1

Chapter 10
Gases
1. Characteristics of Gases
2. Gas Pressure and Its Measurement
3. The Gas Laws
4. Ideal Gas Law
5. Applications
6. Gas Mixtures
7. Kinetic-Molecular Theory
8. Effusion and Diffusion
9. Non-Ideal Gases
2
Some Examples of Gases
Global Biogeochemical Cycles of Gaseous Species
Elements
monoatomic (Noble gases): He, Ne, Ar,
Kr, Xe
molecular (homonuclear diatomics): H
2
,
O
2
, N
2
, F
2
, Cl
2

Other gases (molecular): CH
4
, NO
2
,
NO, N
2
O, CO
2
, NH
3
, HCl
Vapors (boiling points above room
temperature): H
2
O, HNO
3

3
Gases occupy the full volume of their
containers.
Gas volume is dependent on pressure and
temperature.
Gases have low densities and viscosities.
Gases are highly miscible and always form
homogeneous mixtures with other gases.
1. Characteristics of Gases
2
4
Units:
area
on accelerati mass

area
force
pressure
!
= =
Pa 1 pascal 1
s m
kg

m
) s / m ( kg

2 2
2
= =
!
=
!
=
1 atm = 760 mm Hg = 760 torr
= 1.013 ! 10
5
Pa = 101.3 kPa = 1.013 bar
Example: If a weatherman says that atmospheric
pressure is 29.12 inches of mercury, what is it in torr?
SI derived unit
Solution:
torr 6 . 739
mm 1
torr 1
cm 1
mm 10
in 1
cm 2.54
in 12 . 29 = !
"
#
$
%
&
!
"
#
$
%
&
!
"
#
$
%
&
2. Gas Pressure and Its Measurement
5
Common Units of Pressure
Atmospheric Pressure Unit Scientific Field
chemistry atmosphere (atm) 1 atm*
pascal (Pa);
kilopascal (kPa)
1.01325x10
5
Pa;
101.325 kPa
SI unit; physics, chemistry
millimeters of
mercury (Hg)
760 mm Hg* chemistry, medicine, biology
torr 760 torr* chemistry
pounds per square
inch (psi or lb/in
2
)
14.7 lb/in
2
engineering
bar 1.01325 bar meteorology, chemistry,
physics
*This is an exact quantity; in calculations, we use as many significant figures as necessary.
6
A mercury barometer.
F(Hg) = F(atm)

T = 0C,
Sea level

Invented by E. Torricelli
(17
th
century).
3
7
Manometers
The pressure of a gas not in contact with the atmosphere
is measured with a manometer.
A manometer consists of a bulb of gas attached to a
U-tube containing Hg.
There are two types of manometers:
1. closed-end
U-tube
8
2. open-end
P
gas
= P
atm

P
gas
< P
atm

P
gas
= P
atm
- P
"h

P
gas
> P
atm

P
gas
= P
atm
+ P
"h

9
Boyles Law
2 2 1 1
V P V P
constant PV
P
1
constant V
P
1
V
=
=
! =
"
n, T constant
Put m
ore pressure
on som
ething and it
gets sm
aller.
3. The Gas Laws
At constant temperature, the volume of a fixed quantity
of gas is inversely proportional to its pressure.
Robert Boyle (1662)
4
10
Boyle used an open end manometer to carry
out experiments to establish his law.
P
gas
= P
atm
P
gas
V
gas
= P
atm
V
gas
= const.
P
gas
= P
atm
+ P
Hg


= 2P
atm
2P
atm
(V
gas
/2) = const.
P
atm
V
gas
= const.
760 mm
11
Boyles Law (cont.)

Plots of V vs. P and V vs. 1/P
Hyperbola
PV = constant
Straight Line (linearized)
V = constant / P
(y = mx + b)
V V
1/P P
12
Applying the Volume-Pressure Relationship
Example: The air trapped in a U-tube occupies 39.8 cm
3
at 1.87 atm. By
adding mercury to the tube, the pressure on the trapped air is
increased to 2.84 atm. Assuming constant temperature, what is the
new volume of air (in L)?
SOLUTION:
unit
conversion
gas law
calculation
P
1
= 1.87atm P
2
= 2.84 atm
V
1
= 39.8 cm
3
V
2
= unknown
n and T are constant
39.8 cm
3

1 mL
1 cm
3

L
10
3
mL
= 0.0398 L
PV = constant P
1
V
1
= P
2
V
2

P
1
V
1
P
2
V
2
= = 0.0398 L
1.87atm
2.84 atm
= 0.0262 L
5
13
Charles Law
At constant pressure, the volume of a fixed quantity of
gas is directly proportional to its absolute temperature.
Jacques Charles (1787)
2
2
1
1
T
V

T
V
constant
T
V
T constant V
T V
=
=
! =
"
n, P constant
H
eat som
ething
and it expands.
where T = absolute
temperature = K, Kelvin
T (K) = t(
0
C) + 273.15
"(
0
C) = "(K)
14
Charles Law (cont.)
V
o
l
u
m
e

(
c
m
3
)

Temperature (C)
273.15C = 0 K
Extrapolate ! intercept on abscissa ! absolute zero
15
Avogadros Law
At constant pressure and temperature, the volume of a
fixed quantity of gas is directly proportional to the
number of moles of gas. Amadeo Avogadro (1811)
2
2
1
1
n
V

n
V
constant
n
V
n constant V
n V
=
=
! =
"
P, T constant
M
ore gas,
bigger volum
e.
6
16
Example: How will the volume of a gas change if the
quantity of gas, absolute temperature, and pressure,
all double?
! 2
Solution:
Avogadro
! #
Boyle
! 2
Charles
2
2
1
2 2 = ! ! thus, volume doubles
17
4. The Ideal Gas Law
Combining the three empirical laws yields:
P
nT
V !
Introducing a proportionality constant, R, gives:
!
"
#
$
%
&
' =
P
nT
R V
PV = n RT
Rearrange to obtain the ideal gas equation:
K mol
J
314 . 8
K mol
atm L
0.08206 the R
!
=
!
!
= = constant gas
Key relationship!!!
= 62.36
L!torr
mol!K
= 1.987
cal
mol!K
18
The ideal gas equation is not exact, but for most
gases it is quite accurate near STP.
standard temperature and pressure;
STP 0C and 1 atm
An ideal gas is one that obeys the ideal gas
equation.
At STP, 1 mol of an ideal gas occupies 22.41 L.
Most ideal gas equation problems fall into two
categories:
1) 3 of the 4 variables n, P, V & T are given.
2) One or more pairs (initial/final) of values of n, P, V
or T are given (and rest are constant).
7
19
Standard Molar Volume
20
IDEAL GAS LAW
nRT
P
PV = nRT or V =
Boyles Law
V =
constant
P
R =
PV
nT
=
1atm x 22.414L
1mol x 273.15K
=
0.0821atm L
mol K
V = V =
Charless Law
constant x T
Avogadros Law
constant x n
fixed n and T fixed n and P fixed P and T
R is the universal gas constant
3 significant figures
Relating the Ideal Gas Law and
the Gas Laws
PV = nRT
nRT nR/P RT/P
21
Example: For an ideal gas, calculate the pressure of
the gas if 0.215 mol occupies 338 mL at 32C.
Solution: 3 variables given
n = 0.215 mol
V = 338 mL = 0.338 L
T = 32 + 273.15 = 305.15 K
P = ?
( ) ( )
L 338 . 0
K 15 . 305
K mol
atm L
08206 . 0 mol 215 . 0
P
!
"
#
$
%
&
'
'
=
PV = nRT
V
nRT
P =
= 15.928 = 15.9 atm
5. Applications of the Ideal Gas Law
8
22
Exercise: A steel cylinder with a volume of 68.0 L contains O
2

at a pressure of 157.0 atm at 23C. What is the volume of
this gas at STP?
Exercise: A steel cylinder with a volume of 68.0 L
contains O
2
at a pressure of 15,900 kPa at 23C.
What is the volume of this gas at STP?
24
Gas Density (d) and Molar Mass (M)
mass molar
mass

m
n moles of number = = =
M
RT
m
PV
nRT PV
! =
=
M
RT
P

V
m M
= = d, density
P
dRT
= M
RT
P
d
M
= or
Rather than memorize, remember the derivation.
rearrange;
substitute;
9
25
Example:
Calculate the density of hydrogen bromide (HBr)
in grams per liter (g/L) at 733 mmHg and 46C.
P = 733 mmHg M = 80.91 g/mol
T = 46C
Convert to
proper units
733 mmHg = 0.964 atm
1 atm
760 mmHg
=
PM
RT
d =
(0.964 atm)(80.91 g/mol)
(0.0821 L$atm/mol$K)(319 K)
= 2.98 g/L
Solution:
46 + 273.15 = 319 K
26
Standard Molar Volume
The density of a gas is directly proportional to its molar mass.
27
Exercise: A compound with an empirical formula of CH
has a density of 2.67 g/L at 80C and 753 torr. What is
the molecular formula of the compound?
10
28
6. Gas Mixtures and Partial Pressures
partial pressure = the pressure that one component
of a mixture of gases would exert if it were the only
gas in the container
P
total
P
O
2
= nitrogen, N
2
= oxygen, O
2
total pressure = P
total
= P
N
2
+ P
O
2
P
N
2
= partial pressure of nitrogen
P
O
2
= partial pressure of oxygen
29
Daltons Law of Partial Pressures
The pressure exerted by a mixture of gases equals the
sum of the partial pressures of the gases in the mixture.
John Dalton (1803)
P
total
= P
1
+ P
2
+ P
3
+ %
* assuming the
gases do not react
Each gas obeys the ideal gas law (gas particles dont interact):
P
total
= + = =
n
1
RT
V
n
2
RT
V
(n
1
+ n
2
) RT
V
n
total
RT
V
Mole fraction of gas 1:
X
1
= = =
n
1

n
total
P
1
V / RT
P
total
V / RT
P
1

P
total
30
.00040
= 400 ppm
11
31
Pgas adds to vapor pressure of
water (PH2O) to give Ptotal-
As shown Ptotal < Patm
2
Patm
Ptotal is made equal to
Patm by adjusting height
of vessel until water level
equals that in beaker
3
Ptotal
Patm
PH2O
Pgas
=
Ptotal
4 P
atm
=P
total
=P
gas
+ PH2O
Therefore,
Pgas = Patm PH2O
where PH2O is temperature
dependent.
Ptotal
Water-insoluble
gaseous product
bubbles through
water into
collection vessel
1
Collecting a Water-Insoluble Gas and
Determining its Pressure.
2 KClO
3
(s) & 2 KCl (s) + 3 O
2
(g)
32
Oxygen, O
2
, is produced in the laboratory when KClO
3
is heated:
2 KClO
3
(s) 2 KCl(s) + 3 O
2
(g)
A sample of KClO
3
is completely decomposed and all of the O
2
is
collected over water, the total gas pressure (adjusted to barometric
pressure) is 738 torr and the volume is 523 mL. At the temperature of
the gas (23C), the vapor pressure of water is 21 torr. How many grams
of O
2
are collected?
Exercise:
33
P,V,T
of gas A
amount (mol)
of gas A
amount
(mol)
of gas B
P,V,T
of gas B
ideal
gas
law
ideal
gas
law
molar ratio from balanced
stoichiometric equation
e.g. A ! 2B
Combine reaction stoichiometry and ideal gas law to
calculate volume of gas produced/consumed
Example: What volume of N
2
is produced from the decomposition of 45.0 g of
sodium azide at 30
0
C and atmospheric pressure (the air bag reaction) ?
2NaN
3
(s) & 2Na(s) + 3N
2
(g)
45.0g NaN
3
!
1mol NaN
3
65.0g NaN
3
!
3mol N
2
2mol NaN
3
=1.04mol N
2
Moles of N
2
produced:
Volume of N
2
produced:
V =
nRT
P
=
1.04mol !0.0821
L atm
K mol
!303.15K
1.00 atm
=25.9L
Solution:
12
Exercise:
Ethanol burns in air: C
2
H
5
OH(!) + O
2
(g) & CO
2
(g) + H
2
O(!)
Balance the equation and determine the volume of air in liters
at 35.0C and 790. mmHg required to burn 227 g of ethanol.
Assume the air is 21.0 % O
2
by volume.
35
7. The Kinetic-Molecular Theory
The three common gas laws and the ideal gas law
are empirical, i.e., based on observations;
explain how gases behave;
apply to macroscopic (bulk) properties.
The Kinetic-Molecular Theory
was developed by Clausius, Boltzmann, Maxwell;
applies to microscopic (molecular) properties;
explains the behavior of gases in terms of the
behavior of gas particles (atoms or molecules);
a very successful (and useful) theory!
36
Kinetic-Molecular Theory: Postulates
1. Gases consist of huge numbers of particles (molecules)
in continuous, random motion.
2. Gas particles have negligible volumes compared to V
of their container.
3. Gas particles exert no attractive or repulsive forces on
each other intermolecular forces are negligible.
4. Gas particles collide with each other and the walls of
their container;
collisions are elastic (no energy loss), but there is
momentum transfer.
the average E
kin
of gas is constant at a given T.
(Note: Postulates #2 and #3 (and part of #4) are not exactly true.)
13
37
Provides an understanding of P and T on the
molecular level
P results from the number of collisions per unit time
on the walls of container.
Momentum transfer
The magnitude of P depends on how often and how
hard the molecules strike the container walls.
How Does the KMT Explain the Gas Laws?

38
A molecular description of Boyles Law.
At constant T, as V decreases, each particle strikes the
walls more frequently and P increases.
39
A molecular description of Charless Law.
As T increases at constant P, the collision frequency
increases due to greater kinetic energy and V
increases.
(Likewise, Avogadros law (V n) and Daltons law of partial
pressures ...)
14
40
Kinetic Energy Speed Temperature
The average kinetic energy of the particles is proportional to T:
(E
kin
)
avg
T
It can be shown that,
(E
kin
)
avg
= 3/2 RT
(3/2 R is a proportionality constant)
The kinetic energy can be related to particle speed, u,
(E
kin
)
avg
= 1/2 Mu
2
(M is molar mass)
Thus, Mu
2
= RT

solving,
1
2
3
2
M
T
u
3R
=
T increases u increases
M increases u decreases,
but (E
kin
)
avg
remains the same


(E
kin
)
avg
= 3.66 kJ mol
-1
@ 20
0
C

41
0 2x10
2
4x10
2
6x10
2
8x10
2
10x10
2
But not all particles have the same speed
There is actually a range of speeds; described by
a distribution (which depends on T)
F
r
a
c
t
i
o
n

o
f

m
o
l
e
c
u
l
e
s

w
i
t
h

s
p
e
e
d

u

u (m / s)
u
mp
u
avg
u
rms
Specify typical speed
rms = root mean square

u
rms
=
3RT
M
Note tail to higher
speeds
Note no stationary
particles
42
Differences between definitions of typical speeds
(1) mean or average speed
(2) most probable speed
(3) rms speed
Example: assume five speeds: 2, 4, 4, 6 and 8 m/s
-a discrete, as opposed to a continuous, distribution
m/s 4.8
5
24

5
8 6 4 4 2
u
avg
= =
+ + + +
=
m/s 4.0 u
mp
=
m/s 5.2
5
136

5
8 6 4 4 2
u
2 2 2 2 2
rms
= =
+ + + +
=
15
43
Dependence of distribution on temperature
(E
kin
)
avg
= 3.40 kJ mol
-1

(E
kin
)
avg
= 28.35 kJ mol
-1

(E
kin
)
avg
= 15.88 kJ mol
-1

44
O2 (32)
N2 (28)
H2O (18)
He (4)
H2 (2)
Molecular speed at a given T
R
e
l
a
t
i
v
e

n
u
m
b
e
r

o
f

m
o
l
e
c
u
l
e
s

w
i
t
h

a

g
i
v
e
n

s
p
e
e
d

root-mean-square speed
Consider gases at the same T but with different molar
masses. A lighter gas has a higher u than a heavier gas.
Dependence of distribution on particle mass
But, all gases have the same (E
kin
)
avg
= 3/2 RT

u
rms
=
3RT
M
gas u
rms
(m s
-1
)
O
2
482
N
2
515
H
2
O 643
He 1364
H
2
1928
45
8. Effusion and Diffusion
effusion; the
escape of
molecules through
an orifice
diffusion; the movement
of particles through
space
16
46
Grahams Law of Effusion
The effusion rate of a gas is inversely proportional to the
square root of its molar mass. (T. Graham)
the effusion rate; r u
rms
1
2
2
1
2
1
2
1

3RT/
3RT/

u
u

r
r
M
M
M
M
= = =
Explanation:
Particles can only escape, or effuse, by colliding with the orifice.
Particles with a higher u have more collisions with the walls, hence a
greater probability for effusing through the orifice.
r
235
UF
6 ( )
r
238
UF
6 ( )
=
352
349
!
"
#
$
%
&
1 2
=1.004
47
Diffusion of a gas particle through a space
filled with other particles.
At 1 atm and 25C, N
2
and O
2

have u
rms
~ 500 m/s
Each molecule collides roughly
five times every ns.
collision frequency = 5 x 10
9
s
The mean free path is ~100 nm
(500 m/s 510
9
s) or 10
3

molecular diameters.
mean free path = speed collision freq.
collision frequency = the average number of collisions per second
mean free path = the average distance a molecule travels between collisions
mean free path!
T
P
diffusion rate!
T
3
2
PM
1
2
48
Example: Under identical conditions, how does the
effusion rate of He atoms compare to that of N
2

molecules?
Solution:
Molar masses: He 4.00 g/mol
N
2
2(14.01) = 28.02 g/mol
1
2
2
1

r
r
M
M
=
r
He
r
N
2
=
28.02
4.00
= 7.005=2.65
He gas effuses faster by more than a factor of two.
17
49
9. Non-Ideal Gases:
Deviations from Ideal Behavior
Consider 1 mol of gas. For ideal gas,
PV
RT
=n=1
@ 300K
N
2
gas
Significant deviations at high pressure
Extent of deviation depends on gas
'ideal behavior < 10 atm
Deviations increase as temperature
decreases
Become significant near boiling point
50
Recall assumptions of kinetic-molecular theory
Assumption; gas particles have no volume.
Reality; gas particles do have a finite volume.
Correction;
V
ideal
=V!correction
Assumption; gas particles do not interact with each other.
Reality; gas particles do attract each other due to intermolecular
forces.
Correction;
P
ideal
=P+correction
51
The effect of intermolecular attractions on
measured gas pressure.
Consider these corrections on the molecular level
Attractive forces reduce the momentum of molecules
colliding with the walls of a container. Consequently, P
< P
ideal
and a correction term should be added to P in
the ideal gas equation.
18
52
The effect of molecular volume on measured gas volume.
Since real gas molecules do occupy some of the
container volume, V
ideal
< V and a correction term
should be subtracted from V in the ideal gas equation.
53
P+
n
2
a
V
2
!
"
#
#
#
#
#
$
%
&
&
&
&
&
V'nb
!
"
#
#
#
#
$
%
&
&
&
&
=nRT
Corrects for intermolecular
attraction
Corrects for molecular
volume
The Result: The van der Waals Equation
Two terms are introduced into the ideal gas
equation (PV = nRT) to account for non-ideal
(real gas) behavior.
Where a and b are constants that depend on the
particular gas.
54
Van der Waals Constants for Some Common Gases
0.034
0.211
1.35
2.32
4.19
0.244
1.39
1.36
6.49
3.59
2.25
4.17
5.46
He
Ne
Ar
Kr
Xe
H
2

N
2

O
2

Cl
2
CO
2

CH
4

NH
3

H
2
O
0.0237
0.0171
0.0322
0.0398
0.0511
0.0266
0.0391
0.0318
0.0562
0.0427
0.0428
0.0371
0.0305
Gas
a
atm*L
2
mol
2
b
L
mol
(P +
n
2
a
V
2
)(V ! nb) = nRT
Van der Waals
equation
larger
stickier