Infrared continued studies with

The minerals found in United States coals continue to be studied with the availability of improved instrumental procedures such as x-ray diffraction, infrared absorption, and scanning electron microscopy beyond the traditional optical and chemical mineralogical techniques as applied to thin sections, polished pellets, and isolated particles. The minerals may be grouped into the silicates (kaolinite, illite montmorillonite, and chlorite), the oxides (quartz, chalcedony, hematite) the sulfides (pyrite, marcasite, and sphalerite) the sulfates (jarosite, gypsum, barite, and numerous iron sulfate minerals) the carbonates (ankerite, calcite, dolomite, and siderite) and numerous accessory minerals (apatite, phosphorite, zircon, rutile, chlorides, nitrates, and trace minerals). 

In early work (8) we used infrared spectroscopy coupled with attenuated total reflection optics. This work was done before the availability of infrared equipment based on Fourier transform methods. Due to their relative speed these methods now permit in situ, real time measurements with a resolution of 1 sec or less (9), and continue to yield valuable data, particularly in the hands of the Battelle group in a series of studies dating from 1979 (10). In our early infrared work we had to be content to rinse and dry the surface before obtaining the infrared reflection spectrum Nevertheless the values of surface concentration were remarkably close to those determined more recently. Infrared studies of proteins suffer generally from the fact that the main features of protein spectra are similar for all proteins and therefore it is difficult to distinguish one from another. 

Van Huis and Schaefer [8] found that CIO4 has a minimum electronic energy structure of C2v symmetry in contrast with an experimental assignment from infrared spectra by Grothe and Willner [9]. These authors arrived at C31, as the appropriate symmetry group for CIO4 in a neon matrix. The continued interest in the perchlorate radical has prompted the present small study of its electronic features and bonding characteristics. 

For the pressure studies, two phase" compact ion behavior is observed with an inflection point between 7 and 11 atms. For the aqueous solution studies, the hydraulic permeability K and the g-ratio are hardly effected by solute type (within experimental error). The solute diffusive permeability however, varies with solute type in good qualitative agreement with free energy parameters, infrared overtone shifts, and spin echo and continuous wave nuclear magnetic resonance spectroscopy results from the literature. 

Carboxylic acids The smallest carboxylic acid, formic acid, can be measured using infrared spectroscopy (Table 11.2), since it has characteristic absorption bands. As discussed earlier and seen in Fig. 11.33b, mass spectrometry with chemical ionization using SiF5 also revealed HCOOH in an indoor environment (Huey et al., 1998). However, since the sensitivity in these initial studies was about two orders of magnitude less than that for HN03, the detection limit may be about the same as that for FTIR and TDLS. Formic and acetic acids have been monitored continuously from aircraft (Chapman et al., 1995) and their surface flux determined by eddy correlation (Shaw et al., 1998) using atmospheric pressure ionization mass spectrometry. Detection limits are about 30 ppt. 

Output from both gated continuous wave and pulsed carbon dioxide lasers has been used to desorb ions from surfaces and then to photodissociate them in a Fourier transform ion cyclotron resonance mass spectrometer. Pulsed C02 laser irradiation was most successful in laser desorption experiments, while a gated continuous wave laser was used for a majority of the successful infrared multiphoton dissociation studies. Fragmentation of ions with m/z values in the range of 400-1500 daltons was induced by infrared multiphoton dissociation. Such photodissociation was successfully coupled with laser desorption for several different classes of compounds. Either two sequential pulses from a pulsed carbon dioxide laser (one for desorption and one for dissociation), or one desorption pulse followed by gated continuous wave irradiation to bring about dissociation was used. 

There are several major areas of interfacial phenomena to which infrared spectroscopy has been applied that are not treated extensively in this volume. Most of these areas have established bodies of literature of their own. In many of these areas, the replacement of dispersive spectrometers by FT instruments has resulted in continued improvement in sensitivity, and in the interpretation of phenomena at the molecular level. Among these areas are the characterization of polymer surfaces with ATR (127-129) and diffuse reflectance (130) sampling techniques transmission IR studies of the surfaces of powdered samples with adsorbed gases (131-136) alumina(137.138). silica (139). and catalyst (140) surfaces diffuse reflectance studies of organo- modified mineral and glass fiber surfaces (141-143) metal overlayer enhanced ATR (144) and spectroelectrochemistry (145-149). 

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