz (0.045). Me2CO (0.090), CO (0), CH4 (0.015), CzHB (0.030) together with lesser amounts of C3H.8, Me3CH, MeaCMe, and Me3COMe. On additlon of nitric oxide, MezCONO, Me2C0, N20, Nz, HzO, and trace quantities of HZ and CO were the only products observed.The reactionis proposed as the primary process in the decomposition and kinetic evidence is presented that the initially formed t-butoxy radicals possess excess energy and that their principal subsequent reaction is unimolecular cleavage into acetone and methyl. The results furthermore indicate that the substrate itself is quite inert to abstractive attack by the primary radicals.

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Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

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THE REACTION OF t-BUTYL ALCOHOL VAPOR WITH Hg 6(³P₁) ATOMS

Knight¹,

Gunning²

1963

Can. J. Chem.

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“…10 kcal/mole, thereby leading to a strong third-body restriction on the nitrite-forming step in these systems. Pertinently McMillan (6)(7)(8) has recently reported the formation of excited alkoxy radicals in the photolysis of dialkyl peroxides, attributable to the energy difference between D(R0-OR) and that of the exciting quanta. T o investigate the importance of excited isopropoxy radicals in the present system, the effect of increasing pressure of inert gas on the nitrite yield has been examined.…”

Section: Introductionmentioning

confidence: 99%

THE REACTION OF ISOPROPANOL VAPOR WITH Hg 6(³P₁) ATOMS: PART II: REACTION IN THE PRESENCE OF NITRIC OXIDE

Knight¹,

Gunning²

1963

Can. J. Chem.

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The reaction of isopropanol vapor with Hg 6 ( 3 P~) atoms in the presence of nitric oxide has been investigated in a static system a t room temperature as a function of exposure time. In addition to the major products hydrogen, pinacol, and acetone found in the pure substrate reaction, the new products isopropyl nitrite, nitrous oxide, and nitrogen were observed. The effect on the reaction of the inert gas carbon tetrafluoride was also studied.Evidence is adduced for the production of excited isopropoxy radicals in the primary process, and the rise in the nitrite and acetone yields, observed upon increasing the added inert gas pressure, is ascribed to quenching of these excited species.The nitrite produced in the decomposition of MesCDOH was found to be ca. 98% MezCDONO, dictating its formation from the isopropoxy radical and not from Me2COH.A nitrite-producing dark reaction was observed when high pressures of CFd were added and the reaction could be prevented only by measures designed to exclude trace quantities of NO2 from the reaction vessel.

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