Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water.

Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water. Research Abstract Details 

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Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water. Abstract Text:

Timothy W Marin,Kenji Takahashi,Charles D Jonah,Sergey D Chemerisov,David M Bartels,Timothy W Marin,Kenji Takahashi,Charles D Jonah,Sergey D Chemerisov,David M Bartels,

Pulse radiolysis experiments were performed on hydrogenated, alkaline water at high temperatures and pressures to obtain rate constants for the reaction of hydrated electrons with hydrogen atoms (H* + e-(aq) --> H(2) + OH-, reaction 1) and the bimolecular reaction of two hydrated electrons (e-(aq) + e-(aq) --> H(2) + 2 OH-, reaction 2). Values for the reaction 1 rate constant, k(1), were obtained from 100 - 325 degrees C, and those for the reaction 2 rate constant, k(2), were obtained from 100 - 250 degrees C, both in increments of 25 degrees C. Both k(1) and k(2) show non-Arrhenius behavior over the entire temperature range studied. k(1) shows a rapid increase with increasing temperature, where k(1) = 9.3 x 10(10) M(-1) s(-1) at 100 degrees C and 1.2 x 10(12) M(-1) s(-1) at 325 degrees C. This behavior is interpreted in terms of a long-range electron-transfer model, and we conclude that e-aq diffusion has a very high activation energy above 150 degrees C. The behavior of k(2) is similar to that previously reported, reaching a maximum value of 5.9 x 10(10) M(-1) s(-1) at 150 degrees C in the presence of 1.5 x 10(-3) m hydroxide. At higher temperatures, the value of k(2) decreases rapidly and above 250 degrees C is too small to measure reliably. We suggest that reaction 2 is a two-step reaction, where the first step is a proton transfer stimulated by the proximity of two hydrated electrons, followed immediately by reaction 1.

Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water. Publishing Authors By Initials

TW Marin,K Takahashi,CD Jonah,SD Chemerisov,DM Bartels,TW Marin,K Takahashi,CD Jonah,SD Chemerisov,DM Bartels,

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Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: The journal of physical chemistry. A

VOLUME: 111

Page Numbers: 11540-51

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ISSN: 1089-5639

DAY: 12

MONTH: 10

YEAR: 2007

Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water. Information

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LANGUAGE: eng

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Grant and Affiliation Information for Recombination of the hydrated electron at high temperature and pressure in hydrogenated alkaline water.

AFFILIATION: Chemistry Department, Benedictine University, Lisle, Illinois 60532, USA.

Country: United States

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MEDLINETA: J Phys Chem A

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