The Response Behavior of a Polyacrylamide-Benzo-15-C-5 Electrode to Sodium and Calcium Ions in Acetonitrile and Its Application to the Study of Their Complexing with Other Basic Aprotic Solvent Molecules.

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  • Response Behavior of a Polyacrylamide B

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Abstract

The response behaviors of an ionophore-conjugated polymer-based ion sensor, which consists of a polyacrylamide (PAA) coupled to benzo-15-crown-5 (B15C5), for Na+ and Ca2+ in acetonitrile (AN) and N-methylpyrrolidinone (NMP) were studied. The PAA–B15C5 electrode showed a Nerstian response to Na+ in AN and Ca2+ in AN and NMP. The electrode was then applied to investigate the complexation of Na+ in AN with such other solvent molecules (D) as N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO); the successive complex formation constants and Gibbs energies of transfer of Na+ in AN to DMF or DMSO and AN to AN–D mixtures were obtained. Reasonable responses of the electrode to an activity change of Na+ due to the solvation of the basic solvent molecules could be certified. The complex formation constant of Ca2+ in AN with such D as DMF, NMP, N,N-dimethylacetamide (DMA), DMSO and hexamethylphosphoric triamide could be obtained by the electrode. The association constants of Ca2+ with CF3SO3− in AN, propylene carbonate, DMF, and DMSO were determined conductometrically and the constant in AN (K1AN = 1.02 × 104 dm3 mol−1) was used for correcting the variation of calcium ion-activity due to a concentration change of Ca(CF3SO3)2 in AN.

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