Excess protons in water-acetone mixtures. II. A conductivity study

摘要: In the present work we complement a previous simulation study [R. Semino and D. Laria, J. Chem. Phys. 136, 194503 (2012)] on disruption of proton transfer mechanism in water by addition an aprotic solvent, such as acetone. We provide experimental measurements mobility protons aqueous-acetone mixtures wide composition range, for molar fractions, xw, between 0.05 1.00. Furthermore, new molecular dynamics results are presented rich acetone mixtures, which further insight into transport water-non-protic solvent mixtures. The was analyzed xw 1.00 compared to data. Results show two qualitative changes dependence at ∼ 0.25 0.8. At < ratio infinite dilution conductivities HCl LiCl, Λ(0)(HCl).Λ(0)(LiCl)(-1), is approximately constant equal one, since diffusion vehicular that Li(+). 0.25, starts differ from Li(+) indicating above this concentration Grotthuss be possible. Molecular showed threshold probability interconversion Eigen structures non-negligible. 0.8, conductivity qualitatively changes. This result excellent agreement with analysis it has been ascribed interchange molecules second solvation shell hydronium ion.