<b>Photochemical Oxidations. I. Ethyl Iodide</b>

Heicklen, Julian; Johnston, Herrick L.

doi:10.1021/ja00882a006

Cited by 22 publications

(17 citation statements)

References 8 publications

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“…The model included reactions (2a)-(2c), (4), (5a), (5b), (6a), (6b), (7a), (7b), and (8)- (10) for reactions (5a), (5b), (6a), (6b), (7a), (7b), (8), and (9)- (11) [15][16][17][18]. The modeling results indicated that under the present experimental conditions, the ethanol concentration was not sensitive to reactions (5a), (6a), and (7a).…”

Section: Resultsmentioning

confidence: 99%

A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD

Crawford

Heuerman

et al. 2004

Int J of Chemical Kinetics

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The reaction of atomic chlorine with CH 3 CH 2 OD has been examined using a discharge fast flow system coupled to a mass spectrometer combined with the relative rate method (RR/DF/MS). At 298 ± 2 K, the rate constant for the Cl + CH 3 CH 2 OD reaction was determined using cyclohexane as a reference and found to be k 3 = (1.13 ± 0.21) × 10 −10 cm 3 molecule −1 s −1 . Mass spectral studies of the reaction products resulted in yields greater than 97% for the combined hydrogen abstraction at the α and β sites (3a + 3b) and less than 3% at the hydroxyl site (3c). As a calibration of the apparatus and the RR/DF/MS technique, the rate constant of the Cl + CH 3 CH 2 OH reaction was also determined using cyclohexane as the reference, and a value of k 2 = (1.05 ± 0.07) × 10 −10 cm 3 molecule −1 s −1 was obtained at 298 ± 2 K, which was in excellent agreement with the value given in current literature. C

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Section: Resultsmentioning

confidence: 99%

A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD

Crawford

Heuerman

et al. 2004

Int J of Chemical Kinetics

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“…In this manner we find that at 314°K about 2-3 % of the methanol arises from reaction with formaldehyde, and this contribution rises to about 25 % at 364°K. Consequently our reported Arrhenius parameters for reaction (8) are high since they include a contribution from reaction (19) which has a lower activation energy.18 That our value is unlikely to be seriously in error can be deduced as follows : methoxyl radicals are more reactive in abstracting hydrogen atoms from a substrate than are methyl radicals and, in general, this difference in reactivity appears 16 to arise from activation energy differences of ca. 3 kcal mole-1 rather than from variations in the pre-exponential factors, e.g., for ethane, abstraction by methyl 17 requires 10.4 kcal mole-1 and by methoxyl 14 7-1 kcal mole-1, i.e., AE = 3.3 kcal mole-1, the pre-exponential factors being almost exactly equal.…”

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confidence: 84%

“…An estimate of the methanol contribution from this source can be made using the known 15918 kinetic data for reactions (17) and (19), and assuming that the difference between the total methane formed and the amounts calculated for GH4 (10) and RCH4 (12) is that from reaction (17). In this manner we find that at 314°K about 2-3 % of the methanol arises from reaction with formaldehyde, and this contribution rises to about 25 % at 364°K.…”

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confidence: 99%

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Photolysis of dimethyl carbonate

Quee¹,

Thynne²

1966

Trans. Faraday Soc.

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The gas-phase photolysis of dimethyl carbonate (DMC) has been studied in the temperature range 41-93°C. Methoxyl and methyl radicals are generated in this photolysis and their reactions have been studied. Arrhenius parameters have been measured for the following reactions : log A(mo1e-1 cm3 sec-1) E(kca1 mole-1) CH30 + DMC +CH30H + R 10-75 5.9 CH3+DMC +CH4+R 10.19 7-4 CH3+CH30 +CH4+CH20 13-38 0A value of 1014.13(mole-l c m 3 sec-1) at 41°C has been obtained for the auto-disproportionation of methoxyl radicals : X H 3 0 +CH30H+ CH20Using this velocity constant a value of ca. 67 has been deduced for the disproportionation ratio of methoxyl radicals, A(CH30, CH3O).

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“…We make i t not as a pronouncement but as a spur to further research, there being, so far as we can tell, no unambiguous demonstration that disproportionation between two alkoxy radicals occurs with any degree of facility. The disproportionation1combination ratios quoted by Gray et al (30a) for ethoxy (1211) and methoxy (9.311) (31) are based on the assumption that two alkyl peroxy radicals initially yield two alkoxy radicals plus 0,. The one thing demonstrated conclusively by our work is that this supposition is untrue for other than tertiary peroxy radicals.…”

Section: Products Fiom Tlze See-butoxy Radicalsmentioning

confidence: 99%

Hemolytic decomposition of di-sec-butyl peroxide

Hiatt¹,

Szilagyi²

1970

Can. J. Chem.

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Rates and products have been determined for the thermal decomposition of sec-butyl peroxide at 110-150 "C in several solvents.The decomposition was shown to be unimolecular with energies of activation in toluene, benzene, arid cyclohexane of 35.5 & 1.0, 33.2 + 1.0, 33.8 + 1.0 kcal/mole respectively. The activation energy of thermal decomposition for the deuterated peroxide was found to be 37.2 + 1.0 kcal/mole in toluene.About 70-80% of the products could be explained by known reactions of free alkoxy radicals, and very little, if any, disproportionation of two sec-butoxy radicals in the solvent cage could be detected.The other 20-30% of the peroxide yielded Hz and methyl ethyl ketone. The yield of H z was unaffected by the nature or the viscosity of the solvent, but H z was not formed when s-BuZOZ was photolyzed in toluene at 35 "C nor when the peroxide was thermally decomposed in the gas phase.cc,a'-Dideutero-sec-butyl peroxide was prepared and decomposed in toluene at 110-150 "C. The yield of D, was about the same as the yield of H 2 from s-BuZ02, but the rate of decomposition (at 135 "C) was only '11.55 as fast.Mechanisms for hydrogen production are discussed, but none satisfactorily explains all the evidence.Canadian Journal of Chemistry, 48, 615 (1970) Introduction The decomposition of dialkyl peroxides has received less attention than that of other peroxidic species, partly, because being rather more stable, they have been less utilized for commercial purposes (i.e., initiation of free radical chain reactions); partly, because being less easily reduced, they are harder to analyze quantitatively. But perhaps too, because dialkyl peroxides have the reputation of being "well behaved" they have been regarded as uninteresting species. Dialkyl peroxides are commonly supposed to cleave on heating at the 0-0 bond by an exclusively homolytic process, relatively uncomplicated by other types of decomposition either radical or molecular in nature.

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Photochemical Oxidations. I. Ethyl Iodide

Cited by 22 publications

References 8 publications

A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD

A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD

Photolysis of dimethyl carbonate

Hemolytic decomposition of di-sec-butyl peroxide

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Photochemical Oxidations. I. Ethyl Iodide

Cited by 22 publications

References 8 publications

A kinetic and product study of reaction of chlorine atom with CH3CH2OD

A kinetic and product study of reaction of chlorine atom with CH3CH2OD

Photolysis of dimethyl carbonate

Hemolytic decomposition of di-sec-butyl peroxide

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A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD

A kinetic and product study of reaction of chlorine atom with CH₃CH₂OD