It is demonstrated that attenuated total reflection infrared (ATR-IR) spectroscopy coupled with multivariate data analysis can be effectively used for in situ investigation of supported catalyst-liquid interfaces. Both formaldehyde adsorption/dissociation in water and acetonitrile adsorption in hexane on thin (ca 10 mum) films of 5 wt % Pt/gamma-Al(2)O(3) deposited on a germanium waveguide have been investigated. The multivariate analysis applies classical least squares (CLS) and partial least squares (PLS) methods to the ATR-IR data in order to correlate spectral changes with known sources of experimental variation (i.e., time, concentration of solution species, etc.). The formaldehyde adsorption experiments revealed no spectroscopic evidence for adsorbed molecular formaldehyde under the conditions examined. However, the dissociation product carbon monoxide was observed to form in atop configuration on Pt, likely on edges and terrace sites. Isotope labeling experiments suggest that a pair of peaks observed at 1990 and 2060 cm(-)(1) during treatments of Pt in H(2)-saturated water arise at least in part from nu(Pt)(-)(H) stretching of adsorbed atomic hydrogen. Acetonitrile was found to adsorb on the Pt catalyst by sigma-bonding of the CN group with the platinum, yielding apparent surface peaks that are almost identical to that observed in the liquid phase. A peak at 1641 cm(-)(1) was observed which was assigned to the adsorption of the CN group in a tilted configuration involving a combination of end-on and pi interaction with the surface. This species was found to be reactive toward hydrogen, suggesting that it might play a role in nitrile hydrogenation. The prospects of using this approach to examine solid-catalyzed liquid-phase reactions are discussed in light of these findings.
An isothermal equilibrium theory analysis of a simple two-step pressure-swing adsorption (PSA) process utilizing an adsorbate−adsorbent system that exhibits a favorable Langmuir isotherm was carried out. Analytic expressions, either simple or recursive, were obtained that describe process operation and process performance during the approach to periodicity. These expressions are a function of cycle number and various process parameters. A recursive relationship for the dimensionless penetration depth for each cycle was determined and, although no closed form is readily available (and likely does not exist), the recursive relationship is easily applicable in any spreadsheet program. All other expressions were derived as functions of the penetration depth, thus lending a full analysis to the capabilities of a spreadsheet program. The analysis is primarily focused on the case of no breakthrough, because of the fact that breakthrough forces the system prematurely to periodicity and is therefore trivial for the approach analysis. The resulting expressions were used to examine process performance upon the approach to periodicity for several hypothetical systems, and the effects of various parameters on the number of cycles required to reach a periodic, or virtually periodic, state were examined. From an understanding or educational point of view, this analysis clearly shows how the so-called "heel in the bed", i.e., the adsorbate loading remaining in the bed after the end-of-purge step, forms on the very first cycle and continues to increase cycle after cycle until periodicity is attained. This buildup of the heel in the bed is characteristic of all PSA processes, with a slower buildup resulting from a more nonlinear isotherm or a smaller purge-to-feed ratio.
An active spectrophotopolarimeter sensor and support system were developed for a military/civilian defense feasibility study concerning the identification and standoff detection of biological aerosols. Plumes of warfare agent surrogates gamma-irradiated Bacillus subtilis and chicken egg white albumen (analytes), Arizona road dust (terrestrial interferent), water mist (atmospheric interferent), and talcum powders (experiment controls) were dispersed inside windowless chambers and interrogated by multiple CO(2) laser beams spanning 9.1-12.0 microm wavelengths (lambda). Molecular vibration and vibration-rotation activities by the subject analyte are fundamentally strong within this "fingerprint" middle infrared spectral region. Distinct polarization-modulations of incident irradiance and backscatter radiance of tuned beams generate the Mueller matrix (M) of subject aerosol. Strings of all 15 normalized elements {M(ij)(lambda)/M(11)(lambda)}, which completely describe physical and geometric attributes of the aerosol particles, are input fields for training hybrid Kohonen self-organizing map feed-forward artificial neural networks (ANNs). The properly trained and validated ANN model performs pattern recognition and type-classification tasks via internal mappings. A typical ANN that mathematically clusters analyte, interferent, and control aerosols with nil overlap of species is illustrated, including sensitivity analysis of performance.
The complete 16-element Mueller matrices for backscattering from amino acids, sugars, and other enantiomorphic compounds pressed into wafer form were measured at infrared wavelengths. For each compound a pair of CO(2) laser lines was selected from the 9.1-11.6-mum region such that one line excited an absorption band in the compound, whereas the other did not. It was observed that at least some of the matrix elements differed significantly depending on which of the two wavelengths was used in the measurement. We propose that a neural network pattern recognition system can be trained to detect the presence of specific compounds based on multiwavelength backscatter Mueller matrix measurements.
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