Infrared sample cells

FIC. 7 Flushing the infrared sample cell. The solvent used to dissolve the sample is used in this process. 

In-situ FT-IR spectra were recorded with a Mattson RS-10000 infrared spectrometer equipped with a narrowband MCT detector. Each spectrum was taken by averaging 500 scans at an instrument resolution of 4 cm. The infrared sample cell used in this study has been described previously (2,9). Briefly, 50-70 mg zeolite... 

The same principle is used in dispersive spectroscopy to measure the thickness of an infrared sample cell or a film sample. As is illustrated in Fig. 7, some of the radiation striking the sample is transmitted without any reflection, while some of the radiation is internally reflected at the interfaces before passing through the sample. The transmitted radiation and the 2n-times-internally-reflected radiation interfere, and interference patterns appear in the spectra. The patterns are spectral artifacts, not vibrational or rotational bands, and are entirely a function of the thickness of the sample. They are very apparent in almost every polymer spectrum. 

Infrared spectroscopy is routinely used for the analysis of samples in the gas, liquid, and solid states. Sample cells are made from materials, such as NaCl and KBr, that are transparent to infrared radiation. Gases are analyzed using a cell with a pathlength of approximately 10 cm. Longer pathlengths are obtained by using mirrors to pass the beam of radiation through the sample several times. 

Photometric Moisture Analysis TTis analyzer reqiiires a light source, a filter wheel rotated by a synchronous motor, a sample cell, a detector to measure the light transmitted, and associated electronics. Water has two absorption bands in the near infrared region at 1400 and 1900 nm. This analyzer can measure moisture in liquid or gaseous samples at levels from 5 ppm up to 100 percent, depending on other chemical species in the sample. Response time is less than 1 s, and samples can be run up to 300°C and 400 psig. 

The primary reference method used for measuring carbon monoxide in the United States is based on nondispersive infrared (NDIR) photometry (1, 2). The principle involved is the preferential absorption of infrared radiation by carbon monoxide. Figure 14-1 is a schematic representation of an NDIR analyzer. The analyzer has a hot filament source of infrared radiation, a chopper, a sample cell, reference cell, and a detector. The reference cell is filled with a non-infrared-absorbing gas, and the sample cell is continuously flushed with ambient air containing an unknown amount of CO. The detector cell is divided into two compartments by a flexible membrane, with each compartment filled with CO. Movement of the membrane causes a change in electrical capacitance in a control circuit whose signal is processed and fed to a recorder. 

At the time of writing, in all papers published on adsorption studies on oxides surfaces, spectra have been reported of samples held at the ambient temperature of the sample compartment. It is obvious that when dealing with very volatile adsorbates, low temperature sample cells may be required to increase adsorption and also to prevent rapid desorption of the adsorbed species. In some instances, it is also desirable to record the spectra of species held at elevated temperatures for better correlation with industrial catalytic systems. It should be noted that there are only a few infrared spectra reported in the literature for high temperature studies of catalytic reactions. Sample emission at elevated temperature is a significant experimental complication in investigations of this type. 

The various combustion methods differ primarily in the method of measuring the carbon dioxide generated from the organic carbon. The first really sensitive carbon dioxide detector and the one still most used is the non-dispersive infrared gas analyser. The detecting element senses the difference in absorption of infrared energy between a standard cell filled with a gas with no absorption in the infrared, and a sample cell. Water vapour is the only serious interference, hence the carbon dioxide must be dried before any measurements are made. 

The basic instrumentation used for spectrometric measurements has already been described in Chapter 7 (p. 277). The natures of sources, monochromators, detectors, and sample cells required for molecular absorption techniques are summarized in Table 9.1. The principal difference between instrumentation for atomic emission and molecular absorption spectrometry is in the need for a separate source of radiation for the latter. In the infrared, visible and ultraviolet regions, white sources are used, i.e. the energy or frequency range of the source covers most or all of the relevant portion of the spectrum. In contrast, nuclear magnetic resonance spectrometers employ a narrow waveband radio-frequency transmitter, a tuned detector and no monochromator. 

The unique appearance of an infrared spectrum has resulted in the extensive use of infrared spectrometry to characterize such materials as natural products, polymers, detergents, lubricants, fats and resins. It is of particular value to the petroleum and polymer industries, to drug manufacturers and to producers of organic chemicals. Quantitative applications include the quality control of additives in fuel and lubricant blends and to assess the extent of chemical changes in various products due to ageing and use. Non-dispersive infrared analysers are used to monitor gas streams in industrial processes and atmospheric pollution. The instruments are generally portable and robust, consisting only of a radiation source, reference and sample cells and a detector filled with the gas which is to be monitored. 

Vibrational spectra were recorded using the polarization-modulated infrared reflection absorbance technique (PM-IRRAS). The spectrometer, the electrochemical cell, and the sample preparation and cleaning procedures are all described elsewhere (1 7) All of the measurements were performed using 0.5 M SO solutions, either with or without an added nitrile compound or SnCl,. The solutions were saturated with CO by bubbling the gas through their storage reservoirs before admitting them into the sample cell. 

The most straightforward method for analyzing a solid material by infrared spectrometry is to dissolve it in a suitable solvent and then to measure this solution using a liquid sampling cell such as one of the several described in Section 8.8. Thus it becomes a liquid sampling problem, the experimental details of which have already been discussed (Section 8.8). It is the only method of solid sampling suitable for quantitative analysis because it is the only one that has a defined and reproduced pathlength. 

Quantitative analysis procedures using infrared spectrometry utilize Beer s law. Thus only sampling cells with a constant pathlength can be used. Once the percent transmittance or absorbance measurements are made, the data reduction procedures are identical with those outlined in Chapter 7 (preparation of standard curve, etc.). 

Obtain the infrared spectra of the two liquids by whatever method suggested by your instructor (liquid sampling cell or disposable card). 

Infrared detectors are similar in construction to those used in UV detection. The main difference is that the sample cell windows are constructed of sodium chloride, potassium bromide, or calcium fluoride. A limitation of this type of detector is caused by the low transparency of many useful solvents (Skoog et al., 1998). Recent changes to interface systems that use spraying to induce rapid evaporation of the solvent provide good sensitivity and enhanced spectral quality (LaCourse, 2000). 

Most of the above membrane-oriented studies were carried out for peptides in multilayer systems that were collapsed or transferred onto a sample cell surface. An alternative and very interesting way to study membrane systems is by IRRAS (infrared reflection absorption spectroscopy) at the air-water interface. In this way, unilamellar systems can be studied as a function of surface pressure and under the influence of various membrane proteins and peptides added. Mendelsohn et al.[136] have studied a model series of peptides, [K2(LA) ] (n = 6, 8, 10, 12), in nonaqueous (solution), multilamellar (lipid), and unilamellar (peptide-IRRAS) conditions. In the multilamellar vesicles these peptides are predominantly helical in conformation, but as peptide only monolayers on a D20 subphase the conformation is (1-sheet like, at least initially. For different lengths, the peptides show variable surface pressure sensitivity to development of some helical component. These authors further use their IR data to hypothesize the existence of the less-usual parallel (i-sheet conformation in these peptides. A critical comparison is available for different secondary structures as detected using the IRRAS data for peptides on H20 and D20 subphasesJ137 ... 

Spectrometer was used. Normal operating conditions were used normal slit, IX expansion, 12-minute scan speed (4000-200 wave numbers), and normal gain, in accordance with Perkin-Elmer setup instructions. A Beckman 2 cm path length, near infrared silica cell (holds 8 ml sample) was used to hold the desorbing solution in the sample compartment (Figure 1). 

The parameter can change in a vessel being part of the analytical instrument, for example, an ultraviolet-visible (UV-Vis) spectrophotometric cell [39,41,45,14,47, 48], an infrared (IR) cell [42, 46], or a fluorometer cell [45, 51], or a polarimetric tube [27, 49]. It can change in a reactor vessel where the analytical signal can be read in some way, for example using an optical fiber cell for spectrophotometry [52-54] or a conductometric cell [16,34,40]. Another possibility is to transport the solution from the reaction vessel to the analytical instrument by a peristaltic pump [38]. When altenative ways are not practicable, samples can be taken at suitable time intervals and analyzed apart [29,31,35,39,43,50]. 

Fig. 16. Infrared spectra that show the effects on a Pt/Al203 catalyst, initially with v-C2H4, di-o--C2H4, and ethylidyne species, of a sequence of doses of H2 (a) sample under vacuum at 140 K (b) after adding 5.3 X 1016 molecules of H2 (c) after adding 2.4 X 1017 molecules of H2 (d) after warming to 200 K (e) after adding 6.3 X 1018 molecules of H2 (f) after evacuating the sample cell and warming to 200 K. [Reprinted with permission from Ref. 408. Copyright 1988 American Chemical Society.]...

For infrared measurements, cells are commonly constructed of NaCI or KBr. For the 400 to 50 cm 1 far-infrared region, polyethylene is a transparent window. Solid samples are commonly ground to a fine powder, which can be added to mineral oil (a viscous hydrocarbon also called Nujol) to give a dispersion that is called a mull and is pressed between two KBr plates. The analyte spectrum is obscured in a few regions in which the mineral oil absorbs infrared radiation. Alternatively, a 1 wt% mixture of solid sample with KBr can be ground to a fine powder and pressed into a translucent pellet at a pressure of —60 MPa (600 bar). Solids and powders can also be examined by diffuse reflectance, in which reflected infrared radiation, instead of transmitted infrared radiation, is observed. Wavelengths absorbed by the sample are not reflected as well as other wavelengths. This technique is sensitive only to the surface of the sample. 

Evacuated bulbs (Figure 4.7C) are generally used for trapping volatile components. Since this technique does not concentrate the sample, additional sample preparation may be required. For substances with high infrared absorptivity, the sample may be trapped directly in an evacuated infrared gas cell and analyzed directly. For nonvolatile samples that may condense on the inside walls, the cell must be heated before analysis. 

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