IDEAL AND REAL GAS LAWS

Gases, unlike solids and liquids have indefinite shape and indefinite volume. As a
result, they are subject to pressure changes, volume changes and temperature
changes. Real gas behavior is actually complex. For now, let's look at ideal
Gases, since their behavior is simpler. By understanding ideal gas behavior, real
gas behavior becomes more tangible.
How do we describe an ideal gas? An ideal gas has the following properties:
1. An ideal gas is considered to be a "point mass". A point mass is a particle so
small, its mass is very nearly zero. This means an ideal gas particle has virtually
no volume.
2. Collisions between ideal Gases are "elastic". This means that no attractive or
repulsive forces are involved during collisions. Also, the kinetic energy of the gas
molecules remains constant since theses interparticle forces are lacking.
Volume and temperature are by now familiar concepts. Pressure, however, may
need some explanation. Pressure is defined as a force per area. When gas
molecules collide with the sides of a container, they are exerting a force over that
area of the container. This gives rise to the pressure inside the container.
Problems Dealing With The Ideal Gas Law
For a gas, pressure, volume, temperature and the moles of gas are all related by
the following equation:


The units of pressure, volume and temperature are dictated by the ideal gas law
constant, R. The most common used value for R when dealing with gases is
0.0821 L
.
atm/mol
.
K. This unit requires that volume to be expressed in liters,
pressure to be expressed in atmospheres, and temperature to be expressed in
Kelvin. One thing to keep in mind is that temperature will always be expressed
in the Kelvin scale when dealing with any of the gas laws.
Let's start looking at some of the types of questions you may encounter using the
ideal gas law. In some problems, you will know four out of the five possible
variables, and be asked to solve for the fifth variable. It is important to note that
the pressure, volume, moles or temperature of the gas is not changed. When
these variables are changed, a different type of problem is apparent, and we will
shortly look at these types of problems.
Suppose you have 1.00 mol of a gas at 0
o
C, occupying a container which is 500
mL in size. What is the pressure of this gas in atmospheres?
To solve this problem, consider that moles, temperature, volume and the ideal
gas law constant, R, are known. Pressure is the only unknown variable. Recall
that R will dictate the units. The temperature is given in Celsius. This must be
converted to the Kelvin scale. To convert Celsius to Kelvin, add 273 to the
Celsius temperature:
K =
o
C + 273 = 0
o
C + 273 = 273 K
Also, the volume must be in liters, not milliliters. Convert as follows:


Now we are ready to insert the known values into the ideal gas law:


Solve for pressure by dividing both sides of the equation by the volume, 0.500
L:


Notice how the units cancel to give atmospheres.
Next, let's find the volume of 2.50 mol of gas which is at 730 mm Hg of
pressure, and at a temperature of 127
o
C.
As before, we need to convert temperature from Celsius to Kelvins:
K = 127
o
C + 273 = 400 K

Additionally, we need to convert the pressure units of mm Hg to atmospheres.
In one atmosphere of pressure, there are 760 mm Hg:


Remember, the reason for these conversions was to make the units consistent
with the units of the ideal gas law constant, R.
Substitute the known values for pressure, moles, R, and temperature into the
ideal gas law:


Divide both sides of the equation by the pressure, 0.961 atm, to solve for
volume:


Again, notice how the units cancel to give volume units of liters.
Next, let's solve for the Celsius temperature of 0.600 mol of a gas at a pressure
of 40000 torr, and a volume of 160 mL.
Unit conversions of pressure and volume must be done, first. We see here
another pressure unit, torr. There are 760 torr in one atmosphere, and as one can
see, the torr pressure unit is the same as the units of mm Hg.




Once again, since the pressure and volume units are now consistent with the
units of R, the values may be substituted into the ideal gas law:


Divide both sides of the equation by the moles, 6.00 mol, and the ideal gas law
constant, R, 0.0821 L
.
atm/mol
.
K, to solve for temperature:


Notice how the units cancel to give temperature in K.
Convert the Kelvin temperature into Celsius:
o
C = K - 273 = 171 - 273 = -102
o
C

Now let's find how many moles of gas are present when the gas is occupying a
volume of 5.00 L at a pressure of 10.0 atmospheres and a temperature of 310 K.
Substitute the pressure, volume, temperature and the gas constant, R, into the
ideal gas law equation:


Divide both sides of the equation by the gas law constant, R, and the
temperature to solve for n:


Other P,V,T, n Relationships (Empirical Gas Laws)
The ideal gas law may also be used to investigate the behavior of a gas when
pressure, volume, the moles of gas and/or temperature are changed. These
additional laws are often named after the scientist(s) who investigated these
properties.
The relationship between pressure and volume while holding moles and
temperature constant is called Boyle's Law. Let's derive this law. Assign
subscripts to pressure and volume to indicate two different pressures and
volumes:
P
1
V
1
= nRT

P
2
V
2
= nRT

Since both pressures and volumes are equal to nRT, they are equal to each
other:
P
1
V
1
= P
2
V
2
= nRT (Boyle's Law)

Let's look at a problem dealing with Boyle's Law. Suppose you had gas in a
15.0 L container at 5.00 atmospheres pressure, and the volume is decreased to
0.500 L. What is the new pressure in the container?
To recognize that this is a Boyle's Law problem, make yourself a table of the
known quantities and the unknown quantity.


Substitute the know variables into the equation for Boyle's Law. Make sure that
the volume units are consistent. In this case, the volume units are both
expressed in liters.
(5.00 atm)(15.0 L) = P2(0.500 L)

Solve for the new pressure, P2, by dividing both sides of the equation by the
new volume, 0.500 L:


Note that pressure and volume are inversely proportional, so as volume
decreases, the pressure increases.
The relationship between volume and temperature while holding moles and
pressure constant is called Charles' Law. Let's derive this law from the ideal gas
law. Assign subscripts to volume and temperature, and hold moles and pressure
constant:
PV
1
= nRT
1


PV
2
= nRT
2


Collect terms. Bring the constants to one side of the equation and the variables
to the other side of the equation. Divide both sides of each equation by pressure,
P, and by the temperature term, T
1
in the first equation and T
2
in the second
equation. This is Charles' Law:


Let's look at a problem dealing with Charles' Law. Suppose you had 25.0 L of
gas at 0
o
C, and you raised the temperature to 100
o
C. What is the new volume
of the gas?
The first task is to immediately change the temperature values from Celsius to
Kelvin. Remember, when dealing with any gas law, temperature values must be
expressed in the absolute temperature scale (Kelvin scale). Why? Look at
Charles' Law. If temperature were to remain in the Celsius scale, one would
have to divide by 0
o
C in the above problem. Division by 0 is undefined.
Likewise, if one of the temperatures were negative, a negative volume would
result, which is "impossible." By using the absolute temperature scale, negative
temperature values do not exist, hence, negative or undefined volumes are not
possible results.
T
1
= 0
o
C + 273 = 273 K

T
2
= 100
o
C + 273 = 373 K

Once again, to recognize that this is a Charles' Law problem, make a table of
the known quantities and the unknown quantity:


Substitute the known temperatures and volume into the expression for Charles'
Law:


Solve for V
2
by multiplying both sides of the equation by T
2
, 373 K:


Note how volume and temperature are directly proportional. As the temperature
increases, volume increases.
Now let's look at the case where pressure and temperature are varied and the
moles and volume are held constant. This empirical gas law is called the Guy-
Lussac Law. As before, give the terms which are varied, pressure and
temperature, subscripts:
P
1
V = nRT
1


P
2
V = nRT
2


Collect terms. Divide each equation by their respective temperature term and
each equation by the volume, V:


Let's use this law in a gas law problem. Suppose you have a gas at 30.0 atm
pressure and 100
o
C and the temperature is changed to 400
o
C. What is the new
pressure of the gas?
Again, the first step is to convert the temperatures from Celsius to Kelvin:
T
1
= 100
o
C + 273 = 373 K

T
2
= 400
o
C + 273 = 673 K

Set up a table of knowns and unknown:


Substitute the known quantities into the Guy-Lussac equation:


Solve the above expression for the pressure, P
2
, by multiplying both sides of the
equation by the temperature, 673 K:


Notice that pressure and temperature are directly proportional. As the
temperature increased, the pressure also increased.
The next empirical gas law we'll look at is called Avogadro's Law. This law
deals with the relationship between the volume and moles of a gas at constant
pressure and temperature. Let's derive this law from the ideal gas law. Give the
moles and volume subscripts, since their conditions will change:
PV
1
= n
1
RT

PV
2
= n
2
RT

Collect terms. Divide each equation by pressure, P, and divide each equation by
their respective mole term:


Let's use Avogadro's Law in a problem. Suppose you were given that 8.00
moles of a gas occupies a volume of 4.00L at a constant pressure and
temperature. What volume of gas would 16.0 moles of this gas occupy at the
same temperature and pressure?
Set up your table of knowns and unknown:


Substitute the known quantities into the equation for Avogadro's Law:


Solve the above equation for the volume, V
2
, by multiplying both sides of the
equation by 16.0 mol:


Notice how volume and moles are directly proportional. As the number of
moles of gas increased, so did the volume of the gas.
The Combined Gas Law
What happens if none of the variables for a gas are constant (pressure, volume,
temperature, and moles of the gas were changed)? The result would be the
Combined Gas Law. Let's derive this law. Give pressure, volume, moles and
temperature subscripts, since they are all changing:
P
1
V
1
= n
1
RT
1


P
2
V
2
= n
2
RT
2


Collect terms. Divide each equation by their respective mole and temperature
term:


This equation is very useful since it contains any empirical gas law relationship
you may need to come up with. If moles and temperature are held constant, then
the above equation simplifies down to Boyle's Law. If pressure and moles are
held constant, then the equation simplifies down to Charles' Law, etc. If only
moles are held constant, then substitute the known pressure, volume and
temperatures into the above equation and solve for the unknown quantity. For
instance, suppose you had a gas at 15.0 atm pressure, at a volume of 25.0 L and
a temperature of 300 K. What would the volume of the gas be at standard
temperature and pressure? Standard pressure is 1.00 atm and standard
temperature is 0
o
C (or 273 K)
.
Set up a table of knowns and unknown, as before:


Substitute these variables into the combined gas law. Since the moles are
unchanged, the mole terms have dropped out of the equation:


Solve the volume, V
2
. Multiply both sides of the equation by 273 K and divide
both sides of the equation by 1.00 atm:


Other Equations Derived from the Ideal Gas Law
From the ideal gas law, PV = nRT, one can derive other useful expressions--
ones that relate the molar mass and density of Gases to pressures and
temperatures. This is often done just by substituting a different known
expression for one of the variables in the ideal gas law. For instance, you know
that the moles of a gas, n, can also be expressed as the mass of the gas in grams
over the molar mass of that gas:


Substitute this into the ideal gas law, and one obtains the equation:


Multiplying both sides by the molar mass, MM, obtains:
(MM)PV = gRT

This equation is useful for determining the molar mass of a gas from
experimental data, where the mass, pressure, volume and temperature of the gas
is measured.
Now, let's divide both sides of the above expression by the volume, V:


Since we know that g/V is density, D, let's substitute density in for g/V in the
above equation:
(MM)P = DRT

This equation is useful for relating the pressure, density and temperature of a
gas, in the same way as the other empirical gas laws we have encountered.
Real Gases
So far we have only considered the behavior of "ideal" Gases. How does a real
gas differ from an ideal gas? Recall that an ideal gas is considered to be a point
mass -- a particle so small that the volume of that particle is negligible. A real
gas particle does have real volume. For an ideal gas, the collisions between gas
particles was said to be "elastic" -- no attractive or repulsive forces exist, and
thus, no energy is exchanged during collisions. For a real gas, collisions are
non-elastic. There are a number of real gas laws. We will look at only one here,
the van der Waal's equation:


Notice how "corrections" are being made to the pressure term and the volume
term. Since collisions of real Gases are non-elastic, the term n
2
a/V
2
is correcting
for the interactions of these particles. The value of a is a constant, and must be
experimentally determined for each gas. Since real gas particles have real
volume, the nb term is correcting for the excluded volume. The value of b is a
constant, and must be determined experimentally for each gas. The van der
Waals constants, a and b for many gases have been tabulated in the CRC
Handbook of Chemistry and Physics. Needless to say, they would be given to
you if you are required to solve a problem using this equation. At this level,
only pressure or temperature can be solved for easily. Solving for the volume is
nontrivial and involves solving a cubic polynomial equation. Let's show how
the van der Waals equation is rearranged to solve for pressure. Begin by
dividing both sides of the equation by the volume term, V - nb:


Next, subtract the interparticle interaction term, n
2
a/V
2
from both sides of the
equation:


Using the real gas law, let's find the pressure of 2.00 moles of carbon dioxide
gas at 298 K in a
5.00 L container. The van der Waals constants for carbon dioxide are: a = 3.592
L
2.
atm/mol
2
and b = 0.04267 L/mol.
Substituting all of the variables into the appropriate terms of the equation, one
obtains the pressure of :

Compare this to the pressure calculated using the ideal gas law:


Copyrght, 2001, L. Ladon. Permission is granted to use and duplicate these
materials for non-profit educational use, under the following conditions: No
changes or modifications will be made without written permission from the
author. Copyright registration marks and author acknowledgement must be
retained intact.
Properties of Gases
understanding matter at its simplest
c h e m1 v i r t u a l t e x t b o o k
a reference text for General Chemistry
Stephen Lower
Simon Fraser University
The gaseous state of matter is the only one that is based on a simple
model that can be developed from first principles. As such, it serves as
the starting point for the study of the other states of matter.
The Chem1 Virtual Textbook is a resource for General Chemistry aimed
mainly at the first-year university level. It offers a more comprehensive,
organized, and measured approach than is found in most standard
textbooks. It should also be accessible to advanced high-school courses,
and helpful as review material for students in more advanced courses in
chemistry, biology, geology, and engineering.










1- Observable properties of gases
- What's special about gases?
- The pressure of a gas
- atmospheric pressure and the barometer
- Temperature and temperature scales
- Absolute temperature
- The volume occupied by a gas
- What you should be able to do
- Concept map
2- Ideal gas model: the basic gas laws
- The law of Charles and Gay-Lussac: effects of temperature
- Avogadro's Law: number of molecules
- The Ideal Gas Equation of State
- The P-V-T surface of an ideal gas
- What you should be able to do
- Concept map
3- Moles and mixtures of gases, Dalton's law
- Molar volume of a gas: standard temperature and pressure
- Molecular weight and density of a gas
- Mixtures of gases: expressing compositions
- Dalton's Law of partial pressures
- Some applications of Dalton's Law
- Collecting a gas over water
- Scuba diving
- What you should be able to do
- Concept map
4- Molecules in motion ("KMT-lite")
- Introduction
- The kinetic-molecular model
- The gas laws explained
- Some practical applications
- Graham's Law and effusion
- Density fluctuations: why the sky is blue
- Incandescent ight bulbs
- Viscosity of gases
- Distribution of gas molecules in a gravitational field
- What you should be able to do
- Concept map
5- More on kinetic-molecular theory ("KMT-classic")
The material in this section is frequently omitted in more elementary courses.
- Velocities of gas molecules and the Boltzmann distribution
- Retention of planetary atmospheres
- Derivation of the ideal gas equation of state
- RT has the dimensions of energy
- How far does a molecule travel between collisions?
- What you should be able to do
- Concept map
6 - Real gases and critical phenomena
- Effects of intermolecular forces
- The van der Waals equation of state
- Condensation and the critical point
- P-V-T surface of a real gas
- Supercritical fluids
- What you should be able to do
- Concept map













The "ideal gas laws" as we know them do a remarkably good job of describing the
behavior of a huge number chemically diverse substances as they exist in the gaseous
state under ordinary environmental conditions, roughly around 1 atm pressure and a
temperature of 300 K.
This is especially so when we consider that some of the basic tenets of the ideal gas
model have to be abandoned in order to explain such properties as
- the average distance between collisions (the molecules really do take up space!)
- at sufficiently high pressures and low temperatures, intermolecular attractions assume
control and the gas condenses to a liquuid;
- the viscosity of a gas flowing through a pipe (the molecules do get temporarily
"stuck" on the pipe surface, and are therefore affected by intermolecular attractive
forces.)
Even so, many of the common laws such as Boyle's and Charles' continue to describe
these gases quite well even under conditions where these phenomena are evident.
Under ordinary environmental condtions (moderate pressures and above 0C), the
isotherms of substances we normally think of as gases don't appear to differ very
greatly from the hyperbolic form
(PV/RT) = constant.
(PV/RT) = constant.
... but over a wider range of
conditions, things begin to get
more complicated. Thus
isopentane, shown here, behaves
in a reasonably ideal manner
above 210 K, but below this
temperature the isotherms
become somewhat distorted, and
at 185K and below they cease to
be continuous, showing peculiar
horizontal segments in which
reducing the volume does not
change the pressure.
Within this region, any attempt
to compress the gas simply
"squeezes" some of it into the
liquid state whose greater
density exactly compensates for
the smaller volume, thus
maintaining the pressure at a
constant value.
It turns out that real gases eventually begin to follow their own unique equations of
state, and ultimately even cease to be gases.
In this unit we will see why this occurs, what the consequences are, and how we
might modify the ideal gas equation of state to extend its usefulness over a greater
range of temperatures and pressures.
1 Effects of intermolecular forces
According to Boyle's law, the product PV is a constant at any given temperature, so a
plot of PV as a function of the pressure of an ideal gas yields a horizontal straight
line. This implies that any increase in the pressure of the gas is exactly counteracted
by a decrease in the volume as the molecules are crowded closer together. But we
know that the molecules themselves are finite objects having volumes of their own,
and this must place a lower limit on the volume into which they can be squeezed. So
we must reformulate the ideal gas equation of state as a relation that is true only in
the limiting case of zero pressure:

So what happens when a real gas is subjected to a very high pressure? The
outcome varies with both the molar mass of the gas and its temperature, but in
general we can see the the effects of both repulsive and attractive intermolecular
forces:
Repulsive forces: As a gas is compressed, the individual molecules begin to get
in each other's way, giving rise to a very strong repulsive force acts to oppose
any further volume decrease. We would therefore expect the PV vs P line to
curve upward at high pressures, a nd this is in fact what is observed for all gases
at sufficiently high pressures.
Attractive forces: At very close distances, all molecules repel each other as their
electron clouds come into contact. At greater distances, however, brief statistical
fluctuations in the distribution these electron clouds give rise to a universal
attractive force between all molecules. The more electrons in the molecule (and
thus the greater the molecular weight), the greater is this attractive force. As long
as the energy of thermal motion dominates this attractive force, the substance
remains in the gaseous state, but at sufficiently low temperatures the attractions
dominate and the substance condenses to a liquid or solid.
A more comlete discussion of intermolecular forces can be found here.
The universal attractive force described above is known as the dispersion, or
London force. There may also be additional (and usually stronger) attractive
forces related to charge imbalance in the molecule or to hydrogen bonding.
These various attractive forces are often referred to collectively as
van der Waals forces.
A plot of PV/RT as a function of pressure is a very sensitive indicator of
deviations from ideal behavior, since such a plot is just a horizonal line for an
ideal gas. The two illustrations below show how these plots vary with the nature
of the gas, and with temperature.
Intermolecular attractions, which generally increase with molecular weight, cause
the PV product to decrease as higher pressures bring the molecules closer
together and thus within the range of these attractive forces; the effect is to cause
the volume to decrease more rapidly than it otherwise would.
The repulsive forces always eventually win out.
But as the molecules begin to intrude on each others' territory, the stronger
repulsive forces cause the curve to bend upward.











The temperature makes a big difference! At higher temperatures, increased
thermal motions overcome the effects of intermolecular attractions which
normally dominate at lower pressures. So all gases behave more ideally at
higher temperatures.
For any gas, there is a special temperature (the Boyle temperature) at which
attractive and repulsive forces exactly balance each other at zero pressure. As
you can see in this plot for methane, this some of this balance does remain as
the pressure is increased.
2 The van der Waals equation of state
How might we modify the ideal gas equation of state to take into account the
effects of intermolecular interactions?
The first and most well known answer to this question was offered by the Dutch
scientist










J.D. van der Waals (1837-1923) in 1873.
Correcting for molecular volumes
The ideal gas model assumes that the gas molecules are merely points that occupy no
volume; the "V" term in the equation is the volume of the container and is
independent of the nature of the gas.
van der Waals recognized that the
molecules themselves take up space that
subtracts from the volume of the
container, so that the volume of the gas
V in the ideal gas equation should be
replaced by the term (Vb), in which b
relates to the excluded volume, typically
of the order of 20-100 cm
3
mol
1
.
The excluded volume surrounding any molecule defines the closest possible approach
of any two molecules during collision. Note that the excluded volume is greater then
the volume of the molecule, its radius being half again as great as that of a spherical
molecule.
Correcting for intermoleclar attractions
The other effect that van der Waals needed to correct for are the intermolecular
attractive forces. These are ignored in the ideal gas model, but in real gases they exert
a small cohesive force between the molecules, thus helping to hold the gas together
and reducing the pressure it exerts on the walls of the container.
Because this pressure depends on both the frequency and the intensity of collisions
with the walls, the reduction in pressure is proportional to the square of the number
of molecules per volume of space, and thus for a fixed number of molecules such as
one mole, the reduction in pressure is inversely proportional to the square of the
volume of the gas. The smaller the volume, the closer are the molecules and the
greater will be the effect.
The van der Walls equation replaces the P term in the ideal gas equation with
P + (a / V
2
) in which the magnitude of the constant a increases with the strength of
the intermolecular attractive forces. Because the
The complete van der Waals equation of state can be written as

Although most students are not required to memorize this equation, you are expected
to understand it and to explain the significance of the terms it contains. You should
also understand that the van der Waals constants a and b must be determined
empirically for every gas. This can be done by plotting the P-V behavior of the gas
and adjusting the values of a and b until the van der Waals equation results in an
identical plot. The constant a is related in a simple way to the molecular radius; thus
the determination of a constitutes an indirect measurment of an important
microscopic quantity.
van der Waals constants for some gases
Substance
molar mass,
g
a
(L
2
-atm

mole
2
)
b
(L mol
1
)
hydrogen H
2
2 0.244 .0266
helium He 4 0.034 .0237
methane CH
4
16 2.25 .0428
water H
2
O 18 5.46 .0305
nitrogen N
2
28 1.39 .0391
carbon dioxide CO
2
44 3.59 .0427
carbon tetrachloride CCl
4
154 20.4 .1383
The van der Waals equation is only one of many equations of state for real gases.
More elaborate equations are required to describe the behavior of gases over wider
pressure ranges. These generally take account of higher-order nonlinear attractive
forces, and require the use of more empirical constants. Although we will make no use
of them in this course, they are widely employed in chemical engineering work in
which the behavior of gases at high pressures must be accurately predicted.
3 Condensation and the critical point
The most striking feature of real gases is that they cease to remain gases as the
temperature is lowered and the pressure is increased.
PVT Surface of a real gas
The plot illustrates this behavior; as the
volume is decreased, the lower-
temperature isotherms suddenly change
into straight lines. Under these conditions,
the pressure remains constant as the
volume is reduced. This can only mean that
the gas is disappearing" as we squeeze the
system down to a smaller volume. In its
place, we obtain a new state of matter, the
liquid. In the green-shaded region, two
phases, liquid, and gas, are simultaneously
present. Finally, at very small volume all
the gas has disappeared and only the liquid
phase remains. At this point the isotherms
bend strongly upward, reflecting our common experience that a liquid is practically
incompressible.
To better understand this plot, look at the isotherm labeled . As the gas is
compressed from to , the pressure rises in much the same way as Boyle's law
predicts. Compression beyond , however, does not cause any rise in the pressure.
What happens instead is that some of the gas condenses to a liquid. At , the
substance is entirely in its liquid state. The very steep rise to corresponds to our
ordinary experience that liquids have very low compressibilities. The range of
volumes possible for the liquid diminishes as the critical temperature is approached.
The critical point
Liquid and gas can coexist only within the regions indicated by the green-shaded area
in the diagram above. As the temperature and pressure rise, this region becomes more
narrow, finally reaching zero width at the critical point. The values of P, T, and V at
this juncture are known as the critical constants P
c
, T
c
, and V
c
. The isotherm that
passes through the critical point is called the critical isotherm. Beyond this isotherm,
the gas and liquids become indistinguishable; there is only a single fluid phase,
sometimes referred to as a supercritical liquid.
Critical behavior of carbon dioxide
At temperatures below 31C
(the critical temperature),
CO
2
acts somewhat like an
ideal gas even at a rather
high pressure ( ).
Below 31, an attempt to
compress the gas to a
smaller volume eventually
causes condensation to
begin.



Thus at 21C, at a pressure of about 62 atm ( ), the volume can be reduced from
200 cm
3
to about 55 cm
3
without any further rise in the pressure. Instead of the gas
being compressed, it is replaced with the far more compact liquid as the gas is
essentially being "squeezed" into its liquid phase. After all of the gas has disappeared
( ), the pressure rises very rapidly because now all that remains is an almost
incompressible liquid. Above this isotherm ( ), CO
2
exists only as a supercritical
fluid.







What happens if you have some liquid carbon dioxide in a transparent cylinder at just
under its P
c
of 62 atm, and you then compress it slightly? Nothing very dramatic until
you notice that the meniscus has disappeared. By successively reducing and increasing
the pressure, you can "turn the meniscus on and off".
It all seems rather magical as in the disappearance of all but the smile in the
Cheshire Cat .
One intriguing consequence of the very limited bounds of the liquid state is that you
could start with a gas at large volume and low temperature, raise the temperature,
reduce the volume, and then reduce the temperature so as to arrive at the liquid region
at the lower left, without ever passing through the two-phase region, and thus without
undergoing condensation!
Supercritical fluids










The supercritical state of matter, as the fluid above the critical point is often called,
possesses the flow properties of a gas and the solvent properties of a liquid. The
density of a supercritical fluid can be changed over a wide range by adjusting the
pressure; this, in turn, changes its solubility, which can thus be optimized for a
particular application. The picture at the right shows a commercial laboratory device
used for carrying out chemical reactions under supercritical conditions.
Supercritical reactor for laboratory use
Supercritical carbon dioxide is widely used to dissolve the caffeine out of coffee
beans and as a dry-cleaning solvent. Supercritical water has recently attracted
interest as a medium for chemically decomposing dangerous environmental pollutants
such as PCBs.
Supercritical fluids are being increasingly employed as as substitutes for organic
solvents (so-called "green chemistry") in a range of industrial and laboratory
processes. Applications that involve supercritical fluids include extractions, nano
particle and nano structured film formation, supercritical drying, carbon capture and
storage, as well as enhanced oil recovery studies.
What you should be able to do
Make sure you thoroughly understand the following essential concepts that have been
presented above.
- Real gases are subject to the effects of molecular volume (intermolecular repulsive
force) and intermolecular attractive forces.
- The behavior of a real gas approximates that of an ideal gas as the pressure
approaches zero.
- The effects of non-ideal behavior are best seen when the PV product is plotted as a
function of P. You should be able to identify the regions of such a plot in which
attractive and repulsive forces dominate.
- Each real gas has its own unique equation of state. Various general equations of
state have been devised in which adjustable constants are used to approximate the
behavior of a particular gas.
- The most well-known equation of state is that of van der Waals. Although you
need not memorize this equation, you should be able to explain the significance of
its terms.
Concept Map





.
Real Gases
Deviations from Ideal Behavior
Real Gases fail to obey the Ideal Gas equation of state exactly. Why?
For exactly one mole of an ideal gas:

Plotting the experimentally determined value of (pV/RT) for exactly one mole of
various REAL GASes as a function of pressure, p, shows a deviation from ideality
(The quantity (pV)/(nRT) = Z is called the COMPRESSIBILITY FACTOR and
should be unity for an Ideal Gas):

The deviation from ideal behavior is large at high pressure and low temperatue .At
lower pressures and high temperatures, the deviation from ideal behavior is
typically small, and the ideal gas law can be used to predict behavior with little
error.
Deviation from ideal behavior can also be shown for a given gas (Nitrogen, in this
example) as a function of temperature:

As temperature is decreased below a critical value, the deviation from ideal gas
behavior becomes severe, because the gas CONDENSES to become a LIQUID.

The van der Waals Equation (A fix to the Ideal Gas Equation)
One of the most useful equations to predict the behavior of real gases was developed
by Johannes van der Waals (1837-1923) It takes into account Molecular Stickiness
and Molecular Size
The Ideal Gas Equation:

Has been presented as an Empirical relation, but it doesn't work perfectly for all
gases under all conditions because it is based on imperfect assumptions.
Remember the conditions assumed for an Ideal Gas?:
1. Molecules are perfectly elastic (no STICKINESS)
2. Molecules are point masses (no SIZE)
3. Molecules move at random

The first two of these assumptions is clearly wrong for all gases, because at low
temperatures all gases CONDENSE, or form a liquid phase. This must happen
because the molecules stick to one another, at least a little. We can correct the Ideal
Gas equation for stickiness. Moreover, the liquid has measurable molar volume, and
this volume is simply the size of the close-packed molecules of the liquid.
At high pressures, and thus high densities, the intermolecular distances can become
quite short, and attractive forces between molecules becomes significant. Neighboring
molecules exert a relatively long-ranged attractive force on one another, which will
reduce the momentum in which they tranfer to the container walls. The observed
pressure exerted by the gas under these conditions will be less than that for an Ideal
Gas

To put the observed (real) pressure into the Ideal Gas expression, we must correct for
the decrease in pressure due to molecular stickiness. For Stickiness to be a factor, the
two gas molecules must have a collision. The probability of a collision is the
probability of two molecules being in the same place at the same time. The probability
of the first molecule being at the place of the collision is proportional to the number
density (n/V). The probability of the second one being in the same place is the same,
(n/V). Thus the reduction in pressure due to stickiness should be proportional to
(n/V)
2
. If the proportionality constant is called a, then the ideal pressure is

Thus, correcting for molecular stickiness alone, the Ideal Gas equation would become:

As pressures and density increase, the volume of the molecules themselves becomes
significant relative to the size of the container.

To correct for the effect of finite molecular volume, we must recognize that in the
ideal gas equation the volume used is the "free volume" that the molecules find
themselves in. The free volume is just the real (container) volume minus the volume
that is taken up by the molecules of the gas itself.

where b is a constant representing the volume of a mole of gas molecules at rest.
Thus, the ideal gas equation, if corrected for molecular size and stickiness, looks like:

We can rearrange this expression slightly to give the familiar form of the van der
Waals equation.

Unlike the universal gas constant, R, The van der Waals constants a and b are
different for different gases.
Substance a (L
2
atm/mol
2
) b (L/mol)
He 0.0341 0.0237
H
2
0.244 0.0266
O
2
1.36 0.0318
H
2
O 5.46 0.0305
CCl
4
20.4 0.1383
Numerical Example:
Use the van der Waals equation to calculate the pressure of a sample of 1.0000 mol of
oxygen gas in a 22.415 L vessel at 0.0000C (Note: For an ideal gas, this temperature
and volume would lead to conditions of STP, i.e. a pressure of exactly 1.0000 atm)
V = 22.4 L
T = (0.000 + 273.15) = 273.15K
a (O
2
) = 1.36 L
2
atm/mol
2
(From Table)
b (O
2
) = 0.0318 L /mol (From Table)

(nRT)/(V-nb) = 1.0014 atm
- a (n/V)
2
= -0.0027 atm
p = (nRT)/(V-nb) - a (n/V)
2
= 0.9987 atm
- If O
2
was perfectly ideal, the pressure would be 1.0000 atm.
- The first term on the right-hand-side of the van der Waals equation, (nRT)/(V-nb),
represents the ideal gas pressure corrected for finite molecular volume. In other
words the volume is slightly less than 22.415 L due to the mole of O
2
in it. The the
molecules collide a bit more frequently with the walls of the container, because
they have less room to fly around in in the middle of the container. The value of
1.0014 atm for this term represents this increase in pressure.
- The second term in the equation, - a (n/V)
2
, represents the reduction in pressure
due to molecular stickiness. This correction to ideal gas behavior dominates the
finite volume correction, leading to a compressibility factor, Z=pV/nRT of less
than 1 (0.9987, in fact).

Here is a calculator for the numerical evaluation of ideal and real gas equations
of state.








A Molecular Model of Gases
observation hypothesis
Gases are easy to expand gas molecules don't strongly attract each
other
Gases are easy to compress gas molecules don't strongly repel each
other
Gases have densities that are
about 1/1000 of solid or liquid
densities
molecules are much farther apart in gases
than in liquids and solids
Gases completely fill their
containers
gas molecules are in constant motion
Hot gases leak through holes
faster than cold gases
the hotter the gas, the faster the molecules
are moving
Pressure
- definition: pressure = force/area
- units
Unit Symbol Conversions
pascal Pa 1 Pa = 1 N/m
2

psi lb/in
2

atmosphere atm 1 atm = 101325 Pa = 14.7 lb/in
2

bar bar 1 bar = 100000 Pa
torr torr 760 torr = 1 atm
millimeters of
mercury
mm Hg 1 mm Hg = 1 torr
- pressure exerted by a weight
o How much pressure does an elephant with a mass of 2000 kg and
a total footprint area of 5000 cm
2
exert on the ground?
o Estimate the total footprint area of a tyrannosaur weighing 16000
kg. Assume it exerts the same pressure on its feet that the elephant
does.
- measuring pressure
o strategy: relate pressure to fluid column heights
o observation: you can't draw water higher than 34 feet by suction-
why?
o hypothesis: atmospheric pressure supports the fluid column
press
ure
=

force / area
=

mass x g /
area
(because force =
weight of liquid =
mass x g)
=

density x
volume x g /
area
(because mass =
density x volume)
=

density x g x
height
(because volume =
area x height)
- a barometer measures atmospheric pressure as a mercury column height
- a manometer measures gas pressure as a difference in mercury column
heights
o two types
closed manometer: difference in column heights gives absolute
gas pressure
open manometer: difference in column heights gives difference
between gas and atmospheric pressures
- kinetic-molecular view of gas pressure
o gas pressure arises from force of molecular collisions
o anything that increases the number of collisions will increase
pressure
The state of a gas
- most behaviors of a pure gas sample can be related to just 4 physical
properties:
property symbol convenientunits Property type
pressure P atm, torr, Pa intensive
volume V L, cm
3
extensive
temperature T K intensive
moles n mol extensive
- any equation that relates P, V, T, and n for a material is called an
equation of state
- experiment shows PV=nRT is an approximate equation of state for gases
o gases that obey PV=nRT exactly are called ideal gases
o R is the gas law constant
determine experimentally by measuring P, V, T, n, and
computing R = PV/nT
value depends on units chosen for P, V, T
notice: 1 Joule = 1 N m = 1 (N/m
2
)(m
3
) = 1 (Pa)(m
3
)
Experimental foundations of the ideal gas law

- Avogadro's experiment
o objective: relate amount of gas to volume; hold everything else
constant
o sample data at 1 atm, 298 K

gas volume
(mL)
mass of
gas (g)
V/m
(mL/g)
V/n
(L/mol)
O
2
100.0 0.122 26.2
N
2
100.0 0.110 25.5
CO
2
100.0 0.176 25.0
o conclusions
molar volume is almost independent of the type of gas
volume is directly proportional to moles of gas when P, T are
constant
samples of two gases with the same V, P, T contain the same
number of moles, and so, the same number of molecules!
o molecular view
type of gas doesn't influence distance between molecules
much
example: Which is denser: dry air or moist air? Assume both air
samples are at the same P, V, and T.
- Boyle's experiment
o objective: relate volume to pressure, when everything else is held
constant
o sample data at 298 K for a trapped air bubble
Volume (mL) Pressure (Torr) PV (mL Torr)
10.0 760.0 7.60 x 10
3

20.0 379.6 7.59 x 10
3

30.0 253.2 7.60 x 10
3

40.0 191.0 7.64 x 10
3

o conclusions
volume is inversely proportional to pressure, when everything
else is held constant
o molecular view
confining molecules to a smaller space increases the number
of collisions, and so increases the pressure
- Charles' experiment
o objective: relate volume to temperature, holding everything else
constant
o sample data for a trapped He bubble at 1 atm
Volume
(mL)
Temperature
(C)
Temperatur
e
(K)
V/T
(mL/K)
40.0 0.0 273.2 0.146
44.0 25.0 298.2 0.148
47.7 50.0 323.2 0.148
51.3 75.0 348.2 0.147
55.3 100.0 373.2 0.148
80 273.2 546.3 0.146
o conclusions
volume is proportional to kelvin temperature, when everything
else is held constant
o molecular view
raising temperature increases number of collisons with
container wall.
If the walls are flexible, they'll be pushed back: and the gas
expands.
- summary
changing these
variables in an
experiment...
while holding
these variables
constant...
...reveals this
relationship:
P, V n, T P
1
V
1
= P
2
V
2
Boyle's
Law
V, T n, P V
1
/T
1
= V
2
/T
2
Charles'
Law
P, T n, V P
1
/T
1
= P
2
/T
2
Amonton's
Law
n, V P, T V
1
/n
1
= V
2
/n
2
Avogadro'
s Law
P, V, T n P
1
V
1
/T
1
= P
2
V
2
/T
2
Combined
Gas Law
P, V, T, n P
1
V
1
/n
1
T
1
=
P
2
V
2
/n
2
T
2

Ideal Gas Law
- standard temperature and pressure (STP)
- convenient for reporting gas volumes
- standard temperature is 0C (273.15 K).
- standard pressure is 1 atm in America, 1 bar elsewhere
- example
o The gas in the headspace of a soda bottle has a volume of 9.0 mL
at 298 K and 2 atm. What is the volume of gas at STP?
- applying the ideal gas law
- estimating a property from constant values of the other 3 properties
1. make a PVnT table
2. convert to units consistent with R
3. solve PV = nRT for the unknown property
- finding how one property changes when some of the other 3 properties
change
1. make a PVnT table with rows for initial and final conditions
2. convert inconsistent units (always use K, not C!!)
3. Eliminate constant values from P
1
V
1
/n
1
T
1
= P
2
V
2
/n
2
T
2

4. solve the resulting equation for the unknown property
o examples
A steel-belted car tire is inflated to a gauge pressure of 32 psi
at 27C in a garage. What will the gauge pressure be after a
drive on a hot road that brings the temperature to 45C? Note
that gauge pressure is pressure above atmospheric pressure
(14.7 psi).
o finding gas density given pressure, temperature, and molar mass
0. find moles per liter ( n/V = P/RT )
1. convert moles/L to g/L
o finding molar mass
0. find moles of gas ( n = PV/RT)
1. molar mass = g/mol
Reactions involving gases
- predicting volume of gas produced or consumed in a reaction
o strategy: convert between gas volumes and moles using the ideal
gas law
molar volume = V/n = RT/P
o examples
Sodium metal reacts violently with water to produce aqueous
sodium hydroxide and hydrogen gas. How many liters of hydrogen
gas are produced for every gram of sodium that reacts, at STP?
Nitroglycerine explodes according to
2 C
3
H
5
(ONO
2
)
3
3 CO(g) + 2 CO
2
(g) + 4 H
2
O(g) + 6 NO(g) +
H
2
CO(g)
If the product gases are at a temperature of 4500C and a pressure
of 1 atm, what is the total volume of gas produced from detonation
of 1 mole of nitroglycerine?
- easy special case: when all gases have identical P, T, all have identical
molar volumes
o strategy: mole to mole ratios from balanced equation = gas volume to
volume ratios
o example
Ammonia is synthesized by the Haber process:
N
2
(g) + 3 H
2
(g) 2 NH
3
(g)
How many liters of ammonia can be synthesized from 10.0 L of N
2
?
Temperature and molecular speeds
- molecules in a gas move at many different speeds
the Maxwell distribution shows how many molecules are moving

o the distribution shifts to faster speeds at higher temperatures
- average molecular speed
higher temperature = higher average molecular speed
higher molecular weight = lower average molecular speed
many important properties are related to average molecular velocity
diffusion rates: gas movement due to random molecular motion
faster molecules = faster diffusion rate
effusion rate: gas movement through a pinhole in a container
faster molecules = faster effusion rate
heat conduction
faster molecules = faster transfer of heat energy
speed of sound
faster molecules = faster speed of sound
examples
Molecules traveling faster than 1.1 km/s can escape earth's atmosphere. Which is
escaping into space faster: water vapor, or oxygen gas?.
Diving chambers often use helium/oxygen mixtures instead of air. Which would
conduct heat better: helium/oxygen or nitrogen/oxygen atmospheres? In which
atmosphere would sound move fastest?
average molecular kinetic energy
o kinetic energy of one molecule: mv
2

o average kinetic energy of one mole of molecules:
M(v
rms
)
2
= (3/2) RT
o implications
.average molecular kinetic energy depends only on temperature for ideal
gases
Mixtures of gases
mole fraction = moles of component per mole of mixture
by Avogadro's law, mole fraction = volume fraction for ideal gases
examples
2 L of He gas is mixed with 3 L of Ne gas. What is the mole fraction of each
component?
Air is approximately 79% N
2
and 21% O
2
by mass. What is the mole fraction of O
2
in
air?
partial pressure: pressure exerted by one gaseous component in a mixture
partial pressure = mole fraction times total pressure
examples
One mole of air contains 0.79 mole of nitrogen, 0.21 mole of oxygen. Compute the
partial pressure of these gases at a total pressure of 1 atm and at a total pressure of
3 atm (about the pressure experienced by a diver under 66 feet of seawater).
vapor pressure of water: partial pressure of water vapor over water in a sealed
container
examples
What is the mole fraction of water in the headspace of a soda bottle, if the gas is at
2.0 atm and 25C? The vapor pressure of water at 25C is 23.756 torr.
total pressure = sum of all partial pressures
a. k. a. Dalton's Law
useful in correcting calculations for the effect of moisture
examples
1 L of oxygen gas is collected over water at STP. How many
grams of oxygen are present? The vapor pressure of
water at 0C is
Real gases
- differences between ideal and real gases


ideal gas real gas
obey PV=nRT: always only at very low pressures
molecular volume: zero small, but nonzero
molecular attractions: zero small
molecular repulsions: zero small
- distance between molecules is related to gas concentration: n/V = P/RT
- high gas concentration = closer molecules = stronger intermolecular
interactions = deviations from ideal behavior
o repulsions make pressure higher than expected by decreasing free
volume
o attractions make pressure lower than expected by braking molecular
collisions
o tug-of-war between these two effects
repulsions win at very high pressure
attractions win at moderate pressure
neither attractions nor repulsions are important at low pressure.
Ideal Gas Law
An ideal gas is defined as one in which all collisions between atoms or
molecules are perfectly eleastic and in which there are no intermolecular
attractive forces. One can visualize it as a collection of perfectly hard spheres
which collide but which otherwise do not interact with each other. In such a
gas, all the internal energy is in the form of kinetic energy and any change in
internal energy is accompanied by a change in temperature.
An ideal gas can be characterized by three state variables: absolute pressure
(P), volume (V), and absolute temperature (T). The relationship between them
may be deduced from kinetic theory and is called the

- n = number of moles
- R = universal gas constant = 8.3145 J/mol K
- N = number of molecules
- k = Boltzmann constant = 1.38066 x 10
-23
J/K = 8.617385 x 10
-5
eV/K
- k = R/N
A

- N
A
= Avogadro's number = 6.0221 x 10
23
/mol
The ideal gas law can be viewed as arising from the kinetic pressure of gas
molecules colliding with the walls of a container in accordance with Newton's
laws. But there is also a statistical element in the determination of the average
kinetic energy of those molecules. The temperature is taken to be proportional
to this average kinetic energy; this invokes the idea of kinetic temperature. One
mole of an ideal gas at STP occupies 22.4 liters.
Calculation
Departure from an ideal gas: van der Waals equation of state

Index

Gas law concepts

Kinetic theory
concepts


Molecular Constants
In the kinetic theory of gases, there are certain constants which constrain the
ceaseless molecular activity.

A given volume V of any ideal gas will have the same number of
molecules. The mass of the gas will then be proportional to the
molecular mass. A convenient standard quantity is the mole, the mass
of gas in grams equal to the molecular mass in amu. Avogadro's
number is the number of molecules in a mole of any molecular
substance.

The average translational kinetic energy of any kind of molecule in an
ideal gas is given by


Index

Kinetic theory
concepts

HyperPhysics***** Thermodynamics R Nave

Go Back




State Variables
A state variable is a precisely measurable physical property which
characterizes the state of a system, independently of how the system was
brought to that state. It must be inherently single-valued to characterize a
state. For example in the heat-work example, the final state is characterized
by a specific temperature (a state variable) regardless of whether it was
brought to that state by heating, or by having work done on it, or both.
Common examples of state variables are the pressure P, volume V, and
temperature T. In the ideal gas law, the state of n moles of gas is precisely
determined by these three state variables. If a property, e.g., enthalpy H, is
defined as a combination of other state variables, then it too is a state
variable. Enthalpy is one of the four "thermodynamic potentials", and the
other three, internal energy U, Helmholtz free energy F and Gibbs free
energy G are also state variables. The entropy S is also a state variable.
Some texts just use the term "thermodynamic variable" instead of the
description "state variable".
Index

Kinetic
theory
concepts








The Mole
A mole (abbreviated mol) of a pure substance is a mass of the
material in grams that is numerically equal to the molecular mass in
atomic mass units (amu). A mole of any material will contain
Avogadro's number of molecules. For example, carbon has an atomic
mass of exactly 12.0 atomic mass units -- a mole of carbon is
therefore 12 grams. For an isotope of a pure element, the mass
number A is approximately equal to the mass in amu. The accurate
masses of pure elements with their normal isotopic concentrations
can be obtained from the periodic table.
One mole of an ideal gas will occupy a volume of 22.4 liters at STP
(Standard Temperature and Pressure, 0C and one atmosphere
pressure).
Avogadro's number

Standard Temperature and Pressure
STP is used widely as a standard reference point for expression of the
properties and processes of ideal gases. The standard temperature is
the freezing point of water and the standard pressure is one standard
atmosphere. These can be quantified as follows:
Standard temperature: 0C = 273.15 K
Standard pressure = 1 atmosphere = 760 mmHg = 101.3 kPa
Standard volume of 1 mole of an ideal gas at STP: 22.4 liters
Index

Kinetic theory
concepts





Gauge Pressure
Does the flat tire on your automobile have zero air pressure? If it is
completely flat, it still has the atmospheric pressure air in it. To be sure, it
has zero useful pressure in it, and your tire gauge would read zero pounds
per square inch. Most gauges read the excess of pressure over atmospheric
pressure and this excess is called "gauge pressure". While a useful
measurement for many practical purposes, it must be converted to absolute
pressure for applications like the ideal gas law.
Since a partial vacuum will be below atmospheric pressure, the phrase
"negative pressure" is often used. Certainly there is no such thing as a
negative absolute pressure, but small decreases in pressure are commonly
used to entrain fluids in sprayers, in carburetors for automobiles, and
many other applications. In the case of respiration, we say that the lungs
produce a negative pressure of about -4 mmHg to take in air, which of
course means a 4 mmHg decrease from the surrounding atmospheric
pressure.


When a system is at atmospheric pressure like the left image above, the
gauge pressure is said to be zero. In this image, the system has been
opened so that it is at equilibrium with the atmosphere. In the right image,
Index

Kinetic
theory
concepts
the system has been closed and the plunger pushed down until the pressure
reads about 15 lb/in
2
. This implies that the absolute pressure has been
approximately doubled by compressing the gas to half its volume (ideal
gas law). Standard atmospheric pressure in these U.S. common units is
14.7 lb/in
2
, so this must be added to the gauge pressure above to get the
absolute pressure.
Ideal Gas Law with Constraints
For the purpose of calculations, it is convenient to place the ideal gas law
in the form:


where the subscripts i and f refer to the initial and final states of some
process. If the temperature is constrained to be constant, this becomes:


which is referred to as Boyle's Law.
If the pressure is constant, then the ideal gas law takes the form


which has been historically called Charles' Law. It is appropriate for
experiments performed in the presence of a constant atmospheric pressure.
All the possible states of an ideal gas can be represented by a PvT surface
as illustrated below. The behavior when any one of the three state
variables is held constant is also shown.
Index

Gas law
concepts

Kinetic
theory
concepts















Ideal Gases under Constant Volume, Constant Pressure, Constant
Temperature, & Adiabatic Conditions
Note to the student: The following section is a reduction of college notes I
made in introductory thermodynamics. It does not read as easily as the
preceding sections. I include it here because, for me, it represented a
significant unification of the ideas presented in the text and during lecture.
The first year college student will certainly find it useful.
The equation of state for an ideal gas is
pV = RT 1.
where p is gas pressure, V is volume, is the number of moles, R is the
universal gas constant (= 8.3144 j/(
o
K mole)), and T is the absolute
temperature. The first law of thermodynamics, the conservation of energy,
may be written in differential form as
dq = du + p dV 2.
where dq is a thermal energy input to the gas, du is a change in the internal
energy of the gas, and p dV is the work done by the gas in expanding
through the change in volume dV.

Constant Volume Process
If V = const., then dV = 0, and, from 2, dq = du; i.e., all the thermal input to
the gas goes into internal energy of the gas. We should expect a
temperature rise. If the gas has a specific heat at constant volume of C
V

(j/(
o
K mole)), then we may set dq = C
V
dT. It follows, in this case, that
du = C
V
dT 3.
Since du was initially unspecified, we are free to choose its mathematical
form. Equation 2 will be retained for du throughout the remainder of the
cases.

Constant Pressure Process
If p = const., then dp = 0, and, from 1, p dV = R dT; i.e., the work done by
the gas in expanding through the differential volume dV is directly
proportional to the temperature change dT. If the gas has a specific heat at
constant pressure of C
p
, then dq = C
p
dT, and, from 2 (with 3),
C
p
dT = C
V
dT + R dT
Simplifying gives an important constitutive relationship between C
V
, C
p
, and
R, namely:
C
p
= C
V
+ R 4.

Constant Temperature Process
If T = const., then dT = 0, and, from 1, d(pV) = 0, i.e., pressure and volume
are inversely proportional. Further, from 2, dq = p dV; i.e., there is no
change in internal energy (from 3, du = 0), and all the thermal input to the
gas goes into the work of expansion.

Adiabatic Process
If q = const, then dq = 0, and, from 2 (with 3), 0 = C
V
dT + p dV; i.e.,
internal energy of the gas might be reduced in favor of expansion, or vice
versa. This expression may be written in an equivalent form as
0 = (C
V
/R)(dT/T) + dV/V 5.
(division of the first term by RT, and the second term by pV). Further, from
1,
p dV + V dp = R dT
or, equivalently,
dp/p + dV/V = dT/T
6.
(division of the Left Hand Side by pV, and the Right Hand Side by RT).
Equations 5 and 6 may be used to develop relationships between p and V,
or p and T:

Case 1:
To eliminate T, use 6 in 5 for dT/T to obtain 0 = (C
V
/R)(dp/p + dV/V) + dV/V,
or
-(C
V
/R) dp/p = (1 + C
V
/R) dV/V 6a.
Using 4, we may write C
V
/R = C
V
/(C
p
- C
V
) = 1/( - 1) where = C
p
/C
V
, the
ratio of the specific heats (>1; in fact, approximately 1.4 for air at STP).
Thus, equation 6a becomes (after simplification)
-dp/p = dV/V
which, upon integration, yields
p
0
/p = (V/V
0
) 7.
i.e., the pressure varies inversely as the volume raised to the power .

Case 2:
To eliminate V, use equation 6 to write dV/V = dT/T - dp/p, and substitute
for dV/V in eq. 5
(C
V
/R + 1) dT/T = dp/p
Proceeding as before produces the result that

/( - 1)
p/p
0
= (T/T
0
) 8.
Entropy changes may be calculated for each of the above thermodynamic
processes. The definition of entropy is
dS = dq/T 9.
where dS is the differential entropy change.
For constant volume processes, dq = C
V
dT, so that dS = C
V
dT/T, and
S = C
V
ln(T/T
0
) 10.
For constant pressure processes, dq = C
p
dT, so that dS = C
p
dT/T, and
S = C
p
ln(T/T
0
) 11.
For constant temperature processes, dq = p dV, so that dS = p dV/T = R
dV/V, and
S = R ln(V/V
0
) 12.
For adiabatic processes, dq = 0, so that ds = 0, and
S = const.

Problem:
Estimate the dry adiabatic lapse rate for an ascending parcel of air near the
earth's surface.
Solution:
The dry adiabatic lapse rate for an ascending parcel of air near the earth's
surface may be estimated from the above expressions. (For comparison,
the published value is 5.5
o
F per thousand feet). Let us begin with
Bernoulli's equation
p + gh = p
0
13.
where p is the pressure of air at height h above the earth's surface, is the
density of air in kg/m
3
, g is the gravitational acceleration, and p
0
is
atmospheric pressure at the earth's surface. Differentiating this expression
once, we get
dp + g dh = 0 13a.
We now write the equation of state for an ideal gas as p = nkT, where n is
the number density of the gas in m
-3
, and k is Boltzmann's constant. We
may further write n = /M where M is the average molecular mass of air in
kg. Using this expression in the ideal gas equation of state and solving for
, we have = pM/kT. Substituting this result into 13a gives
dp + (pMg/kT) dh = 0
We may now separate variables and integrate. In so doing, it is customary
to assume that the variation of T with h may be ignored (isothermal
approximation). Thus
dp/p = -(Mg/kT) dh
or p/p
0
= e
-(Mg/kT) h
14.
The term kT/Mg is often called the scale height of the atmosphere (i.e., that
height at which the calculated pressure drops to 1/e of its initial value; in an
isothermal atmosphere, this number has physical meaning). At the earth's
surface, at STP (Standard Temperature and Presure, 1 atm.), we have
M = 4.81 x 10
-26
kg
g = 9.81 m/sec
2

k = 1.38 x 10
-23
j/
o
K
T = 273
o
K
so that the scale height is 7.99 km = 2.53 x 10
4
ft. If we now set p
0
= 1 atm,
then at h = 1,000 ft., we find
p = 9.61 x 10
-1
atm.
We may use this pressure in equation 8 as an estimate of atmospheric
pressure (even though eq. 8 pertains to an adiabatic atmosphere rather
than an isothermal one), and calculate the temperature at 1,000 ft. When
we do so, we find
T = 270
o
K
or T = 3
o
K = 5.4
o
F 15.
This value is satisfactorily close to the book value of 5.5
o
F per 1,000 ft. to
meet our needs.






Course Outline
General Chemistry--Unit 2



Kinetic Molecular Theory of Gases

To master this material, you must know the gas laws.




A law is a summary of observations, and a theory is an explanation of those
observations. The individual gas laws give us a set of mathematical tools to help predict
the behavior of gases under specific conditions of pressure, temperature, volume and
number of moles of gas. They do not, however, explain why gases behave the way they
do. Kinetic molecular theory is an attempt to explain some of the bulk properties of
matter by describing how particles interact with one another. Kinetic molecular theory
can help us understand how and why the gas laws work and to predict when the gas
laws wont work.
Daniel Bernoulli started kinetic molecular theory in 1738 when he proposed a thought
model consistent with Boyles Law in an attempt to explain how gases exert pressure.
Clausius refined the theory in the mid-1800s.
The Assumptions of Kinetic Molecular Theory:
In order to explain how gases behave we can make the following assumptions:
A gas is composed of particles in constant motion.
The average kinetic energy depends on temperature, the higher
the temperature, the higher the kinetic energy and the faster the
particles are moving.
Compared to the space through which they travel, the particles
that make up the gas are so small that their volume can be
ignored.
The individual particles are neither attracted to one another nor
do they repel one another.
When particles collide with one another (or the walls of the
container) they bounce rather than stick. These collisions are
elastic; if one particle gains kinetic energy another loses kinetic
energy so that the average remains constant.

The KMT Assumptions and the Gas Law Variables:
We can connect these assumptions with the four variables from the individual gas laws.
Pressure is force per unit area. What we observe as the pressure
of a gas is the force of collisions as the particles strike the walls
of the container. If these collisions occur frequently, the gas
pressure is high. If the collisions dont occur very often, the
pressure is low. Any change in the conditions that results in more
frequent collisions will increase the pressure.
What we observe as the volume of a gas is the empty space the
particles travel through. The larger the volume, the greater the
distance between particles. Any change in the conditions that
results in a longer distance between particles is due to an
increase in volume.
What we observe as n, or number of moles, is the number of
particles.
What we observe as temperature of a gas is the average speed of
the particles. The hotter the gas, the faster the particles are
moving. The speeds of the individual gas particles vary, but they
form a statistical distribution of speeds that looks like the
following graph:


The root mean square speed, u, is the square root of the average of the squares of
the speeds, which is pretty close to the average for this type of distribution. The
higher the temperature of the gas is, the higher the root mean square of the speed.
To put it more simply, the hotter the temperature is, the faster the particles are
moving. The root mean square of the temperature is related to the kinetic energy of
the particles:



where is the kinetic energy, m is the mass of the particle and u is the root mean
square speed.

The KMT and the Individual Gas Laws:
Boyles Law:
Boyles Law states that, at constant number of moles and temperature,
pressure and volume are inversely proportional. Constant number of
moles implies that the number of gas particles remains the same. Constant
temperature implies that the average speed of the particles remains the
same. If the pressure and volume are inversely proportional, an increase in
volume will lead to a decrease in pressure. If volume increases, the distance
each particle travels before it hits the wall increases. If the same number of
particles is traveling the same speed and they have to travel farther to hit
the wall of the container, they must not hit the wall as often. The frequency
with which particles collide with the wall is the same as the gas pressure; if
the collision rate drops, so does the pressure. Therefore, volume and
pressure are inversely proportional.
Charles Law:
Charles Law states that, at constant number of moles and pressure, the
volume and the temperature are directly proportional. Constant number of
2
1
2
mu c =
moles implies that means that the number of gas particles remains the
same. Constant pressure implies that the rate at which the particles collide
with the wall of the container remains the same. If volume and temperature
are directly proportional, an increase in temperature will lead to an increase
in volume. If temperature increases, the average speed of the gas particles
increases. If the same number of particles is colliding at the same rate even
though they are moving faster, they must be traveling farther. The distance
between the particles and the wall is the same as the volume; if the distance
increases, the volume increases. Therefore, volume and temperature are
directly proportional.
The Third Law:
At constant number of moles and volume, the temperature and pressure are
directly proportional. Constant number of moles implies that the number
of gas particles remains the same. Constant volume implies that the
distance between particles and the wall remains the same. If the
temperature and pressure are directly proportional, an increase in
temperature will lead to an increase in pressure. If the temperature
increases, the average speed of the gas particles increases. If the same
number of particles is traveling the same distance and moving faster, they
must strike the wall more often. An increase in the collision rate is an
increase in pressure. Therefore, temperature and pressure are directly
proportional.
Avogadros Law:
Avogadros Law states that at constant temperature and pressure, the
number of moles of gas and the volume are directly proportional. Constant
temperature means that the average speed stays the same. Constant
pressure means that the rate at which the particles strike the wall stays the
same. If the number of moles and the volume are directly proportional, an
increase in the number of moles will lead to an increase in the volume. If the
particles travel the same speed and hit the wall at the same rate, yet there
are more particles, they must spread out more and traveling farther to reach
the wall. A greater distance is the same as an increase in volume. Therefore
number of particles and volume must be directly proportional.
The Combined Gas Law and Ideal Gas Law:
The combined gas law is a statement of the relationships among pressure,
volume and temperature at constant amount of gas. If the kinetic molecular
theory describes each pair of variables, it must also describe the inter-
relationship among pressure, volume and temperature for a set amount of
gas undergoing a change in conditions. The ideal gas law is a statement of
the relationships among pressure, volume, amount of gas, and temperature
for a gas at a set condition. These variables are inter-related as collisions,
speed and distance. If a gas obeys the assumptions of kinetic molecular
theory, it must be ideal.
Grahams Law:
Grahams Law of effusion states that the rate at which a gas effuses is
inversely proportional to the square root of its molar mass. In other words,
the smaller the gas particle the faster it effuses. This works because the
molar mass of a gas increases as the effective diameter of the gas particle
increases. The average speed of an ideal gas depends on temperature rather
than particle size, but this is relative to empty space between particles. As a
gas effuses through a small hole, the size of the particle is no longer
negligible. A gas particle is more likely to pass through any microscopic hole
in the wall of the container if it is small.
Grahams law has its mathematical form because the root mean square
speed is related to the mass of the particle. Different gases at the same
temperature have the same kinetic energy. But, if their masses are different,
they must be moving at different speeds. The heavier the particle is, the
faster its speed must be. For two gases at the same temperature, we get




where m is mass and u is root mean square speed for particles one and
two. The rate of effusion is proportional to the root mean square speed,
and the mass of the particle is proportional to the molar mass. Substituting
and rearranging gives Grahams Law.

The KMT and Non-Ideal Behavior:
As experimental apparatus improved in the late 1800s, chemists recognized
that gas laws were only approximate. The best experimental agreement
with the mathematical predictions occurs when the gas is under relatively
low pressure and high temperature. Some gases obey the laws better than
others, even under the same sets of conditions. Gases with smaller molar
masses and ones that are relatively inert obey better than larger, more
reactive gases. Whether by nature or by conditions such as pressure, gases
that do not obey the gas laws very well are called real gases and those
that do obey are called ideal gases. If an ideal gas is one who obeys the
assumptions of kinetic molecular theory, a real gas must be one that
violates one or more of these assumptions.
High Molar Mass and Reactivity:
2
2
2 2
1 1 2 2
1
2
2
mu
mu
mu m u
c
c
=
=
=
One assumption of the kinetic molecular theory is that the gas particles are
neither attracted to nor repelled by one another. When the particles of a
gas are very large, they have higher induced dipole attractions, so they are
more attracted to one another. When the gas particles collide, they stick
together and the average kinetic energy drops. These sticky gas particles hit
the walls of the container less frequently and with less force than ideal gas
particles do. Polar molecules have greater intermolecular attractions, too,
so a molecule like water vapor is much less ideal than one like helium. The
upshot is that some substances make better gases than others. Under the
same conditions of temperature and pressure, helium is an ideal gas and
water vapor is a real gas.
High Pressure:
One assumption of the kinetic molecular theory is that the volume of the
container is large enough that the volume of the particles is negligible.
When a gas is under very high pressure (and/or the volume for that mass of
gas is very low), the volume of the particles themselves can no longer be
ignored, and calculated volumes are lower than real volumes. To make
matters worse, as the distance between the particles drops, the attractions
between particles increase. As particles stick together, they are less likely to
strike the wall of the container, so calculated pressures are higher than real
pressures.
Low Temperatures:
Even very small, very inert gases like helium have induced dipole attraction
for one another. Hot gas particles have a lot of kinetic energy to overcome
these weak attractions. When a gas is very cold, the average molecular
speeds and kinetic energy are low. The kinetic energy is no longer able to
supply the energy needed to overcome the attractions between particles.
Particles stick together and thus average kinetic energy drops. The upshot is
that really cold gases are so non-ideal that they become liquids or even
solids and the particles are not free to move throughout the container.
The van der Waals Equation
Atoms and molecules are never truly ideal because they all interact with
other gas particles; weak attractions between separate gas particles are
known as intermolecular attractions or van der Waals forces after the
chemist who proposed a correction to the ideal gas law to calculate
pressure of a real gas. Van der Waals proposed that the ideal gas equation
could be corrected for real gas behavior by subtracting the effective gas
particle volume from the volume of the container and by correcting for
intermolecular attractions:


where b is the gas particle volume and a is the relative attractive force of
the gas particles. These values are unique for each gas.

4Concept Check: Water is not a very good ideal gas, which is why it tends
to be a liquid at STP. For water vapor, the van der Waals constants are a =
5.46 L
2
atm/mol
2
and b = 0.0305 L/mol. If water were an ideal gas, one
mole of water vapor would occupy 22.41 L of volume at 273.2 K and 1.000
atm. What pressure does one mole of water vapor actually exert at this
temperature, if the volume is 22.41 L?

( )( )
( )
2
2
PV nRT
P attractions V gasVolume nRT
n a
P V nb nRT
V
=
+ =
| |
+ =
|
\ .
Answer:

This is pretty close to 1 atm, even if water is a real gas!



2.1 Kinetic Theory of Gases




The macroscopic behaviour of gases can be explained by a model containing three
hypotheses.
1) A gas is an ensemble of particles in continuous, fast random motion, moving in
straight lines until they collide.
2) The particles are infinitely small and (on the average) far from each other. (volume
of the particles <<< volume of the gas)
3) The particles do not influence one another except during collisions. The collisions
of the particles with each other and with the wall of the container are elastic, i.e. the
kinetic energy of the particles is maintained (there is no transformation of kinetic
energy into heat of friction).
The pressure of a gas exerted on the walls of the container is caused by the collision
of the gas particles with the wall.

( )
( )
( )
2
2
2
2
2
2
2
2
1.000 5.46
1.000 0.08206 273.2
22.41
22.41 1.000 0.0305
0.991
n a
P V nb nRT
V
becomes
nRT n a
P
V nb V
L atm
L atm
mol
mol K
mol
mol K
P
L
L
L mol
mol
P atm
| |
+ =
|
\ .
=

| | -
-
| |
|
|
-
\ . \ .
=
| |

|
\ .
=