Infrared-transparent

Instrumental Interface. Gc/fdr instmmentation has developed around two different types of interfacing. The most common is the on-the-fly or flow cell interface in which gc effluent is dkected into a gold-coated cell or light pipe where the sample is subjected to infrared radiation (see Infrared and raman spectroscopy). Infrared transparent windows, usually made of potassium bromide, are fastened to the ends of the flow cell and the radiation is then dkected to a detector having a very fast response-time. In this light pipe type of interface, infrared spectra are generated by ratioing reference scans obtained when only carrier gas is in the cell to sample scans when a gc peak appears. 

The unique features of chalcogenide glasses (Chap. 6), such as quasi-stability, photoconductivity, infrared transparency, non-linear optical properties, and ionic... 

The solvent elimination appro2K h is quite straightforward for supercritical fluids lAich are often gases at atmospheric pressure. Each chromatographic peedc is deposited fron the end of a restrictor, connected to the end of the column by a heated transfer line, onto a small area of infrared-transparent support [110,128,129,134]. The support can be moved manually to collect each peak at a n osition or stetq>ed continuously to record the... 

Semiconductors. In Sections 2.4.1, 4.5 and 5.10.4 basic physical and electrochemical properties of semiconductors are discussed so that the present paragraph only deals with practically important electrode materials. The most common semiconductors are Si, Ge, CdS, and GaAs. They can be doped to p- or n-state, and used as electrodes for various electrochemical and photoelectrochemical studies. Germanium has also found application as an infrared transparent electrode for the in situ infrared spectroelectrochemistry, where it is used either pure or coated with thin transparent films of Au or C (Section 5.5.6). The common disadvantage of Ge and other semiconductors mentioned is their relatively high chemical reactivity, which causes the practical electrodes to be almost always covered with an oxide (hydrated oxide) film. 

A great advantage of infrared spectroscopy is that the technique can be used to study catalysts in situ. Several cells for in situ investigations have been described in the literature [4, 5]. The critical point is the construction of infrared-transparent windows that withstand high temperatures and pressures. 

Space available in porous glass [487], ultrafine Nafion [488, 489], and metallic membranes [490, 491] has also been utilized for the development of smal particles. Cylindrical micropores in alumina membranes have been used, for example, as templates for the electrodeposition of parallel arrays of gold particles (0.26 pm in diameter, 0.3 pm to 3 pm in length) which were infrared transparent [491] and could be used as chemical sensors [490],... 

Solvent-elimination approaches include evaporative spray deposition onto infrared-transparent surfaces (141) or reflective surfaces and powders (142, 143). Other approaches include partial evaporation of the mobile phase before spray deposition (144, 145), and continuous liquid-liquid extraction systems that transfer solutes from LC mobile phases to solvents possessing an infrared window (146). Spray systems include both pneumatic and ultrasonic nozzles (147). 

The infrared spectrum of a liquid may conveniently be recorded as a thin film of the substance held in the infrared beam between two infrared-transparent discs without the need for a diluting solvent. It is customary to use polished plates of sodium chloride as the support material this material is adequately transparent in the region 2-15 /im. Spectra in the longer wavelength region (12-25 m) can be recorded using potassium bromide plates. Sealed cells (p. 267) should be used for volatile liquids. 

In the pressed disc technique a known weight of sample is intimately ground with pure, dry potassium bromide and the mixture inserted into a special die and subjected to pressure under vacuum. The concentration of sample in the disc is usually in the region of 1.0 per cent. The disc so produced may be mounted directly in the sample beam path of the spectrophotometer and the spectrum recorded. This method has the advantage that the spectrum so produced is entirely due to the sample since pure dry potassium bromide is infrared transparent in the 2-25 /xm region. To eliminate the possibility of impurities in the potassium bromide, however, a blank disc (no sample) can be made and mounted in the reference beam path of the spectrophotometer. Care should be taken to ensure that both discs are of equal thickness otherwise inverse peaks may occur if the potassium bromide is damp or impure, and this will be particularly noticeable if the reference disc is thicker than the sample disc. 

There continues to be major problems with coupling HPLC to FTIR (Fourier transform infrared) due to the interference caused by water. The interface is the critical component in the system [126]. The two basic types of interfaces are continuous and capture. A continuous interface has been developed that uses a liquid-liquid extraction. In this approach, the analytes are extracted from the mobile phase by mixing postcolumn with a stream of IR (infrared) transparent, water-immiscible solvent. In the ca-pure technique, the eluent is deposited on a continuously moving, IR transparent, inert substrate from which the eluent can be easily removed by evaporation. These techniques have been applied to identification of racemic precursors of diltizam, AZT derivatives, and steroids [127]. 

Care has to be taken in selecting materials for the die and punches. Metals are of little use above 1000 °C because they become ductile, and the die bulges under pressure so that the compact can only be extracted by destroying the die. However, zinc sulphide (an infrared-transparent material) has been hot pressed at 700 °C in stainless steel moulds. Special alloys, mostly based on molybdenum, can be used up to 1000 °C at pressures of about 80 MPa (5 ton in-2). Alumina, silicon carbide and silicon nitride can be used up to about 1400 °C at similar pressures and are widely applied in the production of transparent electro-optical ceramics based on lead lanthanum zirconate as discussed in Section 8.2.1. 

Foss, C. A., Jr., Tierney, M. J., and Martin, C. R., Template synthesis of infrared-transparent metal microcylinders—comparison of optical properties with the predictions of effective medium theory. /. Phys. Chem. 96, 9001 (1992). 

ATR is a technique based on total internal reflections at the crystal surface. The infrared spectrum is measured from a very thin volume surrounding the infrared transparent ATR crystal. This technique is one of the best IR sampling techniques suitable for analyses of chemicals in water. Detection limit is less than 1 mg/ml for nerve agents (10). 

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