Ion—Molecule Experiments Involving Negative Ions of Tungsten and Rhenium Oxides

Rate constants for the reactions of ${\mathrm{ReO}}_3^{-}$ and $({\mathrm{WO}}_3{)}_{\text{n=1,2,3}}^{-}$ with Cl₂ and NO₂ have been measured in a drift tube/mass spectrometer apparatus from thermal energies (295°K) to $\text{∼ 0.07}\mathrm{eV}$ in the center of mass system. The rate constants for these reactions involving atom exchange agreed to within a factor of 2 with the theoretical orbiting rate constant of approximately ${\text{7 × 10}}^{\text{−10}}\mathrm{cm}\text{3/}\sec$ for both reactants. ${\mathrm{ReO}}_4^{-}$ did not react with either NO₂ or Cl₂. Ordinary charge transfer was not observed, implying electron affinities in excess of 2.5 eV for these metal oxides. The mass‐identified zero‐field mobilities of these ions in Ar were measured at 295°K and were found to be 1.94, 1.67, 1.96, 1.50, and 1.20 cm² V⁻¹·sec⁻¹ for ${\mathrm{ReO}}_3^{-}$ , ${\mathrm{ReO}}_4^{-}$ , ${\mathrm{WO}}_3^{-}$ , $({\mathrm{WO}}_3{)}_2^{-}$ , and $({\mathrm{WO}}_3{)}_3^{-}$ , respectively.