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Influence of Water Content on Basicities in Acetonitrile

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Abstract

The influence of water content at impurity level (5–10,000 ppm) in acetonitrile, on the changes in relative basicity differences (ΔpK a values) of 13 pairs of bases, was studied both experimentally and computationally (COSMO-RS). The ΔpK a values involving smaller bases with localized charge in the cationic form were found to be more affected. A computational parameter, weighted average negative sigma (WANS), was proposed to quantify the charge delocalization in cations and succeeded in describing the observed changes of ΔpK a. The results validate the previously published basicity scale in acetonitrile with respect to solvent dryness and give guidelines for better experimental planning.

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Acknowledgments

This work was supported by Grant No. 8689 from the Estonian Science Foundation, by the Institutional Funding project TLOKT14014I of Ministry of Education and Research of Estonia and by the Estonian Centre of Excellence HIGHTECHMAT SLOKT117T.

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  1. Institute of Chemistry, University of Tartu, Ravila Str 14a, 50411, Tartu, Estonia

    Karl Kaupmees, Ivari Kaljurand & Ivo Leito

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  1. Karl Kaupmees
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  2. Ivari Kaljurand
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  3. Ivo Leito
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Correspondence to Ivo Leito.

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Kaupmees, K., Kaljurand, I. & Leito, I. Influence of Water Content on Basicities in Acetonitrile. J Solution Chem 43, 1270–1281 (2014). https://doi.org/10.1007/s10953-014-0201-4

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