The Thermal Decomposition of Chloroform. I. Products<sup>1a</sup>

Semeluk, G. P.; Bernstein, R. B.

doi:10.1021/ja01643a060

Cited by 43 publications

(18 citation statements)

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“…3. In mixtures of CDCl 3 with Ar, the experimental data are well described by a hyperbolic decay showing that the radicals' disappearance follows a second-order kinetic decay due to the self-recombination reaction (2). At high HCl pressures, the decays were found to be described by a single exponential.…”

Section: Methodsmentioning

confidence: 85%

“…The major products obtained determined by FTIR spectrometry were CHCl 3 and C 2 Cl 4 . In mixtures of CDCl 3 with Ar, the experimental data are described by a hyperbolic decay showing that the radicals' disappearance follows a second-order kinetics due to the occurrence of the self-recombination reaction (2).…”

Section: Discussionmentioning

confidence: 99%

“…Mono‐ and dihalocarbenes were particularly well studied regarding the determination of kinetic rate constants. The determination of the steps that follow CHCl 3 pyrolysis has been the subject of numerous investigations . Flow and shock tube techniques have been employed using diverse detection methods to resolve the kinetics .…”

Section: Introductionmentioning

confidence: 99%

“…The determination of the steps that follow CHCl 3 pyrolysis has been the subject of numerous investigations [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. Flow and shock tube techniques have been employed using diverse detection methods to resolve the kinetics [2][3][4][16][17][18][19][20]. Herman et al [5], in a molecular beam study of the multiphoton dissociation of chloroform (CDCl 3 ), showed that the three-center DCl elimination is the dominant dissociation pathway:…”

Section: Introductionmentioning

confidence: 99%

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Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Gómez

D'Accurso

Manzano

et al. 2014

Int J of Chemical Kinetics

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The rate constant of the reaction between CCl2 radicals and HCl was experimentally determined. The CCl2 radicals were obtained by infrared multiphoton dissociation of CDCl3. The time dependence of the CCl2 radicals' concentration in the presence of HCl was determined by laser‐induced fluorescence. The experimental conditions allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4 and to the reaction with HCl to form CHCl3. The rate constant for the self‐recombination reaction was determined to be in the high‐pressure regime. The value obtained at 300 K was (5.7 ± 0.1) × 10−13 cm3 molecule−1 s−1, whereas the value of the rate constant measured for the reaction with HCl was (2.7 ± 0.1) × 10−14 cm3 molecule−1 s−1.

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Section: Methodsmentioning

confidence: 85%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Gómez

D'Accurso

Manzano

et al. 2014

Int J of Chemical Kinetics

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“…The thermal gase phase decomposition of chloroform has been studied by Semeluk and Bernstein [38], G. Le Moan [39], Shilov and Sabirova [13], and Spokes and Benson [40]. It is common to all of these studies, that complications of the reaction mechanism due to wall catalyzed and/or chain reactions are reported.…”

Section: Chloroformmentioning

confidence: 99%

Gas Phase α,α Elimination of Hydrogen Halides from Halomenthanes. I. Thermal Decomposition of Chlorodifluoromethane, Trifluoromethane, and Trichloromethane Behind Shock Waves

Schug

Wagner

Zabel

1979

Ber Bunsenges Phys Chem

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The thermal decomposition of CHClF2, CHF3, and CHCl3 has been studied behind incident and reflected shock waves. The unimolecular decomposition was observed to proceed via the α,α elimination reactions in agreement with previous work. The progress of reaction was monitored via time resolved absorption spectrometry of CF2 at 253 nm (for (1) and (2)) and of the secondary reaction product C2Cl4 at 230 nm (for (3)). The pressure dependence of k1, k2, and k3 was investigated over a pressure range of a factor of ∼ 100. From the experiments in the fall off region, low and high pressure limiting rate constants (k0 and k∞) were obtained by application of a modified Kassel theory. For k∞, the Arrhenius expressions were deduced. Excellent agreement with previous work is achieved for k1∞ and k2∞, provided that fall off is properly taken into account.

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Chloroform

Holbrook¹

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Chloroform, CHCl 3 , at normal temperature and pressure is a heavy, clear, volatile liquid with a pleasant, ethereal, nonirritant odor. It is produced almost exclusively by the chlorination of methane or lower chlorinated methanes, though methane oxychlorination and carbon tetrachloride hydrogenation have been proposed. The U.S. chloroform capacity has been estimated at 258,000 t/yr but the actual capability is probably much higher because of the producer's ability to change their product mix between methylene chloride and chloroform. The main uses for chloroform are in the production of HCFC‐22 and fluoropolymers. Growth projections as high as 6% per year have been made for the early 1990s. Chloroform is regulated under a number of federal and state laws.

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The Thermal Decomposition of Chloroform. I. Products^1a

Cited by 43 publications

References 0 publications

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Gas Phase α,α Elimination of Hydrogen Halides from Halomenthanes. I. Thermal Decomposition of Chlorodifluoromethane, Trifluoromethane, and Trichloromethane Behind Shock Waves

Chloroform

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The Thermal Decomposition of Chloroform. I. Products1a

Cited by 43 publications

References 0 publications

Determination of the Rate Constant of the Reaction of CCl2 with HCl

Determination of the Rate Constant of the Reaction of CCl2 with HCl

Gas Phase α,α Elimination of Hydrogen Halides from Halomenthanes. I. Thermal Decomposition of Chlorodifluoromethane, Trifluoromethane, and Trichloromethane Behind Shock Waves

Chloroform

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The Thermal Decomposition of Chloroform. I. Products^1a

Determination of the Rate Constant of the Reaction of CCl₂ with HCl

Determination of the Rate Constant of the Reaction of CCl₂ with HCl