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(a) See, for example, ref 5b for an example of the strong ion-pairing effect on the electrochemical reduction of aromatic compounds.
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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
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(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.
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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.
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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.
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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
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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
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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.
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(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.
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The ferrocene/ferrocenium couple is usually chosen as a model of electroactive systems in many studies performed in organic solvents and RTILs.4
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The ferrocene/ferrocenium couple is usually chosen as a model of electroactive systems in many studies performed in organic solvents and RTILs.4
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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.
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(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.
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