Gases

Chapter 5

1
Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display.
Elements that exist as gases at 250C and 1 atmosphere

2
3
 Physical Characteristics of Gases
• Gases assume the volume and shape of their containers.
• Gases are the most compressible state of matter.
• Gases will mix evenly and completely when confined to
the same container.
• Gases have much lower densities than liquids and solids.

NO2 gas 4
 Force
Pressure = Area

(force = mass x acceleration)

Units of Pressure

1 pascal (Pa) = 1 N/m2

1 atm = 760 mmHg = 760 torr
1 atm = 101,325 Pa

5
10 miles 0.2 atm

4 miles 0.5 atm

Sea level 1 atm

6
Example 5.1

The pressure outside a jet plane flying at high altitude falls

considerably below standard atmospheric pressure. Therefore,
the air inside the cabin must be pressurized to protect the
passengers.

What is the pressure in atmospheres in the cabin if the

barometer reading is 688 mmHg?
Example 5.1
Strategy Because 1 atm = 760 mmHg, the following
conversion factor is needed to obtain the pressure in
atmospheres:

Solution The pressure in the cabin is given by

Manometers Used to Measure Gas Pressures

closed-tube open-tube

9
Apparatus for Studying the Relationship Between
Pressure and Volume of a Gas

10
As P (h) increases V decreases
 Boyle’s Law

P  1/V
P x V = constant Constant temperature
Constant amount of gas
P1 x V1 = P2 x V2
11
Variation in Gas Volume with Temperature at Constant Pressure

As T increases V increases 12
 Variation of Gas Volume with Temperature
at Constant Pressure

Charles’s &
Gay-Lussac’s
Law

VT Temperature must be

V = constant x T in Kelvin
V1/T1 = V2 /T2 T (K) = t (0C) + 273.15 13
 Avogadro’s Law
V  number of moles (n) Constant temperature
Constant pressure
V = constant x n

V1 / n1 = V2 / n2

14
 Summary of Gas Laws

Boyle’s Law

15
Charles’s Law

16
Avogadro’s Law

17
 Ideal Gas Equation
1
Boyle’s law: P (at constant n and T)
V
Charles’s law: V  T(at constant n and P)
Avogadro’s law: V n(at constant P and T)

nT
V
P
nT nT
V = constant x =R R is the gas constant
P P

PV = nRT
18
The conditions 0 0C and 1 atm are called standard
temperature and pressure (STP).

Experiments show that at STP, 1 mole of an ideal

gas occupies 22.414 L.

PV = nRT
PV (1 atm)(22.414L)
R= =
nT (1 mol)(273.15 K)

R = 0.082057 L • atm / (mol • K)

19
Example 5.2

Sulfur hexafluoride (SF6) is a

colorless and odorless gas.

Due to its lack of chemical

reactivity, it is used as an
insulator in electronic
equipment.

Calculate the pressure (in atm)

exerted by 1.82 moles of the SF6
gas in a steel vessel of volume
5.43 L at 69.5°C.
Example 5.2

Strategy
The problem gives the amount of the gas and its volume and
temperature.

Is the gas undergoing a change in any of its properties?

What equation should we use to solve for the pressure?

What temperature unit should we use?

Example 5.2
Solution Because no changes in gas properties occur, we can
use the ideal gas equation to calculate the pressure.

Rearranging Equation (5.8), we write

Example 5.3

Calculate the volume (in L) occupied by 7.40 g of NH3 at STP.

NH3
Example 5.3
Strategy
What is the volume of one mole of an ideal gas at STP?

How many moles are there in 7.40 g of NH3?

Solution
Recognizing that 1 mole of an ideal gas occupies 22.41 L at
STP and using the molar mass of NH3 (17.03 g), we write the
sequence of conversions as
Example 5.3
So the volume of NH3 is given by

It is often true in chemistry, particularly in gas-law calculations, that a

problem can be solved in more than one way. Here the problem can
also be solved by first converting 7.40 g of NH3 to number of moles of
NH3, and then applying the ideal gas
equation (V = nRT/P). Try it.

Check Because 7.40 g of NH3 is smaller than its molar mass, its
volume at STP should be smaller than 22.41 L. Therefore, the
answer is reasonable.
Example 5.4

A small bubble rises from the bottom of a lake, where the

temperature and pressure are 8°C and 6.4 atm, to the water’s
surface, where the temperature is 25°C and the pressure
is 1.0 atm.

Calculate the final volume (in mL) of the bubble if its initial
volume was 2.1 mL.
Example 5.4
Strategy In solving this kind of problem, where a lot of
information is given, it is sometimes helpful to make a sketch of
the situation, as shown here:

What temperature unit should be used in the calculation?

Example 5.4
Solution According to Equation (5.9)

We assume that the amount of air in the bubble remains

constant, that is, n1 = n2 so that

which is Equation (5.10).

Example 5.4
The given information is summarized:

Initial Conditions Final Conditions

P1 = 6.4 atm P2 = 1.0 atm
V1 = 2.1 mL V2 = ?
T1 = (8 + 273) K = 281 K T2 = (25 + 273) K = 298 K

Rearranging Equation (5.10) gives

Example 5.4
Check We see that the final volume involves multiplying the
initial volume by a ratio of pressures (P1/P2) and a ratio of
temperatures (T2/T1).

Recall that volume is inversely proportional to pressure, and

volume is directly proportional to temperature.

Because the pressure decreases and temperature increases as

the bubble rises, we expect the bubble’s volume to increase.

In fact, here the change in pressure plays a greater role in the

volume change.
Density (d) Calculations

m PM m is the mass of the gas in g

d= =
V RT M is the molar mass of the gas

Molar Mass (M ) of a Gaseous Substance

dRT
M= d is the density of the gas in g/L
P

31
Example 5.5

A chemist has synthesized a greenish-yellow gaseous

compound of chlorine and oxygen and finds that its density is
7.71 g/L at 36°C and 2.88 atm.

Calculate the molar mass of the compound and determine its

molecular formula.
Example 5.5
Strategy
Because Equations (5.11) and (5.12) are rearrangements of
each other, we can calculate the molar mass of a gas if we
know its density, temperature, and pressure.

The molecular formula of the compound must be consistent

with its molar mass. What temperature unit should we use?
Example 5.5
Solution From Equation (5.12)

Alternatively, we can solve for the molar mass by writing

From the given density we know there are 7.71 g of the gas
in 1 L.
Example 5.5
The number of moles of the gas in this volume can be obtained
from the ideal gas equation

Therefore, the molar mass is given by

Example 5.5
We can determine the molecular formula of the compound by
trial and error, using only the knowledge of the molar masses of
chlorine (35.45 g) and oxygen (16.00 g).

We know that a compound containing one Cl atom and one O

atom would have a molar mass of 51.45 g, which is too low,
while the molar mass of a compound made up of two Cl atoms
and one O atom is 86.90 g, which is too high.

Thus, the compound must contain one Cl atom and two O

atoms and have the formula ClO2, which has a molar mass of
67.45 g.
Gas Stoichiometry

37
Example 5.6
Sodium azide (NaN3) is used in some
automobile air bags. The impact of a
collision triggers the decomposition of
NaN3 as follows:

2NaN3(s) → 2Na(s) + 3N2(g)

The nitrogen gas produced quickly

inflates the bag between the driver and
the windshield and dashboard.

Calculate the volume of N2 generated at An air bag can protect

the driver in an
80°C and 823 mmHg by the
decomposition of 60.0 g of NaN3. automobile collision.
Example 5.6
Strategy From the balanced equation we see that
2 mol NaN3 ≏ 3 mol N2 so the conversion factor between NaN3
and N2 is

Because the mass of NaN3 is given, we can calculate the

number of moles of NaN3 and hence the number of moles of N2
produced.

Finally, we can calculate the volume of N2 using the ideal gas

equation.
Example 5.6
Solution First we calculate number of moles of N2 produced by
60.0 g NaN3 using the following sequence of conversions

so that

The volume of 1.38 moles of N2 can be obtained by using the

ideal gas equation:
 Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
41
Consider a case in which two gases, A and B, are in a
container of volume V.

nART
PA = nA is the number of moles of A
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB n A + nB

PA = XA PT PB = XB PT

ni
Pi = Xi PT mole fraction (Xi ) =
nT
42
Example 5.7

A mixture of gases contains 4.46 moles of neon (Ne), 0.74 mole

of argon (Ar), and 2.15 moles of xenon (Xe).

Calculate the partial pressures of the gases if the total pressure

is 2.00 atm at a certain temperature.
Example 5.7
Strategy What is the relationship between the partial pressure
of a gas and the total gas pressure?

How do we calculate the mole fraction of a gas?

Solution According to Equation (5.14), the partial pressure of

Ne (PNe) is equal to the product of its mole fraction (XNe) and the
total pressure (PT)
Example 5.7
Using Equation (5.13), we calculate the mole fraction of Ne as
follows:

Therefore,
Example 5.7
Similarly,

and

Check Make sure that the sum of the partial pressures is equal
to the given total pressure; that is,

(1.21 + 0.20 + 0.586) atm = 2.00 atm.

Collecting a Gas over Water

2KClO3 (s) 2KCl (s) + 3O2 (g)

47
PT = PO2 + PH 2O
Vapor of Water and Temperature

48
Example 5.8
Oxygen gas generated by the decomposition of potassium
chlorate is collected as shown in Figure 5.15.

The volume of oxygen collected at 24°C and atmospheric

pressure of 762 mmHg is 128 mL.

Calculate the mass (in grams) of oxygen gas obtained.

The pressure of the water vapor at 24°C is 22.4 mmHg.

Example 5.8
Strategy To solve for the mass of O2 generated, we must first
calculate the partial pressure of O2 in the mixture.

What gas law do we need?

How do we convert pressure of O2 gas to mass of O2 in grams?

Solution From Dalton’s law of partial pressures we know that

Example 5.8
Therefore,

From the ideal gas equation we write

where m and are the mass of O2 collected and the molar

mass of O2, respectively.
Example 5.8
Rearranging the equation we obtain

Check The density of the oxygen gas is (0.164 g/0.128 L), or

1.28 g/L, which is a reasonable value for gases under
atmospheric conditions (see Example 5.8).
 Kinetic Molecular Theory of Gases
1. A gas is composed of molecules that are separated from
each other by distances far greater than their own
dimensions. The molecules can be considered to be points;
that is, they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions,
and they frequently collide with one another. Collisions
among molecules are perfectly elastic.
3. Gas molecules exert neither attractive nor repulsive forces
on one another.
4. The average kinetic energy of the molecules is proportional
to the temperature of the gas in kelvins. Any two gases at
the same temperature will have the same average kinetic
energy
KE = ½ mu2
53
 Kinetic theory of gases and …
• Compressibility of Gases
• Boyle’s Law
P  collision rate with wall
Collision rate  number density
Number density  1/V
P  1/V
• Charles’s Law
P  collision rate with wall
Collision rate  average kinetic energy of gas molecules
Average kinetic energy  T
PT
54
 Kinetic theory of gases and …
• Avogadro’s Law
P  collision rate with wall
Collision rate  number density
Number density  n
Pn
• Dalton’s Law of Partial Pressures
Molecules do not attract or repel one another
P exerted by one type of molecule is unaffected by the
presence of another gas
Ptotal = Pi

55
 The distribution of speeds
of three different gases
at the same temperature

The distribution of speeds

for nitrogen gas molecules
at three different temperatures

urms =  3RT
M
56
Example 5.9

Calculate the root-mean-square speeds of helium atoms and

nitrogen molecules in m/s at 25°C.
Example 5.9
Strategy To calculate the root-mean-square speed we need
Equation (5.16).

What units should we use for R and so that urms will be

expressed in m/s?

Solution
To calculate urms, the units of R should be 8.314 J/K · mol and,
because 1 J = 1 kg m2/s2, the molar mass must be in kg/mol.

The molar mass of He is 4.003 g/mol, or 4.003 × 10−3 kg/mol.

Example 5.9
From Equation (5.16),

Using the conversion factor 1 J = 1 kg m2/s2 we get

Example 5.9
The procedure is the same for N2, the molar mass of which is 28.02
g/mol, or 2.802 × 10−2 kg/mol so that we write

Check
Because He is a lighter gas, we expect it to move faster, on average,
than N2. A quick way to check the answers is to note that the ratio of
the two urms values (1.36 × 103/515 ≈ 2.6) should be equal to the
square root of the ratios of the molar masses of N2 to He, that is,
.
Gas diffusion is the gradual mixing of molecules of one gas
with molecules of another by virtue of their kinetic properties.


r1 M2
=
r2 M1

molecular path
NH4Cl

NH3 HCl
17 g/mol 36 g/mol
61
Gas effusion is the process by which gas under pressure
escapes from one compartment of a container to another by
passing through a small opening.


r1 t2 M2
= =
r2 t1 M1

62
Example 5.10
A flammable gas made up only of
carbon and hydrogen is found to
effuse through a porous barrier in
1.50 min.

Under the same conditions of

temperature and pressure, it
takes an equal volume of bromine
vapor 4.73 min to effuse through
Gas effusion. Gas
the same barrier.
molecules move from a
high-pressure
Calculate the molar mass of the region (left) to a low-
unknown gas, and suggest what pressure
this gas might be. one through a pinhole.
Example 5.10
Strategy The rate of diffusion is the number of molecules
passing through a porous barrier in a given time.

The longer the time it takes, the slower is the rate.

Therefore, the rate is inversely proportional to the time required

for diffusion.

Equation (5.17) can now be written as r1/r2 = t2/t1 = ,

where t1 and t2 are the times for effusion for gases 1 and 2,
respectively.
Example 5.10
Solution From the molar mass of Br2, we write

Where is the molar mass of the unknown gas. Solving for

we obtain

Because the molar mass of carbon is 12.01 g and that of

hydrogen is 1.008 g, the gas is methane (CH4).
 Deviations from Ideal Behavior

1 mole of ideal gas

Repulsive Forces
PV = nRT
PV = 1.0
n=
RT
Attractive Forces

66
Effect of intermolecular forces on the pressure exerted by a gas.

67
Van der Waals equation
nonideal gas

an
( P + V2 ) (V – nb) = nRT
2

corrected corrected
pressure volume

68
Example 5.11
Given that 3.50 moles of NH3 occupy 5.20 L at 47°C, calculate
the pressure of the gas (in atm) using

(a)the ideal gas equation and

(b)the van der Waals equation.

Example 5.11
Strategy
To calculate the pressure of NH3 using the ideal gas equation,
we proceed as in Example 5.3.

What corrections are made to the pressure and volume terms in

the van der Waals equation?
Example 5.11
Solution
(a)We have the following data:
V = 5.20 L
T = (47 + 273) K = 320 K
n = 3.50 mol
R = 0.0821 L · atm/K · mol
Substituting these values in the ideal gas equation, we
write
Example 5.11
(b) We need Equation (5.18). It is convenient to first calculate
the correction terms in Equation (5.18) separately. From
Table 5.4, we have

a = 4.17 atm · L2/mol2

b = 0.0371 L/mol

so that the correction terms for pressure and volume are

Example 5.11
Finally, substituting these values in the van der Waals equation,
we have

(P + 1.89 atm)(5.20 L – 0.130 L) = (3.50 mol)(0.0821 L∙atm/K∙mol)(320 K)

P = 16.2 atm

Check Based on your understanding of nonideal gas behavior,

is it reasonable that the pressure calculated using the van der
Waals equation should be smaller than that using the ideal gas
equation? Why?