A blood gas machine has electrodes to measure pH, pCO2 and pO2 and often measures Hb and some biochemistry as well [King et al. 2000]. Derived values from such a device include O2 saturation, O2 content, bicarbonate, base excess and total CO2. This is the Clarke electrode described in the previous section on gas analysers and is suitable for both respiratory and blood O2 analysis. A pH unit has been defined in Chapter 1 as. In words, this can be described as ‘the negative logarithm, to base ten, of the hydrogen ion concentration’. The physical principle on which the pH electrode is based depends on the fact that when a membrane separates two solutions of different [H+], a potential difference exists across the membrane. In a pH electrode, such a membrane is usually made of glass and the development of a potential difference between the two solutions is thought to be due to the migration of H+ into the glass matrix. If one solution consists of a standard [H+], the pH of the other solution can be estimated by measurement of the potential difference between them. The glass membrane used is selectively permeable to H+. No current flows in this device, which does not wear out, in contrast to the Clark electrode, in which current does flow and that does need periodic replacement. The pH measurement system is shown diagrammatically in Figure 17.1. It consists of two half cells. In one half it has an Ag/AgCl electrode and in the other a Hg/HgCl2 (calomel) electrode. Each electrode maintains a fixed electrical potential. The Ag/AgCl electrode is surrounded by a buffer solution of known pH, surrounded by the pH sensitive glass. Outside the glass membrane is the test solution, usually blood, whose pH is to be measured. It is the potential difference across the glass, between these two solutions, which is variable. The blood or other solution is separated from the calomel electrode by a porous plug and a potassium chloride salt bridge to minimise KCl diffusion. The potential difference across the system is about 60 mV per unit of pH change at 37◦C.