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Part 4: Gases
A gas consists of many microscopic
molecules, each with 1 or (usually)
more atoms.
They move in different directions at
different speeds and interact very
little, except when colliding with each
other or with their container *
Ideal gas Law
Ideal gas does not exist but:
Good approx. to real gas if pressure not
very high
In an ideal gas molecules only interact by
elastic collisions i.e. sum of kinetic
energies is conserved (same before and
after collision)
Forces between molecules assumed
negligible except during collisions *
Relative Mass
All atoms and most molecules are small
Define mass in terms of standard small unit:
atomic mass unit:
1 u =(mass of carbon-12 atom)/12
Relative atomic mass is:
A
r
=(mass of atom)/(1 u)
Relative molecular mass is:
M
r
=(mass of molecule)/(1 u) *
Amount of Substance: Mole
Basic SI unit: mol
1 mole is simply a group of 6.02210
23
particles
N
A
=6.02210
23
mol
-1
=Avogadros Number or
Avogadro Constant
*
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Molar Mass: M
M
Mass per mole of a substance
By definition 1 mol of carbon-12 has mass
exactly 12 grams so:
M
M
=A
r
10
-3
kg mol
-1
(for atoms)
M
M
=M
r
10
-3
kg mol
-1
(for molecules)
Often molar mass is still expressed in units
of g mol
-1
so be careful! *
N.B! Dont get these mixed up!
Molecular mass is mass per molecule
e.g. mass of one oxygen molecule O
2
is
m=5.3110
-26
kg
Molar mass is mass per mole
e.g. molar mass of O
2
is
M
M
=mN
A
=0.032 kg mol
-1
Relative molecular mass is molecular mass
relative to 1 atomic mass unit
e.g. relative molecular mass of O
2
is
M
r
=5.3110
-26
kg/(1.660510
-27
kg) =32.0
so: M
M
=M
r
10
-3
kg mol
-1
*
Finding the Ideal Gas Law
For a given amount n of gas (in mol) with
temperature T volume V and pressure P:
We obtain relationships between pairs of
quantities when the other two are kept
constant: *
Finding the Ideal Gas Law (cont.)
By the definition of absolute temperature:
P T (constant nand V)
When V and T are constant: P n
When nand T are constant: P 1/V
Combining the above:
P n(1/V)T
or: PV nT *
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Finding Ideal Gas Law (cont.)
The constant of proportionality is called
the Molar Gas Constant R giving:
PV =nRT
Or: in terms of N, the total number of
molecules:
PV =NkT
(k is the Boltzmann Constant)
*
Quick Quiz
What are the units of R?
What are the units of k?
J mol
-1
K
-1
J K
-1
Number of molecules N is dimensionless
Number of moles n is not (by convention) *
Kinetic Theory of Gases
Gas consists of molecules in motion
colliding with each other and with
container
This provides a microscopic (small scale)
explanation for the macroscopic (large
scale) properties described by the ideal
gas law:
PV =nRT *
Microscopic explanation of T
Molecules move in different directions with
a range of speeds
Higher average kinetic energy E
k
of the
molecules means higher temperature
Note that this microscopic kinetic energy is
classed under internal energy U
For given amount nof a given type of gas:
T depends only on U (not P or V) *
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Microscopic Explanation of P
Pressure on a surface (e.g. container wall)
in a gas is the combined effect of
molecules colliding with the surface
So many collisions occur per second that
the effect seems to be constant *
Piston
http://www2.biglobe.ne.jp/~norimari/science/J avaApp/e-gas.html
Microscopic Explanation of P 1/V
(const. n and T)
Say you increase V:
Number of molecules m
-3
(per m
3
volume)
decreases
This reduces the number of collisions on
any given surface per second
Hence P decreases *
Microscopic Explanation of why
P n(const. V, T)
For constant V and T
Say you increase n:
Number of molecules m
-3
increases
This increases the number of collisions on
any given surface per second
Hence P increases *
Microscopic Explanation of
Adiabatic Temperature Change
Adiabatic simply means Q=0
Say you compress a sample of gas (by
pushing on a piston):
You do work W on the gas. This
increases the energy, hence speed, of the
molecules colliding with the piston
U (and hence T) are thus increased
Increased T and smaller V increase P as
collisions are faster and more frequent *
Piston
http://www2.biglobe.ne.jp/~norimari/science/J avaApp/e-gas.html
1-d W
http://galileo.phys.virginia.edu/classes/109N/more_stuff/Applets/Piston/jarapplet.html
5
Heat Flow
This termis often used
More accurate to say Energy transfer by
heating (Q)
We just sawthat T can change by heating
and by working
Therefore heat is not a separate fluid
which flows fromone place to another *
Average kinetic energy
The sum of the kinetic energies of all N
molecules in a gas, divided by N, gives the
average kinetic energy:
E
k
=(1/2)mv
2

Where v
2
is the average of the square
of the speed of each molecule
and mis the mass of each molecule
(molecular mass in kg) *
Average kinetic energy (cont.)
The square root of the average of the
square of speed, is the root-mean-square
speed:
v
rms
=(v
2
)
1/2
so:
E
k
=(1/2)mv
rms
2
*
Average kinetic energy (cont.)
Agreement with the gas law PV =NkT
requires:
E
k
=(3/2)kT
Where k =Boltzmann const
T =gas temperature
*
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Example
For helium (He) all internal energy is in the
form of microscopic kinetic energy.
Find the change in internal energy for 10
mol of He changing from 300 K to 350 K
(N
A
=6.022x10
23
mol
-1
k =1.381x10
-23
J K
-1
) *
Maxwell-Boltzmann Distribution
T depends on the average (microscopic)
translational kinetic energy of molecules
Individual molecules cover a wide range of
energies (hence speeds)
The Maxwell-Boltzmann distribution is a
function giving the fraction of total
molecules which exist at different speeds *
Maxwell-Boltzmann
simple example:
Imagine a sample of gas at a certain
temperature consistingof 10 molecules
Say at some instant the speeds of the
molecules (in ms
-1
) are:
1.2, 4.1, 2.5, 1.5, 2.3, 2.9, 3.2, 2.1, 1.8, 3.8
Count howmany in each 1 ms
-1
interval
Divide by total number to get fraction
Plot graphically as a histogram, with bars 1
m s
-1
wide *
Maxwell-Boltzmann (cont.)
The distribution for 10 molecules is not
smooth and would also fluctuate (vary)
over time
At normal temperatures and with a large
number of molecules the speeds of most
molecules are much higher and
fluctuations have little effect
This makes the shape smoother and
steadier and the graph becomes more like
a smooth curve. *
http://intro.chem.okstate.edu/1314F00/Laboratory/GLP.htm
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Maxwell-Boltzmann (cont.)
The total area under the curve is still 1
Area between any 2 values of v gives the fraction
of molecules within that speed range
For higher T: Peak moves to the right (higher
average speed) and curve is flatter:
*
Formula of Maxwell-Boltzmann
Distribution function
(

|
.
|

\
|
=
2kT
mv -
exp
kT 2
m
v 4 v) (
2
2 / 3
2
t
t f
The theoretical smooth curve giving
fraction of molecules per ms
-1
is given by
the following function:
Where:
mis the molecular mass (mass of
each molecule)
k is the Boltzmann constant *