Condensed-phase infrared

About 70 % of the IR spectra collected by the OPCW are in a condensed phase. The largest commercial condensed phase infrared library (Sadtler Condensed Phase IR Standards library) has over 75 000 spectra, while the largest vapor phase library (Sadtler Vapor Phase IR Standards library) has less than 10000 spectra. There are no commercial MI libraries available. 

Condensed phase infrared (IR) data exist for many chemical warfare agents and related compounds as this technique was routinely used prior to the advent of GC-MS. Capillary column GC-FTIR offers considerably more promise for the identification and characterization of chemical warfare agents in multiple component sample extracts and has been utilized as a complementary confirmation technique. 

Another method by which spectral SNR improvement may be accomplished is by Fourier smoothing, which, in effect, is a form of apodization. Most condensed-phase infrared spectral bands have a bandshape that is very close to a Lorentzian function (see Section 1.4) ... 

Some vibrations which are both Raman and infrared inactive may be allowed in the hyper Raman effect. Indeed, the occasional appearance of such vibrations in Raman spectra in a condensed phase has sometimes been attributed to an effect involving the hyperpolarizability. 

Molecules vibrate at fundamental frequencies that are usually in the mid-infrared. Some overtone and combination transitions occur at shorter wavelengths. Because infrared photons have enough energy to excite rotational motions also, the ir spectmm of a gas consists of rovibrational bands in which each vibrational transition is accompanied by numerous simultaneous rotational transitions. In condensed phases the rotational stmcture is suppressed, but the vibrational frequencies remain highly specific, and information on the molecular environment can often be deduced from hnewidths, frequency shifts, and additional spectral stmcture owing to phonon (thermal acoustic mode) and lattice effects. 

The infrared carbonyl stretching frequencies of n- and isobutyraldehyde in the condensed phase occur at 1727.6 and 1738.0 cm , respectively (38). The proton nmr spectra of both aldehydes are weU-known (39). 

The blue colour of oxygen in the liquid and solid phases is due to electronic transitions by which molecules in the triplet ground state are excited to the singlet states. These transitions are normally forbidden in pure gaseous oxygen and, in any case, they occur in the infrared region of the spectrum at 7918 cm" ( Ag) and 13 195 cm" ( ]+). However, in the condensed phases a... 

Detection in SFC can be achieved in the condensed phase using optical detectors similar to those used in liquid chromatography or in the gas phase using detectors similar to those used in gas chromatography. Spectroscopic detectors, such as mass spectrometry and Fourier transform infrared spectroscopy, are relatively easily interfaced to SFC compared to the problems observed with liquid mobile phases (see Chapter 9). The range of available detectors for SFC is considered one of its strengths. 

The situation with 7V-acyloxy-/V-alkoxyureas and carbamates is similar although infrared data were mostly determined by liquid film or condensed phase (KBr/nujol mull).52,131 However, the limited data for V-acyloxy-TV-alkoxyureas (Table 2, entries 69-72) give amide carbonyl frequencies ca. 1730 cm-1 that are raised by some 37-40 cm-1 by acyloxylation. Values for carbamates (Table 2, entries 73-77) are higher (mostly 1780 cm-1) but are raised to a lesser extent (10-20 cm-1) relative to their parent carbamates. Clearly, carbonyl vibrational frequencies will be influenced strongly by the adjacent amino or alkoxyl group in both analogues. 

The functional groups almost exclusively involved in NIRS are those involving the hydrogen atom C-H, N-H, O-H (see Figure 5.1). These groups are the overtones and combinations of their fundamental frequencies in the mid-infrared and produce absorption bands of useful intensity in the NIR. Because the absorptivi-ties of vibrational overtone and combination bands are so much weaker, in NIRS the spectra of condensed phase, physically thick samples, can be measured without sample dilution or the need to resort to difficult short-path length sampling techniques. Thus conventional sample preparation is redundant, and fortunately so, because most PAT applications require direct measurement of the sample " either in situ, or after extraction of the sample from the process in a fast loop or bypass. 

The condensed-phase reaction zone of a burning-interrupted BAMO copolymer is identified by infrared (IR) spectral analysis. In the non-heated zone, the absorption of the N3 bond, along with the absorptions of the C-O, C-H, and N-H bonds. 

Gold s method has been used by a number of workers, including Siska (1973), who applied it to molecular-beam scattering data, MacNeil and Dixon (1977), who applied it to photoelectron spectra, and Jones et al. (1967), who restored infrared spectra of condensed-phase samples. The author is unaware of any experimental results with this method, however, that illustrate the full potential achievable by constrained methods to be described later in this chapter. In the work of Jones et al., the resulting resolution is probably limited by the inherent breadth of spectral lines observed with condensed-phase samples. 

Royce, B. S. H., Teng, Y. C. Fourier Transform Infrared Photoacoustic Spectroscopy of Condensed Phases Proceedings of the Institute of Acoustics, PAS Conference London, U.K. 1981... 

The flame retardant mechanism of PC/ABS compositions using bisphenol A bis(diphenyl phosphate) (BDP) and zinc borate have been investigated (54). BDP affects the decomposition of PC/ABS and acts as a flame retardant in both the gas and the condensed phase. The pyrolysis was studied by thermogravimetry coupled with fourier transform infrared spectroscopy (FUR) and nuclear magnetic-resonance spectroscopy. Zinc borate effects an additional hydrolysis of the PC and contributes to a borate network on the residue. 

Infrared emission spectroscopy can be used for the laboratory study of heated samples as one would encounter in pyrot reactions or in the detonation of primary expls. One difficulty associated with the measurement of emission spectra of condensed phase samples is that the temp of the sample has to be uniform, or else radiation emitted from elements situated below the surface will be absorbed by the cooler particles near the surface. Emission spectrometry finds application in the study of flames and smoke... 

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