Oxygen-for-Sulfur Switching in the Gas Phase: Reactions of Al and Si Oxyanions with H2S

Journal Article · Thu Mar 01 04:00:00 EST 2001 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp004495q· OSTI ID:1010344

Groenewold, Gary Steven; Hodges, Brittany DM; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Kessinger, Glen Frank; Wright, J B

Gas-phase Si and Al oxyanions were formed by particle bombardment, isolated by mass, and then reacted with H{sub 2}S in an ion trap secondary ion mass spectrometer (IT-SIMS). The reactions proceeded by different reaction pathways depending on whether the oxyanions were even- or odd-electron species. The radical anion SiO{sub 2}{sm_bullet}{sup -} reacted with H{sub 2}S by abstracting a {sm_bullet}SH radical to form the even-electron SiO{sub 2}SH{sup -}. Once formed, the even electron SiO{sub 2}SH{sup -} reacted with a second H{sub 2}S molecule by O-for-S exchange to form SiOS{sub 2}H{sup -}. The radical anion SiO{sub 3}{sm_bullet}{sup -} abstracted an {sm_bullet}H radical from H{sub 2}S to form even-electron SiO{sub 3}H{sup -}, which then underwent two consecutive O-for-S exchange reactions with H{sub 2}S to form SiO{sub 2}SH{sup -} and SiOS{sub 2}H{sup -}. For the reactions of the even-electron anion AlO{sub 2}{sup -}, the products of two consecutive O-for-S exchange reactions with H{sub 2}S were AlOS{sup -} and AlS{sub 2}{sup -}. The radical abstraction reactions and the O-for-S exchange reactions of SiO3H{sup -}, AlO{sub 2}{sup -}, and AlOS{sup -} were efficient in the 30-50% range. The efficiency of the O-for-S exchange reaction of SiO{sub 2}SH{sup -} (producing SiOS{sub 2}H{sup -}) was substantially less efficient at 8%.

• Research Organization: Idaho National Laboratory (INL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC07-05ID14517
• OSTI ID: 1010344
• Report Number(s): INEEL/JOU-00-01564
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 16 Vol. 105; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

99 GENERAL AND MISCELLANEOUS
ANIONS
EFFICIENCY
ELECTRONS
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RADICALS