PRIMARY QUANTUM EFFICIENCIES IN THE REACTION OF CYCLOPENTANE WITH MERCURY 6(3P1) ATOMS

Abstract

An investigation has been made of the reaction of cyclopentane with Hg 6(3P1) atoms at a substrate pressure of 107 mm, under static conditions at 24 °C. Low light intensities were used in order to minimize secondary reactions.The products of the reaction, for small extents of decomposition, have been shown to be exclusively hydrogen, bicyclopentyl, and cyclopentene. With increasing duration of exposure, the cyclopentene-to-cyclopentane ratio achieves a steady-state value of 5.7 × 10−3. Furthermore, it has been found that the same ratio is ultimately reached, upon prolonged exposure of a substrate initially containing cyclopentene at a concentration higher than the steady-state value. In the runs with added cyclopentene, a fourth product appeared in measurable quantities. Its molecular weight corresponded to the formula, C10H16, and it was assumed to be a cyclopentyl cyclopentene. The same compound appears in extensive decomposition of the pure substrate.The addition of small amounts of nitric oxide was found to have a marked inhibiting effect on the reaction. Bicyclopentyl formation was completely suppressed when 0.7 mole% of nitric oxide was present; and the cyclopentene yield was reduced to one-fifth of its value for the pure substrate, by adding 0.98 mole% of nitric oxide.In order to obtain primary quantum yields for the reaction, a series of runs were performed of 1 to 33 minutes in duration, with a cyclopentane which had been purified by gas–liquid chromatography. By a short extrapolation of the mean quantum yields of product formation to zero extent of reaction, it was found that the primary quantum yields for hydrogen, bicyclopentyl, and cyclopentene were respectively 0.8, 0.4, and 0.4.On the basis of a simple four-step paraffinic mechanism, taken in conjunction with the primary quantum yield data, it is concluded that the reaction has a primary quantum yield of substrate decomposition of 0.8, and that cyclopentyl radicals have the same rates for disproportionation and recombination at 24 °C.