CHAPTER 12

GASES AND KINETIC-MOLECULAR

THEORY
1. Pressure
2. Boyle’s Law: The V-P Relationship
3. Charles’ Law: The V-T Relationship
4. Standard T&P
5. The Combined Gas Law Equation
6. Avogadro’s Law and the Standard Molar Volume
7. Summary of Gas Laws: The Ideal Gas Equation
8. Dalton’s Law of Partial Pressures
9. The Kinetic-Molecular Theory
10. Diffusion and Effusion of Gases
11. Real Gases: Deviations from Ideality
1
 Pressure

{ Pressure is force per unit area.

z lb/in2
z N/m2
{ Gas pressure as most people think
of it.
{ Atmospheric pressure is measured
using a barometer.
{ Definitions of standard pressure
z 76 cm Hg
z 760 mm Hg
z 760 torr
z 1 atmosphere
z 101.3 kPa
Hg density = 13.6 g/mL
2
 Boyle’s Law:
The Volume-Pressure Relationship

{ V ∝ 1/P or
{ V= k (1/P) or PV = k
{ P1V1 = k1 for one sample of a gas.
{ P2V2 = k2 for a second sample of a
gas.
{ k1 = k2 for the same sample of a gas
at the same T.
{ Thus we can write Boyle’s Law
mathematically as P1V1 = P2V2

3
 Boyle’s Law:
The Volume-Pressure Relationship
{ At 25oC a sample of He has a volume of 4.00
x 102 mL under a pressure of 7.60 x 102
torr. What volume would it occupy under a
pressure of 2.00 atm at the same T?

P1 V1 = P2 V2
P1 V1
V2 =
P2

=
(760 torr )(400 mL )
1520 torr
= 2.00 × 10 2 mL 4
 Charles’ Law:
The Volume-Temperature Relationship;
35
The Absolute Temperature Scale
30

25

20 Volume (L)
vs.
15 Temperature (K)

10 Gases liquefy
before reaching 0K
5

0
0 50 100 150 200 250 300 350 400

absolute zero = -273.15 0C

5
 Charles’ Law:
The Volume-Temperature Relationship;
The Absolute Temperature Scale
{ Charles’s law states that the volume of
a gas is directly proportional to the
absolute temperature at constant
pressure.
z Gas laws must use the Kelvin scale to be
correct.
{ Relationship between Kelvin and
centigrade.
K = o C + 273
6
 Charles’ Law:
The Volume-Temperature Relationship;
The Absolute Temperature Scale

{ Mathematical form of Charles’ law.

V
V ∝ T or V = kT or = k
T
V1 V2
= k and = k however the k' s are equal so
T1 T2
V1 V2
= in the most useful form
T1 T2
7
 Charles’ Law:
The Volume-Temperature Relationship;
The Absolute Temperature Scale
{ A sample of hydrogen, H2, occupies 1.00 x
102 mL at 25.0oC and 1.00 atm. What
volume would it occupy at 50.0oC under the
same pressure?
T1 = 25 + 273 = 298
T2 = 50 + 273 = 323

V1 V2 V1T2
= ∴ V2 =
T1 T2 T1
1.00 × 10 mL × 323 K
2
V2 =
298 K
= 108 mL 8
 Standard Temperature and
Pressure

{ Standard temperature and pressure is

given the symbol STP.

{ Standard P ≡ 1.00000 atm or 101.3 kPa

{ Standard T ≡ 273.15 K or 0.00oC

9
 The Combined Gas Law Equation

{ Boyle’s and Charles’ Laws combined into one

statement is called the combined gas law
equation.
z Useful when the V, T, and P of a gas are changing.

Boyle' s Law Charles' Law

V1 V2
P1V1 = P2 V2 =
T1 T2
For a given sample of gas : The combined gas law is :
PV P1 V1 P2 V2
=k =
T T1 T2

10
 The Combined Gas Law Equation
{ A sample of nitrogen gas, N2, occupies 7.50 x
102 mL at 75.00C under a pressure of 8.10 x
102 torr. What volume would it occupy at STP?
V 1 = 750 mL V2 = ?
T1 = 348 K T 2 = 273 K
P1 = 810 torr P 2 = 760 torr
P1 V 1 T 2
Solve for V 2 =
P 2 T1

=
(810 torr )(750 mL )(273 K )
(760 torr )(348 K )
= 627 mL
11
 The Combined Gas Law Equation
{ A sample of methane, CH4, occupies 2.60 x
102 mL at 32oC under a pressure of 0.500
atm. At what temperature would it occupy
5.00 x 102 mL under a pressure of 1.20 x 103
torr?

V1 = 260 mL V 2 = 500 mL
P1 = 0.500 atm P 2 = 1200 torr
= 380 torr
T1 = 305 K T2 = ?

T2 =
T1 P 2 V 2
=
(305 K )(1200 torr )(500 mL )
P1 V1 (380 torr )(260 mL )
= 1852 K ≈ 1580 o
C 12
 Avogadro’s Law and the
Standard Molar Volume
{ Avogadro’s Law states that at the same
temperature and pressure, equal volumes of
two gases contain the same number of
molecules (or moles) of gas.
{ If we set the temperature and pressure for
any gas to be STP, then one mole of that
gas has a volume called the standard
molar volume.
volume
{ The standard molar volume is 22.4 L at STP.
z This is another way to measure moles.
z For gases, the volume is proportional to the
number of moles.

13
 Summary of Gas Laws:
The Ideal Gas Law
{ Boyle’s Law - V ∝ 1/P (at constant T & n)
{ Charles’ Law – V ∝ T (at constant P & n)
{ Avogadro’s Law – V ∝ n (at constant T & P)
{ Combine these three laws into one statement
V ∝ nT/P
{ Convert the proportionality into an equality.
V = nRT/P
{ This provides the Ideal Gas Law.
PV = nRT
{ R is a proportionality constant called the
universal gas constant.
14
 Summary of Gas Laws:
The Ideal Gas Law
{ We must determine the value of R.
z Recognize that for one mole of a gas at 1.00 atm,
and 273 K (STP), the volume is 22.4 L.
z Use these values in the ideal gas law.

PV (1.00 atm)( 22.4 L)

R = =
nT (1.00 mol)( 273 K)
L atm
= 0.0821
mol K
15
 Summary of Gas Laws:
The Ideal Gas Law
{ R has other values if the units are changed.
{ R = 8.314 J/mol K
z Use this value in thermodynamics.
{ R = 8.314 kg m2/s2 K mol
z Use this later in this chapter for gas velocities.
{ R = 8.314 dm3 kPa/K mol
z This is R in all metric units.
{ R = 1.987 cal/K mol
z This the value of R in calories rather than J.

16
 Summary of Gas Laws:
The Ideal Gas Law
{ What volume would 50.0 g of ethane, C2H6,
occupy at 1.40 x 102 oC under a pressure of
1.82 x 103 torr?
1. T = 140 + 273 = 413 K
2. P = 1820 torr (1 atm/760 torr) = 2.39 atm
3. 50 g (1 mol/30 g) = 1.67 mol
nRT
V=
P
 L atm 
(1.67 mol) 0.0821 (413 K )
 mol K 
=
2.39 atm
= 23.6 L 17
 Summary of Gas Laws:
The Ideal Gas Law
{ Calculate the number of moles in, and the
mass of, an 8.96 L sample of methane, CH4,
measured at standard conditions.

PV (1.00 atm)( 896

. L)
n = = = 0.400 mol CH4
RT  L atm
 0.0821  ( 273 K)
 mol K
16.0 g
? g CH4 = 0400
. mol × = 6.40 g
mol
18
 Summary of Gas Laws:
The Ideal Gas Law
{ Calculate the pressure exerted by 50.0 g of
ethane, C2H6, in a 25.0 L container at
25.0oC.

n = 1.67 mol and T = 298 K

n R T
P =
V
 L atm 
(1.67 mol ) 0.0821  (298 K )
 mol K 
P =
25.0 L
P = 1 . 63 atm
19
 Dalton’s Law of Partial Pressures

{ Dalton’s law states that the pressure

exerted by a mixture of gases is the
sum of the partial pressures of the
individual gases.
Ptotal = PA + PB + PC + .....

20
 Dalton’s Law of Partial Pressures
{ Vapor Pressure is the pressure
exerted by a substance’s vapor over
the substance’s liquid at equilibrium.

21
 The Kinetic-Molecular Theory
{ The basic assumptions of kinetic-
molecular theory are:
{ Postulate 1
z Gases consist of discrete molecules
that are relatively far apart.
z Gases have few intermolecular
attractions.
z The volume of individual molecules is
very small compared to the gas’s
volume.
{ Proof - Gases are easily compressible. 22
 The Kinetic-Molecular Theory
{ Postulate 2
z Gas molecules are in constant, random, straight
line motion with varying velocities.
{ Proof - Brownian motion displays molecular
motion.
{ Postulate 3
z Gas molecules have elastic collisions with
themselves and the container.
z Total energy is conserved during a collision.
{ Proof - A sealed, confined gas exhibits no
pressure drop over time.
23
 The Kinetic-Molecular Theory
{ Postulate 4
z The kinetic energy of the molecules is
proportional to the absolute temperature.
z The average kinetic energies of
molecules of different gases are equal at
a given temperature.
{ Proof - Brownian motion increases as
temperature increases.

24
 The Kinetic-Molecular Theory
• The kinetic energy of the molecules is
proportional to the absolute temperature.
The kinetic energy of the molecules is
proportional to the absolute temperature.
• Displayed in a Maxwellian distribution.

25
 The Kinetic-Molecular Theory
{ Boyle’s Law
z P ∝ 1/V

z As the V increases the molecular collisions with container

walls decrease and the P decreases.
{ Dalton’s Law
z Ptotal = PA + PB + PC + .....

z Because gases have few intermolecular attractions, their

pressures are independent of other gases in the container.
{ Charles’ Law
z V ∝ T

z An increase in temperature raises the molecular velocities,

thus the V increases to keep the P constant.

26
Diffusion and Effusion of Gases
{ Diffusion is the intermingling of
gases.
{ Effusion is the escape of gases
through tiny holes.

27
Diffusion and Effusion of Gases
{ The rate of effusion is inversely
proportional to the square roots of the
molecular weights or densities.

R1 M2
=
R2 M1
or
R1 D2
=
R2 D1
28
 Real Gases:
Deviations from Ideality
{ Real gases behave ideally at ordinary
temperatures and pressures.
{ At low temperatures and high pressures
real gases do not behave ideally.
{ The reasons for the deviations from
ideality are:
1. The molecules are very close to one
another, thus their volume is important.
2. The molecular interactions also become
important.

29
 Real Gases:
Deviations from Ideality
{ van der Waals’ equation accounts for the
behavior of real gases at low T and high P.
 n 2a 
2 (
P + V − nb ) = nRT
 V 
• The van der Waals constants a and b take into
account two things:
1. a accounts for intermolecular attraction
2. b accounts for volume of gas molecules

30