A laser augmented reaction: SF6+ SiH4→S*2+ SiF4+ HF + H2· retention of isotopic selectivity during detonation

A single unfocused pulse of a free running CO2laser, area ～ 8 cm², initiates an explosive reaction between SF6and SiH4. This occurs at a minimum energy of 4 J full width at half maximum (FWHM)sim 1.5 /mus] of which about one half is absorbed in an 8 cm long cell; total pressure 12 torr; 0.65 <p(SiH4)/p(SF6) < 1.8. The spectral and temporal distributions of the emitted chemiluminescence depend sensitively on the fuel to oxidizer ratio, and on the pulse energy; we investigated the range 4 → 20 J. The principal emission is due to S2(B^{3}Sigma-_{u} rightarrow X^{3}Sigma-_{g}). Transitionsupsilon' (0-4) rightarrow upsilon" (2-15)were recorded. In the³Sigma-_{u}state, vibrational temperatures range from 3000-13000 K. The luminosity peaks sharply at (SiH4)/(SF6) = 1.0 ± 0.05. On each side of the maximum of the emission versus composition curve at (SiH4)/(SF6) ≈ 0.95 and 1.22, for a 12 J pulse] the residual SF6(0.2-0.5 percent of initial amount) is enriched in³⁴SF6; the observed fractionation factors at these two compositions are 8 ± 2. The separation between the two sharply peaked optimum compositions appears to increase with increasing pulse energy. Preliminary results with other fuels suggest that the concurrent absorption of CO2laser radiation by the fuel, as well as a highly exothermic reaction, are pre-requisite for fine tuning of composition, injected power, and total pressure for optimum isotope fractionation.