Accurate pH Monitoring of Highly Concentrated Saline Aqueous Solutions (Seawater-like) with a pH Colorimetric Sensor Array.

ABSTRACT

A pH colorimetric sensor array (CSA) was prepared on a nitrocellulose membrane and used for accurate pH measurement in highly concentrated saline solutions. The CSAs consisted of sensing spots made of a suitable OrMoSil polymer prepared from organo-fluorinated-silane precursors and/or organosilane with tetraethyl orthosilicate hosting an acid-base indicator. Four CSAs were prepared D, 1F, 2F, and 3F. In D, a nonfluorinated organosilane was present. From 1F to 3F, the concentration of the fluorinated organosilane increased and improved the pH measurement accuracy in highly saline concentrations. No recalibrations were required, and the analytical signal was stable in time. D, 1F, 2F, and 3F were deposited in triplicate, and they were prepared to work in the seawater pH interval (7.50-8.50). The use of fluorinated precursors led to a lower pH prediction error and tailored the interval of the CSA at more basic pH values so that the inflection points of the sigmoidal calibrations of D, 1F, 2F, and 3F moved from 6.97 to 7.98. The overall pH prediction error was 0.10 pH (1F), 0.02 pH (2F), and 0.04 pH units (3F). The CSAs were stable, reversible, reusable, and independent of salinity (S) between 20 and 40. The performances of the CSA were compared with those of a glass electrode, whose pHNIST values were converted in the pHSWS scale through a conversion equation. Being unaffected by the typical drawback of the glass electrode, the CSAs can be used directly in seawater real samples, and it validated the proposed conversion equation.