Silver-silver cryptate(2,2) ion electrode as a reference electrode in nonaqueous solvents.

概要

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A silver-silver Cryptate(2, 2) ion electrode (Ag/0.005M AgCryp(2, 2)ClO4, 0.005M Cryp(2, 2), 0.05M Et4NClO4- (S)//0.05M Et4NClO4(S)//) was studied with respect to its applicability as the reference electrode in acetonitrile (AN), propylene carbonate (PC), methanol (MeOH), dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF). The apparent formation constant of AgCryp(2, 2)+ and the potential of the AgCryp(2, 2)+/Ag electrode vs. ferrocene/ferricinium reference system, respectively, were 7.8 and -422mV in AN, 15.5 and -400mV in PC, 9.8 and -253mV in MeOH, 7.3 and -463mV in DMSO, and 9.9 and -466mV in DMF. The exchange current densities of the AgCryp(2, 2)+/Ag electrode were in the range of (3-5)×10-6A cm-2 in all the solvents. The electrode potential was not influenced by the total concentration of (AgCryp(2, 2)++Cryp(2, 2)), provided that the ratio of both species was kept 1:1. The effect of water on the potential was also relatively small. The disadvantages of the silver-silver ion reference electrode especially encountered in PC and DMF were removed with this electrode, and the potential was reproducible and stable enough in all the solvents.
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