Ion Molecule Reactions of Gas-Phase Chromium Oxyanions:CrxOyHz- + O2
Chromium oxyanions, CrxOyHz-, were generated in the gas-phase using a quadrupole ion trap secondary ion mass spectrometer (IT-SIMS), where they were reacted with O2. Only CrO2- of the Cr1OyHz- envelope was observed to react with oxygen, producing primarily CrO3-. The rate constant for the reaction of CrO2- with O2 was 38% of the Langevin collision constant at 310 K. CrO3-, CrO4-, and CrO4H- were unreactive with O2 in the ion trap. In contrast, Cr2O4- was observed to react with O2 producing CrO3- + CrO3 via oxidative degradation at a rate that was 15% efficient. The presence of background water facilitated the reaction of Cr2O4- + H2O to form Cr2O5H2-; the hydrated product ion Cr2O5H2- reacted with O2 to form Cr2O6- (with concurrent elimination of H2O) at a rate that was 6% efficient. Cr2O5- also reacted with O2 to form Cr2O7- (4% efficient) and Cr2O6- + O (2% efficient); these reactions proceeded in parallel. By comparison, Cr2O6- was unreactive with O2, and in fact, no further O2 addition could be observed for any of the Cr2O6Hz- anions. Generalizing, CrxOyHz- species that have low coordinate, low oxidation state metal centers are susceptible to O2 oxidation. However, when the metal coordination is >3, or when the formal oxidation state is =5, reactivity stops.
- Research Organization:
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Organization:
- DOE - EM
- DOE Contract Number:
- DE-AC07-99ID-13727
- OSTI ID:
- 912174
- Report Number(s):
- INEEL/JOU-03-00167; JAMSEF; TRN: US200801%%627
- Journal Information:
- Journal of the American Society for Mass Spectrometry, Vol. 14, Issue 10; ISSN 1044-0305
- Country of Publication:
- United States
- Language:
- English
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