This paper addresses the kinetic aspects of the thermal decomposition
of H2S in a flow reactor. Experiments conducted in a quartz tube with
argon/H2S feed over a wide composition spectrum (20-100% H2S) at four
temperatures (1030-1070 K) show that the reaction is essentially first
order in H2S partial pressure. Theoretical models based on a free rad
ical mechanism involving the abstraction of hydrogen from H2S as the r
ate-determining step show the linear dependency of thermolysis rate on
reactant composition. Hydrogen yield also increases monotonically wit
h feed composition at all temperatures. Interestingly, the activation
energy for H-2 production of 200 kJ mol(-1) is lower than that for the
global decomposition reaction of about 241 kJ mol(-1), consistent wit
h the view that the initiation step requiring the breaking of the H-S
bond is the rate-controlling step rather than the termination involvin
g the combination of two hydrogen radicals.