KINETICS AND EQUILIBRIA OF ELECTRON TRANSFER REACTIONS: NEGATIVE A + B = A + NEGATIVE B. DETERMINATION OF ELECTRON AFFINITIES. STRUCTURE AND STABILITIES OF IONS NEGATIVE A, NEGATIVE B AND ADDUCT IONS NEGATIVE A.B, AND NEGATIVE B.

The gas phase electron transfer reactions: A$sp{-}$ + B = A + B$sp{-}$, where A and B are substituted benzenes, substituted naphthalenes, azulene, perfluoro aromatic systems, sulfurhexafluoride, perfluoromethylcyclohexane, benzo- and naphthoquinones, maleic and phthalicanhydride, di- and tetracyanoethylene and small molecules like SO$sb{2}$, NO$sb{2}$, CS$sb{2}$, CH$sb{3}$NO$sb{2}$ etc. were studied with a pulsed electron high pressure mass spectrometer.;The rate constants for 77 reactions were determined. The majority, when exothermic, proceeded with rate constants k$sb{1}$ which were near the Langevin-ADO collision limit. However, when SF$sb{6}$ and perfluoromethylcyclohexane were used, k$sb{1}$ was observed to be very small, and was found to increase with the increase of exothermicity of the reaction. The slowness was attributed to a large energy barrier in the reaction coordinate which decreases as the exothermicity increases. The barrier is due to a large geometry change between SF$sbsp{6}{-}$ and SF$sb{6}$, and stability differences between SF$sbsp{6}{-}$.B and SF$sb{6}$.B$sp{-}$.;Determination of equilibrium constants K$sb{1}$ leads to an evaluation of the $Delta$G$sbsp{1}{0}$. While the temperature dependence of K$sb{1}$ provides, via van't Hoff plots, $Delta$H$sbsp{1}{0}$ and $Delta$S$sbsp{1}{0}$ changes. These measurements permit the construction of interconnecting $Delta$H$sbsp{1}{0}$, $Delta$S$sbsp{1}{0}$ and $Delta$G$sbsp{1}{0}$ scales containing 100 molecules. The electron affinities EA(A) of all compounds in the $Delta$H$sbsp{1}{0}$ scale were determined by anchoring the scale to the precisely known electron affinity of SO$sb{2}$. The resulting electron affinity scale extends from 0.5 to 3.2 eV. $Delta$H$sbsp{rm a}{0}$(A) (= - EA(A)), $Delta$S$sbsp{rm a}{0}$(A) and $Delta$G$sbsp{rm a}{0}$(A) data for electron attachment process (A + e $to$ A$sp{-}$) was also obtained.;The equilibria: A$sp{-}$ + Sl = A$sp{-}$.Sl and A$sp{-}$ + B (or A) = A$sp{-}$.B (or A$sp{-}$.A), where A and B are 27 different substituted nitrobenzenes and quinones and Sl are the solvent molecules: MeOH, MeCN, DMSO, DMF and THF were studied also. A decrease of binding energy in A$sp{-}$.Sl with increasing electron affinity of A was observed. The decrease is attributed to increasing charge delocalization in A$sp{-}$ with the increase of EA(A). The observed changes in bond energies for the adducts A$sp{-}$.B were examined and possible structures of the A$sp{-}$.B and A.B$sp{-}$ adducts are proposed.