In a discharge-flow experiment, chemiluminescent reactions of oxygen a
toms (O(P3)) with organic nitriles (RCN) are studied. For unsaturated
nitriles RCN (R: CH2=CH; CH2=C(CH3); CH2=CH(CH2)) the observed emissio
n is attributed to CN (B-->X) and NO* (gamma: A-->X and beta: B-->X,
bands). For saturated and phenyl nitriles (R: CH3; C2H5; C6H5) emissio
n is only observed from CN (B2 SIGMA+). A suitable reaction mechanism
for the observed emission is proposed.