Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetic Study of the Thermal Decomposition of Isocyanic Acid in Shock Waves
Okitsugu KajimotoOsamu KondoKazuo OkadaJiro FujikaneTakayuki Fueno
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1985 Volume 58 Issue 12 Pages 3469-3474

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Abstract

Thermal decomposition of isocyanic acid HNCO diluted to less than 2.0 mol% in argon was studied behind incident shock waves over the temperature range 2100–2500 K. The decomposition course was followed by monitoring the light absorption of HNCO and NH(3Σ) at 206 and 336 nm, respectively. It is confirmed that the primary step of the decomposition is a bimolecular process HNCO+Ar→NH(3Σ)+CO+Ar, ΔH°0=337 kJ mol−1, with the low-pressure limit rate constants k=1017.23±0.36exp[−(402±17) kJ mol−1/RT] cm3 mol−1 s−1. The siglet-to-triplet crossing point is estimated on the basis of the RRKM low-pressure-limit rate constant calculations. The overall decomposition mechanism is suggested and its validity is confirmed by computer simulation of the time–concentration profiles of NH(3Σ) at varying temperature.

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