Solvated electron reaction rates in alcohols and water. Solvent effect

Bolton, Gerald L.; Freeman, Gordon R.

doi:10.1021/ja00438a008

Cited by 17 publications

(8 citation statements)

References 3 publications

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“…In partial support of the possibility of bound C2H5OH', there is an electron resonance at ~(0.6 + ) eV in the solid. 13 Also, optical excitation of es' at 77 K produces H and not e". 18 This requires an excited dissociative state of C2H5OH' and consequently the ground state radical anion in the solid must also exist.…”

Section: Discussionmentioning

confidence: 99%

Electron scavenging in ethanol and in water

Ražem¹,

Hamill²

1977

J. Phys. Chem.

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Rate constants for scavenging solvated electrons, ea", mostly in the range ke-< 108 M"1 s"1, have been measured in ethanol and, as needed for comparison, in water. There is a tendency for feCs-to equal fce>q-over a 103-fold range, but there are instances where ke-is much greater. Inefficient scavengers for ea" provide relatively efficient traps for dry electrons e' with 37% survival often at C37 ^1M scavenger but also as low as ~0.2 M. The outstanding exceptions are olefins for which k< 107 M"1 s"1, but they do not measurably react with e". Negative ion resonances for alkenes as large as 2.2 eV have been reported and neither e" nor ea" is expected to react. It is proposed that ea" is C2H5OH" and eaq~i s H20". The radical anions may transfer either e" or H to appropriate acceptors, the latter accounting for possible reaction of ea" with olefins and alkenols. The reaction eaq" + eaq" = H2 is explained in terms of H20~. Whenever e" and ea" produce a common electron adduct S", and an equilibrium es" + S ^S" is approximated, then C3-"1 is proportional to ke~.

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Section: Discussionmentioning

confidence: 99%

Electron scavenging in ethanol and in water

Ražem¹,

Hamill²

1977

J. Phys. Chem.

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“…This reaction is nearly diffusion controlled (18). Figure 5 shows the plot of k, against q in the mixtures at two temperatures.…”

Section: A Yields O F Solvated Electrorzsmentioning

confidence: 97%

“…In this laboratory, various aspects of electron behaviour in hydroxylic solvents have been studied (16)(17)(18)(19)(20)(21)(22)(23)(24). Recently (22,23) it was found that the optical absorption spectra of solvated electrons in alcohol-water mixtures display a strong composition dependence, which was attributed to changes in solvent structure.…”

Section: Introductionmentioning

confidence: 99%

Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Cygler¹,

Freeman²

1984

Can. J. Chem.

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. Can. J. Chem. 62, 1265Chem. 62, (1984.Reaction of solvated electrons with nitrobenzene, N, is nearly diffusion controlled in both pure solvents; kN -10"'dm3/mol s. The value of kN is approximately proportional to the inverse viscosity -r-' in the pure solvents, and in the mixed solvents at different temperatures. However, on going from zero to 74 mol% water at the same temperature kN is independent of the 40% increase of -q. Electron diffusion in the mixed solvents is not a simple function of fluidity.Reaction with the inefficient scavengers tryptophane (ks -10" dm3/mol s) and phenol (ks -lo7-10' dm3/mol s) correlates inversely with the electron optical absorption energy. The latter is related to the trap depth in the solvent; electrons in deeper traps have less tendency to react with molecules of low electron affinity.Addition of 3 mol% 2-PrOH to water at 296 K increases the value of GE,,,.,, by 16%. although the value in pure 2-PrOH is three-fold smaller than that in pure water. The increase is attributed to an increase in the free ion yield, caused by an increase in the product of the electron thermalization range and the microscopic dielectric constant of the fluid between the ion and electron, averaged over the time that they exist as a correlated pair. Addition of a small amount of alcohol to water increases the orderliness of the water structure.JOANNA CYCLER et GORDON R. FREEMAN. Can. J . Chem. 62, 1265 (1984). La reaction des Clectrons solvatCs avec le nitrobenzkne, N, est une rCaction qui est a toutes fins pratiques contr61Ce par la diffusion dans les deux solvants a I'Ctat pur; kN -10"' dm2/mol s. La valeur de kN est approximativement proportionnelle I'inverse de la viscositC -r-' dans les solvants purs et dans les solvants mixtes a diffkrentes tempkratures. Cependant, si on opkre a une temptrature constante et que I'on fait varier la quantitC d'eau de zCro jusqu'i 74 mol% d'eau, la valeur de kN ne varie pas malgrC une augmentation de 40% de la valeur de T. La diffusion des Clectrons dans les solvants mixtes n'est pas une fonction simple de la fluiditC.

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“…In aqueous solution the Cu: ion is unstable with respect to CU;' and Cu. The equilibrium [8] 2Cu: * Cu:' + Cu, lies far to the right, and compounds of Cu(1) are covalent (17). Compounds of Al(I1) are not known.…”

Section: Effect Of Solvetlt Viscosi9mentioning

confidence: 99%

Solvent structure effects on solvated electron reactions with ions in 2-butanol/water mixed solvents

Peiris¹,

Freeman²

1991

Can. J. Chem.

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The Smoluchowski-Debye-Stokes-Einstein equation for the rate constant kz of a bimolecular reaction between charged or polar species was used to evaluate effects of bulk solvent properties on reaction rates of solvated electrons with NOT,,, H: , TI:, Cu:' , and AI:' in 2-butanol/water mixed solvents. To explain detailed effects it was necessary to consider more specific behavior of the solvent. Rate constants k 2 , activation energies E2, and pre-exponential factors Az of these reactions vary with the composition of 2-butanol/water mixtures. The values of E2 were in general similar to activation energies of ionic conductance EAo of the solutions, except for much higher values of E2 of (e; + NOT,,) in alcohol-rich solvents and of (e; + ~1:') in pure water solvent.The solvent apparently participates chemically in the NOT, reaction, and the ~1:' reaction is multistep. Rate constant and conductance measurements of thallium acetate solutions in 2-butanol containing zero and 10 mol% water were complicated by the formation of ion clusters larger than pairs.

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Solvated electron reaction rates in alcohols and water. Solvent effect

Cited by 17 publications

References 3 publications

Electron scavenging in ethanol and in water

Electron scavenging in ethanol and in water

Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Solvent structure effects on solvated electron reactions with ions in 2-butanol/water mixed solvents

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