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The negative ion icr spectra of SO,, HC1, HBr, BC13, BF3, PF5, SiF4, AsF5, SF6, and combinations thereof were studied at various electron energies and pressures in an effort to obtain evidence for ion-molecule reactions yielding halide ion adducts. Only primary negative ions were observed with pure samples except for the previously reported SiF=r, BFr, and AsF,-~and the additional species Si2F8~and B.Fr. Addition of SFe greatly enhanced halide adduct formation and was utilized in the reaction mixtures for all systems investigated. The relative order of fluoride ion affinity has been found to be: SF4, SF3• < SO,, HC1, AsF3 < SiF4 < BF3 < PF3 < BC13 < AsF3. Fluoride ion affinities of these compounds and the enthalpies of formation of the corresponding fluoroanions have been estimated.

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