Absolute rate constants were obtained for CN radical reactions with HCN and C2N2 employing the method of laser photolysis/laser induced fluorescence. The rate constants were found to be temperature dependent in the range 300–740 K and pressure independent in the range 100–600 Torr. The rates for CN+HCN may be described well, in units of cm3/s, by k(HCN)=2.50×1017T1.71 exp(−770/T), which includes the shock tube results of Szekely etal. at 3000 K [Int. J. Chem. Kinetics 15, 1237 (1983)]. The measured rates for CN+C2N2 may be described well by k(C2N2)=2.19×1021T2.70 exp(−325/T). Rice–Ramsperger–Kassel–Marcus (RRKM) theory calculations employing transition state parameters predicted by the BAC‐MP4 method were able to account for the effects of temperature and pressure on both reactions.

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