Absorption spectroscopy

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Jump to: navigation, search Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum. Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet-visible spectroscopy are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing. There are a wide range of experimental approaches to measuring absorption spectra. The most common arrangement is to direct a generated beam of radiation at a sample and detect the intensity of the radiation that passes through it. The transmitted energy can be used to calculate the absorption. The source, sample arrangement and detection technique vary significantly depending on the frequency range and the purpose of the experiment.

Contents

1 Basic Theory 2 Absorption spectrum o 2.1 Relation To Emission Spectrum o 2.2 Relation To Scattering and Reflection Spectra 3 Applications o 3.1 Analytical Chemistry o 3.2 Remote Sensing o 3.3 Astronomy o 3.4 Atomic and Molecular Physics 4 Experimental Methods o 4.1 Basic Approach o 4.2 Specific Approaches 5 See also 6 External links 7 References

[edit] Basic Theory

More technically,[1][2] absorption spectroscopy is based on the absorption of photons by one or more substances present in a sample, which can be a solid, liquid, or gas, and subsequent promotion of electrons from one energy level to another in that substance. Note that the sample can be a pure, homogeneous substance or a complex mixture. The frequency at which the incident photon is absorbed is determined by the difference in the available energy levels of the different substances present in the sample; it is the selectivity of absorbance spectroscopy - the ability to generate photon (light) sources that are absorbed by only some of the components in a sample - that gives absorbance spectroscopy much of its utility. Typically, X-rays are used to reveal chemical composition, and near ultraviolet to near infrared wavelengths are used to distinguish the configurations of various isomers in detail. In absorption spectroscopy the absorbed photons are not re-emitted (as in fluorescence) rather, the energy that is transferred to the chemical compound upon absorbance of a photon is lost by non-radiative means, such as transfer of energy as heat to other molecules. While the relative intensity of the absorption lines do not vary with concentration, at any given frequency the measured absorbance ( log(I / I0)) has been shown to be proportional to the molar concentration of the absorbing species and the thickness of the sample the light passes through. This is known as the Beer-Lambert law. The plot of amount of radiation absorbed versus frequency for a particular compound is referred to as the absorption spectrum. The normalized absorption spectrum is characteristic for a particular compound, does not change with varying concentration and is like the chemical "fingerprint" of the compound. At frequencies corresponding to the resonant energy levels of the sample, some of the incident photons are absorbed, resulting in a drop in the measured transmission intensity and a corresponding dip in the spectrum. The absorption spectrum can be measured using a spectrometer and by knowing the shape of the spectrum ,the optical path length and the amount of radiation absorbed, one can determine the structure and concentration of the compound.

[edit] Absorption spectrum

A material's absorption spectrum shows the fraction of incident electromagnetic radiation absorbed by the material over a range of frequencies. Atoms, for example, have absorption lines at wavelengths corresponding to the differences between the energy levels of its atomic orbitals. Each chemical element has a distinct absorption spectrum. Absorption spectra can therefore be used to identify the elements present in a gas or liquid. This method is used in deducing the presence of elements in stars and other gaseous objects which cannot be measured directly. The complete absorption spectrum of a material will depend not only on the atoms present but also how they are combined into molecules, how those molecules are packed together and the environment the material is in (e.g., temperature, pressure, electromagnetic fields and other materials present).

Absorption spectrum observed by the Hubble Space Telescope

[edit] Relation To Emission Spectrum

Emission is a process by which a substance releases energy in the form of electromagnetic radiation. Emission can occur at any frequency at which absorption can occur, and this allows the absorption lines to be determined from an emission spectrum. The emission spectrum will typically have a quite different intensity pattern from the absorption spectrum, though, so the two are not equivalent. The absorption spectrum can be calculated from the emission spectrum using appropriate theoretical models and additional information about the quantum mechanical states of the substance.

[edit] Relation To Scattering and Reflection Spectra

The scattering and reflection spectra of a material are influenced by both its index of refraction and its absorption spectrum. In an optical context, the absorption spectrum is typically quantified by the extinction coefficient, and the extinction and index coefficients are quantitatively related through the Kramers-Kronig relation. Therefore, the absorption spectrum can be derived from a scattering or reflection spectrum. This typically requires simplifying assumptions or models, and so the derived absorption spectrum is an approximation.

[edit] Applications
[edit] Analytical Chemistry

Absorption spectroscopy is useful in chemical analysis because of its specificity and its quantitative nature. The specificity of absorption spectra allows compounds to be distinguished from one another in a mixture. For example, absorption spectroscopy is used to identify the presence of pollutants in the air, distinguishing the pollutant from the nitrogen, oxygen, water and the other expected constituents.[3] The specificity also allows unknown samples to be identified by comparing a measured spectrum with a library of reference spectra. In many cases, it is possible to determine qualitative information about a sample even if it is not in a library. Infrared spectra, for instance, have characteristics absorption bands that indicate if carbon-hydrogen or carbon-oxygen bonds are present. An absorption spectrum can be quantitatively related to the amount of material present using the Beer-Lambert law. Determining the absolute concentration of a compound requires knowledge of the compound's absorption coefficient. The absorption coefficient for some compounds is available from reference sources, and it can also be determined by measuring the spectrum of a calibration standard with a known concentration of the target.

[edit] Remote Sensing

One of the unique advantages of spectroscopy as an analytical technique is that measurements can be made without bringing the instrument and sample into contact. Radiation that travels between a sample and an instrument will contain the spectral information, so the measurement can be made remotely. Remote spectral sensing is valuable in many situations. For example, measurements can be made in toxic or hazardous environments without placing an operator or instrument at risk. Also, sample material does not have to be brought into contact with the instrument--preventing possible cross contamination. Remote spectral measurements present several challenges compared to laboratory measurements. The space in between the sample of interest and the instrument may also have spectral absorptions. These absorptions can mask or confound the absorption spectrum of the sample. These background interferences may also vary over time. The source of radiation in remote measurements is often an environmental source, such as sunlight or the thermal radiation from a warm object, and this makes it necessary to distinguish spectral absorption from changes in the source spectrum.

[edit] Astronomy
Astronomical spectroscopy is a particularly significant type of remote spectral sensing. In this case, the objects and samples of interest are so distant from earth that electromagnetic radiation is the only means available to measure them. Astronomical spectra contain both absorption and emission spectral information. Absorption spectroscopy has been particularly important for understanding interstellar clouds and determining that some of them contain molecules. Absorption spectroscopy is also employed in the study of extrasolar planets. Detection of extrasolar planets by the transit

method also measures their absorption spectrum and allows for the determination of the planet's atmospheric composition.

[edit] Atomic and Molecular Physics

Theoretical models, principally quantum mechanical models, allow for the absorption spectra of atoms and molecules to be related to other physical properties such as electronic structure, atomic or molecular mass, and molecular geometry. Therefore, measurements of the absorption spectrum are used to determine these other properties. Microwave spectroscopy, for example, allows for the determination of bond lengths and angles with high precision. In addition, spectral measurements can be used to determine the accuracy of theoretical predictions. For example, the Lamb shift measured in the hydrogen atomic absorption spectrum was not expected to exist at the time it was measured. Its discovery spurred and guided the development of quantum electrodynamics, and measurements of the Lamb shift are now used to determine the fine-structure constant.

[edit] Experimental Methods

[edit] Basic Approach
The most straight-forward approach to absorption spectroscopy is to generate radiation with a source, measure a reference spectrum of that radiation with a detector and then remeasure the sample spectrum after placing the material of interest in between the source and detector. The two measured spectra can then be combined to determine the material's absorption spectrum. The sample spectrum alone is not sufficient to determine the absorption spectrum because it will be affected by the experimental conditions--the spectrum of the source, the absorption spectra of other materials in between the source and detector and the wavelength dependent characteristics of the detector. The reference spectrum will be affected in the same way, though, by these experimental conditions and therefore the combination yields the absorption spectrum of the material alone. A wide variety of radiation sources are employed in order to cover the electromagnetic spectrum. For spectroscopy, it is generally desirable for a source to cover a broad swath of wavelengths in order to measure a broad region of the absorption spectrum. Some sources inherently emit a broad spectrum. Examples of these include globars or other black body sources in the infrared, mercury lamps in the visible and ultraviolet and x-ray tubes. One recently developed, novel source of broad spectrum radiation is synchotron radiation which covers all of these spectral regions. Other radiation sources generate a narrow spectrum but the emission wavelength can be tuned to cover a spectral range. Examples of these include klystrons in the microwave region and lasers across the infrared, visible and ultraviolet region (though not all lasers have tunable wavelengths). The detector employed to measure the radiation power will also depend on the wavelength range of interest. Most detectors are sensitive to a fairly broad spectral range

and the sensor selected will often depend more on the sensitivity and noise requirements of a given measurement. Examples of detectors common in spectroscopy include heterodyne receivers in the microwave, bolometers in the millimeter-wave and infrared, mercury cadmium telluride and other cooled semiconductor detectors in the infrared, and photodiodes and photomultiplier tubes in the visible and ultraviolet. If both the source and the detector cover a broad spectral region, then it is also necessary to introduce a means of resolving the wavelength of the radiation in order to determine the spectrum. Often a spectrograph is used to spatially separate the wavelengths of radiation so that the power at each wavelength can be measured independently. It is also common to employ interferometry to determine the wavelength. Fourier transform infrared spectroscopy is a widely used implementation of this technique. Two other issues that must be considered in setting up an absorption spectroscopy experiment include the optics used to direct the radiation and the means of holding or containing the sample material. In both cases, it is important to select materials that have relatively little absorption of their own in the wavelength range of interest. The absorption of other materials could interfere with or mask the absorption from the sample. For instance, in several wavelength ranges it is necessary to measure the sample under vacuum or in a rare gas environment because gases in the atmosphere have interfering absorption features.

[edit] Specific Approaches

Cavity Ring Down Spectroscopy (CRDS) Mossbauer spectroscopy Photoemission spectroscopy Reflectance spectroscopy Laser Absorption Spectrometry (LAS) Tunable Diode Laser Absorption Spectroscopy (TDLAS) X-ray absorption fine structure (XAFS) X-ray Absorption Near Edge Structure (XANES) Astronomical spectroscopy

[edit] See also

Absorption (optics) Densitometry Fraunhofer lines Lyman-alpha forest Optical density Photoemission spectroscopy Spectrometer Spectroscopy Emission spectrum X-ray absorption spectroscopy

Absorption (electromagnetic radiation) HITRAN Transparent materials Water absorption

[edit] External links

Solar absorption spectrum Visible Absorption Spectrum Simulation Plot Absorption Intensity for many molecules in HITRAN database

[edit] References
1. ^ Modern Spectroscopy (Paperback) by J. Michael Hollas ISBN 0470844167 2. ^ Symmetry and Spectroscopy: An Introduction to Vibrational and Electronic Spectroscopy (Paperback) by Daniel C. Harris, Michael D. Bertolucci ISBN 048666144X 3. ^ "Gaseous Pollutants - Fourier Transform Infrared Spectroscopy". http://www.epa.gov/apti/course422/ce4b4.html. Retrieved 2009-09-30. Retrieved from "http://en.wikipedia.org/wiki/Absorption_spectroscopy" Categories: Scientific techniques | Analytical chemistry | Spectroscopy | Electromagnetic radiation | Astrochemistry
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