Proton-Transfer Reactions between H3+ and Saturated Hydrocarbons

The γ-ray radiolysis of H2 has been investigated in the presence of relatively small concentrations of C2D6, C3D8, iso-C4H10, (CH3)3CD, (CD3)4C and n-C5D12. It is shown that, in all cases, the proton-transfer reaction H3++RD→RDH++H1, occurs even when the additive is only 0.01% of the hydrogen. The protonated hydrocarbon decomposes mainly to form a carbonium ion and a neutral alkane molecule. From the radiolysis of D2—CH4—C3D8 mixtures, it could be deduced that CH4D+ is produced, which subsequently transfers a proton or deuteron to C3D8. It is suggested that the study of the radiolysis of H2, in the presence of additives offers the possibility of producing well-specified ions, the reactions of which can be followed in the absence of interfering processes.