Proton affinity of SO3 |
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Authors: | Cynthia Ann Pommerening Steven M Bachrach Lee S Sunderlin |
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Institution: | 1. Department of Chemistry, Northern Illinois University, DeKalb, Illinois, USA
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Abstract: | Collision-induced dissociation (CID) of the radical cation H2SO4+ gives the product pairs H2O++SO3 and HO+HSO3+ with a 1:3 ratio that is essentially independent of collision energy. Statistical analysis of the two channels indicates that the proton affinity of HO is 3±4 kJ/mol lower than that of SO3. This can be used to derive PA(SO3)=591±4 kJ/mol at 0 K and 596±4 kJ/mol at 298 K. Previously, Munson and Smith bracketed the proton affinity as PA(HBr)=584 kJ/mol<PA(SO3)<PA(CO)=594 kJ/mol. The threshold of 152±16 kJ/mol for formation of H2O++SO3 indicates that the barrier to CID is small or nonexistent, in contrast to the substantial barriers to decomposition for H3SO4+ and H2SO4. |
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