Vibrational Nonequilibrium Effects in the (H2, H2) Reactive System

The decrease in the forward rate of the (H₂, H₂) reaction from its equilibrium value due to the perturbation of the vibrational distribution function by reaction is calculated from a numerical solution of a non‐linear Master equation. The inelastic and reactive cross sections that are required for this calculation were obtained from a Monte Carlo average of many quasiclassical collision trajectories. At 3200°K, the highest temperature studied, the decrease in the equilibrium rate of reaction was 0.21%. The vibrational relaxation time for H₂ in the absence of reaction was also calculated and found to obey a Landau‐Teller temperature dependence ${\mathrm{(P\tau )}}_{\mathrm{calc}}{\text{=62× 10}}^{\text{−9}}\hspace{0.17em}\exp {\text{(148/T}}^{\text{1/3}}\mathrm{)\hspace{0.17em}}\mathrm{atm}·\sec$ . over the range 1200–3200°K.