Qualitative analysis infrared spectrometry

Multidimensional gas chromatography has also been used in the qualitative analysis of contaminated environmental extracts by using spectral detection techniques Such as infrared (IR) spectroscopy and mass spectrometry (MS) (20). These techniques produce the most reliable identification only when they are dealing with pure substances this means that the chromatographic process should avoid overlapping of the peaks. 

A feature of this analytical scheme is the marked reliance on infrared spectrometry and titrimetry. The former is particularly applicable to the qualitative characterization of unknown organic materials whilst titrimetry provides a rapid, precise and cheap means of quantitative analysis. The routine titrimetric determination of water, total acid (acid number) and total base (base number) forms a significant proportion of the work load in some analytical laboratories. It is instructive to consider how other techniques might have been applied to the solution of this particular problem, e.g. NMR spectrometry and chromatography. 

In order to perform qualitative and quantitative analysis of the column effluent, a detector is required. Since the column effluent is often very low mass (ng) and is moving at high velocity (50-100 cm/s for capillary columns), the detector must be highly sensitive and have a fast response time. In the development of GC, these requirements meant that detectors were custom-built they are not generally used in other analytical instruments, except for spectroscopic detectors such as mass and infrared spectrometry. The most common detectors are flame ionization, which is sensitive to carbon-containing compounds and thermal conductivity which is universal. Among spectroscopic detectors, mass spectrometry is by far the most common. 

We discussed the fundamentals of mass spectrometry in Chapter 10 and infrared spectrometry in Chapter 8. The quadrupole mass spectrometer and the Fourier transform infrared spectrometer have been adapted to and used with GC equipment as detectors with great success. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography-infrared spectrometry (GC-IR) are very powerful tools for qualitative analysis in GC because not only do they give retention time information, but, due to their inherent speed, they are also able to measure and record the mass spectrum or infrared (IR) spectrum of the individual sample components as they elute from the GC column. It is like taking a photograph of each component as it elutes. See Figure 12.14. Coupled with the computer banks of mass and IR spectra, a component s identity is an easy chore for such a detector. It seems the only real... 

An unknown substance, X, was isolated from rabbit muscle. Its structure was determined from the following observations and experiments. Qualitative analysis showed that X was composed entirely of C, H, and 0. A weighed sample of X was completely oxidized, and the H20 and C02 produced were measured this quantitative analysis revealed that X contained 40.00% C, 6.71% H, and 53.29% O by weight. The molecular mass of X, determined by mass spectrometry, was 90.00 u (atomic mass units see Box 1-1). Infrared spectroscopy showed that X contained one double bond. X dissolved readily in water to give an acidic solution the solution demonstrated optical activity when tested in a polarimeter. 

Like infrared spectrometry, Raman spectrometry is a method of determining modes of molecular motion, especially the vibrations, and their use in analysis is based on the specificity of these vibrations. The methods are predominantly applicable to die qualitative and quantitative analysis of covalently bonded molecules rather than to ionic structures. Nevertheless, they can give information about the lattice structure of ionic molecules in the crystalline state and about the internal covalent structure of complex ions and the ligand structure of coordination compounds both in the solid state and in solution. 

In Chapter 6 we saw that, by itself, chromatography is not well suited to qualitative analysis thus it is often combined with other methods. The most successful combination has been GC with mass spectrometry (MS) GC s ability to separate materials and MS s ability to identify them has made the combination one of the most powerful analytical techniques available today. The other forms of chromatography are also being combined with MS and with infrared spectroscopy (IR). The resulting analytical methods are usually designated by their combined abbreviations (e.g., GC/MS or GC-MS) and are known as hyphenated techniques. The current status of these methods will be described briefly. 

Due to the absorption bands in NIR being weaker than in UV-Vis absorption, NIR spectrometry is not as useful for quantitative measurements but offers better qualitative analysis because of improved selectivity. NIR techniques can handle both liquid and solid samples. Near infrared reflectance analysis (NIRA) has found wide application in process analysis, especially for highly absorbing compounds such as foodstuffs Coal, grain, pulp and paper products and some pharmaceuticals can also be determined by NIRA ". The reflectance from the sample is reported relative to reflectance from a standard reference surface. 

SP-2401" and 3% SP-2250. ° Detectors used by EPA standards procedures, include photoionization (PID)," electron capture (ECD)," Eourier transform infrared spectrometry (PTIR), " and mass spectrometry detectors (MSD)." ° Method 8061 employs an ECD, so identification of the phthalate esters should be supported by al least one additional qualitative technique. This method also describes the use of an additional column (14% cyanopropyl phenyl polysiloxane) and dual ECD analysis, which fulfills the above mentioned requirement. Among MSDs, most of the procedures employ electron impact (El) ionization, but chemical ionization (CI) ° is also employed. In all MSD methods, except 1625, quantitative analysis is performed using internal standard techniques with a single characteristic m/z- Method 1625 is an isotope dilution procedure. The use of a FTIR detector (method 8410) allows the identification of specific isomers that are not differentiated using GC-MSD. 

Fluorescence spectrometry is a well-known method for quantitative analysis of various classes of molecules. Compared to absorption spectrometry it provides in general higher sensitivity and selectivity. However, conventional room-temperature fluorescence excitation and emission spectra are usually broad (e.g., 10 nm or more) and show no or hardly any fine structure. Obviously, its potential for qualitative analysis would be strongly extended if an increase in spectral resolution could be obtained, so that the vibrational fine structure of the spectra became visible (see Figure 1). This has been realized in high-resolution fluorescence spectroscopy, which has a sensitivity similar to that of conventional fluorescence spectroscopy and a selectivity comparable to that of infrared (IR) spectroscopy. 

If the objective is identification (qualitative analysis), it suffices to compare the spectrum of the analyte with that of a standard, both recorded in the same solvent and at an identical pH. This is not the main application of UV-Vis spectrophotometry as the best results in this context are provided by spectroscopic methods considered more effective for the study of the molecular structure of organic compounds (infrared, nuclear magnetic resonance, mass spectrometry, and X-ray diffraction). However, UV-Vis spectrophotometry is a source of relevant supplementary information that helps in the elucidation of molecular structures of drugs, impurities, metabolites, intermediate compounds of degradation, etc. 

Analytical techniques used in qualitative analysis include flame tests (Chapter 2) and precipitation reactions (Chapters 3 and 13). Analytical techniques used in quantitative analysis include titrations (Chapter 1), inductively coupled plasma (ICP) spectroscopy (Chapter 22 on the accompanying website), ultraviolet—visible spectroscopy (Chapter 23 on the accompanying website), infrared spectroscopy and various chromatographic techniques (Chapter 23). Analytical techniques used in structural analysis include NMR, IR spectroscopy, mass spectrometry and visible—ultraviolet spectroscopy. Important areas that employ analytical techniques include ... 

Commercial analytical instruments are developed when manufacturers perceive that a profit can be derived from meeting the demand of the marketplace. Demand in the marketplace develops when consumers are convinced of the practical value of the instrument in the solution of problems at hand, and when an instrument is readily available and supported by the manufacturer. Demonstrations of feasibility are the break into this circular conundrum. Over the past decade, TLC/MS has been shown to be technically feasible, and applicable to a wide variety of problems in both qualitative and quantitative analysis. Commercial interest in TLC/MS, however, is still limited. The same path of development was followed for TLC/Infrared spectrometry, which is now in a rapid growth phase with the proliferation of commercial instruments and accessories. Widespread TLC/MS instrument combinations are soon to follow. 

R. B. Barnes, et at., Qualitative Organic Analysis and Infrared Spectrometry, Anal. Chem. 20, 402, 1948. 

If the reflectance of a sample is low, as it is with gaseous samples, e(v), is approximately equal to 1 — r(. Thus, for any sample for which a transmittance spectrum with discrete absorption bands can be measured, the emittance spectmm should yield equivalent information. As a result, qualitative analysis of the components of hot gases by infrared emission spectroscopy can be as easy as it is by transmission spectrometry. The problem of obtaining quantitative information by infrared emission spectroscopy is more difficult, since not only must the temperature of the sample be known if the radiant power from the blackbody is to be calculated, but the instrument response function must also be taken into account [1]. 

Spectroscopic analysis of ethanol-soluble portion This is usually performed by infrared spectroscopy. If the spectroscopist is experienced with these products, and if the spectral library is adequate, this step will tell the nature of the surfactant and indicate what other components are present in the ethanol-solubles. Since this fraction is usually a mixture, spectral interpretation is far from trivial. Mass spectrometry is also frequently applied to qualitative analysis of the ethanol-solubles. Experience is necessary, since ionization is quite dependent on the surfactant type (9). 

Mattson and Mark [55,56] reported some criticism of Kawahara s technique. They claim that evaporation of the solvent chloroform by infrared heating removes volatiles and causes large changes in the ratios. An oil sample was shown to suffer such alteration by the infrared during repeated analysis. The absorption of all bands decreased nonuniformly between 20 and 100% over a period of 30 min. They propose the application of internal reflection spectrometry as a rapid, direct qualitative technique requiring no sample pretreatment. 

NMR) [24], and Fourier transform-infrared (FT-IR) spectroscopy [25] are commonly applied methods. Analysis using mass spectrometric (MS) techniques has been achieved with gas chromatography-mass spectrometry (GC-MS), with chemical ionisation (Cl) often more informative than conventional electron impact (El) ionisation [26]. For the qualitative and quantitative characterisation of silicone polyether copolymers in particular, SEC, NMR, and FT-IR have also been demonstrated as useful and informative methods [22] and the application of high-temperature GC and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) is also described [5]. 

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. 

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