Gas Laws
Boyle's
Law
Torricelli's experiment did more than just show that air
has weight; it also provided a way of creating a vacuum
because the space above the column of mercury at the top of a barometer is almost
completely empty. (It is free of air or other gases except a
negligible amount of mercury vapor.) Torricelli's work with a
vacuum soon caught the eye of the British scientist Robert
Boyle.
Boyle's most famous experiments with gases dealt with what
he called the "spring of air." These experiments
were based on the observation that gases are elastic.
(They return to their original size and shape after being
stretched or squeezed.) Boyle studied the elasticity of gases
in a J-tube similar to the apparatus shown in the figure
below. By adding mercury to the open end of the tube, he
trapped a small volume of air in the sealed end.
Boyle studied what happened to the volume
of the gas in the sealed end of the tube as he added mercury
to the open end.
Boyle noticed that the product of the pressure times the
volume for any measurement in this table was equal to the
product of the pressure times the volume for any other
measurement, within experimental error.
P1V1
= P2V2
This expression, or its equivalent,

is now known as Boyle's Law.

Amonton's Law
Toward the end of the 1600s, the French physicist
Guillaume Amontons built a thermometer based on the fact that
the pressure of a gas is directly proportional to its
temperature. The relationship between the pressure and the
temperature of a gas is therefore known as Amontons'
law.
P
T
Amontons' law explains why car manufacturers recommend
adjusting the pressure of your tires before you start on a
trip. The flexing of the tire as you drive inevitably raises
the temperature of the air in the tire. When this happens,
the pressure of the gas inside the tires increases.
Amontons' law can be demonstrated with the apparatus shown
in the figure below, which consists of a pressure gauge
connected to a metal sphere of constant volume, which is
immersed in solutions that have different temperatures.
 |
The apparatus for demonstrating Amonton's law
consists of . |
The following data were obtained with this
apparatus.

In 1779 Joseph Lambert proposed a definition for absolute
zero on the temperature scale that was based on the
straight-line relationship between the temperature and
pressure of a gas shown in the figure above.
He defined absolute zero as the
temperature at which the pressure of a gas becomes zero when
a plot of pressure versus temperature for a gas is
extrapolated. The pressure of a gas approaches zero when the
temperature is about -270°C. When more accurate measurements
are made, the pressure of a gas extrapolates to zero when the
temperature is -273.15°C. Absolute zero on the Celsius scale
is therefore -273.15°C.
The relationship between temperature and pressure can be
greatly simplified by converting the temperatures from the
Celsius to the Kelvin scale.
TK = ToC + 273.15
When this is done, a plot of the temperature versus the
pressure of a gas gives a straight line that passes through
the origin. Any two points along the line therefore fit the
following equation.
It is important to remember that this equation is only
valid if the temperatures are converted from the Celsius to
the Kelvin scale before calculations are done.

Charles' Law
On 5 June 1783, Joseph and Etienne Montgolfier used a fire
to inflate a spherical balloon about 30 feet in diameter that
traveled about a mile and one-half before it came back to
earth. News of this remarkable achievement spread throughout
France, and Jacques-Alexandre-Cesar Charles immediately tried
to duplicate this performance. As a result of his work with
balloons, Charles noticed that the volume of a gas is
directly proportional to its temperature.
V
T
This relationship between the temperature and volume of a
gas, which became known as Charles' law,
provides an explanation of how hot-air balloons work. Ever
since the third century B.C., it has been known that an
object floats when it weighs less than the fluid it
displaces. If a gas expands when heated, then a given weight
of hot air occupies a larger volume than the same weight of
cold air. Hot air is therefore less dense than cold air. Once
the air in a balloon gets hot enough, the net weight of the
balloon plus this hot air is less than the weight of an
equivalent volume of cold air, and the balloon starts to
rise. When the gas in the balloon is allowed to cool, the
balloon returns to the ground.
Charles' law can be demonstrated with the apparatus shown
in the figure below. A 30-mL syringe and a thermometer are
inserted through a rubber stopper into a flask that has been
cooled to 0ºC. The ice bath is then removed and the flask is
immersed in a warm-water bath. The gas in the flask expands
as it warms, slowly pushing the piston out of the syringe.
The total volume of the gas in the system is equal to the
volume of the flask plus the volume of the syringe.
The figure below shows a plot of the
typical data obtained from this experiment.
This graph provides us with another way of
defining absolute zero on the temperature scale. Absolute
zero is the temperature at which the volume of a gas
becomes zero when the a plot of the volume versus temperature
for a gas are extrapolated. As expected, the value of
absolute zero obtained by extrapolating the data is
essentially the same as the value obtained from the graph of
pressure versus temperature in the preceding section.
Absolute zero can therefore be more accurately defined as the
temperature at which the pressure and the volume of a gas
extrapolate to zero.
A plot of the volume versus the temperature of a gas (when
the temperatures obtained are converted from Celsius to the
Kelvin scale) becomes a straight line that passes through the
origin. Any two points along this line can therefore be used
to construct the following equation, which is known as Charles'
law.
Before using this equation, it is important to remember
that temperatures must be converted from ºC to K.

Gay-Lussac's Law
Joseph Louis Gay-Lussac (1778-1850) began his career in
1801 by very carefully showing the validity of Charles' law
for a number of different gases. Gay-Lussac's most important
contributions to the study of gases, however, were
experiments he performed on the ratio of the volumes of gases
involved in a chemical reaction.
Gay-Lussac studied the volume of gases consumed or
produced in a chemical reaction because he was interested in
the reaction between hydrogen and oxygen to form water. He
argued that measurements of the weights of hydrogen
and oxygen consumed in this reaction could be influenced by
the moisture present in the reaction flask, but this moisture
would not affect the volumes of hydrogen and oxygen
gases consumed in the reaction.
Much to his surprise, Gay-Lussac found that 199.89 parts
by volume of hydrogen were consumed for every 100 parts by
volume of oxygen. Thus, hydrogen and oxygen seemed to combine
in a simple 2:1 ratio by volume.
hydrogen |
+ |
oxygen |
 |
water |
2 volumes |
|
1 volume |
|
|
Gay-Lussac found similar whole-number
ratios for the reaction between other pairs of gases. The
compound we now know as hydrogen chloride (HCl) combined with
ammonia (NH3) in a simple 1:1 ratio by volume:
hydrogen chloride |
+ |
ammonia |
 |
ammonium chloride |
1 volume |
|
1 volume |
|
|
Carbon monoxide combined with oxygen in a
2:1 ratio by volume:
carbon monoxide |
+ |
oxygen |
 |
carbon dioxide |
2 volumes |
|
1 volume |
|
|
Gay-Lussac obtained similar results when he
analyzed the volumes of gases given off when compounds
decomposed. Ammonia, for example, decomposed to give three
times as much hydrogen by volume as nitrogen:
ammonia |
 |
nitrogen |
+ |
hydrogen |
|
|
1 volume |
|
3 volumes |
On 31 December 1808, Gay-Lussac announced
his law of combining volumes to a meeting of
the Societ Philomatique in Paris. At that time, he summarized
the law as follows: Gases combine among themselves in very
simple proportions. Today, Gay-Lussac's law is stated as
follows: The ratio of the volumes of gases consumed
or produced in a chemical reaction is equal to the ratio of
simple whole numbers.

Avogadro's
Hypothesis
Gay-Lussac's law of combining volumes was announced only a
few years after John Dalton proposed his atomic theory. The
link between these two ideas was first recognized by the
Italian physicist Amadeo Avogadro three years later, in 1811.
Avogadro argued that Gay-Lussac's law of combining volumes
could be explained by assuming that equal volumes of
different gases collected under similar conditions contain
the same number of particles.
HCl and NH3 therefore combine in a 1:1 ratio by
volume because one molecule of HCl is consumed for every
molecule of NH3 in this reaction and equal volumes
of these gases contain the same number of molecules.
NH3(g) |
+ |
HCl(g) |
 |
NH4Cl(s) |
Anyone who has blown up a balloon should
accept the notion that the volume of a gas is proportional to
the number of particles in the gas.
V
n
The more air you add to a balloon, the bigger it gets.
Unfortunately this example does not test Avogadro's
hypothesis that equal volumes of different gases
contain the same number of particles. The best way to probe
the validity of this hypothesis is to measure the number of
molecules in a given volume of different gases, which can be
done with the apparatus shown in the figure below.
A small hole is drilled through the plunger
of a 50-mL plastic syringe. The plunger is then pushed into
the syringe and the syringe is sealed with a syringe cap. The
plunger is then pulled out of the syringe until the volume
reads 50 mL and a nail is inserted through the hole in the
plunger so that the plunger is not sucked back into the
barrel of the syringe. The "empty" syringe is then
weighed, the syringe is filled with 50 mL of a gas, and the
syringe is reweighed. The difference between these
measurements is the mass of 50 mL of the gas.
The results of experiments with six gases are given in the
table below.
Experimental Data for the Mass of 50-mL
Samples of Different Gases
Compound |
|
Mass of
50 mL of Gas (g) |
|
Molecular
Weight of Gas |
|
Number of
Gas Molecules |
H2 |
|
0.005 |
|
2.02 |
|
1 x 1021 |
N2 |
|
0.055 |
|
28.01 |
|
1.2 x 1021 |
O2 |
|
0.061 |
|
32.00 |
|
1.1 x 1021 |
CO2 |
|
0.088 |
|
44.01 |
|
1.2 x 1021 |
C4H10 |
|
0.111 |
|
58.12 |
|
1.15 x 1021 |
CCl2F2 |
|
0.228 |
|
120.91 |
|
1.14 x 1021 |
The number of molecules in a 50-mL sample
of any one of these gases can be calculated from the mass of
the sample, the molecular weight of the gas, and the number
of molecules in a mole. Consider the following calculation of
the number of H2 molecules in 50 mL of hydrogen
gas, for example.

The last column in the table above summarizes the results
obtained when this calculation is repeated for each gas. The
number of significant figures in the answer changes from one
calculation to the next. But the number of molecules in each
sample is the same, within experimental error. We therefore
conclude that equal volumes of different gases collected
under the same conditions of temperature and pressure do in
fact contain the same number of particles.

The Ideal Gas
Equation
Gases can described in terms of four variables: pressure (P),
volume (V), temperature (T), and the amount
of gas (n). There are five relationships between
pairs of these variables in which two of the variables were
allowed to cahnge while the other two were held constant.
|
|
P |
 |
n |
|
(T and V constant) |
|
Boyle's law: |
|
P |
 |
1/V |
|
(T and n constant) |
|
Amontons' law: |
|
P |
 |
T |
|
(V and n constant) |
|
Charles' law: |
|
V |
 |
T |
|
(P and n constant) |
|
Avogadro's hypothesis: |
|
V |
 |
n |
|
(P and T constant) |
|
Each of these relationships is a special
case of a more general relationship known as the ideal
gas equation.
PV = nRT
In this equation, R is a proportionality constant
known as the ideal gas constant and T is
the absolute temperature. The value of R depends on
the units used to express the four variables P, V,
n, and T. By convention, most chemists use
the following set of units.
P: atmospheres |
T: kelvin |
V: liters |
n: moles |

Ideal Gas
Calculations
The ideal gas equation can be used to
predict the value of any one of the variables that describe a
gas from known values of the other three.
Practice Problem 1:
Many gases are available for use inthe
laboratory in compressed gas cylinders, in which they are
stored at high pressures. Let's calculate the mass of O2
that can be stored at 21ºC and 170 atm in a cylinder with a
volume of 60.0 L.
Click here to
check your answer to practice problem 1
The key to solving ideal gas problems
often involves recognizing what is known and deciding how to
use this information.
Practice Problem 2:
Let's calculate the mass of the air in a hot-air balloon
that has a volume of 4.00 x 105 liters when the
temperature of the gas is 30ºC and the presure is 748 mmHg.
Let's assume the average molar mass of air is 29.0 grams per
mole.
Click here to
check your answer to practice problem 2
The ideal gas equation can be applied
to problems that don't seem to ask for one of the variables
in this equation.
Practice Problem 3:
Let's calculate the molecular weight of butane if 0.5813
gram of this gas fills a 250.0-mL flask at a temperature of
24.4ºC and a pressure of 742.6 mmHg.
Click here to
check your answer to practice problem 3
The ideal gas equation can even be used
to solve problems that don't seem to contain enough
information.
Practice Problem 4:
Let's calculate the density in grams per liter of O2
gas at 0ºC and 1.00 atm.
Click here to
check your answer to practice problem 4
Gas law problems often ask you to predict what happens
when one or more changes are made in the variables that
describe the gas. There are two ways of working these
problems. A powerful approach is based on the fact that the
ideal gas constant is in fact a constant.
We start by solving the ideal gas equation for the ideal
gas constant.

We then note that the ratio of PV/nT at
any time must be equal to this ratio at any other time.

We then substitute the known values of pressure,
temperature, volume, and amount of gas into this equation and
solve for the appropriate unknown. This approach has two
advantages. First, only one equation has to be remembered.
Second, it can be used to handle problems in which more than
one variable changes at a time.

Dalton's Law
of Partial Pressures
The CRC Handbook of Chemistry and Physics
describes the atmosphere as 78.084% N2, 20.946% O2,
0.934% Ar, and 0.033% CO2 by volume when the water
vapor has been removed. What image does this description
evoke in your mind? Do you believe that only 20.463% of the
room in which you are sitting contains O2? Or do
you believe that the atmosphere in your room is a more or
less homogeneous mixture of these gases?
Gases expand to fill their containers. The volume of O2
in your room is therefore the same as the volume of N2.
(Both gases expand to fill the room.) When we describe the
atmosphere as 20.946% O2 by volume, we mean that
the volume of the atmosphere would shrink by 20.946% if the O2
is removed.
What about the pressure of the different gases in your
room? Is the pressure of the O2 in the atmosphere
the same as the pressure of the N2? We can answer
this question by rearranging the ideal gas equation as
follows.

According to this equation, the pressure of a gas is
proportional to the number of moles of gas, if the
temperature and volume are held constant. Because the
temperature and volume of the O2 and N2
in the atmosphere are the same, the pressure of each gas must
be proportional to the number of the moles of the gas.
Because there is more N2 in the atmosphere than O2,
the contribution to the total pressure of the atmosphere from
N2 is larger than the contribution from O2.
John Dalton was the first to recognize that the total
pressure of a mixture of gases is the sum of the
contributions of the individual components of the mixture. By
convention, the part of the total pressure of a mixture that
results from one component is called the partial
pressure of that component. Dalton's law of
partial pressures states that the total pressure of
a mixture of gases is the sum of the partial pressures of the
various components.
PT = P1
+ P2 + P3 + ...
Dalton derived the law of partial pressures from his work
on the amount of water vapor that could be absorbed by air at
different temperatures. It is therefore fitting that this law
is used most often to correct for the amount of water vapor
picked up when a gas is collected by displacing water.
Suppose, for example, that we want to collect a sample of O2
prepared by heating potassium chlorate until it decomposes.
2 KClO3(s) |
 |
2 KCl(s) |
+ |
3 O2(g) |
The gas given off in this reaction can be
collected by filling a flask with water, inverting the flask
in a trough, and then letting the gas bubble into the flask
as shown in the figure below.
Because some of the water in the flask will
evaporate during the experiment, the gas that collects in
this flask is going to be a mixture of O2 and
water vapor. The total pressure of this gas is the sum of the
partial pressures of these two components.
PT = Poxygen
+ Pwater
The total pressure of this mixture must be equal to
atmospheric pressure. (If it was any greater, the gas would
push water out of the container. If it was any less, water
would be forced into the container.) If we had some way to
estimate the partial pressure of the water in this system, we
could therefore calculate the partial pressure of the oxygen
gas.
By convention, the partial pressure of the gas that
collects in a closed container above a liquid is known as the
vapor pressure of the liquid. If we know the
temperature at which a gas is collected by displacing water,
and we assume that the gas is saturated with water vapor at
this temperature, we can calculate the partial pressure of
the gas by subtracting the vapor pressure of water from the
total pressure of the mixture of gases collected in the
experiment.
Practice
Problem 5:
Let's calculate the number of grams of O2 that
can be collected by displacing water from a 250-mL flask at
21ºC and 746.2 mmHg.
Click here to check your answer
to practice problem 5

