Fourier transform infrared techniques

Fleischmann, M., Sockalingum, D. and Musiani, M.M. (1990) The use of near-infrared Fourier transform techniques in the study of surface-enhanced Raman spectra. Spectrochimica Acta Part A, 46A, 285. 

In recent years, infrared spectroscopy has been enhanced by the possibility of applying Fourier transform techniques to it. This improved spectroscopic technique, known as Fourier transform infrared spectroscopy (FTIR), is of much greater sensitivity than conventional dispersive IR spectroscopy (Skoog West, 1980). Moreover, use of the Fourier transform technique enables spectra to be recorded extremely rapidly, with scan times of only 0-2 s. Thus it is possible to record spectra of AB cements as they set. By comparison, conventional dispersive IR spectroscopy requires long scan times for each spectrum, and hence is essentially restricted to examining fully-set cements. 

A significant advance was the application of the Fourier transform technique to enhance the signal. The optical arrangement of a Fourier transform infrared (FUR) spectrometer is shown in Fig. 27.37 (Habib and Bockris, 1984). A beam of light from an IR source is directed to a beamsplitter, where part of the beam is transmitted to a... 

Most chemists tend to think of infrared (IR) spectroscopy as the only form of vibrational analysis for a molecular entity. In this framework, IR is typically used as an identification assay for various intermediates and final bulk drug products, and also as a quantitative technique for solution-phase studies. Full vibrational analysis of a molecule must also include Raman spectroscopy. Although IR and Raman spectroscopy are complementary techniques, widespread use of the Raman technique in pharmaceutical investigations has been limited. Before the advent of Fourier transform techniques and lasers, experimental difficulties limited the use of Raman spectroscopy. Over the last 20 years a renaissance of the Raman technique has been seen, however, due mainly to instrumentation development. 

In the diffuse reflectance mode, samples can be measured as loose powders, with the advantages that not only is the tedious preparation of wafers unnecessary but also diffusion limitations associated with tightly pressed samples are avoided. Diffuse reflectance is also the indicated technique for strongly scattering or absorbing particles. The often-used acronyms DRIFT or DRIFTS stand for diffuse reflectance infrared Fourier transform spectroscopy. The diffusely scattered radiation is collected by an ellipsoidal mirror and focussed on the detector. The infrared absorption spectrum is described the Kubelka-Munk function ... 

Give plausible reasons why Fourier transform techniques are used for the infrared region but not the visible and ultraviolet spectral regions. 

Fourier transform methods have revolutionized many fields in physics and chemistry, and applications of the technique are to be found in such diverse areas as radio astronomy [52], nuclear magnetic resonance spectroscopy [53], mass spectroscopy [54], and optical absorption/emission spectroscopy from the far-infrared to the ultraviolet [55-57]. These applications are reviewed in several excellent sources [1, 54,58], and this section simply aims to describe the fundamental principles of FTIR spectroscopy. A more theoretical development of Fourier transform techniques is given in several texts [59-61], and the interested reader is referred to these for details. 

The development of Fourier transform techniques with infrared spectra has made the use of infrared spectroscopy available to many more polymer chemists. 

A new rapid mid-infrared spectroscopic method called diffuse reflectance infrared Fourier transform spectra (DRIFTS), coupled with chemometrics, has been developed by Janik, Merry, and Skjemstad (1998) and routinely applied to rapidly screen and compare crime scene samples (Figure 1.1). Added to these rapid methods and techniques are the use of rapid mass and volume magnetic susceptibility methods, which should also always be used before moving to the more costly methods (Figure 1.1). Mineral magnetic techniques are a relatively recent development (post-1971) and have now become a very powerful and widely used research tool to characterize natural materials in landscapes (e.g., Thompson and Oldfield 1986). 

Infrared microscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and photoacoustic spectroscopy (PAS) techniques may be suitable for some types of sample but the use of... 

Fourier transform techniques are used throughout the whole spectroscopic region, particularly in the infrared and visible. As we pass from the microwave region to the far-infrared, Fourier transform methods are still used, but based now on interferometry rather than pulsed methods. Perhaps this region of the spectrum will, in... 

For readers interested in greater detail, Fourier transform techniques are treated in the following references (a) Marshall, A.G. Verdun, F.R. Fourier Transforms in NMR, Optical, and Mass Spectrometry Elsevier Amsterdam, 1986 (b) Griffiths, P.R., DeHaseth, J.A. Fourier Transform Infrared Spectrometry Wiley-Interseience New York, 1986 (c) Chamberlain, J. The Principles of Interferometric Spectroscopy Wiley-Interscience Chichester, 1979 (d) Bell, R. J. Introductory Fourier Transform Spectrometry Academic Press New York, 1972. 

A number of experimental alternatives to traditional IR transmission spectroscopy are suitable for overcoming some of these complicating experimental factors. In the technique of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (Hartauer et al. 1992 Neville et al. 1992) the sample is dispersed in a matrix of powdered alkali halide, a procedure which is less likely to lead to polymorphic transformations or loss of solvent than the more aggressive grinding necessary for mull preparation or pressure required to make a pellet (Roston et al. 1993). For these reasons, Threlfall (1995) suggests that DRIFTS should be the method of choice for the initial IR examination of polymorphs. He has also discussed the possible use of attenuated total reflection (ATR) methods in the examination of polymorphs and provided a comparison and discussion of the results obtained on sulphathiazole polymorphs from spectra run on KBr disks, Nujol mulls and ATR. 

The stretching and bending modes of zeolite lattices have weak Raman cross sections, which makes measuring high quality Raman spectra difficult. Laser induced fluorescence is also a common problem with dehydrated zeolites, although this can be overcome with the Fourier transform technique. As with the corresponding infrared spectra, the frequencies of the Raman active lattice modes depend on both the local structure and the composition of the zeolite lattice. 

The constitution of oxygen-containing sites in carbonaceous materials of various types was a subject of inquiry of many authors. The first systematized results were outlined in a review by Boehm [77]. In the past few years numerous researches were carried out applying the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique [78-81], and their results were summarized in a paper by Fanning and Vannice [82]. Analogous results concerning... 

High quality IR spectra of different carbon surfaces were obtained by photo-thermal beam deflection spectroscopy (IR-PBDS) [123,124]. This technique was developed with the intention of providing an IR technique that could be used to study the surface properties of materials that are difficult or impossible to examine by conventional means. Recently, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) has been successfully applied to study the effect of different pretreatments on the surface functional groups of carbon materials [101,125-128]. Several studies aiming to improve the characterization of the carbon electrode surface and the electrode-electrolyte interface have been carried out using various in situ IR techniques [14,128-132]. The development of in situ spec-troelectrochemical methods has made it possible to detect changes in the surface oxides in electrolyte solutions during electrochemical actions. 

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