Donald Pilipovich

Chemical generation of a population inversion between the spin‐orbit states of atomic iodine

When I2 is injected into a stream of chemically produced O*2(1Δg), electronically excited iodine atoms [I* (52P1/2)] are created. For suitably high O*2/O2 ratios, a population inversion is established between the 52P1/2 and 52P3/2 atomic states of iodine. The inversion was observed using an optical double‐resonance technique.

New HCl chemical lasers: Chlorine reactions with group IV, V, and VI hydrides

Abstract The reactions of chlorine with hydrides of elements in groups IV, V, and VI have been investigated with respect to their potential as sources for HCl chemical lasers. For these systems, chain reactions involving Cl 2 should contribute in some measure to the production of chlorine atoms. New HCl lasers based on the reactions of chlorine atoms with H 2 S, H 2 Se, and PF 3 H 2 were observed.

Vibrational spectrum of bromine trifluoride

Abstract The infrared spectrum of matrix isolated BrF 3 has been recorded. All six fundamental vibrations expected for a T -shaped molecule of symmetry C 2 v were observed. A modified valence force field and some thermodynamic properties have been computed for BrF 3 .

Titanium tetraperchlorate and chromyl perchlorate

Abstract Syntheses of titanium tetraperchlorate and chromyl perchlorate are reported using chlorine perchlorate and the respective metal chlorides. These anhydrous metal perchlorates were found to contain bidentate perchlorato ligands.

Kinetics of the reaction of atomic fluorine with phosphorous trifluoride: ESR determination

Abstract The reaction rate constant of the addition of atomic fluorine to excess PF 3 was determined by fast flow ESR measurements to be (8.6 ± 0.6) × 10 12 cm 3 mole −1 s −1 at 300 K. The stoichiometry of the overall reaction of F with PF 3 was 2:1. Finite difference calculations simulating several reaction mechanisms suggest that the reaction occurs in two consecutive addition steps, F + PF 3 = PF 4 and F + PF 4 = PF 5 . Assuming this mechanism is correct, the rate constant for the second reaction would be approximately (1.2 ± 0.2) × 10 13 cm 3 mole −1 s −1 .

Mechanism and kinetics of the reaction of F with trivalent phosphorus iodide using electron spin resonance detection

Abstract The reaction of iodobistrifluoromethylphosphine, P(CF 3 ) 2 I, with atomic fluorine was studied by fast-flow ESR methods. The initial stage of the reaction is the abstraction of I by F, to form IF with a bimolecular rate constant of (1.0 ± 0.3) × 10 14 cm 3 mol −1 s −1 at 297 K. In the presence of excess F, stepwise addition to the phosphorous occurs. In the presence of excess P(CF 3 ) 2 I, the reaction P(CF 3 ) 2 + IF → P (CF 3 ) 2 F + I appears to take place. This reaction rate is slow relative to P(CF 3 ) 2 + F → P(CF 3 ) 2 F.