The Metathetical Reactions of Methyl Radicals with Ethane, Dimethyl Ether, Acetone and Propylene<sup>1</sup>

Varnerin, Robert E.

doi:10.1021/ja01611a007

Cited by 9 publications

(3 citation statements)

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“…CD3COCD2 + CD2CO + CD3 loglo 1 1 2 1 ) at 290°C does not deviate significantly from the Arrhenius line in Figure 2, and Brinton 1191 found that acetonyl radicals decompose only above 300°C. Therefore reaction (17) With Arrhenius parameters for k7 [16], which are assumed to be equal to those of kq it follows: The Arrhenius plot of k can be extended by literature data obtained for displacement reactions of C14H3 and CD3 radicals, respectively [20,21]:…”

Section: Discussionmentioning

confidence: 99%

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃

Knöll

Richter

Schliebs

1980

Int J of Chemical Kinetics

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The gas-phase free radical displacement reactionhas been studied in the temperature range of 240-290°C and at 14OOC with the thermal decomposition of azomethane (AM) and di-tert -butylperoxide (DTBP), respectively, as methyl radical sources. The reaction products of the CD3 radicals were analyzed by mass spectrometry. Assuming negligible isotope effects, Arrhenius parameters for the elementary radical addition reactionwere derived: loglo kl(cm3/mol sec) = (10.5 f 0.4) -(11,500 f 1100)/4.5762'The data are discussed with respect to the back reaction and general features of elementary addition reactions.

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Section: Discussionmentioning

confidence: 99%

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃

Knöll

Richter

Schliebs

1980

Int J of Chemical Kinetics

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“…[191. ) That the conjugate C= 0 double bonds in the a-diketones have substantially higher reactivity than isolated C = O bonds in single ketones is shown by the comparison of the ratio of displacement/H abstraction for the following reactions: C14H3 + acetone [15], 0.036; CDs + acetone [16], 0.011; CH3 + biacetyl [this work], 0.3.…”

Section: Discussionmentioning

confidence: 99%

The thermal decomposition of biacetyl

Knöll

Scherzer

Geiseler

1973

Int J of Chemical Kinetics

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The thermal decomposition of biacetyl has been studied at small percentage conversion For these conditions, an almost quantitative The following equation over the temperature range 375-41 7°C. mass balance was obtained by gas-chromatographic analysis. was obtained for the overall reaction loglo k,, = (17.2 + 0.7) -(67400 +z 2300)/4.575TBetween 240" and 277"C, the decomposition of biacetyl initiated by methyl radicals has also been studied. Moreover, the Arrhenius parameters of the following reactions were determined :As source of radicals, the thermolysis of azomethane was used. where A is in sec-' for reaction (1) and in ~m~rno1e-l sec-l for reactions (3) and (4); E is in kcal/mole. Evidence is provided that the displacement reaction (4) proceeds by a twostep mechanism.

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“…In the latter system the low probability of metath etical reactions hail b een studied theoretically [13] and experimentally [14]. An important objection to these reactions is the high energy of activation of these steps due to the shielding of the carbon and the low resonance energy in the activated complex resulting from the large displacement of the carbon atom from its eq uilibrium position.…”

Section: Discussionmentioning

confidence: 99%

Further studies on the pyrolysis of polytetrafluoroethylene in the presence of various gases

Michaelsen¹,

Wall²

1957

J. RES. NATL. BUR. STAN.

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Th e t h er mal decomposit ion of polytetrafluoroeth ylene in t he presence o f gases or vapors h as bee n exp lored in t he range 450 0 to 500 0 C. Gases th a t have been used ca n be di vid ed into t hree groups, d ep ending on whether t hey inhibit, catalyze, or e xert no effect on the t herma l-deco mpos it ion process. Fluorin e-containing gases, i. c., ClF3 and IFs, which are capa ble of dissocia t ing at t he py rolys is te mperatures to give fluori ne atoms, showed t he most m ar ked inhibi t io n ye t obser ved. From the brevity of t he dura tio n of inhibi t ion , i t is concluded t hat t he fluorine a toms directly atta ck t he pol y mer to produ ce sc iss io ns t hrough a metathetica] r eaction.

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The Metathetical Reactions of Methyl Radicals with Ethane, Dimethyl Ether, Acetone and Propylene¹

Cited by 9 publications

References 0 publications

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃

The thermal decomposition of biacetyl

Further studies on the pyrolysis of polytetrafluoroethylene in the presence of various gases

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The Metathetical Reactions of Methyl Radicals with Ethane, Dimethyl Ether, Acetone and Propylene1

Cited by 9 publications

References 0 publications

On the gas‐phase free radical displacement reaction CH3 + CD3COCD3 → CD3 + CH3COCD3

On the gas‐phase free radical displacement reaction CH3 + CD3COCD3 → CD3 + CH3COCD3

The thermal decomposition of biacetyl

Further studies on the pyrolysis of polytetrafluoroethylene in the presence of various gases

Contact Info

Product

Resources

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The Metathetical Reactions of Methyl Radicals with Ethane, Dimethyl Ether, Acetone and Propylene¹

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃

On the gas‐phase free radical displacement reaction CH₃ + CD₃COCD₃ → CD₃ + CH₃COCD₃