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Beer–Lambert law

The Beer–Lambert law is commonly applied to chemical analysis measurements to determine the concentration of chemical species that absorb light. It is often referred to as Beer's law. In physics, the Bouguer–Lambert law is an empirical law which relates the extinction or attenuation of light to the properties of the material through which the light is travelling. It had its first use in astronomical extinction. The fundamental law of extinction (the process is linear in the intensity of radiation and amount of radiatively active matter, provided that the physical state is held constant) is sometimes called the Beer–Bouguer–Lambert law or the Bouguer–Beer–Lambert law or merely the extinction law. The extinction law is also used in understanding attenuation in physical optics, for photons, neutrons, or rarefied gases. In mathematical physics, this law arises as a solution of the BGK equation.

History edit

Bouguer–Lambert law: This law is based on observations made by Pierre Bouguer before 1729.[1] It is often attributed to Johann Heinrich Lambert, who cited Bouguer's Essai d'optique sur la gradation de la lumière (Claude Jombert, Paris, 1729) – and even quoted from it – in his Photometria in 1760.[2] Lambert expressed the law, which states that the loss of light intensity when it propagates in a medium is directly proportional to intensity and path length, in the mathematical form used today.

Lambert began by assuming that the intensity I of light traveling into an absorbing body would be given by the differential equation:   which is compatible with Bouguer's observations. The constant of proportionality μ was often termed the "optical density" of the body. Integrating to find the intensity at a distance d into the body, one obtains:   For a homogeneous medium, this reduces to:   from which follows the exponential attenuation law:  [3]

Beer's law: Much later, in 1852, the German scientist August Beer studied another attenuation relation. In the introduction to his classic paper,[4] he wrote: "The absorption of light during the irradiation of a colored substance has often been the object of experiment; but attention has always been directed to the relative diminution of the various colors or, in the case of crystalline bodies, the relation between the absorption and the direction of polarization. Concerning the absolute magnitude of the absorption that a particular ray of light suffers during its propagation through an absorbing medium, there is no information available." By studying absorption of red light in colored aqueous solutions of various salts, he concluded that "the transmittance of a concentrated solution can be derived from a measurement of the transmittance of a dilute solution". It is clear that he understood the exponential relationship, as he wrote: "If   is the coefficient (fraction) of diminution, then this coefficient (fraction) will have the value   for double this thickness." Furthermore Beer stated: "We shall take the absorption coefficient to be the coefficient giving the diminution in amplitude suffered by a light ray as it passes through a unit length of an absorbing material. We then have, according to theory, and as I have found verified by experiment,   where   is the absorption coefficient and   the length of the absorbing material traversed in the experiment." This is the relationship that might properly be called Beer's law. There is no evidence that Beer saw concentration and path length as symmetrical variables in an equation in the manner of the Beer-Lambert law.[5]

Beer–Lambert law: The modern formulation of the Beer–Lambert law combines the observations of Bouguer and Beer into the mathematical form of Lambert. It correlates the absorbance, most often expressed as the negative decadic logarithm of the transmittance, to both the concentrations of the attenuating species and the thickness of the material sample.[6] An early, possibly the first, modern formulation was given by Robert Luther and Andreas Nikolopulos in 1913.[7]

Differences between Bouguer and Beer in application areas edit

While the observations of Bouguer and Beer have a similar form in the Beer–Lambert law, their areas of observation were very different. For both experimenters, the incident beam was well collimated, with a light sensor which preferentially detected directly transmitted light.

Beer specifically looked at solutions. Solutions are homogeneous and do not scatter light (Ultraviolet, visible, Infrared) of wavelengths commonly used in analytical spectroscopy (except upon entry and exit). The attenuation of a beam of light within a solution is assumed to be only due to absorption. In order to approximate the conditions required for the Beer Lambert law to hold, often the intensity of transmitted light through a reference sample   consisting of pure solvent is measured, and compared to the intensity of light transmitted through a sample  , with the absorbance of the sample taken as:  . It is for this case that the common mathematical formulation (see below) applies:  

Bouguer looked at astronomical phenomena where the size of a detector is very small compared to the distance traveled by the light. In this case, any light that is scattered by a particle, either in the forward or backward direction, will not strike the detector. The loss of intensity to the detector will be due to both absorption and scatter. Consequently, the total loss is called attenuation (rather than absorption). A single measurement cannot separate the two, but conceptually the contribution of each can be separated in the attenuation coefficient. If   is the intensity of the light at the beginning of the travel and   is the intensity of the light detected after travel of a distance  , the fraction transmitted,  , is given by:  , where   is called an attenuation constant or coefficient. The amount of light transmitted is falling off exponentially with distance. Taking the natural logarithm in the above equation, we get:   . For scattering media, the constant is often divided into two parts,  , separating it into a scattering coefficient,  , and an absorption coefficient,  .[8]

Absorptivity, cross-sections, and units of coefficients edit

The fundamental law of extinction states[9] that the extinction process is linear in the intensity of radiation and amount of radiatively active matter, provided that the physical state is held constant. (Neither concentration or length are fundamental parameters.) There are two factors that determine the degree to which a medium containing particles will attenuate a light beam: the number of particles encountered by the light beam, and the degree to which each particle extinguishes the light.[10]

For the case of absorption (Beer), this later quantity is called the absorptivity [ ], which is defined as "the property of a body that determines the fraction of incident radiation absorbed by the body".[11] The Beer–Lambert law   uses concentration and length in order to determine the number of particles the beam encounters. For a collimated beam (directed radiation) of cross-sectional area  , the number of particles encountered over a distance   is  , where   is the Avogadro constant,   the molar concentration (in mol/m3), and   the particle cross section.

There must be a large number of particles that are uniformly distributed for this relationship to hold. In practice, the beam area is thought of as a constant, and since the fraction [ ] has the area in both the numerator and denominator, the beam area cancels in the calculation of the absorbance. The units of the absorptivity must match the units in which the sample is described. For example, if the sample is described by mass concentration (g/L) and length (cm), then the units on the absorptivity would be [ L g−1 cm−1], so that the absorbance has no units.

For the case of "extinction" (Bouguer), the sum of absorption and scatter, the terms absorption, scattering, and extinction cross-sections are often used.[12] The fraction of light extinguished by the sample may be described by the extinction cross section (fraction extinguished per particle). the number of particles in a unit distance and the distance in those units. For example: [ (fraction extinguished / particle) (# particles / meter) (# meters / sample) = fraction extinguished / sample ]

Mathematical formulations edit

A common and practical expression of the Beer–Lambert law relates the optical attenuation of a physical material containing a single attenuating species of uniform concentration to the optical path length through the sample and absorptivity of the species. This expression is:

 
where

A more general form of the Beer–Lambert law states that, for N attenuating species in the material sample,

 
or equivalently that
 
where

In the above equations, the transmittance T of material sample is related to its optical depth τ and to its absorbance A by the following definition

 
where
  •   is the radiant flux transmitted by that material sample;
  •   is the radiant flux received by that material sample.

Attenuation cross section and molar attenuation coefficient are related by

 
and number density and amount concentration by
 
 
where NA is the Avogadro constant. In case of uniform attenuation, these relations become[13]
 
or equivalently
 
 
Cases of non-uniform attenuation occur in atmospheric science applications and radiation shielding theory for instance.

The law tends to break down at very high concentrations, especially if the material is highly scattering. Absorbance within range of 0.2 to 0.5 is ideal to maintain linearity in the Beer–Lambert law. If the radiation is especially intense, nonlinear optical processes can also cause variances. The main reason, however, is that the concentration dependence is in general non-linear and Beer's law is valid only under certain conditions as shown by derivation below. For strong oscillators and at high concentrations the deviations are stronger. If the molecules are closer to each other interactions can set in. These interactions can be roughly divided into physical and chemical interactions. Physical interaction do not alter the polarizability of the molecules as long as the interaction is not so strong that light and molecular quantum state intermix (strong coupling), but cause the attenuation cross sections to be non-additive via electromagnetic coupling. Chemical interactions in contrast change the polarizability and thus absorption.

Expression with attenuation coefficient edit

The law can be expressed in terms of attenuation coefficient, but in this case is better called the Bouguer-Lambert's law. The (Napierian) attenuation coefficient   and the decadic attenuation coefficient   of a material sample are related to its number densities and amount concentrations as

 
respectively, by definition of attenuation cross section and molar attenuation coefficient. Then the law becomes
 
and
 
In case of uniform attenuation, these relations become
 
or equivalently
 

In many cases, the attenuation coefficient does not vary with  , in which case one does not have to perform an integral and can express the law as:

 
where the attenuation is usually an addition of absorption coefficient   (creation of electron-hole pairs) or scattering (for example Rayleigh scattering if the scattering centers are much smaller than the incident wavelength).[14] Also note that for some systems we can put   (1 over inelastic mean free path) in place of  .[15]

Derivation edit

Assume that a beam of light enters a material sample. Define z as an axis parallel to the direction of the beam. Divide the material sample into thin slices, perpendicular to the beam of light, with thickness dz sufficiently small that one particle in a slice cannot obscure another particle in the same slice when viewed along the z direction. The radiant flux of the light that emerges from a slice is reduced, compared to that of the light that entered, by   where μ is the (Napierian) attenuation coefficient, which yields the following first-order linear, ordinary differential equation:

 
The attenuation is caused by the photons that did not make it to the other side of the slice because of scattering or absorption. The solution to this differential equation is obtained by multiplying the integrating factor
 
throughout to obtain
 
which simplifies due to the product rule (applied backwards) to
 

Integrating both sides and solving for Φe for a material of real thickness , with the incident radiant flux upon the slice   and the transmitted radiant flux   gives

 
and finally
 

Since the decadic attenuation coefficient μ10 is related to the (Napierian) attenuation coefficient by   we also have

 

To describe the attenuation coefficient in a way independent of the number densities ni of the N attenuating species of the material sample, one introduces the attenuation cross section   σi has the dimension of an area; it expresses the likelihood of interaction between the particles of the beam and the particles of the species i in the material sample:

 

One can also use the molar attenuation coefficients   where NA is the Avogadro constant, to describe the attenuation coefficient in a way independent of the amount concentrations   of the attenuating species of the material sample:

 

Validity edit

Under certain conditions the Beer–Lambert law fails to maintain a linear relationship between attenuation and concentration of analyte.[16] These deviations are classified into three categories:

  1. Real—fundamental deviations due to the limitations of the law itself.
  2. Chemical—deviations observed due to specific chemical species of the sample which is being analyzed.
  3. Instrument—deviations which occur due to how the attenuation measurements are made.

There are at least six conditions that need to be fulfilled in order for the Beer–Lambert law to be valid. These are:

  1. The attenuators must act independently of each other.
  2. The attenuating medium must be homogeneous in the interaction volume.
  3. The attenuating medium must not scatter the radiation—no turbidity—unless this is accounted for as in DOAS.
  4. The incident radiation must consist of parallel rays, each traversing the same length in the absorbing medium.
  5. The incident radiation should preferably be monochromatic, or have at least a width that is narrower than that of the attenuating transition. Otherwise a spectrometer as detector for the power is needed instead of a photodiode which cannot discriminate between wavelengths.
  6. The incident flux must not influence the atoms or molecules; it should only act as a non-invasive probe of the species under study. In particular, this implies that the light should not cause optical saturation or optical pumping, since such effects will deplete the lower level and possibly give rise to stimulated emission.

If any of these conditions are not fulfilled, there will be deviations from the Beer–Lambert law.

Chemical analysis by spectrophotometry edit

The Beer–Lambert law can be applied to the analysis of a mixture by spectrophotometry, without the need for extensive pre-processing of the sample. An example is the determination of bilirubin in blood plasma samples. The spectrum of pure bilirubin is known, so the molar attenuation coefficient ε is known. Measurements of decadic attenuation coefficient μ10 are made at one wavelength λ that is nearly unique for bilirubin and at a second wavelength in order to correct for possible interferences. The amount concentration c is then given by

 

For a more complicated example, consider a mixture in solution containing two species at amount concentrations c1 and c2. The decadic attenuation coefficient at any wavelength λ is, given by

 

Therefore, measurements at two wavelengths yields two equations in two unknowns and will suffice to determine the amount concentrations c1 and c2 as long as the molar attenuation coefficients of the two components, ε1 and ε2 are known at both wavelengths. This two system equation can be solved using Cramer's rule. In practice it is better to use linear least squares to determine the two amount concentrations from measurements made at more than two wavelengths. Mixtures containing more than two components can be analyzed in the same way, using a minimum of N wavelengths for a mixture containing N components.

The law is used widely in infra-red spectroscopy and near-infrared spectroscopy for analysis of polymer degradation and oxidation (also in biological tissue) as well as to measure the concentration of various compounds in different food samples. The carbonyl group attenuation at about 6 micrometres can be detected quite easily, and degree of oxidation of the polymer calculated.

Application for the atmosphere edit

The Bouguer–Lambert law may be applied to describe the attenuation of solar or stellar radiation as it travels through the atmosphere. In this case, there is scattering of radiation as well as absorption. The optical depth for a slant path is τ = , where τ refers to a vertical path, m is called the relative airmass, and for a plane-parallel atmosphere it is determined as m = sec θ where θ is the zenith angle corresponding to the given path. The Bouguer-Lambert law for the atmosphere is usually written

 
where each τx is the optical depth whose subscript identifies the source of the absorption or scattering it describes:
  • a refers to aerosols (that absorb and scatter);
  • g are uniformly mixed gases (mainly carbon dioxide (CO2) and molecular oxygen (O2) which only absorb);
  • NO2 is nitrogen dioxide, mainly due to urban pollution (absorption only);
  • RS are effects due to Raman scattering in the atmosphere;
  • w is water vapour absorption;
  • O3 is ozone (absorption only);
  • r is Rayleigh scattering from molecular oxygen (O2) and nitrogen (N2) (responsible for the blue color of the sky);
  • the selection of the attenuators which have to be considered depends on the wavelength range and can include various other compounds. This can include tetraoxygen, HONO, formaldehyde, glyoxal, a series of halogen radicals and others.

m is the optical mass or airmass factor, a term approximately equal (for small and moderate values of θ) to   where θ is the observed object's zenith angle (the angle measured from the direction perpendicular to the Earth's surface at the observation site). This equation can be used to retrieve τa, the aerosol optical thickness, which is necessary for the correction of satellite images and also important in accounting for the role of aerosols in climate.

See also edit

References edit

  1. ^ Bouguer, Pierre (1729). Essai d'optique sur la gradation de la lumière [Optics essay on the attenuation of light] (in French). Paris, France: Claude Jombert. pp. 16–22.
  2. ^ Lambert, J.H. (1760). Photometria sive de mensura et gradibus luminis, colorum et umbrae [Photometry, or, On the measure and gradations of light intensity, colors, and shade] (in Latin). Augsburg, (Germany): Eberhardt Klett.
  3. ^ "Bouguer-Lambert-Beer Absorption Law - Lumipedia". www.lumipedia.org. Retrieved 2023-04-25.
  4. ^ Beer (1852). "Bestimmung der Absorption des rothen Lichts in farbigen Flüssigkeiten" [Determination of the absorption of red light in colored liquids]. Annalen der Physik und Chemie (in German). 162 (5): 78–88. Bibcode:1852AnP...162...78B. doi:10.1002/andp.18521620505.
  5. ^ Pfieffer, Heinz; Liebhafshy, Herman (1951). "The Origins of Beer's Law". Journal of Chemical Education (March, 1951): 123–125.
  6. ^ Ingle, J. D. J.; Crouch, S. R. (1988). Spectrochemical Analysis. New Jersey: Prentice Hall.
  7. ^ Mayerhöfer, Thomas G.; Pahlow, Susanne; Popp, Jürgen (2020). "The Bouguer–Beer–Lambert Law: Shining Light on the Obscure". ChemPhysChem. 21 (18): 2031. doi:10.1002/cphc.202000464. PMC 7540309. PMID 32662939.
  8. ^ Van de Hulst, H. C. (1957). Light Scattering by Small Particles. New York: John Wiley & Sons, Inc. ISBN 9780486642284.
  9. ^ Sokolik, Irina N. (2009). "The Beer–Bouguer–Lambert law. Concepts of extinction (scattering plus absorption) and emission" (PDF).
  10. ^ Dahm, Donald J. (2010). "Speaking Theoretically ... ... Things Nobody Knows but Me". NIR News. 21 (2): 14–16. doi:10.1255/nirn.1176. ISSN 0960-3360.
  11. ^ "Definition of ABSORPTIVITY". www.merriam-webster.com. Retrieved 2023-05-17.
  12. ^ Striebel, Moritz; Wrachtrup, Jӧrg; Gerhardt, Ilja (2017-11-13). "Absorption and Extinction Cross Sections and Photon Streamlines in the Optical Near-field". Scientific Reports. 7 (1): 15420. doi:10.1038/s41598-017-15528-w. ISSN 2045-2322. PMC 5684246. PMID 29133925.
  13. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Beer–Lambert law". doi:10.1351/goldbook.B00626
  14. ^ Fox, Mark (2010). Optical Properties of Solids (2 ed.). Oxford University Press. p. 3. ISBN 978-0199573370.
  15. ^ Attard, Gary; Barnes, Colin (1998). Surfaces. Oxford Chemistry Primers. p. 26. ISBN 978-0198556862.
  16. ^ Oshina, Ilze; Spigulis, Janis (2021-10-28). "Beer–Lambert law for optical tissue diagnostics: current state of the art and the main limitations". Journal of Biomedical Optics. 26 (10): 100901. doi:10.1117/1.JBO.26.10.100901. ISSN 1083-3668. PMC 8553265. PMID 34713647.

External links edit

  • Beer–Lambert Law Calculator
  • Beer–Lambert Law Simpler Explanation

beer, lambert, this, article, needs, additional, citations, verification, please, help, improve, this, article, adding, citations, reliable, sources, unsourced, material, challenged, removed, find, sources, news, newspapers, books, scholar, jstor, february, 20. This article needs additional citations for verification Please help improve this article by adding citations to reliable sources Unsourced material may be challenged and removed Find sources Beer Lambert law news newspapers books scholar JSTOR February 2008 Learn how and when to remove this message The Beer Lambert law is commonly applied to chemical analysis measurements to determine the concentration of chemical species that absorb light It is often referred to as Beer s law In physics the Bouguer Lambert law is an empirical law which relates the extinction or attenuation of light to the properties of the material through which the light is travelling It had its first use in astronomical extinction The fundamental law of extinction the process is linear in the intensity of radiation and amount of radiatively active matter provided that the physical state is held constant is sometimes called the Beer Bouguer Lambert law or the Bouguer Beer Lambert law or merely the extinction law The extinction law is also used in understanding attenuation in physical optics for photons neutrons or rarefied gases In mathematical physics this law arises as a solution of the BGK equation Contents 1 History 1 1 Differences between Bouguer and Beer in application areas 2 Absorptivity cross sections and units of coefficients 3 Mathematical formulations 3 1 Expression with attenuation coefficient 4 Derivation 5 Validity 6 Chemical analysis by spectrophotometry 7 Application for the atmosphere 8 See also 9 References 10 External linksHistory editBouguer Lambert law This law is based on observations made by Pierre Bouguer before 1729 1 It is often attributed to Johann Heinrich Lambert who cited Bouguer s Essai d optique sur la gradation de la lumiere Claude Jombert Paris 1729 and even quoted from it in his Photometria in 1760 2 Lambert expressed the law which states that the loss of light intensity when it propagates in a medium is directly proportional to intensity and path length in the mathematical form used today Lambert began by assuming that the intensity I of light traveling into an absorbing body would be given by the differential equation d I m I d x displaystyle mathrm d I mu I mathrm d x nbsp which is compatible with Bouguer s observations The constant of proportionality m was often termed the optical density of the body Integrating to find the intensity at a distance d into the body one obtains ln I 0 I 0 d m d x textstyle ln I 0 I int 0 d mu mathrm d x nbsp For a homogeneous medium this reduces to ln I 0 I m d displaystyle ln I 0 I mu d nbsp from which follows the exponential attenuation law I I 0 e m d displaystyle I I 0 e mu d nbsp 3 Beer s law Much later in 1852 the German scientist August Beer studied another attenuation relation In the introduction to his classic paper 4 he wrote The absorption of light during the irradiation of a colored substance has often been the object of experiment but attention has always been directed to the relative diminution of the various colors or in the case of crystalline bodies the relation between the absorption and the direction of polarization Concerning the absolute magnitude of the absorption that a particular ray of light suffers during its propagation through an absorbing medium there is no information available By studying absorption of red light in colored aqueous solutions of various salts he concluded that the transmittance of a concentrated solution can be derived from a measurement of the transmittance of a dilute solution It is clear that he understood the exponential relationship as he wrote If l displaystyle lambda nbsp is the coefficient fraction of diminution then this coefficient fraction will have the value l 2 displaystyle lambda 2 nbsp for double this thickness Furthermore Beer stated We shall take the absorption coefficient to be the coefficient giving the diminution in amplitude suffered by a light ray as it passes through a unit length of an absorbing material We then have according to theory and as I have found verified by experiment l m D displaystyle lambda mu D nbsp where m displaystyle mu nbsp is the absorption coefficient and D displaystyle D nbsp the length of the absorbing material traversed in the experiment This is the relationship that might properly be called Beer s law There is no evidence that Beer saw concentration and path length as symmetrical variables in an equation in the manner of the Beer Lambert law 5 Beer Lambert law The modern formulation of the Beer Lambert law combines the observations of Bouguer and Beer into the mathematical form of Lambert It correlates the absorbance most often expressed as the negative decadic logarithm of the transmittance to both the concentrations of the attenuating species and the thickness of the material sample 6 An early possibly the first modern formulation was given by Robert Luther and Andreas Nikolopulos in 1913 7 Differences between Bouguer and Beer in application areas edit While the observations of Bouguer and Beer have a similar form in the Beer Lambert law their areas of observation were very different For both experimenters the incident beam was well collimated with a light sensor which preferentially detected directly transmitted light Beer specifically looked at solutions Solutions are homogeneous and do not scatter light Ultraviolet visible Infrared of wavelengths commonly used in analytical spectroscopy except upon entry and exit The attenuation of a beam of light within a solution is assumed to be only due to absorption In order to approximate the conditions required for the Beer Lambert law to hold often the intensity of transmitted light through a reference sample I R displaystyle I R nbsp consisting of pure solvent is measured and compared to the intensity of light transmitted through a sample I S displaystyle I S nbsp with the absorbance of the sample taken as log 10 I R I S displaystyle log 10 bigl I R I S big nbsp It is for this case that the common mathematical formulation see below applies log 10 I R I S A e ℓ c displaystyle log 10 I R I S A varepsilon ell c nbsp Bouguer looked at astronomical phenomena where the size of a detector is very small compared to the distance traveled by the light In this case any light that is scattered by a particle either in the forward or backward direction will not strike the detector The loss of intensity to the detector will be due to both absorption and scatter Consequently the total loss is called attenuation rather than absorption A single measurement cannot separate the two but conceptually the contribution of each can be separated in the attenuation coefficient If I 0 displaystyle I 0 nbsp is the intensity of the light at the beginning of the travel and I d displaystyle I d nbsp is the intensity of the light detected after travel of a distance d displaystyle d nbsp the fraction transmitted T displaystyle T nbsp is given by T I d I 0 exp m d displaystyle T frac I d I 0 exp mu d nbsp where m displaystyle mu nbsp is called an attenuation constant or coefficient The amount of light transmitted is falling off exponentially with distance Taking the natural logarithm in the above equation we get ln T ln I 0 I d m d displaystyle ln T ln frac I 0 I d mu d nbsp For scattering media the constant is often divided into two parts m m s m a displaystyle mu mu s mu a nbsp separating it into a scattering coefficient m s displaystyle mu s nbsp and an absorption coefficient m a displaystyle mu a nbsp 8 Absorptivity cross sections and units of coefficients editThe fundamental law of extinction states 9 that the extinction process is linear in the intensity of radiation and amount of radiatively active matter provided that the physical state is held constant Neither concentration or length are fundamental parameters There are two factors that determine the degree to which a medium containing particles will attenuate a light beam the number of particles encountered by the light beam and the degree to which each particle extinguishes the light 10 For the case of absorption Beer this later quantity is called the absorptivity ϵ displaystyle epsilon nbsp which is defined as the property of a body that determines the fraction of incident radiation absorbed by the body 11 The Beer Lambert law log 10 I 0 I A ϵ ℓ c displaystyle log 10 I 0 I A epsilon ell c nbsp uses concentration and length in order to determine the number of particles the beam encounters For a collimated beam directed radiation of cross sectional area S displaystyle S nbsp the number of particles encountered over a distance ℓ displaystyle ell nbsp is N A c s ℓ S displaystyle N mathrm A c sigma ell S nbsp where N A displaystyle N mathrm A nbsp is the Avogadro constant c displaystyle c nbsp the molar concentration in mol m3 and s displaystyle sigma nbsp the particle cross section There must be a large number of particles that are uniformly distributed for this relationship to hold In practice the beam area is thought of as a constant and since the fraction I I 0 displaystyle I I 0 nbsp has the area in both the numerator and denominator the beam area cancels in the calculation of the absorbance The units of the absorptivity must match the units in which the sample is described For example if the sample is described by mass concentration g L and length cm then the units on the absorptivity would be L g 1 cm 1 so that the absorbance has no units For the case of extinction Bouguer the sum of absorption and scatter the terms absorption scattering and extinction cross sections are often used 12 The fraction of light extinguished by the sample may be described by the extinction cross section fraction extinguished per particle the number of particles in a unit distance and the distance in those units For example fraction extinguished particle particles meter meters sample fraction extinguished sample Mathematical formulations editA common and practical expression of the Beer Lambert law relates the optical attenuation of a physical material containing a single attenuating species of uniform concentration to the optical path length through the sample and absorptivity of the species This expression is log 10 I 0 I A e ℓ c displaystyle log 10 I 0 I A varepsilon ell c nbsp where A is the absorbance e is the molar attenuation coefficient or absorptivity of the attenuating species ℓ is the optical path length c is the concentration of the attenuating species A more general form of the Beer Lambert law states that for N attenuating species in the material sample T exp i 1 N s i 0 ℓ n i z d z 10 i 1 N e i 0 ℓ c i z d z displaystyle begin aligned T amp exp left sum i 1 N sigma i int 0 ell n i z mathrm d z right 4pt amp 10 wedge left sum i 1 N varepsilon i int 0 ell c i z mathrm d z right end aligned nbsp or equivalently thatt i 1 N t i i 1 N s i 0 ℓ n i z d z A i 1 N A i i 1 N e i 0 ℓ c i z d z displaystyle begin aligned tau amp sum i 1 N tau i sum i 1 N sigma i int 0 ell n i z mathrm d z 4pt A amp sum i 1 N A i sum i 1 N varepsilon i int 0 ell c i z mathrm d z end aligned nbsp where si is the attenuation cross section of the attenuating species i in the material sample ni is the number density of the attenuating species i in the material sample ei is the molar attenuation coefficient or absorptivity of the attenuating species i in the material sample ci is the amount concentration of the attenuating species i in the material sample ℓ is the path length of the beam of light through the material sample In the above equations the transmittance T of material sample is related to its optical depth t and to its absorbance A by the following definitionT F e t F e i e t 10 A displaystyle T frac Phi mathrm e mathrm t Phi mathrm e mathrm i e tau 10 A nbsp where F e t displaystyle mathrm Phi e t nbsp is the radiant flux transmitted by that material sample F e i displaystyle mathrm Phi e i nbsp is the radiant flux received by that material sample Attenuation cross section and molar attenuation coefficient are related bye i N A ln 10 s i displaystyle varepsilon i frac mathrm N A ln 10 sigma i nbsp and number density and amount concentration byt ℓ i 1 N s i n i A ℓ i 1 N e i c i displaystyle begin aligned tau amp ell sum i 1 N sigma i n i 4pt A amp ell sum i 1 N varepsilon i c i end aligned nbsp c i n i N A displaystyle c i frac n i mathrm N A nbsp where NA is the Avogadro constant In case of uniform attenuation these relations become 13 T exp ℓ i 1 N s i n i 10 ℓ i 1 N e i c i displaystyle begin aligned T amp exp left ell sum i 1 N sigma i n i right 4pt amp 10 wedge left ell sum i 1 N varepsilon i c i right end aligned nbsp or equivalentlyt ℓ i 1 N s i n i A ℓ i 1 N e i c i displaystyle begin aligned tau amp ell sum i 1 N sigma i n i 4pt A amp ell sum i 1 N varepsilon i c i end aligned nbsp t ℓ i 1 N s i n i A ℓ i 1 N e i c i displaystyle begin aligned tau amp ell sum i 1 N sigma i n i 4pt A amp ell sum i 1 N varepsilon i c i end aligned nbsp Cases of non uniform attenuation occur in atmospheric science applications and radiation shielding theory for instance The law tends to break down at very high concentrations especially if the material is highly scattering Absorbance within range of 0 2 to 0 5 is ideal to maintain linearity in the Beer Lambert law If the radiation is especially intense nonlinear optical processes can also cause variances The main reason however is that the concentration dependence is in general non linear and Beer s law is valid only under certain conditions as shown by derivation below For strong oscillators and at high concentrations the deviations are stronger If the molecules are closer to each other interactions can set in These interactions can be roughly divided into physical and chemical interactions Physical interaction do not alter the polarizability of the molecules as long as the interaction is not so strong that light and molecular quantum state intermix strong coupling but cause the attenuation cross sections to be non additive via electromagnetic coupling Chemical interactions in contrast change the polarizability and thus absorption Expression with attenuation coefficient edit The law can be expressed in terms of attenuation coefficient but in this case is better called the Bouguer Lambert s law The Napierian attenuation coefficient m displaystyle mu nbsp and the decadic attenuation coefficient m 10 m ln 10 displaystyle mu 10 tfrac mu ln 10 nbsp of a material sample are related to its number densities and amount concentrations asm z i 1 N m i z i 1 N s i n i z m 10 z i 1 N m 10 i z i 1 N e i c i z displaystyle begin aligned mu z amp sum i 1 N mu i z sum i 1 N sigma i n i z 4pt mu 10 z amp sum i 1 N mu 10 i z sum i 1 N varepsilon i c i z end aligned nbsp respectively by definition of attenuation cross section and molar attenuation coefficient Then the law becomesT exp 0 ℓ m z d z 10 0 ℓ m 10 z d z displaystyle begin aligned T amp exp left int 0 ell mu z mathrm d z right 4pt amp 10 wedge left int 0 ell mu 10 z mathrm d z right end aligned nbsp andt 0 ℓ m z d z A 0 ℓ m 10 z d z displaystyle begin aligned tau amp int 0 ell mu z mathrm d z 4pt A amp int 0 ell mu 10 z mathrm d z end aligned nbsp In case of uniform attenuation these relations becomeT e m ℓ 10 m 10 ℓ displaystyle T e mu ell 10 mu 10 ell nbsp or equivalentlyt m ℓ A m 10 ℓ displaystyle begin aligned tau amp mu ell 4pt A amp mu 10 ell end aligned nbsp In many cases the attenuation coefficient does not vary with z displaystyle z nbsp in which case one does not have to perform an integral and can express the law as I z I 0 e m z displaystyle I z I 0 e mu z nbsp where the attenuation is usually an addition of absorption coefficient a displaystyle alpha nbsp creation of electron hole pairs or scattering for example Rayleigh scattering if the scattering centers are much smaller than the incident wavelength 14 Also note that for some systems we can put 1 l displaystyle 1 lambda nbsp 1 over inelastic mean free path in place of m displaystyle mu nbsp 15 Derivation editAssume that a beam of light enters a material sample Define z as an axis parallel to the direction of the beam Divide the material sample into thin slices perpendicular to the beam of light with thickness dz sufficiently small that one particle in a slice cannot obscure another particle in the same slice when viewed along the z direction The radiant flux of the light that emerges from a slice is reduced compared to that of the light that entered by d F e z m z F e z d z displaystyle mathrm d Phi e z mu z Phi mathrm e z mathrm d z nbsp where m is the Napierian attenuation coefficient which yields the following first order linear ordinary differential equation d F e z d z m z F e z displaystyle frac mathrm d Phi mathrm e z mathrm d z mu z Phi mathrm e z nbsp The attenuation is caused by the photons that did not make it to the other side of the slice because of scattering or absorption The solution to this differential equation is obtained by multiplying the integrating factorexp 0 z m z d z displaystyle exp left int 0 z mu z mathrm d z right nbsp throughout to obtaind F e z d z exp 0 z m z d z m z F e z exp 0 z m z d z 0 displaystyle frac mathrm d Phi mathrm e z mathrm d z exp left int 0 z mu z mathrm d z right mu z Phi mathrm e z exp left int 0 z mu z mathrm d z right 0 nbsp which simplifies due to the product rule applied backwards tod d z F e z exp 0 z m z d z 0 displaystyle frac mathrm d mathrm d z left Phi mathrm e z exp left int 0 z mu z mathrm d z right right 0 nbsp Integrating both sides and solving for Fe for a material of real thickness ℓ with the incident radiant flux upon the slice F e i F e 0 displaystyle mathrm Phi e i mathrm Phi e 0 nbsp and the transmitted radiant flux F e t F e ℓ displaystyle mathrm Phi e t mathrm Phi e ell nbsp givesF e t F e i exp 0 ℓ m z d z displaystyle mathrm Phi e t mathrm Phi e i exp left int 0 ell mu z mathrm d z right nbsp and finallyT F e t F e i exp 0 ℓ m z d z displaystyle T mathrm frac Phi e t Phi e i exp left int 0 ell mu z mathrm d z right nbsp Since the decadic attenuation coefficient m10 is related to the Napierian attenuation coefficient by m 10 m ln 10 displaystyle mu 10 tfrac mu ln 10 nbsp we also haveT exp 0 ℓ ln 10 m 10 z d z 10 0 ℓ m 10 z d z displaystyle begin aligned T amp exp left int 0 ell ln 10 mu 10 z mathrm d z right 4pt amp 10 wedge left int 0 ell mu 10 z mathrm d z right end aligned nbsp To describe the attenuation coefficient in a way independent of the number densities ni of the N attenuating species of the material sample one introduces the attenuation cross section s i m i z n i z displaystyle sigma i tfrac mu i z n i z nbsp si has the dimension of an area it expresses the likelihood of interaction between the particles of the beam and the particles of the species i in the material sample T exp i 1 N s i 0 ℓ n i z d z displaystyle T exp left sum i 1 N sigma i int 0 ell n i z mathrm d z right nbsp One can also use the molar attenuation coefficients e i N A ln 10 s i displaystyle varepsilon i tfrac mathrm N A ln 10 sigma i nbsp where NA is the Avogadro constant to describe the attenuation coefficient in a way independent of the amount concentrations c i z n i z N A displaystyle c i z n i tfrac z mathrm N A nbsp of the attenuating species of the material sample T exp i 1 N ln 10 N A e i 0 ℓ n i z d z exp i 1 N e i 0 ℓ n i z N A d z ln 10 10 i 1 N e i 0 ℓ c i z d z displaystyle begin aligned T amp exp left sum i 1 N frac ln 10 mathrm N A varepsilon i int 0 ell n i z mathrm d z right 4pt amp exp left sum i 1 N varepsilon i int 0 ell frac n i z mathrm N A mathrm d z right ln 10 4pt amp 10 wedge left sum i 1 N varepsilon i int 0 ell c i z mathrm d z right end aligned nbsp Validity editUnder certain conditions the Beer Lambert law fails to maintain a linear relationship between attenuation and concentration of analyte 16 These deviations are classified into three categories Real fundamental deviations due to the limitations of the law itself Chemical deviations observed due to specific chemical species of the sample which is being analyzed Instrument deviations which occur due to how the attenuation measurements are made There are at least six conditions that need to be fulfilled in order for the Beer Lambert law to be valid These are The attenuators must act independently of each other The attenuating medium must be homogeneous in the interaction volume The attenuating medium must not scatter the radiation no turbidity unless this is accounted for as in DOAS The incident radiation must consist of parallel rays each traversing the same length in the absorbing medium The incident radiation should preferably be monochromatic or have at least a width that is narrower than that of the attenuating transition Otherwise a spectrometer as detector for the power is needed instead of a photodiode which cannot discriminate between wavelengths The incident flux must not influence the atoms or molecules it should only act as a non invasive probe of the species under study In particular this implies that the light should not cause optical saturation or optical pumping since such effects will deplete the lower level and possibly give rise to stimulated emission If any of these conditions are not fulfilled there will be deviations from the Beer Lambert law Chemical analysis by spectrophotometry editThe Beer Lambert law can be applied to the analysis of a mixture by spectrophotometry without the need for extensive pre processing of the sample An example is the determination of bilirubin in blood plasma samples The spectrum of pure bilirubin is known so the molar attenuation coefficient e is known Measurements of decadic attenuation coefficient m10 are made at one wavelength l that is nearly unique for bilirubin and at a second wavelength in order to correct for possible interferences The amount concentration c is then given byc m 10 l e l displaystyle c frac mu 10 lambda varepsilon lambda nbsp For a more complicated example consider a mixture in solution containing two species at amount concentrations c1 and c2 The decadic attenuation coefficient at any wavelength l is given bym 10 l e 1 l c 1 e 2 l c 2 displaystyle mu 10 lambda varepsilon 1 lambda c 1 varepsilon 2 lambda c 2 nbsp Therefore measurements at two wavelengths yields two equations in two unknowns and will suffice to determine the amount concentrations c1 and c2 as long as the molar attenuation coefficients of the two components e1 and e2 are known at both wavelengths This two system equation can be solved using Cramer s rule In practice it is better to use linear least squares to determine the two amount concentrations from measurements made at more than two wavelengths Mixtures containing more than two components can be analyzed in the same way using a minimum of N wavelengths for a mixture containing N components The law is used widely in infra red spectroscopy and near infrared spectroscopy for analysis of polymer degradation and oxidation also in biological tissue as well as to measure the concentration of various compounds in different food samples The carbonyl group attenuation at about 6 micrometres can be detected quite easily and degree of oxidation of the polymer calculated Application for the atmosphere editThe Bouguer Lambert law may be applied to describe the attenuation of solar or stellar radiation as it travels through the atmosphere In this case there is scattering of radiation as well as absorption The optical depth for a slant path is t mt where t refers to a vertical path m is called the relative airmass and for a plane parallel atmosphere it is determined as m sec 8 where 8 is the zenith angle corresponding to the given path The Bouguer Lambert law for the atmosphere is usually writtenT exp m t a t g t R S t N O 2 t w t O 3 t r displaystyle T exp big m tau mathrm a tau mathrm g tau mathrm RS tau mathrm NO 2 tau mathrm w tau mathrm O 3 tau mathrm r cdots bigr nbsp where each tx is the optical depth whose subscript identifies the source of the absorption or scattering it describes a refers to aerosols that absorb and scatter g are uniformly mixed gases mainly carbon dioxide CO2 and molecular oxygen O2 which only absorb NO2 is nitrogen dioxide mainly due to urban pollution absorption only RS are effects due to Raman scattering in the atmosphere w is water vapour absorption O3 is ozone absorption only r is Rayleigh scattering from molecular oxygen O2 and nitrogen N2 responsible for the blue color of the sky the selection of the attenuators which have to be considered depends on the wavelength range and can include various other compounds This can include tetraoxygen HONO formaldehyde glyoxal a series of halogen radicals and others m is the optical mass or airmass factor a term approximately equal for small and moderate values of 8 to 1 cos 8 displaystyle tfrac 1 cos theta nbsp where 8 is the observed object s zenith angle the angle measured from the direction perpendicular to the Earth s surface at the observation site This equation can be used to retrieve ta the aerosol optical thickness which is necessary for the correction of satellite images and also important in accounting for the role of aerosols in climate See also editApplied spectroscopy Atomic absorption spectroscopy Absorption spectroscopy Cavity ring down spectroscopy Clausius Mossotti relation Infra red spectroscopy Job plot Laser absorption spectrometry Lorentz Lorenz relation Logarithm Polymer degradation Scientific laws named after people Quantification of nucleic acids Tunable diode laser absorption spectroscopy Transmittance Beer Lambert lawReferences edit Bouguer Pierre 1729 Essai d optique sur la gradation de la lumiere Optics essay on the attenuation of light in French Paris France Claude Jombert pp 16 22 Lambert J H 1760 Photometria sive de mensura et gradibus luminis colorum et umbrae Photometry or On the measure and gradations of light intensity colors and shade in Latin Augsburg Germany Eberhardt Klett Bouguer Lambert Beer Absorption Law Lumipedia www lumipedia org Retrieved 2023 04 25 Beer 1852 Bestimmung der Absorption des rothen Lichts in farbigen Flussigkeiten Determination of the absorption of red light in colored liquids Annalen der Physik und Chemie in German 162 5 78 88 Bibcode 1852AnP 162 78B doi 10 1002 andp 18521620505 Pfieffer Heinz Liebhafshy Herman 1951 The Origins of Beer s Law Journal of Chemical Education March 1951 123 125 Ingle J D J Crouch S R 1988 Spectrochemical Analysis New Jersey Prentice Hall Mayerhofer Thomas G Pahlow Susanne Popp Jurgen 2020 The Bouguer Beer Lambert Law Shining Light on the Obscure ChemPhysChem 21 18 2031 doi 10 1002 cphc 202000464 PMC 7540309 PMID 32662939 Van de Hulst H C 1957 Light Scattering by Small Particles New York John Wiley amp Sons Inc ISBN 9780486642284 Sokolik Irina N 2009 The Beer Bouguer Lambert law Concepts of extinction scattering plus absorption and emission PDF Dahm Donald J 2010 Speaking Theoretically Things Nobody Knows but Me NIR News 21 2 14 16 doi 10 1255 nirn 1176 ISSN 0960 3360 Definition of ABSORPTIVITY www merriam webster com Retrieved 2023 05 17 Striebel Moritz Wrachtrup Jӧrg Gerhardt Ilja 2017 11 13 Absorption and Extinction Cross Sections and Photon Streamlines in the Optical Near field Scientific Reports 7 1 15420 doi 10 1038 s41598 017 15528 w ISSN 2045 2322 PMC 5684246 PMID 29133925 IUPAC Compendium of Chemical Terminology 2nd ed the Gold Book 1997 Online corrected version 2006 Beer Lambert law doi 10 1351 goldbook B00626 Fox Mark 2010 Optical Properties of Solids 2 ed Oxford University Press p 3 ISBN 978 0199573370 Attard Gary Barnes Colin 1998 Surfaces Oxford Chemistry Primers p 26 ISBN 978 0198556862 Oshina Ilze Spigulis Janis 2021 10 28 Beer Lambert law for optical tissue diagnostics current state of the art and the main limitations Journal of Biomedical Optics 26 10 100901 doi 10 1117 1 JBO 26 10 100901 ISSN 1083 3668 PMC 8553265 PMID 34713647 External links editBeer Lambert Law Calculator Beer Lambert Law Simpler Explanation Retrieved from https en wikipedia org w index php title Beer Lambert law amp oldid 1220721311, wikipedia, wiki, book, books, library,

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