Background:

Ideal Gas Law:

Pressure x Volume = Moles x Ideal Gas Constant x Temperature
Substituting in variables, the formula is:
PV=nRT
Explanation and Discussion:
The Ideal Gas Law may be the largest and most complex of the gas laws. This is in part because
of the number of variables in the equation, and in part to the abstraction of an "ideal" gas that the
law is built on. The Ideal Gas Law is also designed as a sort of umbrella for Boyle's, Charles',
and Avogadro's laws.
First, we'll go over the parts of the equation, PV=nRT. P is pressure. Pressure can be in either
atmospheres (atm) or kilopascals (kPa). V is volume in liters (L). n is the number of moles of the
gas. Because moles of a substance are determined by mass divided by molecular mass, it can
create an interesting variant we will discuss later. R is the Ideal Gas Constant. Depending on
whether atmosphers or kilospascals were used, the value is either 0.0821 L-atm/mol-K or 8.31 LkPa/mol-K, respectively. Temperature is in absolute degrees Kelvin.
An interesting aspect of the Ideal Gas Law is its flexibility. It contains elements that allow you to
solve for other quantities, such as density or molecular mass. To solve for molecular mass:
PV=nRT - start with the equation
PV=mass/mol. mass x RT - change moles to mass(m) in grams divided by molecular mass in
grams
mol. mass x PV = mRT - multiply by molecular mass
molecular mass = mRT/PV - divide by pressure and volume.
We can also see density in that last equation, m/V (grams/liter). The same equation, but with
density(d) in place of mass per volume (m/V), is:
molecular mass = dRT/P
To solve just for density, the equation would become:
density = (molecular mass x pressure)/(constant x temperature)
So far, we have been skirting the concept of an ideal gas. What exactly is an ideal gas? An ideal
gas is one that exactly conforms to the kinetic theory. The kinetic theory, as stated by Rudolf
Clausius in 1857, has five key points. These are:

1. Gases are made of molecules in constant, random movement. Gases like Argon have 1atom molecules.
2. The large portion of the volume of a gas is empty space. The volume of all gas molecules,
in comparison, is negligible.
3. The molecules show no forces of attraction or repulsion.
4. No energy is lost in collision of molecules; the impacts are completely elastic.
5. The temperature of a gas is the average kinetic energy of all of the molecules.
Non-Ideal Behavior
The Kinetic Theory makes several assumptions about an ideal gas. These cause problems
because real gases are not ideal. The main causes of error are related to pressure and temperature.
Pressure
At high pressures, the behavior of real gases changes dramatically from that predicted by the
Ideal Gas Law. Under 10 atmospheres of pressure or less, Ideal Gas Law predictions are very
close to real amounts and do not generate serious error.
Temperature
When the temperature of a gas is close to its liquefaction point, the behavior is very different
from Ideal Gas Law predictions. With increasing temperatures, the Ideal Gas Law predictions
become close to real values.
Why?
The answer is simple: ideal gases have molecular volume and show no attraction between
molecules at any distance; real gas molecules have volume and show attraction at short
distances. Let us first consider what pressure does. Pressure at high degrees will bring the
molecules very close together. This causes more collisions and also allows the weak attractive
forces to come into play. With low temperatures, the molecules do not have enough energy to
continue on their path to avoid that attraction.
The van der Waals Equation
In order to overcome the errors in the Ideal Gas Law, Johannes van der Waals developed an
equation to predict the behavior of real gases. Johannes van der Waals' equation included
corrections for the finite volume of the molecules of the gas and the attractive forces between the
molecul
es. Two new constants, a and b, were added. The corrected equation is:
P = (nRT)/(V-nb) - (n2a)/(V2)

The correction nb subtracts the volume of the molecules. b is measured in liters/mole. The
correction with a reflects the strength of attraction and is measured in liters2-atmosperes per
moles2.
The equation is generally put in the form:

Values of a and b are different for each gas. The values of a and b generally increase with
increased mass of the molecule and complexity of the molecule.

Gas Laws

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Discussion
introduction
The gas laws are a set of intuitively obvious statements to most everyone in the Western world
today. It's hard to believe that there was ever a time when they weren't understood. And yet
someone had to notice these relationships and write them down. For this reason, many students
are taught the three most important gas laws by the names of their discoverers. However, since
the laws are known by different names in different countries and (more importantly) since I can
never remember who gets credit for which law without referring to notes, I will not follow this
convention.

pressure-volume (constant temperature)

What happens to the volume of a gas as the pressure on it changes. Let's try the following
experiment using equipment that might be found in your kitchen.
Marshmallows in a kitchen vacuum pump. Do try this experiment at home. Do it!

The volume of a marshmallow increases as the pressure on it

decreases

and vice versa.

Marshmallows are a mixture of sugar, air, and gelatin. Sugar makes them sweet, air makes them
fluffy, and gelatin makes them elastic. Marshmallows are a frozen foam and are mostly air by
volume. When placed in a vacuum pump, they expand as the pressure decreases. Break the seal
on their container and they shrink during the return to normal atmospheric pressure. Since the
vacuum pump pulls on the marshmallows hard enough to burst some of the air bubbles, they are
actually a bit smaller and more shriveled at the end of this experiment. This illustrates a
fundamental, yet important, property of gases. The pressure of a gas is inversely proportional to
its volume when temperature is constant. Symbolically
P

1
V

(T constant)

or
P1V1 = P2V2 = constant
This correlation was discovered independently by Robert Boyle (1627-1691) of Ireland in 1662
and Edme Mariotte (1620-1684) of France in 1676. In Great Britain, America, Australia, the
West Indies and other remnants of the British Empire it is called Boyle's law, while in
Continental Europe and other places it is called Mariotte's law.
Mariotte added the important provision that temperature remain constant. Boyle neglected to
mention it, but the data he used to derive his law were most likely collected during a period in
which the temperature did not experience any significant change. Since the gas needs to be in
thermal equilibrium with its environment (or some other heat reservoir) to maintain an even
temperature, the pressure-volume relationship normally applies only to "slow" processes. The
marshmallow-vacuum experiment shown above is an example of a "slow" process. The pressure
is reduced at a rate slow enough that heat from the environment is able to keep the jar and its
contents at nearly room temperature. Such a transformation that takes place without a change in
temperature is said to be isothermal.
Pumping a bicycle tire with a hand pump is an example of a "fast" process. The work done
pushing the piston transforms into an increase in the internal energy (and thus an increase in the
temperature) of the air molecules within the pump. People familiar with hand bicycle pumps will
attest to the fact that they get hot after use. Likewise, when a gas is allowed to expanded into a
region of reduced pressure it does work on its surroundings. The energy to do this work comes
from the internal energy of the gas and so the temperature of the gas drops. You can experience
this yourself without the aid of any apparatus other than your mouth. Purse your lips so that your
mouth has only a tiny opening to the outside and blow hard. The air rushing from your mouth
will be quite cool despite coming from the core of your body, which is normally quite hot
(around 37 ). During a "fast" process like the ones just described, pressure and volume are
changing so rapidly that heat doesn't have enough time to get into or out of the gas to keep the
temperature constant. Such a transformation that takes place without any flow of heat is said to
be adiabatic.

volume-temperature (constant pressure)

What happens to the volume of a gas when its temperature changes? Let's try another kitchen
experiment.
Bread dough before and after baking. Do try this experiment at home. Do it!
[dough]
[bread]
Increasing the temperature of bread dough increases its volume.
Bread is made from wheat flour, water, yeast, and a bit of sugar. Yeast are tiny microorganisms.
They are quite possibly the very first domesticated animals and, much like dogs and horses, yeast
have been bred for different purposes. Just as we have guard dogs, lap dogs, and hunting dog;
draft horses, race horses, and war horses; we also have brewer's yeast, champagne yeast, and

bread yeast. Bread yeast have been selectively bred to eat sugar and burp carbon dioxide (CO2).
When wheat flour and water are mixed together and kneaded, the protein molecules are mashed
and stretched until they line up neatly to form a substance called gluten that, like chewing gum,
is both elastic and plastic. Let this special matrix sit and the the CO2 vented from the yeast get
trapped in thousands of tiny resilient, stretchy pockets. As this process continues these tiny
pockets expand, which causes the volume of the dough to expand or rise in a process called
proofing. We now have a fluffy gummy blob ready for the oven.
While there the dough expands again, but his time it's not due to the action of microorganisms
(they all die around the boiling point of water). This time it's the heat, or rather the temperature.
The temperature inside a bread oven is roughly 50% greater (in absolute terms) than the
temperature outside. And similarly, the baked bread that comes out of a bread oven is also
roughly 50% greater than the room temperature dough that goes in. This domestic example
illustrates quite nicely a fundamental property of gases. The volume of a gas is directly
proportional to its temperature when pressure is constant. Symbolically
V T (P constant)
While no doubt known and understood informally by billions of bakers since the dawn of
civilization, the precise mathematical relationship was first discovered by the French physicist
Guillaume Amontons (1663-1705) in 1699. The experiment was repeated much later by Jacques
Alexander Csare Charles (1746-1823) in 1787 and much, much later by Joseph Louis GayLussac (1778-1850) in 1802. Charles did not publish his findings, but Gay-Lussac did. It is most
frequently called Charles' law in the British sphere of influence and Gay-Lussac's law in the
French, but never Amonton's law.
An isobaric process is one that takes place without any change in pressure.
Let's recall what it means when two quantities are directly proportional like volume and
temperature. Heat up a gas and it's volume will expand. Cool it down and it's volume will
contract. The two quantities change in the same direction. More specifically, an increase in one
results in a proportional increase in the other and a decrease in one results in a proportional
decrease in the other. For example

Doubling the absolute temperature of the air in an engine cylinder will double its volume.

Halving the absolute temperature of the air in a bag of potato chips will cause it to shrink
to one half its original volume.

The absolute temperature of a bread oven is one and a half times that of room
temperature. Therefore, the loaf of baked bread that comes out of an oven has 50% more
volume than the ball of dough that went into it.

There's a symmetry at work here somewhere. A symmetry is a change in one quantity that leaves
another, more fundamental quantity unchanged. It's something like multiplying both the
numerator and denominator of a fraction by the same thing.

a
b

x
x

ax
bx

a
b

No wait, it's exactly like that. The only way two quantities can change in direct proportion is if
their ratio remains constant. Thus
V1
T1

V2
T2

= constant

pressure-temperature (constant volume)

Fix this, too.
The pressure of a gas is directly proportional to its temperature when volume is constant.
Symbolically
PT
An isochoric process is one that takes place without any change in volume.
This relationship doesn't really have a name, but I have heard it called the "pressure law" or
(mistakenly) "Gay-Lussac's law".
Temperatures drop 6 for every 1000 m of altitude.
P1
T1

P2
T2

= constant

absolute temperature
In 1703, Amontons stated ?
[magnify].
Double room temperature, 293 K = 20 , and you get 586 K = 313 not 40 .

a complete ideal gas law

Proportionality statements aren't as popular today in the Twenty first Century as they were in the
Nineteenth Century and earlier. We live in an era where it's all about the equation. There's good
and bad in this focus. Equations convey a lot of information in a very few symbols, which is why
they're so popular, but they're also a crutch; a device used to support a weak understanding and
make it seem strong. Equations can be used by a student with no understanding to fake
competency.

"I put the numbers into the equation and I got the right answer. Since I have the right answer, I
am smart."
Skilled? Certainly. Smart? Not necessarily.
Still, it would be nice to have an equation around for those times when all you want to do is just
get the job done with a minimum of hassle.
Combine the three together.
P1V1
T1

P2V2
T2

= constant

There are two ways to write the complete statement of the ideal gas law as an equation
functional thermodynamics
PV = nRT
where

statistical thermodynamics
PV = NkT

P = absolute pressure
T = absolute temperature
V = volume
and
or
n = number of moles
N = number of particles
R = gas constant = 8.315 J/mol K
k = Boltzmann's constant = 1.382 1023J/K
Mass is one of the most fundamental quantities in physics and it's difficult to get through a
physics course without getting a hang of basic mass formulas. Almost every fundamental physics
equation has mass as a variable in it because it is an inseparable quantity.
What is Mass?
Mass is an inherent property of matter in all its forms. Mass should not be confused with weight.
Weight is the force of gravity acting on a mass, whereas mass is a measure of matter content that
responds to gravity and has the property of inertia. There are two defined types of mass. One is
inertial mass and the other is gravitational mass. Inertial mass is the property of matter that offers
resistance to change by a force. Gravitational mass is the property of matter which exerts the
gravitational force. The inertial mass and gravitational mass were shown to be equal by the
Eotvos experiment. In the SI system of units, mass has the unit of 'Kilogram (Kg)'.
Formulas
There are various physics equations that can yield the value of mass. Each one of them is useful
in deriving a value of mass given certain known quantities.
Calculating Mass Using Density and Volume

When the density and volume of any substance are known, it is possible to calculate its mass. It
is made possible due to the relation between density mass and volume. The density formula,
itself provides the relation.
Mass (in Kilograms) = Density (in Kg per m3) x Volume (in m3)
Formula For Center of Mass
Center of mass is the point in a body where the whole mass can be hypothetically assumed to be
concentrated. Center of mass is a function of the individual masses of particles and their relative
positions with respect to each other. The center of mass can only be defined for rigid bodies who
have fixed positions of mass particles.
R (Center of Mass) = (m1r1 + m2r2 + m3r3. . + miri) / (m1 + m2 + m3. . + mi)
= ( miri) / ( mi)
Thus the center of mass is calculated as a ratio of individual masses weighed by position vectors
and total mass of the whole body of particles.
Formula For Molecular Mass
The atomic mass formula derives the masses of atoms in comparison to 1/12th the mass of a
carbon C12 atom. All these masses are derived experimentally. A molecule is a collection of
atoms bonded together. So the molecular mass is the sum of individual masses of atoms bonded
in it.
Molecular Mass = (Mass of an Atom x Number of Atoms)
Molar Mass Formula
Molar mass of a molecule or substance is simple the molecular weight expressed in grams. Its
unit is gm/mole.
Molar Mass = (Molecular Weight) x 1 g/mol
Formula For Mass in Newtonian Mechanics
Mass (in Kg) = Force (in Newtons) / Acceleration (Meter/s2)
So, knowing the acceleration of a body and the force acting on it, you can easily calculate its
mass.
Special Relativistic Formula
Special relativity changed the way we see the world. It demolished the notion of absolute time
which was prevalent in Newtonian mechanics and time was now known to be relative. In
mechanics, based on the special relativity, everything is dependent on the frame of reference
except the speed of light in vacuum, which remains constant. Here is the relativistic formula:

m = (m0)/((1 - v2/c2))
where m0 is rest mass of the particle, v is the velocity of the particle and c is the velocity of light.
Recently, physicists have provided a hypothesis which tries to explain how particles of matter
acquire mass. The theory says that there is a Higgs field pervading all space which interacts with
all matter. A particle acquires mass through its interaction with Higgs boson. Current
experiments at CERN's 'Large Hadron Collider (LHC)' are aimed at finding the Higgs boson.
One day we will know how matter acquires mass.
Read more at Buzzle: http://www.buzzle.com/articles/mass-formula.html

1 Counting atoms: Avogadro's number

Owing to their tiny size, atoms and molecules cannot be
counted by direct observation. But much as we do when
"counting" beans in a jar, we can estimate the number of
particles in a sample of an element or compound if we have
some idea of the volume occupied by each particle and the
volume of the container.
Once this has been done, we know the number of formula units (to use the most general term for
any combination of atoms we wish to define) in any arbitrary weight of the substance. The
number will of course depend both on the formula of the substance and on the weight of the
sample. But if we consider a weight of substance that is the same as its formula (molecular)
weight expressed in grams, we have only one number to know: Avogadro's number, 6.022141527
1023, usually designated by NA.
[image ]
Amadeo Avogadro (1766-1856) never knew his own number!
Avogadro only originated the concept of this number, whose actual value was first estimated by
Josef Loschmidt, an Austrian chemistry teacher, in 1895.
You should know it to three significant figures:
NA = 6.02 1023
6.02 1023 of what? Well, of anything you like: apples, stars in the sky, burritos. But the only
practical use for NA is to have a more convenient way of expressing the huge numbers of the tiny
particles such as atoms or molecules that we deal with in chemistry. Avogadro's number is a
collective number, just like a dozen.
Think of 6.02 1023 as the "chemist's dozen".

videos on Avogadro's Number and the mole

The basic idea (CurtisWang, 4 min) ****
The Mole Explained (utaustinchem, 9 min) ****
Simple mole calculations (bozemanscience, 5m) ****
Mole and Avogadro's number (Khan, 9 m) **
The mole concept (IsaacsTeach, 5 min) ****
Mr Causey (7 m) ***
Mole problems review (LindaHanson, 23 min) ****
Before we get into the use of Avogadro's number in problems, take a moment to convince
yourself of the reasoning embodied in the following examples.

Problem Example 1: mass ratio from atomic weights

The atomic weights of oxygen and of carbon are 16.0 and 12.0, respectively. How much heavier
is the oxygen atom in relation to carbon?
Solution: Atomic weights represent the relative masses of different kinds of atoms. This means
that the atom of oxygen has a mass that is 16/12 = 4/3 1.33 as great as the mass of a carbon
atom.

Problem Example 2: Mass of a single atom

The absolute mass of a carbon atom is 12.0 unified atomic mass units (What are these?). How
many grams will a single oxygen atom weigh?
Solution: The absolute mass of the carbon atom is 12.0 u,
or 12 1.6605 1027 g = 19.9 1027 kg. The mass of the oxygen atom will be 4/3 greater, or
2.66 1026 kg.
Alternatively: (12 g/mol) (6.022 1023 mol1) (4/3) = 2.66 1023 g.

Problem Example 3: Relative masses from atomic weights

Suppose that we have N carbon atoms, where N is a number large enough to give us a pile of
carbon atoms whose mass is 12.0 grams. How much would the same number, N, of oxygen
atoms weigh?

Solution: The collection of N oxygen atoms would have a mass of

4/3 12 g = 16.0 g.

(If the foregoing problems don't make sense, you should review the previous lesson.)
Things to understand about Avogadro's number NA
It is a number, just as is "dozen", and thus is dimensionless.
It is a huge number, far greater in magnitude than we can visualize; see here for some
interesting comparisons with other huge numbers.
Its practical use is limited to counting tiny things like atoms, molecules, "formula units",
electrons, or photons.
The value of NA can be known only to the precision that the number of atoms in a measurable
weight of a substance can be estimated. Because large numbers of atoms cannot be counted
directly, a variety of ingenious indirect measurements have been made involving such things as
brownian motion and X-ray scattering.
The current value was determined by measuring the distances between the atoms of silicon in
an ultrapure crystal of this element that was shaped into a perfect sphere. (The measurement was
made by X-ray scattering.) When combined with the measured mass of this sphere, it yields
Avogadro's number. But there are two problems with this: 1) The silicon sphere is an artifact,
rather than being something that occurs in nature, and thus may not be perfectly reproducible. 2)
The standard of mass, the kilogram, is not precisely known, and its value appears to be changing.
For these reasons, there are proposals to revise the definitions of both NA and the kilogram. See
here for more, and stay tuned!
History of the determination of Avogadro's number
Wikipedia has a good discussion of Avogadro's number 2 Moles and their uses

The Kinetic Molecular Theory Postulates

The experimental observations about the behavior of gases discussed so far can be explained
with a simple theoretical model known as the kinetic molecular theory. This theory is based on
the following postulates, or assumptions.
1. Gases are composed of a large number of particles that behave like hard, spherical objects
in a state of constant, random motion.
2. These particles move in a straight line until they collide with another particle or the walls
of the container.
3. These particles are much smaller than the distance between particles. Most of the volume
of a gas is therefore empty space.
4. There is no force of attraction between gas particles or between the particles and the
walls of the container.
5. Collisions between gas particles or collisions with the walls of the container are perfectly
elastic. None of the energy of a gas particle is lost when it collides with another particle
or with the walls of the container.
6. The average kinetic energy of a collection of gas particles depends on the temperature of
the gas and nothing else.
The assumptions behind the kinetic molecular theory can be illustrated with the apparatus shown
in the figure below, which consists of a glass plate surrounded by walls mounted on top of three
vibrating motors. A handful of steel ball bearings are placed on top of the glass plate to represent
the gas particles.

When the motors are turned on, the glass plate vibrates, which makes the ball bearings move in a
constant, random fashion (postulate 1). Each ball moves in a straight line until it collides with
another ball or with the walls of the container (postulate 2). Although collisions are frequent, the
average distance between the ball bearings is much larger than the diameter of the balls
(postulate 3). There is no force of attraction between the individual ball bearings or between the
ball bearings and the walls of the container (postulate 4).
The collisions that occur in this apparatus are very different from those that occur when a rubber
ball is dropped on the floor. Collisions between the rubber ball and the floor are inelastic, as
shown in the figure below. A portion of the energy of the ball is lost each time it hits the floor,
until it eventually rolls to a stop. In this apparatus, the collisions are perfectly elastic. The balls
have just as much energy after a collision as before (postulate 5).

Any object in motion has a kinetic energy that is defined as one-half of the product of its mass
times its velocity squared.
KE = 1/2 mv2
At any time, some of the ball bearings on this apparatus are moving faster than others, but the
system can be described by an average kinetic energy. When we increase the "temperature" of
the system by increasing the voltage to the motors, we find that the average kinetic energy of the
ball bearings increases (postulate 6).

How the Kinetic Molecular Theory Explains the Gas Laws

The kinetic molecular theory can be used to explain each of the experimentally determined gas
laws.
The Link Between P and n
The pressure of a gas results from collisions between the gas particles and the walls of the
container. Each time a gas particle hits the wall, it exerts a force on the wall. An increase in the
number of gas particles in the container increases the frequency of collisions with the walls and
therefore the pressure of the gas.

Amontons' Law (P

T)

The last postulate of the kinetic molecular theory states that the average kinetic energy of a gas
particle depends only on the temperature of the gas. Thus, the average kinetic energy of the gas
particles increases as the gas becomes warmer. Because the mass of these particles is constant,
their kinetic energy can only increase if the average velocity of the particles increases. The faster
these particles are moving when they hit the wall, the greater the force they exert on the wall.
Since the force per collision becomes larger as the temperature increases, the pressure of the gas
must increase as well.
Boyle's Law (P = 1/v)
Gases can be compressed because most of the volume of a gas is empty space. If we compress a
gas without changing its temperature, the average kinetic energy of the gas particles stays the
same. There is no change in the speed with which the particles move, but the container is smaller.
Thus, the particles travel from one end of the container to the other in a shorter period of time.
This means that they hit the walls more often. Any increase in the frequency of collisions with
the walls must lead to an increase in the pressure of the gas. Thus, the pressure of a gas becomes
larger as the volume of the gas becomes smaller.
Charles' Law (V

T)

The average kinetic energy of the particles in a gas is proportional to the temperature of the gas.
Because the mass of these particles is constant, the particles must move faster as the gas becomes
warmer. If they move faster, the particles will exert a greater force on the container each time
they hit the walls, which leads to an increase in the pressure of the gas. If the walls of the
container are flexible, it will expand until the pressure of the gas once more balances the pressure
of the atmosphere. The volume of the gas therefore becomes larger as the temperature of the gas
increases.
Avogadro's Hypothesis (V

N)

As the number of gas particles increases, the frequency of collisions with the walls of the
container must increase. This, in turn, leads to an increase in the pressure of the gas. Flexible
containers, such as a balloon, will expand until the pressure of the gas inside the balloon once
again balances the pressure of the gas outside. Thus, the volume of the gas is proportional to the
number of gas particles.
Dalton's Law of Partial Pressures (Pt = P1 + P2 + P3 + ...)
Imagine what would happen if six ball bearings of a different size were added to the molecular
dynamics simulator. The total pressure would increase because there would be more collisions
with the walls of the container. But the pressure due to the collisions between the original ball
bearings and the walls of the container would remain the same. There is so much empty space in
the container that each type of ball bearing hits the walls of the container as often in the mixture
as it did when there was only one kind of ball bearing on the glass plate. The total number of

collisions with the wall in this mixture is therefore equal to the sum of the collisions that would
occur when each size of ball bearing is present by itself. In other words, the total pressure of a
mixture of gases is equal to the sum of the partial pressures of the individual gases.

Graham's Laws of Diffusion and Effusion

A few of the physical properties of gases depend on the identity of the gas. One of these physical
properties can be seen when the movement of gases is studied.
In 1829 Thomas Graham used an apparatus similar to the one shown in the figure below to study
the diffusion of gases
the rate at which two gases mix. This apparatus consists of a glass tube
sealed at one end with plaster that has holes large enough to allow a gas to enter or leave the
tube. When the tube is filled with H2 gas, the level of water in the tube slowly rises because the
H2 molecules inside the tube escape through the holes in the plaster more rapidly than the
molecules in air can enter the tube. By studying the rate at which the water level in this apparatus
changed, Graham was able to obtain data on the rate at which different gases mixed with air.

Graham found that the rates at which gases diffuse is inversely proportional to the square root of
their densities.

This relationship eventually became known as Graham's law of diffusion.

To understand the importance of this discovery we have to remember that equal volumes of
different gases contain the same number of particles. As a result, the number of moles of gas per
liter at a given temperature and pressure is constant, which means that the density of a gas is
directly proportional to its molecular weight. Graham's law of diffusion can therefore also be
written as follows.

Similar results were obtained when Graham studied the rate of effusion of a gas, which is the
rate at which the gas escapes through a pinhole into a vacuum. The rate of effusion of a gas is
also inversely proportional to the square root of either the density or the molecular weight of the
gas.

Graham's law of effusion can be demonstrated with the apparatus in the figure below. A thickwalled filter flask is evacuated with a vacuum pump. A syringe is filled with 25 mL of gas and
the time required for the gas to escape through the syringe needle into the evacuated filter flask is
measured with a stop watch.

As we can see when data obtained in this experiment are graphed in the figure below, the time
required for 25-mL samples of different gases to escape into a vacuum is proportional to the

square root of the molecular weight of the gas. The rate at which the gases effuse is therefore
inversely proportional to the square root of the molecular weight. Graham's observations about
the rate at which gases diffuse (mix) or effuse (escape through a pinhole) suggest that relatively
light gas particles such as H2 molecules or He atoms move faster than relatively heavy gas
particles such as CO2 or SO2 molecules.

The Kinetic Molecular Theory and Graham's Laws

The kinetic molecular theory can be used to explain the results Graham obtained when he studied
the diffusion and effusion of gases. The key to this explanation is the last postulate of the kinetic
theory, which assumes that the temperature of a system is proportional to the average kinetic
energy of its particles and nothing else. In other words, the temperature of a system increases if
and only if there is an increase in the average kinetic energy of its particles.
Two gases, such as H2 and O2, at the same temperature, therefore must have the same average
kinetic energy. This can be represented by the following equation.

This equation can be simplified by multiplying both sides by two.

It can then be rearranged to give the following.

Taking the square root of both sides of this equation gives a relationship between the ratio of the
velocities at which the two gases move and the square root of the ratio of their molecular
weights.

This equation is a modified form of Graham's law. It suggests that the velocity (or rate) at which
gas molecules move is inversely proportional to the square root of their molecular weights.

3.1 The Physics of Diffusion

Diffusion is the kinetic process that leads to the homogenization, or uniform mixing, of the
chemical components in a phase. Although mixing in a fluid (liquid or gas) may occur on many
length scales, as induced by macroscopic flow, diffusive mixing in solids, by contrast, occurs
only on the atomic or molecular level. As time increases, the extent of homogenization by
diffusion also increases, and the length scale over which chemical homogeneity persists within a
phase gradually extends to macroscopic distances.
In the silicon process technology, depending on the complexity of the model, dopant
redistribution does not only include dopant atoms itself, but also point defects. The point defects
can be divided into simple and extended point defects.
Additionally, the presence of the large number of the charged dopant atoms causes an electrical
field in the inside of the wafer, which reversely influences the diffusion of dopants.
The continuum-based diffusion models are successfully applied in many process simulation
programs [6]. These models use the so-called methodology of diffusion-reaction equations,
which was shown to be very efficient for the numerical simulation of the diffusion phenomena.
The method itself can be generalized to design a set of coupled partial differential equations from
some assumption about possible reactions between intrinsic point defects and dopants.

Principal ingredients of the diffusion-reaction models are: Fick's diffusion laws, electrical field
enhanced diffusion, and species generation and recombination theory. In the following we will
briefly discuss and illustrate each of these basic concepts.
Fick's diffusion laws
The laws of diffusion are mathematical relationships which relate the rate of diffusion to the
concentration gradient for net mass transfer. Such laws are considered to be phenomenological.
We define vector

to be a mass flux of the diffusing component. In Cartesian

coordinates, with the unit coordinates , and

sum:

, the mass flux may be written as a vectorial

(3.1
)

The individual flux magnitudes appearing in (3.1) can be expressed by component

equations through Ficks's first law:
(3.2
)

where denotes the diffusion coefficient and

is the concentration of the diffusing
component.
By imposing a mass conservation on the diffusing system we obtain Ficks's second law in the
form:
(3.3
)

The interpretation of (

) is clear: If there is a converging flow of species at a point, so that

, the concentration rises with time; if there is a divergent flow, so that

, the

concentration falls.
Influence of the Electrical field
We consider a single charged particle moving in the electrical field with potential
The gradient of this potential describes the force on the particle [18],

(3.4
)

where is the valence of the charged species. A potential gradient tends to produce a flux of the
species, and this flux must be added to that produced by the concentration gradient to arrive at
the equation for the total flux. It is found empirically that a potential gradient gives rise to a
mean diffusion velocity for the affected atoms. This fact is mathematically expressed by the
equation,
(3.5
)

in which is called mobility. The force gives rise to a steady-state velocity instead
of continuing acceleration.

In applying a potential gradient instead of concentration gradient we are simply replacing one
small force with another. Thus is plausible that the mobility is proportional to the diffusion
coefficient . This fact is expressed by Einstein's relationship,
(3.6
)

where

is the Boltzmann constant. The flux that results in a homogenous system is thus,
(3.7
)

Combining the last equation with Fick's diffusion law we obtain a partial differential
equation describing the behavior of the charged particle in the concentration and
electrical gradient field,
(3.8
)

Electric fields arise from the large differences in diffusion constants of the ionized
dopants and the charge carriers associated with them [4]. The charge carriers would
ordinary tend to diffuse away faster then the ions, thus creating a space charge.
The electric field originating from this space charge acts on the ions and charge
carriers to counteract the separation.

Generally, in the case of non-uniform concentrations of dopants, the electric field calculation is
based on third Maxwell's equation,
(3.9
)

div

where
is the electric displacement vector and the space charge concentration.
The electric displacement vector is related to the electric field vector
and thus to
the electrostatic potential,
(3.1
0)

Finally, under the assumption of complete ionization, (3.9) takes the form [4],

div

sinh

(3.1
1)

denotes the electron charge associated with the defects and

concentration.

is their

Assuming local charge neutrality,

(3.1
2)

it can be shown that electron and hole concentration is expressed by [4],

(3.1
3)

where

is intrinsic carrier concentration (see Section 3.3.1).

Species generation and recombination theory

During the diffusion process species may arrange in pairs with species of another
type and thereby the new species are created. Let we take three species
,
and
, whereas the third one is constructed by pairing of first and second. This
chemical reaction can be symbolically displayed as [19],
(3.1
4)

The intensity of these reaction is expressed by a rate coefficient

Also the reverse
process is thinkable, dissolution of the compound species
into the original
species and
,
(3.1
5)

The rate coefficient of the reverse reaction is

also define the rate of reaction by,

. For these two reactions we can

(3.1
6)

We say that the reactions are in global thermal equilibrium if everywhere is fullfiled,
(3.1
7)

A thermal dependence of the reaction rates is always assumed, and with taking
, (3.17) can be written in the form of the law of mass action,
(3.1
8)

However, if the reactions are not in global thermal equilibrium, there is obviously a
change in concentration of each species and the following equations hold,

(3.1
9)