Você está na página 1de 2

Absorption Spectra

An absorption spectrum is a plot of absorbance versus wavelength.

Figure 1: http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/UVVis/spectrum.htm The colour of a solution is related to its absorption spectrum. Atomic absorption When a beam of polychromatic ultraviolet or visible radiation passes through a medium containing gaseous atoms, only a few frequencies are attenuated by absorption. In spectroscopy, to attenuate means to decrease the energy per unit area of a beam of radiation. In terms of the photon model, to attenuate means to decrease the number of photons per second in the beam. When recorded on a very high resolution spectrometer, the spectrum consists of a number of very narrow absorption lines. Transitions between two different orbitals are termed electronic transitions. Atomic absorption spectra are not ordinarily recorded because of instrumental difficulties. Instead, atomic absorption is measured at a single wavelength using a very narrow, near monochromatic source. Molecular absorption Molecules undergo three different types of quantized transitions when excited by ultraviolet, visible, and infrared radiation.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

For UV and IR radiation, excitation involves promotion of an electron residing in a low-energy molecular or atomic orbital to a higher energy orbital. The energy h of the photon must be exactly the same as the energy difference between the two orbital energies. Molecules also exhibit two other types of radiation-induced transitions: 1. Vibrational transitions 2. Rotational transitions Vibrational transitions occur because a molecule has a multitude of quantized energy levels (or vibrational states) associated with the bonds that hold the molecule together. An electronic transition involves transfer of an electron from one orbital to another. Both atoms (atomic orbitals) and molecules (molecular orbitals) can undergo this type of transition. Infrared absorption Infrared radiation generally is not sufficiently energetic to cause electronic transitions, but it can induce transitions in the vibrational and rotational states associated with the ground electronic state of the molecule. Absorption of Ultraviolet and Visible radiation Molecular absorption in the ultraviolet and visible regions consists of absorption bands made up of closely spaced lines. In a solution, the absorbing species are surrounded by solvent and the band nature of the molecular absorption often becomes blurred because collisions tend to spread the energies of the quantum states, giving smooth and continuous absorption peaks. In the gas phase, the individual molecules are sufficiently separated from one another to vibrate and rotate freely, so many individual absorption peaks resulting from transitions among the various vibrational and rotational states appear in the spectrum. In the liquid state and in solution, however, the molecules are unable to rotate freely, so we see no fine structure in the spectrum.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

Você também pode gostar