IR spectrometry

Fingerprint region stretching, bending, and rocking vibrations 

IR spectra would be difficult enough to interpret completely if all bands observed were fundamentals, but unfortunately they are not. Many peaks are due to overtones (the first one occurring at slightly less than twice the frequency of the fundamental), combinations (two vibrations can become excited simultaneously, giving a band at about the sum of their separate frequencies), and Fermi resonance (an insidious phenomenon Where a fundamental and an overtone or combination band are expected to occur at very nearly the same frequency, one sometimes finds instead two about equally intense bands, one shifted to higher and one to lower fi-equency). 

As suggested in Fig. 3-5, IR provides a valuable means of studying deuteriated compounds. It is a simple matter to calculate the effect that an isotopic change will have on stretching vibrations, using the formula = 23[ 2 r ( i + s)( 2 + which and are the vibrational 

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This is an analysis frequently conducted on oil lubricants. Generally, the additive is known and its concentration can be followed by direct comparison of the oil with additive and the base stock. For example, concentrations of a few ppm of dithiophosphates or phenols are obtained with an interferometer. However, additive oils today contain a large number of products their identification or their analysis by IR spectrometry most often requires preliminary separation, either by dialysis or by liquid phase chromatography. 

Applications. The most ubiquitous use of infrared spectrometry is chemical identification. It has long been an important tool for studying newly synthesi2ed compounds in the research lab, but industrial identification uses cover an even wider range. In many industries ir spectrometry is used to assay feedstocks (qv). In the flavors (see Flavors and spices), fragrances (see Perfumes), and cosmetics (qv) industries, it can be used not only for gross identification of feedstocks, but for determining specific sources. The spectra of essential oils (see Oils, essential), essences, and other natural products vary with the season and source. Adulteration and dilution can also be identified. 

Latexes of synthetic resins are identified by ir spectrometry. Selective extraction with organic solvents is used to obtain purified fractions of the polymers for spectrometric identification. Polymeric films can be identified by the multiple internal reflectance ir technique, if the film is smooth enough to permit intimate contact with the reflectance plate. TAPPI and ASTM procedures have not been written for these instmmental methods, because the interpretation of spectra is not amenable to standardization. 

Methods and iastmments that are used to monitor phosgene content ia air are well developed and have been reviewed (46—48). One detection iastmment is a porous tape that measures the concentration of phosgene ia air ia quantities as small as 6 ppb (49). Fourier transform ir spectrometry techniques have been developed to permit line and area monitoring ia the area around phosgene plants (50). 

The aim of this work is the determination of several nutritional parameters, such as Energetic Value, Protein, Fat, and Carbohydrates content, in commercially available yoghurt samples by using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FT-IR) spectrometry and a partial least square approach. 

The catalytic experiments were performed at the stationnary state and at atmospheric pressure, in a gas flow microreactor. The gas composition (NO, CO, O2, C3H, CO2 and H2O diluted with He) is representative of the composition of exhaust gases. The analysis, performed by gas chromatography (TCD detector for CO2, N2O, O2, N2, CO and flame ionisation detector for C3H6) and by on line IR spectrometry (NO and NO2) has been previously described (1). A small amount of the sample (10 mg diluted with 40 mg of inactive a AI2O3 ) was used in order to prevent mass and heat transfer limitations, at least at low conversion. The hourly space velocity varied between 120 000 and 220 000 h T The reaction was studied at increasing and decreasing temperatures (2 K/min) between 423 and 773 K. The redox character of the feedstream is defined by the number "s" equal to 2[02]+[N0] / [C0]+9[C3H6]. ... 

TXRF has recently also been used to discriminate between green PE garbage bags, based on Ti, Pb, Cr and Cu analysis (forensic evidence) [288], XRF provided a more effective method of discrimination when compared to IR spectrometry or DSC. 

Infrared absorption detectors arc available for hple, although they have never become very popular. From what you know about ir spectrometry and what you have read so far about hple detectors, see if you can decide whether the following statements are true or false. 

In the case of H in low-temperature deposited silicon nitride films, ion beam techniques have again been used to calibrate IR absorption. The IR absorption cross sections most often quoted in the literature for Si—H and N—H bonds in plasma-deposited material are those of Lanford and Rand (1978) who used 15N nuclear reaction to calibrate their IR spectrometry. Later measurements in CVD nitride films, using similar techniques, confirmed these cross sections (Peercy et al., 1979). 

FIGURE 7.20 Examples of sample containers. Left, cuvettes used in UV-VIS spectrophotometry (pathlength is the inner diameter—approximately 1 cm) center, liquid sampling cell used in IR spectrometry (pathlength is thickness of spacer to the left of the pencil tip—approximately 0.1 mm) right, atomic absorption flame (pathlength is the width of the flame—approximately 4 in.). 

Distinguish between UV-VIS spectrophotometry, IR spectrometry, and atomic spectroscopy. 

Photomultiplier tubes or photodiodes (light sensors) are used as detectors in UV-VIS spectrophotometers, while thermcouples (heat sensors) are used as detectors for infrared (IR) spectrometry. This is the reason UV-VIS instruments are called spectrophotometers while IR instrument are called spectrometers. 

IR spectrometry differs from UV-VIS spectrophotometry in the following ways ... 

Gases, such as automobile exhausts and polluted air, can be measured by IR spectrometry. A special cell is used for containing the gas. This cell is cylindrically shaped and has inlet and outlet stopcocks for introducing the sample. The side windows of the cylinder are nonabsorbing inorganic salt crystals. 

Compare the cuvettes used for UV-VIS spectrophotometry to the liquid sampling cells used for IR spectrometry. 

CIR-FTIR spectroscopy provides a direct technique for studying in situ hydrous metal oxide surfaces and molecules adsorbed on these surfaces (37). By itself, FTIR spectrometry is a well established technique which offers numerous advantages over dispersive (grating) IR spectrometry (1) improved accuracy in frequency measurements through the use of a HeNe laser (2) simultaneous frequency viewing (3) rapid, repetitive scanning which allows many spectra to be collected in a small time interval (4) miriimal thermal effects from IR beam and (5) no detection of sample IR emissions (38). 

Freon-extractable material is reported as total organic material from which polar components may be removed by treatment with silica gel, and the material remaining, as determined by infrared (IR) spectrometry, is defined as total recoverable petroleum hydrocarbons (TRPHs, or total petroleum hydrocarbons-IR). A number of modifications of these methods exist, but one particular method (EPA 418.1 see also EPA 8000 and 8100) has been one of the most widely used for the determination of total petroleum hydrocarbons in soils. Many states use or permit the use of this method (EPA 418.1) for identification of petroleum products and during remediation of sites. This method is subject to limitations, such as interlaboratory variations and inherent inaccuracies. In addition, methods that use Preon-113 as the extraction solvent are being phased out and the method is being replaced by a more recent method (EPA 1664) in which n-hexane is used as the solvent and the n-hexane extractable material (HEM) is treated with silica gel to yield the total petroleum hydrocarbons. 

Molecular spectroscopic techniques have been widely used in pharmaceutical analysis for both qualitative (identification of chemical species) and quantitative purposes (determination of concentration of species in pharmaceutical preparations). In many cases, they constitute effective alternatives to chromatographic techniques as they provide results of comparable quality in a more simple and expeditious manner. The differential sensitivity and selectivity of spectroscopic techniques have so far dictated their specihc uses. While UV-vis spectroscopy has typically been used for quantitative analysis by virtue of its high sensitivity, infrared (IR) spectrometry has been employed mainly for the identihcation of chemical compounds on account of its high selectivity. The development and consolidation of spectroscopic techniques have been strongly influenced by additional factors such as the ease of sample preparation and the reproducibility of measurements, which have often dictated their use in quality control analyses of both raw materials and finished products. 

IR spectrometry is a convenient method of examination of template copolymerization and polymerization kinetics. For instance, IR spectroscopy was applied in order to examine kinetics of template polymerization of multiacrylate according to the reaction ... 

A similar method of hydrolysis was described for poly( vinyl alcohol) used as a template. In this case, T was -CH2-CH- and, after hydrolysis, poly(vinyl alcohol) and polyacrylic or polymethacrylic acid were obtained. The hydrolyzed product gives the color reaction with I2 in the presence of H3BO3 - specific to poly(vinyl alcohol). The second product of hydrolysis, after esterification by diazomethane, was identified as polyfmethyl methacrylate) by NMR and IR spectrometry. Hydrolysis was also applied in the case of ladder-type polymers obtained by polymerization of mutliallyl monomers. The polymerization should result in polymer consisting, at least partly, ladder-type blocks ... 

After hydrolysis by 2N methanol solution of H2SO4, the product was neutralized with KOH to pH=5 and methanol evaporated. The dry residue was expected to be poly(allilamine), polymethacrylic acid, and K2SO4. Indeed, after extraction with anhydrous methanol and acetone, poly(allilamine) was identified by NMR and IR spectrometries. After evaporation, solvent from the methanol part of the extract insoluble in chloroform part was obtained. After esterification by diazomethane the product was identified as polyfmethyl methacrylate) on the basis of IR and H-NMR spectroscopy. IR spectroscopy was applied in order to examine the copolymerization of multimethacrylate (p-cresyl-formaldehyde oligomers with methacrylic groups) with st3rrene. It was found that double bond peak at 1650 cm disappeared during the process and it was absent in the product of polymerization. Polymerization and... 

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