CHEM 1620 Chapter 10

Lecture Presentation
Chapter 10
Gases
© 2017 Pearson Education, Inc.

Gases differ from liquids and solids:
They are compressible.
Pressure, volume, temperature, and amount
are related.

5|2
Gas
• Gases are composed of particles that are
moving around very fast in their
container(s).
• These particles move in straight lines until

they collide with either the container wall or
another particle, and then they bounce off.
• A snapshot of these particles in a gas will

reveal that there is a lot of empty space
in the container.
Gas Pressure
• Pressure is the force
exerted per unit area by
gas molecules as they
strike the surfaces
around them.
• Just as a ball exerts a

force when it bounces
against a wall, a
gaseous atom or
molecule exerts a force
when it collides with a
surface.
Pressure: The Result of Molecular Collision
• Gas pressure is a result of the constant

movement of the gas molecules and their
collisions with the surfaces around them.
• The pressure of a gas depends on several

factors:
– Number of gas particles in a given volume
– Volume of the container
– Average speed of the gas particles

Gas Pressure
• The total pressure exerted by a gas depends
on several factors, including the
concentration of gas molecules in the
sample.
– The higher the concentration, the greater the
pressure.
• As volume increases, concentration of gas
molecules decreases (number of molecules
does not change, but since the volume
increases, the concentration goes down).
– This, in turn, results in fewer molecular
collisions, which results in lower pressure.
Atmospheric Pressure Effects
• Variation in pressure in Earth’s atmosphere creates wind and
pressure.
– The H on this map indicates a region of high pressure, usually
associated with clear weather.
– The L indicates a region of low pressure, usually associated with
unstable weather.
• The number of gas particles in a given volume decreases with
increasing altitude.
– Pressure decreases with increasing altitude.

Gas Pressure
• Pressure exerted by a gas is

dependent on the number of
gas particles in a given
volume.
• The fewer gas particles, the
lower the force per unit area
and the lower the pressure.
– A low density of gas particles
results in low pressure. A high
density of gas particles results
in high pressure.

Pressure Imbalance in the Ear
• If there is a difference
in pressure across the
eardrum membrane,
the membrane will be
pushed out—what we
commonly call a
“popped eardrum.”

The Manometer
• The pressure of a gas trapped in a container can
be measured with an instrument called a
manometer.
• Manometers are U-shaped tubes partially filled with
a liquid that are connected to the gas sample on
one side and open to the air on
the other.
• A competition is established between the pressures
of the atmosphere and the gas.
• The difference in the liquid levels is a measure
of the difference in pressure between the gas and
the atmosphere.
The Manometer
For this sample, the gas pressure is greater than the

atmospheric pressure; the mercury level on the left side of
the tube is higher than the level on the right.

Blood Pressure
• Blood pressure is the force within arteries that
drives the circulation of blood throughout the body.
• Blood pressure is measured with an instrument
called a sphygmomanometer—an inflatable cuff
equipped with a pressure gauge and a
stethoscope.

Blood Pressure

Empirical Gas Laws
All gases behave quite simply with respect
to temperature, pressure, volume, and molar
amount. By holding two of these physical
properties constant, it becomes possible to
show a simple relationship between the
other two properties.
The studies leading to the empirical gas

laws occurred from the mid-17th century to
the mid-19th century.
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The Simple Gas Laws
• There are four basic properties of a gas:
pressure (P), volume (V), temperature (T),
and amount in moles (n).
– These properties are interrelated—when one

changes, it affects the others.
– The simple gas laws describe the relationships
between pairs of these properties.

Boyle’s Law: Robert Boyle (1627–1691)
• Robert Boyle and Robert
Hooke used a J-tube to
measure the volume of a
sample of gas at different
pressures.
• They trapped a sample of
air in the J-tube and added
mercury to increase the
pressure on the gas.
• They observed an inverse relationship between

volume and pressure.
• Hence, an increase in one causes a decrease in the
other.
Boyle’s Law

Boyle’s Law
• The pressure of a gas is inversely proportional to

its volume.
– Constant T and amount of gas.
– Graph P vs. V is a curve.
– Graph P vs. 1/V is a straight line.
• As P increases, V decreases by the same factor.
• P × V = constant
• P1 × V1 = P2 × V2

Molecular Interpretation of Boyle’s Law
As the volume of a gas sample decreases, gas molecules

collide with surrounding surfaces more frequently, resulting
in greater pressure.
Boyle’s Law and Diving
• For every 10 m of depth, a diver experiences
approximately one additional atmosphere of
pressure due to the weight of the
surrounding water.
• At 20 m, for example,
the diver experiences
approximately 3 atm
of pressure.

Boyle’s Law and Diving
• If a diver holds his or her breath and rises

to the surface quickly, the outside pressure
drops to 1 atm.
– According to Boyle’s law, what should happen
to the volume of air in the lungs?
• Because the pressure is decreasing by a
factor of 3, the volume will expand by a
factor of 3, causing damage to internal
organs.
Always exhale when rising!
A volume of oxygen gas occupies 38.7
mL at 751 mmHg and 21°C. What is
the volume if the pressure changes to
359 mmHg while the temperature
remains constant?
Vi = 38.7 mL Vf = ?
Pi = 751 mmHg Pf = 359 mmHg
Ti = 21°C Tf = 21°C
PiVi
Vf 
Pf
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Vi = 38.7 mL Vf = ?
Ti = 21°C Tf = 21°C
PiVi
Vf 
Pf
(38.7 mL)(751 mmHg)

Vf 
(359 mmHg)
= 81.0 mL
(3 significant figures)

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Charles’s Law: Volume and Temperature
• The volume of a fixed amount of gas at a
constant pressure increases linearly with
increasing temperature in kelvins:
– The volume of a gas increases with increasing
temperature.
• Kelvin T = Celsius T + 273
• V = constant × T
(if T is measured in kelvins)

Charles’s Law
If the lines are

extrapolated back to
a volume of “0,” they
all show the same
temperature,
−273.15 °C = 0 K,
called absolute
zero.
The extrapolated lines cannot be measured experimentally

because all gases condense into liquids before –273.15 °C is
reached.
Charles’s Law—A Molecular View
If we move a balloon from an ice water bath to a boiling water

bath, its volume expands as the gas particles within the
balloon move faster (due to the increased temperature) and
collectively occupy more space.
Charles’s Law—A Molecular View
• When the temperature of a gas sample

increases, the gas particles move faster.
– Collisions with the walls are more frequent.
– The force exerted with each collision is greater.
• The only way for the pressure (the force per
unit area) to remain constant is for the gas to
occupy a larger volume so that collisions
become less frequent and occur over a
larger area.

You prepared carbon dioxide by adding
HCl(aq) to marble chips, CaCO3.
According to your calculations, you
should obtain 79.4 mL of CO2 at 0°C
and 760 mmHg. How many milliliters of
gas would you obtain at 27°C?
Vi = 79.4 mL Vf = ?
Ti = 0°C = 273 K Tf = 27°C = 300. K
T fVi
Vf 
Ti
5 | 28
Vi = 79.4 mL Vf = ?
Ti = 0°C = 273 K Tf = 27°C = 300. K
T fVi
Vf 
Ti
(300. K)(79.4 mL)
Vf 
(273 K)
= 87.3 mL

5 | 29
Combined Gas Law
The volume of a sample of gas at constant
pressure is inversely proportional to the
pressure and directly proportional to the
absolute temperature.
The mathematical relationship: V  T

P
PV
In equation form:  constant
T
PiVi PfVf

Ti Tf
5 | 30
Divers working from a North Sea
drilling platform experience pressure of
5.0 × 101 atm at a depth of 5.0 × 102 m.
If a balloon is inflated to a volume of
5.0 L (the volume of the lung) at that
depth at a water temperature of 4°C,
what would the volume of the balloon
be on the surface (1.0 atm pressure) at
a temperature of 11°C?
Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K
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Vi = 5.0 L Vf = ?
Pi = 5.0 × 101 atm Pf = 1.0 atm
Ti = 4°C = 277 K Tf = 11°C = 284 K
T f PiVi
Vf 
Ti Pf
(284 K)(5.0  10 atm)(5.0 L)
1
Vf 
(277 K)(1.0 atm)
= 2.6  102 L

5 | 32
Avogadro’s Law: Volume and Amount
(Moles)
• Volume is directly proportional to the number
of gas molecules.
– V = constant × n
– Constant P and T
– More gas molecules = larger volume
• Count the number of gas molecules by
moles.
• Equal volumes of gases contain equal
numbers of molecules.
– The gas doesn’t matter.

Avogadro’s Law
When the amount of

gas in a sample
increases at constant
temperature and
pressure, its volume
increases in direct
proportion because
the greater number
of gas particles fill
more space.
The volume of a gas sample increases linearly with the

number of moles of gas in the sample.
Ideal Gas Law
• The relationships that we have discussed so
far can be combined into a single law that
encompasses all of them.

Ideal Gas Law
· By combining the gas laws, we can write a general
equation.
· R is called the gas constant.
· The value of R depends on the units of P and V.
– We will use and convert P to atm and V to liters.
· The other gas laws are found in the ideal gas law if
two variables are kept constant.
· The ideal gas law allows us to find one of the
variables if we know the other three.

Ideal Gas Law

Standard Conditions
• Because the volume of a gas varies with

pressure and temperature, chemists have
agreed on a set of conditions to report our
measurements so that comparison is easy.
– We call these standard conditions.
– STP
• Standard pressure = 1 atm
• Standard temperature = 273 K = 0 °C

Molar Volume
• The volume occupied by one mole of a
substance is its molar volume at STP
(T =273 K or 0 °C and P = 1atm).

Molar Volume at STP
• Solving the ideal gas equation for the volume
of 1 mol of gas at STP gives 22.4 L.
– 6.022 × 1023 molecules of gas
– Notice that the gas is immaterial.
• We call the volume of 1 mole of gas at STP
the molar volume.
– It is important to recognize that one mole
measurements of different gases have different
masses, even though they have the same
volume.

Molar Volume at STP

You put varying amounts of a gas into a
given container at a given temperature. Use
the ideal gas law to show that the amount
(moles) of gas is proportional to the pressure
at constant temperature and volume.
PV  nRT
 V 
n  P 
 RT 
V
where is constant.
RT

5 | 42
A 50.0-L cylinder of nitrogen, N2, has a pressure
of 17.1 atm at 23°C. What is the mass of
nitrogen in the cylinder?
V = 50.0 L PV
P = 17.1 atm n
RT
T = 23°C = 296 K
(17.1 atm)(50.0 L)
n
 L  atm 
 0.08206 (296 K)
 mol  K 
28.02 g mass = 986 g

mass  35.20 mol (3 significant figures)
mol
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Density of a Gas at STP
• Density is the ratio of mass to volume.

• Density of a gas is generally given in g/L.
• The mass of 1 mole = molar mass.
• The volume of 1 mole at STP = 22.4 L.

Density of a Gas at STP
• For example, the densities of helium and
nitrogen gas at STP are as follows:

Gas Density
• Density is directly proportional to molar mass.

Molar Mass of a Gas
• One of the methods chemists use to

determine the molar mass of an unknown
substance is to heat a weighed sample
until it becomes a gas; measure the
temperature, pressure, and volume; and
then use the ideal gas law.

What is the density of methane gas (natural
gas), CH4, at 125°C and 3.50 atm?
Mm = 16.04 g/mol MmP

d
P = 3.50 atm RT
T = 125°C = 398 K
g
(16.04 )(3.50 atm) g
mol d  1.72
d L
 L  atm 
 0.08206 (398 K) (3 significant figures)
 mol  K 

5 | 48
A 500.0-mL flask containing a sample
of octane (a component of gasoline) is
placed in a boiling water bath in
Denver, where the atmospheric
pressure is 634 mmHg and water boils
at 95.0°C. The mass of the vapor
required to fill the flask is 1.57 g. What
is the molar mass of octane? (Note:
The empirical formula of octane is
C4H9.) What is the molecular formula of
octane?

5 | 49
d = 1.57 g/0.5000 L dRT
= 3.140 g/L Mm 
P
P = 634 mmHg
= 0.8342 atm
T = 95.0°C = 368 K
 g  L  atm 
 3.140  0.08206  368 K 
 L  mol  K 
Mm 
(0.8342 atm)
g
M m  114
mol

5 | 50
Molar mass = 114 g/mol
Empirical formula: C4H9
Empirical formula molar mass = 57 g/mol
g
114
n mol  2
g
57
mol
Molecular formula: C8H18

5 | 51
Concept Check 5.3
Three 3.0-L fl asks, each at a pressure of 878 mmHg,
are in a room. The flasks contain He, Ar, and Xe,
respectively.
a. Which of the flasks contains the most atoms of
gas?
b. Which of the flasks has the greatest density of gas?
c. If the He flask were heated and the Ar flask
cooled, which of the three flasks would be at the
highest pressure?
d. Say the temperature of the He was lowered
while that of the Xe was raised. Which of the three
flasks would have the greatest number of moles of
gas?
5 | 52
Assume the flasks are closed.
a. All flasks contain the same number of

atoms.
b. The gas with the highest molar mass, Xe,
has the greatest density.
c. The flask at the highest temperature (the
one containing He) has the highest
pressure.
d. The number of atoms is unchanged.
5 | 53
Stoichiometry and Gas Volumes
Use the ideal gas law to find moles from a
given volume, pressure, and temperature,
and vice versa.

5 | 54
When a 2.0-L bottle of concentrated
HCl was spilled, 1.2 kg of CaCO3 was
required to neutralize the spill. What
volume of CO2 was released by the
neutralization at 735 mmHg and 20.°C?

5 | 55
First, write the balanced chemical equation:
CaCO3(s) + 2HCl(aq) 
CaCl2(aq) + H2O(l) + CO2(g)
Second, calculate the moles of CO2 produced:
Molar mass of CaCO3 = 100.09 g/mol
1mol CaCO3 1mol CO2

1.2  10 g CaCO3 3
100.09 g CaCO3 1mol CaCO3
Moles of CO2 produced = 11.99 mol

5 | 56
nRT
n = 11.99 mol V 
P = 735 mmHg P
= 0.967 atm
T = 20°C = 293 K
 L  atm 
11.99 mol   0.08206 (293 K)
 mol  K 
V
(0.967 atm)
= 2.98 × 102 L

5 | 57
Mixtures of Gases
• Many gas samples

are not pure but are
mixtures of gases.
• Dry air, for example,
is a mixture
containing nitrogen,
oxygen, argon,
carbon dioxide, and a
few other gases in
trace amounts.

Mixtures of Gases
• Therefore, in certain applications, the

mixture can be thought of as one gas.
– Even though air is a mixture, we can measure

the pressure, volume, and temperature of air
as if it were a pure substance.
– We can calculate the total moles of molecules

in an air sample, knowing P, V, and T, even
though they are different molecules.

Partial Pressure
• The pressure of a single gas in a mixture of
gases is called its partial pressure.
• We can calculate the partial pressure of a gas if
– we know what fraction of the mixture it composes and
the total pressure, or
– we know the number of moles of the gas in a
container of known volume and temperature.
• The sum of the partial pressures of all the gases
in the mixture equals the total pressure:
– Dalton’s law of partial pressures
– Gases behave independently.

Partial Pressure
• The pressure due to any individual

component in a gas mixture is its partial
pressure (Pn).
• We can calculate partial pressure from the
ideal gas law by assuming that each gas
component acts independently.

Dalton’s Law of Partial Pressures
• For a multicomponent gas mixture, we calculate

the partial pressure of each component from the
ideal gas law and the number of moles of that
component (nn) as follows:
• The sum of the partial pressures of the

components in a gas mixture equals the total
pressure:

Dalton’s Law of Partial Pressures
P total is the total pressure and Pa, Pb, Pc, . . .

are the partial pressures of the components.
This relationship is known as Dalton’s law of
partial pressures.

Mole Fraction
• The ratio of the partial pressure a single gas
contributes and total pressure is equal to the
mole fraction.
• The number of moles of a component in a

mixture divided by the total number of moles in
the mixture is the mole fraction.

Mole Fraction
• The partial pressure of a component in a gaseous
mixture is its mole fraction multiplied by the total
pressure.
• For gases, the mole fraction of a component is
equivalent to its percent by volume divided
by 100%.
– Nitrogen has a 78% composition of air; find its partial
pressure.

Deep-Sea Diving and Partial Pressures
When a diver breathes compressed air, the abnormally high

partial pressure of oxygen in the lungs leads to an elevated
concentration of oxygen in body tissues.

A 100.0-mL sample of air exhaled from
the lungs is analyzed and found to
contain 0.0830 g N2, 0.0194 g O2,
0.00640 g CO2, and 0.00441 g water
vapor at 35°C. What is the partial
pressure of each component and the
total pressure of the sample?

5 | 67
 1 mol N 2  L  atm 
 0.0830 g N 2  0.08206  308 K 
 28.01 g N 2  mol  K 
PN2   0.749 atm
 1L 
 100.0 mL   3 

 10 mL 
 1 mol O 2  L  atm 
 0.0194 g O 2  0.08206  308 K 
 32.00 g O 2  mol  K 
PO2   0.153 atm
 1L 
 100.0 mL   3 

 10 mL 
 1 mol CO 2  L  atm 
 0.00640 g CO 2  0.08206  308 K 
 44.01 g CO 2  mol  K 
PCO2   0.0368 atm
 1L 
 100.0 mL    3 

 10 mL 
 1 mol H 2 O  L  atm 
 0.00441 g H 2 O  0.08206  308 K 
 18.01 g H 2 O  mol  K 
PH2O   0.0619 atm
 
 100.0 mL   13L 
 10 mL 
5 | 68
PN2  0.749 atm
PO2  0.153 atm
PCO2  0.0368 atm
PH2O  0.0619 atm
P  PN2  PO2  PCO2  PH2O
P = 1.00 atm

5 | 69
The partial pressure of air in the alveoli
(the air sacs in the lungs) is as follows:
nitrogen, 570.0 mmHg; oxygen, 103.0
mmHg; carbon dioxide, 40.0 mmHg;
and water vapor, 47.0 mmHg. What is
the mole fraction of each component of
the alveolar air?
PN2  570.0 mmHg
PO2  103.0 mmHg
PCO2  40.0 mmHg
PH2O  47.0 mmHg

5 | 70
P  PN2  PO2  PCO2  PH2O
570.0 mmHg
103.0 mmHg
40.0 mmHg
47.0 mmHg
P = 760.0 mmHg

5 | 71
Mole fraction of N2 Mole fraction of O2
570.0 mmHg 103.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction of CO2 Mole fraction of H2O
40.0 mmHg 47.0 mmHg
 
760.0 mmHg 760.0 mmHg
Mole fraction N2 = 0.7500
Mole fraction O2 = 0.1355
Mole fraction CO2 = 0.0526
Mole fraction O2 = 0.0618

5 | 72
Kinetic Molecular Theory
• The simplest model
for the behavior of
gases is the kinetic
molecular theory.
• In this theory, a gas is
modeled as a
collection of particles
(either molecules or
atoms, depending on
the gas) in constant
motion.

• The particles of the gas (either atoms or

molecules) are constantly moving.
• The attraction between particles is negligible.
• When the moving gas particles hit another gas
particle or the container, they do not stick, but
they bounce off and continue moving in another
direction.
• There is a lot of empty space between the gas
particles compared to the size of the particles.

• The average kinetic energy of the gas particles is
directly proportional to the Kelvin temperature.
– As you raise the temperature of the gas, the
average speed of the particles increases.
• But not all the gas particles are moving at the
same speed!
• The collision of one particle with another (or with
the walls of its container) is completely elastic.
– This means that when two particles collide, they
may exchange energy, but there is no overall loss of
energy.
• Any kinetic energy lost by one particle is completely
gained by the other.

An elastic collision is one in which no kinetic energy is
lost. The collision on the left causes the ball on the right
to swing the same height as the ball on the left had
initially, with essentially no loss of kinetic energy.

5 | 76

The Nature of Pressure
• Because the gas particles are constantly

moving, they strike the sides of the container
with a force.
• The result of many particles in a gas sample
exerting forces on the surfaces around them
is a constant pressure.

Gas Laws Explained—Boyle’s Law
• Boyle’s law states that the volume of a gas

is inversely proportional to the pressure.
– Decreasing the volume forces the molecules
into a smaller space.
• More molecules will collide with the

container at any one instant, increasing the
pressure.

Gas Laws Explained—Charles’s Law
• Charles’s law states that the volume of a gas

is directly proportional to the absolute
temperature.
– According to kinetic molecular theory, when we
increase the temperature of a gas, the average
speed, and thus the average kinetic energy, of
the particles increases.
• The greater volume spreads the collisions
out over a greater surface area, so that the
pressure is unchanged.

Gas Laws Explained—Avogadro’s Law
• Avogadro’s law states that the volume of a

gas is directly proportional to the number of
gas molecules.
• Increasing the number of gas molecules
causes more of them to hit the wall at the
same time.
• To keep the pressure constant, the volume
must then increase.

Gas Laws Explained—Dalton’s Law
• Dalton’s law: The total pressure of a gas
mixture is the sum of the partial pressures.
• According to kinetic molecular theory, the
particles have negligible size, and they do
not interact.
– Particles of different masses have the same
average kinetic energy at a given temperature.
• Because the average kinetic energy is the
same, the total pressure of the collisions is
the same.

Kinetic Molecular Theory and the Ideal
Gas Law
• The kinetic molecular
theory is a quantitative
model that implies
PV = nRT.
• The pressure on a wall
of a container occupied
by particles in constant
motion is the total force
on the wall (due to the
collisions) divided by
the area of the wall.

Temperature and Molecular Velocities
• Average kinetic energy of the gas molecules
depends on the average mass and velocity.
• Gases in the same container have the same

temperature; therefore, they have the same
average kinetic energy.
• If they have different masses, the only way for
them to have the same kinetic energy is to have
different average velocities.
– Lighter particles will have a faster average velocity than
more massive particles.

Molecular Speeds
According to kinetic theory, molecular
speeds vary over a wide range of values.
The distribution depends on temperature, so
it increases as the temperature increases.
Root-Mean Square (rms) Molecular

Speed, u
A type of average molecular speed, equal to
the speed of a molecule that has the
3RT
average molecular kinetic energy u
Mm
5 | 85
When using the equation
R = 8.3145 J/(mol · K).
T must be in Kelvins
Mm must be in kg/mol

5 | 86
What is the rms speed of carbon
dioxide molecules in a container at
23°C?
T = 23°C = 296 K 3RT

CO2 molar mass =
u rms 
Mm
0.04401 kg/mol

5 | 87
Recall  kg  m 2 
 
kg  m 2 2
J 3 8.3145 s  296 K 
s2 mol  K 
 
 
u rms 
 kg 
 0.04401 
 mol 
2
m
urms  1.68  105 2
s
m
urms  4.10  10
2
s
5 | 88
Molecular Speed versus Molar Mass
• To have the same average kinetic energy,
heavier molecules must have a slower
average speed.

Temperature and Molecular Velocities
• KEavg = ½NAmu2
– NA is Avogadro’s number.
• KEavg = (3/2)RT
– R is the gas constant in energy units, 8.314
J/mol ∙ K.
• 1 J = 1 kg ∙ m2/s2
• Equating and solving we get the following:
– NA ∙ mass = molar mass in kg/mol
As temperature increases, the average velocity increases.

Temperature versus Molecular Speed
• As the temperature of
a gas sample
increases, the velocity
distribution of the
molecules shifts
toward higher
velocity.
– The distribution
function “spreads out,”
resulting in more
molecules with faster
speeds.

Mean Free Path
• Molecules in a gas
travel in straight lines
until they collide with
another molecule or
the container.
• The average distance
a molecule travels
between collisions is
called the mean
free path.
• Mean free path
decreases as the
pressure increases.
Diffusion and Effusion
• The process of a collection of molecules
spreading out from high concentration to low
concentration is called diffusion.
• The process by which a collection of
molecules escapes through a small hole into
a vacuum is called effusion.
– The rates of diffusion and effusion of a gas are
both related to its rms average velocity.
– For gases at the same temperature, this means
that the rate of gas movement is inversely
proportional to the square root of its molar mass.

Diffusion
The process
whereby a gas
spreads out
through another
gas to occupy the
space uniformly.
Below NH3 diffuses
through air. The
indicator paper
tracks its progress.

5 | 94
Effusion
The process by which a gas flows through a
small hole in a container. A pinprick in a
balloon is one example of effusion.

5 | 95
Effusion

Graham’s Law of Effusion
• For two different gases at the same

temperature, the ratio of their rates of
effusion is given by the following equation:

Relative Rate of Effusion
Graham’s Law of Effusion
r1 t 2 M2
 
r2 t1 M1

In Class Problem
Carbon dioxide effuses through a pinhole at a rate of 0.232 ml/min
at 25.0 °C. Another gas effuses at a rate of 0.363 ml/min. What is
the molar mass of the gas?
Rate CO2 M unk.
=
Rate unk.
M CO2
Solving for the molar mass of the unknown gas:

2
æ Rate CO2 ö
M unk. = M CO2 ´ ç ÷
è Rate unk. ø
2
æ ml ö
g ç 0.232
min ÷ g
M unk. = 44.0 ´ç ÷ =18.0 Water!
mol ml mol
ç 0.363 ÷
è min ø
Both hydrogen and helium have been
used as the buoyant gas in blimps. If a
small leak were to occur, which gas
would effuse more rapidly and by what
factor?
1
Rate H 2 2.016 4.002
 
Rate He 1 2.016
4.002
Hydrogen will diffuse more quickly by a factor of 1.4.

5 | 100
Real Gases
• Real gases often do not behave like ideal gases at
high pressure or low temperature.
• Ideal gas laws assume
1. no attractions between gas molecules.
2. gas molecules do not take up space.
• Based on the kinetic molecular theory
• At low temperatures and high pressures these
assumptions are not valid.

Deviations from the Ideal Gas Law
 Real particles have volume.

 Real particles interact via
intermolecular forces.
 At high pressure and low
temperature, these factors
become significant!

The Effect of the Finite Volume of Gas
Particles
• At low pressures, the molar volume of argon
is nearly identical to that of an ideal gas.
• But as the pressure increases, the molar
volume of argon becomes greater than that
of an ideal gas.
– At the higher pressures, the argon atoms
themselves occupy a significant portion of the
gas volume, making the actual volume greater
than that predicted by the ideal gas law.

Real Gas Behavior
Because real molecules take up space, the molar volume of

a real gas is larger than predicted by the ideal gas law at
high pressures.
Modification of the Ideal Gas Equation
• In 1873, Johannes van der Waals (1837–1923)
modified the ideal gas equation to fit the behavior
of real gases at high pressure.
• The molecular volume makes the real volume

larger than the ideal gas law would predict.
• Van der Waals modified the ideal gas equation to

account for the molecular volume.
– b is called a van der Waals constant and is different for
every gas because their molecules are different sizes.

The Effect of Intermolecular Attractions
• At high temperature, the pressures of the

gases are nearly identical to that of an
ideal gas.
• But at lower temperatures, the pressures of
the gases are less than that of an ideal gas.
– At the lower temperatures, the gas atoms spend
more time interacting with each other and less
time colliding with the walls, making the actual
pressure less than that predicted by the ideal
gas law.

The Effect of Intermolecular Attractions
• Van der Waals
modified the ideal gas
equation to account
for the intermolecular
attractions.
– a is another van der
Waals constant and
is different for every
gas because their
molecules have
different strengths of
attraction.

Van der Waals’s Equation
• Combining the equations

to account for molecular
volume and intermolecular
attractions we get the
following equation.
– Used for real gases

Deviations from the Ideal Gas Law
The “VAN DER WAALS’s EQUATION” makes corrections

for the volume of particles and any intermolecular forces that
exist
Measured P Measured V = V(ideal)
æ n2a ö
çP + V 2 ÷´ (V - nb ) =nRT
è ø
vol. correction
intermol. forces
Van der Waals Equation
An equation that is similar to the ideal gas
law, but which includes two constants, a and
b, to account for deviations from ideal
behavior.
The term V becomes (V – nb).

The term P becomes (P + n2a/V2).
Values for a and b are found in tables.
 n 2a 
P  V  nb   nRT
 V 2 
 
5 | 110
Use the van der Waals equation to
calculate the pressure exerted by 2.00
mol CO2 that has a volume of 10.0 L at
25°C. Compare this with value with the
pressure obtained from the ideal gas
law.
n = 2.00 mol For CO2:

V = 10.0 L a = 3.658 L2 atm/mol2
T = 25°C = 298 K b = 0.04286 L/mol

5 | 111
n = 2.00 mol Ideal gas law:
V = 10.0 L nRT
P
T = 25°C = 298 K V
 2.00 mol   0.08206 L  atm (298 K)

 mol  K 
P
10.0 L 
= 4.89 atm

5 | 112
n = 2.00 mol For CO2:
V = 10.0 L a = 3.658 L2 atm/mol2
T = 25°C = 298 K b = 0.04286 L/mol
nRT n2a
P  2
V  nb  V
 L  atm  2 L2  atm 
 2.00 mol   0.08206  298 K   2.00 mol   3.658 2


 mol  K   mol 
P 

10.0 L  2.00 mol 0.04286
L 

 10.0 L  2
 mol 
P  4.933 atm  0.146 atm
Pactual = 4.79 atm

5 | 113
Real Gases
• A plot of PV/RT versus P for 1 mole of a gas
shows the difference between real and
ideal gases.
• It reveals a curve that shows the PV/RT ratio for
a real gas is generally lower than ideal for “low”
pressures—meaning that the most important
factor is the intermolecular attractions.
• It reveals a curve that shows the PV/RT ratio for
a real gas is generally higher than ideal for
“high” pressures—meaning that the most
important factor is the molecular volume.
Real versus Ideal Behavior

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CHEM 1620 Chapter 10

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Lecture Presentation

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• These particles move in straight lines until

• A snapshot of these particles in a gas will

• Just as a ball exerts a

• Gas pressure is a result of the constant

• The pressure of a gas depends on several

© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

• Pressure exerted by a gas is

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For this sample, the gas pressure is greater than the

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© 2017 Pearson Education, Inc.

The studies leading to the empirical gas

– These properties are interrelated—when one

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• They observed an inverse relationship between

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• The pressure of a gas is inversely proportional to

© 2017 Pearson Education, Inc.

As the volume of a gas sample decreases, gas molecules

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• If a diver holds his or her breath and rises

(38.7 mL)(751 mmHg)

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© 2017 Pearson Education, Inc.

If the lines are

The extrapolated lines cannot be measured experimentally

If we move a balloon from an ice water bath to a boiling water

• When the temperature of a gas sample

© 2017 Pearson Education, Inc.

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The mathematical relationship: V  T

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When the amount of

The volume of a gas sample increases linearly with the

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© 2017 Pearson Education, Inc.

© 2017 Pearson Education, Inc.

• Because the volume of a gas varies with

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© 2017 Pearson Education, Inc.

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28.02 g mass = 986 g

• Density is the ratio of mass to volume.

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• One of the methods chemists use to

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Mm = 16.04 g/mol MmP

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Molecular formula: C8H18

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a. All flasks contain the same number of