Chapter 5

Gases
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Tro, Chemistry: A Molecular Approach 2
Air Pressure & Shallow Wells
water for many homes is
supplied by a well less than
30 ft. deep with a pump at
the surface
the pump removes air from
the pipe, decreasing the air
pressure in the pipe
the outside air pressure then
pushes the water up the pipe
the maximum height the
water will rise is related to
the amount of pressure the
air exerts
Tro, Chemistry: A Molecular Approach 3
Atmospheric Pressure
pressure is the force
exerted over an area
on average, the air
exerts the same
pressure that a column
of water 10.3 m high
would exert
14.7 lbs./in
2

so if our pump could
get a perfect vacuum,
the maximum height
the column could rise is
10.3 m
Area
Force
Pressure=
Tro, Chemistry: A Molecular Approach 4
Gases Pushing
gas molecules are constantly in motion
as they move and strike a surface, they
push on that surface
push = force
if we could measure the total amount of
force exerted by gas molecules hitting
the entire surface at any one instant, we
would know the pressure the gas is
exerting
pressure = force per unit area
Tro, Chemistry: A Molecular Approach 5
The Effect of Gas Pressure
the pressure exerted by a gas can cause some
amazing and startling effects
whenever there is a pressure difference, a gas
will flow from area of high pressure to low
pressure
the bigger the difference in pressure, the stronger
the flow of the gas
if there is something in the gass path, the gas
will try to push it along as the gas flows
Tro, Chemistry: A Molecular Approach 6
Atmospheric Pressure Effects
differences in air pressure result in weather
and wind patterns
the higher up in the atmosphere you climb, the
lower the atmospheric pressure is around you
at the surface the atmospheric pressure is 14.7 psi,
but at 10,000 ft it is only 10.0 psi
rapid changes in atmospheric pressure may
cause your ears to pop due to an imbalance
in pressure on either side of your ear drum
Tro, Chemistry: A Molecular Approach 7
Pressure Imbalance in Ear
If there is a difference
in pressure across
the eardrum membrane,
the membrane will be
pushed out what we
commonly call a
popped eardrum.
Tro, Chemistry: A Molecular Approach 8
The Pressure of a Gas
result of the constant
movement of the gas
molecules and their collisions
with the surfaces around them
the pressure of a gas depends
on several factors
number of gas particles in a
given volume
volume of the container
average speed of the gas
particles
Tro, Chemistry: A Molecular Approach 9
Measuring Air Pressure
use a barometer
column of mercury
supported by air
pressure
force of the air on the
surface of the mercury
balanced by the pull of
gravity on the column
of mercury
gravity
Tro, Chemistry: A Molecular Approach 10
Common Units of Pressure
Unit Average Air Pressure at
Sea Level
pascal (Pa), 101,325
kilopascal (kPa) 101.325
atmosphere (atm) 1 (exactly)
millimeters of mercury (mmHg) 760 (exactly)
inches of mercury (inHg) 29.92
torr (torr) 760 (exactly)
pounds per square inch (psi, lbs./in
2
) 14.7
2
m
N
1 Pa 1 =
Example 5.1 A high-performance bicycle tire has a pressure
of 132 psi. What is the pressure in mmHg?
since mmHg are smaller than psi, the answer
makes sense



1 atm = 14.7 psi, 1 atm = 760 mmHg

132 psi
mmHg
Check:
Solution:
Concept Plan:



Relationships:
Given:
Find:
psi 14.7
atm 1
mmHg 10 .82 6
atm 1
mmHg 760
psi 14.7
atm 1
psi 132
3
=
atm 1
mmHg 760
psi atm mmHg
Tro, Chemistry: A Molecular Approach 12
Manometers
the pressure of a gas trapped in a container can be
measured with an instrument called a manometer
manometers are U-shaped tubes, partially filled with a
liquid, connected to the gas sample on one side and
open to the air on the other
a competition is established between the pressure of the
atmosphere and the gas
the difference in the liquid levels is a measure of the
difference in pressure between the gas and the
atmosphere
Tro, Chemistry: A Molecular Approach 13
Manometer
for this sample, the gas has
a larger pressure than the
atmosphere, so
(mm) levels Hg in difference (mmHg) Pressure (mmHg) Pressure
Pressure Pressure Pressure
atmosphere gas
h atmosphere gas
+ =
+ =
Tro, Chemistry: A Molecular Approach 14
Boyles Law
pressure of a gas is inversely proportional
to its volume
constant T and amount of gas
graph P vs V is curve
graph P vs 1/V is straight line
as P increases, V decreases by the same
factor
P x V = constant
P
1
x V
1
= P
2
x V
2
Tro, Chemistry: A Molecular Approach 15
Boyles Experiment
added Hg to a J-tube with
air trapped inside
used length of air column
as a measure of volume
Length of Air
in Column
(in)
Difference in
Hg Levels
(in)
48 0.0
44 2.8
40 6.2
36 10.1
32 15.1
28 21.2
24 29.7
22 35.0
Tro, Chemistry: A Molecular Approach 16
Boyle's Expt.
0
20
40
60
80
100
120
140
0 10 20 30 40 50 60
Volume of Air, in
3
P
r
e
s
s
u
r
e
,

i
n
H
g
Tro, Chemistry: A Molecular Approach 17
Inverse Volume vs Pressure of Air, Boyle's Expt.
0
20
40
60
80
100
120
140
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
Inv. Volume, in
-3
P
r
e
s
s
u
r
e
,

i
n
H
g
Tro, Chemistry: A Molecular Approach 18
Boyles Experiment, P x V
Pressure Volume P x V
29.13 48 1400
33.50 42 1400
41.63 34 1400
50.31 28 1400
61.31 23 1400
74.13 19 1400
87.88 16 1400
115.56 12 1400
Tro, Chemistry: A Molecular Approach 19
When you double the pressure on a gas,
the volume is cut in half (as long as the
temperature and amount of gas do not change)
Tro, Chemistry: A Molecular Approach 20
Boyles Law and Diving
since water is denser
than air, for each 10 m
you dive below the
surface, the pressure
on your lungs
increases 1 atm
at 20 m the total
pressure is 3 atm

if your tank
contained air at 1
atm pressure you
would not be able to
inhale it into your
lungs



P
1
V
1
= P
2
V
2

Example 5.2 A cylinder with a movable piston has a volume
of 7.25 L at 4.52 atm. What is the volume at 1.21 atm?
since P and V are inversely proportional, when the pressure
decreases ~4x, the volume should increase ~4x, and it does
V
1
=7.25 L, P
1
= 4.52 atm, P
2
= 1.21 atm
V
2
, L
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
2
1 1
2
P
V P
V
-
=
V
1
, P
1
, P
2
V
2

( ) ( )
( )
L 1 . 27
atm 1.21
L 7.25 atm 4.52
P
V P
V
2
1 1
2
=
-
=
-
=
Tro, Chemistry: A Molecular Approach 22
Practice A balloon is put in a bell jar and the pressure is
reduced from 782 torr to 0.500 atm. If the volume of the
balloon is now 2780 mL, what was it originally?




P
1
V
1
= P
2
V
2
, 1 atm = 760 torr (exactly)
A balloon is put in a bell jar and the pressure is reduced
from 782 torr to 0.500 atm. If the volume of the balloon is
now 2780 mL, what was it originally?
since P and V are inversely proportional, when the pressure
decreases ~2x, the volume should increase ~2x, and it does
V
2
=2780 mL, P
1
= 762 torr, P
2
= 0.500 atm
V
1
, mL
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
1
2 2
1
P
V P
V
-
=
V
1
, P
1
, P
2
V
2

( ) ( )
( )
mL 1350
atm 1.03
L 2780 atm 0.500
P
V P
V
1
2 2
1
=
-
=
-
=
atm 03 . 1
torr 760
atm 1
torr 782 =
Tro, Chemistry: A Molecular Approach 24
Charles Law
volume is directly proportional to
temperature
constant P and amount of gas
graph of V vs T is straight line
as T increases, V also increases
Kelvin T = Celsius T + 273
V = constant x T
if T measured in Kelvin
2
2
1
1
T
V
T
V
=
Tro, Chemistry: A Molecular Approach 25
Charles Law A Molecular View
the pressure of gas inside
and outside the balloon
are the same
at low temperatures, the
gas molecules are not
moving as fast, so they
dont hit the sides of the
balloon as hard
therefore the volume is
small
the pressure of gas inside
and outside the balloon
are the same
at high temperatures, the
gas molecules are moving
faster, so they hit the sides
of the balloon harder
causing the volume to
become larger
26
Charles' Law & Absolute Zero
0
0.1
0.2
0.3
0.4
0.5
0.6
-300 -250 -200 -150 -100 -50 0 50 100 150
Temperature, C
V
o
l
u
m
e
,

L
Volume (L) of 1 g O2 @ 1500 torr
Volume (L) of 1 g O2 @ 2500 torr
Volume (L) of 0.5 g O2 @ 1500 torr
Volume (L) of 0.5 g SO2 @ 1500
torr
The data fall on a
straight line.
If the lines are
extrapolated back to a
volume of 0, they all
show the same
temperature, -273.15C,
called absolute zero



T(K) = t(C) + 273.15,
2
2
1
1
T
V
T
V
=
Example 5.3 A gas has a volume of 2.57 L at 0.00C. What
was the temperature at 2.80 L?
since T and V are directly proportional, when the volume
decreases, the temperature should decrease, and it does
V
1
=2.57 L, V
2
= 2.80 L, t
2
= 0.00C
t
1
, K and C
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
2
1
2 1
V
V
T T - =
V
1
, V
2
, T
2
T
1

( ) ( )
( )
K 6 . 7 29
L 2.80
L 2.57 K 273.15
V
V T
T
2
1 2
1
=
-
=
-
=
K 273.15 T
273.15 0.00 T
2
2
=
+ =
C 4 2 t
273.15 6 . 7 29 t
273.15 T t
1
1
1 1
=
=
=
Tro, Chemistry: A Molecular Approach 28
Practice The temperature inside a balloon is raised from
25.0C to 250.0C. If the volume of cold air was 10.0 L,
what is the volume of hot air?




T(K) = t(C) + 273.15,
2
2
1
1
T
V
T
V
=
The temperature inside a balloon is raised from 25.0C to 250.0C.
If the volume of cold air was 10.0 L, what is the volume of hot air?
since T and V are directly proportional, when the temperature
increases, the volume should increase, and it does
V
1
=10.0 L, t
1
= 25.0C L, t
2
= 250.0C
V
2
, L
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
1
2
1 2
T
T
V V - =
V
1
, T
1
, T
2
V
2

( ) ( )
( )
L 5 . 17
K 298.2
L 10.0 K 523.2
T
V T
V
1
1 2
2
=
-
=
-
=
K 523.2 T
273.15 0 . 50 2 T
K 298.2 T
273.15 0 . 5 2 T
2
2
1
1
=
+ =
=
+ =
Tro, Chemistry: A Molecular Approach 30
Avogadros Law
volume directly proportional to
the number of gas molecules
V = constant x n
constant P and T
more gas molecules = larger
volume
count number of gas molecules
by moles
equal volumes of gases contain
equal numbers of molecules
the gas doesnt matter
2
2
1
1
n
V
n
V
=



mol added = n
2
n
1
,
2
2
1
1
n
V
n
V
=
Example 5.4 A 0.225 mol sample of He has a volume of 4.65 L.
How many moles must be added to give 6.48 L?
since n and V are directly proportional, when the volume
increases, the moles should increase, and it does
V
1
=4.65 L, V
2
= 6.48 L, n
1
= 0.225 mol
n
2
, and added moles
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
2
1
2
1
n
V
V
n = -
V
1
, V
2
, n
1
n
2

( ) ( )
( )
mol 314 . 0
L 4.65
L 6.48 mol 0.225
V
V n
n
1
2 1
2
=
-
=
-
=
mol 089 . 0 added moles
225 . 0 314 . 0 added moles
=
=
Tro, Chemistry: A Molecular Approach 32
Ideal Gas Law
By combing the gas laws we can write a general equation
R is called the gas constant
the value of R depends on the units of P and V
we will use 0.08206 and convert P to atm and V to L
the other gas laws are found in the ideal gas law if
two variables are kept constant
allows us to find one of the variables if we know the other 3


K mol
L atm
-
-
( ) ( )
( ) ( )
nRT PV or R
T n
V P
= =
-
-



1 atm = 14.7 psi
T(K) = t(C) + 273.15
K mol
L atm
0.08206 R nRT, PV
-
-
= =
Example 5.6 How many moles of gas are in a basketball
with total pressure 24.3 psi, volume of 3.24 L at 25C?
1 mole at STP occupies 22.4 L, since there is a much smaller
volume than 22.4 L, we expect less than 1 mole of gas
V = 3.24 L, P = 24.3 psi, t = 25 C,
n, mol
Check:
Solution:
Concept Plan:


Relationships:
Given:

Find:
RT
PV
n =
P, V, T, R n
( ) ( )
( ) ( )
mol 219 . 0
K 98 2 0.08206
L 24 . 3 atm 31 5 1.6
T R
V P
n
K mol
L atm
=
-
-
=
-
-
=
-
-
atm 31 5 1.6
psi 14.7
atm 1
psi 24.3 =
K 298 T
273.15 C 25 T(K)
=
+ =
Tro, Chemistry: A Molecular Approach 34
Standard Conditions
since the volume of a gas varies with pressure
and temperature, chemists have agreed on a set
of conditions to report our measurements so that
comparison is easy we call these standard
conditions
STP
standard pressure = 1 atm
standard temperature = 273 K
0C
Tro, Chemistry: A Molecular Approach 35
Practice A gas occupies 10.0 L at 44.1 psi and 27C.
What volume will it occupy at standard conditions?

( ) ( ) ( )
( )
L 3 . 27
atm .00 1
K 73 2 0.08206 mol 9 1 2 . 1
P
T R n
V
K mol
L atm
=
- -
=
- -
=
-
-
( ) ( )
( ) ( )
mol 9 1 2 . 1
K 00. 3 0.08206
L 0.0 1 atm 3.00
T R
V P
n
K mol
L atm
=
-
-
=
-
-
=
-
-



1 atm = 14.7 psi
T(K) = t(C) + 273.15
K mol
L atm
0.08206 R nRT, PV
-
-
= =
A gas occupies 10.0 L at 44.1 psi and 27C. What
volume will it occupy at standard conditions?
1 mole at STP occupies 22.4 L, since there is more than 1 mole, we
expect more than 22.4 L of gas
V
1
= 10.0 L, P
1
= 44.1 psi, t
1
= 27 C, P
2
= 1.00 atm, t
2
= 0C
V
2
, L
Check:
Solution:
Concept Plan:


Relationships:
Given:

Find:
RT
PV
n =
P
1
, V
1
, T
1
, R n
atm 00 . 3
psi 14.7
atm 1
psi 44.1 =
K . 00 3 T
273.15 C 27 T(K)
1
=
+ =
P
2
, n, T
2
, R V
2

P
nRT
V=
Tro, Chemistry: A Molecular Approach 37
Molar Volume
solving the ideal gas equation for the volume of
1 mol of gas at STP gives 22.4 L
6.022 x 10
23
molecules of gas
notice: the gas is immaterial
we call the volume of 1 mole of gas at STP the
molar volume
it is important to recognize that one mole of
different gases have different masses, even though
they have the same volume
Tro, Chemistry: A Molecular Approach 38
Molar Volume
Tro, Chemistry: A Molecular Approach 39
Density at Standard Conditions
density is the ratio of mass-to-volume
density of a gas is generally given in g/L
the mass of 1 mole = molar mass
the volume of 1 mole at STP = 22.4 L
L 22.4
g Mass, Molar
Density =
Tro, Chemistry: A Molecular Approach 40
Gas Density
T R
mass) (molar P
density
V
mass
T R
mass molar
mass
V P
T R n V P
liters in volume
grams in mass
density
mass molar
mass
moles moles
mass molar
mol 1
mass

= =
=
=
=
= =
density is directly proportional to molar mass



1 atm = 760 mmHg, MM = 28.01 g
T(K) = t(C) + 273.15
K mol
L atm
0.08206 R

T R
MM P
d
-
-
=
-
-
=
Example 5.7 Calculate the density of N
2

at 125C and 755 mmHg
since the density of N
2
is 1.25 g/L at STP, we expect the density
to be lower when the temperature is raised, and it is
P = 755 mmHg, t = 125 C,
d
N2
,

g/L
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
( )
T R
MM P
d
-
-
=
P, MM, T, R d
( ) ( )
( ) ( )
g/L 852 . 0
K 98 3 0.08206
8.01 2 atm 42 3 0.99
T R
MM P
d
K mol
L atm
mol
g
=
-
-
=
-
-
=
-
-
atm 42 3 99 . 0
mmHg 760
atm 1
mmHg 755 =
K 398 T
273.15 C 125 T(K)
=
+ =
Tro, Chemistry: A Molecular Approach 42
Molar Mass of a Gas
one of the methods chemists use to determine
the molar mass of an unknown substance is to
heat a weighed sample until it becomes a gas,
measure the temperature, pressure, and volume,
and use the ideal gas law

moles
grams in mass
Mass Molar =
Example 5.8 Calculate the molar mass of a gas with mass
0.311 g that has a volume of 0.225 L at 55C and 886 mmHg
the value 31.9 g/mol is reasonable
m=0.311g, V=0.225 L, P=886 mmHg, t=55C,
molar mass,

g/mol
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
T R
V P
n
-
-
=
n, m MM
( ) ( )
( ) ( )
mol 10 54 4 7 . 9
K 28 3 0.08206
L .225 0 atm 58 6 1.1
T R
V P
n
3
K mol
L atm

=
-
-
=
-
-
=
-
-
atm 58 6 1 . 1
mmHg 760
atm 1
mmHg 886 =
K 328 T
273.15 C 55 T(K)
=
+ =
P, V, T, R n
n
m
MM =
g/mol 31.9
mol 10 9.7454
g 311 . 0
n
m
MM
3 -
=

= =
1 atm = 760 mmHg,
T(K) = t(C) + 273.15
K mol
L atm
0.08206 R nRT, PV
-
-
= =
n
m
MM =
m=0.311g, V=0.225 L, P=1.1658 atm, T=328 K,
molar mass,

g/mol
Tro, Chemistry: A Molecular Approach 44
Practice - Calculate the density of a gas at 775 torr
and 27C if 0.250 moles weighs 9.988 g

( ) ( ) ( )
( )
L 55 3 0 . 6
atm 1.0197
K . 0 0 3 0.08206 mol .250 0
P
T R n
V
K mol
L atm
=
- -
=
- -
=
-
-
Calculate the density of a gas at 775 torr and 27C if
0.250 moles weighs 9.988 g
the value 1.65 g/L is reasonable
m=9.988g, n=0.250 mol, P=775 mmHg, t=27C,
density,

g/L
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
P
T R n
V
- -
=
V, m d
atm 97 1 0 . 1
torr 760
atm 1
torr 775 =
K 300. T
273.15 C 27 T(K)
=
+ =
P, n, T, R V
V
m
d =
g/L 1.65
L 55 3 .0 6
g .988 9
V
m
d
=
= =
1 atm = 760 mmHg,
T(K) = t(C) + 273.15
K mol
L atm
0.08206 R nRT, PV
-
-
= =
V
m
d =
m=9.988g, n=0.250 mol, P=1.0197 atm, T=300. K
density,

g/L
Tro, Chemistry: A Molecular Approach 46
Mixtures of Gases
when gases are mixed together, their molecules
behave independent of each other
all the gases in the mixture have the same volume
all completely fill the container each gass volume = the volume
of the container
all gases in the mixture are at the same temperature
therefore they have the same average kinetic energy
therefore, in certain applications, the mixture can be
thought of as one gas
even though air is a mixture, we can measure the pressure,
volume, and temperature of air as if it were a pure substance
we can calculate the total moles of molecules in an air sample,
knowing P, V, and T, even though they are different molecules
Tro, Chemistry: A Molecular Approach 47
Partial Pressure
the pressure of a single gas in a mixture of gases is
called its partial pressure
we can calculate the partial pressure of a gas if
we know what fraction of the mixture it composes and the
total pressure
or, we know the number of moles of the gas in a container of
known volume and temperature
the sum of the partial pressures of all the gases in the
mixture equals the total pressure
Daltons Law of Partial Pressures
because the gases behave independently
Tro, Chemistry: A Molecular Approach 48
Composition of Dry Air

Tro, Chemistry: A Molecular Approach 49
The partial pressure of each gas in a mixture can
be calculated using the ideal gas law
V
T x R x n
P P P
n n n
same the are mixture in the
everything of volume and re temperatu the
V
T x R x n
P
V
T x R x n
P
together mixed B, and A gases, for two
total
B A total
B A total
B
B
A
A
= + =
+ =
= =
( ) ( )
( ) ( )
mol 10 125 . 1
K 298 0.08206
L 00 . 1 atm .275 0
T R
V P
n
2
K mol
L atm

=
-
-
=
-
-
=
-
-
Example 5.9 Determine the mass of Ar in the mixture
the units are correct, the value is reasonable
P
He
=341 mmHg, P
Ne
=112 mmHg, P
tot
= 662 mmHg,
V = 1.00 L, T=298 K
mass
Ar
,

g
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
T R
V P
n
-
-
=
atm 275 . 0
mmHg 760
atm 1
mmHg 209 =
P
tot
, P
He
, P
Ne
P
Ar

MM n m - =
Ar g 0.449
mol 1
g 39.95
mol 10 125 . 1
2
=


P
tot
= P
a
+ P
b
+ etc.,
1 atm = 760 mmHg, MM
Ar
= 39.95 g/mol
K mol
L atm
0.08206 R nRT, PV
-
-
= =
n
m
MM =
P
Ar
= 0.275 atm, V = 1.00 L, T=298 K

mass
Ar
,

g
P
Ar
, V, T n
Ar
m
Ar

P
Ar
= P
tot
(P
He
+ P
Ne
)
( )
mmHg 209
mmHg 112 341 662 P
Ar
=
+ =
Tro, Chemistry: A Molecular Approach 51
Practice Find the partial pressure of neon in a mixture
with total pressure 3.9 atm, volume 8.7 L, temperature
598 K, and 0.17 moles Xe.

( ) ( ) ( )
atm 89 5 9 . 0
L 8.7
K 98 5 0.08206 mol 0.17
V
T R n
P
K mol
L atm
Xe
Xe
=
- -
=
- -
=
-
-
Xe Ne total
,
K mol
L atm
P P P 0.08206 R nRT, PV + = = =
-
-
Find the partial pressure of neon in a mixture with total pressure
3.9 atm, volume 8.7 L, temperature 598 K, and 0.17 moles Xe
the unit is correct, the value is reasonable
P
tot
= 3.9 atm, V = 8.7 L, T = 598 K, Xe = 0.17 mol
P
Ne
, atm
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
V
T R n
P
Xe
Xe
- -
=
n
Xe
, V, T, R P
Xe

atm 2.9
atm 89 5 0.9 atm 9 . 3
P P P
Xe total Ne
=
=
=
P
tot
, P
Xe
P
Ne

Xe total Ne
P P P =
Tro, Chemistry: A Molecular Approach 53
Mole Fraction
the fraction of the total pressure that a
single gas contributes is equal to the
fraction of the total number of moles
that a single gas contributes
total
A
total
A
n
n
P
P
=
the ratio of the moles of a single
component to the total number of
moles in the mixture is called the
mole fraction, _
for gases, = volume % / 100%
total
A
A
n
n
= _
the partial pressure of a gas is equal to
the mole fraction of that gas times the
total pressure
total A A
P P - = _
Tro, Chemistry: A Molecular Approach 54
Mountain Climbing & Partial Pressure
our bodies are adapted to breathe O
2

at a partial pressure of 0.21 atm
Sherpa, people native to the Himalaya
mountains, are adapted to the much
lower partial pressure of oxygen in
their air
partial pressures of O
2
lower than
0.1 atm will lead to hypoxia
unconsciousness or death
climbers of Mt Everest carry O
2
in
cylinders to prevent hypoxia
on top of Mt Everest, P
air
= 0.311 atm,
so P
O2
= 0.065 atm
Tro, Chemistry: A Molecular Approach 55
Deep Sea Divers & Partial Pressure
its also possible to have too much O
2
, a condition called
oxygen toxicity
P
O2
> 1.4 atm
oxygen toxicity can lead to muscle spasms, tunnel vision, and
convulsions
its also possible to have too much N
2
, a condition called
nitrogen narcosis
also known as Rapture of the Deep
when diving deep, the pressure of the air divers breathe
increases so the partial pressure of the oxygen increases
at a depth of 55 m the partial pressure of O
2
is 1.4 atm
divers that go below 50 m use a mixture of He and O
2
called
heliox that contains a lower percentage of O
2
than air
Tro, Chemistry: A Molecular Approach 56
Partial Pressure & Diving
2
2
2
O mol 135 . 0
g 32.00
O mol 1
O g 4.32 =
( ) ( ) ( )
atm 99 0 . 12
L 12.5
K 98 2 0.08206 mol 5 8 6.1
V
T R n
P
K mol
L atm
t ot al
t ot al
=
- -
=
- -
=
-
-
Ex 5.10 Find the mole fractions and partial pressures in
a 12.5 L tank with 24.2 g He and 4.32 g O
2
at 298 K
m
He
= 24.2 g, m
O2
= 43.2 g V = 12.5 L, T = 298 K
_
He
, _
O2
, P
He
, atm, P
O2
, atm, P
total
, atm
Solution:
Concept Plan:




Relationships:
Given:

Find:
V
T R n
P
total
total
- -
=
He mol 05 . 6
g 4.00
He mol 1
He g 24.2 =
n
tot
, V, T, R P
tot
m
gas
n
gas
_
gas

total
A gas
A gas
n
n
= _
_
gas
, P
total
P
gas

total A A
,
K mol
L atm
P P 0.08206 R nRT, PV - = = =
-
-
_
MM
He
= 4.00 g/mol
MM
O2
= 32.00 g/mol
n
He
= 6.05 mol, n
O2
= 0.135 mol V = 12.5 L, T = 298 K
_
He
=0.97817, _
O2
=0.021827, P
He
, atm, P
O2
, atm, P
total
, atm
17 8 97 . 0
O mol 0.135 He mol 6.05
He mol 6.05

2
He
=
+
= _
27 8 021 . 0
O mol 0.135 He mol 6.05
O mol 0.135

2
2
O
2
=
+
= _
total A A
P P - = _
atm 11.8
atm 99 0 . 12 17 8 97 . 0
P P
total He He
=
- =
- = _
atm 264 . 0
atm 99 0 . 12 27 8 021 . 0
P P
total O O
2 2
=
- =
- = _
Tro, Chemistry: A Molecular Approach 58
Collecting Gases
gases are often collected by having them displace
water from a container
the problem is that since water evaporates, there is
also water vapor in the collected gas
the partial pressure of the water vapor, called the
vapor pressure, depends only on the temperature
so you can use a table to find out the partial pressure of
the water vapor in the gas you collect
if you collect a gas sample with a total pressure of
758.2 mmHg* at 25C, the partial pressure of the
water vapor will be 23.78 mmHg so the partial
pressure of the dry gas will be 734.4 mmHg
Table 5.4*
Tro, Chemistry: A Molecular Approach 59
Vapor Pressure of Water

Tro, Chemistry: A Molecular Approach 60
Collecting Gas by Water Displacement
( ) ( )
( ) ( )
mol 10 75 1 1 . 4
K . 293 0.08206
L 02 . 1 atm 9 5 0.970
T R
V P
n
2
K mol
L atm

=
-
-
=
-
-
=
-
-
atm 9 5 970 . 0
mmHg 760
atm 1
mmHg 5 6 737. =
Ex 5.11 1.02 L of O
2
collected over water at 293 K
with a total pressure of 755.2 mmHg. Find mass O
2
.
V=1.02 L, P=755.2 mmHg, T=293 K
mass O
2
,

g
Solution:
Concept Plan:



Relationships:
Given:

Find:
T R
V P
n
-
-
=
P
tot
, P
H2O
P
O2

mmHg 5 6 . 37 7 P
5.4) (Table 17.55 55.2 7 P
2
2
O
O
=
=
C 20 @ O H total O
2 2
P P P

=
g 1.32
mol 1
g 2.00 3
mol 10 75 1 1 . 4
2
=


1 atm = 760 mmHg,
P
total
= P
A
+ P
B
, O
2
= 32.00 g/mol
K mol
L atm
0.08206 R nRT, PV
-
-
= =
V=1.02 L, P
O2
=737.65 mmHg, T=293 K
mass O
2
,

g
P
O2
,V,T n
O2
g
O2

Tro, Chemistry: A Molecular Approach 62
Practice 0.12 moles of H
2
is collected over water in a
10.0 L container at 323 K. Find the total pressure.

( ) ( ) ( )
( )
atm 81 1 3 . 0
L 10.0
K 323 0.08206 mol 0.12
V
T R n
P
K mol
L atm
2
H
=
- -
=
- -
=
-
-
V=10.0 L, n
H2
=0.12 mol, T=323 K
P
total
,

atm
0.12 moles of H
2
is collected over water in a 10.0 L
container at 323 K. Find the total pressure.
Solution:
Concept Plan:



Relationships:
Given:

Find:
V
T R n
P
- -
=
P
H2
, P
H2O
P
total

mmHg 330 P
5.4) (Table 6 . 2 9 1.8 4 2 P
total
total
=
+ =
C 50 @ O H H total
2 2
P P P

+ =
1 atm = 760 mmHg
P
total
= P
A
+ P
B
,
K mol
L atm
0.08206 R nRT, PV
-
-
= =
n
H2
,V,T P
H2

mmHg 8 . 1 4 2
atm 1
mmHg 760
atm 81 1 0.3 =
Tro, Chemistry: A Molecular Approach 64
Reactions Involving Gases
the principles of reaction stoichiometry from
Chapter 4 can be combined with the gas laws for
reactions involving gases
in reactions of gases, the amount of a gas is often
given as a volume
instead of moles
as weve seen, must state pressure and temperature
the ideal gas law allows us to convert from the
volume of the gas to moles; then we can use the
coefficients in the equation as a mole ratio
when gases are at STP, use 1 mol = 22.4 L
P, V, T of Gas A mole A mole B P, V, T of Gas B
( ) ( ) ( )
( )
L 9 . 66
atm 05 1 0.97
K 355 0.08206 mol 84 2 .2 2
P
T R n
V
K mol
L atm
=
- -
=
- -
=
-
-
Ex 5.12 What volume of H
2
is needed to make 35.7 g of CH
3
OH
at 738 mmHg and 355 K?
CO(g) + 2 H
2
(g) CH
3
OH(g)
m
CH3OH
= 37.5g, P=738 mmHg, T=355 K
V
H2
,

L
Solution:
Concept Plan:


Relationships:
Given:
Find:
P
T R n
V
- -
=
atm 05 1 97 . 0
mmHg 760
atm 1
mmHg 738 =
2
3
2 3
3
H mol 84 2 2.2
OH CH mol 1
H mol 2
g 32.04
OH CH mol 1
OH CH g 5 . 37
=

P, n, T, R V
1 atm = 760 mmHg, CH
3
OH = 32.04 g/mol
1 mol CH
3
OH : 2 mol H
2


K mol
L atm
0.08206 R nRT, PV
-
-
= =
g CH
3
OH mol CH
3
OH mol H
2

OH CH mol 1
H mol 2
3
2
n
H2
= 2.2284 mol, P=0.97105 atm, T=355 K
V
H2
,

L
g 32.04
OH CH mol 1
3
Ex 5.13 How many grams of H
2
O form when 1.24 L H
2
reacts
completely with O
2
at STP?
O
2
(g) + 2 H
2
(g) 2 H
2
O(g)
V
H2
= 1.24 L, P=1.00 atm, T=273 K
mass
H2O
,

g
Solution:
Concept Plan:


Relationships:
Given:
Find:
O H mol 1
g 02 . 18

2
O H g 998 . 0
O H mol 1
O H g 8.02 1
H mol 2
O H mol 2
H L 22.4
H mol 1
H L .24 1
2
2
2
2
2
2
2
2
=

H
2
O = 18.02 g/mol, 1 mol = 22.4 L @ STP
2 mol H
2
O : 2 mol H
2


O H mol 2
H mol 2
2
2
L 22.4
H mol 1
2
g H
2
O L H
2
mol H
2
mol H
2
O
Tro, Chemistry: A Molecular Approach 67
Practice What volume of O
2
at 0.750 atm and 313 K is
generated by the thermolysis of 10.0 g of HgO?
2 HgO(s) 2 Hg(l) + O
2
(g)
(MM
HgO
= 216.59 g/mol)

( ) ( ) ( )
( )
L 791 . 0
atm 0.750
K 313 0.08206 mol 85 0 023 . 0
P
T R n
V
K mol
L atm
=
- -
=
- -
=
-
-
What volume of O
2
at 0.750 atm and 313 K is generated by
the thermolysis of 10.0 g of HgO?
2 HgO(s) 2 Hg(l) + O
2
(g)
m
HgO
= 10.0g, P=0.750 atm, T=313 K
V
O2
,

L
Solution:
Concept Plan:


Relationships:
Given:
Find:
P
T R n
V
- -
=
2
2
O mol 85 0 023 . 0
HgO mol 2
O mol 1
g 216.59
HgO mol 1
HgO g 0.0 1
=

P, n, T, R V
1 atm = 760 mmHg, HgO = 216.59 g/mol
2 mol HgO : 1 mol O
2


K mol
L atm
0.08206 R nRT, PV
-
-
= =
g HgO mol HgO mol O
2

HgO mol 2
O mol 1
2
n
O2
= 0.023085 mol, P=0.750 atm, T=313 K
V
O2
,

L
g 216.59
HgO mol 1
Tro, Chemistry: A Molecular Approach 69
Properties of Gases
expand to completely fill their container
take the shape of their container
low density
much less than solid or liquid state
compressible
mixtures of gases are always homogeneous
fluid
Tro, Chemistry: A Molecular Approach 70
Kinetic Molecular Theory
the particles of the gas (either atoms
or molecules) are constantly moving
the attraction between particles is
negligible
when the moving particles hit another
particle or the container, they do not
stick; but they bounce off and
continue moving in another direction
like billiard balls

Tro, Chemistry: A Molecular Approach 71
Kinetic Molecular Theory
there is a lot of empty space
between the particles
compared to the size of the particles
the average kinetic energy of the
particles is directly proportional to
the Kelvin temperature
as you raise the temperature of the
gas, the average speed of the particles
increases
but dont be fooled into thinking all the
particles are moving at the same speed!!
Tro, Chemistry: A Molecular Approach 72
Gas Properties Explained
Indefinite Shape and Indefinite Volume
Because the gas
molecules have
enough kinetic
energy to overcome
attractions, they
keep moving around
and spreading out
until they fill the
container.
As a result, gases
take the shape and
the volume of the
container they
are in.
Tro, Chemistry: A Molecular Approach 73
Gas Properties Explained -
Compressibility
Because there is a lot of unoccupied space in the structure
of a gas, the gas molecules can be squeezed closer together
Tro, Chemistry: A Molecular Approach 74
Gas Properties Explained
Low Density
Because there is a lot of
unoccupied space in the
structure of a gas, gases do
not have a lot of mass in a
given volume, the result is
they have low density
Tro, Chemistry: A Molecular Approach 75
Density & Pressure
result of the constant movement
of the gas molecules and their
collisions with the surfaces
around them
when more molecules are added,
more molecules hit the container
at any one instant, resulting in
higher pressure
also higher density
Tro, Chemistry: A Molecular Approach 76
Gas Laws Explained -
Boyles Law
Boyles Law says that the volume of a gas is inversely
proportional to the pressure
decreasing the volume forces the molecules into a
smaller space
more molecules will collide with the container at any
one instant, increasing the pressure
Tro, Chemistry: A Molecular Approach 77
Gas Laws Explained -
Charless Law
Charless Law says that the volume of
a gas is directly proportional to the
absolute temperature
increasing the temperature increases
their average speed, causing them to
hit the wall harder and more
frequently
on average
in order to keep the pressure constant,
the volume must then increase
Tro, Chemistry: A Molecular Approach 78
Gas Laws Explained
Avogadros Law
Avogadros Law says that the volume of a gas is
directly proportional to the number of gas
molecules
increasing the number of gas molecules causes
more of them to hit the wall at the same time
in order to keep the pressure constant, the
volume must then increase
Tro, Chemistry: A Molecular Approach 79
Gas Laws Explained
Daltons Law of Partial Pressures
Daltons Law says that the total pressure of a mixture of
gases is the sum of the partial pressures
kinetic-molecular theory says that the gas molecules are
negligibly small and dont interact
therefore the molecules behave independent of each
other, each gas contributing its own collisions to the
container with the same average kinetic energy
since the average kinetic energy is the same, the total
pressure of the collisions is the same
Tro, Chemistry: A Molecular Approach 80
Daltons Law & Pressure
since the gas
molecules are not
sticking together,
each gas molecule
contributes its own
force to the total
force on the side
Tro, Chemistry: A Molecular Approach 81
Deriving the Ideal Gas Law from
Kinetic-Molecular Theory
pressure = Force
total
/Area
F
total
= F
1 collision
x number of collisions
in a particular time interval
F
1 collision
= mass x 2(velocity)/time interval
no. of collisions is proportional to the number of particles
within the distance (velocity x time interval) from the wall
F
total
massvelocity
2

x Area x no. molecules/Volume
Pressure mv
2
x n/V
Temperature mv
2
P Tn/V, PV=nRT
Tro, Chemistry: A Molecular Approach 82
Calculating Gas Pressure
Tro, Chemistry: A Molecular Approach 83
Molecular Velocities
all the gas molecules in a sample can travel at different
speeds
however, the distribution of speeds follows a pattern
called a Boltzman distribution
we talk about the average velocity of the molecules,
but there are different ways to take this kind of average
the method of choice for our average velocity is called
the root-mean-square method, where the rms average
velocity, u
rms
, is the square root of the average of the
sum of the squares of all the molecule velocities
2
2
n
v
u u
rms
=

=
Tro, Chemistry: A Molecular Approach 84
Boltzman Distribution
Distribution Function
Molecular Speed
F
r
a
c
t
i
o
n

o
f

M
o
l
e
c
u
l
e
s
O2 @ 300 K
Tro, Chemistry: A Molecular Approach 85
Kinetic Energy and
Molecular Velocities
average kinetic energy of the gas molecules depends on
the average mass and velocity
KE = mv
2

gases in the same container have the same temperature,
the same average kinetic energy
if they have different masses, the only way for them to
have the same kinetic energy is to have different
average velocities
lighter particles will have a faster average velocity than more
massive particles
Tro, Chemistry: A Molecular Approach 86
Molecular Speed vs. Molar Mass
in order to have the same average kinetic
energy, heavier molecules must have a slower
average speed
Tro, Chemistry: A Molecular Approach 87
Temperature and Molecular Velocities
_
KE
avg
= N
A
mu
2
N
A
is Avogadros number
KE
avg
= 1.5RT
R is the gas constant in energy units, 8.314 J/molK
1 J = 1 kgm
2
/s
2

equating and solving we get:
N
A
mass = molar mass in kg/mol
MM
RT
m N
RT
u
A
3 3
rms
=
-
=
as temperature increases, the average velocity increases
Tro, Chemistry: A Molecular Approach 88
Temperature vs. Molecular Speed
as the absolute
temperature increases,
the average velocity
increases
the distribution
function spreads out,
resulting in more
molecules with faster
speeds
( )
( )
m/s 482
10 32.00
K 298 314 . 8 3
MM
3RT
mol
kg
3 -
K mol
s
m kg
rms
2
2
=

-
|
|
.
|

\
|
-
=
=
-
-
u



T(K) = t(C) + 273.15, O
2
= 32.00 g/mol
MM
3RT
rms
= u
Ex 5.14 Calculate the rms velocity of O
2
at 25C
O
2
, t = 25C
u
rms

Solution:
Concept Plan:



Relationships:
Given:

Find:
MM, T u
rms

MM
3RT
rms
= u
K 298 T
273.15 25 T
273.15 C) t( T(K)
=
+ =
+ =
Tro, Chemistry: A Molecular Approach 90
Mean Free Path
molecules in a gas travel in
straight lines until they collide
with another molecule or the
container
the average distance a
molecule travels between
collisions is called the mean
free path
mean free path decreases as the
pressure increases
Tro, Chemistry: A Molecular Approach 91
Diffusion and Effusion
the process of a collection of molecules spreading out
from high concentration to low concentration is called
diffusion
the process by which a collection of molecules escapes
through a small hole into a vacuum is called effusion
both the rates of diffusion and effusion of a gas are
related to its rms average velocity
for gases at the same temperature, this means that the
rate of gas movement is inversely proportional to the
square root of the molar mass
MM
1
rate o
Tro, Chemistry: A Molecular Approach 92
Effusion
Tro, Chemistry: A Molecular Approach 93
Grahams Law of Effusion
for two different gases at the same temperature,
the ratio of their rates of effusion is given by the
following equation:
A gas
B gas
B gas
A gas
Mass Molar
Mass Molar
rate
rate
=
Ex 5.15 Calculate the molar mass of a gas that
effuses at a rate 0.462 times N
2

MM, g/mol
Solution:
Concept Plan:



Relationships:
Given:

Find:
rate
A
/rate
B
, MM
N2
MM
unknown

462 . 0
rate
rate
2
N
gas unknown
=



N
2
= 28.01 g/mol
A gas
B gas
B gas
A gas
Mass Molar
Mass Molar
rate
rate
=
2
N
unknown
N
unknown
2
2
rate
rate
Mass Molar
Mass Molar
|
|
.
|

\
|
=
( )
( )
mol
g
2
mol
g
2
N
unknown
N
unknown
131
0.462
01 . 28
rate
rate
Mass Molar
Mass Molar
2
2
= =
|
|
.
|

\
|
=
95
Ideal vs. Real Gases
Real gases often do not behave like ideal gases
at high pressure or low temperature
Ideal gas laws assume
1) no attractions between gas molecules
2) gas molecules do not take up space
based on the kinetic-molecular theory
at low temperatures and high pressures these
assumptions are not valid
Tro, Chemistry: A Molecular Approach 96
The Effect of Molecular Volume
at high pressure, the amount of space occupied
by the molecules is a significant amount of the
total volume
the molecular volume makes the real volume
larger than the ideal gas law would predict
van der Waals modified the ideal gas equation
to account for the molecular volume
b is called a van der Waals constant and is
different for every gas because their molecules are
different sizes
b n
P
nRT
V + =
Tro, Chemistry: A Molecular Approach 97
Real Gas Behavior
because real
molecules take up
space, the molar
volume of a real gas
is larger than
predicted by the ideal
gas law at high
pressures
Tro, Chemistry: A Molecular Approach 98
The Effect of Intermolecular Attractions
at low temperature, the attractions between the
molecules is significant
the intermolecular attractions makes the real pressure
less than the ideal gas law would predict
van der Waals modified the ideal gas equation to
account for the intermolecular attractions
a is called a van der Waals constant and is different for
every gas because their molecules are different sizes

2
V
n
V
nRT
P
|
.
|

\
|
= a
Tro, Chemistry: A Molecular Approach 99
Real Gas Behavior
because real
molecules attract each
other, the molar
volume of a real gas
is smaller than
predicted by the ideal
gas law at low
temperatures
Tro, Chemistry: A Molecular Approach 100
Van der Waals
Equation
combining the equations to
account for molecular volume
and intermolecular attractions
we get the following equation
used for real gases
a and b are called van der Waal
constants and are different for each
gas
( ) nRT n - V
V
n
P
2
=
|
|
.
|

\
|
|
.
|

\
|
+ b a
Tro, Chemistry: A Molecular Approach 101
Real Gases
a plot of PV/RT vs. P for 1 mole of a gas shows
the difference between real and ideal gases
it reveals a curve that shows the PV/RT ratio for
a real gas is generally lower than ideality for
low pressures meaning the most important
factor is the intermolecular attractions
it reveals a curve that shows the PV/RT ratio for
a real gas is generally higher than ideality for
high pressures meaning the most important
factor is the molecular volume

Tro, Chemistry: A Molecular Approach 102
PV/RT Plots
Tro, Chemistry: A Molecular Approach 103
Structure of the Atmosphere
the atmosphere shows several
layers, each with its own
characteristics
the troposphere is the layer closest
to the earths surface
circular mixing due to thermal currents
weather
the stratosphere is the next layer up
less air mixing
the boundary between the
troposphere and stratosphere is
called the tropopause
the ozone layer is located in the
stratosphere
Tro, Chemistry: A Molecular Approach 104
Air Pollution
air pollution is materials added to the atmosphere that
would not be present in the air without, or are increased
by, mans activities
though many of the pollutant gases have natural sources as
well
pollution added to the troposphere has a direct effect on
human health and the materials we use because we
come in contact with it
and the air mixing in the troposphere means that we all get a
smell of it!
pollution added to the stratosphere may have indirect
effects on human health caused by depletion of ozone
and the lack of mixing and weather in the stratosphere means
that pollutants last longer before washing out
Tro, Chemistry: A Molecular Approach 105
Pollutant Gases, SO
x

SO
2
and SO
3
, oxides of sulfur, come from coal
combustion in power plants and metal refining
as well as volcanoes
lung and eye irritants
major contributor to acid rain
2 SO
2
+ O
2
+ 2 H
2
O 2 H
2
SO
4
SO
3
+ H
2
O H
2
SO
4

Tro, Chemistry: A Molecular Approach 106
Pollutant Gases, NO
x

NO and NO
2
, oxides of nitrogen, come from burning of
fossil fuels in cars, trucks, and power plants
as well as lightning storms
NO
2
causes the brown haze seen in some cities
lung and eye irritants
strong oxidizers
major contributor to acid rain
4 NO + 3 O
2
+ 2 H
2
O 4 HNO
3
4 NO
2
+ O
2
+ 2 H
2
O 4 HNO
3

Tro, Chemistry: A Molecular Approach 107
Pollutant Gases, CO
CO comes from incomplete burning of fossil
fuels in cars, trucks, and power plants
adheres to hemoglobin in your red blood cells,
depleting your ability to acquire O
2

at high levels can cause sensory impairment,
stupor, unconsciousness, or death
Tro, Chemistry: A Molecular Approach 108
Pollutant Gases, O
3

ozone pollution comes from other pollutant
gases reacting in the presence of sunlight
as well as lightning storms
known as photochemical smog and ground-level
ozone
O
3
is present in the brown haze seen in some
cities
lung and eye irritants
strong oxidizer
Tro, Chemistry: A Molecular Approach 109
Major Pollutant Levels
government
regulation has
resulted in a
decrease in the
emission levels for
most major
pollutants
Tro, Chemistry: A Molecular Approach 110
Stratospheric Ozone
ozone occurs naturally in the stratosphere
stratospheric ozone protects the surface of the earth
from over-exposure to UV light from the sun
O
3
(g) + UV light O
2
(g) + O(g)
normally the reverse reaction occurs quickly, but
the energy is not UV light
O
2
(g) + O(g) O
3
(g)
Tro, Chemistry: A Molecular Approach 111
Ozone Depletion
chlorofluorocarbons became popular as aerosol
propellants and refrigerants in the 1960s
CFCs pass through the tropopause into the stratosphere
there CFCs can be decomposed by UV light, releasing
Cl atoms
CF
2
Cl
2
+ UV light CF
2
Cl + Cl
Cl atoms catalyze O
3
decomposition and removes O
atoms so that O
3
cannot be regenerated
NO
2
also catalyzes O
3
destruction
Cl + O
3
ClO + O
2
O
3
+ UV light O
2
+ O
ClO + O O
2
+ Cl
Tro, Chemistry: A Molecular Approach 112
Ozone Holes
satellite data over
the past 3 decades
reveals a marked
drop in ozone
concentration over
certain regions