Chapter 5

Gases

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 Elemental Gases
Elements that exist as gases at 25°C and 1
atmosphere (normal atmospheric conditions)

© McGraw-Hill Education. 5-2

 Common Gases
Table 5.1 Some Substances Found as Gases at 1 atm and 25°C
Elements
H2 (molecular hydrogen) N2 (molecular nitrogen)
O2 (molecular oxygen) O3 (ozone)
F2 (molecular fluorine) Cl2 (molecular chlorine)
He (helium) Ne (neon)
Ar (argon) Kr (krypton)
Xe (xenon) Rn (radon)
Compounds
HF (hydrogen fluoride) HCL (hydrogen chloride)
HBr (hydrogen bromide) HI (hydrogen iodide)
CO (carbon monoxide) CO2 (carbon dioxide)
CH4 (methane) C2H2 (acetylene)
NH3 (ammonia) NO (nitric acid)
NO2 (nitrogen dioxide) N2O (nitrous oxide)
SO2 (sulfur dioxide) SF6 (sulfur hexafluoride)
H2S (hydrogen sulfide) HCN (hydrogen cyanide)
*The boiling point of HCN is 26° C, but it is close enough to qualify as a gas at ordinary atmospheric conditions.
© McGraw-Hill Education. 5-3
 Physical Characteristics of Gases
The gases He, Ne, and Ar are chemically inert; that is, they do not
react with any other substance.
Most gases are colorless. Exceptions are F2, Cl2, and NO2.
The dark brown color of NO2 is sometimes visible in
polluted air.

All gases have the following physical characteristics:

NO2 gas
➢ 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.

© McGraw-Hill Education. 5-4
 Pressure
Gases exert pressure on any surface or container with which they come in
contact, because gas particles are constantly in motion.

The second law of motion, formulated by Sir Isaac Newton

(force = mass × acceleration) SI unit of force is the newton (N)

1 N = 1 kg m/s2

Force The SI unit of pressure is the pascal (Pa)

Pressure =
Area 1 pascal (pa) = 1N / m2

© McGraw-Hill Education. 5-5

 Atmospheric Pressure
Atmospheric pressure is the pressure exerted by Earth’s atmosphere

Standard atmospheric pressure (1 atm) is equal to the pressure that supports a

column of mercury exactly 760 mm (or 76 cm) high at 0°C at sea level. In other
words, the standard atmosphere equals a pressure of 760 mmHg.

1 atm = 760 mmHg = 760 torr

1 atm = 101325 Pa

Barometer
Device used to measure atmospheric pressure.

Mercury flows out of the tube until the pressure of the column
of mercury standing on the surface of the mercury in the dish
is equal to the pressure of the air on the rest of the surface of
the mercury in the dish.
© McGraw-Hill Education. 5-6
Manometers Used to Measure Gas Pressures
Manometer
is a device used to measure the pressure of gases other than the atmosphere.

a) Closed tube

The closed-tube manometer is normally used

to measure pressures below atmospheric
pressure

b) Open tube

the open-tube manometer is better suited

for measuring pressures equal to or
greater than atmospheric pressure

© McGraw-Hill Education. 5-7

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

A gas sample is placed into a closed-end tube, and mercury is added. As

more mercury is added to the tube, the pressure increases, and the volume
of the gas sample decreases. Thus, pressure and volume are inversely
related.
© McGraw-Hill Education. 5-8
 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?
1 atm
1 atm = 760 mmHg
760 mmHg
Solution
The pressure in the cabin is given by
1 atm
pressure = 688 mmHg ×
760 mmHg

= 0.905 atm

© McGraw-Hill Education. 5-9

 Example 5.2
The atmospheric pressure in San Francisco on a certain day was 732
mmHg. What was the pressure in kPa?

1 atm = 1.01325 × 105 Pa = 760 mmHg

Solution
The pressure in kPa is

1.011325 × 105 Pa
pressure = 732 mӍ mӍ HӍ g Ӎ ×
760 mӍ mӍ HӍ g Ӎ

= 9.76 × 104 Pa

= 97.6 kPa

© McGraw-Hill Education. 5-10

 Variables to describe gases

P, pressure of the container

V, volume of the container
T, Kelvin temperature of the gas
n, number of molecules in the container

© McGraw-Hill Education. 5-11

 Boyle’s Law
Boyle found that pressure and volume are inversely related. A plot of pressure versus
volume shows an inverse relationship, while a plot of pressure versus 1/volume
shows a straight line.

Boyle’s law, which states that the

pressure of a fixed amount of gas at
a constant temperature is inversely
proportional to the volume of the
gas.

𝟏 Constant temperature
𝑷𝜶
𝑽 And Constant amount of gas
As V , P 
𝑷 × 𝑽 = constant
𝑷𝟏 × 𝑽𝟏 = 𝑷𝟐 × 𝑽𝟐

© McGraw-Hill Education. 5-12

Variation in Gas Volume with Temperature at Constant
Pressure

➢ a small sample of gas is placed into a capillary

tube at a low temperature
➢ mercury is added to the tube.

When temperature increases, the volume of the

sample increases, while the mercury in the tube
stays the same (constant pressure).

As temperature increases, volume increases, so

temperature and volume are directly proportional.

© McGraw-Hill Education. 5-13

Variation of Gas Volume with Temperature at Constant
Pressure
Charles’ & Gay-Lussac’s Law
Their studies showed that, at constant pressure,
the volume of a gas sample increases when
heated and decreases when cooled as long as
temperature is measured in Kelvin.

For all gas samples, the volume of the sample approaches 0 L as the temperature
approaches 0 K, or -273.15 degrees Celsius.

𝑽𝜶𝑻
𝑽 = constant × 𝑻 Temperature must be in Kelvin
𝑽𝟏 𝑽𝟐 T (K) = t (°C) + 273.15
=
𝑻𝟏 𝑻𝟐
© McGraw-Hill Education. 5-14
 Charles’s Law
Low T, Low P
Another form of Charles’ law shows that
at constant amount of gas and volume, P
the pressure of a gas is proportional to High T, High P
temperature; that is
T (K)

𝒑𝜶𝑻

p = constant × 𝑻 at constant V&n

𝒑𝟏 𝒑𝟐
=
𝑻𝟏 𝑻𝟐

© McGraw-Hill Education. 5-15

 Avogadro’s Law
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

𝑽 𝜶 number of moles 𝒏
Constant temperature
𝑽 = constant × 𝒏 Constant pressure
𝑽𝟏 𝑽𝟐
=
𝒏𝟏 𝒏𝟐

© McGraw-Hill Education. 5-16

Summary of Gas Laws

© McGraw-Hill Education. 5-17

 Ideal Gas Equation
1
Boyle’s law: 𝑃 𝛼 (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)
We can combine all three expressions to form
𝒏𝑻
𝑽 ∝
𝑷
𝑛𝑇 𝑛𝑇
𝑉 = constant × =𝑅 R is the gas constant
𝑃 𝑃
(R = 0.08206 L.atm/K.mol)

PV = nRT ideal gas equation

© McGraw-Hill Education. 5-18

The individual gas laws as special
cases of the ideal gas law.

© McGraw-Hill Education. 5-19

 Ideal Gas Equation

PV = nRT ideal gas equation

ideal gas equation, describes the relationship among the four

variables P, V, T, and n.
An ideal gas is a hypothetical gas whose pressure-volume-
temperature behavior can be completely accounted for by the ideal
gas equation.

➢ The molecules of an ideal gas do not attract or repel one another

➢ their volume is negligible compared with the volume of the container.

© McGraw-Hill Education. 5-20

 Combined Gas Law
• Constant for fixed amount of gas (n)

𝑷𝑽
• =𝑪 for fixed amount (moles)
𝑻
• OR can equate 2 sets of conditions to give combined gas
law
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
= fixed amount (moles)
𝑻𝟏 𝑻𝟐
or
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
= 𝒏𝟏 ≠ 𝒏𝟐
𝑻𝟏 𝒏𝟏 𝑻𝟐 𝒏𝟐

© McGraw-Hill Education. 5-21

 Standard Temperature and Pressure
The conditions 0 °C 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 22.414 L
𝑅= =
𝑛𝑇 1 mol 273.15 K

atm
𝑅 = 0.08205 L ⋅
mol ⋅ K

© McGraw-Hill Education. 5-22

 Example 5.3
Sulfur hexafluoride (SF6) is a colorless and odorless gas. Calculate the
pressure (in atm) exerted by 1.82 moles of the gas in a steel vessel of
volume 5.43 L at 69.5 °C
Solution
Because no changes in gas properties occur, we can use the ideal gas
equation to calculate the pressure.
𝑛𝑅𝑇
𝑃 =
𝑉
atm
1.82 mol 0.0821 L ⋅ 69.5 + 273 K
= K ⋅ mol
5.43 L
= 9.42 atm

© McGraw-Hill Education. 5-23

 Example 5.4
Calculate the volume (in L) occupied by 7.40 g of NH3 at STP

Solution
Recognizing that 1 mole of an ideal gas occupies 22.41 L at STP and using
the molar mass of (17.03 g), we write the sequence of conversions as

grams of NH3 → moles of NH3 → litres of NH3 at STP

So the volume

1 mol NӍ HӍ 3Ӎ 22.41 L
𝑉 = 7.40 g Ӎ NӍ HӍ 3Ӎ × ×
17.03 g NӍ HӍ 3Ӎ 1 mol NӍ HӍ 3Ӎ
= 9.74 L

Or use the ideal gas equation (V=nRT/P)

© McGraw-Hill Education. 5-24

 Example 5.5
An inflated helium balloon with a volume of 0.55 L at sea level (1.0 atm) is
allowed to rise to a height of 6.5 km, where the pressure is about 0.40 atm.
Assuming that the temperature remains constant, what is the final volume
of the balloon?

Solution
𝑃1 𝑉1 𝑃2 𝑉2
=
𝑛1 𝑇1 𝑛2 𝑇2

Because 𝑛1 = 𝑛2 and 𝑇1 = 𝑇2 ,

𝑃1 𝑉1 = 𝑃2 𝑉2

© McGraw-Hill Education. 5-25

 Example 5.5

The given information is tabulated:

Intial Conditions Final Conditions
𝑃1 = 1.0 atm 𝑃2 = 0.40 atm
𝑉1 = 0.55L 𝑉2 = ?
Therefore, 𝑃1
𝑉2 = 𝑉1 ×
𝑃2
1.0 atm
= 0.55 L ×
0.40 atm
= 1.4 L
Check
When pressure applied on the balloon is reduced (at constant
temperature), the helium gas expands and the balloon’s volume
increases. The final volume is greater than the initial volume, so the
answer is reasonable.
© McGraw-Hill Education. 5-26
 Example 5.6
A certain lightbulb containing argon at 1.20 atm and 18°C is heated
to 85°C at constant volume. Calculate its final pressure (in atm).

Solution

Because 𝑛1 = 𝑛2 and 𝑉1 = 𝑉2 ,

becomes
𝑃1 𝑃2
=
𝑇1 𝑇2

© McGraw-Hill Education. 5-27

 Example 5.6
Next we write
Intial Conditions Final Conditions
𝑃1 = 1.20 atm 𝑃2 = ?
𝑇1 = (18 + 273) K = 291 K 𝑇2 = (85 + 273)K = 358 K
The final pressure is given by
𝑇1
𝑃2 = 𝑃1 ×
𝑇2
358 K
= 1.20 atm ×
291 K
= 1.48 atm
Check
At constant volume, the pressure of a given amount of gas is
directly proportional to its absolute temperature. Therefore the
increase in pressure is reasonable
© McGraw-Hill Education. 5-28
 Example 5.7
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.

© McGraw-Hill Education. 5-29

 Example 5.7
Solution
According to
𝑃1 𝑉1 𝑃2 𝑉2
=
𝑛1 𝑇1 𝑛2 𝑇2

We assume that the amount of air in the bubble remains constant, that is,

n1 = n2 so that

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2

© McGraw-Hill Education. 5-30

 Example 5.7

The given information is summarized:

Intial 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 gives

𝑃1 𝑇2
𝑉2 = 𝑉1 × ×
𝑃2 𝑇1
6.4 atm 298 K
= 2.1 mL × ×
1.0 atm 281 K
= 14 mL
© McGraw-Hill Education. 5-31
 Density and Molar Mass
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 d is the density of the gas in g/L

𝑴 =
𝑷

© McGraw-Hill Education. 5-32

 Example 5.8
Calculate the density of carbon dioxide (CO2) in grams per liter (g/ L) at
0.990 atm and 55°C.

Solution
we convert temperature to kelvins (T = 273 + 55 = 328 K) and use 44.01 g for the
molar mass of CO2

𝑃𝑀
𝑑 =
𝑅𝑇

g
0.990 atm 44.01
= mol
atm
0.0821 L ⋅ 328 K
K ⋅ mol
g
= 1.62
L
© McGraw-Hill Education. 5-33
 Example 5.8
Alternatively, we can solve for the density by writing
mass
density =
volume

Assuming that we have 1 mole of CO2 the mass is 44.10 g. The

volume of the gas can be obtained from the ideal gas equation
𝑛𝑅𝑇
𝑉=
𝑃
atm
1 mol 0.0821 L ⋅ 328 K
= K ⋅ mol
= 27.2 L
0.990 atm
Therefore, the density of
44.01 g g
𝑑= = 1.62
27.2 L L

© McGraw-Hill Education. 5-34

 Example 5.9
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.

Solution

𝑑𝑅𝑇
𝑀 =
𝑃
g atm
7.71 L 0.0821 L ⋅ 36 + 273 K
= K ⋅ mol
2.88 atm
g
= 67.9
mol
© McGraw-Hill Education. 5-35
 Example 5.9
Alternatively, we can solve for the molar mass by writing
mass of compound
molar mass of compound =
moles of compound

From the given density we know there are 7.71 g of the gas in 1 L.
The number of moles of the gas in this volume can be obtained from
the ideal gas equation
𝑃𝑉 2.88 atm 1.00 L
𝑛 = = = 0.1135 mol
𝑅𝑇 atm
0.0821 L ⋅ 309 K
K ⋅ mol

Therefore, the molar mass is given by

mass 7.71 g g
𝑀= = = 67.9
number of moles 0.1135 mol mol

© McGraw-Hill Education. 5-36

 Example 5.9
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.

© McGraw-Hill Education. 5-37

 Example 5.10

Chemical analysis of a gaseous compound showed that it contained 33.0

percent silicon (Si) and 67.0 percent fluorine (F) by mass.

At 35°C, 0.210 L of the compound exerted a pressure of 1.70 atm.

If the mass of 0.210 L of the compound was 2.38 g, calculate the

molecular formula of the compound.

© McGraw-Hill Education. 5-38

 Example 5.10
Solution
to calculate the empirical formula by assuming that we have 100 g
of the compound, so the percentages are converted to grams.

The number of moles of Si and F are given by

1 mol Si
𝑛𝑆𝑖 = 33.0 g Ӎ S𝑖Ӎ Ӎ × = 1.17 mol Si
28.09 g Ӎ SiӍ Ӎ

1 mol F
𝑛𝐹 = 67.0 g Ӎ FӍ × = 3.53 mol F
18.998 g Ӎ FӍ

Therefore, the empirical formula is Si1.17F3.53, or, dividing by the

smaller subscript (1.17), we obtain SiF3

© McGraw-Hill Education. 5-39

 Example 5.10
we need first to calculate the number of moles contained in 2.38 g of
the compound. From the ideal gas equation

𝑃𝑉 1.70 atm 0.210 L

𝑛 = = atm = 0.0141 mol
𝑅𝑇 0.0821L ⋅ 308 K
K ⋅ mol

Because there are 2.38 g in 0.0141 mole of the compound, the mass in
1 mole, or the molar mass, is given by

2.38 g g
𝑀 = = 169
0.0141 mol mol

The molar mass of the empirical formula SiF3 is 85.09 g. Recall that the
ratio (molar mass/empirical molar mass) is always an integer
(169/85.09 ≈ 2). Therefore, the molecular formula of the compound
must be SiF3 2 or Si2 F6 .

© McGraw-Hill Education. 5-40

 Gas Stoichiometry
P, V, T P, V, T
of gas A of gas B

Amount (mol) Amount (mol)

of gas A of gas B

If a mass of reactant gas is given, use the molar mass of the gas to convert to
moles. If a volume of gas is given, use the ideal gas law to calculate the moles of
gas.
© McGraw-Hill Education. 5-41
 Example 5.11
Calculate the volume of O2 (in liters) required for the complete combustion
of 7.64 L of acetylene (C2H2) measured at the same temperature and
pressure.

2C2 H2 g + 5O2 g → 4CO2 g + 2H2 O l

Solution
According to Avogadro’s law, at the same temperature and pressure, the
number of moles of gases are directly related to their volumes.

5 LO2
volume of O2 = 7.64 LC2Ӎ Ӎ HӍ 2Ӎ ×
2 LC2Ӎ Ӎ HӍ 2Ӎ
= 19.1 L

© McGraw-Hill Education. 5-42

 Example 5.12
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

Calculate the volume of N2 generated at 80°C and 823 mmHg by the

decomposition of 60.0 g of NaN3.

© McGraw-Hill Education. 5-43

 Example 5.12
Solution
First we calculate number of moles of N2 produced by 60.0 g NaN3
using the following sequence of conversions

grams of NaN3 → moles of NaN3 → moles of N2

so that
1 mol NӍ aN
Ӎ Ӎ 3Ӎ 3 mol N2
Ӎ
moles of N2 = 60.0 g NaN Ӎ
Ӎ 3Ӎ × ×
65.02 g NӍ aNӍ Ӎ 3Ӎ 2 mol NӍ aN
Ӎ Ӎ 3Ӎ
= 1.38 mol N2
The volume of 1.38 moles of N2 can be obtained by using the ideal
gas equation:
atm
𝑛𝑅𝑇 1.38 mol 0.0821 L ⋅ 80 + 273 K
𝑉 = = K ⋅ mol = 36.9 L
𝑃 823
760 atm
© McGraw-Hill Education. 5-44
 Example 5.13
Aqueous lithium hydroxide absorbs carbon dioxide, according to
the equation

2LiOH 𝑎𝑞 + CO2 𝑔 → Li2 CO3 𝑎𝑞 + H2 O 𝑙

The pressure of carbon dioxide inside the cabin of a submarine

having a volume of 2.4 × 105 L is 7.9 × 10−3 atm at 312 K.
A solution of lithium hydroxide (LiOH) of negligible volume is
introduced into the cabin. Eventually the pressure of CO2 falls to
1.2 × 10−4 atm. How many grams of lithium carbonate are formed
by this process?

© McGraw-Hill Education. 5-45

 Example 5.13
Strategy

At constant T and V, the change in pressure of CO2, ΔP, corresponds to

the change in the number of moles of CO2, Δn. Thus,

𝑉
Δ𝑛 = Δ𝑃 ×
𝑅𝑇
Solution
The drop in CO2 pressure is
7.9 × 10−3 atm − 1.2 × 10−4 atm or 7.8 × 10−3 atm

Therefore, the number of moles of CO2 reacted is given by

2.4 × 105L
Δ𝑛 = 7.8 × 10−3 atm × atm = 73 mol
0.0821 L ⋅ 312K
K ⋅ mol

© McGraw-Hill Education. 5-46

 Example 5.13
From the chemical equation we see that

1 mol CO2 ≏ 1 mol Li2CO3

so the amount of Li2CO3 formed is also 73 moles.

Then, with the molar mass of Li2CO3(73.89 g), we calculate its

mass:

73.89 g Li2 CO3

Ӎ Ӎ 3Ӎ ×
mass of Li2 CO3 formed = 73 mol LiӍ 2Ӎ Ӎ CO Ӎ Ӎ 3Ӎ
1 mol LiӍ 2Ӎ Ӎ CO

= 5.4 × 103 g Li2 CO3

© McGraw-Hill Education. 5-47

 Dalton’s Law of Partial Pressures
Suppose there are two samples of gas, both at constant temperature and volume.
Each gas has a pressure. If the two samples are combined into a container with the
same volume and temperature, the total pressure inside the container will be equal
to the sum of the pressures of each gas.

V and T are constant

P1 P2 Ptotal= P1+ P2

Dalton’s law of partial pressures, which states that the total pressure of a
mixture of gases is just the sum of the pressures that each gas would exert if it
were present alone (V and T are constant).
© McGraw-Hill Education. 5-48
 Partial Pressure
Consider a case in which two gases, A and B, are in a container of volume V.

𝑛𝐴 𝑅𝑇
𝑃𝐴 = nA is the number of moles of A
𝑉
𝑷𝑻 = 𝑷𝑨 + 𝑷𝑩
𝑛𝐵 𝑅𝑇
𝑃𝐵 = nB is the number of moles of B
𝑉

𝒏𝑨
𝑷𝑨 = 𝑿 𝑨 𝑷𝑻 𝑿𝑨 =
𝒏𝑨 + 𝒏𝑩
Partial pressure mole fraction
𝒏𝑩
𝑷𝑩 = 𝑿𝑩 𝑷𝑻 𝑿𝑩 =
𝒏𝑨 + 𝒏𝑩

© McGraw-Hill Education. 5-49

 Partial Pressure
Partial pressure is the pressure exerted by a particular component of a gas
mixture

𝑷 𝒊 = 𝑿 𝒊 𝑷𝑻

The mole fraction is the ratio of the number of moles of one component to the
number of moles of all components present.

𝒏𝒊
mole fraction 𝑿𝒊 =
𝒏𝑻

Note that the sum of the mole fractions for a mixture of gases must equal 1. If only
two components are present, then

XA + XB = 1

© McGraw-Hill Education. 5-50

 Example 5.14
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.

Solution

© McGraw-Hill Education. 5-51

 Example 5.14
calculate the mole fraction of Ne as follows:
𝑛𝑁𝑒 4.46 mol
𝑋𝑁𝑒 = = = 0.607
𝑛𝑁𝑒 + 𝑛𝐴𝑟 + 𝑛𝑋𝑒 4.46 mol + 0.74 mol + 2.15 mol

Therefore,
𝑃𝑁𝑒 = 𝑋𝑁𝑒 𝑃𝑇

= 0.607 × 2.00 atm = 1.21 atm

1.21
Similarly,
𝑃𝐴𝑟 = 𝑋𝐴𝑟 𝑃𝑇 +

= 0.10 × 2.00 atm = 0.20 atm 0.20

and +
𝑃𝑋𝑒 = 𝑋𝑋𝑒 𝑃𝑇

= 0.293 × 2.00 atm = 0.586 atm 0.586

© McGraw-Hill Education. = 2.00 atm. 5-52
 Collecting a Gas over Water
• Application of Dalton’s Law of Partial Pressures
• Gases that don’t react with water can be trapped over water
• Whenever gas is collected by displacement of water, mixture of gases results
Gas in bottle is mixture of water vapor and gas being collected

2KClO3 s → 2KCl s + 3O2 g

𝑃T = 𝑃O2 + 𝑃H2O

© McGraw-Hill Education. 5-53

Vapor of Water and Temperature

Table 5.3 Pressure of water

vapor at various temperatures

Water Vapor Temperature Water Vapor

Temperature
Pressure (°C) Pressure (mmHg)
(°C)
(mmHg)
0 4.58 55 118.04

5 6.54 60 149.38

10 9.21 65 187.54
70 233.7
15 12.79
75 289.1
20 17.57
80 355.1
25 23.76
85 433.6
30 31.82
90 525.76
35 42.18
95 633.90
40 55.32
100 760.00
45 71.88
50 92.51

© McGraw-Hill Education. 5-54

 Example 5.15
Oxygen gas generated by the decomposition of potassium chlorate.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.

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

𝑃T = 𝑃O2 + 𝑃H2O

© McGraw-Hill Education. 5-55

 Example 5.15
Therefore,
𝑃O2 = 𝑃T − 𝑃H2O

= 762 mmHg − 22.4 mmHg = 740 mmHg

From the ideal gas equation we write

𝑚
𝑃𝑉 = 𝑛𝑅𝑇 = 𝑅𝑇
𝑀

where m and M are the mass of O2 collected and the molar mass of O2,
respectively. Rearranging the equation we obtain

740 g
𝑃𝑉𝑀 atm 0.128 L 32.00
𝑚 = = 760 mol
𝑅𝑇 atm
0.0821 L ⋅ 273 + 24 K
𝐾 ⋅ mol
= 0.164 g

© McGraw-Hill Education. 5-56

 Kinetic Molecular Theory of Gases

The findings of Maxwell, Boltzmann, and others resulted in a

number of generalizations about gas behavior that have since
been known as the kinetic molecular theory of gases, or
simply the kinetic theory of gases. Central to the kinetic theory
are the following assumptions:

1. The particles are so small compared with the distances between them that the
volume of the individual particles can be assumed to be negligible (zero).

2. Gas molecules are in constant motion in random directions, and they frequently
collide with one another. Collisions among molecules are perfectly elastic.
(Energy is transferred but not lost in the collisions.)

gas pressure is the result of collisions between molecules and the walls of
their container.( number collisions  Pgas)
© McGraw-Hill Education. 5-57
 Kinetic Molecular Theory of Gases
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
𝟏
KE = 𝐦𝐮𝟐
𝟐
where m is the mass of the molecule and u is its speed. The horizontal bar
denotes an average value. The quantity u2 is called mean square speed; it is
the average of the square of the speeds of all the molecules
As increase T,  KEave,  number collisions with walls, thereby increasing P

© McGraw-Hill Education. 5-58

 Kinetic theory of gases

Compressibility of Gases

Because molecules in the gas phase are separated by large distances,

gases can be compressed easily to occupy less volume.

© McGraw-Hill Education. 5-59

 Molecular Interpretation of Boyle’s Law

As the volume of a gas sample is decreased, gas molecules collide with

surrounding surfaces more frequently, resulting in greater pressure. As a
result
1
𝑃𝛼
𝑉
 V, means gas particles hit wall more often  P
 Charles’s Law – A Molecular View

At T1, Pgas = Patm. Higher T increases Thus, V increases

collision frequency, until Pgas = Patm at T2.
Hence, the pressure
increases

Average Kinetic energy  T

Speeds of molecules  Gas particles hit wall more often So  P

PT
 Avogadro’s Law – A Molecular View

For a given amount, When gas is added to As a result, V increases

n1, of gas, Pgas = Patm. reach n2 the collision until Pgas = Patm again.
frequency of the particles
increases, so Pgas > Patm.

Vn
Dalton’s Law – A Molecular View

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
 Apparatus for Studying Molecular Speed
Distribution
The vacuum pump causes the molecules to
travel from left to right

© McGraw-Hill Education. 5-64

 Distribution of Gas Speeds
Maxwell speed distribution curves for nitrogen
gas at three different temperatures. At a given
temperature, the distribution curve tells us the
number of molecules moving at a certain
speed.
As increasing temperature, larger numbers of
molecules are moving at greater speed.

The distribution of speeds of three

different gases at the same temperature

The difference in the curves can be explained

by noting that lighter molecules move faster,
on average, than heavier ones.

© McGraw-Hill Education. 5-65

 Distribution of Gas Speeds
Root Mean Square Velocity

3RT
urms =
M
R = 8.3145 J/K·mol
(J = joule = kg·m2/s2)
T = temperature of gas (in K)
M = mass of a mole of gas in kg

• Final units are in m/s.

© McGraw-Hill Education. 5-66
 Example 5.16
Calculate the root-mean-square speeds of helium atoms and nitrogen
molecules in m/s at 25°C.

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

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

J
3 8.314 298 K J
K ⋅ mol
=
kg = 1.86 × 106
4.003 × 10−3 kg
mol

© McGraw-Hill Education. 5-67

 Example 5.16
m2
Using the conversion factor 1 J = 1 kg 2 we get
s
kg m2
u𝑟𝑚𝑠 = 1.86 × 106
kg ⋅ s2

m2 m
= 1.86 × 106 = 1.36 × 103
s2 s

The procedure is the same for N2 the molar mass of which is

g −2
kg
28.02 , 2.802 × 10 so that we write
mol mol

J
3 8.314 298 K
u𝑟𝑚𝑠 = K ⋅ mol
kg
2.802 × 10−2
mol

m2 m
= 2.65 × 105 = 515
s2 s
© McGraw-Hill Education. 5-68
 Gas Diffusion
Gas diffusion is the gradual mixing of molecules of one
gas with molecules of another by virtue of their kinetic
properties.

Molecular path
Each change in direction represents a When a sample of NH3 and a sample of
collision with another molecule. HCl are opened at the same time, a cloud
of white NH4Cl forms over the HCl sample,
instead of in the middle of the two samples.
The cloud forms preferentially over the HCl
sample because NH3 diffuses faster than
HCl.
© McGraw-Hill Education. 5-69
 Gas Effusion

Gas effusion is the process by which gas under pressure

escapes from one compartment of a container to another by
passing through a small hole into an evacuated space.

Gas effusion. Gas molecules move from a

high-pressure region (left) to a low-
pressure one

Smaller gas particles will escape the

compartment first

© McGraw-Hill Education. 5-70

 Graham’s Law
Graham’s law states that under the same conditions of temperature and
pressure the rate of diffusion or effusion of a gas is inversely proportional to
the square root of its molar mass

1
Rate of diffusion or effusion 
√M
A lighter gas moves more quickly and therefore has a higher rate of
diffusion or effusion than a heavier gas at the same T.

𝒓𝟏 𝒕𝟐 𝑴𝟐
= =
𝒓𝟐 𝒕𝟏 𝑴𝟏

© McGraw-Hill Education. 5-71

 Example 5.17

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 the same
barrier.

Calculate the molar mass of the unknown gas, and suggest what this
gas might be.

© McGraw-Hill Education. 5-72

 Example 5.17

Solution
From the molar mass of Br2 , we write
1.50 min 𝑀
= g
4.73 min 159.8
mol

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

obtain 2
1.50 min g
𝑀= × 159.8
4.73 min mol

g
= 16.1
mol

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

hydrogen is 1.008 g, the gas is methane CH4
© McGraw-Hill Education. 5-73
 Deviations from Ideal Behavior
1 mole of ideal gas

𝑃𝑉 = 𝑛𝑅𝑇
𝑃𝑉
𝑛= = 1.0
𝑅𝑇

1. At high pressures, gas behavior deviates from

ideal behavior.

At very high pressures, gas particles are

forced very close together. As a result, the
repulsive forces arise to prevent any further
compression.

© McGraw-Hill Education. 5-74

 Deviations from Ideal Behavior

2. At low temperatures, gas particles move more slowly, they have lower kinetic
energies and the attractive forces between molecules affect how much pressure
is exerted by the molecules on the wall of the container. The attractive forces
decrease the likelihood of a molecule imparting a force on the container,
decreasing the pressure from expected ideal behavior.

Generally, a gas behaves more like an ideal gas at

higher temperature and lower pressure

© McGraw-Hill Education. 5-75

 Effect of intermolecular forces on the
pressure exerted by a gas

➢ The speed of a molecule that is moving toward the

container wall (red sphere) is reduced by the
attractive forces exerted by its neighbors (gray
spheres).

➢ Consequently, the impact this molecule makes with

the wall is not as great as it would be if no
intermolecular forces were present.

➢ In general, the measured gas pressure is lower than

the pressure the gas would exert if it behaved ideally.

© McGraw-Hill Education. 5-76

 Van der Waals Equation
Van der Waals suggested that the pressure exerted by an ideal gas, Pideal, is
related to the experimentally measured pressure, Preal, by the equation

𝒂𝒏𝟐
𝑷𝒊𝒅𝒆𝒂𝒍 = 𝑷𝒓𝒆𝒂𝒍 +
𝑽𝟐

observed correction
pressure term

For a real gas, the actual observed pressure is lower than the pressure
expected for an ideal gas due to the intermolecular attractions that occur in
real gases.

© McGraw-Hill Education. 5-77

 Van der Waals Equation
Van der Waals equation nonideal gas

where a is a constant and n and V are the number of moles

and volume of the container
• The value of a indicates how strongly molecules of a
given type of gas attract one another. We see that
helium atoms have the weakest attraction for one
another, because helium has the smallest a value.

• The constant b relates to particle volume (size).

intermolecular forces will affect “ideality”.
The stronger the intermolecular forces(or larger molar mass) , the more is the
deviation from the ideality
© McGraw-Hill Education. 5-78
 Example 5.18
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.

© McGraw-Hill Education. 5-79

 Example 5.18
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

𝑛𝑅𝑇
𝑃=
𝑉

0.0821 L. atm
3.50 mol 320 K
= K. mol = 17.7 atm
5.20 L

© McGraw-Hill Education. 5-80

 Example 5.18
b) From Table 5.4, we have
atm. L2 L
a = 4.17 b = 0.0371
mol2 mol
so that the correction terms for pressure and volume are
4.17 atm. L2 2
an2 3.50 mol
mol2
= = 1.89 atm
v2 5.20 L 2

0.0371 L
nb = 3.50 mol = 0.130 L
mol

Finally, substituting these values in the van der Waals equation, we have
0.0821 L. atm
𝑃 + 1.89 atm 5.20 L– 0.130 L = 3.50 mol 320 K
K. mol
𝑃 = 16.2 atm
© McGraw-Hill Education. 5-81
 Example 5.18
the pressure calculated using the van der Waals equation should be
smaller than that using the ideal gas equation? Why?

© McGraw-Hill Education. 5-82

 A sample of gas occupies 2.78 x 103 mL at 25oC and 760 mm Hg. What volume will the gas
sample occupy at the same temperature and 475 mm Hg?
A) 0.130 L
B) 1.04 L
C) 1.74 L
D) 4.45 L

A steel tank contains carbon dioxide at a pressure of 13.0 atm when the temperature is 34oC.
What will be the internal gas pressure when the tank and its contents are heated to 100oC.
A) 38.2 atm
B) 9.40 atm
C) 10.7 atm
D) 15.8 atm

© McGraw-Hill Education. 5-83

Calculate the density of nitrogen gas, in grams per liter, at STP.
A) 0.625 g/L
B) 0.800 g/L
C) 1.25 g/L
D) 2.50 g/L

A gas evolved during the fermentation of alcohol had a volume of 19.4 L at 17oC and 746 mm
Hg. How many moles of gas were collected?
A) 1.25 mol
B) 0.800 mol
C) 10.5 mol
D) 13.6 mol
E) 608 mol

© McGraw-Hill Education. 5-84

How many grams of carbon dioxide are contained in 550 mL of this gas at STP?
A) 0.0245 g
B) 0.0280 g
C) 1080 g
D) 0.560 g
E) 1.1 g

What volume of chlorine gas at 646 torr and 32oC would be produced by the reaction of 14.75
g of MnO2 according to the following chemical equation?
MnO2(s) + 4 HCl(aq) ----> MnCl2(aq) + Cl2(g) + 2 H2O(l)
A) 5.00 L
B) 0.170 L
C) 2.33 L
D) 0.200 L

© McGraw-Hill Education. 5-85

A mixture of neon, argon, and xenon had a total pressure of 1560 mm Hg at 298 K. The
mixture was found to contain 1.50 mol Ne, 2.65 mol Ar, and 1.75 mol Xe. What is the
partial pressure of Xe?
A) 701 mm Hg
B) 658 mm Hg
C) 396 mm Hg
D) 463 mm Hg

The thermal decomposition of potassium chlorate can be used to produce oxygen in the
laboratory.
2KClO3 (s) → 2KCl (s) + 3O2 (g)

What volume (L) of O2 gas at 25 °C and 1.00 atm pressure is produced by the
decomposition of 5.5 g of KClO3?

A) 4.5
B) 7.5
C) 1.6
D) 3.7
E) 11
© McGraw-Hill Education. 5-86
A sample of H2 gas effused through a pinhole in 5.5 s. It will take __________ s
for the same amount of CH4 to effuse under the same conditions.

A) 7.3
B) 15.6
C) 13.1
D) 4.2

A gas mixture contains 3.0 mol of hydrogen (H2) and 7.3 mol of nitrogen (N2). The
total pressure of the mixture is 304 kPa. What is the partial pressure of H2?

A) 68.2 kPa
B) 15.6 kPa
C) 88.5 kPa
D) 40.2 kPa

© McGraw-Hill Education. 5-87

The root-mean-square velocity of O2 gas at 0°C is

A) 614 m/s
B) 461 m/s
C) 324 m/s
D) 484 m/s

193 mL of O2 was collected over water on a day when the atmospheric pressure
was 762 mmHg. The temperature of the water was 23.0 o C. How many grams
of oxygen were collected? At 23.0 o C the vapor pressure of water is 21.1 mmHg

A. 6.40 X 10-2 g
B. 4.06 X 10-2 g
C. 3.26 X 10-2 g
D. 2.46 X 10-2 g

© McGraw-Hill Education. 5-88

Diethyl ether (C2H5)2O vaporizes at room temperature. If the vapor exerts a
pressure of 233 mm Hg in a flask at 25 °C, what is the density of the vapor?

A) 614 m/s
B) 0.297 g/L
C) 0.927 g/L
D) 484 m/s

At what temperature will 0.0421 g of Ar in a 23.0mL incandescent light bulb

have a pressure of 952 mmHg?

A. 80 K
B. 460 K
C. 60 K
D. 333 K

© McGraw-Hill Education. 5-89

Hydrazine gas, N2H4, will react with oxygen gas to form nitrogen gas and liquid
water. Assume the oxygen gas needed for the reaction is in a 450. L tank at 23
°C. What must be the oxygen pressure (in kPa) in the tank to have enough
oxygen to consume 1.00 kg of hydrazine completely?
N2H4(g) + O2 (g) --> N2 (g) + 2 H2O (l)

A) 1.7
B) 172
C) 17
D) 271

For the following reaction:

Zn(s) + H2SO4(aq) → ZnSO4(aq) + H2(g)
If 159 mL of wet H2 is collected over water at 24°C and a barometric pressure of
738 torr, how many grams of Zn have been consumed? (P H2O, 24°C) = 22.38
torr.

A) 1.7 g
B) 0.162 g
C) 0.402 g
D) 0.771 g
© McGraw-Hill Education. 5-90