Boyle's law PV = constant (k) P1V1 = P2V2

V1 V2
Charles's law =
T1 T2

Avogadro’s law V=kn

Ideal gas equation PV = nRT

d = PM M = dRT
RT P
Combined gas law P1V1 P2V2
=
T1 T2

Pt=(n1+n2+n3…. )( RT
V
( n
= t (
RT
V
(
Example: Calcium carbonate, CaCO3(s), decomposes upon heating to give CaO(s) and CO2(g). A sample
of CaCO3 is decomposed, and the carbon dioxide is collected in a 250-mL flask. After the decomposition
is complete, the gas has a pressure of 1.3 atm at a temperature of 31 °C. How many moles of CO2 gas
were generated?

PV = nRT
Example: The gas pressure in an aerosol can is 1.5 atm at 25 °C. Assuming that the gas inside obeys the
ideal-gas equation, what would the pressure be if the can were heated to 450 °C?

PV = nRT
Example: A large natural-gas storage tank is arranged so that the pressure is maintained at 2.20 atm. On a cold day
in December when the temperature is –15 °C (4 °F), the volume of gas in the tank is 3.25 × 103 m3. What is
the volume of the same quantity of gas on a warm July day when the temperature is 31 °C (88 °F)?

P1= 2.20 atm P1V1 P2V2

V1 = 3.25 x 103 m3 =
T1= -15oC = -15+273 = 258 K
T1 T2
P2 = 2.20 atm
V2 = ? V1 V2
T2= -15oC = 31+273 = 304 K =
T1 T2

Answer: 3.83 × 103 m3

 Partial Pressures

• When one collects a gas over water, there is

water vapor mixed in with the gas.
• To find only the pressure of the desired gas,
one must subtract the vapor pressure of
water from the total pressure.
 Collecting gases over water

2KClO3 (s) 2KCl (s)+ 3O2 (g)

PT = PO2 + PH2O
Example 2: Oxygen gas generated by the decomposition of potassium
chlorate is collected over water. The volume of oxygen collected at
24C and atmospheric pressure of 762 mmHg is 128 mL. Calculate the
mass (in grams) of oxygen gas obtained. The pressure of the water
vapor at 24 C is 22.4 mmHg.
PT = PO2 + PH2O P O2 = PT - PH2O = 762 mmHg – 22.4 mmHg
=739.6 mmHg
1 atm
= 739.6 mmHg  = 0.973 atm
760 mmHg
P = 0.973 atm
m
T = 273 + 24 = 297 K number of mole, n =
M
V = 128 mL = 0.128 L M = molar mass = 32 g / mol
R = 0.08206 L.atm /K.mol m =mass in gram ?

m
PV = nRT = RT
M
PVM 0.973 atm  0.128 L  32 g / mol
m= = = 0.163 g
RT 0.0821 L.atm / K.mol  297 K
 10.7 Kinetic-molecular theory
The kinetic-molecular theory is summarized by the
following statements:

1. Gases consist of large numbers of molecules that are in

continuous, random motion
2. The combined volume of all the molecules of the gas is
negligible relative to the total volume in which the gas is
contained
3. Attractive and repulsive forces between gas molecules are
negligible
4. Energy can be transferred between molecules during
collisions, but the average kinetic energy of the molecules
does not change with time
5. The average kinetic energy of the molecules is
proportional to the absolute temperature
 Distribution of molecular speed
Average kinetic energy of a
gas molecules:

 1 mu2
= 2
u, root-mean-square (rms)
m, mass of individual molecule
rms and average speed :
If we have four objects with speeds
of 4.0, 6.0, 10.0 and 12.0 m/s The effect of temperature on
molecular speeds
4.0 + 6.0 + 10.0 + 12.0
Average speed = = 8 m/s
4

rms speed = ( (
4.02 + 6.02 + 10.02 + 12.02
4

= ( 16 + 36 + 100+ 144
4
(
= 74 = 8.6 m/s
 10.8 Molecular effusion and diffusion

u= (
3RT
M
(
M, molar mass
T, temperature
R, gas constant
The effect of molecular mass on molecular speeds

Example : Calculate the rms speed, u, of an N2 molecule at 25C

T = 25 +273 =298 K ; M = 28.0 g/mol = 28.0  10-3 kg/mol

R= 8.314 J/mol-K = 8.314 kg-m2/s2-mol-K

3(8.314 kg-m2/s2-mol-K) 298 K

u=
28.0  10-3 kg/mol

= 5.15  102 m/s

 The dependence of molecular speeds on mass has
two consequences:

1. Effusion : escape of gas 2. Diffusion : spread of

molecule through a tiny one substance through a
hole into an evacuated space or throughout a
space second substance

Gas molecule effuse through a Each short segment of line represents

pinhole in the partitioning wall only travel between collisions. The blue
when they happen to hit the hole arrow indicates the net distance
traveled by the molecule
 Graham’s law of effusion
At same temperature and pressure, and in containers
with identical pinholes,
if rates of effusion of two substance are r1 and r2 and
their respective molar mass are M1 and M2, Graham’s
law states
r1 M2
r2 = M1

At identical pressure and temperature, the lighter gas effuses more rapidly
 rN2
Example : Calculate the ratio of the effusion rates of N2 and O2,
rO2

M N2= 28 g/mol

M O2= 32 g/mol

rN2 MO2
rO2 = M N2

32
= 28
rN2
rO2 = 1.07
10.9 Real gases : Deviations from ideal behavior

For a gas to exhibit idea behavior two

assumptions are considered:

1. Intermolecular forces: The attractions and

repulsions between the particles are negligible
(i.e., small or non existent intermolecular forces)

2. Negligible volume: A gas is made up of a large

number of particles (atoms or molecules) whose
size is negligible compared to the size of the
container. These particles are also small
compared to the distances between particles.
Real molecules, however, do have finite volumes
and they do attract one another
 For ideal gas:
PV = nRT
PV
RT = n
for one mole of gas
PV = 1
RT
For real gas
PV = 1
RT
is true only at moderately
low pressure ( 5 atm)

Intermolecular attractions, increase with molecular weight, cause the PV

product to decrease as higher pressures bring the molecules closer
together, attractive forces; molecules begin to intrude on each others'
territory, repulsive forces always eventually win out.
 For ideal gas:
PV = nRT
PV
RT = n
for one mole of gas
PV = 1
RT
For real gas
PV
=1 The effect of temperature and
RT
nearly true only at very pressure on the behavior of
high temperature nitrogen gas

At high pressure and low temperature gases will not

behave ideally
 The Van der Waals equation
The two factor leading to deviations from ideal behavior
1. molecular attractions
2. molecular volume

Van der Waal’s suggested correction for real gas :

Pressure correction : Pideal = Preal an

+ 2
2 “a” is a correction for
intermolecular forces
V

Volume correction : Videal = (Vreal – nb) “nb” represents volume

occupied by n moles of the gas

Taking into account the corrections for pressure and volume:

an2 V – nb = nRT Van der Waals equation

P +
V2

a and b are van der Waals constants and different for different gases
Example : If a sample of 1.00 mol of CO2(g) is confined to a volume of
3.00 L at 0.0 C, calculate the pressure of the gas using (a) the ideal-
gas equation and (b) the van der Waals equation. [For CO2(g) a = 3.59
atm.L2/mol2 and b = 0.0427 L/mol]
n = 1.00 mol V = 3.00 L T = 0 +273 = 273 K R = 0.0821 L.atm/K.mol

(a) For ideal gas :

nRT 1 mol  0.0821 L.atm/K.mol  273 K

P= = = 7.471 atm
V 3.00 L

(b) For real gas : P + an 2 nRT

=
V2 V -nb
an2 3.59 atm.L2/mol2 (1 mol)2
2
= = 0.399 atm
V (3.00 L)2
V – nb = 3.00 L – (1 mol  0.0427 L/mol) = 2.957 L

1.0 mol  0.0821 L.atm/K.mol  273 K

P + 0.399 atm =
2.957 L
P + 0.399 atm = 7.580 atm P = 7.181 atm