Gases

Chapter 5

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Elements that exist as gases at 250C and 1 atmosphere

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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.

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NO2 gas
 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

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10 miles 0.2 atm

4 miles 0.5 atm

Sea level 1 atm

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

Solution 1 atm = 1.01325 × 105 Pa = 760 mmHg

the conversion factor we need is

The pressure in kPa is

Manometers Used to Measure Gas Pressures

closed-tube open-tube

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10
Apparatus for Studying the Relationship Between
Pressure and Volume of a Gas

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

P a 1/V
P x V = k1=constant Constant temperature
Constant amount of gas
P1 x V1 = P2 x V2 12
Variation in Gas Volume with Temperature at Constant Pressure

As T increases V increases 13
 Variation of Gas Volume with Temperature
at Constant Pressure

Charles’s &
Gay-Lussac’s
Law

VaT Temperature must be

V = k2(constant) x T in Kelvin
V1/T1 = V2 /T2 T (K) = t (0C) + 273.15 14
 Avogadro’s Law
V a number of moles (n) Constant temperature
Constant pressure
V = k3(constant) x n

V1 / n1 = V2 / n2

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 Summary of Gas Laws

Boyle’s Law

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Charles’s Law

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Avogadro’s Law

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

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

PV = nRT
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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)

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Example 5.3

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
gas in a steel vessel of volume
5.43 L at 69.5°C.
Example 5.3
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 5.4
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 NH3 (17.03 g), we write the
sequence of conversions as
Example 5.4
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 5.5
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?

Because n1 = n2 and T1 = T2,

A scientific research
helium balloon.
Example 5.5 Because n1 = n2 and T1 = T2,
The given information is tabulated:
Initial Conditions Final Conditions
P1 = 1.0 atm P2 = 0.40 atm
V1 = 0.55 L V2 = ?
Therefore,

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.
Example 5.6
Argon is an inert gas used in
lightbulbs to retard the
vaporization of the tungsten
filament.

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,
Electric lightbulbs are
usually filled with argon.
Example 5.6
Next we write
Initial 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

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.
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.
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

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

Solution To use Equation (5.11), we convert temperature to

kelvins (T = 273 + 55 = 328 K) and use 44.01 g for the molar
mass of CO2:
Example 5.8
Alternatively, we can solve for the density by writing

Assuming that we have 1 mole of CO2, the mass is 44.01 g.

The volume of the gas can be obtained from the ideal gas
equation
Example 5.8
Therefore, the density of CO2 is given by

Comment ln units of grams per milliliter, the gas density is

1.62 × 10−3 g/mL, which is a very small number. In comparison,
the density of water is 1.0 g/mL and that of gold is 19.3 g/cm3.
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.
Example 5.9
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 5.9
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

The molar masses of chlorine (35.45 g) and oxygen (16.00 g).

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.
5.5 Gas Stoichiometry

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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:

The nitrogen gas produced quickly

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

Calculate the volume of N2 generated

at 80°C and 823 mmHg by the
An air bag can
decomposition of 60.0 g of NaN3.
protect the driver in
an automobile
collision.
Example 5.12
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:
Example 5.13
Aqueous lithium hydroxide solution is used to purify air in
spacecrafts and submarines because it absorbs carbon dioxide,
which is an end product of metabolism, according to the
equation

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?

At constant T and V,
Example 5.13
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

From the chemical equation we see that

1 mol CO2 ≏ 1 mol Li2CO3

so the amount of Li2CO3 formed is also 73 moles.
Example 5.13
Then, with the molar mass of Li2CO3 (73.89 g), we calculate its
mass:
5.6 Dalton’s Law of Partial Pressures
V and T are constant

P1 P2 Ptotal = P1 + P2
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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 nA + nB

PA = XA PT PB = XB PT

ni
Pi = Xi PT mole fraction (Xi ) =
nT
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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.

The partial pressure of Ne (PNe) is equal to the product of its

mole fraction (XNe) and the total pressure (PT)
Example 5.14
Using Equation (5.13), we calculate the mole fraction of Ne as
follows:

Therefore,
Example 5.14
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)

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PT = PO2 + PH2 O
Vapor of Water and Temperature

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Example 5.15
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 5.15
Therefore,

From the ideal gas equation we write

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

mass of O2, respectively.
Rearranging the equation we obtain
 Chemistry in Action:
Scuba Diving and the Gas Laws
Depth (ft) Pressure
(atm)
0 1

33 2

66 3

P V

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 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
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 Kinetic theory of gases and …
• Compressibility of Gases
• Boyle’s Law
P a collision rate with wall
Collision rate a number density
Number density a 1/V
P a 1/V

• Charles’s Law
P a collision rate with wall
Collision rate a average kinetic energy of gas molecules
Average kinetic energy a T
PaT
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 Kinetic theory of gases and …
• Avogadro’s Law
P a collision rate with wall
Collision rate a number density
Number density a n
Pan

• 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 = SPi

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Apparatus for Studying Molecular Speed Distribution

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 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 = M3RT

root-mean square speed, urms p. 207

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 Maxwell-Boltzmann Probability
Distribution equation

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Example 5.16

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

nitrogen molecules in m/s at 25°C.

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 5.16
From Equation (5.16),

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

Example 5.16
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.
Graham’s law of diffusion states that under the same
conditions of temperature and pressure, rates of diffusion for
gases are inversely proportional to the square roots of their
molar masses.


r1 M2
=
r2 M1 NH4Cl

NH3 HCl
17 g/mol 36 g/mol
molecular path 62
Gas effusion is the process by which gas under pressure
escapes from a high-pressure region (left) to a low-pressure
one through a pinhole.


r1 t2 M2
= =
r2 t1 M1

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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. Gas effusion. Gas
molecules move from a
Calculate the molar mass of the high-pressure
unknown gas, and suggest what region (left) to a low-
this gas might be. pressure
one through a pinhole.
Example 5.17
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).
 5.8 Deviations from Ideal Behavior

1 mole of ideal gas

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

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

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Van der Waals equation
nonideal gas

an 2
( P + V2 ) (V – nb) = nRT
}

corrected corrected
pressure volume

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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.

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
Example 5.18
(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 5.18
Finally, substituting these values in the van der Waals equation,
we have

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?