Radiation Chemistry of Organic Compounds. I. n-Alkane Liquids

Abstract

A series of -alkane liquids, pentane to hexadecane, have been irradiated with 800 kvp. electrons. The hydrogen yield, <?(H2) ™ 4.9, was found to be independent of the length of the carbon atom chain, whereas the methane yield decreased with increase in the length of the carbon atom chain. Infrared analysis has shown that the unsaturation produced is largely trans vinylene with a smaller amount of vinyl. Gas-liquid partition chromatography has shown that three primary product groups are formed: a dimer group, an intermediate group between the dimer and parent, and degradation group. These results show that C-C bond scission is an important process, contrary to conclusions based only on gas analysis.

Electron beam irradiation of r-SANEX and i-SANEX solvent extraction systems: analysis of gaseous products

“…G(H 2 ) values in the  and electron beam irradiated liquid n-alkanes are in the range of 430-545 nmolJ -1 [7,12,13]. In general, these values are lower for branched alkanes.…”

“…In general, these values are lower for branched alkanes. For instance, G(H 2 ) is equal to 210 nmolJ -1 for 2,2-dimethylbutane [7] comparing with 520 nmolJ -1 for n-hexane [12]. Unsaturated alkanes reveal also lower G(H 2 ) values: for 1-hexene, G(H 2 ) is equal to 83 nmolJ -1 [14].…”

Gamma radiolysis of carbon-14 labeled isobutane

“…This would favor neopentane formation over isopentane formation if the reaction occurred principally by a radical mechanism such as C^H 9 + CH 3 = 0^H 12 (37) or %H 9 + C U H 10 -C 5 H 12 + C 3 H 7 .…”

Gamma radiolysis of carbon-14 labeled isobutane

“…Mass spectra observations (39) showed that the tertiary hydrogen of isobutane was removed 55 times more rapidly than, the primary hydrogen. This would favor neopentane formation over isopentane formation if the reaction occurred principally by a radical mechanism such as C^H 9 + CH 3 = 0^H 12 (37) or %H 9 + C U H 10 -C 5 H 12 + C 3 H 7 .…”

“…These straight chain hydrocarbons had GfEg) values between lj.,2 and 5.2(3, 11,18,36,37). The yield of hydrogen in hydro carbons was essentially statistical in nature; as the branching The dependence of hydrogen and methane yield on temperature in the hydrocarbon increased the amount of hydrogen was found to decrease.The value of G(Eg) = 3*92 obtained in this investigation at 20°C is in agreement with the general trend of decreasing hydrogen with increasing branching.…”