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Volumn 113, Issue 7, 2009, Pages 2019-2023

Diffusion of molecules in ionic liquids/organic solvent mixtures. Example of the reversible reduction of O2 to superoxide

Author keywords

[No Author keywords available]

Indexed keywords

DIFFUSION; DIMETHYLFORMAMIDE; DISSOLUTION; DISSOLVED OXYGEN SENSORS; IONIZATION OF LIQUIDS; IONS; MOLECULES; OXYGEN; REDUCTION; SCANNING ELECTRON MICROSCOPY; SCANNING PROBE MICROSCOPY; TRANSPORT PROPERTIES;

EID: 65249139995     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp8095314     Document Type: Article
Times cited : (50)

References (57)
  • 1
    • 0004145285 scopus 로고    scopus 로고
    • Wasserscheid, P, Welton, T, Eds, Wiley-VCH: Weinheim, Germany
    • (a) Ionic Liquids in Synthesis; Wasserscheid, P., Welton, T., Eds.; Wiley-VCH: Weinheim, Germany, 2003.
    • (2003) Ionic Liquids in Synthesis
  • 3
    • 84906389016 scopus 로고    scopus 로고
    • Green Industrial Applications of Ionic Liquids; Roger, R. D., Seddon, K. R., Volkov, S., Eds.; NATO Sciences Series; Kluwer: Dordrecht, The Netherlands, 2002; 92.
    • (c) Green Industrial Applications of Ionic Liquids; Roger, R. D., Seddon, K. R., Volkov, S., Eds.; NATO Sciences Series; Kluwer: Dordrecht, The Netherlands, 2002; Vol. 92.
  • 7
    • 38949195651 scopus 로고    scopus 로고
    • and references therein
    • (c) Paul, A.; Samanta, A. J. Phys. Chem. B 2008, 112, 947, and references therein. .
    • (2008) J. Phys. Chem. B , vol.112 , pp. 947
    • Paul, A.1    Samanta, A.2
  • 15
    • 84906375073 scopus 로고    scopus 로고
    • See, for example, ref 5b for an example of the strong ion-pairing effect on the electrochemical reduction of aromatic compounds
    • (a) See, for example, ref 5b for an example of the strong ion-pairing effect on the electrochemical reduction of aromatic compounds.
  • 29
    • 84906360808 scopus 로고    scopus 로고
    • The consequences of an inequality of diffusion coefficients on electrochemical measurements are complex and often difficult to detect even if g values are considerably different from unity.10b-e Large inequalities could lead to substantial errors in the extracted data. For example, E 1/ 2, E, RT /F log(D red/D ox)1/2 in cyclic voltammetry or E 1/ 2, E, RT /F log(D red/D ox) in steady-state voltammetry on an ultramicroelectrode. Concerning the effects of g on the determinations of kinetics data, see for example refs 10c-e and the references therein
    • (a) The consequences of an inequality of diffusion coefficients on electrochemical measurements are complex and often difficult to detect even if g values are considerably different from unity.10b-e Large inequalities could lead to substantial errors in the extracted data. For example, E 1/ 2 ) E + RT /F log(D red/D ox)1/2 in cyclic voltammetry or E 1/ 2 ) E + RT /F log(D red/D ox) in steady-state voltammetry on an ultramicroelectrode. Concerning the effects of g on the determinations of kinetics data, see for example refs 10c-e and the references therein.
  • 36
    • 0003853137 scopus 로고    scopus 로고
    • Bard, A. J, Mirkin, M. V, Eds, Marcel Dekker: New York
    • Scanning Electrochemical Microscopy; Bard, A. J., Mirkin, M. V., Eds.; Marcel Dekker: New York, 2001.
    • (2001) Scanning Electrochemical Microscopy
  • 39
    • 84906375074 scopus 로고    scopus 로고
    • For more quantitative descriptions of diffusion concentration profiles at an ultramicroelectrode corrupted by natural convection, see: Amatore, C, Knobloch, K, Thouin, L. J. Electroanal. Chem. 2007, 106, 17
    • For more quantitative descriptions of diffusion concentration profiles at an ultramicroelectrode corrupted by natural convection, see: Amatore, C.; Knobloch, K.; Thouin, L. J. Electroanal. Chem. 2007, 106, 17.
  • 40
    • 84906389013 scopus 로고    scopus 로고
    • The reason for using the 36 ?C temperature instead of the classical room temperature is to reduce the viscosity and thus to increase the diffusion coefficients. The drawback is also a likely decrease of the O2 concentration in the ionic liquid. Experimentally, we found that globally passing from 20 to 36?C improves the situation both in terms of signal/noise ratio and diffusion rates.
    • The reason for using the 36 ?C temperature instead of the classical room temperature is to reduce the viscosity and thus to increase the diffusion coefficients. The drawback is also a likely decrease of the O2 concentration in the ionic liquid. Experimentally, we found that globally passing from 20 to 36?C improves the situation both in terms of signal/noise ratio and diffusion rates.
  • 50
    • 84906403755 scopus 로고    scopus 로고
    • 2 ·- in the pure ionic liquid [Et3BuN][NTf2] (D O2 ) 3.2 × 10-6 cm2 s-1 and D O2 ·- ) 1.45 × 10-7 cm2 s-1 at 36 ?C) are in the same range as those previously reported in the same RTIL [Et3BuN][NTf2] (D O2 ) 3.9 × 10-6 cm2 s-1 and D O2 ·- ) 9.2 × 10-8 cm2 s-1 at 25 ?C7a) or as those in another quaternary ammonium-based ionic liquid [N6222][NTf2],6c taking into account the higher working temperature of our experiments that also leads to a decrease of solvent viscosity.2,3
    • 2 ·- in the pure ionic liquid [Et3BuN][NTf2] (D O2 ) 3.2 × 10-6 cm2 s-1 and D O2 ·- ) 1.45 × 10-7 cm2 s-1 at 36 ?C) are in the same range as those previously reported in the same RTIL [Et3BuN][NTf2] (D O2 ) 3.9 × 10-6 cm2 s-1 and D O2 ·- ) 9.2 × 10-8 cm2 s-1 at 25 ?C7a) or as those in another quaternary ammonium-based ionic liquid [N6222][NTf2],6c taking into account the higher working temperature of our experiments that also leads to a decrease of solvent viscosity.2,3
  • 52
    • 84906389014 scopus 로고    scopus 로고
    • In DMSO, D O2 ) 3.23 × 10-5 cm2 s-1 and D O2 ·- 1.08 × 10-5 cm2 s-1 (γ ) 0.33),24 and in DMF, D O2 ) 4.76 ×10-5 cm2 s-1.25b.
    • (a) In DMSO, D O2 ) 3.23 × 10-5 cm2 s-1 and D O2 ·- ) 1.08 × 10-5 cm2 s-1 (γ ) 0.33),24 and in DMF, D O2 ) 4.76 ×10-5 cm2 s-1.25b.
  • 54
    • 84906389015 scopus 로고    scopus 로고
    • The ferrocene/ferrocenium couple is usually chosen as a model of electroactive systems in many studies performed in organic solvents and RTILs.4
    • The ferrocene/ferrocenium couple is usually chosen as a model of electroactive systems in many studies performed in organic solvents and RTILs.4
  • 55
    • 84906403756 scopus 로고    scopus 로고
    • Concerning the exponential variation of the viscosity with the molecular solvent molar fraction, such observations have been reported in several instances and more than a decade ago for the variations of the viscosity in pure fused electrolyte/organic solvent mixtures.27b This empirical law was proposed as an effective general formula in RTIL/molecular solvents.2a.
    • (a) Concerning the exponential variation of the viscosity with the molecular solvent molar fraction, such observations have been reported in several instances and more than a decade ago for the variations of the viscosity in pure fused electrolyte/organic solvent mixtures.27b This empirical law was proposed as an effective general formula in RTIL/molecular solvents.2a.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.