Graham's law', known as Graham's law of effusion, was formulated by Scottish physical

chemist Thomas Graham in 1848. Graham found experimentally that the rate of effusion of a gas is
inversely proportional to the square root of the mass of its particles.
[1]
This formula can be written as:

where:
Rate1 is the rate of effusion of the first gas (volume or number of moles per unit time).
Rate2 is the rate of effusion for the second gas.
M1 is the molar mass of gas 1
M2 is the molar mass of gas 2.
Graham's law states that the rate of effusion or of diffusion of a gas is inversely
proportional to the square root of its molecular weight. Thus, if the molecular
weight of one gas is four times that of another, it would diffuse through a porous
plug or escape through a small pinhole in a vessel at half the rate of the other
(heavier gases diffuse more slowly). A complete theoretical explanation of
Graham's law was provided years later by the kinetic theory of gases. Graham's
law provides a basis for separating isotopes by diffusion a method that came
to play a crucial role in the development of the atomic bomb.
[2]

Graham's law is most accurate for molecular effusion which involves the
movement of one gas at a time through a hole. It is only approximate
for diffusion of one gas in another or in air, as these processes involve the
movement of more than one gas.
[2]

Contents
[hide]
1 History
2 Example
3 See also
4 References
History[edit]
Graham's research on the diffusion of gases was triggered by his reading about
the observation of German chemist Johann Dbereiner that hydrogen gas
diffused out of a small crack in a glass bottle faster than the surrounding air
diffused in to replace it. Graham measured the rate of diffusion of gases through
plaster plugs, through very fine tubes, and through small orifices. In this way he
slowed down the process so that it could be studied quantitatively. He first
stated the law as we know it today in 1831. Graham went on to study the
diffusion of substances in solution and in the process made the discovery that
some apparent solutions actually are suspensions of particles too large to pass
through a parchment filter. He termed these materialscolloids, a term that has
come to denote an important class of finely divided materials.
[citation needed]

At the time Graham did his work, the concept of molecular weight was being
established, in large part through measurements of gases. Italian
physicist Amedeo Avogadro had suggested in 1811 that equal volumes of
different gases contain equal numbers of molecules. Thus, the relative
molecular weights of two gases are equal to the ratio of weights of equal
volumes of the gases. Avogadro's insight together with other studies of gas
behaviour provided a basis for later theoretical work by Scottish physicist James
Clerk Maxwell to explain the properties of gases as collections of small particles
moving through largely empty space.
[citation needed]

Perhaps the greatest success of the kinetic theory of gases, as it came to be
called, was the discovery that for gases, the temperature as measured on
the Kelvin (absolute) temperature scale is directly proportional to the average
kinetic energy of the gas molecules. The kinetic energy of any object is equal to
one-half its mass times the square of its velocity. Thus, to have equal kinetic
energies, the velocities of two different molecules would have to be in inverse
proportion to the square roots of their masses. The rate of effusion is
determined by the number of molecules entering an aperture per unit time, and
hence by the average molecular velocity. Graham's law for diffusion could thus
be understood as a consequence of the molecular kinetic energies being equal
at the same temperature.
[citation needed]

Example[edit]
Let gas 1 be H2 and gas 2 be O2.

Therefore, hydrogen molecules effuse four times faster than those of
oxygen.
[1]

Graham's Law can also be used to find the approximate molecular weight of
a gas if one gas is a known species, and if there is a specific ratio between
the rates of two gases (such as in the previous example). The equation can
be solved for the unknown molecular weight.

Graham's law was the basis for separating
235
U from
238
U found in
natural uraninite (uranium ore) during the Manhattan project to build the
first atomic bomb. The United States government built a gaseous
diffusion plant at the then phenomenal cost of $100 million in Clinton,
Tennessee. In this plant, uranium from uranium ore was first converted
to uranium hexafluoride and then forced repeatedly to diffuse through
porous barriers, each time becoming a little more enriched in the
slightly lighter
235
U isotope.
[2]

Diffusion and osmosis are related concepts, which involve movement of materials
from areas of high concentration to areas of low concentration. Diffusion involves
movement of any chemical from one place to another; osmosis refers to movement of
water across a membrane. Only water can undergo osmosis.

The rate of diffusion depends on the molecular weight of the chemical.
In this demonstration, the blue dye, methylene blue, has
a higher molecular weight than the compound potassium
permanganate. Smaller, lighter molecules diffuse faster
than larger, heavier ones, and the potassium
permanganate solution (on the right) has diffused further
from the well than the methylene blue (on the left).







The rate of diffusion depends on the characteristics of the medium through
which the substance diffuses.
Crystals of potassium permanganate were placed in distilled
water (left) and on an agar gel (right). The agar gel is still
about 98% water, but the gel forms a crisscrossing network
of carbohydrate that the potassium permanganate ions must
work through. Since the ions must move up, down, forward,
and even backwards to diffuse, it takes much longer for
them to move away from the source.







The rate of diffusion through a membrane depends on the characteristics of the
membrane and of the materials.
In this demonstration, we put starch inside a dialysis bag, and an
iodine solution outside it. The dialysis bag is made of a membrane that
prevents molecules with molecular weights of more than about 10,000
from passing through. Starch, with a molecular weight in the
100,000's, can't pass through the membrane and remains inside the
bag. Iodine, with a molecular weight of less than 100, can pass
through the bag, and reacts with the starch inside to turn purple.
Dialysis tubing is an example of a semipermeable membrane, because
only small molecules can get through it. Other membranes are
selectively permeable because they can restrict passage to specific
molecules.









Osmosis is the diffusion of water across a membrane.
In this demonstration, we put dialysis bags of either water or a sucrose solution into
beakers that contain either water or the sucrose solution:
1. 1. water in water
2. 2. water in sucrose
3. 3. sucrose in water
4. 4. sucrose in sucrose
If we consider distilled water to be 100% water, and the sucrose solution to be 90%
water and 10% sucrose, then we can see that there is a concentration difference
between water and sucrose in beakers 2 and 3, but that there is no concentration
difference in beakers 1 and 4. We should see no net movement of water or sucrose in
beakers 1 and 4, but we should see a net movement of water iout of the dialysis bag in
beaker 2, and into the bag in beaker 3. Osmosis will occur in beakers 2 and 3.
We can also refer to the relative concentrations of water and sucrose in the solutions
as hypotonic, isotonic, and hypertonic. In a hypotonic solution, the concentration of
solute (sucrose, in this demonstration) is lower than in the solution you are comparing
it to. So in beaker 2, the water in the dialysis bag is hypotonic to the sucrose solution
in the beaker. In a hypertonic solution, the concentration of solute (sucrose, in this
case) is higher than in the solution you are comparing it to. So in beaker 2, the sucrose
solution in the beaker is hypertonic to the water in the dialysis bag. In beaker 4, the
solution inside the bag has the same solute concentration as the solution in the beaker.
The solutions are isotonic. Now, for practice, describe the relationships of the
solutions in beakers 1 and 3. Check your answer.