Photochlorination studies. Part 5.—Concurrent geometrical isomerization of cis- and trans-1, 2-dichloroethylene

Ayscough, P. B.; Cocker, A. J.; Dainton, F. S.

doi:10.1039/tf9625800284

Cited by 16 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…At present the photochlorination of methane, ethane, and ethylene and all their chlorinated derivatives are well understood and good values for all relevant elementary constants are available (63). Such questions as the point of attack of a chlorine atom on an asymmetric chlorinated ethylene, the difference in reactivities of isomeric chlorinated ethanes (62, 88a), the cis-trans isomerization of 1-2 dichloroethylene (11), and the kinetic isotope effect are being clarified (44).…”

Section: Introductionmentioning

confidence: 99%

“…There are, of course, several questions which remain unsettled and which shall be discussed in this review. One of these is the possibility of observing an unstable intermediate addition product between an olefin and a chlorine atom (10,11,13,54); another is the occurrence of chlorinechlorine atom recombinations and the possibility of observing them (12,43).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Chiltz¹,

Goldfinger²,

Huybrechts³

et al. 1963

Chem. Rev.

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Chiltz¹,

Goldfinger²,

Huybrechts³

et al. 1963

Chem. Rev.

View full text Add to dashboard Cite

“…If laser excited TDCE undergoes C---CI bond cleavage, the CI atoms can promote reversible cis-trans isomerization, providing an explanation for the inability to drive the reaction to completion. Steel s suggest a CI atom chain reaction in the thermal isomerization of TDCE, while Ayscough et al 9 and Knox and Riddick found evidence from photochlorination studies that isomerization proceeds via a chemically activated CI atom adduct. Furthermore, C--CI bond scission has been observed in MPD of several halocarbons, including trichloreothylene, xx The following reactions should then be considered.…”

Section: Discussionmentioning

confidence: 99%

Infrared Laser Photochemistry of Trans‐1, 2‐Dichloroethylene. Evidence For A CI Atom Chain Reaction

Guckert

Carr

1989

Laser Chemistry

View full text Add to dashboard Cite

The TEA-CO2 laser induced reaction of trans-l,2-dichloroethylene (TDCE) was investigated at 925 cm-1. The laser radiation was focused to yield beam waist fluences of approximately 125 J cm-2. The major reaction product was c/s-l, 2-dichloroethylene (CDCE), with a few per cent of chloroacetylene, and minor amounts of acetylene, dichloroacetylene, chloroethylene and an unidentified C4 compound also being formed. The reaction of pure TDCE was studied as a function of number of laser pulses and total pressure (0.02 to 5 torr). Some experiments were also done with added ethane (20%) and propane (2%). Evidence was obtained that the formation of the cis isomer occurs via two mechanisms, (1) a unimolecular isomerization, and (2) a CI atom chain reaction. The results are consistent with laser induced decomposition of TDCE occurring through the three lowest energy channels: unimolecular structural isomerization (57.4 kcal/mol); molecular HCI elimination (69 kcal/mol); and C-CI bond scission (89 kcal/mol).

show abstract

“…In photolysis of gaseous 1,2-C 2 H 2 Cl 2 [20,21 ], gaseous C 2 C1 4 [12,13] and liquid 1,2-C 2 H 2 C1 2 [22] no dimerisation or polymerisation reactions have been mentioned. However, chloroethylenes are efficient scavengers for hydrocarbon radicals as has been demonstrated in the photolysis and radiolysis of mixtures of n-C 5 H 12 and c-C 6 H 12 with low concentration of C 2 C1 4 and C 2 HC1 3 , where high G-values for the addition products have been found [22]: C s H n +C 2 C1 4 C 7 H n Cl 4 (14) C-jHuCU C 7 H"C1 3 +C1.…”

Section: High Boiling Compoundsmentioning

confidence: 99%

Reactions of ^34m,38Cl Recoil Atoms with Chloroethylenes

Briνkman¹,

Gerritsen²,

Visser³

1980

Radiochimica Acta

View full text Add to dashboard Cite

The yield of 23% C 2 Cl 3 34m Cl measured in liquid C 2 Cl 4 is formed by direct hot replacement (5%) and via a 34m Cl addition/ CI elimination reaction sequence in an excited cage (18%). In the case of 1, 2-C 2 H 2 C1 2 2.6%ofthe 1, 2-C 2 H 2 tl 34m Cl yield is formed via a direct hot replacement reaction with retention of the original configuration and 13.3% by addition-elimination reactions with full racemisation. The addition of 34m Cl to 1,1-C 2 H 2 Cl 2 in a reaction cage proceeds mainly at the carbon atom of the CH 2 group. Replacement of H atoms can proceed via a direct hot reaction or via a cage reaction between a 34m Cl atom and a C 2 X 3 radical. The yield of high boiling compounds (about 44%) can be due to fragmentation/ addition reactions started by hot 34m Cl atoms, and partly by more thermal-like addition reactions of C 2 X s radicals. No satisfactory explanation could be given for the formation of inorganic yield of about 32%.

show abstract

Photochlorination studies. Part 5.—Concurrent geometrical isomerization of cis- and trans-1, 2-dichloroethylene

Cited by 16 publications

References 0 publications

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Infrared Laser Photochemistry of Trans‐1, 2‐Dichloroethylene. Evidence For A CI Atom Chain Reaction

Reactions of ^34m,38Cl Recoil Atoms with Chloroethylenes

Contact Info

Product

Resources

About

Photochlorination studies. Part 5.—Concurrent geometrical isomerization of cis- and trans-1, 2-dichloroethylene

Cited by 16 publications

References 0 publications

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Infrared Laser Photochemistry of Trans‐1, 2‐Dichloroethylene. Evidence For A CI Atom Chain Reaction

Reactions of 34m,38Cl Recoil Atoms with Chloroethylenes

Contact Info

Product

Resources

About

Reactions of ^34m,38Cl Recoil Atoms with Chloroethylenes