Chapter 5

Gases

This chapter examines the properties of gases. Upon completion of Chapter 5, your
students should be able to:

1. List at least ten common substances that exist as gases at 1 atmosphere (atm) pressure
and 25oC.
2. Explain the difference between the terms gas and vapor.
3. List four physical characteristics of all gases.
4. Define the terms velocity, acceleration, force, newton, energy, joule, kinetic energy,
pressure and pascal.
5. Describe the construction of and its functions.
6. Convert between torr, mmHg, atmospheres, and pascals.
7. State the difference between open-tube manometers and closed-tube manometers and
explain how each is used.
8. Write, explain, and apply each of the following:
9. Boyle’s law (P ∝ 1/ V and P1V1 = P2V2).
10. Charles’s law (P ∝ T and V1/ T1 = V2/ T2).
11. Avogadro’s law (V ∝ n).
12. Ideal gas law (PV = nRT).
13. Explain the difference between the Kelvin temperature scale and the Celsius scale.
14. Describe the gas constant (R).
15. Define standard temperature and pressure (STP) and demonstrate that at STP one
mole of gas occupies 22.4 liters.
16. Perform calculations involving density, the Ideal gas equation and molar mass.
17. Using the Ideal gas equation, determine the moles of a gas.
18. State Dalton’s law of partial pressures and utilize it in problems involving mixtures of
gases including the collection of gases over water.
19. Define mole fraction and verify that Pa = XaPtotal.
20. Explain the four assumptions upon which the kinetic molecular theory of gases is
based.
21. State how the kinetic molecular theory of gases qualitatively explains the following:
22. The compressibility of gases.
23. Boyle’s law.
24. Charles’s law.
25. Avogadro’s law.
26. Dalton’s law of partial pressure.
27. Perform calculations using root-mean-square speeds.
28. Describe the process of gaseous diffusion.
29. Explain how a real gas, behaving non-ideally, differs from an ideal gas as described
by the four assumptions in the kinetic molecular theory of gases.
30. Describe conditions under which a real gas will approximate an ideal gas.
31. Apply van der Waal’s equation to real gases.

Section 5.1 Substances that Exist as Gases

Gases are all around us in the air we breathe. Our students know that gases fill the
container in which they are placed, taking on the container’s shape. Most students have
experienced that air-filled water toys float, helping them understand that air is less dense
than water. It is likely that students have not grasped the fact that there is no such thing as
an insoluble solute gas in a gaseous solution. That is not to say, however, that mixtures of
gases never separate. For example, carbon dioxide gas has a density of 1.977 g/L at 0oC.
This is compared to the density of dry air of 1.293 g/L. This fact has grave significance in
that carbon dioxide will accumulate in low-confined spaces. This is one of the reasons
that strict laws exist in the procedures for employees entering confined spaces in the
workplace.
Refer students to Table 5.1 for a list of the common gaseous substances.

Section 5.2 Pressure of a Gas

Pressure is defined as force per area yet we often refer to a pressure of one atmosphere of
gas as 760 mmHg. This can be very confusing to students since certainly force divided by
area does not have the units of distance as mm of Hg does. It is important that your
students understand the way a mercury barometer functions and that the column height of
760 mm is just the height of a column of mercury that is supported by a pressure that we
define as one atmosphere.
Recalling that some students best understand if the concepts are placed in short
logical steps, Example 5.2 could be solved in the following way:
⎛ 1 atm ⎞
(
732mmHg ⎜ )
⎜ 760mmHg ⎟
⎟ = 0.963 atm
⎝ ⎠

⎛ 1.01325 × 105 Pa ⎞
( 0.963 atm ) ⎜
⎝ 1 atm
⎟ = 9.76 × 10 Pa
⎠
4

⎛ 1 kPa ⎞
( 9.76 × 10 4
Pa ) ⎜ ⎟ = 97.6 kPa
⎝ 1000 Pa ⎠
Section 5.3 The Gas Laws

In general, the gas laws are easily understood by students because of their everyday
experiences. For example, Boyle’s law states that the volume of a gas is inversely
proportional to pressure. A balloon will shrink when squeezed (increasing pressure).
Showing Table 5.2 will enable the student to see the inverse relationship between pressure
and volume. Charles’s law states that volume and temperature are directly proportional.
We know objects shrink when they are cooled. To demonstrate this principle, place an air-
filled balloon in a container of liquid nitrogen. The balloon will contract in size until it
looks like it contains no air at all. This is an excellent manifestation of Charles’s law. An
enlightening exercise is to ask students to predict what will happen to the balloon when it
returns to room temperature. Some of them may have the misconception that the balloon
will become over-pressurized and pop.
Avogadro’s law states that at constant pressure and temperature, the volume of a gas
is directly proportional to the number of moles of the gas present. Students are willing to
accept this because “more is bigger.”
Figure 5.6 provides an excellent visual depiction of different gas laws.

Section 5.4 The Ideal Gas Equation

The ideal gas equation is the direct result of combining Boyle’s law, Charles’s law and
Avogadro’s law and replacing the proportionality sign with an equals sign and
incorporation the gas constant. The gas constant most commonly used by chemists is R =
0.0821 L · atm/mol · K. Later in Section 5.7 your author will show an example in which
he uses R = 8.314 J/mol · K. Another value for R which may be useful is R = 1.987
cal/mol · K. Point out to your students that with these three values of R, we now have unit
analysis factors for the following conversions:

0.082 L · atm = 8.314 J = 1.987 calories

or the more familiar conversion of

8.314 J
= 4.184 J/cal
1.987 cal

Sometimes students feel there is something special about 22.4 L being the volume of
one mole of gas at STP. Point out to them, however, that using P = 1 atm, T = 273 K,
n = 1.00 mole, and R = 0.0821 L · atm/mol · K, and solving the ideal gas equation for V
results in 22.4 L.
To solve the problem described in Example 5.3, your author rearranged Equation 5.8
to yield:
nRT
P =
V

It is interesting to point out that all the gas laws discussed in Section 5.3 can be derived
from Equation (5.8). Equation (5.9) and (5.10) are the result of Equation (5.8).
Students may attempt to memorize these equations and in doing so will get the
ratios of pressures and temperatures incorrect. Therefore, it might be valuable to describe
the following logic to your students. In this problem, the initial volume will be multiplied
by two fractions. These fractions could be either greater than or less than one depending
upon what the starting and final conditions are. For example, if the initial pressure is 6.1
atm and the final pressure is 1.0 atm, we know that there has been a decrease in pressure
so that the volume should become larger due to this term. Or that is to say, the fraction is
6.4 atm/1.0 atm. This happens to be P1/P2. The second fraction is for the change in
temperature. The temperature of the system goes from 281 K to 298 K. As temperature
increases, the volume also increases so the fraction must be greater than 1 or is 298 K/281
K which corresponds to T2/T1 . In mathematical form, we have:

P1 T 2
V 2 = V 1 × (6.4/1.0) × (298/281) = V 1 × ×
P2 T 1

Another way to solve this problem is to realize that initially we know pressure, volume,
and temperature; therefore, we can solve the ideal gas equation for n, the number of moles.

PV (6.4 atm ) (0.0021 L )

n = = = 5.8 × 10 −4 mole
RT ⎛ 0.0821 L · atm ⎞
⎜ ⎟ (281 K )
⎝ mol · K ⎠

Since the moles are held constant in this example, and we now know the final pressure,
temperature, and moles, it is possible to use the ideal gas equation one more time but solve
for V instead of n as we did above.

nRT (5.8 × 10 −4 mol ) (0.0821 L · atm / mol · K ) (298 K )

V = =
P (1 atm )
V = 1.4 × 10 −2 L = 14 mL
While this method is longer and more time consuming than the way the author solved the
problem, it may be more logical for some students.
An interesting side light to this problem is to calculate how the diameter of the bubble
in Example 5.7 changes as it rises from the bottom of the lake. The initial volume of the
bubble is 2.1 mL. The equation for the volume of a sphere is

4 3
V = πr
3
1/3
⎛ 3V ⎞
r = ⎜ ⎟
⎝ 4π ⎠
1/3
⎡ ⎛ 1 L ⎞ ⎛ 1 m3 ⎞⎤
⎢ (3) (2.1 mL ) ⎜ ⎟ ⎜ ⎟⎥
⎢ ⎝ 1000 mL ⎠ ⎝ 1000 L ⎠⎥
thus r =
⎢ 4π ⎥
⎢ ⎥
⎢⎣ ⎥⎦
r = 7.9 × 10 −3 m or 7.9 mm
d = 15.8 mm

The bubble grows to a volume of 14 mL as it reaches the top; therefore, following the
same procedure one finds that:

1/ 3
⎡ ⎛ 1 L ⎞ ⎛ 1 m3 ⎞ ⎤
⎢ (3) (14 mL ) ⎜ ⎟ ⎜ ⎟⎥
⎢ ⎝ 1000 mL ⎠ ⎜ 1000 L ⎟ ⎥
r=⎢ ⎝ ⎠
⎥
⎢ 4π ⎥
⎢ ⎥
⎣ ⎦
r = 1.5 × 10−2 m or 15 mm
d = 30. mm
It is interesting to note that even though the volume of the bubble has increased 6.7 times,
its diameter has not quite doubled.
An interesting demonstration is to show your students how you can boil water with
ice. The process is to use a flat-bottomed flask that is about three-quarters full of water.
Place the flask on a hot plate and heat to a vigorous boil. Remove the flask from the heat
and secure the stopper firmly. Carefully invert the flask onto a ring attached to a ring
stand, taking precautions to be sure the stopper does not fall out. Place small chunks of ice
on the inverted flask. As the flask cools, the water will start to boil again. The
explanation is that cooling the air above the water in the flask reduces the pressure to a
point where the water starts to boil. The boiling point of a liquid is defined as the
temperature at which the saturated vapor pressure of the liquid equals the pressure of the
atmosphere above it. Because the ice has cooled the air, the pressure has dropped. This
lower pressure allows the water to boil at a temperature below its normal boiling point.
This is similar to the effect that is experience when trying to cook food at high altitudes.
At high altitudes, water will boil at a lower temperature because there is less atmospheric
pressure (less air pushing down). If the water boils at a lower temperature, it will be
“colder” than water boiling at sea level, thus it will take longer to cook certain foods at
higher elevations.
Density and molar mass calculations use Equation (5.11), which is yet another
manipulation of Equation (5.8). Example 5.8 and 5.9 can be solved using Equation (5.8) or
(5.11).

Section 5.5 Gas Stoichiometry

In Example 5.11, your author suggests that according to Avogadro’s law, the reacting
volumes of gases are related to their coefficients in the balanced equation. One way to
assist students in understanding this is to point out that the conditions are constant for both
gases. In the example the conditions are STP. However, as we will see, it doesn’t matter
what the conditions are as long as they are the same for both gases. By rearranging the
ideal gas law, we have:
( n C2 H2 ) RT
V C2 H 2 =
P

( n O ) RT
2
V O2 =
P
V O2 n O2 5
therefore = =
V C2 H 2 n C2 H 2 2
where the 5/2 are the coefficients of O2 and C2H2 from the balanced equation. It follows
then that
(
VO2 = VC2 H 2 ) (5 / 2) = ( 7.64 L )(5 / 2) = 6.60 L
In Example 5.13, your author uses the drop in pressure as the pressure in the ideal
gas equation to determine the number of moles of carbon dioxide consumed. This is
explained in the following way:
P initial V
n initial =
RT
 P final V
n final =
RT

P final V − P initial V
n CO 2 = n final − n initial =
RT RT

( P final
− P initial ) V ( Pr essure drop) V
n CO 2 = =
RT RT
It should be realized that nCO2 is the number of moles of CO2 consumed.

Section 5.6 Dalton’s Law of Partial Pressures

Dalton’s law of partial pressures states that the total pressure in a container is the sum of
the pressures of each gas that makes up the mixture of gases in the container. Or stated in
equation fashion
P T = P1 + P 2 + P 3 + . . .

Dalton’s law of partial pressure will hold for ideal gases that do not react with each other.
In this section your author introduces another concentration term, mole fraction.
Mole fraction is defined as the ratio of the moles of one component to the sum of the
moles of all components in the mixture. Even though this concentration unit is introduced
in this chapter on gases, it is also used for solid and liquid mixtures as well.
Your author shows how Equation (5.14) is developed. Equation (5.14) states

Pi = X i PT

or that the pressure of a component gas is equal to the mole fraction of that gaseous
component in the mixture times the total pressure of all the gases in the container.
Your author uses Equation (5.14) to solve Example 5.14.

Example 5.14 can be more difficult for students to understand. For students who have
difficulty with the logic used in Example 5.14, another more lengthy solution is as
follows:

The total number of moles of gases is

4.46 + 0.74 + 2.15 = 7.35 moles
 The volume of the container is
nRT 7.35 moles RT
V container = = = 3.675 RT
P 2 atm
thus the pressure of neon is
nNe RT 4.46 RT
PNe = = = 1.21 atm of Ne
V container 3.675 RT

The pressure of argon is

nAr RT 0.74 RT
PAr = = = 0.20 atm of Ar
Vcontainer 3.675 RT

The pressure of xenon is

nXe RT 2.15 RT
PXe = = = 0.585 atm of Xe
Vcontainer 3.675 RT

In Example 5.15, your author uses the equation m = PVM /RT to find the mass of the O2
collected. For some students, it may be more logical to first find the pressure of O2 as
your author did
P O 2 = 0.974 atm
PV
and then use n = to find the moles of oxygen gas formed
RT

⎛ 1 L ⎞
(0.974 atm ) (128 mL ) ⎜ ⎟
= ⎝ 1000 mL ⎠
n O2
⎛ 0.0821 L ⋅ atm ⎞
⎜ ⎟ (24 + 273 K )
⎝ mol ⋅ K ⎠
n O 2 = 5.11 × 10 mole formed
-3

Now we can find the mass of O2 formed in one more step

⎛ 32 g O 2 ⎞
mass O 2 = (5.11 × 10 mol O 2 ) ⎜⎜
−3
⎟⎟
⎝ 1 mol O 2 ⎠

mass O 2 = 0.164 grams of O 2 formed.

Section 5.7 The Kinetic Molecular Theory of Gases

The four assumptions that are fundamental to the kinetic theory of gases are:

a) All gases are composed of molecules (atoms for monatomic gases) which are
very, very small in comparison to the container that they are in. It is assumed
that the sum of the volume of all molecules of gas is negligible with respect to
the volume of the container
b) All gas molecules are in random motion and upon collision with other
molecules, these collisions are perfectly elastic. That is to say that when two
gas molecules collide, they may transfer energy from one to another but no
energy is lost when these collisions occur.
c) Gas molecules have no attractive or repulsive forces on each other. Therefore
these gas molecules can never be condensed to a liquid.
d) The average kinetic energy of a gas molecule is proportional to the
temperature in Kelvins. Since
KE = 1/2 mu 2
the more massive the molecule is, the slower it will move about the container.
Yet a less massive molecule will have the same kinetic energy as a more
massive molecule assuming both molecules are at the same temperature.
These four assumptions can be used to explain several properties of gases. For
example, since the volume of the gas molecules themselves is very small as compared to
the volume of the container, then most of the “space” in a container is a vacuum (nothing
at all). Therefore if the pressure is increased on the sides of the container, the gas will
easily be compressed. This is in contrast to solids and liquids where the molecules
“touch” each other and are much less compressible.
Boyle’s law states that the volume of a gas is inversely proportional to pressure. The
pressure on a container’s walls is due to the collision of gas molecules with those walls. If
the volume is decreased, then the number of collisions of molecules with the walls must
increase or the pressure goes up.
Charles’s law states that an increase in temperature results in an increase in the
volume of the gas. This is explained by the kinetic theory of gases in that as the
temperature of a gas increases, the kinetic energy of the gas molecules also increases. As
the kinetic energy increases, the average velocity must increase since the mass remains
constant. As the velocity increases, the molecules will impact the walls with a greater
momentum, thus exerting a greater force per area or increasing the pressure. As the
pressure increases, the container wall will move until the internal pressure equals the
external pressure or the volume will increase.
 Avogadro’s law suggests that an increase in the number of moles of gas in a
container results in an increase in volume. The logic for this is that even though the
molecules have the same average kinetic energy and thus impact the same momentum with
the walls of the container, the number of collisions increases. Thus the total force per unit
area is increased. Just as stated above, an increase in pressure will increase the volume
until the pressure on the inside equals the pressure on the outside of the container.
Dalton’s law of partial pressure states that the total pressure of a gas is equal to the
sum of the partial pressures of each of the gases in the container. Since it is assumed that
all molecule/molecule collisions are perfectly elastic (no attraction or repulsion), then each
component gas is independent of any other gas in the container. Therefore the total force
per unit area (pressure) on the container walls is directly proportional to the number of
molecules that collide with the walls or the sum of all the individual gas pressures.
In Example 5.16, your author uses 8.314 J/K · mol for R. See our previous
discussion about values of the gas constant. Certainly in this case, the use of 0.0821 L ·
atm/mol · K would not be appropriate.

Section 5.8 Deviation from Ideal Behavior

An interesting question to ask your students is under what conditions a real gas behaves
like ideal gas. The logic to the solution of this question is to realize that as a real gas
cools, it forms a liquid; therefore, since a liquid is not at all like an ideal gas, the real gas
would behave like an ideal gas at high temperature. It is also possible to apply pressure to
a real gas to force it to form a liquid. A familiar example is the liquid in a butane lighter.
(Note that the boiling point of butane is –0.5oC.) Therefore a real gas at lower pressure is
more ideal than one at high pressure.
Since real gases may deviate from ideal gases, van der Waals proposed his equation:
⎛ an ⎞
2

⎜ P + 2 ⎟
(V − nb) = nRT
⎝ V ⎠

The first term takes into account that molecules of all real gases have attractive forces for
each other. (All real gases can be liquefied.) Thus a term (an2/ V2) must be added to the
real pressure (measured pressure) to get the ideal gas pressure. The second term accounts
for the fact that all real gas molecules have some volume thus a term must be subtracted
(nb) from the real volume to get the ideal volume.
A thought-provoking question to pose to your students is to ask whether it is hot or
cold in outer space given that the molecules, ions, etc., in outer space are moving at very
high speeds. From the kinetic theory of gases, we found that temperature is directly
proportional to a molecule’s speed. From this one would assume that it is very hot in
outer space. On the other hand, we measure temperature with a thermometer wherein the
molecules collide with the glass, thereby depositing some of their kinetic energy. This
energy is then transferred to the mercury which causes it to expand. Therefore, if only a
few molecules collide with the thermometer as would be expected in outer space, very
little energy will be transmitted to the mercury and the thermometer will report that it is
very cold. So, is it hot or is it cold in outer space?