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Chronopotentiometric Carbonate Detection with All-Solid-State Ionophore-Based Electrodes
Journal article   Peer reviewed

Chronopotentiometric Carbonate Detection with All-Solid-State Ionophore-Based Electrodes

Z Jarolimova, G A Crespo, X Xie, M Ghahraman Afshar, M Pawlak and Eric Bakker
Analytical Chemistry, Vol.86(13), pp.6307-6314
2014
DOI: https://doi.org/10.1021/ac5004163
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https://doi.org/10.1021/ac5004163View
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Abstract

Analytical Chemistry Chemical Engineering Other Chemical Sciences diffusion electrodes electrolytes ionophores ions organometallics sensors titration
We present here for the first time an all-solid-state chronopotentiometric ion sensing system based on selective ionophores, specifically for the carbonate anion. A chronopotentiometric readout is attractive because it may allow one to obtain complementary information on the sample speciation compared to zero-current potentiometry and detect the sum of labile carbonate species instead of only ion activity. Ferrocene covalently attached to the PVC polymeric chain acts as an ion-to-electron transducer and provides the driving force to initiate the sensing process at the membrane-sample interface. The incorporation of a selective ionophore for carbonate allows one to determine this anion in a background electrolyte. Various inner electrolyte and all-solid-state-membrane configurations are explored, and localized carbonate depletion is only observed for systems that do not contain ion-exchanger additives. The square root of the transition times extracted from the inflection point of the chronopotentiograms as a function of carbonate specie concentration follows a linear relationship. The observed linear range is 0.03-0.35 mM in a pH range of 9.50-10.05. By applying the Sand equation, the diffusion coefficient of carbonate is calculated as (9.03±0.91) 10-6 cm2 s-1, which corresponds to the established value. The reproducibility of assessed carbonate is better than 1%. Additionally, carbonate is monitored during titrimetric analysis as a precursor to an in situ environmental determination. Based on these results, Fc-PVC membranes doped with ionophores may form the basis of a new family of passive/active all-solid-state ion selective electrodes interrogated by a current pulse.

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