Carbon disulfide, flash photolysis

Electronic excitation from atom-transfer reactions appears to be relatively uncommon, with most such reactions producing chemiluminescence from vibrationaHy excited ground states (188—191). Examples include reactions of oxygen atoms with carbon disulfide (190), acetylene (191), or methylene (190), all of which produce emission from vibrationaHy excited carbon monoxide. When such reactions are carried out at very low pressure (13 mPa (lO " torr)), energy transfer is diminished, as with molecular beam experiments, so that the distribution of vibrational and rotational energies in the products can be discerned (189). Laser emission at 5 p.m has been obtained from the reaction of methylene and oxygen initiated by flash photolysis of a mixture of SO2, 2 2 6 (1 )-... 

They flash-photolyzed mixtures of NO2 and CS2, in concentration ratios of about 1 10 in an excess of Ar, at conditions under which no CS2 was photo-dissociated directly. With such excess of CS2, the O formed from the photolysis of NO2 reacted almost entirely with the carbon disulfide. The rate of reaction (22) was measured by monitoring the absorption spectrum of the CS formed. They obtained a value of 22 = 2.5 x 10 l.mole . sec at 305 °K, and found the activation energy of the reaction to be 0.6+0.3 kcal.mole . Smith has also reported the relative yield of CS and SO in various excited vibrational states. 

Wright FL. 1960. Flash photolysis of carbon disulfide and its photochemically initiated oxidation. J Phys Chem 64 1648-1652. 

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