We investigated the in vitro and in vivo relation between pH and ionized calcium during acute respiratory pH changes. The in vitro slope delta 1gcCa2+/delta pH determined in 20 healthy volunteers after equilibration at two different pCO2 values was -0.22 +/- 0.04 (mean +/- 2 SD) for whole blood and -0.24 +/- 0.04 (mean +/- SD) for serum. The in vivo slope delta 1gcCa2+/delta pH during acute respiratory changes in 10 healthy volunteers was -0.17 +/- 0.04 (mean +/- 2 SD) for capillary blood. A mathematical formula which describes the relation between pH and ionized calcium is presented.