The oxidation of CO by O2 or NO over Rh( 11 1) and Rh( 100) single crystals has been studied in a high-pressure reaction-high-vacuum surface analysis apparatus. Steady-state catalytic activity as a function of temperature and partial pressures of CO, 02, and NO has been measured. The CO-02 reaction was found to be insensitive to the structure of the surface as evidenced by the identical rates, activation energies, and partial pressure dependencies measured on the two single-crystal surfaces. Both surfaces deactivated at high O2 partial pressures due to the formation of a near-surface oxide (probably Rh203) which is catalytically inactive for this reaction. The deactivation occurred at a slightly lower O2 partial pressure on Rh( loo), likely due to the relative ease of oxygen diffusion through this surface leading to more rapid bulk oxidation. Unlike the CO-02 reaction, CO oxidation by NO was very sensitive to the geometric structure of the surface. This behavior was evident in all kinetic parameters measured on the two surfaces. The kinetic data obtained on Rh(ll1) agree quantitatively with a surface chemistry model previously developed for this reaction. The model predicts that the rate is limited by the formation of N2 from the recombination of adsorbed N atoms, and that the surface, under steady-state reaction conditions, is covered largely with adsorbed N atoms and smaller amounts of adsorbed NO. On Rh(100) the data are consistent with a reaction rate limited by the formation of N2 from the surface reaction of adsorbed NO and N atoms.

The transport of trichloroethylene, 1,1,1-trichloroethane, and toluene in aqueous solutions through a polydimethylsiloxane film was modeled using a Fickian diffusion model to fit data obtained from an evanescent fiber-optic chemical sensor (EFOCS). The resultant diffusion coefficients for these analytes were respectively 3 × 10(-)(7), 5 × 10(-)(7), and 1 × 10(-)(7) cm(2)/s. Inclusion of an interfacial conductance term, defined as the ratio of the mass transport coefficient across the polymer surface and the analyte diffusion coefficient in the polymer, was required to accurately model the data. It was determined that the interfacial conductance terms were generally of the same order of magnitude for the analytes examined, suggesting a constant transport mechanism for the analytes. Linear chemometric algorithms were used to model the EFOCS response to aqueous mixtures of the three analytes with individual analyte concentrations between 20 and 300 ppm. Both partial least-squares and principal component regression algorithms performed comparably on the calibration sets, with cross-validated root-mean-squared errors of prediction for trichloroethylene, 1,1,1-trichloroethane, and toluene of approximately 26, 29, and 22 ppm, respectively. The resultant prediction model was then used to determine analyte concentrations in an independent data set with comparable precision.

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The diffusion rates of various polar and nonpolar analytes in dimethylsiloxane were examined with the use of a commercially available 200-μm silica-core/300-μm silicone-clad fiber as the optical element for evanescent wave spectroscopy in the near-infrared spectral region. An analytical solution to Fick's second law was used to model the time-dependent analyte concentration at the core/cladding interface. Successful fit of the analytical solutions to infrared data verifies the assumption of constant diffusion coefficients that is necessary to solve the equation. Transport rates of polar analytes in silicone can be estimated with the use of a single-parameter model that results in diffusion coefficients of 3.2 × 10−1, 1.6 × 10−1, 8.1 × 10−7, and 3.9 × 10−7 cm2/s for methanol, ethanol, 2-propanol, and n-butanol, respectively. Estimating the transport of larger nonpolar analytes in the silicone cladding requires a two-parameter model that includes a diffusion coefficient and an interfacial conductance term. For pentane, hexane, heptane, and cyclohexane the resultant diffusion coefficients and interfacial conductance parameters are 6.9 × 10−7, 4.6 × 10−7, 4.4 × 10−7, and 2.3 × 10−7 cm2/s and 2500, 2000, 2000, and 600 μm−1, respectively.