Formation of the trihalide ion Cl3- in the gas phase

Gas phase nucleophilic displacement reactions of negative ions with carbonyl compounds

“…HCN + e--CN-+ H CN-+ CH3COF -4» CH2COF-+ HCN (2i) 37cr + cf3co35ci -35cr + cf3co37ci °This is the fraction of collisions which result in reaction, k/kCoii¡s¡on• The collision rate constants were calculated by the average dipole orientation theory (ADO) of Bowers.16 b Gas-phase thermochemical data for the ions and neutral compounds used here were taken from the following sources. (1) heats of formation of CH3COF, CH3COCI, CH3COBr, CH2CO, CH3COOCH3, CH3OH, H2S, HCN, and HF from S. W. Benson, "Thermochemical Kinetics", 2nd ed., Wiley, New York, 1976. (2) Heats of formation of CH3CH2COCI, CH3CH2COF, CH3CHC0, (CH3)3CHC0C1, (CH3)2CCO, (CH3)3CCOCl, (CH3)3CCOF, CF3COCI, CF3COF, CF3COOCH3, and CF3COOCOCF3 were calculated by Benson's group additivity method.…”

“…(H20)" -F h2o + M -H30+. (H20)"+, + M (1) where M is an inert third body which serves to deactivate the hydrated H30+ ion. For example, Kebarle and co-workers'…”

Negative ion-molecule reactions in sulfuryl halides

“…Since Eyring and Rollefson4 have predicted the stability of the neutral CI3 and since this molecule has also been suggested as the active intermediate in a number of photochemical reactions of chlorine, Melton and co-workers3 were not able to decide whether the CI3-ion observed was the product of an ionmolecule reaction or resulted from direct electron attachment of CI3. Stockdale, Compton, and Reinhardt5 described the reaction of SFe-with hydrochloric acid leading to the formation of F2CI-and the existence of the Br^-ion was established by the three body attachment reaction of Br-with bromine.6 Tiernan and co-workers7 observed the formation of several heteronuclear trihalide ions and concluded, from isotope distribution measurements in CI2-, that the intermediate of the endoergic charge transfer reaction Cl-+ Cl2 -Cl2-+ Cl (1) at low translational energies is CI3-. Their data suggest that the CI3-intermediate is linear in accordance with earlier theoretical calculations8 and with IR and Raman studies9•10 carried out with various salts of 1X2" (X = Cl, Br) which indicated a linear structure of the negative trihalide ions.…”