Direct potentiometric determination of sodium ion in blood. III. Influence of (bi)carbonate.

We measured the emf of a sodium ion-selective electrode in NaCl-NaHCO3 solutions (160 mmol of Na+, 160-120 mmol of Cl-, and 0-40 mmol HCO3- per liter) with a home-built cell in steady-state after 10 min and with two commercial direct potentiometric analyzers about 20 s after the sample was introduced. Substitution of HCO3- for Cl- resulted in a small decrease in emf. We calculated the effect of chloride ion replacement by bicarbonate ion on the liquid-junction potential and found that this accounted only for one-third of the emf decrease. The exact composition of bicarbonate solutions is closely related to the pH. To control the formation of carbonate, we performed measurements with the home-built cell at two pH values (7.0 and 8.2), controlled by tonometry with carbon dioxide. From the differences in the slope of the emf vs the amount of bicarbonate added at the two pHs we calculated the thermodynamic association constants of the sodium bicarbonate and sodium carbonate complexes (KNaHCO3(0) = 0.53 and KNaCO3- = 24). We conclude that, for the direct potentiometric measurement of sodium ion, only fresh serum should be used, to avoid pH changes. Replacement of sodium chloride by sodium bicarbonate caused different results when emf was measured with commercial analyzers, owing to their short measuring time of about 20 s.