Boyle’s Law: Volume and Pressure

Learning Objective

 Apply Boyle’s Law using mathematical calculations.

Key Points

o According to Boyle’s Law, an inverse relationship exists between

pressure and volume.
o Boyle’s Law holds true only if the number of molecules (n) and the
temperature (T) are both constant.
o Boyle’s Law is used to predict the result of introducing a change in
volume and pressure only, and only to the initial state of a fixed
quantity of gas.
o The relationship for Boyle’s Law can be expressed as follows: P1V1
= P2V2, where P1 and V1 are the initial pressure and volume values,
and P2 and V2 are the values of the pressure and volume of the gas
after change.

Terms

 isotherm in thermodynamics, a curve on a p-V diagram for an isothermal process

 Boyle’s law the absolute pressure and volume of a given mass of confined gas are
inversely proportional, while the temperature remains unchanged within a closed
system
 ideal gas a theoretical gas composed of a set of randomly-moving, non-interacting
point particles

Boyle’s Law

Boyle’s Law (sometimes referred to as the Boyle-Mariotte Law) states that the absolute
pressure and volume of a given mass of confined gas are inversely proportional,
provided the temperature remains unchanged within a closed system. This can be
stated mathematically as follows:

P1V1=P2V2
History and Derivation of Boyle’s Law

The law was named after chemist and physicist Robert Boyle, who published the
original law in 1662. Boyle showed that the volume of air trapped by a liquid in the
closed short limb of a J-shaped tube decreased in exact proportion to the pressure
produced by the liquid in the long part of the tube.

Boyle’s Law An animation of Boyle’s Law, showing the relationship between volume and pressure
when mass and temperature are held constant.

The trapped air acted much like a spring, exerting a force opposing its compression.
Boyle called this effect “the spring of the air” and published his results in a pamphlet
with that title. The difference between the heights of the two mercury columns gives the
pressure (76 cm = 1 atm), and the volume of the air is calculated from the length of the
air column and the tubing diameter.

The law itself can be stated as follows: for a fixed amount of an ideal gas kept at a fixed
temperature, P (pressure) and V (volume) are inversely proportional—that is, when one
doubles, the other is reduced by half.
Remember that these relations hold true only if the number of molecules (n) and the
temperature (T) are both constant.

Interactive: The Volume-Pressure Relationship Gases can be compressed into smaller

volumes. How does compressing a gas affect its pressure? Run the model, then change the
volume of the containers and observe the change in pressure. The moving wall converts the
effect of molecular collisions into pressure and acts as a pressure gauge. What happens to the
pressure when the volume changes?

Example

In an industrial process, a gas confined to a volume of 1 L at a pressure of 20 atm is

allowed to flow into a 12-L container by opening the valve that connects the two
containers. What is the final pressure of the gas?

Set up the problem by setting up the known and unknown variables. In this case, the
initial pressure is 20 atm (P1), the initial volume is 1 L (V1), and the new volume is 1L +
12 L = 13 L (V2), since the two containers are connected. The new pressure (P 2)
remains unknown.
P1V1 = P2V2
(20 atm)(1 L) = (P2)(13 L).
20 atom = (13) P2.
P2 = 1.54 atm.

The final pressure of the gas is 1.54 atm.

Boyle An introduction to the relationship between pressure and volume, and an explanation of how to
solve gas problems with Boyle’s Law.

Charles’ and Gay-Lussac’s Law: Temperature and Volume

Learning Objective

 State Charles’ Law and its underlying assumptions

Key Points

o The lower the pressure of a gas, the greater its volume (Boyle’s
Law); at low pressures, V273V273 will have a larger value.
o Charles’ and Gay-Lussac’s Law can be expressed algebraically
as ΔVΔT=constant ΔVΔT=constant or V1T1=V2T2V1T1=V2T

Terms

 absolute zero the theoretical lowest possible temperature; by international

agreement, absolute zero is defined as 0 K on the Kelvin scale and as −273.15°
on the Celsius scale
 Charles’ law at constant pressure, the volume of a given mass of an ideal gas
increases or decreases by the same factor as its temperature on the absolute
temperature scale (i.e. gas expands as temperature increases)

Charles’ and Guy-Lussac’s Law

Charles’ Law describes the relationship between the volume and temperature of a gas.
The law was first published by Joseph Louis Gay-Lussac in 1802, but he referenced
unpublished work by Jacques Charles from around 1787. This law states that at
constant pressure, the volume of a given mass of an ideal gas increases or decreases
by the same factor as its temperature (in Kelvin); in other words, temperature and
volume are directly proportional. Stated mathematically, this relationship is:

V1T1=V2T2

Interactive: The Temperature-Volume Relationship This model contains gas molecules on

the left side and a barrier that moves when the volume of gas expands or contracts, keeping the
pressure constant. Run the model and change the temperature. Why does the barrier move
when the temperature changes? (Note: Although the atoms in this model are in a flat plane,
volume is calculated using 0.1 nm as the depth of the container.)
Example
 A car tire filled with air has a volume of 100 L at 10°C. What will the expanded
volume of the tire be after driving the car has raised the temperature of the tire to
40°C?
 V1T1=V2T2V1T1=V2T2
 100 L283 K=V2313 K100 L283 K=V2313 K
 V2=110 LV2=110 L

V vs. T Plot and Charles’ Law

A visual expression of Charles’ and Gay-Lussac’s Law is shown in a graph of the
volume of one mole of an ideal gas as a function of its temperature at various constant
pressures. The plots show that the ratio VTVT (and thus ΔVΔTΔVΔT) is a constant at any
given pressure. Therefore, the law can be expressed algebraically as ΔVΔT=constant
ΔVΔT=constant or V1T1=V2T2V1T1=V2T2.
Charles’ and Gay–Lussac’s Law A visual expression of the law of Charles and Gay-Lussac;

specifically, a chart of the volume of one mole of an ideal gas as a function of its temperature at
various constant pressures.
Extrapolation to Zero Volume

If a gas contracts by 1/273 of its volume for each degree of cooling, it should contract to
zero volume at a temperature of –273°C; this is the lowest possible temperature in the
universe, known as absolute zero. This extrapolation of Charles’ Law was the first
evidence of the significance of this temperature.

Why Do the Plots for Different Pressures Have Different Slopes?

The lower a gas’ pressure, the greater its volume (Boyle’s Law), so at low pressures,
the fraction \frac{V}{273} will have a larger value; therefore, the gas must “contract
faster” to reach zero volume when its starting volume is larger.

Charles Discusses the relationship between volume and temperature of a gas, and explains how to
solve problems using Charles’ Law.

Avogadro’s Law: Volume and Amount

Learning Objective

 State Avogadro’s Law and its underlying assumptions

Key Points

o The number of molecules or atoms in a specific volume of ideal gas

is independent of size or the gas’ molar mass.
o Avogadro’s Law is stated mathematically as follows: Vn=kVn=k ,
where V is the volume of the gas, n is the number of moles of the
gas, and k is a proportionality constant.
o Volume ratios must be related to the relative numbers of molecules
that react; this relationship was crucial in establishing the formulas of
simple molecules at a time when the distinction between atoms and
molecules was not clearly understood.

Term

 Avogadro’s Law under the same temperature and pressure conditions, equal
volumes of all gases contain the same number of particles; also referred to as
Avogadro’s hypothesis or Avogadro’s principle

Definition of Avogadro’s Law

Avogadro’s Law (sometimes referred to as Avogadro’s hypothesis or Avogadro’s
principle) is a gas law; it states that under the same pressure and temperature
conditions, equal volumes of all gases contain the same number of molecules. The law
is named after Amedeo Avogadro who, in 1811, hypothesized that two given samples of
an ideal gas—of the same volume and at the same temperature and pressure—contain
the same number of molecules; thus, the number of molecules or atoms in a specific
volume of ideal gas is independent of their size or the molar mass of the gas. For
example, 1.00 L of N2 gas and 1.00 L of Cl2 gas contain the same number of molecules
at Standard Temperature and Pressure (STP).

Avogadro’s Law is stated mathematically as:

Vn=kVn=k

V is the volume of the gas, n is the number of moles of the gas, and k is a
proportionality constant.

As an example, equal volumes of molecular hydrogen and nitrogen contain the same
number of molecules and observe ideal gas behavior when they are at the same
temperature and pressure. In practice, real gases show small deviations from the ideal
behavior and do not adhere to the law perfectly; the law is still a useful approximation
for scientists, however.

Interactive: The Number-Volume Relationship The model contains gas molecules under
constant pressure. The barrier moves when the volume of gas expands or contracts. Run the
model and select different numbers of molecules from the drop-down menu. What is the
relationship between the number of molecules and the volume of a gas? (Note: Although the
atoms in this model are in a flat plane, volume is calculated using 0.1 nm as the depth of the
container.)

Significance of Avogadro’s Law

Discovering that the volume of a gas was directly proportional to the number of particles
it contained was crucial in establishing the formulas for simple molecules at a time
(around 1811) when the distinction between atoms and molecules was not clearly
understood. In particular, the existence of diatomic molecules of elements such as H 2,
O2, and Cl2 was not recognized until the results of experiments involving gas volumes
was interpreted.
Early chemists calculated the molecular weight of oxygen using the incorrect formula
HO for water. This lead to the molecular weight of oxygen being miscalculated as 8,
rather than 16. However, when chemists found that an assumed reaction of H +
Cl →→ HCl yielded twice the volume of HCl, they realized hydrogen and chlorine were
diatomic molecules. The chemists revised their reaction equation to be H 2 +
Cl2→→ 2HCl.
When chemists revisited their water experiment and their hypothesis
that HO→H+OHO→H+O, they discovered that the volume of hydrogen gas consumed
was twice that of oxygen. By Avogadro’s Law, this meant that hydrogen and oxygen
were combining in a 2:1 ratio. This discovery led to the correct molecular formula for
water (H2O) and the correct reaction 2H2O→2H2+O22H2O→2H2+O2.
Experiment confirming the correct formula for water It was originally assumed that 1 hydrogen
and 1 oxygen atom went into a water molecule. Using Avogadro’s Law, this experiment confirmed that 2
hydrogen and 1 oxygen form 1 water molecule.

Avogadro Practice problems and examples, looking at the relationship between the volume and
amount of gas (number of moles) in a gas sample.

Combined and Ideal Gas Law

Relationships between Boyle's, Charles's, Gay-Lussac's, Avogadro's, combined and ideal gas laws, with

the Boltzmann constantkB = R/NA = n R/N  (in each law, properties circled are variable and properties
not circled are held constant)
Main article:  Ideal gas law
The Combined gas law or General Gas Equation is obtained by combining Boyle's Law,
Charles's law, and Gay-Lussac's Law. It shows the relationship between the pressure,
volume, and temperature for a fixed mass (quantity) of gas:
This can also be written as:

With the addition of Avogadro's law, the combined gas law develops into the ideal gas law:
where
 P is pressure
 V is volume
 n is the number of moles
 R is the universal gas constant
 T is temperature (K)

The proportionality constant, now named R, is the universal gas constant with a value of

8.3144598 (kPa∙L)/(mol∙K).
An equivalent formulation of this law is:

where
 P is the pressure
 V is the volume
 N is the number of gas molecules
 kB is the Boltzmann constant(1.381×10−23J·K−1 in SI units)
 T is the temperature (K)

These equations are exact only for an ideal gas, which neglects various intermolecular
effects (see real gas). However, the ideal gas law is a good approximation for most gases
under moderate pressure and temperature.
This law has the following important consequences:

1. If temperature and pressure are kept constant, then the volume of the gas is directly
proportional to the number of molecules of gas.
2. If the temperature and volume remain constant, then the pressure of the gas changes is
directly proportional to the number of molecules of gas present.
3. If the number of gas molecules and the temperature remain constant, then the pressure is
inversely proportional to the volume.
4. If the temperature changes and the number of gas molecules are kept constant, then either
pressure or volume (or both) will change in direct proportion to the temperature.