Dalton’s Law of Partial Pressures

• Mole fraction is related to the total pressure by:

Pi  X i Ptot
• On a humid day in summer, the mole fraction of
gaseous H2O (water vapor) in the air at 25°C can be
as high as 0.0287. Assuming a total pressure of
0.977 atm, what is the partial pressure (in atm) of
H2O in the air?

1
 Graham’s Law: Diffusion and Effusion
• Diffusion is the mixing
of different gases by
random molecular
motion and collision.

• Effusion is when gas

molecules escape
without collision, through
a tiny hole into a vacuum.
2 Chapter 9
Graham's Law of Effusion - Under the
same conditions of pressure and
temperature, the rates of effusion of gases
are inversely proportional to the square
roots of their molar masses or densities .
D) What does this mean?
 U1 d2 M2
 
U2 d1 M1
U1 t 2

U 2 t1

t = time of effusion
E) How many times faster does H2 effuse
than O2 at the same temperature and
pressure?

The rate of effusion of H2 is 4 times

faster than the rate of effusion of O2.
If it takes 205 seconds for 1.50 L of an
unknown gas to effuse through a porous
cup, and 95 seconds for the same volume
of N2 at the same T and P, what is the
approximate molar mass of the gas?
• The variation of the potential energy of
two molecules on their separation.
• High positive potential energy (little
separation)
– Repulsive interactions
• Intermediate separations
– attractive interactions dominate
• Large separations (on the right)
– the potential energy is zero and there is no
interaction between the molecules.
 Behavior of Real Gases
• Deviations from Ideal behavior result from
two key assumptions about ideal gases.
1. Molecules in gaseous state do not exert any force,
either attractive or repulsive, on one another.
2. Volume of the molecules is negligibly small compared
with that of the container.

10
A plot of PV vs. P constructed from actual data for several gases at 0.0 ⁰C is shown in
the fig. 1 ,the fact immediately apparent is that PV is not constant over most of the
pressure range shown .
The curves are in general of two types ; one , including H2 starts at the value of PV
demanded by PV = nRT and increases continually with pressure . In every case the
product PV is greater than expected .
In the second type the plot starts a gain at the same point as before , but now the
product PV decreases at first with pressure passes through a minimum characteristic
of each gas and temp. and then increases to values which may rise appreciably above
that for nRT .
Actually , both types of curves are part of a single pattern of behavior exhibited by all
gases . To show this , it is convenient to employ a quantity z , called the
compressibility factor , which is defined as :
PV
z
nRT
For an ideal gas z=1 at all temp. & pressure . Z for real gas vary with both T & P ; z≠ 1
for real gas except at Boyle temp & special range of pressure .
High Pressures •
 Compressibility Factor
• Recall Z plot?
• Z = pVm / RT; also called
the compressibility factor
• Z should be 1 at all
conditions for an ideal gas
• For real gases, Z not
equals to 1

– At high p, Vm > Vm,id, Z >

1
– Repulsive forces
dominant
– At intermediate p, Z < 1
– Attractive forces
dominan .
• The compressibility of a gas is defined by

pVm
Z
RT
• If the gas behaves ideally, then Z=1 at all pressures and
temperatures.
• Z >1 molecules occupy more volume than IG (e.g. H2):
repulsive forces
• Z < 1 molecules occupy less volume than IG (e.g. CO2):
attractive forces
• For a perfect gas,
the slope is zero
• Boyle temperature
– the slope is zero and
the gas behaves
perfectly over a wider
range of conditions
than at other
temperatures.
Boyle’s temperature
 Virial equation of state

Z=

It is based on statistical mechanical theory, where

each power level indicates a higher level of
interaction.

The virial equation does not tend to be very good at

high densities (low T, high P).
Van der Waals equation differs from the ideal gas law in that it
makes allowance both for the volume occupied by the molecules
themselves & for the attractive forces between them .

• Real gas molecules do attract one another

(Pid = Pobs + constant)
• Real gas molecules are not point masses
(Vid = Vobs - const.)