The Beer-Lambert law

Radiation from a source is passed through a monochromator,

which filters out all frequency components except one,
generating monochromatic radiaion of a single frequency . The beam is
then split into to two by a beam-splitter. One of the two rays is allowed to
pass through the a cell containing the sample whose spectrum is sought. The
other is allowed to pass through a reference cell, which is just the cell
without the sample. We'll come back to the role of the reference cell later.

Let be the intensity of radiation entering the sample, and be the

intensity of radiation emerging from the sample. The output beam with

intensity is then sent to a photodetector that measures the actual

intensity, the photosignal is then amplified and sent to a recording device,
where a final readout of the intensity at frequency is noted.

Let us first analyze what happens as the beam is sent through the sample.
Let the direction of propagation of the radiation through the sample be
the direction and let the sample extend from to on the axis.
Thus, is the intensity at . We wish to determine the
intensity as the beam passes through the sample. As it does, there will
be an attenuation of intensity due to absorption events. Remember that the
beam contains many many photons, and the sample contains many
molecules, so we are interested in a measure of the number of photons
absorbed vs. the number of photons that pass through without being
absorbed. This will give us a measure of the attenuation in the intensity,
since intensity is directly proportional to the number of photons passing
through a given area of the sample at any instant in time.

We expect the following. If is the intensity at point in the sample,

then the fractional loss of intensity when the beam passes through
a length of the sample will be proportional to the concentration of the
sample as well as :

The constant of proportionality is denoted and is called the molar

extinction coefficient:

(The reason for the prime will be clarified below.) The units of the molar
extinction coefficient are L mol m . Rearranging this as a simple first-
order differential equation gives

The solution gives us the intensity as a function of through the

sample:

Or taking the log of both sides

When , , so we can write this as

or

The common form of the Beer-Lambert law uses base 10 logarithms rather
than natural logarithms and redefines the extinction coefficient
as , which gives

The attenuation of the beam through the sample will be due to only in part to
the actual material whose spectrum is sought. There is another contribution
to the cell, itself, and whatever material it is composed of. This is where the
reference beam comes in. By observing the attenuation of the beam through
the reference cell, we can determine how much of the attenuation is due to
the cell alone. Thus, we are not interested in the ratio as much as the
ratio , where is the beam that emerges from the reference cell,
partly attenuated. For the ratio , we assign the molar extinction and
write

The quantity is called the absorbance (the

quantity is called the transmittance ). Thus, we have finally
This result is known as the Beer-Lambert law, and it is one of the
fundamental principles of molecular spectroscopy. The extinction
coefficient measures the extent to which the sample is able to absorb
radiation at a given frequency or wavelength (remember we can use
either since ). Hence, it is an intrinsic property of the material. We
will revisit the Beer-Lambert law when we cover spectroscopy in greater
detail toward the end of the semester.