Examples

4.00 L 1.50 L 3.50 L

CH4 N2 O2

2.70 atm 4.58 atm 0.752 atm

• When these valves are opened, what
is each partial pressure and the total
pressure?
 Vapor Pressure

• Water evaporates!
• When that water evaporates, the
vapor has a pressure.
• Gases are often collected over water
so the vapor. pressure of water must
be subtracted from the total
pressure.
• Water vapor pressure must be given.
 Example
• N2O can be produced by the
following reaction
• NH4NO3  N2O + 2H2O
• what volume of N2O collected over
water at a total pressure of 94 kPa
and 22ºC can be produced from 2.6
g of NH4NO3? ( the vapor pressure of
water at 22ºC is 21 torr)
 Kinetic Molecular Theory
1) Gases are composed of molecules
whose size is negligible compared with
the average distance between them.
(Ideal gas molecules are point masses.)
2) Gas molecules are in constant motion, in
random directions, and at various speeds.
(Properties of a gas that depend on motion
like pressure are the same in all directions.)
3) Ideal gas molecules exert neither an
attractive force nor repulsive force on
each other.
4) When molecules collide with one
another, the collisions are elastic.
What does this mean?
5) The average kinetic energy of the
molecules is proportional to the
temperature on the Kelvin scale.
What does this mean?
All gases at the same temperature on the K
scale have the same average kinetic energy.

K.E. = 1/2 mv2 or 1/2 mu2 where v is

velocity and is a vector quantity, and u is
speed which is a scaler quantity.
Two gases at the same T have the
same average K.E.
If one gas is heavier than the other, what
must be different if the average K.E. must
be the same?
This is the basis for Graham's Law.
avg. KEA = avg. KEB
1/2 mAu2A = 1/2 mBu2B
mAu2A = mBu2B
 Using force factor of gases
• (KE)avg = 3/2 RT
• This the meaning of temperature.
• Finding root mean squre velocity:
u is the average particle velocity.
• u 2 is the average particle velocity
squared.
• the root mean square velocity is
 u 2 = urms
 Combine these two
equations
• (KE)avg = NA(1/2 mu 2 )
• (KE)avg = 3/2 RT
 Combine these two
equations
• (KE)avg = NA(1/2 mu 2 )
• (KE)avg = 3/2 RT Where M is the
molar mass in kg/mole, and R has
3RT
theu rms
units
= 8.3145 J/Kmol.
M
• The velocity will be in m/s
 root mean square velocity urms
urms =  3RT/M
M = molar mass (kg)
KE = ½ mu2 m = mass R = 8.314 J/K mol
u = average velocity
= H2 (2.01 g/mol) urms = 1926 m/s
= UF6 (352 g/mol) urms = 145 m/s

Dalton’s Law
Ptotal= P1+ P2+ P3+ …
 Example

• Calculate the root mean square

velocity of carbon dioxide at
25ºC.
• Calculate the root mean square
velocity of hydrogen at 25ºC.
• Calculate the root mean square
velocity of chlorine at 25ºC.
Boltzman-Maxwell Distribution of
gases

Starting in the 1850's, Boltzmann in

Germany and Maxwell in England
found that
properties of gases could be
satisfactorily explained in terms of the
motion of the individual gas molecules.
1) in a given sample of gas, the speeds
of the molecules vary over a wide
range of values - a few are moving
very slow, a few are moving very fast,
most have intermediate speeds.
2) Graphically we represent it as:
3) If we raise the temperature, then
the curve moves to the right and
lowers.
 Velocity

• Average increases as
temperature increases.
• Spread increases as
temperature increases.
Effusion - a process in which a gas flows
through a small hole.
Theoretically simpler than diffusion since
we don't have to be concerned with
molecules hitting each other and
zigzagging across the room.
 Graham’s Law of Effusion
escape of gases through a small hole

rate1 =
rate2 M / M
2 1

diffusion mixing of gases

mean free path
1 atm 6 x 10-9 m
space 3 x 1010 m
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.
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?
 Examples
• A compound effuses through a porous
cylinder 3.20 time faster than helium.
What is it’s molar mass?
• If 0.00251 mol of NH3 effuse through a
hole in 2.47 min, how much HCl would
effuse in the same time?
• A sample of N2 effuses through a hole
in 38 seconds. what must be the
molecular weight of gas that effuses
in 55 seconds under identical
conditions?
 Diffusion
• The spreading of a gas through a
room.
• Slow considering molecules move
at 100’s of meters per second.
• Collisions with other molecules
slow down diffusions.
• Best estimate is Graham’s Law.
 Real Gases

• Real molecules do take up

space and they do interact with
each other (especially polar
molecules).
• Need to add correction factors
to the ideal gas law to account
for these.
 Volume Correction
• The actual volume free to move in
is less because of particle size.
• More molecules will have more
effect.
• Corrected volume Vreal = V - nb
• b is a constant that differs for each
gas.
• P’ = nRT
(V-nb)
 Pressure correction
 Because the molecules are attracted
to each other, the pressure on the
container will be less than ideal
 depends on the number of molecules
per liter.
 since two molecules interact, the
effect must be squared. 2
Pobserved = P’ - a
()
n
V
 Altogether
()
• Pobs= nRT -a n 2 V-
nb V
• Called the Van der Wall’s
equation if rearranged
 2
 n
 x  V - nb  nRT
 Pobs + a  Corrected
• Corrected
 PressureV Volume

 Where does it come
from
• a and b are determined by
experiment.
• Different for each gas.
• Bigger molecules have larger b.
• a depends on both size and
polarity.
• once given, plug and chug.
 Example

• Calculate the pressure exerted

by 0.5000 mol Cl2 in a 1.000 L
container at 25.0ºC
• Using the ideal gas law.
• Van der Waal’s equation
• a = 6.49 atm L2 /mol2
• b = 0.0562 L/mol
Boyle’s Law
V 1/P

Charles’ Law
V T

Avogadro’s Law
Vn

Dalton’s Law
Ptotal= P1+ P2+ P3+ …
 Real Gases
n = PV
RT

need to correct V for Vgas

need to correct P for interactions

P + n2a V - nb = nRT
V2

3. Attractive and repulsive forces negligible.

 van der Waals Equation

P + n2a V - nb = nRT
V2

a, b experimental

a related to Intermolecular Forces

molecular complexity

b related to molecular volume