Cylindrical internal reflectance crystal

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. 

An infrared spectrum is a plot of percent radiation absorbed versus the frequency of the incident radiation given in wavenumbers (cm ) or in wave length ( xm). A variation of this method, diffuse reflectance spectroscopy, is used for samples with poor transmittance, e.g. cubic hematite crystals. Increased resolution and sensitivity as well as more rapid collection of data is provided by Fourier-transform-IR (FTIR), which averages a large number of spectra. Another IR technique makes use of attenuated total reflectance FTIR (ATR-FTIR) often using a cylindrical internal reflectance cell (CIR) (e.g. Tejedor-Tejedor Anderson, 1986). ATR enables wet systems and adsorbing species to be studied in situ. 

Sabo et al. [35] developed an LC/FTIR interface for both normal and reversed phase chromatography using an attenuated total reflectance cell. The cylindrical internal reflectance flow cell contained in a ZnSe crystal, had a nominal volume of 24 pi and an equivalent transmission cell path length of 4-22 pi over the usable range. On-the-fly spectra of the components from a 100 pi sample of a solution containing 2% of acetophenone and ethyl benzoate and 1% of nitrobenzene gave clearly identifiable spectra. Nevertheless, relative to other LC/FTIR systems this was not a very sensitive device. 

A technique which has proven useful for our studies is that of cylindrical internal reflectance (CIR), coupled with a Fourier transform infrared spectrometer. In this study, an IBM-85 FTIR equipped with either a DTGS (deuterated triglycine sulfate) or MCT (mercury-cadmium-tellurium) detector was used. The infrared radiation is focused by concave mirrors onto the 45° conical ends of a transmitting crystal (Figure 1). The crystal may be made of any material which is optically transparent, has a high mechanical strength and high index of refraction, and is resistant to thermal shock and chemical attack. Suitable materials include ZnS, ZnSe,... 

The use of cylindrical internal reflectance cells for HP-IR was pioneered by Moser and further modified by others.This method involves the use of an optically transparent internal reflectance crystal (typically ZnS, ZnSe, sapphire). Due to the inherently short path length, the method is not as sensitive as transmission-based IR, and a Fourier transform infrared (FTIR) spectrometer is therefore generally required. In addition, the type of crystal may need to be changed depending on the reaction of interest, as the optics may be corroded by some reagents or catalysts. However, as the path length is fixed regardless of conditions, it is much easier to quantify catalyst species, and unlike transmission systems the cells can also be used for the study of liquid-solid and gas-liquid-solid mixtures. ... 

A new experimental arrangement is described whereby thin films (about 1 micrometre thick) of polypyrrole were electrochemically deposited onto a silicon rod single crystal that formed an element of the cylindrical internal reflectance accessory of an FTIR spectrometer. Polypyrrole was deposited from acetonitrile solutions of pyrrole in the presence of lithium perchlorate, tetrabutylammonium perchlorate and tetrabutyl-ammonium tetrafluoroborate. Excellent quality in situ... 

Two cases corresponding to small and large convexity of the rounded crystal/melt interface toward the melt were studied in detail. The first can be achieved when the cylindrical side surface is diSuse, and the second, when it is specularly reflecting. Computations showed that the relation between the facet radius and supercooling is very close to a well-known square root law in the first case and it is strongly different in the second. Thus, in the case of large convexity of the rounded interface the effect of internal radiation on the facet formation turns out to be very significant. 

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