Infrared radiation bands

Most infrared spectroscopy of complexes is carried out in tire mid-infrared, which is tire region in which tire monomers usually absorb infrared radiation. Van der Waals complexes can absorb mid-infrared radiation eitlier witli or without simultaneous excitation of intennolecular bending and stretching vibrations. The mid-infrared bands tliat contain tire most infonnation about intennolecular forces are combination bands, in which tire intennolecular vibrations are excited. Such spectra map out tire vibrational and rotational energy levels associated witli monomers in excited vibrational states and, tluis, provide infonnation on interaction potentials involving excited monomers, which may be slightly different from Arose for ground-state molecules. 

As discussed earlier in Section lOC.l, ultraviolet, visible and infrared absorption bands result from the absorption of electromagnetic radiation by specific valence electrons or bonds. The energy at which the absorption occurs, as well as the intensity of the absorption, is determined by the chemical environment of the absorbing moiety. Eor example, benzene has several ultraviolet absorption bands due to 7t —> 71 transitions. The position and intensity of two of these bands, 203.5 nm (8 = 7400) and 254 nm (8 = 204), are very sensitive to substitution. Eor benzoic acid, in which a carboxylic acid group replaces one of the aromatic hydrogens, the... 

Q are the absorbance and wavenumber, respectively, at the peak (center) of the band, p is the wavenumber, and y is the half width of the band at half height. Liquid band positions ate usually shifted slightly downward from vapor positions. Both band positions and widths of solute spectra are affected by solute—solvent interactions. Spectra of soHd-phase samples are similar to those of Hquids, but intermolecular interactions in soHds can be nonisotropic. In spectra of crystalline samples, vibrational bands tend to be sharper and may spHt in two, and new bands may also appear. If polarized infrared radiation is used, both crystalline samples and stressed amorphous samples (such as a stretched polymer film) show directional effects (28,29). 

Infrared Spectra of Ionomers. Infrared absorption data, first pubHshed in 1964 (11), show that partial neutralization of ethylene—methacryhc acid introduced new absorption bands at 1480 1670 cm for the ionized carboxylate group while the 1698 — cm band of the free acid carboxyl diminishes in size (21). In addition to providing information on stmctural features, the numerous absorption bands ate significant in apphcations technology, providing rapid warmup of film and sheet under infrared radiation. 

A powerful characteristic of RAIR spectroscopy is that the technique can be used to determine the orientation of surface species. The reason for this is as follows. When parallel polarized infrared radiation is specularly reflected off of a substrate at a large angle of incidence, the incident and reflected waves combine to form a standing wave that has its electric field vector (E) perpendicular to the substrate surface. Since the intensity of an infrared absorption band is proportional to / ( M), where M is the transition moment , it can be seen that the intensity of a band is maximum when E and M are parallel (i.e., both perpendicular to the surface). / is a minimum when M is parallel to the surface (as stated above, E is always perpendicular to the surface in RAIR spectroscopy). 

As with electronic spectra, the use of infrared spectra for quantitative determinations depends upon the measurement of the intensity of either the transmission or absorption of the infrared radiation at a specific wavelength, usually the maximum of a strong, sharp, narrow, well-resolved absorption band. Most organic compounds will possess several peaks in their spectra which satisfy these criteria and which can be used so long as there is no substantial overlap with the absorption peaks from other substances in the sample matrix. 

CFC-12. These manmade chemicals absorb infrared radiation in a part of the spectrum where water vapor and CO2 do not already have strong bands. On the other hand, the manmade increase of CO2 is so large (currently ca. 25% since the mid-1800s - see Chapter 11) that it is the largest anthropogenic input to the greenhouse effect (not counting feedbacks). 

From this equation it can be seen that the depth of penetration depends on the angle of incidence of the infrared radiation, the refractive indices of the ATR element and the sample, and the wavelength of the radiation. As a consequence of lower penetration at higher wavenumber (shorter wavelength), bands are relatively weaker compared to a transmission spectrum, but surface specificity is higher. It has to be kept in mind that the refractive index of a medium may change in the vicinity of an absorption band. This is especially the case for strong bands for which this variation (anomalous dispersion) can distort the band shape and shift the peak maxima, but mathematical models can be applied that correct for this effect, and these are made available as software commands by some instrument manufacturers. 

Note about infrared radiation (IR) filters In the bolometer just described, the optimum conductance to the heat sink is G 2 x 10-10 W/K. This means that an absorbed power of the order of 1(T10 W saturates the bolometer. Since the bolometer is a broad-band detector, it would receive, e.g., a power of the order of 10 7 W from a 30 K black body. Of course, optical filtering is needed to reduce the bandwidth of the impinging radiation. Filtering takes usually place in several steps a room temperature filter eliminates visible light an intermediate temperature filter (at about 77 K) rejects the micron wavelengths, whereas the submillimetre or millimetre filter is made up of a low-pass and an interference band-pass filter. 

Each dip in the spectrum is called a band or peak. The transmittance is 0 % if all the radiation is absorbed and with no absorption the transmittance is 100%. The absorption of infrared radiations can be expressed either in terms of wave length (A.) or in wave number (y). Mostly infra red spectra of organic compounds are plotted as percentage transmittance against wave number. The relationship between wave length and wave number is as follows ... 

Fourier-transform infrared (FTIR) spectroscopy Spectroscopy based on excitation of vibrational modes of chemical bonds in a molecule. The energy of the infrared radiation absorbed is expressed in inverse centimeters (cm ), which represents a frequency unit. For transition-metal complexes, the ligands -C N and -C=0 have characteristic absorption bands at unusually high frequencies, so that they are easily distinguished from other bonds. The position of these bonds depends on the distribution of electron density between the metal and the ligand an increase of charge density at the metal results in a shift of the bands to lower frequencies. 

A fiber-optic device has been described that can monitor chlorinated hydrocarbons in water (Gobel et al. 1994). The sensor is based on the diffusion of chlorinated hydrocarbons into a polymeric layer surrounding a silver halide optical fiber through which is passed broad-band mid-infrared radiation. The chlorinated compounds concentrated in the polymer absorb some of the radiation that escapes the liber (evanescent wave) this technique is a variant of attenuated total reflection (ATR) spectroscopy. A LOD for chloroform was stated to be 5 mg/L (5 ppm). This sensor does not have a high degree of selectivity for chloroform over other chlorinated aliphatic hydrocarbons, but appears to be useful for continuous monitoring purposes. 

Furthermore, polyatomic molecules consisting of n atoms have 3n - 6 vibrational degrees of freedom (or 3n — 5 in the special case of a linear polyatomic molecule), instead of just one as in the case of a diatomic molecule. Some or all of these may absorb infrared radiation, leading to more than one infrared absorption band. In addition, overtone bands (Av > 1)... 

These weaker bands can have significant effects on the calculated outgoing infrared radiation. For example, Ho et al. (1998) show that much of the reported discrepancy between modeled outgoing long-wavelength radiation and satellite measurements can be attributed to not including weaker absorption bands due to C02 at 4.3 /xrn and 03 at 14 pm and the weaker O, lines located far from the center of the strong 9.6-pm band. 

The emitting species for sulfur compounds is excited S2. The lambda maximum for emission of excited S2 is approximately 394 nm. The emitter for phosphorus compounds in the flame is excited HPO with a lambda maximum equal to doublet 510-526 nm. In order to detect one or the other family of compounds selectively as it elutes from the GC column, the suitable band-pass filter should be placed between the flame and the photomultiplier tube to isolate the appropriate emission band. In addition, a thermal infrared filter is mounted between the flame and the photomultiplier tube to isolate only the visible and UV radiation emitted by the flame. Without this filter, the large amounts of infrared radiation emitted by the combustion reaction of the flame would heat up the photomultiplier tube, thus increasing its background signal. 

---