ASSIGNMENT NO.

ABDUL AHAD KHAN

30th of July, 2020

—
Dyestuff Engineering
—
Dr. Gulzar Ahmad Baig
 : ASSIGNMENT TOPICS :
1. WHAT IS LAMBERT’S LAW?
2. DERIVE MATHEMATICAL EXPRESSION FOR LAMBERT’S LAW.

Lambert’s Law
 “When a beam of light is allowed to pass through a
transparent medium, the rate of decrease of intensity with
the thickness of medium is directly proportional to the
intensity of light.”

Basically, Pierre Bouger discovered the law in 1729 and published it in

Essai D'Optique Sur La Gradation De La Lumière. Johann Lambert quoted
Bouger's discovery in his Photometria in 1760, saying the absorbance of a
sample is directly proportional to the path length of light.
Even though Lambert didn't claim discovery, he was often credited with it.
August Beer discovered a related law in 1852. Beer's Law stated that the
absorbance is proportional to the concentration of the sample. Technically,
Beer's Law relates only to concentration, while the Beer-Lambert Law
relates absorbance to both concentration and sample thickness.
Lambert law was stated by Johann Heinrich Lambert which states that
absorbance and path length are directly proportional.
Lambert invented the first practical hygrometer. In 1760, he published a
book on photometry, the Photometria.
In Photometria Lambert also formulated the law of light absorption (the
Beer–Lambert law) and introduced the term albedo. Lambertian reflectance
is named after Johann Heinrich Lambert, who introduced the concept of
perfect diffusion in his 1760 book Photometria. He wrote a classic work on
perspective and contributed to geometrical optics.

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From the assumption that light travels in straight lines, he showed that
illumination was proportional to the strength of the source, inversely
proportional to the square of the distance of the illuminated surface and the
sine of the angle of inclination of the light's direction to that of the surface.
These results were supported by experiments involving the visual
comparison of illuminations and used for the calculation of illumination.
The non-SI unit of luminance, Lambert, is named in recognition of his work
in establishing the study of photometry.
Mathematically, the Lambert’s law may be expressed as follows.
- dI / dt  α I
-dI / dt = KI          . . . . . . . . . .(1)
Where I = intensity of incident light
         t = thickness of the medium
  K= proportionality constant
By integration of equation (1), and putting I=I0 when t=0,
I0/ It = kt    or    It= I0 e-kt
Where, I0 = intensity of incident light
          It  = intensity of transmitted light
           k = constant which depends upon wavelength and absorbing medium
used.
By changing the above equation from natural log, we get,
                     It = I0 e-Kt          . . . . . . . . . .(2)
Where K = k/ 2.303
           So,     It = I0 e-0.4343 kt   
                    It = I010-Kt          . . . . . . . . . .(3)

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Absorption of energy causes the absorption of light as well usually by
electrons. Different forms of light such as visible light and ultraviolet light get
absorbed in this process. Therefore, change in the intensity of light due to
absorption, interference, and scattering leads to:
ΔI = I0 – IT
The following equations are necessary for us to obtain our ultimate
derivative equation. Transmittance is measured as the ratio of light passing
through a substance. It can be calculated as IT/I0. To calculate the of
transmittance percentage we can do so by:

Percent Transmittance Another key metric is absorbance that is defined as

the amount of light absorbed. This is usually calculated as the negative of
transmittance and is given by:

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Absorbance (A) The rate of decrease in the intensity of light with the
thickness of the material the light is directly proportional to the intensity of
the incident light. Mathematically, it can be expressed as:

As k’= Proportionality constant

Taking in the reciprocal of the equation we get,

Integrating the above equation we also get,

In the above equation, b and C is the constant of integration and IT is the

intensity being transmitted at the thickness
In order to solve the above equation with the constant of integration, we
then get,

While solving for C in the equation will give us,

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Converting to log10 we get,

Rearranging the equation we get, 

Thus, Lambert’s law was formed and it states that the monochromatic
radiation changes exponentially and decreases when it passes through a
medium of uniform thickness.

Also, the Beer’s Law is important. Without it the Lambert Law is not
explained properly and hence the Beer-Lambert law finds application in real
life.
Lambert's law stated that the loss of light intensity when it propagates in
a medium is directly proportional to intensity and path length.
Beer's law stated that the transmittance of a solution remains constant if
the product of concentration and path length stays constant.
Thus, this concludes the derivation of Beer-Lambert law. This goes to
show that in order to derive a particular law, there are a lot of different
equations that need to be found out first, to achieve the ultimate result.

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 Beer-Lambert Law Statement

The Beer-Lambert law states that:

“for a given material sample path length and concentration of the sample
are directly proportional to the absorbance of the light.”

The Beer-Lambert law is expressed as:

A = εLc 

where,

 A is the amount of light absorbed for a particular wavelength by the

sample
 ε is the molar extinction coefficient
 L is the distance covered by the light through the solution
 c is the concentration of the absorbing species
Following is an equation to solve for molar extinction coefficient:

ϵ=ALc
But Beer-Lambert law is a combination of two different laws: Beer’s law and
Lambert law.

Beer-Lambert Law Formula

I=I0e−μ(x)
Where,

 I is the intensity
 I0 is the initial intensity
 x is the depth in meters
 𝜇 is the coefficient of absorption

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Calculating the absorbance of a sample using the equation depends on two
assumptions:

1. The absorbance is directly proportional to the path length of the

sample (the width of the cuvette).
2. The absorbance is directly proportional to the concentration of the
sample.

Derivation of the Beer-Lambert law

The Beer-Lambert law can be derived from an approximation for the
absorption coefficient for a molecule by approximating the molecule by an
opaque disk whose cross-sectional area,  , represents the effective area seen
by a photon of frequency w. If the frequency of the light is far from
resonance, the area is approximately 0, and if w is close to resonance the
area is a maximum. Taking an infinitesimal slab, of sample:

Io is the intensity entering the sample at z=0, Iz is the intensity entering the
infinitesimal slab at z, dI is the intensity absorbed in the slab, and I is the
intensity of light leaving the sample. Then, the total opaque area on the slab

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due to the absorbers is   * N * A * dz. Then, the fraction of photons
absorbed will be   * N * A * dz / A so,

dI / Iz = -   * N * dz

Integrating this equation from z = 0 to z = b gives:

ln(I) - ln(Io) = -   * N * b

or - ln(I / Io) =   * N * b.

Since N (molecules/cm3) * (1 mole / 6.023x1023 molecules) * 1000 cm3 / liter

= c (moles/liter) and 2.303 * log(x) = ln(x) then

- log(I / Io) =   * (6.023x1020 / 2.303) * c * b

- log(I / Io) = A =   * b * c

where   =   * (6.023x1020 / 2.303) =   * 2.61x1020

Typical cross-sections and molar absorptivities are:

          absorption      (cm2)         (M-1 cm-1)     
atoms       10-12           3x108 
             molecules   10-16           3x104 
             infrared    10-19           3x10 
Raman scattering   10-29           3x10-9

Limitations of the Beer-Lambert law

The linearity of the Beer-Lambert law is limited by chemical and
instrumental factors. Causes of nonlinearity include:
 deviations in absorptivity coefficients at high concentrations
(>0.01M) due to electrostatic interactions between molecules in close
proximity
 scattering of light due to particulates in the sample
 fluoresecence or phosphorescence of the sample

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  changes in refractive index at high analyte concentration
 shifts in chemical equilibria as a function of concentration
 non-monochromatic radiation, deviations can be minimized by using a
relatively flat part of the absorption spectrum such as the maximum of
an absorption band
 stray light

Beer-Lambert Law Applications

This law finds applications in various fields such as:
 Analytical chemistry: This analysis mainly concentrates on the
separation, quantification and identification of matter by
spectrophotometry. There is no involvement of extensive pre-
processing of the sample to get the results. For example, bilirubin
count in a blood sample can be determined by using a
spectrophotometer.
 In atmosphere: Solar or stellar radiation in the atmosphere can be
described using this law. The law in atmospheric applications has a
modified equation:

Where,
a: aerosols
g: mixed gases
RS: Raman scattering effects
NO2: Nitrogen dioxide
w: water vapour absorption

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 O3: Ozone
r: Rayleigh scattering

REFERENCES

 https://byjus.com/physics/beer-lambert-law/
 https://en.wikipedia.org/wiki/Johann_Heinrich_Lambert#:~:text=La
mbert%20invented%20the%20first%20practical
%20hygrometer.&text=In%20Photometria%20Lambert%20also
%20formulated,in%20his%201760%20book%20Photometria.
 https://www.pharmatutor.org/pharma-analysis/analytical-aspects-of-
uv-visible-spectroscopy/beer-lambert-law.html
 http://life.nthu.edu.tw/~labcjw/BioPhyChem/Spectroscopy/beerslaw.
htm
 https://www.thoughtco.com/beers-law-definition-and-equation-
608172

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