Establishing the direct-potentiometric "normal" range for Na/K: residual liquid junction potential and activity coefficient effects.

The observed reference ranges for sodium and potassium as determined by direct potentiometry vary from instrument to instrument, depending on the composition of the calibration standards. To resolve the existing confusion as to which reference intervals are most appropriately considered "normal," we propose a straightforward convention (based on plasma-water concentration units) in which the difference between direct (undiluted sample) and indirect (diluted sample) methodologies is accounted for by the volume displacement effect of proteins, lipids, and other dissolved substances in a typical plasma sample. Thus, the proposed reference intervals for sodium and potassium are approximately 7% greater by direct potentiometry than by procedures involving dilution. Data consistent with this convention can be obtained with a variety of aqueous-based calibrants, provided care is taken to minimize the errors resulting from activity coefficient and liquid junction potential effects. Additional experimental results are presented to show that these effects also account for the apparent suppression of the sodium ion concentration observed in the presence of bicarbonate ion.