Visible radiation, absorption

The depth of vertical mixing may also be directly affected by increased UVR. In many systems (particularly fresh waters), the major component responsible for determining UVR penetration, chromophoric dissolved organic matter (CDOM), is also the primary absorber of visible radiation. Absorption of solar radiation by CDOM results in near-surface heating and shallow stratification [10,11]. However, CDOM absorbance is not constant, due to photobleaching by UVR [12]. As CDOM bleaches, there is deeper penetration of solar radiation and less pronounced surface heating, allowing deeper mixed layers to develop ([13] also see Chapters 3 and 6). 

IR radiation is not energetic enough to bring about the kinds of electronic transitions that we have encountered in our di.scussions of ultraviolet and visible radiation. Absorption of IR radiation is thus confined largely to molecular species that have small energy differences between various vibrational and rotational states. 

In absorption spectroscopy a beam of electromagnetic radiation passes through a sample. Much of the radiation is transmitted without a loss in intensity. At selected frequencies, however, the radiation s intensity is attenuated. This process of attenuation is called absorption. Two general requirements must be met if an analyte is to absorb electromagnetic radiation. The first requirement is that there must be a mechanism by which the radiation s electric field or magnetic field interacts with the analyte. For ultraviolet and visible radiation, this interaction involves the electronic energy of valence electrons. A chemical bond s vibrational energy is altered by the absorbance of infrared radiation. A more detailed treatment of this interaction, and its importance in deter-... 

Energy level diagram showing difference between the absorption of Infrared radiation (left) and ultravlolet-visible radiation (right). 

The determination of an analyte s concentration based on its absorption of ultraviolet or visible radiation is one of the most frequently encountered quantitative analytical methods. One reason for its popularity is that many organic and inorganic compounds have strong absorption bands in the UV/Vis region of the electromagnetic spectrum. In addition, analytes that do not absorb UV/Vis radiation, or that absorb such radiation only weakly, frequently can be chemically coupled to a species that does. For example, nonabsorbing solutions of Pb + can be reacted with dithizone to form the red Pb-dithizonate complex. An additional advantage to UV/Vis absorption is that in most cases it is relatively easy to adjust experimental and instrumental conditions so that Beer s law is obeyed. 

Spectroscopic techniques based on the absorption of UV or visible radiation depend on the excitation of an electron from one quantum state to another. References in physical and/or analytical chemistry should be consulted for additional details, but the present summary is sufficient for our purposes ... 

Reagents which form a derivative that strongly absorbs UV/visible radiation are called chromatags an example is the reagent ninhydrin, commonly used to obtain derivatives of amino acids which show absorption at about 570 nm. Derivatisation for fluorescence detectors is based on the reaction of non-fluorescent reagent molecules (fluorotags) with solutes to form fluorescent... 

The function of the detector in hplc is to monitor the mobile phase emerging from the column. The output of the detector is an electrical signal that is proportional to some property of the mobile phase and/or the solutes. Refractive index, for example, is a property of both the solutes and the mobile phase. A detector that measures such a property is called a bulk property detector. Alternatively, if the property is possessed essentially by the solute, such as absorption of uv/visible radiation or electrochemical activity, the detector is called a solute property detector. Quite a large number of devices, some of them rather complicated and tempremental, have been used as hplc detectors, but only a few have become generally useful, and we will examine five such types. Before doing this, it is helpful to have an idea of the sort of characteristics that are required of a detector. 

The absorption of UV or visible radiation corresponds to the excitation of outer electrons. There are three types of electronic transition which can be considered ... 

Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy (Figure 4). The spectrum of a molecule containing these chromophores is complex. This is because the superposition of rotational and vibrational transitions on the electronic transitions gives a combination of overlapping lines. This appears as a continuous absorption band. 

From comparison of the data presented in Table 2.2 [8], it is obvious that the energy of the microwave photon at a frequency of 2.45 GHz (0.0016 eV) is too low to cleave molecular bonds and is also lower than Brownian motion. It is therefore clear that microwaves cannot induce chemical reactions by direct absorption of electromagnetic energy, as opposed to ultraviolet and visible radiation (photochemistry). 

The ideal HPLC detector should have the same characteristics as those required for GC detectors, i.e. rapid and reproducible response to solutes, a wide range of linear response, high sensitivity and stability of operation. No truly universal HPLC detector has yet been developed but the two most widely applicable types are those based on the absorption of UV or visible radiation by the solute species and those which monitor refractive index differences between solutes dissolved in the mobile phase and the pure mobile phase. Other detectors which are more selective in their response rely on such solute properties as fluorescence, electrical conductivity, diffusion currents (amperometric) and radioactivity. The characteristics of the various types of detector are summarized in Table 4.14. 

Although this example, at face value, looks to be a case of the use of the absorption of UV/visible radiation to determine the concentration of a single ionic species (the Cu2+ ion) in solution, and, therefore, the province of the previous chapter, it is, in fact, the quantification of a molecular absorption band. In a sulfate solution, the copper ion actually exists, not as a bare ion, but as the pentaquo species, in which the central copper ion is surrounded by five water molecules and a sulfate ion in an octahedral structure (Fig. 4.1). The color of the transition metal ions arises directly from the interaction between the outer d orbital electrons of the transition metal and the electric field created by the presence of these co-ordinating molecules (called ligands). Without the aquation... 

Further details of the theory and application of Raman spectroscopy in polymer studies can be found elsewhere (1. 9). However, vibrational frequencies of functional groups in polymers can be characterized from the spacing of the Raman lines and thus information complementary to IR absorption spectroscopy can be obtained. In addition, since visible radiation is used the technique can be applied to aqueous media in contrast to IR spectroscopy, allowing studies of synthetic polyelectrolytes and biopolymers to be undertaken. Conformation and crystallinity of polymers have also been shown to influence the Raman spectra Q.) while the possibility of studying scattering from small sample volumes in the focussed laser beam (-100 pm diameter) can provide information on localized changes in chemical structure. 

Energy changes upon absorption of UV/visible radiation resulting in fluorescence. 

Being black, this atmospheric carbon is a strong absorber of visible radiation. The specific mass absorption coefficient, bap, has been measured to be in the... 

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