Gas laws

Ideal and real gaes

The molar volume of a gas at stp

• 1 mole of any gas occupies 22.4 dm3 at stp (standard temperature

and pressure, taken as 0°C and 1 atmosphere pressure).
• You may also have used a value of 24.0 dm3 at room temperature and
pressure (taken as about 20°C and 1 atmosphere).
• These figures are actually only true for an ideal gas, and we'll have a
look at where they come from.
 ideal gas law

• The ideal gas equation is:

• this is an easy equation to remember and use.

• The problems lie almost entirely in the units.
• I am assuming below that you are working in
strict SI units
 ideal gas law

many gases behave approximately as if they were

ideal at ordinary working temperatures and pressures

• P is the absolute pressure (SI units Pascals),

• V is the volume of gas (SI units m3),
• n is the chemical amount of gas (SI units mole),
• T is thermodynamic temperature (SI units Kelvin).
Pressure, p

• Pressure is measured in pascals, Pa - sometimes expressed as

newtons per square metre, N m-2. These mean exactly the same
thing.
• You must make that conversion before you use the ideal gas equation.
• Should you want to convert from other pressure measurements:
• 1 atmosphere = 101,325 Pa
• 1 bar = 100 kPa = 100,000 Pa
 Volume, V
• the SI unit of volume is the cubic metre, m3 - not cm3 or dm3.
• 1 m3 = 1000 dm3 = 1,000,000 cm3
• So if you are inserting values of volume into the equation, you first have to
convert them into cubic metres.
• You would have to divide a volume in dm3 by 1000, or in cm3 by a million.
• Similarly, if you are working out a volume using the equation, remember to
covert the answer in cubic metres into dm3 or cm3 if you need to - this time
by multiplying by a 1000 or a million.
• If you get this wrong, you are going to end up with a silly answer, out by a
factor of a thousand or a million. So it is usually fairly obvious if you have
done something wrong, and you can check back again.
Number of moles, n

• it is just a number. You already know

that you work it out by dividing the mass
in grams by the mass of one mole in
grams.
• You will most often use the ideal gas
equation by first making the substitution
to give:
The gas constant, R

• A value for R , you can look it up in a data source.

• The SI value for R is 8.31441 J K-1 mol-1

• You may come across other values for this with different units.

A commonly used one in the past was 82.053 cm3 atm K-1 mol-1.
• The units tell you that the volume would be in cubic centimetres and
the pressure in atmospheres.
JOULE UNIT

9
The temperature, T

• The temperature has to be in kelvin.

• Don't forget to add 273 if you are given a temperature in degrees
Celsius
The molar volume of an ideal gas is 22.4 dm3 at stp.

• We can use the ideal gas equation to calculate the volume of 1 mole of an ideal gas at
0°C and 1 atmosphere pressure.
• First, we have to get the units right.
• 0°C is 273 K. T = 273 K
• 1 atmosphere = 101325 Pa. p = 101325 Pa
• We know that n = 1, because we are trying to calculate the volume of 1 mole of gas.
• And, finally, R = 8.31441 J K-1 mol-1.
• Slotting all of this into the ideal gas equation and then rearranging it gives:
Finding the relative formula mass of a gas from its density

• The density of ethane is 1.264 g dm-3 at 20°C and 1 atmosphere.

• Calculate the relative formula mass of ethane.

The density value means that 1 dm3 of ethane weighs 1.264 g.

Finding the relative formula mass of a gas from its density

• The density of ethane is 1.264 g dm-3 at 20°C and 1 atmosphere.

Calculate the relative formula mass of ethane.
before we do anything else, get the awkward units sorted out.
• A pressure of 1 atmosphere is 101325 Pa.
• The volume of 1 dm3 has to be converted to cubic metres, by dividing
by 1000. We have a volume of 0.001 m3.
• The temperature is 293 K.
• Now put all the numbers into the form of the ideal gas equation
which lets you work with masses, and rearrange it to work out the
mass of 1 mole.
• The mass of 1 mole of anything is
simply the relative formula mass in
grams.
• So the relative formula mass of
ethane is 30.4, to 3 sig figs.
Now, if you add up the relative formula mass of ethane, C2H6 using
accurate values of relative atomic masses, you get an answer of 30.07
to 4 significant figures. Which is different from our answer - so what's
wrong?
• There are two possibilities.
• The density value I have used may not be correct. I did the sum again
using a slightly different value quoted at a different temperature from
another source. This time I got an answer of 30.3. So the density
values may not be entirely accurate, but they are both giving much
the same sort of answer.
The idealness of ethane gas

• Ethane isn't an ideal gas. Well, of course it isn't an ideal gas –

• there's no such thing! However, assuming that the density values are
close to correct, the error is within 1% of what you would expect.
• So although ethane isn't exactly behaving like an ideal gas, it isn't far
off.
Helium gas
• at 273 K and 1 atmosphere pressure, the density of
helium is 0.1785 g dm-3.
• That means that 0.1785 g of helium occupies 1 dm3
at stp.
• It is a fairly simple sum to work out what 1 mole of
helium, He, would occupy.
• 1 mole of He weighs 4 g, and would occupy 4 /
0.1785 dm3 = 22.4 dm3.
• That's the same (at least to 3 significant figures) as
the ideal gas value, suggesting that helium behaves
as an ideal gas under these conditions.
• If you do this for a random sample of other gases, you get these values
for the molar volume at stp (273 K and 1 atmosphere pressure).
 density (g dm-3) molar volume at stp

He 0.1785 22.4

N2 1.2506 22.4

O2 1.4290 22.4

CH4 0.717 22.3

CO2 1.977 22.3

C2H4 1.260 22.2

NH3 0.769 22.1

SO2 2.926 21.9

Kinetic Theory assumptions about ideal gases
The assumptions are:
• Gases are made up of molecules which are in constant random motion in
straight lines.
• The molecules behave as rigid spheres.
• Pressure is due to collisions between the molecules and the walls of the
container.
• All collisions, both between the molecules themselves, and between the
molecules and the walls of the container, are perfectly elastic. (That means
that there is no loss of kinetic energy during the collision.)
• The temperature of the gas is proportional to the average kinetic energy
of the molecules.
• For an ideal gas, pV = nRT. If pV and nRT are the
same, and you divide one by the other, then
the answer will, of course, be 1. For real gases,
pV doesn't equal nRT, and so the value will be
something different.
• The term pV / nRT is called the compression
factor. The graphs below show how this varies
for nitrogen as you change the temperature
and the pressure.
• The kinetic theory assumes that, for an ideal gas, the volume taken up by the
molecules themselves is entirely negligible compared with the volume of the
container.
• For a real gas, that assumption isn't true. The molecules themselves do take up a
proportion of the space in the container. The space in the container available for
things to move around in is less than the measured volume of the container.
Compression factor for N2 gas

• If nitrogen was an ideal gas under all

conditions of temperature and
pressure, every one of these curves
would be a horizontal straight line
showing a compression factor of 1.
That's obviously not true!
Compression factor for other gases

• If you were to redo the set of original

nitrogen graphs (at varying temperatures)
for any of these other gases, you would
find that each of them will produce a set
of curves similar to the nitrogen ones.
What varies is the temperature at which
the different graph shapes occur.
• For example, if you look at the carbon
dioxide graph at 273 K, it looks similar to
the nitrogen one at 100 K from the first
set of curves, although it doesn't increase
so steeply at higher pressures.
Compression factor for other gases

• It is easy to say that gases become less

ideal at low temperatures, but what
counts as a low temperature varies
from gas to gas.
• The closer you get to to the
temperature at which the gas would
turn into a liquid (or, in the case of
carbon dioxide, a solid), the more non-
ideal the gas becomes.
•
The compression factor
• For an ideal gas, the compression factor
would be 1 over the whole pressure
range. For a real gas like nitrogen,
notice how the compression factor
tends to increase with pressure.
• The value of the compression factor is
too high at high pressures for a real gas.
The reason for that is that the
measured volume that you put into the
expression is too high because you
aren't allowing for the volume taken up
by the molecules. That error gets
relatively worse the more compressed
the gas becomes.
The pressure problem

• Another key assumption of the Kinetic Theory for ideal gases

is that there are no intermolecular forces between the
molecules. That is wrong for every real gas.
• If there weren't any intermolecular forces then it would be
impossible to condense the gas as a liquid. Even helium, with
the weakest of all intermolecular forces, can be turned to a
liquid if the temperature is low enough.
• So what effect do intermolecular forces have?
• For a gas molecule in the middle of the gas, there is no net
effect. It will be attracted to some extent to all the other
molecules around it, but, on average, those attractions will
cancel each other out. Attractions from behind a molecule,
tending to slow it down, will be cancelled out by attractions
from in front of it, tending to speed it up
The pressure problem

• Despite all the intermolecular forces it is

experiencing, the molecule picked out in green
will just continue to move in the same direction
at the same speed.
• That's different if the molecule is just about to
hit the wall of the container.
if the molecule is just about to hit the wall of the
container
• Now there aren't any gas molecules in front of it, and
the net pull is backwards into the body of the gas. The
molecule will slow down just before it hits the wall.
• If it slows down, it will hit the wall less hard, and so
exert less pressure.
• The overall effect of this is to make the measured
pressure less than it would be if the gas was ideal. That
means that if you put the measured pressure into the
expression pV / nRT, the value of the compression
factor will be less than it would be if the gas was ideal.
• This is why, under some conditions, graphs of
compression factors drop below the ideal value of 1.
N2 gas
• This effect is most important at low
temperatures. Why is that?
• At lower temperatures, the molecules are moving
more slowly on average. Any pull they feel back
into the gas will have relatively more effect on a
slow moving particle than a faster one.
• At higher temperatures, where the molecules are
moving a lot faster, any small pull back into the
body of the gas is hardly going to be noticeable.
At high temperatures, the effect of
intermolecular forces is indeed negligible.
• And there is one final effect concerning
intermolecular forces which is slightly more
hidden away.
•
N2 gas

• As pressure increases, the molecules are forced more closely

together. If they are closer, the intermolecular forces will
become more important. So, as pressure increases, you
would expect more lowering of the compression factor
relative to the ideal case. The molecules which slow down
the one just about to hit the wall will be closer to it, and so
more effective.
• Is that what happens? Yes, up to a point.
• Look again at the nitrogen curve at 100 K. As the pressure
increases, at first the value of the compression factor falls.
• But it soon starts to rise again. Why? Because at this point,
the effect of the size of the molecules starts to become
more important - and as the pressure is increased even
more, this other effect becomes dominant.
•
Which is the most ideal gas?

• You are looking for a gas with the smallest

possible molecules, and the lowest possible
intermolecular forces. That is helium.
• A helium molecule consists of a single small
atom, and the van der Waals dispersion forces
are as low as it is possible for them to be.
• Like helium, a hydrogen molecule also has two
electrons, and so the intermolecular forces are
going to be small - but not as small as helium.
• the hydrogen has two atoms that you can
distribute the charges over.
• As molecules get larger, then dispersion forces
will increase, and you may get other
intermolecular forces such as dipole-dipole
attractions as well. Gases made of molecules
such as these will be much less ideal.
 The van der Waals Equation

• The van der Waals equation was the

first attempt to try to produce an
equation which related p, V, n and T for
real gases. It looks like this:
• If you think this looks complicated, you should
see some of the more modern attempts!
Incidentally, you may come across the equation
in a simpler form for 1 mole of a gas rather than
for n moles. Under those circumstances, every
single n in the equation disappears.
• Look at the left-hand side in two stages.
• the pressure term.  Remember from above, that the
measured pressure is less than the ideal pressure for a real
gas. van der Waals has added a term to compensate for that.
• In the volume term, van der Waals has subtracted the value
nb to allow for the space taken up by the molecules
themselves.
• a and b are constants for any particular gas, but they vary
from gas to gas to allow for the different intermolecular
forces, and molecular sizes. That means that, unfortunately,
you no longer have a single equation that you can use for
any gas.
• Fortunately, however, the ideal gas equation works well
enough for most gases at ordinary pressures, as long as the
temperature is reasonably high.