Lambert Beer Law

History
 The law was discovered by Pierre Bouguer before 1729.[5] 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.[6] Much later,
August Beer extended the exponential absorption law in 1852 to include
the concentration of solutions in the absorption coefficient.[7]

Qualitative generic formula

T= I1/Io  100% T= I1/Io x 100 %

where 0 and are the intensity (or power) of the incident light and the
transmitted light
whereas for solution

Absorption of light by a sample

Quanitatively, for liquids these relations are usually written as:

T= transmission (or transmissivity), α= absorption coefficient , Α=

absorbance, ℓ =the distance the light travels through the material , ε= molar
absorptivity (extinction coefficient), c= molar concentration .
whereas for gases

σ is cross section of light absorption by a single particle and N is the density

(number per unit volume) of absorbing particles.

The base 10 and base e conventions must not be confused because they give
different values for the absorption coefficient: . However, it is easy to
convert one to the other, using

The transmission (or transmissivity) is expressed in terms of an absorbance

which, for liquids, is defined as

whereas, for gases, it is usually defined as

This implies that the absorbance becomes linear with the concentration (or
number density of absorbers) according to

And
for the two cases, respectively.

Note that the Law is not

obeyed at high
concentrations. This
deviation from the Law is
not dealt with here.

 Thus, if the path length and the molar absorptivity (or the absorption
cross section) are known and the absorbance is measured, the
concentration of the substance (or the number density of absorbers) can
be deduced.
 Although several of the expressions above often are used as Beer–
Lambert law, the name should strictly speaking only be associated with
the latter two. The reason is that historically, the Lambert law states that
absorption is proportional to the light path length, whereas the Beer law
 states that absorption is proportional to the concentration of absorbing
species in the material.[1]
 If the concentration is expressed as a mole fraction i.e., a dimensionless
fraction, the molar absorptivity (ε) takes the same dimension as the
absorption coefficient, i.e., reciprocal length (e.g., m−1).
 However, if the concentration is expressed in moles per unit volume, the
molar absorptivity (ε) is used in L·mol−1·cm−1, or sometimes in converted
SI units of m2·mol−1.
 The absorption coefficient α' is one of many ways to describe the
absorption of electromagnetic waves. For the others, and their
interrelationships, see the article: Mathematical descriptions of opacity.
For example, α' can be expressed in terms of the imaginary part of the
refractive index, κ, and the wavelength of the light (in free space), λ0,
according to

 In molecular absorption spectrometry, the absorption cross section σ is

expressed in terms of a linestrength, S, and an (area-normalized)
lineshape function, Φ.
 The frequency scale in molecular spectroscopy is often in cm−1,
wherefore the lineshape function is expressed in units of 1/cm−1, which
can look funny but is strictly correct. Since N is given as a number
density in units of 1/cm3, the linestrength is often given in units of
cm2cm−1/molecule. A typical linestrength in one of the vibrational
overtone bands of smaller molecules, e.g., around 1.5 μm in CO or CO2,
is around 10−23 cm2cm−1, although it can be larger for species with strong
transitions, e.g., C2H2. The linestrengths of various transitions can be
found in large databases, e.g., HITRAN. The lineshape function often
takes a value around a few 1/cm−1, up to around 10/cm−1 under low
pressure conditions, when the transition is Doppler broadened, and below
this under atmospheric pressure conditions, when the transition is
collision broadened. It has also become commonplace to express the
linestrength in units of cm−2/atm since then the concentration is given in
terms of a pressure in units of atm. A typical linestrength is then often in
the order of 10−3 cm−2/atm. Under these conditions, the detectability of a
given technique is often quoted in terms of ppm•m.
 The fact that there are two commensurate definitions of absorbance (in
base 10 or e) implies that the absorbance and the absorption coefficient
for the cases with gases, A' and α', are ln 10 (approximately 2.3) times as
 large as the corresponding values for liquids, i.e., A and α, respectively.
Therefore, care must be taken when interpreting data that the correct form
of the law is used.
 The law tends to break down at very high concentrations, especially if the
material is highly scattering. If the light is especially intense, nonlinear
optical processes can also cause variances. The main reason, however, is
the following. At high concentrations, the molecules are closer to each
other and begin to interact with each other. This interaction will change
several properties of the molecule, and thus will change the molar
aborbtivity. If the absorbtivity is different at higher concentrations than at
lower ones, then the plot of the absorbance will not be linear, as is
suggested by the equation, so you can only use it when all the
concentrations you are working with are low enough that the absorbtivity
is the same for all of them.

Derivation
 Classically, the Beer-Lambert law was first devised independently where
Lambert's law stated that absorbance is directly proportional to the
thickness of the sample, and Beer's law stated that absorbance is
proportional to the concentration of the sample. The modern derivation of
the Beer-Lambert law combines the two laws and correlate the
absorbance to both, the concentration as well as the thickness (path
length) of the sample.[2]

 In concept, the derivation of the Beer–Lambert law is straightforward.

Divide the absorbing sample into thin slices that are perpendicular to the
beam of light. The light that emerges from a slice is slightly less intense
than the light that entered because some of the photons have run into
 molecules in the sample and did not make it to the other side. For most
cases where measurements of absorption are needed, a vast majority of
the light entering the slice leaves without being absorbed. Because the
physical description of the problem is in terms of differences—intensity
before and after light passes through the slice—we can easily write an
ordinary differential equation model for absorption. The difference in
intensity due to the slice of absorbing material is reduced; leaving the
slice, it is a fraction of the light entering the slice . The thickness of
the slice is , which scales the amount of absorption (thin slice does not
absorb much light but a thick slice absorbs a lot). In symbols,
, or . This conceptual overview uses to
describe how much light is absorbed. All we can say about the value of
this constant is that it will be different for each material. Also, its values
should be constrained between −1 and 0. The following paragraphs cover
the meaning of this constant and the whole derivation in much greater
detail.
 Assume that particles may be described as having an absorption cross
section (i.e., area), σ, perpendicular to the path of light through a solution,
such that a photon of light is absorbed if it strikes the particle, and is
transmitted if it does not.
 Define z as an axis parallel to the direction that photons of light are
moving, and A and dz as the area and thickness (along the z axis) of a 3-
dimensional slab of space through which light is passing. We assume that
dz is sufficiently small that one particle in the slab cannot obscure another
particle in the slab when viewed along the z direction. The concentration
of particles in the slab is represented by N.
 It follows that the fraction of photons absorbed when passing through this
slab is equal to the total opaque area of the particles in the slab, σAN dz,
divided by the area of the slab A, which yields σN dz. Expressing the
number of photons absorbed by the slab as dIz, and the total number of
photons incident on the slab as Iz, the number of photons absorbed by the
slab is given by

 Note that because there are fewer photons which pass through the slab
than are incident on it, dIz is actually negative (It is proportional in
magnitude to the number of photons absorbed).

The solution to this simple differential equation is obtained by integrating both

sides to obtain Iz as a function of z
The difference of intensity for a slab of real thickness ℓ is I0 at z = 0, and Il at
z = ℓ. Using the previous equation, the difference in intensity can be written as,

rearranging and exponentiating yields,

This implies that

and

 The derivation assumes that every absorbing particle behaves

independently with respect to the light and is not affected by other
particles. Error is introduced when particles are lying along the same
optical path such that some particles are in the shadow of others. This
occurs in highly concentrated solutions. In practice, when large
absorption values are measured, dilution is required to achieve accurate
results. Measurements of absorption in the range of to 1 are
less affected by shadowing than other sources of random error. In this
range, the ODE model developed above is a good approximation;
measurements of absorption in this range are linearly related to
concentration. At higher absorbances, concentrations will be
underestimated due to this shadow effect unless one employs a more
sophisticated model that describes the non-linear relationship between
absorption and concentration.
Deviations from Beer-Lambert Law
 Under certain conditions Beer-Lambert law fails to maintain a linear
relationship between absorbance and concentration of analyte.[3] These
deviations are classified into three categories:

o Real Deviations - These are fundamental deviations due to the

limitations of the law itself.
o Chemical Deviations- These are deviations observed due to
specific chemical species of the sample which is being analyzed.
o Instrument Deviations - These are deviations which occur due to
how the absorbance measurements are made.

Prerequisites
 There are at least six conditions that need to be fulfilled in order for
Beer’s law to be valid. These are:

o The absorbers must act independently of each other;

o The absorbing medium must be homogeneous in the interaction
volume
o The absorbing medium must not scatter the radiation – no
turbidity;
o The incident radiation must consist of parallel rays, each
traversing the same length in the absorbing medium;
o The incident radiation should preferably be monochromatic, or
have at least a width that is narrower than that of the absorbing
transition; and
o 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 Beer’s
law.
Chemical analysis
 Beer's 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
absorbance is known. Measurements are made at one wavelength that is
nearly unique for bilirubin and at a second wavelength in order to correct
for possible interferences.The concentration is given by c = Acorrected / ε.
 For a more complicated example, consider a mixture in solution
containing two components at concentrations c1 and c2. The absorbance at
any wavelength, λ is, for unit path length, given by

 Therefore, measurements at two wavelengths yields two equations in two

unknowns and will suffice to determine the concentrations c1 and c2 as
long as the molar absorbances 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[disambiguation needed] to determine the two concentrations from
measurements made at more than two wavelengths. Mixtures containing
more than two components can be analysed 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). The carbonyl group absorption at about 6 micrometres
can be detected quite easily, and degree of oxidation of the polymer
calculated.

Beer–Lambert law in the atmosphere

 This law is also 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 Beer–Lambert law for
the atmosphere is usually written
 where each is the optical depth whose subscript identifies the source of
the absorption or scattering it describes:
o refers to aerosols (that absorb and scatter)
o are uniformly mixed gases (mainly carbon dioxide ( ) and
molecular oxygen ( ) which only absorb)
o is nitrogen dioxide, mainly due to urban pollution (absorption
only)
o is water vapour absorption
o is ozone (absorption only)
o is Rayleigh scattering from molecular oxygen ( ) and nitrogen (
) (responsible for the blue color of the sky).
 is the optical mass or airmass factor, a term approximately equal (for
small and moderate values of ) to , where 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 , 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.
 When the path taken by the light is through the atmosphere, the density of
the absorbing gas is not constant, so the original equation must be
modified as follows:

 where z is the distance along the path through the atmosphere, all other
symbols are as defined above.[4] This is taken into account in each in
the atmospheric equation above.