Direct potentiometric determination of sodium ion in blood. I. Potentiometric response in simple sodium chloride solutions.

We measured the emf of NaCl solutions (120-160 mmol/L) with a home-built cell in steady-state and with some commercial direct potentiometric analyzers about 20 s after the sample is introduced into the instrument. We compared the results with the theoretical sodium ion activity calculated according to different thermodynamic theories. The slope of the calibration graph was calculated with and without correction for the influence of NaCl concentration on the liquid junction potential of the calomel reference electrode. We conclude that different theories used to calculate the sodium ion activity in the concentration range investigated give almost the same results; furthermore, introduction of the liquid junction potential leads to a more nernstian-like slope of the calibration graph. Measurement of identical NaCl solutions with various commercial analyzers showed different displayed concentrations, presumably because of differences in junction structure, measuring time, and concentration of calibration solutions.