Optical sensors for the determination of concentrated hydroxide. Characterization of the sensor materials and evaluation of the sensor performance.

Optical sensors for the determination of highly concentrated bases such as NaOH (1-10 M) and materials to make these sensors have been characterized by X-ray photoelectron spectroscopy, 29Si solid-state NMR, FT-IR, and measurements of film porosity, surface area, and thickness. The bonding character and composition of the Si-Zr mixed oxides-organic polymer composites were evaluated. These studies suggest that there are Si-O-Zr matrixes in the mixed oxides, and that the Si-O-Zr matrixes contribute to the durability of the base sensors in highly alkaline solutions. The performance of these base sensors has been studied in detail as well. These sensors were stable for approximately 120 days, exhibited short response times (typically <10 s), and were fully reversible with minimal hysteresis effects in NaOH-ROH-H2O solutions (R = Me, Et, and i-Pr).

High-basicity determination in mixed water-alcohol solutions by a dual optical sensor approach.

The activity of NaOH is known to be significantly affected by the presence of an alcohol in aqueous solutions. A novel linear relationship between (deltaA/deltaC(alcohol)) and C(base) was found in the highly alkaline, mixed H2O-ROH solutions (R = Me, Et, i-Pr). The use of this linear relationship led to a dual-transducer approach to decompose the optical signals of optical base sensors and to give base and alcohol concentrations in concentrated NaOH-H2O-ROH solutions ([OH-] = 0.05-3.6 M). The scope of the new dual-sensor approach was evaluated, and errors in C(base) and C(alcohol) were analyzed. The optical base sensors consist of sol-gel SiO2-ZrO2-organic polymer composites doped with high-pKa indicators. The pKa(s) of the indicators encapsulated in the composite films were determined and found to be affected by the composition of the sol-gel composites. Optical sensors and their uses in multicomponent systems are of intense current interest.( 1-7) In the multicomponent systems, the activity of the analyte and sensor response are often affected by change in ionic strength. For optical sensors that are based on indicator equilibria involving the analyte as their transducing mechanism, such effect is particularly significant. The concentrations of both the analyte and other chemicals affect ionic strength, and the sensor response to concentration of the analyte is thus often indistinguishable from those of other chemicals. An accurate measurement of each component in these multicomponent systems is actively studied. Several approaches have been developed to correct ionic strength in optical sensing for the pH region and solutions of low-to-medium ionic strength. (1-9) We recently reported a dual-transducer approach to measure acid concentrations (2-9 M HCl) in salt-containing, concentrated strong acids such as MClx-HCl (M = Li, Ca, Al) solutions. (10) This approach was shown to reduce the error in C(acid) from, for example,

High-acidity determination in salt-containing acids by optical sensors. The scope of a dual-transducer approach and the Hammett acidity function.

A dual-transducer approach based on sol-gel optical sensors was recently reported to measure acid and salt concentrations, C(acid) and C(salt), in concentrated aqueous LiCl-HCl, CaCl2-HCl, and AlCl3-HCl solutions (C(acid) at 5-6 M; C(salt) < or = 2 M). The scope of this new approach has been studied in salt-containing HCl solutions with C(acid) at 2-9 M, and factors that influence sensor responses and accuracy have been investigated. A linear relationship between (deltaA/deltaC(salt))C(acid) and (dA/dC(acid))C(salt)=0, which is the basis of this dual-transducer approach, was found to lead to an empirical linear relationship between (deltaH0)C(acid) and (deltaC(salt))C(acid) (H0: Hammett acidity function of the indicator encapsulated in the sensor).