Chemistry of large hydrated anion clusters X sup minus (H sub 2 O) sub n , n = 0-59 and X = OH, O, O sub 2 , and O sub 3. 2. Reaction of CH sub 3 CN

Journal Article · Wed Oct 30 23:00:00 EST 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100175a021· OSTI ID:7203061

Yang, X; Zhang, X; Castleman, Jr, A W ^[1]

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1. Pennsylvania State Univ., University Park (United States)

The kinetics and mechanisms of the gas-phase reactions of acetonitrile with large hydrated anion clusters X{sup {minus}}(H{sub 2}O){sub n = 0-59}, X = OH, O, O{sub 2}, and O{sub 3}, were studied in a fast flow reactor under thermal conditions. OH{sup {minus}}(H{sub 2}O){sub n = 0-1} react with CH{sub 3}CN at near collision rate via proton-transfer and ligand-switching mechanisms; further hydration greatly reduces the reactivity of OH{sup {minus}}(H{sub 2}O){sub n>1} due to the thermodynamic instability of the products compared to the reactants. On the contrary, for all cluster sizes studied, O{sup {minus}}(H{sub 2}O){sub n} reacts with CH{sub 3}CN at near the collision rate via a hydrogen transfer from acetonitrile to the anion clusters. A new reaction channel was found for the reaction of O{sup {minus}} with CH{sub 3}CN to form CHCN{sup {minus}}, which can react further with CH{sub 3}CN to form CH{sub 2}CN and CH{sub 2}CN{sup {minus}}. Only very slow associations were observed for the reactions of O{sub 2}{sup {minus}} and O{sub 3}{sup {minus}} and their hydrates. The possible application of the present experimental results to an understanding of the hydrolysis mechanism of C H{sub 3}CN in aqueous solution in the presence of OH{sup {minus}} and protons as a catalyst is also discussed.

• DOE Contract Number: FG02-88ER60668
• OSTI ID: 7203061
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:22; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
EXPERIMENTAL DATA
HYDRATES
HYDROGEN COMPOUNDS
HYDROLYSIS
HYDROXIDES
INFORMATION
IONS
KINETICS
LYSIS
NITRILES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
OZONE
REACTION KINETICS
SOLVOLYSIS
WATER