On calculating concentrations of "HCO3" from pH and PCO2.

1. As used in the Henderson-Hasselbalch equation, [HCO3], [CO2] and pH may all be variously defined; values of pK'1 must be chosen accordingly. 2. In common usage, "HCO3" may include CO3, carbamate, various ion pairs and possibly other bound CO2, as well as free HCO3 ions. 3. pH measurements may be systematically affected by the choice of standard buffers and by proteins and blood cells, and the errors in pH may be pH-dependent. 4. According to how it is expressed, the solubility coefficient for CO2 (S) may be influenced by sample water content, proteins and lipids. However, it need not feature in the calculation. 5. pK'1 is often found to decrease with increasing pH. This may be partly due to inclusion of CO3 and carbamate, but not of H2CO3.HCO3-, in "HCO3" and partly, perhaps, to errors in pH measurement. 6. To the extent that pH measurements are reliable, concentrations or activities of true HCO3 are calculable from pH and PCO2, but, if pH measurements are likely to be systematically erroneous, it may be preferable to define "HCO3" as "total bound CO2" and to base pK'1 on gasometric or titrimetric determinations of that.