CH 12 Gases and The Kinetic-Molecular Theory

1
CHAPTER 12
GASES AND KINETIC-MOLECULAR THEORY
Comparison of Solids, Liquids,

and Gases
The density of gases is much less than that
of solids or liquids.
Densities
(g/mL)
Solid Liquid Gas
H
O 0.917 0.998 0.000588

CCl
4
1.70 1.59 0.00503
Gas molecules must be very far apart
compared to liquids and solids.
3
Composition of the Atmosphere and
Some Common Properties of Gases
Gas % by Volume
N
78.09
O
0.94
Ar 0.93
CO
0.03
He, Ne, Kr, Xe 0.00
CH
4
0.00015
H
0.00005
Composition of Dry Air
4
Pressure
!ressure is force per unit area.
lb/in
N/m
Gas pressure as most people think of it.

5
Pressure
Atmospheric pressure is measured using a
barometer.
Definitions of standard pressure
76 cm Hg
760 mm Hg
760 torr
1 atmosphere
101.3 k!a
Hg donsily = 13.6 g/nL
6
oyle's Law:
The Volume-Pressure Relationship
V 1/! or
V= k (1/!) or !V = k
!
1
V
1
= k
1
for one sample of a gas.
!
= k

for a second sample of a
gas.
k
1
= k

for the same sample of a gas
at the same T.
Thus we can write Boyles Law
mathematically as !
1
V
1
= !
7
oyle's Law:
Example 1-1: At 5
o
C a sample of He has a
volume of 4.00 x 10
mL under a pressure
of 7.60 x 10
torr. What volume would it

occupy under a pressure of .00 atm at the
same T?
) )
torr 1520
mL 400 torr 760
P
V P
V
V P V P
2
1 1
2
2 2 1 1
=
=
=
8
oyle's Law:
Notice that in Boyles law we can use any
pressure or volume units as long as we
consistently use the same units for both
!
1
and !
or V
1
and V
.
Use your intuition to help you decide if
the volume will go up or down as the
pressure is changed and vice versa.
9
Charles' Law:
The Volume-Temperature Relationship;
The Absolute Temperature Scale
0
5
10
15
20
25
30
35
0 50 100 150 200 250 300 350 400
VoIume (L)
vs.
Temperature (K)
Gases Iiquefy
before reaching 0K
,-soIulo zoio = -273.15
O
C
10
Charles' Law:
Charless law states that the volume
of a gas is directly proportional to
the absolute temperature at
constant pressure.
Gas laws must use the Kelvin scale to
be correct.
Relationship between Kelvin and
centigrade.
C 273
o
11
Charles' Law:
Mathematical form of Charles law.
1orm use1ul most in the
T
V
T
V
so equal are s k' e however th k
T
V
and k
T
V
k
T
V
or kT V or T V
2
2
1
1
2
2
1
1
=
= =
=
1
Charles' Law:
Example 1-: A sample of hydrogen, H
,
occupies 1.00 x 10
mL at 5.0
o
C and 1.00
atm. What volume would it occupy at
50.0
o
C under the same pressure?
T
1
= 5 + 73 = 98
T
= 50 + 73 = 33
mL 108
298
323 mL 10 1.00
V
T
T V
V
T
V
T
V
2
2
1
2 1
2
2
2
1
1
=
- -
=
13
Standard Temperature and
Pressure
Standard temperature and pressure is
given the symbol ST!.
It is a reference point for some gas
calculations.
Standard ! 1.00000 atm or 101.3 k!a
Standard T 73.15 K or 0.00
o
C
14
The Combined Gas Law Equation
Boyles and Charles Laws combined into
one statement is called the combined gas
law equation.
Useful when the V, T, and ! of a gas are
changing.
2
2 2
1
1 1
2
2
1
1
2 2 1 1
T
V P
T
V P
k
T
V P
: is law gas combined The : gas o1 sample given a For
T
V
T
V
V P V P
Law Charles' Law s Boyle'
= =
= =
15
Example 1-3: A sample of nitrogen gas, N
,
occupies 7.50 x 10
mL at 75.0
0
C under a
pressure of 8.10 x 10
torr. What volume

would it occupy at ST!?
) ) )
) )
mL 627
348 torr 760
273 mL 750 torr 810
T P
T V P
V 1or Solve
torr 760 P torr 810 P
273 T 348 T
? V mL 750 V
1 2
2 1 1
2
2 1
2 1
2 1
=
=
16
Example 1-4 : A sample of methane,
CH
4
, occupies .60 x 10
mL at 3
o
C
under a pressure of 0.500 atm. At
what temperature would it occupy 5.00
x 10
mL under a pressure of 1.0 x

10
3
torr?
4:/49 4:/49
17
) ) )
) )
C 1580 1852
mL 260 torr 380
mL 500 torr 1200 305
V P
V P T
T
? T 305 T
torr 380
torr 1200 P atm 0.500 P
mL 500 V mL 260 V
o
1 1
2 2 1
2
2 1
2 1
2 1
<
=
18
Avogadro's Law and the
Standard Molar Volume
Avogadros 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 ST!, then one mole of that gas has a
volume called the standard molar volume standard molar volume.
The standard molar volume is .4 L at ST!.
This is another way to measure moles.
For ,808, the volume is proportional to the
number of moles.
11. L of a gas at ST! = 0.500 mole
44.8 L = ? moles
19
Avogadro's Law and the
Standard Molar Volume
Example 1-5: One mole of a gas
occupies 36.5 L and its density is 1.36 g/L
at a given temperature and pressure. (a)
What is its molar mass? (b) What is its
density at ST!?
? . .
.
g
mol
L
mol
g
L
g / mol = - =
365 136
49 6
g/L 21 . 2
L 4 . 22
mol 1
mol
g 6 . 49
L
g ?
STP
= - =
0
Summary of Gas Laws:
The deal Gas Law
Boyles Law - V 1/! (at constant T & n)
Charles Law - V T (at constant ! & n)
Avogadros Law - V n (at constant T & !)
Combine these three laws into one statement
V nT/!
Convert the proportionality into an equality.
V = nRT/!
This provides the Ideal Gas Law.
!' = nRT
R is a proportionality constant called the
universal gas constant.
1
The deal Gas Law
We must determine the value of R.
Recognize that for one mole of a gas at 1.00
atm, and 73 K (ST!), the volume is .4 L.
Use these values in the ideal gas law.
) )
) )
#
PV
nT
1.00 atm L
1.00 mol
L atm
mol
=
=
22 4
273
0 0821
.
.

The deal Gas Law
R has other values if the units are
changed.
R = 8.314 J/mol K
Use this value in thermodynamics.
R = 8.314 kg m
/s
K mol
Use this later in this chapter for gas velocities.
R = 8.314 dm
3
k!a/K mol
This is R in all metric units.
R = 1.987 cal/K mol
This the value of R in calories rather than J.
3
The deal Gas Law
Example 1-6: What volume would
50.0 g of ethane, C
H
6
, occupy at 1.40
x 10
o
C under a pressure of 1.8 x
10
3
torr?
To use the ideal gas law correctly, it is very
important that all of your values be in the
correct units!
1. T = 140 + 73 = 413 K
. ! = 180 torr (1 atm/760 torr) = .39 atm
3. 50 g (1 mol/30 g) = 1.67 mol
4
The deal Gas Law
) )
L 6 . 23
atm 39 . 2
413
mol
atm L
0821 . 0 mol 67 . 1
P
T # n
V
=
'
+
'
=
5
The deal Gas Law
Example 1-7: Calculate the
number of moles in, and the mass
of, an 8.96 L sample of methane,
CH
4
, measured at standard
conditions.
4:/49 4:/49
6
The deal Gas Law
) )
)
n
PV
#T
1.00 atm L
0.0821
L atm
mol

0.400 mol CH
g CH mol
16.0 g
mol
6.40 g
4
4
=
'
+
'
=
= - =
8 96
273
0 400
.
? .
7
The deal Gas Law
Example 1-8: Calculate the pressure
exerted by 50.0 g of ethane, C
H
6
, in a
5.0 L container at 5.0
o
C.
4:/49 4:/49
) )
atm 63 . 1 P
L 25.0
298
mol
atm L
0.0821 mol 1.67
P
V
T # n
P
298 T and mol 1.67 n
=
'
+
'
=
8
etermination of Molecular Weights and
Molecular Formulas of Gaseous Substances
Example 1-9: A compound that
contains only carbon and hydrogen
is 80.0% carbon and 0.0%
hydrogen by mass. At ST!, 546 mL
of the gas has a mass of 0.73 g .
What is the molecular (true)
formula for the compound?
100 g of compound contains 80 g of
C and 0 g of H.
9
15 mass with CH is 1ormula empirical the 3
6.67
19.8
ratio. number hole smallest w the Determine
H mol 8 . 19
H g 1.01
H mol 1
H g 20.0 atoms H mol ?
C mol 67 . 6
C g 12.0
C mol 1
C g 80.0 atoms C mol ?
3
=
= -
= -
30
)
6 2
2
3
H C CH
doubled. 1ormula empirical the
is 1ormula molecular the Thus
2
0 . 15
0 . 30
mass empirical
mass actual
mol
g
0 . 30
mol 0.0244
g 0.732
n
moles. o1 number by the divided mass
the is mass molar the #emember,
=
= =
=
31
Example 1-10: 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
ST! 101 mL of the gas has a mass of
0.6 gram. What is its molecular
formula?
4:/49 4:/49
3
) )
)
mol 00451 . 0
273
mol
atm L
0.0821
L 0.101 atm 00 . 1
#T
PV
n
29 mass with H C 5 . 2
0.120
0.297
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 ?
5 2
=
'
+
'
=
=
= -
= -
33
)
10 4
2
5 2
H C H C 2
29
58.1
g/mol 1 . 58
mol 0.00451
g 262 . 0
mol
g ?
= =
= =
34
alton's Law of Partial Pressures
Daltons law states that the
pressure exerted by a mixture of
gases is the sum of the partial
pressures of the individual gases.
!
total
= !
A
+ !
B
+ !
C
+ .....
35
Example 1-11: If 1.00 x 10
mL of
hydrogen, measured at 5.0
o
C and 3.00
atm pressure, and 1.00 x 10
mL of
oxygen, measured at 5.0
o
C and .00
atm pressure, were forced into one of the
containers at 5.0
o
C, what would be the
pressure of the mixture of gases?
P P P
3.00 atm 2.00 atm
5.00 atm
Total H O
2 2
= +
=
36
Vapor !ressure is the pressure
exerted by a substances vapor over
the substances liquid at
equilibrium.
37
Example 1-1: A sample of hydrogen
was collected by displacement of water at
5.0
o
C. The atmospheric pressure was
748 torr. What pressure would the dry
hydrogen exert in the same container?
)
P P P P P P
P torr 724 torr
P 1rom table
Total H H O H Total H O
H
H O
2 2 2 2
2
2
= + =
= 748 24
38
Example 1-13: A sample of oxygen
was collected by displacement of
water. The oxygen occupied 74 mL
at 7.0
o
C. The barometric pressure
was 753 torr. What volume would the
dry oxygen occupy at ST!?
4:/49 4:/49
39
)
V 742 mL V ?
T T
P 726 torr P torr
V mL
273
300
726 torr
torr
645 mL STP
1 2
1 2
1 2
2
= =
= =
= =
= - - =
300 273
753 27 760
742
760
40
Mass-Volume Relationships
in Reactions nvolving Gases
mol KClO
3
yields mol KCl and 3 mol O
(1.6g) yields (74.6g) and 3 (3.0g)

Those 3 moles of O
can also be thought of as:

3(.4L)
or 67.
L at ST!
g) (
2 (s)
& MnO
(s)
3
O 3 Cl 2 ClO 2
2
P P P F P

WIn this section we are looking at
reaction stoichiometry, like in Chapter 3,
just including gases in the calculations.
41
Mass-Volume Relationships in
Reactions nvolving Gases
Example 1-14: What volume of oxygen
measured at ST!, can be produced by
the thermal decomposition of 10.0 g of
KClO
3
?
4:/49 4:/49
4
Mass-Volume Relationships in
Reactions nvolving Gases
2 STP 2 STP
2
2 STP
3
2
3
3
3 2 STP
O L 9 . 32 O L ?
O mol 1
O L 4 . 22
ClO mol 2
O mol 3

ClO g 122.6
ClO mol 1
ClO g 120.0 O L ?
=
- - - =
43
The Kinetic-Molecular Theory
The basic assumptions of kinetic-
molecular theory are:
!ostulate 1
Gases consist of discrete molecules that are
relatively far apart.
Gases have few intermolecular attractions.
The volume of individual molecules is very
small compared to the gass volume.
!roof - Gases are easily compressible.
44
!ostulate
Gas molecules are in constant, random,
straight line motion with varying
velocities.
!roof - Brownian motion displays
molecular motion.
45
!ostulate 3
Gas molecules have elastic collisions
with themselves and the container.
Total energy is conserved during a
collision.
!roof - A sealed, confined gas
exhibits no pressure drop over time.
46
!ostulate 4
The kinetic energy of the molecules is
proportional to the absolute temperature.
The average kinetic energies of
molecules of different gases are equal at
a given temperature.
!roof - Brownian motion increases as
temperature increases.
47
W The kinetic energy of the molecules is
The kinetic energy of the molecules is
W Displayed in a Maxwellian distribution.
48
The gas laws that we have looked at earlier in this
chapter are proofs that kinetic-molecular theory is the
basis of gaseous behavior.
Boyles Law
! 1/V
As the V increases the molecular collisions with
container walls decrease and the ! decreases.
Daltons Law
!
total
= !
A
+ !
B
+ !
C
+ .....
Because gases have few intermolecular attractions,
their pressures are independent of other gases in the
container.
Charles Law
V T
An increase in temperature raises the molecular
velocities, thus the V increases to keep the !
constant.
49
u
#T
M
rms
m
=
3
The root-mean square velocity of gases is
a very close approximation to the average
gas velocity.
Calculating the root-mean square velocity
is simple:
To calculate this correctly:
The value of R = 8.314 kg m
/s
K mol
And M must be in kg/mol.
50
Example 1-17: What is the root mean
square velocity of N
molecules at room T,
5.0
o
C?
)
u
3 8.314
kg m
sec mol

kg / mol
m / s 1159 mi / hr
rms
2
2
=
'
+
'
=
298
0 028
515
.
51
Example 1-18: What is the root
mean square velocity of He atoms
at room T, 5.0
o
C?
4:/49 4:/49
5
)
u
3 8.314
kg m
sec mol

kg / mol
m / s 3067 mi / hr
rms
2
2
=
'
+
'
=
298
0 004
1363
.
Can you think of a physical situation that
proves He molecules have a velocity that
is so much greater than N
molecules?
What happens to your voice when you
breathe He?
53
iffusion and Effusion of Gases
Diffusion is the intermingling of
gases.
Effusion is the escape of gases
through tiny holes.
54
The rate of effusion is inversely
proportional to the square roots of the
molecular weights or densities.
1
2
2
1
1
2
2
1
D
D
#
#
or

M
M
#
#
=
=
55
Example 1-15: Calculate the ratio of the
rate of effusion of He to that of sulfur
dioxide, SO
, at the same temperature and

pressure.
#
#
M
M
g / mol
4.0 g / mol
# #
He
SO
SO
He
He SO
2
2
2
=
=
= = =
641
16 4 4
.
56
Example 1-16: A sample of hydrogen, H
, was
found to effuse through a pinhole 5. 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?
4:/49 4:/49
g/mol 54 g/mol) 0 . 2 ( 27 M
g/mol 0 . 2
M
27
g/mol 0 . 2
M
2 . 5
M
M
#
#
unk
unk
unk
H
unk
unk
H
2
2
=
=
=
=
57
Real Gases:
eviations from deality
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.
. The molecular interactions also become
important.
58
Real Gases:
van der Waals equation accounts for the
behavior of real gases at low
temperatures and high pressures.
)
P
n a
V
V nb n#T
2
2
'
+
'
=
W The van der Waals constants a and b take into
account two things:
1. a accounts for intermolecular attraction
. b accounts for volume of gas molecules
W At large volumes a and b are relatively small
and van der Waals equation reduces to ideal
gas law at high temperatures and low
pressures.
59
Real Gases:
What are the intermolecular forces
in gases that cause them to deviate
from ideality?
1. For nonpolar gases the attractive
forces are London Forces
. For polar gases the attractive forces
are dipole-dipole attractions or
hydrogen bonds.
60
Real Gases:
Example 1-19: Calculate the pressure
exerted by 84.0 g of ammonia, NH
3
, in a
5.00 L container at 00.
o
C using the ideal
gas law.
4:/49 4:/49
) )
atm 4 . 38 P
L 5.00
473
mol
atm L
0821 . 0 mol 94 . 4
V
n#T
P
mol 94 . 4
g 17.0
mol 1
NH g 84.0 n
3
=
'
+
'
=
= -
61
Real Gases:
Example 1-0: Solve Example 1-
19 using the van der Waals
equation.
)
2
2
2
2
2
2
V
a n
nb - V
n#T
P
n#T nb - V
V
a n
P
mol
L
0.0371 b
mol
atm L
4.17 a mol 4.94 n
'
+
'
6
Real Gases:
) ) )
) )
)
ideal 1rom di11erence 7.6 a is which atm 7 . 35 P
) atm 1 . 4 atm 8 . 39 ( atm 07 . 4
L 817 . 4
atm L 8 . 191
P
L 00 . 5
17 . 4 mol 94 . 4
) 0371 . 0 )( mol 94 . 4 ( L 00 . 5
473 0821 . 0 mol 94 . 4
P
2
mol
atm L
2
mol
L
mol
atm L
2
2
=
= =
=
63
Synthesis Question
The lethal dose for hydrogen sulfide
is 6.0 ppm. In other words, if in 1
million molecules of air there are six
hydrogen sulfide molecules then
that air would be deadly to breathe.
How many hydrogen sulfide
molecules would be required to
reach the lethal dose in a room that
is 77 feet long, 6 feet wide and 50.
feet tall at 1.0 atm and 5.0
o
C?
64
Synthesis Question
L 10 6.76
cm 1000
L 1
cm 10 6.76
cm 10 6.76 cm 1524 cm 1890 cm 2347 V
cm 1524
in
cm 54 . 2
1t
in 12
1t 0 5
cm 1890
in
cm 54 . 2
1t
in 12
1t 2 6
cm 2347
in
cm 54 . 2
1t
in 12
1t 77
6
3
3 9
3 9
- =
'
+
'
-
- = - - =
=
'
+
'
'
+
'
'
+
'
'
+
'
'
+
'
'
+
'
65
Synthesis Question
) )
) )
S H o1 molecules 10 96 . 9
air o1 molecules 10
S H o1 molecule 6.0
air o1 molecules 10 66 . 1 dose Lethal
air o1 molecules 10 66 . 1
mol
molecules 10 6.022
mol 276,000
air o1 mol 276,000
298 0.0821
L 10 6.76 atm 1
#T
PV
n
298 25 273 T
L 10 6.76
cm 1000
L 1
cm 10 6.76
2
23
6
2 29
29
23
mol
atm L
6
6
3
3 9
- =
'
+
'
- =
- =
'
+
'
-
=
-
= =
= + =
- =
'
+
'
-
66
Group Question
Tires on a car are typically filled to a
pressure of 35 psi at 3.00 x 10 K.
A tire is 16 inches in radius and 8.0
inches in thickness. The wheel that
the tire is mounted on is 6.0 inches
in radius. What is the mass of the
air in the tire?

CH 12 Gases and The Kinetic-Molecular Theory

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1

Comparison of Solids, Liquids,

O 0.917 0.998 0.000588

Gas pressure as most people think of it.

torr. What volume would it

torr. What volume

mL under a pressure of 1.0 x

Summary of Gas Laws:

(1.6g) yields (74.6g) and 3 (3.0g)

can also be thought of as:

, at the same temperature and

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