Gas-Sensinc Evectropes A number of membrane electrodes respond to the concentration of a dis- tometer solved gas. The basic design of a cas-sensiNc ELECTRODE is shown in Figure 11.19, consisting of a thin membrane that separates the sample from an inner solution containing an ion-selective electrode. The membrane is per- meable to the gascous analyte, but impermeable to nonvolatile components ae (SE in the sample’s matrix, The gascous analyte passes through the membrane where it reacts with the inner solution, producing a species whose concen- uation is monitored by the ion-selective electrode. For example, ina CO} electrode, CO, diffuses across the membrane where it reacts in the inner solution to produce HO CO, (ag) + 2H, OW = HCOS (aq) + H,O* (ag) 11.12 inner The change in the activity of HO in the inner solution is monitored with solution a pH electrode, for which the cell potential is given by equation 11.11. To find the relationship between the activity of HO" in the inner solution and the activity CO} in the inner solution we rearrange the equilibrium constant expression for reaction 11.10; thus Feo, Aygo = KX 11.13 “ 4.00; gas permeable where X, is the equilibrium constant. If the activity of HCO,- in the inter- membrane nal solution is sufficiently large, then its activity is noc affected by the small Figure 11.19 Schematic diagram of a amount of CO, that passes through the membrane. Substituting equation _8%-fensing membrane electrode. 11.13 into equation 11.11 givesE. K’ + 0.05916 loga.,, where K/ is a constant that includes the constant for the pH electrode, the equilibrium constant for reaction 11.12 and the activity of HCO3- in the inner solution Table 11.4 lists the properties of several gas-sensing, electrodes. The composition of the inner solution changes with use, and both the inner so- lution and the membrane must be replaced periodically. Gas-sensing: elec- trodes are stored in a solution similar to the internal solution to minimize their exposure to atmospheric gases.Table 11.4 Representative Examples of Gas-Sensing Electrodes 10 mM NaHCO. nce - CO, gE NCL 2 COntet)-+ 2H,0t) = HCO; (ay) + HO") glass pH ISE HON 10mM KAg(CN), HCN(ap)+H,OW = CN"(ap)-+H,O" (as) AggS solid-state SE HE 1MH;0° HP aq) + HOU) Faq) +H,0% Gq) F solid-state ISE H,S pH Scitrate buffer H,S(ag)+H,O1) => HS-(ag)+H,O° (ag) _AgyS solid-state ISE 10 mM NH,CL . . NBs aM KNO, — Ns(«) + HOW SNEZ4n+ OH) gla pHISE 2NO, (ag) + 3H,O() = No, 20mMNaNO, (2) +3H,00 = ; san piise OOEIENGS NO§ (az) + NO} (aq) + 2H,O*) 50, MM NSHS05 50, (aj) = 2H, 010 = H905 (aj) H,0" a) glass pH ISE pH 5