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Standard electromotive force of the H2---AgCl;Ag cell in 30, 40, and 50 mass% dimethyl sulfoxide/water from −20 to 25 °C: pK2 and pH values for a standard “Bicine” buffer solution at subzero temperatures
Authors:Rabindra N Roy  James J Gibbons  Gigi Baker  Roger G Bates
Institution:1. Department of Chemistry, Drury College, Springfield, Missouri 65802, USA;2. Department of Chemistry, University of Florida, Gainesville, Florida 32611 USA
Abstract:The establishment of the pH (designated pH*) of a standard buffer solution suitable as a pH reference in 30, 40, and 50 mass% dimethyl sulfoxide (DMSO)/H2O mixtures at temperatures in the range −20 to 0 °C is reported. The buffer material selected was the ampholyte Bicine (N,N-bis(2-hydroxyethyl)glycine), and the reference standard consists of equal molal quantities of Bicine and its sodium salt. The assignment of pH* values rests on measurements of the emf of cells without liquid junction, Pt;H2(g, 1 atm) ¦Bicine, Na Bicinate, NaCl ¦AgCl;Ag, and the pH* was derived from a determination of K2, the equilibrium constant for the dissociation process (Bicine) ± (Bicinate) + H+. The standard emf in the DMSO/H2O solvents at subzero temperatures was determined from emf measurements of the cell with solutions of HCl replacing the buffer-chloride mixture.
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