Reflectance ATR crystals

Some important functional groups and their region of absorbance are highlighted. Cheddar cheese was scanned by pressing 0.5 g of cheese on a diamond attenuated total reflectance (ATR) crystal. Extracts was scanned by drying 10 pi of the extract on a zinc selenide ATR crystal. 

Attenuated total reflection (ATR), also called internal reflection, is based on the phenomenon of total internal reflection. In ATR the infrared beam is directed into an infrared-transmitting crystal so that it strikes the crystal surface at less than the critical angle and undergoes total internal reflection. 

Fixed pathlength transmission flow-cells for aqueous solution analysis are easily clogged. Attenuated total reflectance (ATR) provides an alternative method for aqueous solution analysis that avoids this problem. Sabo et al. [493] have reported the first application of an ATR flow-cell for both NPLC and RPLC-FUR. In micro-ATR-IR spectroscopy coupled to HPLC, the trapped effluent of the HPLC separation is added dropwise to the ATR crystal, where the chromatographic solvent is evaporated and the sample is enriched relative to the solution [494], Detection limits are not optimal. The ATR flow-cell is clearly inferior to other interfaces. 

ATR is one of the most useful and versatile sampling modes in IR spectroscopy. When radiation is internally reflected at the interface between a high-refractive index ATR crystal (usually Ge, ZnSe, Si, or diamond) and the sample, an evanescent wave penetrates inside the sample to a depth that depends on the wavelength, the refractive indices, and the incidence angle. Because the penetration depth is typically less than 2 pm, ATR provides surface specific information, which can be seen as an advantage or not if surface orientation differs from that of the bulk. It also allows one to study thick samples without preparation and can be used to characterize highly absorbing bands that are saturated in transmission measurements. 

Simply visualised, the infrared beam penetrates (of the order 0.3-3 pm, dependent on its wavelength) just beyond the ATR crystal-specimen boundary before it is reflected back and makes its way through the crystal to the detector. On this short path (of the evanescent wave) into the sample surface layer, light is absorbed, and the reflected beam carries characteristic spectral information of the sample. The decaying amplitude of the evanescent wave and the depth of penetration dp at which it has decreased to a proportion of 1 /e is defined by the Harrick equation (Equation (2)), where X is the wavelength of the incoming... 

Internal reflectance (attenuated total reflectance ATR ). The internal reflectance or, more usually, attenuated total reflectance (ATR), technique depends on the total reflectance of an IR beam at the internal face of an IR-transparent crystal of high IR refractive index, as shown in Figure 2.38. Medium 1 is a prism of such a material (for example, Si, Ge or KRS-5 [thallous bromide- iodide]), medium 2 is a thin coating of a metal (Au, Pt, Fe) which forms the working electrode and medium 3 is the electrolyte. The... 

The ATR technique is now routinely used for IR spectroscopy as it allows measurement of spectra for a variety of sample types with minimal preparation. The crystals employed are generally prismatic in shape, allowing contact of a flat surface with the sample. The ATR method was first adapted for HP IR spectroscopy by Moser [29-33], who realised that a conventional autoclave could easily be adapted for in situ IR spectroscopy by fitting an ATR crystal of cylindrical cross section. The technique developed by Moser is thus known as cylindrical internal reflectance (CIR) spectroscopy and high pressure cells based upon the CIR method have been commercialised by Spectra-Tech. A typical CIR cell is illustrated in Figure 3.8. 

Attenuated total reflection (ATR) is the most common reflectance measurement modahty. ATR spectra cannot be compared to absorption spectra. While the same peaks are observed, their relative intensities differ considerably. The absorbances depend on the angle of incidence, not on sample thickness, since the radiation penetrates only a few micrometers into the sample. The major advantage of ATR spectroscopy is ease of use with a wide variety of solid samples. The spectra are readily obtainable with a minimum of preparation Samples are simply pressed against the dense ATR crystal. Plastics, rubbers, packaging materials, pastes, powders, solids, and dosage forms such as tablets can all be handled directly in a similar way. 

Attenuated Total Reflection (ATR).4c A sample brought in contact with the totally reflecting surface of a high-refractive-index material (the ATR crystal), will, on IR irradiation, give an evanescent wave in the less dense medium that extends beyond the reflecting interface. This wave will be attenuated in regions of the IR spectrum where the sample absorbs energy. Observation of such waves constitute ATR measurements. Only the small amounts of beads necessary to cover the area of the ATR crystal are required. 

When melted fat or oil is placed on the surface of an ATR crystal like diamond, the infrared light penetrates a distance of only a few micrometers into the test sample, when the conditions of total internal reflection apply... 

X-ray photoelectron spectroscopy (XPS) was used for elemental analysis of plasma-deposited polymer films. The photoelectron spectrometer (Physical Electronics, Model 548) was used with an X-ray source of Mg Ka (1253.6 eV). Fourier transform infrared (FTIR) spectra of plasma polymers deposited on the steel substrate were recorded on a Perkin-Elmer Model 1750 spectrophotometer using the attenuated total reflection (ATR) technique. The silane plasma-deposited steel sample was cut to match precisely the surface of the reflection element, which was a high refractive index KRS-5 crystal. 

Attenuated total internal reflection (ATR) probes offer several advantages over other probe types. ATR is a phenomenon that relies on a difference in the index of refraction of a crystal and that of the solution with which it is in contact to prevent light from escaping the crystal. Only the evanescent wave of the light interacts with the solution layer at the crystal face. The result is an optical pathlength of only a few microns. Typical designs make use of faceted crystals or hemispheres (see Figure 6.1). The most common ATR material in the UV-vis is sapphire. In rare cases, fused silica may be used. ATR allows spectra to be taken of neat samples with optical density (OD) of 500-1000... 

The cross section area of the collinear IR beam is -1 cm2 and thus sufficient to cover the entire area of the C face of the ATR crystal, and as a result, a complete coverage of faces A by the IR radiation is achieved. Hence, the measured absorbance should be proportional to the fraction of the total area of faces A and C covered by the monolayer. Of course, all six faces of the crystal are covered with the monolayer film. However, only the A faces contribute to the measured signal via internal reflection. This is because the area of the C faces is only 7% of the total area (A + C) in a typical ATR crystal, and the differences between transition mode (in the C faces) and ATR mode (in the A faces) are not very large. Therefore, it was suggested by Maoz and Sagiv that no corrections for this effect are needed (1). 

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