Kinetics and Equilibria of Electron Transfer Reactions: A− + B = A + B−. Determinations of Electron Affinities of A and B and Stabilities of Adducts A 2 − and (A • B)−

摘要: The kinetics and equilibria of electron transfer reactions: (1) A− + B = A B− can be determined with a pulsed beam high pressure mass spectrometer. Determination the equilibrium constant K1 its temperature dependence lead to ΔG 1 o , ΔH ΔS values. series interconnected involving different ladders (scales) which converted absolute 7 values for capture (7): e using known selected standard compound (SO2). Measurements over 100 compounds were performed. These are mostly benzenes, naphthalenes, anthracenes substituted withdrawing substituents, benzo, naphtho anthroquinones various other conjugated molecules groups. All these have low lying vacant π* orbitals accommodate extra electron. number perfluoro or σ* studied also. most reactions also studied. vast majority exothermic proceeded at collision rates. Reactions SF6 perfluorinated cycloalkanes slow rates increasing as exothermicity reaction is increased. believed due large geometry change between neutral negative ion A−. barriers evaluated Marcus equations. To obtain agreement experiment one must consider energy changes complexes • caused by bonding A.