Normal hydrocarbon spectra

Fig. 2.4 Infrared spectrum of four normal hydrocarbons in C—H stretching region plotted as absorbance and obtained with LiF prisms.

Infrared (IR) spectroscopy offers many unique advantages for measurements within an industrial environment, whether they are for environmental or for production-based applications. Historically, the technique has been used for a broad range of applications ranging from the composition of gas and/or liquid mixtures to the analysis of trace components for gas purity or environmental analysis. The instrumentation used ranges in complexity from simple filter-based photometers to optomechanically complicated devices, such as Fourier transform infrared (FTIR) spectrometers. Simple nondispersive infrared (NDIR) insttuments are in common use for measurements that feature well-defined methods of analysis, such as the analysis of combustion gases for carbon oxides and hydrocarbons. For more complex measurements it is normally necessary to obtain a greater amount of spectral information, and so either Ml-spectrum or multiple wavelength analyzers are required. 

Under normal conditions the catacondensed hydrocarbons of molecular formula C4n+2H2n+4 adopt a crystal lattice104 shown schematically as Type A in Figure 13 in which the (rotational and translational) displacement of adjacent molecular planes to produce a symmetric sandwich configuration is prohibited by the interaction of neighboring molecules. These crystals exhibit a structured ( molecular ) fluorescence spectrum red-shifted by 100 cm-1 from the molecular spectrum observed in dilute solutions. 

The infrared active v (CH2), v (CH2), 8 (CH2), and yr (CH2) fundamentals can be readily assigned as a result of the extensive spectroscopic studies on hydrocarbons which have been undertaken [Sheppard and Simpson (795)]. In addition, because of the polarized radiation studies on single crystals of normal paraffins [Krimm (95)], it is possible to assign uniquely the components of the doublets found in the spectrum for these bands to symmetry species. Similarly, the Raman active va(CH. ), vs(CH2), (CHg), v+ (0), and v+ (n) fundamentals can be unambiguously assigned, the latter two on the basis of normal vibration calculations... 

The largest application segment for filter photometers is in the area of combustion gases analysis, primarily for CO, CO2, hydrocarbons, SO2, etc. Other major areas of application include the petrochemical industry, with natural gas and other hydrocarbon process gas streams being important applications. As measurements become more complex, there is the need for more advanced instrumentation. Variable or tunable filter solutions (as described above) or full-spectrum FTIR or NIR instruments are normally considered for these applications, primarily in terms of overall versatility. Now that array-based systems are becoming available, there is a potential for an intermediate, less expensive, and more compact solution. Note that compact instrumentation tends to be environmentally more stable, and is well suited for industrial applications. 

The removal of hydrocarbon from the IRE surface can be monitored by the changes in the intensity of the intense CH2 stretching band near 2850 cm 1 in the series of time-resolved spectra recorded during the exposure of the layer to surfactant solution. The absolute intensity of this band varies somewhat from layer to layer. Normalized intensities were obtained by dividing the intensity of the band in the spectrum of the initial, dry layer by the intensity of the band in each of the time-resolved spectra. These normalized intensities are plotted versus time. Values slightly greater than 1.0 occur because of the difference in refractive index between air and water, the media "behind" the thin hydrocarbon layers in the case of the initial and time - resolved spectra, respectively. Normalized intensities in excess of 1.0 can only be detected in detergency runs where little or no removal occurs. 

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