GENERAL CHEMISTRY

Gases and the

Kinetic Molecular
Theory
LECTURE
12
Gases
CONTENTS
14-1 Properties of Gases: Gas Pressure
14-2 The Simple Gas Laws
14-3 Combining the Gas Laws: The Ideal
Gas Equation and The General Gas
Equation
14-4 Applications of the Ideal Gas
Equation
14-5 Gases in Chemical Reactions
14-6 Mixtures of Gases
14-7 KineticMolecular Theory of Gases
14-8 Gas Properties Relating to the
KineticMolecular Theory
14-9 Nonideal (Real) Gases
The Distinction of Gases from
Liquids and Solids
1. Gas expand to fill and assume the shape of their
containers.
The Distinction of Gases from
Liquids and Solids
1. Gas expand to fill and assume the shape of their
containers.
3. Gases are invisible no visible particles (except Cl
2
,
Br
2
, I
2
)
2. Most gases have relatively low densities under normal
conditions.
The gaseous state of three halogens (group 17)
The Distinction of Gases from
Liquids and Solids
1. Gas expand to fill and assume the shape of their
containers.
5. Gases are miscible.
3. Gases are invincible no visible particles (except Cl
2
,
Br
2
, I
2
)
2. Most gases have relatively low densities under normal
conditions.
4. Some gases are combustible (H
2
, CH
4
) and some are
unreactive (He, Ne)
Gas % by
Volume
N
2
78.09
O
2
20.94
Ar 0.93
CO
2
0.03
He, Ne,
Kr, Xe
0.002
CH
4
0.00015
H
2
0.00005
The Concept of Pressure
P (Pa) =
Area (m
2
)
Force (N)
Pressure
1.00 atm, 101.325 kPa, 1.01325 bar,
760 torr, 760 mm Hg
Units of Pressure
pascual (Pa) *SI unit
standard atmosphere (atm) 1 atm = 101.325 kPa
millimeter of mercury (mmHg)
Standard Atmospheric Pressure
1 torr = 1 mmHg = atm
1
760
bar (bar) 1 bar = 1000 Pa
Physical behavior of gases
1. Pressure, P
2. Volume, V
3. Temperature, T
4. Amount, (number of moles, n)
Relationship between gas volume and
pressure Boyles Law
PV = constant P o
1
V
14-2 Simple Gas Laws
*(at constant T and n)
A molecular description of Boyles law.
Relationship between gas volume and
temperature- Charles Law
V = constant x T
V o T
*(at constant P and n)
A molecular description of Charless law.
V n V = constant x n
Relationship between gas volume and amount of
gas- Avogadros Law
*(at constant T and P)
A molecular description of Avogadros law.
Standard Temperature and Pressure (STP)
IUPAC defines standard conditions of temperature
and pressure (STP).



At STP:

P = 1 atm = 760 torr = 760 mmHg
T = 0C = 273.15 K
Volume of 1 mol of an ideal gas = 22.414 L = 22.4 L
(standard molar volume)
14-3 Combining the Gas Laws:
The Ideal Gas Equation
and the General Gas Equation
Boyles law V 1/P
Charless law V T
Avogadros law V n
V
nT

P

PV nT

or
The Ideal Gas Equation
R =
PV

nT

PV = nRT
Applying the ideal gas equation
The General Gas Equation
R = =
P
2
V
2
n
2
T
2
P
1
V
1
n
1
T
1
=
P
2
T
2
P
1
T
1
The amount and volume of
the gas are constant:
Using the Gas Laws
Exercise 1
A 50.0 L cylinder contains nitrogen gas at a
pressure of 21.5 atm. The contents of the cylinder
are emptied into an evacuated tank of unknown
volume. If the final pressure in the tank is 1.55 atm,
then what is the volume of the tank?
Exercise 1 (Continued)
Use Boyles Law
P
1
V
1
= P
2
V
2
V
2
=
P
1
V
1
P
2
V
tank
= 644 L
V
2
=
21.5 atm x 50.0 L

1.55 atm

Exercise 2
A sample of hydrogen, H
2
, occupies 1.00 x 10
2
mL
at 25.0
o
C and 1.00 atm. What volume would it
occupy at 50.0
o
C under the same pressure?
T
1
= 25
o
C + 273 = 298 K
T
2
= 50
o
C + 273 = 323 K

Using Charles Law:

=
V
2
T
2
V
1
T
1
V
2
=
V
1
T
2
T
1
=
100 mL x 323 K

298

V
2
= 108 mL
Exercise 3
A steel tank used for fuel delivery is fitted with a safety valve
that opens if the internal pressure exceeds 1.00 x 10
3
torr. It
is filled with methane at 23
o
C and 0.991 atm and placed in
boiling water at exactly 100
o
C. Will the safety valve open?

P
1
= 0.991 atm (convert to torr)
P
2
= unknown
T
1
= 23
o
C (convert to K) T
2
= 100
o
C (convert to K)
P
1
V
1

n
1
T
1

P
2
V
2

n
2
T
2

=
V and n remain constant
P
1

T
1

P
2

T
2

=
0.991 atm x
1 atm
760 torr
= 753 torr
P
2
= P
1
x
T
2

T
1

= 753 torr x
373 K
296 K
P
2
= 949 torr
Exercise 4
A steel tank has a volume of 438 L and is filled with
0.885 kg of O
2
. Calculate the pressure of O
2
at 21
o
C.

V = 438 L
T = 21
o
C (convert to K)
n = 0.885 kg O
2
(convert to mol) P = unknown
21
o
C + 273.15 = 294 K
0.885 kg x
10
3
g
kg
mol O
2

32.00 g O
2

= 27.7 mol O
2
x
P =
nRT
V
=
27.7 mol
294 K
L-atm
mol-K
0.0821 x
x
438 L
P = 1.53 atm
14-4 Applications of the Ideal Gas
Equation
PV = nRT and n =
m

M

PV =
m

M

RT
M =
m

PV

RT
Molar Mass Determination
Gas Density
=
m

V

PV =
m

M

RT
MP

RT V

m
= =
KEEP IN MIND
that gas densities are
typically much smaller than
those of liquids and solids.
Gas densities are usually
expressed in grams per liter
rather than grams per
milliliter.
Sample Problem 5 Finding the Molar Mass of a Volatile Liquid
An organic chemist isolates a colorless liquid from a petroleum
sample. She places the liquid in a flask and puts the flask in a boiling
water bath, which vaporizes the liquid and fills the flask with gas. She
closes the flask, reweighs it, and obtains the following data:
SOLUTION:
Volume (V) of flask = 213 mL
Mass of flask + gas = 78.416 g
T = 100.0
o
C
Mass of empty flask = 77.834 g
P = 754 torr
m = (78.416 - 77.834) g = 0.582 g
M =
m RT
VP
=
0.582 g
atmL
molK
0.0821 373.2 K
x
x
0.213 L x 0.992 atm
= 84.4 g/mol
PV = nRT PV =
m

M

RT
M =
m

PV

RT
Sample Problem 6 Calculating Gas Density
A chemical engineer uses waste CO
2
from a manufacturing process,
instead of chlorofluorocarbons, as a blowing agent in the
production of polystyrene containers. Find the density (in g/L) of
CO
2
(a) at STP (0
o
C and 1 atm) and (b) at room conditions (20.
o
C and
1.00 atm).
SOLUTION:
PV = nRT d =
RT
M x P
d =
44.01 g/mol x 1.00 atm
atmL
molK
0.0821 x 273 K
= 1.96 g/L
(a)
PV =
m

M

RT
Sample Problem 6 (continued) Calculating Gas Density
(b) = 1.83 g/L
d =
44.01 g/mol x 1.00 atm
x 293 K
atmL
molK
0.0821
A chemical engineer uses waste CO
2
from a manufacturing process,
instead of chlorofluorocarbons, as a blowing agent in the
production of polystyrene containers. Find the density (in g/L) of
CO
2
(a) at STP (0
o
C and 1 atm) and (b) at room conditions (20.
o
C and
1.00 atm).
d =
RT
M x P
PV = nRT PV =
m

M

RT
12-5 Gases in Chemical Reactions
Ideal gas equation relates the amount of a gas to
volume, temperature and pressure

Stoichiometric factors relate gas quantities to
quantities of other reactants or products.



Sample Problem 7
Using Gas Variables to Find Amounts of Reactants or
Products
Copper reacts with oxygen impurities in the ethylene used to
produce polyethylene. The copper is regenerated when hot H
2

reduces the copper(II) oxide, forming the pure metal and H
2
O. What
volume of H
2
at 765 torr and 225
o
C is needed to reduce 35.5 g of
copper(II) oxide?
SOLUTION:
CuO(s) + H
2
(g) Cu(s) + H
2
O(g)
35.5 g CuO x
mol CuO
79.55 g CuO
1 mol H
2

1 mol Cu
= 0.446 mol H
2

0.446 mol H
2
x
498 K
atmL
molK
0.0821 x
1.01 atm
= 18.1 L
x
V = nRT/P
PV = nRT
Sample Problem 8 Using the Ideal Gas Law in a Limiting-Reactant Problem
The alkali metals [Group 1A(1)] react with the halogens [Group
7A(17)] to form ionic metal halides. What mass of potassium
chloride forms when 5.25 L of chlorine gas at 0.950 atm and 293 K
reacts with 17.0 g of potassium?
SOLUTION: 2K(s) + Cl
2
(g) 2KCl(s)
n =
PV
RT
Cl
2

5.25 L
=
0.950 atm x
atmL
molK
0.0821 x 293 K
= 0.207 mol Cl
2

17.0 g K x
39.10 g K
1 mol K
= 0.435 mol K
V = 5.25 L
T = 293K n = unknown
P = 0.950 atm
Cl
2
Sample Problem 8 Using the Ideal Gas Law in a Limiting-Reactant Problem
SOLUTION:
0.207 mol Cl
2
x


2 mol KCl
1 mol Cl
2

= 0.414 mol KCl formed
0.435 mol K x
2 mol KCl
2 mol K
= 0.435 mol KCl formed
0.414 mol KCl x
74.55 g KCl
mol KCl
= 30.9 g KCl
continued
Cl
2
is the limiting reactant.
12-6 Mixtures of Gases
Gas laws apply to mixtures of gases.
Partial pressure
Each component of a gas mixture exerts a
pressure that it would exert if it were in the
container alone.
Daltons law of partial pressures
P
total
= P
1
+ P
2
+ P
3
+ ...
Daltons Law of Partial Pressure
Partial Pressure
The mole fraction of a component in a mixture is
described by the equation:


_
1
=
n
1

n
1
+ n
2
+ n
3
+...
=
n
1

n
total

P
1
= _
1
x P
total

where _
1
is the mole fraction
_
n
=
_
1
+ _
2
+ _
3
+...
= 1
Sample Problem 9 Applying Daltons Law of Partial Pressures
In a study of O
2
uptake by muscle at high altitude, a physiologist
prepares an atmosphere consisting of 79 mol N
2
, 17 mol
16
O
2,
and 4.0
mol
18
O
2
. (The isotope
18
O will be measured to determine the O
2

uptake.) The pressure of the mixture is 0.75 atm to simulate high
altitude. Calculate the mole fraction and partial pressure of
18
O
2
in the
mixture.
SOLUTION:
_
18
O
2

=
4.0 mol
18
O
2

100
= 0.040
= 0.030 atm
P = _ x P
total
= 0.040 x 0.75 atm
18
O
2

18
O
2

P = _ x P
total

18
O
2
18
O
2

_ =
n
n
total

18
O
2

18
O
2

A gaseous mixture contains 3.23 g of chloroform, CHCl
3
, and 1.22 g
of methane, CH
4
. Assuming that both compounds remains as
gases, what pressure is exerted by the mixture inside a 50.0-mL
metal container at 275
o
C? What pressure is contributed by CHCl
3
?
Sample Problem 10 Applying Daltons Law of Partial Pressures
P
total
=
n
total
RT
V
3.23 g CHCl
3

mol CHCl
3

119.35 g
x
= 0.027 mol CHCl
3
SOLUTION:
1.22 g CH
4

mol CH
4

16.05 g
x
= 0.076 mol CH
4
n
total


= 0.103 mol

=
0.103 mol
atmL
molK
0.0821
548 K
x
x
0.050 L
P
total
= 92.68 atm
A gaseous mixture contains 3.23 g of chloroform, CHCl
3
, and 1.22 g
of methane, CH
4
. Assuming that both compounds remains as
gases, what pressure is exerted by the mixture inside a 50.0-mL
metal container at 275
o
C? What pressure is contributed by CHCl
3
?
Sample Problem 10 (continued) Applying Daltons Law of Partial Pressures
n
CHCl3
= 0.027 mol

n
CH4
= 0.076 mol

n
total


= 0.103 mol

P
total
= 92.68 atm
P
CHCl3
= _
CHCl3
x P
total

SOLUTION:
_
CHCl3
=
0.027 mol
0.103 mol
= 0.262

P
CHCl3
= 0.0262 x 92.68 atm
P
CHCl3
= 24.29 atm
Collecting a gas over water
P
tot
= P
bar
= P
gas
+ P
H
2
O

P
gas
= P
bar
- P
H
2
O

Sample Problem 11 Calculating the Amount of Gas Collected over Water
Acetylene (C
2
H
2
), an important fuel in welding, is produced in the laboratory
when calcium carbide (CaC
2
) reacts with water:
CaC
2
(s) + 2H
2
O(l) C
2
H
2
(g) + Ca(OH)
2
(aq)
For a sample of acetylene that is collected over water, total gas pressure
(adjusted to barometric pressure) is 738 torr and the volume is 523 mL. At the
temperature of the gas (23
o
C), the vapor pressure of water is 21 torr. How many
grams of acetylene are collected?
0.943 atm 0.523 L
x
n
C
2
H
2

=
atmL
molK
0.0821 x
296 K
= 0.0203 mol
0.0203 mol x
26.04 g C
2
H
2

mol C
2
H
2

= 0.529 g C
2
H
2

SOLUTION:
P
C
2
H
2

= 738 torr 21 torr = 717 torr
717 torr x
atm
760 torr
= 0.943 atm
grams ?
PV = nRT n=
PV
RT
moles grams
Visualizing Molecular Motion
12-7 Kinetic Molecular Theory of Gases
Particles are point masses in constant,
random, straight line motion.
Particles are separated by great
distances.
Collisions are rapid and elastic.
No force between particles.
Total energy remains constant.
Distribution of molecular speeds at three temperatures.
Kinetic Energy and Temperature
N
A
m = M
w
:
E
k
= m x u
2
1

2

E
k
= mass x speed
2

1

2

E
k
= T
3

2

R

N
A
m u
2

= T
3

2

R

N
A
1

2

u
2

= T
3

2

R

N
A
m

1

2

u
2

=
3RT

M
w
M
3RT
u
rms
=
M
3RT
u
rms
=
Distribution of Molecular Speeds the effect
of mass and temperature
14-8 Gas Properties Relating to the
Kinetic-Molecular Theory
A. Diffusion
Migration of molecules of
different substances due to
random molecular motion.

B. Effusion
Escape of gas molecules
from their container through
a tiny pinhole.
Grahams Law
rate of effusion of A
rate of effusion of B
=
(u
rms
)
A
(u
rms
)
B
=
3RT/M
A
3RT/MB
=
M
B
M
A
rate
A
rate
B
=
M
w B
M
w A
Applying Grahams Law of Effusion
A mixture of helium (He) and methane (CH
4
) is placed in an
effusion apparatus. Calculate the ratio of their effusion rates
(He: CH
4
).
SOLUTION:
M of CH
4
= 16.04 g/mol M of He = 4.003 g/mol
CH
4
He rate
rate
=
16.04
4.003
= 2.002
/
Sample Problem 12
A sample of hydrogen, H
2
, was found to effuse through a
pinhole 5.2 times as rapidly as the same volume of unknown
gas (at the same temperature and pressure). What is the
molecular weight of the unknown gas?
Applying Grahams Law of Effusion Sample Problem 13
rate
H2
rate
unk
=
M
unk
M
H
2
5.2

=
M
unk
2 g/mol

2
27.04

=
M
unk
2 g/mol

M
unk
= 54.08 g/mol

SOLUTION:
12-9 Real Gases: Deviation from
Ideal Behavior
Gas particles have finite volume
V
real gas
> V
ideal gas
Presence of attractive force between
gas molecules
P
real gas
< P
ideal gas

Compressibility factor
PV/nRT = 1 for ideal gas.

Deviations for real gases.
PV/nRT > 1 - molecular volume is significant.
PV/nRT < 1 intermolecular forces of attraction.
Deviation from Ideal Behavior
The behaviour of real gases compressibility
factor as a function of pressure at 0C
Gases tend to behave ideally at high temperatures
and low pressure.

Gases tend to behave nonideally at low
temperature and high pressure.
Behavior of Gases
van der Waals Equation
P +
n
2
a
V
2

V nb = nRT
a - intermolecular attraction
b - volume of gas molecules
adjusts
pressure up
adjusts
volume down
A 1.74 g sample of a compound that contains
only carbon and hydrogen contains 1.44 g of
carbon and 0.300 g of hydrogen. At STP 101 mL
of the gas has a mass of 0.262 gram. What is its
molecular formula?
QUIZ
( )
( )( )
10 4 2 5 2
5 2
H C ) H (C : formula Molecular
2
29
58.1
g/mol 1 . 58
L 0.101 atm 00 . 1
K 273
K mol
atm L
0.0821 )( 262 . 0
PV
RT g
= MW
RT
MW
g
PV
nRT PV
29 = mass with H C
5 . 2
0.120
0.297
1
0.120
0.120
H mol 297 . 0
H g 1.01
H mol 1
H g 0.300 = atoms H mol ?
C mol 120 . 0
C g 0 . 12
C mol 1
C g 1.44 = atoms C mol ?
=
=
=
|
.
|

\
|
=
=
=
= = = =
=
=
g
H C
Answer
3 pts
4 pts
1 pt
Summary
Simple gas laws and the Ideal gas equation
Determining MW and densities of gases using
the ideal gas equation
Chemical reactions involving gases
Mixtures of gases
Kinetic molecular theory
Rate of effusion
Ideal gas vs. Real gases