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Proton Medium Effect Based on the Ferrocinium Assumption in 80 Mass-% Propylene Carbonate + 20 Mass-% p-Xylene Medium

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Abstract

Conventional electrochemical studies on the ferrocinium–ferrocene (Fc+–Fc) redox system in 80 mass-% propylene carbonate (PC) + 20 mass-% p-xylene (PX) medium are reported, leading to a calculation of the proton medium effect. The dissociation constant of ferrocinium picrate in this medium was determined by conductivity measurements. The value of \(E_{\mathrm{Fe^{+} /Fe}}^{\mathrm{o}}\) against the Hg/HgCl2(s) reference electrode in 80 mass-% PC + 20 mass-% PX was determined potentiometrically in conjunction with conductivity data, and found to be 0.133±0.001 V versus the SHE at 25 °C. The \(E_{\mathrm{Fe^{+} /Fe}}^{\mathrm{o}}\) value has also been calculated using cyclic voltammetric data obtained in 80 mass-% PC + 20 mass-% PX at a micro platinum working electrode against the Ag/AgCl (nonaq.) reference electrode, and found to be comparable with the value obtained by potentiometry. The proton medium effect for transfer from water to the present mixed solvent medium was calculated using the value of \(E_{\mathrm{Fe^{+}/Fe}}^{\mathrm{o}}\) versus SHE at 25 °C and found to be 4.5. Based on values of proton medium effect reported in the literature, it is inferred that the present mixed solvent medium is slightly more basic than pure PC.

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  1. Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (E), Mumbai, 400 098, Maharashtra, India

    Damaraju Parvatalu & Ashwini K. Srivastava

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  1. Damaraju Parvatalu
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  2. Ashwini K. Srivastava
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Correspondence to Ashwini K. Srivastava.

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Parvatalu, D., Srivastava, A.K. Proton Medium Effect Based on the Ferrocinium Assumption in 80 Mass-% Propylene Carbonate + 20 Mass-% p-Xylene Medium. J Solution Chem 40, 403–414 (2011). https://doi.org/10.1007/s10953-011-9656-8

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