Infrared transient absorption spectroscopy was used to determine the total product branching fractions for the gas-phase hot atom reaction H + (CN)(2) --> HCN/HNC + CN (a) and the reaction CN + CH3SH --> HCN/ HNC + CH3S/CH2SH (b) at 293 K. The reactive H atoms had an initial mean translational energy of 92 kJ mol(-1), with a 38 kJ mol(-1) fwhm Gaussian energy distribution. The branching fractions determined for the product channels forming HCN and HNC, respectively, are 0.88 and 0.12 (+/- 0.05) for reaction (a) and 0.81 and 0.19 (+/-0.08) for reaction (b). The bimolecular rate constant for reaction (b) was measured to be (2.7 +/- 0.3) x 10(-10) cm(3) molec(-1) s(-1) at 293 K. The observed product branching fractions for reaction (a) are consistent with the assumption that the average reactive cross sections for the two product channels are approximately equal above their respective energy thresholds. The results for reaction (a) are compared with the related H + XCN (X = Br, Cl) reactions. The large rate coefficient for reaction (b) suggests an interaction via a long-range intermolecular potential, which is facilitated by the small ionization energy of CH3SH and large electron affinity of CN. The results for reaction (b) are compared with the related reactions of Cl and OH with CH3SH.