Solvated electron mobility in liquid <i>tert</i>-butanol

Zhao, Yue; Freeman, Gordon R.

doi:10.1139/v95-051

Cited by 4 publications

(8 citation statements)

References 16 publications

(9 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The variation of E2 for the efficient reactions of es-with nitrobenzene and acetone is qualitatively similar to that of Erl The larger values of EZ compared to E,, in the amine-rich solutions might be attributed to a larger mobility p and activation energy of mobility E,, of electrons than of molecules in the amine. A similar situation was noted in tert-butanol solvent (10).…”

Section: Activation Energiessupporting

confidence: 75%

“…We have chosen 1-butylamine-water, for practical reasons (ease of handling). The optical absorption spectra of es-in these mixed solvents have recently been reported (14). There appears to be less selective solvation of electrons by water in these mixtures than was expected.…”

Section: Introductionmentioning

confidence: 91%

“…The diffusion-controlled rate constant k2(eSp + S) for reaction of e,-with a polar solute S is approximately related to the solvent viscosity q by the Smoluchowski-Stokes-Debye equation (3,8,10,25):…”

Section: Smoluchowskistokes-debye Modelmentioning

confidence: 99%

See 2 more Smart Citations

Solvent effects on the reactivity of solvated electrons with organic solutes in 1-butylamine–water mixtures

Zhao¹,

Freeman²

1996

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

The values of the rate constants of the reactions of e,-with the efficient scavengers nitrobenzene and acetone are 2 2 x lo6 m3 mol-I s-' in the whole range of 1-butylamine-water mixtures at 298 K; the reaction rates in the mixed solvents vary approximately as the solvent fluidity. In pure butylamine at 298 K, kz(e,-+ nitrobenzene) = 84 x lo6 m3 mol-I s-I and kz(es-+ acetone) = 7.3 x lo6 m3 mol-' sK'. The values of the rate constants of the reactions of es-with the inefficient scavengers phenol and toluene are < 2 x lo5 m3 mol-I s-I in the whole range of l-butylaminewater mixtures at 298 K and have a maximum at 50 mol% water and a minimum at 99 mol% water. In pure 1-butylamine at 298 K, k2(es-+ phenol) = 1.0 x 10' m%olol-' s-I and k2(es-+ toluene) = 0.28 x lo4 m%olKl s-I. The reaction rates with inefficient scavengers show strong dependence on the solvent composition and selective solvation of electron and scavenger. In the amine-rich region (G30 mol% water), the rate constants increase with the itzcrease of viscosity, indicating the chemical participation of solvent molecules in the reaction. In the water-rich region from 50 to 99 mol% water, the decrease of the rate constants indicates the nonhomogeneous solvation of the electrons by water and of the organic solutes by 1-butylamine. From 99 mol% to pure water the rate constant increases rapidly, which we attribute to insufficient I-butylamine to coat the phenol or toluene molecules. The variation of the activation energies E2 for the efficient scavengers, 14-27 kJ mol-I, are similar to the variation of E, in the mixed solvents. The values of E1 for the inefficient scavengers are from 15 to 38 kJ mol-I for phenol and from 6 to 21 kJ mol-I for toluene. Both k2 and E2 for the inefficient scavenger reactions show a correlation with the temperature coefficient -dEA,,,/dT of the optical absorption of es-in the mixed solvents, but the reason is obscure.Key words: 1-butylamine-water solvent, solvated electron, organic solutes, reactivity, solvent effects.RCsumC : Les constantes de vitesse pour les reactions des es-avec les capteurs efficaces que sont le nitrobenzkne et l'acttone sont 2 2 x lo6 m3 rnolK' s-I pour I'ensemble des concentrations de la I-butylamine-eau, h 298 K; la variation des vitesses de rCaction dans les solvants mixtes suit approximativement celle de la fluidit6 du solvant. Dans la butylamine pure, B 298 K, k2(es-+ nitrobenzkne) = 84 x lo6 m3 mol-' s-I et k2(es-+ acCtone) = 7,3 x lo6 m h o l -I s-I. Les valeurs des constantes de vitesse des rtactions des es-avec les capteurs inefficaces que sont le phCnol et le tolukne sont <2 x lo5 m3 mol-I s-I pour l'ensemble des concentrations de la I-butylamine-eau h 298 K et elles prCsentent un maximum h 50 mol% d'eau et un minumum h 99 mol% d'eau. Dans la I-butylamine pure, h 298 K, k2(e,-+ phtnol) = 1,O x lo4 m3 mol-I s-I et k2(e,-+ tolukne) = 0,28 x lo4 m"01-l-l s-I. Les vitesses de rtaction avec les capteurs inefficaces prtsentent une forte dipendance sur le composition et une solvation selective de...

show abstract

Section: Activation Energiessupporting

confidence: 75%

Section: Introductionmentioning

confidence: 91%

See 1 more Smart Citation

Solvent effects on the reactivity of solvated electrons with organic solutes in 1-butylamine–water mixtures

Zhao¹,

Freeman²

1996

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…5). We attribute this to a decrease in mobility of e;, which is unusually high in pure tert-butanol (17).…”

Section: LImentioning

confidence: 85%

“…In the solvents 10 to 0% water E2 increases greatly, while EAo for the salts decrease and that for HC104 remains constant. The increase of E2 is attributed to a large temperature coefficient of diffusion of e;, which reaches 41 kJ mol-' in pure tert-butanol (17).…”

Section: E2 and Eaomentioning

confidence: 95%

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Zhao¹,

Freeman²

1995

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Reactions of e; with the ions N H i V s , and H: showed different variations of rate with solvent composition in rerr-butanollwater mixtures from 0 to 100 mol% water. In pure rerr-butanol solvent at 298 K the respective values of k2 (lo6 m3 mol-I s-I) are 3.2, 13, and 42. The estimated value of reaction radius R, depends on the minimum number of solvent molecules needed between e; and the reactant ion to attain the static values of E of the bulk solvent used in the calculation of the Debye factor f ; R, is assumed to be larger in the alcohol-rich region than in the water-rich region, because the solvent molecules are larger. The Smoluchowski-Debye-Nernst-Einstein model is used to evaluate the effective reaction radius KR,, where K is the probability of reaction per encounter; KR, decreases from pure ferr-butanol to pure water. In the water-rich region the activation energies E2 of the efficient reactions, 11-24 kJ mol-I, are similar to EAo of the reactant electrolyes, 12-23 kJ mol-l. For the inefficient reactant NH: CIO;, E2 = 30 kJ mol-I. The high values of E2 = 43-53 kJ mol-I in pure rerr-butanol solvent are attributed to a high activation energy for diffusion of e; in this solvent.Ke.y words: rert-butanollwater solvents, solvated electron, ions, reactivity, solvent effects. RCsumC : Les vitesses de rtaction des e; avec les ions N H i T S et H l prtsentent des variationsdifferentes avec la composition des mtlanges de solvant rerr-butanolleau en allant de 0 B 100% en eau. Dans le tert-butanol pur, B 298 K, les valeurs relatives de k? (lo6 m h o l -I s-I) sont 3,2, 13 et 42.La valeur estimte du rayons de reaction R, dtpend du nombre minimal de moltcules de solvant requis entre le e; et I'ion rtactif pour atteindre les valeurs statiques de E de I'ensemble du solvant utiliste par le facteur f de Debye; comme les moltcules de solvant sont plus volumineuses que celles de I'eau, on considere que R, est plus Clevt dans la rtgion riche en alcool que dans la rtgion riche en eau. On a utilist le rnodttle de Smoluchowski-Debye-Nernst-Einstein pour tvaluer le rayon rtactionnelle efficace, KRI., dans lequel K est la probabilitt de rtaction par rencontre; KRr diminue en allant du rerr-butanol pur B l'eau pure.Dans la rtgion riche en eau, les energies d'activation E? des reactions efficaces, 11-24 kJ mol-l, sont semblables aux valeurs de EA0 des Clectrolytes qui rtagissent, 12-23 kJ mol-I. Pour le reactif inefficace N H ; CIO;, E? = 30 kJ mol-I. On attribue les valeurs tlevtes de E2 = 43-53 kJ rnol-' observtes dans le rerr-butanol B une Cnergie tlevte d'activation de la diffusion des e; dans ce solvant.

show abstract

Lithium interaction with polyaromatic hydrocarbons and properties of lithium solvated electron solutions

Liu¹

View full text Add to dashboard Cite

This thesis contains rn:rtcrials from papcrs published in the following pccr-rcvicu,cd journals u.hcru l was the {irst, rurthol ol co-author. Chapter 4 contains materials published a,t journal ACS Omega with title " Electro chemical Properties of Anthracene-Baserl Lithium-solvated Electron Solutions" u,ith DOI 10.7021 I acsomega.8b03621. 'I'he contributions are as follows:. I co-rlcsignerl the str:rly u.ith Prof Su Haibin and Prof Aridrcu,.. Andrey.!. Lu.nchcva pelforrned tlte expcrirrtcrrts;. I performed the DFT calculation and analysed the experimental datat. I modelled the properties of the solutions and prepared the rnanuscript;. Prof Su Haibin, Prof Rachid and Prof Arrdrew injected idr-'as on the topic revised the manuscript.

show abstract

Solvated electron mobility in liquid tert-butanol

Cited by 4 publications

References 16 publications

Solvent effects on the reactivity of solvated electrons with organic solutes in 1-butylamine–water mixtures

Solvent effects on the reactivity of solvated electrons with organic solutes in 1-butylamine–water mixtures

Solvent effects on the reactivity of solvated electrons with ions in tert-butanol/water mixtures

Lithium interaction with polyaromatic hydrocarbons and properties of lithium solvated electron solutions

Contact Info

Product

Resources

About