Spectroscopic detection and reactivity of the chlorine atom-carbon disulfide molecular complex
Journal Article
·
· Journal of the American Chemical Society
- Univ. of Notre Dame, IN (United States)
Pulse radiolysis and laser flash photolysis techniques have been used to generate and kinetically characterize the chlorine atom-carbon disulfide molecular complex (Cl{sup {sm_bullet}}/CS{sub 2}) in CCl{sub 4} solution. The transient absorption spectrum of Cl{sup {sm_bullet}}/CS{sub 2} has been generated from three independent Cl{sup {sm_bullet}} sources: pulse radiolysis of CCl{sub 4} 266-nm photodecomposition of CCl{sub 4}, and photodissociation of Cl{sub 2}. An absolute rate constant of 1.7 {times} 10{sup 10} M{sup {minus}1} s{sup {minus}1} for the reaction of Cl{sup {sm_bullet}} + CS{sub 2} was obtained from both the direct measurement of the decay of the charge-transfer band of Cl{sup {sm_bullet}} in CCl{sub 4} ({lambda}{sub max} = 330 mm) and from the formation kinetics of Cl{sup {sm_bullet}}/CS{sub 2} ({lambda}{sub max} = 370 nm; shoulder = 490 nm). The properties of Cl{sup {sm_bullet}}/CS{sub 2} are compared with those of the molecular complexes of Cl{sup {sm_bullet}} with benzene and pyridine. The reactivity observed monitoring the Cl{sup {sm_bullet}}CS{sub 2} absorption band toward 2,3-dimethylbutane has also been investigated to determine the equilibrium constant (K) of the Cl{sup {sm_bullet}}/CS{sub 2} complex, and the value of K is compared to that determined by direct spectroscopic method. K for the Cl{sup {sm_bullet}}/pyridine complex has also been reevaluated. 38 refs., 7 figs., 1 tab.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 139259
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 115; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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