Chemiluminescence in the gas-phase reactions of ozone with cyanoacetylene, carbon disulfide and thiophene

Toby, Sidney; Toby, Frina S.; Kaduk, Bruce A.

doi:10.1016/0047-2670(76)85087-3

Cited by 5 publications

(3 citation statements)

References 8 publications

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“…Soc. 1979, 101, 3340-3344. '5 3 Ch302C ChaOgC CH302C (6) All new compounds reported in this paper showed spectral data and combustion analysis in accord with their structures. (7) Peterson, D. J. J. Org.…”

supporting

confidence: 64%

A silicon-mediated homo-Claisen rearrangement

Wilson¹,

Price²

1982

J. Am. Chem. Soc.

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supporting

confidence: 64%

A silicon-mediated homo-Claisen rearrangement

Wilson¹,

Price²

1982

J. Am. Chem. Soc.

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“…The intensity of bands due to triplet SO2 is much stronger than in the case of CS2. Emissions in the region of 500 to 800 nm were also recorded and number of bands, similar to those reported by Toby et al (2), was observed. These are due to the electronically excited HSO radical (2A') (10).…”

Section: Thiophenesupporting

confidence: 69%

Chemiluminescence from the reactions of ozone with sulphur compounds

Arora¹,

Chatha²

1984

Can. J. Chem.

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. Can. J. Chem. 62, 417 (1984). Emissions from excited SO2 in its singlet state ('B, and/or 'A,) and triplet state ('B,) have been observed in gas-phase chemiluminescent reactions of ozone with a number of sulphur compounds. The compounds studied are carbon disulphide, thiophene, diallyl sulphide, diallyl disulphide, dimethyl sulphide, dimethyl disulphide, and thiophenol. The reaction pathways responsible for the formation of excited molecules are discussed. The remarkable similarity between the emission spectra of the reactions and the chemiluminescence from the SO + O3 reaction confirms that SO is a precursor for the observed chemiluminescence. Disulphides are found to be more chemiluminescent than monosulphides. The absence of chemiluminescence from HCHO* in the reactions of ozone with allyl sulphide and disulphide indicates that the attack of ozone molecule is on the C-S bond in organic sulphides. [Traduit par le journal]

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“…There is some possible evidence for this: the reaction of 0, with H2S probably produces HSO which may participate in a chain sequence [ll, 191, and which has been tentatively identified by its chemiluminescence [20]. The reaction of 0 8 with thiophene is also chemiluminescent with bands identified as due to electronically excited SO2 and HSO [21].…”

Section: Mechanismmentioning

confidence: 97%

The reaction of ozone with thiophene in the gas phase

Kaduk¹,

Toby²

1977

Int J of Chemical Kinetics

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The reaction between ozone and thiophene was studied from 30 to 125°C over a pressure range of 0.005-0.3 torr ozone and 0.1-1 torr thiophene. The most abundant product was 0 2 with smaller amounts of CO, and SOZ. The mass balance was 100% for oxygen and approached 100yo for sulfur a t the higher values of [O&. The carbon balance, however, was only 25% and no H-containing products were found, suggesting that the missing product is a hydrocarbon which may be a polymer. The rate law found waswhere 1,og kl(M-l.sec-l) = 7.8 f 0.5 -(8400 =t 700)/2.3RT, and log k,(M-z-sec-l) = 12.4 f 0.4 -(4700 f 400)/2.3RT. Added O2 had no effect on kl but reduced kz to a limiting value.It is thus not possible to measure the primary rate constant in this system by measuring the overall rate in the presence of oxygen, and this restriction may also apply to other ozone systems. A mechanism is postulated involving two chain sequences, one of which is inhibited by added lo2. A comparison with other ozone systems is made, and the chain lengths are far greater for ozone + thiophene than other systems, under the conditions employed. Possible intermediates in the mechanism are discussed.

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Chemiluminescence in the gas-phase reactions of ozone with cyanoacetylene, carbon disulfide and thiophene

Cited by 5 publications

References 8 publications

A silicon-mediated homo-Claisen rearrangement

A silicon-mediated homo-Claisen rearrangement

Chemiluminescence from the reactions of ozone with sulphur compounds

The reaction of ozone with thiophene in the gas phase

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