Reduction potentials of CO sub 2 sup minus and the alcohol radicals

Journal Article · Thu Jan 12 04:00:00 EST 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100338a079· OSTI ID:5174258

Schwarz, H A; Dodson, R W ^[1]

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1. Brookhaven National Lab., Upton, NY (USA)

Equilibrium constants were measured at 25{degree}C for the reactions CO{sub 2}{sup {sm bullet}{minus}} + Tl{sup +} {rightleftharpoons} CH{sub 3}CHO + Tl{sup 0} (K = 0.53), and (CH{sub 3}){sub 2}CO{sup {sm bullet}{minus}} + Tl{sup +} {rightleftharpoons} (CH{sub 3}){sub 2}CO + Tl{sup 0} (K = 520). These constants give reduction potentials for CO{sub 2}{sup {sm bullet}{minus}}, CH{sub 2}O{sup {sm bullet}{minus}}, CH{sub 3}CHO{sup {sm bullet}{minus}}, and (CH{sub 3}){sub 2}CO{sup {sm bullet}{minus}} of {minus}1.90, {minus}1.81, {minus}1.93, and {minus}2.10 V, and for {sup {sm bullet}}CH{sub 2}OH, CH{sub 3}CHOH, and (CH{sub 3)3}COH of {minus}1.18, {minus}1.25, and {minus}1.39 V. All potentials are based on E{degree} (Tl{sup +}/Tl{sub aq}{sup 0}) = {minus}1.94 V. The stability constant for the reaction Tl{sup 0} + Tl{sup +} {rightleftharpoons} Tl{sub 2}{sup +} was found to be 140 M{sup {minus}1}. Values of {Delta}G{sub f}{sup 0} for the radicals in solution are given and values of {Delta}G{sub f}{degree} and {Delta}H{sub f}{degree} for the radicals in the gas phase are estimated based on the assumption that the free energy of solution of the neutral radicals is the same as for the corresponding alcohol or formic acid.

• DOE Contract Number: AC02-76CH00016
• OSTI ID: 5174258
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 93:1; 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
ALKOXY RADICALS
ANIONS
BUTOXY RADICALS
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CATIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ENERGY
ENTHALPY
EQUILIBRIUM
ETHOXY RADICALS
EXPERIMENTAL DATA
INFORMATION
IONS
KINETICS
METHOXY RADICALS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POTENTIAL ENERGY
RADICALS
REACTION KINETICS
REDUCTION
SOLUTION HEAT
THALLIUM COMPOUNDS
THERMODYNAMIC PROPERTIES