Reevaluation of Arrhenius parameters for H + OH sup minus yields (e sup minus ) sub aq + H sub 2 O and the enthalpy and entropy of hydrated electrons

Journal Article · Thu Sep 06 00:00:00 EDT 1990 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100381a062· OSTI ID:5387734

Han, P; Bartels, D M ^[1]

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1. Argonne National Lab., IL (USA)

The rate constant for the reaction H{sup {sm bullet}} + OH{sup {minus}} {yields} (e{sup {minus}}){sub aq} + H{sub 2}O in aqueous solution has been measured in the temperature range 5-70{degree}C by the pulsed EPR free induction decay (fid) attenuation technique. The Arrhenius parameters for the reaction are A = (1.4 {plus minus} 0.4) {times} 10{sup 14} M{sup {minus}1} s{sup {minus}1} and E{sub a} = 38.5 {plus minus} 1.7 kJ/mol (9.2 {plus minus} 0.4 kcal/mol), in sharp disagreement with other work based on a less direct kinetic method. From these values the enthalpy of activation {Delta}H{sup {double dagger}} = 36.1 {plus minus} 1.7 kJ/mol and entropy of activation {Delta}S{sup {double dagger}} = 17.3 {plus minus} 6.0 J/(mol{center dot}deg) are deduced. The combination of this data with Arrhenius parameters for the reverse reaction allows reevaluation of the enthalpy, entropy, and free energy of formation for the hydrated electron.

• OSTI ID: 5387734
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 94:18; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
SOLVATED ELECTRONS
ENTHALPY
ENTROPY
AQUEOUS SOLUTIONS
EXPERIMENTAL DATA
FORMATION FREE ENERGY
HYDROXYL RADICALS
REACTION KINETICS
DATA
DISPERSIONS
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
FERMIONS
FREE ENERGY
INFORMATION
KINETICS
LEPTONS
MIXTURES
NUMERICAL DATA
PHYSICAL PROPERTIES
RADICALS
SOLUTIONS
THERMODYNAMIC PROPERTIES
400600* - Radiation Chemistry