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Absorption Spectroscopy

Absorption Spectroscopy

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Absorption spectroscopy
From Wikipedia, the free encyclopedia
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Absorption spectroscopy
refers tospectroscopictechniques that measure the absorptionof radiation, as a function of frequency or wavelength, due to its interaction with asample. The sample absorbs energy, i.e., photons, from the radiating field. The intensityof the absorption varies as a function of frequency, and this variation is theabsorptionspectrum. Absorption spectroscopy is performed across theelectromagnetic spectrum. Absorption spectroscopy is employed as ananalytical chemistry tool to determine the  presence of a particular substance in a sample and, in many cases, to quantify the amountof the substance present.Infraredandultraviolet-visible spectroscopyare particularly common in analytical applications. Absorption spectroscopy is also employed in studiesof molecular and atomic physics, astronomical spectroscopy and remote sensing.There are a wide range of experimental approaches to measuring absorption spectra. Themost common arrangement is to direct a generated beam of radiation at a sample anddetect the intensity of the radiation that passes through it. The transmitted energy can beused to calculate the absorption. The source, sample arrangement and detection techniquevary significantly depending on the frequency range and the purpose of the experiment.
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[edit] Basic Theory
 
More technically,
absorption spectroscopy is based on the absorption of photons byone or more substances present in a sample, which can be asolid, liquid, or  gas, and subsequent promotion of electron(s) from oneenergy level to another in that substance.  Note that the sample can be a pure, homogeneous substance or a complex mixture. Thefrequency at which the incident photon is absorbed is determined by the difference in theavailable energy levels of the different substances present in the sample; it is theselectivity of absorbance spectroscopy - the ability to generate photon(light) sources thatare absorbed by only some of the components in a sample - that gives absorbancespectroscopy much of its utility. Typically, X-rays are used to reveal chemicalcomposition, and near ultravioletto near  infraredwavelengths are used to distinguish the configurations of variousisomersin detail. In absorption spectroscopy the absorbed photons are not re-emitted (as in fluorescence) rather, theenergythat is transferred to the chemical compound upon absorbance of a photon is lost by non-radiative means, such astransfer of energy asheat to other molecules. While the relative intensity of the absorption lines do not vary with concentration, at anygiven frequency the measured absorbance (
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) has been shown to be proportional to themolar  concentration of the absorbing species and the thickness of the sample the light passes through. This is known as theBeer-Lambert law. The plot of amount of radiation absorbed versus frequency for a particular compound is referred to astheabsorption 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 energylevels of the sample, some of the incident photons are absorbed, resulting in a drop in themeasured transmission intensity and a corresponding dip in the spectrum. The absorptionspectrum can be measured using aspectrometer  and by knowing the shape of the spectrum,the optical path length and the amount of radiationabsorbed, one can determine the structure and concentration of the compound.
[edit] Relation To Emission Spectroscopy
Emissionis a process by which a substance releases energy in the form of electromagnetic radiation. Emission can occur at any frequency at which absorption canoccur, and this allows the absorption lines to be determined from an emission spectrum.Theemission 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 andadditional information about the quantum mechanical states of the substance.
[edit] Relation To Scattering and Reflection Spectroscopy
The scattering and reflection spectra of a material are influenced by both itsindex of refractionand its absorption spectrum. In an optical context, the absorption spectrum istypically quantified by theextinction coefficient, and the extinction and indexcoefficients are quantitatively related through theKramers-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 absorptionspectrum is an approximation.
[edit] Applications
[edit] Analytical Chemistry
Absorption spectroscopy is useful in chemical analysis because of its specificity and itsquantitative nature. The specificity of absorption spectra allows compounds to bedistinguished from one another in a mixture. For example, absorption spectroscopy isused to identify the presence of pollutants in the air, distinguishing the pollutant from thenitrogen, oxygen, water and the other expected constituents.
The specificity also allowsunknown 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 abouta sample even if it is not in a library. Infrared spectra, for instance, have characteristicsabsorption bands that indicate if carbon-hydrogen or carbon-oxygen bonds are present.An absorption spectrum can be quantitatively related to the amount of material presentusing the Beer-Lambert law. Determining the absolute concentration of a compoundrequires 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 thetarget.
[edit] Remote Sensing
One of the unique advantages of spectroscopy as an analytical technique is thatmeasurements can be made without bringing the instrument and sample into contact.Radiation that travels between a sample and an instrument will contain the spectralinformation, so the measurement can be maderemotely. Remote spectral sensing isvaluable in many situations. For example, measurements can be made in toxic or hazardous environments without placing an operator or instrument at risk. Also, samplematerial does not have to be brought into contact with the instrument--preventing possible cross contamination.Remote spectral measurements present several challenges compared to laboratorymeasurements. The space in between the sample of interest and the instrument may alsohave spectral absorptions. These absorptions can mask or confound the absorptionspectrum of the sample. These background interferences may also vary over time. Thesource of radiation in remote measurements is often an environmental source, such assunlight or the thermal radiation from a warm object, and this makes it necessary todistinguish spectral absorption from changes in the source spectrum.
[edit] Astronomy

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