Homogeneous gas-phase thermolysis kinetics. Improved flow technique for direct study of rate processess in the gas phase

Kwart, Harold; Sarner, Stanley F.; Olson, J.H.

doi:10.1021/j100846a005

Cited by 19 publications

(11 citation statements)

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“…The helium carrier gas sweeps the injected material into a gold flow tube reactor (internal volume 6 cm3) where pyrolysis occurs in the presence of the toluene. Similar experiments (without toluene) have been carried out by Kwart and coworkers [6]. The pyrolyzed gases are then separated on Poropak columns.…”

Section: Methodsmentioning

confidence: 63%

Thermal decomposition of trimethylene sulfone and 3‐methyl sulfolane

Cornell

Tsang

1975

Int J of Chemical Kinetics

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Section: Methodsmentioning

confidence: 63%

Thermal decomposition of trimethylene sulfone and 3‐methyl sulfolane

Cornell

Tsang

1975

Int J of Chemical Kinetics

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“…It is instructive to analyze the time dependence of DCI formation using reaction d as a possible pathway. The rate of DCI growth at early times is given by the expression d(DCl)/d< = &eXl(Cl)(CD4) (3) Assuming that the production of chlorine atoms is mainly from reaction c rather than the dissociation of hydrogen chloride, it follows that the rate of c will de-pend upon the concentration of methyl radicals which are generated via reactions a and b. If it is further assumed that under the reaction conditions of this investigation the growth of methyl radical is linear with respect to reaction time, there arise two conditions that lead to different time dependencies for DCI formation.…”

Section: Discussionmentioning

confidence: 99%

“…(G,)'• -(! : '( ' m Integrating eq (3) with the substitution for chlorine atoms results in a linear formation of the product DC1.…”

Section: D(clmentioning

confidence: 99%

Exchange reaction of methane-d4 with hydrogen chloride

Kern¹,

Nika²

1972

J. Phys. Chem.

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A shock tube coupled to a time-of-flight mass spectrometer was used to study the exchange reaction, CD4 + HC1 CDsH + DC1, over a density range 1.7-4.1 X 10"6 mol cm"3 in the temperature region 1600-2500°K. In the lower temperature range (1600-1900°K) DC1 exhibits a quadratic time-dependent growth rate while at higher temperatures (2200-2500°K) increase of DC1 is a linear function of time. The only chlorine-containing product is deuterium chloride. Rate constants extracted from the quadratic and linear regions yielded activation energies of 51 and 30 kcal mol"1, respectively. An atomic mechanism for the exchange predicts both time dependencies and the transition between them. Pyrolysis of methane occurred along with the exchange but the growth rate of the products ethane, acetylene, and diacetylene was shown not to be catalyzed by the presence of HC1. Acetylene was the major product of the pyrolysis. Exchange was observed in both major and. minor products. The ratio CHACEE was less than one when pyrolysis products were not detected and greater than one when they were present. This finding suggests the presence of methyl radical in the reaction mixture. The results are discussed in terms of an atomic mechanism.Professor Bauer and his coworkers studied the CH4 + D2 reaction in the temperature range 1440-1755°K (SPST) under conditions of negligible 02 impurities.6 Samples extracted from the reflected zone were analyzed with a mass spectrometer for CH4, D2, CHgD, and HD. Evidence for methane pyrolysis was not found. The reaction is reported to proceed through a four-center complex in accordance with the vibrational excitation mechanism proposed by Bauer.3a Burcat and Lifshitz (BL)6 studied the exchange system CH4 + CD4 in the temperature region 1340-1745°K (SPST). They report a zero-order dependence with respect to inert gas although Bauer found an order of 0.6 for the inert diluent. BL interpreted their results in terms of a methyl radical chain mechanism resulting from the pyrolytic initiation step CH4 CHg + H, followed by the exchange reaction CHa+ CD4-> CH3D + CD3.Several questions are apparent from a comparison of these two methane exchange reactions. Both studies are in the same temperature range, yet Bauer argues against the importance of pyrolysis in the exchange (1) (a) Support of this work by the National Science Foundation under Grant No. GP-23137 and also funds for equipment from NSF Departmental Science Development Program GU-2632 are gratefully acknowledged, (b) Paper presented in part at the Southwest

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“…The 1969 volume of "Gas Chromatography Abstracts" edited by K n a p man and containing 1100 abstracts was published by the Gas Chromatography Discussion Group of the British Institute of Petroleum during this biennium (569). The 1970/71 (480) and the 1971/72 International Chromatography Guides (gf?…”

Section: Books and Reviewsmentioning

confidence: 99%

Gas chromatography

Cram¹,

Juvet²

1972

Anal. Chem.

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review surveys developments in the field of gas chromatography since publication of the last review in this series (496) and covers the years 1970-71. Gas chromatography continues to be one of the most active areas in analytical chemistry. A recent report by the American Chemical Society ( 791) is based on the employment specialty choices of 84,925 chemists and chemical engineers who reported to the 1970 National Register of Scientific and Technical Personnel, an activity of

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Homogeneous gas-phase thermolysis kinetics. Improved flow technique for direct study of rate processess in the gas phase

Cited by 19 publications

References 2 publications

Thermal decomposition of trimethylene sulfone and 3‐methyl sulfolane

Thermal decomposition of trimethylene sulfone and 3‐methyl sulfolane

Exchange reaction of methane-d4 with hydrogen chloride

Gas chromatography

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