Abstract
The heat of formation (..delta..H/sub f/(298 K)) of HNCO is determined to be -24.9/sub -2.8//sup +0.7/ kcal/mol (based on ..delta..H/sub f/(NH) = 85.2 kcal/mol). This value is obtained by measuring the threshold for the production of NH(a/sup 1/..delta..) and by determining the energy contents of the NH fragment and the CO cofragment produced by photolysis of HNCO at wavelengths near the threshold. Saturated laser-induced fluorescence is used to determine the internal state distribution of NH(a/sup 1/..delta..), and multiphoton ionization is used to measure the internal state distribution of CO. An upper limit for the branching ratio of NCO/NH production from photodissociation of HNCO at 193 nm is determined from an analysis of kinetic experiments to be 0.10. To clarify the mechanism of photodissociation, HNCO fluorescence-excitation and NH(a/sup 1/..delta..) action spectra are also measured. They imply that two excited states of HNCO are present where only one had previously been considered.
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