Chapter 10

Gases
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Characteristic of Gases
Of the three phases of matter
solids, liquids, and gasesgases have
the least order associated with their
particles.
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Characteristic of Gases
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Characteristic of Gases
Gases are compressible and that they
assume the shape and volume of any
container.
Gases are all infinitely soluble in one
another.
Each of these characteristics can be
explained by the distances between the
molecules (or atoms) in a gaseous sample.
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Characteristic of Gases
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Characteristic of Gases
Gases are one of the three states of
matter.
A gas is compressible and will assume
the shape and volume of its
container.
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Characteristic of Gases
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Kinetics Energy in Gas
Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Pressure
One of the important properties of a
sample of gas is its pressure.
Pressure is defined as force per unit
area.
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Pressure
The SI unit for pressure is the pascal (Pa),
the name given to 1 N/m2, although units
of atmosphere (atm) and torr are more
commonly encountered.
Pressure can be measured with a
barometer like the one pictured in Figure
10.2.
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Pressure
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Pressure
The mercury in the inverted tube is pushed
upward by the force of atmospheric pressure
pushing down on the surface of the mercury in
the dish.
The height of the mercury in the tube changes
with changing atmospheric pressure.
Under conditions of standard atmospheric
pressure, the height of the mercury in the tube is
760 mm. (1 atm = 760 mm Hg = 760 torr = 1.01325
x 10
5
Pa)
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Pressure
Gas pressure can also be measured
using a manometer like those shown
in Figure 10.3.
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Pressure
Figure 10. 3. Closed-end manometer (a) and open-
ended manometers (b and c). In (b) gas pressure is
less than atmospheric pressure; in (c) gas pressure
exceeds atmospheric pressure.
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Pressure
The physical condition, or state, of a
gas is defined by four variables:
temperature,
pressure,
volume, and the
number of moles (the amount of the
gas).
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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The Gas Law
Four variables must be specified to define
the physical condition of a gas:
temperature, T;
pressure, P;
volume, V; and
the amount of the gas, usually expressed in
moles, n.
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The Gas Law
The equations that express the
relationships among these variables
are known as the gas laws.
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The Gas Law
Boyle's law states that at constant
temperature the volume of a fixed amount of
gas is inversely proportional to its pressure.
The value of the constant depends on the
other two variablestemperature and moles.
c PV
P
c V
1
.
or
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The Gas Law
PV relationship
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The Gas Law
Charles's law states that at constant
pressure the volume of a fixed amount of
gas is directly proportional to its
absolute temperature.
T
V
c T c V .
or
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The Gas Law
Again, the value of the constant depends
on the other two variables:
pressure and
moles.
Note that the constant in the equation for
Charles's law is not the same constant as
the one in Boyle's law.
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The Gas Law
Avogadro's law states that at constant
pressure and temperature, the volume of a
gas depends on the number of moles.
n c V .
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The Gas Law
The constant depends on the values
of
pressure
temperature
The constant in Avogadro's law is
different from either of the
constants in the other gas laws.
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The Gas Law
Figure 10.11. Gay-Lussac's experimental
observation of combining volumes shown together
with Avogadro's explanation of this phenomenon.
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The Gas Law
Related to Avogadro's law,
Avogadro's hypothesis says that
equal volumes of gas at the same
temperature and pressure contain equal
numbers of molecules.
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The Gas Law
Gas Laws
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Kinetic-Molecular Theory
Molecular Effusion and Diffusion
Real Gases: Deviations from Ideal Behavior
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The Ideal-Gas Equation
The equations for Boyle's law,
Charles's law, and Avogadro's law can
all be combined to give a more
general equation.
PV = nRT
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The Ideal-Gas Equation
We call the constant in this general
expression R, the gas constant.
R is often expressed as 0.08206 L-
atm/mol-K;
it can, however, be expressed in
other units, depending on the units
used for the variables V, T, and P.
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The Ideal-Gas Equation
R = 8.314 (kPa)(m
3
)/(kmol)(K)
R= 0.0831 (MPa)(m
3
)/(kmol)(K)
R= 0.08314 (bar)(m
3
)/(kmol)(K)
R= 10.73 (psia)(ft
3
)/(lb-mol)(R)
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The Ideal-Gas Equation
An ideal gas being a hypothetical gas, its
behavior is described by this equation.
We start by using the ideal-gas equation
to determine the molar volume (volume of 1
mol) of an ideal gas under conditions of
standard temperature and pressure
(STP).
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The Ideal-Gas Equation
The standard pressure is, as always, 1
atm.
The standard temperature is 0C.
Note that this standard temperature
is different from the standard
temperature given in Chapter 5 for
thermodynamics (25C).
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The Ideal-Gas Equation
Rearranging the ideal-gas equation to
solve for V we get
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The Ideal-Gas Equation
Entering the values for n, R, T, and P,
we get the volume of 1.000 mol of
any ideal gas at 0C and 1.000 atm.
V = 22.41 L
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The Ideal-Gas Equation
Although real gases do not behave ideally,
under many conditions the difference
between their behavior and the behavior
predicted by the ideal-gas equation is
small enough to ignore.
This allows us to apply the ideal-gas
equation to most problems involving real
gases.
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The Ideal-Gas Equation
Returning to Boyle's and Charles's
laws, we see that each can be
considered a version of the ideal-gas
equation in which two of the four
variables are fixed.
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The Ideal-Gas Equation
This restatement of Boyle's law
allows us to set the product of V and
P for any two conditions (provided n
and T are constant) equal to each
other.
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The Ideal-Gas Equation
If we know that a particular sample
of gas at constant temperature
occupies 2.5 L at 1.0 atm, we can
predict the volume it will occupy at
5.0 atm.
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The Ideal-Gas Equation
This restatement of Charles's law
lets us set the quotient of any two V
and T values (at constant n and P)
equal to each other.
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The Ideal-Gas Equation
We can use this relationship to solve
gas problems in which only volume and
temperature change.
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The Ideal-Gas Equation
Combining the three gas laws yields a
general equation for solving gas
problems, PV = nRT.
Although the equation strictly holds
only for ideal gases, it is adequate to
solve most gas problems.
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Further Application of
the Ideal-Gas Equation
The ideal-gas equation can be
manipulated to solve a variety of
different types of problems.
In order to determine the density of
a gas, we rearrange the equation to
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Further Application of
the Ideal-Gas Equation
Density of a gas is generally
expressed in g/L.
Multiplication of the left and right
sides of the equation by the molar
mass (M) of the gas gives
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Further Application of
the Ideal-Gas Equation
This allows us to determine the
density of a gas when we know the
molar mass, or vice versa.
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Further Application of
the Ideal-Gas Equation
The ideal-gas equation frequently is
used to interconvert between
volumes and molar amounts in
chemical equations.
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Further Application of
the Ideal-Gas Equation
What volume of carbon dioxide gas is
produced at STP by the
decomposition of 0.150 g CaCO3 via
the equation:
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Further Application of
the Ideal-Gas Equation
Begin by converting the mass of
calcium carbonate to moles.
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Further Application of
the Ideal-Gas Equation
The stoichiometry of the reaction dictates
that the number of moles CaCO
3

decomposed equals the number of moles
CO
2
produced.
Use the ideal-gas equation to convert
moles of CO
2
to a volume.
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Further Application of
the Ideal-Gas Equation
The reaction responsible for inflation
of an automobile air bag is the
decomposition of sodium azide, NaN
3
.
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Further Application of
the Ideal-Gas Equation
Air Bags
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Further Application of
the Ideal-Gas Equation
The ideal-gas equation can be used to
solve a variety of problems involving
gases.
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Gas Mixtures and Partial
Pressures
Dalton's law of partial pressures
states that the total pressure (Pt)
exerted by a mixture of gases is the
sum of the pressures that would be
exerted by each individual gas were
it the only gas present.
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Gas Mixtures and Partial
Pressures
where P1 is the partial pressure of gas 1
(the pressure exerted by gas 1), P2 is the
partial pressure of gas 2, and so on.
Each component of a gaseous mixture
behaves independently of the other
components, and a separate ideal-gas
equation can be written for each
component.
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Gas Mixtures and Partial
Pressures
or for the sum of all components
where n
t
is the total number of moles
in the mixture.
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Gas Mixtures and Partial
Pressures
The total pressure exerted by a
mixture of 3.00 g CO
2
and 1.53 g He
in a 1.25-L vessel at 0 C is:
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Gas Mixtures and Partial
Pressures
The ratio of partial pressure of a
particular component of a gaseous mixture
to the total pressure exerted by the gas
mixture is the mole fraction.
Mole fraction, denoted X, is a measure of
a gas's concentration in a mixture.
It can also be calculated as the ratio of
moles of the component to the total
number of moles in the mixture.
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Gas Mixtures and Partial
Pressures
Knowing the mole fraction of a
component and the total pressure of
a mixture, we can calculate the
partial pressure of the component.
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Gas Mixtures and Partial
Pressures
Dalton's law of partial pressures
states that
each component of a gaseous mixture
exerts a pressure independent of the
other components of the mixture and
that the total pressure exerted by the
mixture is the sum of the partial
pressures for all components.
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Gases
Characteristic of Gases
Pressure
The Gas Law
The Ideal-Gas Equation
Further Application of the Ideal-Gas Equation
Gas Mixtures and Partial Pressures
Real Gases: Deviations from Ideal Behavior
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Real Gases: Deviations
from Ideal Behavior
Although the differences in behavior
between real and ideal gases are
usually small, it is worthwhile to
consider the small differences.
For one mole of an ideal gas
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Real Gases: Deviations
from Ideal Behavior
at all values of P. Figure 10.22 shows
the graph of PV/RT for one mole of
gas as a function of pressure for
several gases, all at around 300 K.
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Real Gases: Deviations
from Ideal Behavior
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Real Gases: Deviations
from Ideal Behavior
Note how the deviation from ideal
behavior is significant, especially at
very high pressures.
Low pressure is one of the conditions
under which real gases tend to
behave ideally.
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Real Gases: Deviations
from Ideal Behavior
Figure 10.23 shows the graph of
PV/RT for nitrogen gas at three
different temperatures.
This figure illustrates the other
condition, high temperature, under
which real gases tend to behave
ideally.
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Real Gases: Deviations
from Ideal Behavior
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Real Gases: Deviations
from Ideal Behavior
Deviations from ideal behavior result from
the error in assuming that
(1) gas molecules occupy no volume, and
(2) gas molecules exhibit no intermolecular
forces.
At very low pressures and very high
temperatures, these assumptions are
reasonably valid.
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Real Gases: Deviations
from Ideal Behavior
Calculations for problems involving real
gases are done with a modified gas
equation known as the van der Waals
equation.
2
2
V
a n
nb V
nRT
P

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Real Gases: Deviations
from Ideal Behavior
The terms a and b are the van der Waals
constants that are unique to a particular
gas.
The values of van der Waals constants
for a selection of gases are given in
Table 10.3.
2
2
V
a n
nb V
nRT
P

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Real Gases: Deviations
from Ideal Behavior
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Thank You
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