Visible-ultraviolet spectroscopy solvent

Table 7.9 Electronic Absorption Bands for Representative Chromophores Table 7.10 Ultraviolet Cutoffs of Spectrograde Solvents Table 7.11 Absorption Wavelength of Dienes Table 7.12 Absorption Wavelength of Enones and Dienones Table 7.13 Solvent Correction for Ultraviolet-Visible Spectroscopy Table 7.14 Primary Bands of Substituted Benzene and Heteroaromatics Table 7.15 Wavelength Calculation of the Principal Band of Substituted Benzene Derivatives...

TABLE 7.13 Solvent Correction for Ultraviolet-Visible Spectroscopy... 

The tautomerism of 4 (Figure 1) was also studied by UV-Vis (ultraviolet-visible) spectroscopy in polar aprotic solvents the effect of added water, darkness, and indirect sunlight were also evaluated. The experimental spectroscopic results are discussed in Section 13.14.3.1.1 (i). Theoretical calculations using ZINDO/S were performed to state the allowed absorption transitions <2005SAA875>. The five tautomeric structures of 4 as well as the calculated energies for each are depicted in Figure 2. 

Chatteijee, P., Bagchi, S., "Study of Preferential Solvation in Mixed Binary Solvents by Ultraviolet-Visible Spectroscopy," J. Chem. Soc. Farad. 

Several spectroscopic techniques, namely, Ultraviolet-Visible Spectroscopy (UV-Vis), Infrared (IR), Nuclear Magnetic Resonance (NMR), etc., have been used for understanding the mechanism of solvent-extraction processes and identification of extracted species. Berthon et al. reviewed the use of NMR techniques in solvent-extraction studies for monoamides, malonamides, picolinamides, and TBP (116, 117). NMR spectroscopy was used as a tool to identify the structural parameters that control selectivity and efficiency of extraction of metal ions. 13C NMR relaxation-time data were used to determine the distances between the carbon atoms of the monoamide ligands and the actinides centers. The II, 2H, and 13C NMR spectra analysis of the solvent organic phases indicated malonamide dimer formation at low concentrations. However, at higher ligand concentrations, micelle formation was observed. NMR studies were also used to understand nitric acid extraction mechanisms. Before obtaining conformational information from 13C relaxation times, the stoichiometries of the... 

A solvent for ultraviolet/visible spectroscopy must be transparent in the region of the spectrum where the solute absorbs and should dissolve a sufficient quantity of the sample to give a well-defined analyte spectrum. In addition, we must consider possible interactions of the solvent with the absorbing species. For example, polar solvents, such as water, alcohols, esters, and ketones, tend to obliterate vibration spectra and should thus be avoided to preserve spectral detail. Nonpolar solvents, such as cyclohexane, often provide spectra that more closely approach that of a gas (compare, for example, the three spectra in Figure 24-14). In addition, the polarity of the solvent often influences the position of absorption maxima. For qualitative analysis, it is therefore important to compare analyte spectra with spectra of known compounds measured in the same solvent. 

NMR is not, of course, the only analytical technique used to establish the composition and microstructure of polymeric materials. Others include >66 ultraviolet-visible spectroscopy (UV-Vis), Raman spectroscopy, and infrared (IR) spectroscopy. IR and Raman spectroscopy are particularly useful, when by virtue of cross-linking (see. e.g. Chapter 9), or the presence of rigid aromatic units (see Chapter 4). the material neither melts nor dissolves in any solvent suitable for NMR. The development of microscopy based on these spectroscopic methods now makes such analysis relatively simple (see below). Space precludes a detailed account of these and many other techniques familiar to the organic chemist. Instead we focus for the remainder of the chapter on some of the techniques used to characterize the physical properties of polymeric materials. 

In view of the unusual mechanism of anionic polymerization, especially the absence of termination and chain transfer reactions, the kinetics of these systems can be treated quite differently than for the other mechanisms. Thus it is possible, by suitable experimental techniques, to examine separately the rates of the initiation and propagation reactions [172,173], since the stable organometallic chain ends are present in concentrations [10 -10 M] which are easily measured by ultraviolet-visible spectroscopy [174]. The propagation reaction is, of course, of considerable main interest and can be studied by making sure that initiation is complete. In this way, the kinetics of homogeneous anionic polymerization have been extensively elucidated with special reference to the nature of counterion and role of the solvent. 

The preceding empirical measures have taken chemical reactions as model processes. Now we consider a different class of model process, namely, a transition from one energy level to another within a molecule. The various forms of spectroscopy allow us to observe these transitions thus, electronic transitions give rise to ultraviolet—visible absorption spectra and fluorescence spectra. Because of solute-solvent interactions, the electronic energy levels of a solute are influenced by the solvent in which it is dissolved therefore, the absorption and fluorescence spectra contain information about the solute-solvent interactions. A change in electronic absorption spectrum caused by a change in the solvent is called solvatochromism. 

There have been relatively little ultraviolet-visible (UV-Vis) spectroscopic data for 1,4-oxazines, but selected data are presented in Table 8. UV spectroscopy is important for photochromic compounds, such as spirooxazines. The UV spectra of 33 spirooxazines in five different solvents are collected in a review <2002RCR893>, and the more recently reported examples of photochromic oxazines 65, 66, 101, and 102 are shown here. It can be seen from Table 8 that both adding methoxy substituents to the oxazine and changing to a more polar solvent give a UV maximum at a higher wavelength. This solvent effect can also be seen in the case of 102, which also has important fluorescence properties, discussed in Section 8.06.12.2. 

Nuclear magnetic resonance (NMR) spectroscopy is a method of absorption spectroscopy that has some characteristics similar to ultraviolet and visible spectroscopy but also some that are unique. In NMR, a molecular sample, usually dissolved in a liquid solvent, is placed in a magnetic field... 

Spectroscopic properties. The techniques of optical spectroscopy (ultraviolet, visible, and infrared spectrophotometry) are often used to examine the reactants or products of an electrode reaction. Obviously the solvent (and supporting electrolyte) must be transparent at the wavelength region of interest all of the commonly used dipolar aprotic solvents are transparent in the visible region. However, those solvents that contain aromatic or conjugated unsatu-... 

Solvents used in ultraviolet, visible, infrared, microwave, and radiowave spectroscopy must meet the following requirements transparency and stability toward the radiation used, solubility and chemical stability of the substance to be examined, and a high and reproducible purity ( optical constancy ). Normally, intermolecular interaction with the solute should be minimal. On the other hand, important information about the solute can be obtained from the changes in the absorption spectrum arising from such interactions. 

Using matched cuvettes for solvent and analyte is seldom practical for infrared measurements because it is difficult to obtain cells with identical transmission characteristics. Part of this difficulty results from degradation of the transparency of infrared cell windows (typically polished sodium chloride) with use due to attack by traces of moisture in the atmosphere and in samples. In addition, pathlengths are hard to reproduce because infrared cells are often less than 1 mm thick. Such narrow cells are required to permit the transmission of measurable intensities of infrared radiation through pure samples or through very concentrated solutions of the analyte. Measurements on dilute analyte solutions, as is done in ultraviolet or visible spectroscopy, are usually difficult because there are few good solvents that transmit over appreciable regions of the infrared spectrum. 

The biochemist is quite familiar with ultraviolet and visible spectroscopy, in which a compound is frequently dissolved in an aqueous solution, a good spectrum is obtained, and quantitative analysis can be readily applied. In the case of infrared spectroscopy a common method of obtaining a spectrum is to dissolve the sample in an appropriate solvent, place the solution in a suitable cell, and record the spectrum. Certainly the solvent must have reasonable transparency to infrared radiation in the region to be used. This method is used widely in qualitative analysis, and is the most commonly used method in quantitative analysis. 

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