The Thermal Decomposition of Chloroform. II. Kinetics<sup>1a</sup>

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

doi:10.1021/ja01558a010

Cited by 45 publications

(19 citation statements)

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“…The FTIR spectra showed that the major products obtained following photolysis were C 2 Cl 4 and CHCl 3 and that there is no evidence of other halogenated hydrocarbons different from CDCl 3 , consistent with the mechanism determined by (1)-(3).…”

Section: Methodssupporting

confidence: 75%

“…The rate of CCl 2 radicals' removal after the photolysis of CDCl 3 where kT is the rate constant of the termolecular reaction and kHCl the rate constant of the reaction with HCl. Therefore, the time dependence of the CCl 2 concentration will be given by (5) where k = k HCl [HCl] defines the pseudo-first-order decay coefficient associated with the reaction between CCl 2 radicals and HCl.…”

Section: Methodsmentioning

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: Methodssupporting

confidence: 75%

Section: Methodsmentioning

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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“…A number of researchers have considered the pathways of chloroform decomposition and reaction processes in chloroform conversion to CCl 4 . Semeluk and Bernstein [2] investigated the decomposition kinetics of gaseous CHCl 3 and CDCl 3 from 725 to 800 K in 1957. They did not consider HCl elimination, reaction (a), and they estimated a rate constant of 6.3 × 10 8 exp(−37.2 kcal/mol/RT ) s −1 for reaction (b).…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism for the thermal chlorination of chloroform in the gas phase: Inclusion of HCl elimination from CHCl₃

Zhu

Bozzelli

2003

Int J of Chemical Kinetics

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HCl elimination from chloroform is shown to be the lowest energy channel for initiation in the thermal conversion of chloroform to CCl 4 , with chlorine gas in the temperature range of 573-635 K. Literature data on this reaction is surveyed and we further estimate its kinetic parameters using ab initio and density functional calculations at the G3//B3LYP/6-311G(d,p) level. Rate constants are estimated and reported as functions of pressure and temperature using quantum RRK theory for k(E) and master equation analysis for fall-off. The high-pressure limit rate constant of this channel is k(CHCl 3 → 1 CCl 2 + HCl) = 5.84 × 10 40 × T −8.7 exp(−63.9 kcal/mol/RT ) s −1 , which is in good agreement with literature values. The reactions of 1 CCl 2 with itself, with CCl 3 , and with CHCl 3 are incorporated in a detailed mechanistic analysis for the CHCl 3 + Cl 2 reaction system. Inclusion of these reactions does not significantly change the mechanism predictions of Cl 2 concentration profiles in previous studies (Huybrechts, Hubin, and Van Mele, Int J Chem Kinet 2000, 32, 466) over the temperature range of 573-635 K; but Cl 2 , CHCl 3 , C 2 Cl 6 species profiles are significantly different at elevated temperatures. Inclusion of the 1 CCl 2 + Cl 2 → CCl 3 + Cl reaction (abstraction and chain branching), which is found to have dramatic effects on the ability of the model to match to the experimental data, is discussed. C

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Halocyclopropanes from Halocarbenes

Parham

Schweizer

2011

Organic Reactions

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This chapter reviews methods for the generation of halocarbenes and the reaction of the latter with unsaturated substrates. Chemical transformations of the derived halocyclopropanes are discussed in sufficient detail to demonstrate the synthetic utility of this class. The formation of dihalocyclopropanes from dihalocarbenes was first accomplished in 1954 by Doering and Hoffmann who used chloroform t‐ butoxide to generate the dichlorocarbene. Since that time a variety of other methods have been developed for the generation of halocarbenes. The various methods are discussed.

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The Thermal Decomposition of Chloroform. II. Kinetics^1a

Cited by 45 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

Kinetics and mechanism for the thermal chlorination of chloroform in the gas phase: Inclusion of HCl elimination from CHCl₃

Halocyclopropanes from Halocarbenes

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The Thermal Decomposition of Chloroform. II. Kinetics1a

Cited by 45 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

Kinetics and mechanism for the thermal chlorination of chloroform in the gas phase: Inclusion of HCl elimination from CHCl3

Halocyclopropanes from Halocarbenes

Contact Info

Product

Resources

About

The Thermal Decomposition of Chloroform. II. Kinetics^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

Kinetics and mechanism for the thermal chlorination of chloroform in the gas phase: Inclusion of HCl elimination from CHCl₃