Temperature dependence of the rate constant for the reaction e–aq+ OH in water up to 150 °C

Elliot, A. John; Ouellette, Denis C.

doi:10.1039/ft9949000837

Cited by 48 publications

(97 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although this number has been widely accepted, Buxton and Wood 16 in 1989 insisted a better estimate is 13 100 M -1 cm -1 . The basis for Buxton and Wood's argument is the comparison of pulse radiolysis G values (yields) for • MV + from a study of Mulazzani et al 17 and for Fe(CN) 6 3-in a study of Schuler et al 18 However, in 1995 it was shown 19 that the dosimetry used in the earlier papers was incorrect. After correction of the dosimetry, the numbers agree within error, and there is no need to adjust the • MV + extinction coefficient.…”

Section: Resultsmentioning

confidence: 96%

Hydrated Electron Extinction Coefficient Revisited

2008

View full text Add to dashboard Cite

The extinction coefficient of the hydrated electron (e(-))aq generated by pulse radiolysis is evaluated relative to the methyl viologen radical cation (*)MV(+), whose extinction coefficient at 605 nm has been carefully measured in the past. We find that the room temperature (e(-))aq extinction coefficients reported in the literature are underestimated by 10-20%. We obtain = 22,700 M(-1) cm(-1) for the 20 degrees C hydrated electron at 720 nm, assuming the (*)MV(+) extinction is 13,700 M(-1) cm(-1) at 605 nm. This has implications both for second-order reaction rate measurements of (e(-))aq and for the estimate of its integrated oscillator strength.

show abstract

Section: Resultsmentioning

confidence: 96%

Hydrated Electron Extinction Coefficient Revisited

2008

View full text Add to dashboard Cite

show abstract

“…Estimated from the reaction distance r = 0.58 nm.' e Data from ref 10 recalculated using extinction coefficient data for eq-from ref 9. f Data from ref 11 recalculated using extinction coefficient data for e,-from ref 9. g Fitted to the experimental data corrected for changes in extinction coefficient.…”

Section: Numerical Methods and Reaction Schemementioning

confidence: 99%

Modeling of radiation spur processes in water at temperatures up to 300.degree.

Swiatla-Wojcik¹,

Buxton²

1995

J. Phys. Chem.

View full text Add to dashboard Cite

Deterministic diffusion-kinetic modeling has been performed to calculate the temperature dependence of the radiation chemical yields (G-values) of the radiolysis products of water. The FACSIMILE numerical method has been used to solve a set of coupled differential equations describing the diffusion and reactions of the species for the temperature range 20-300 "C. The low LET spherically symmetrical case of an "average" spur with 62.5 eV deposited in it has been considered. Modeling calculations have been compared for Gaussian, an exponential distribution, and a distribution with a central minimum assumed as the initial spatial distribution of the hydrated electron (eaq-). In all cases spatial distributions of the other radiolytic products started as Gaussian. To fit the experimental data it has been necessary to assume that the reaction eaq-+ eaq--H2

show abstract

“…No provision was made to take into account rxn. (3), whose rate increases with the temperature, because the concentration of hydroxide was too low (56 mM) to observe deprotonation of OH on the time scale of 600 ps, even at 97 o C [16].…”

Section: B Biphotonic Excitation Of Oh -mentioning

confidence: 99%

“…It is not presently clear, whether this discrepancy is significant. The estimates by Elliot and Ouellette [16] were obtained from a global fit to a complex kinetic scheme that involved >5 other reactions occurring on the same time scale. On the other hand, our simulations neglected a possible temperature effect on the initial electron distribution, which may be significant.…”

Section: B Biphotonic Excitation Of Oh -mentioning

confidence: 99%

Ultrafast dynamics for electron photodetachment from aqueous hydroxide

Crowell

Lian

Shkrob

et al. 2004

The Journal of Chemical Physics

105

View full text Add to dashboard Cite

Charge-transfer-to-solvent (CTTS) reactions of hydroxide induced by 200 nm monophotonic or 337 nm and 389 nm biphotonic excitation of this anion in aqueous solution have been studied by means of pump-probe ultrafast laser spectroscopy. Transient absorption kinetics of the hydrated electron, e aq -, have been observed, from a few hundred femtoseconds out to 600 ps, and studied as function of hydroxide concentration and temperature. The geminate decay kinetics are bimodal, with a fast exponential component (ca. 13 ps) and a slower power "tail" due to the diffusional escape of the electrons. For the biphotonic excitation, the extrapolated fraction of escaped electrons is 1.8 times higher than for the monophotonic 200 nm excitation (31% vs. 17.5% at 25 o C, respectively), due to the broadening of the electron distribution. The biphotonic electron detachment is very inefficient; the corresponding absorption coefficient at 400 nm is < 4 cm TW -1 M -1 (assuming unity quantum efficiency for the photodetachment).

show abstract

Temperature dependence of the rate constant for the reaction e–aq+ OH in water up to 150 °C

Cited by 48 publications

References 22 publications

Hydrated Electron Extinction Coefficient Revisited

Hydrated Electron Extinction Coefficient Revisited

Modeling of radiation spur processes in water at temperatures up to 300.degree.

Ultrafast dynamics for electron photodetachment from aqueous hydroxide

Contact Info

Product

Resources

About