Thermal II 1

Thermal Properties of Matter

Equations of State
Quantities that describe the state in which a material exist are called state variables. Some examples of
state variables include pressure (p), volume (V), temperature (T), and mass (m) of a substance. How the
state variables relate to one another in an equation is called an equation of state.

Boyle’s Law

At constant temperature and number of molecules, the absolute pressure of a gas is inversely
proportional to its volume. That is,
1
𝑝∝ . (18.1)
𝑉

We can also write it as

𝑝𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡. (18.2)

If states 1 and 2 are two states that are at the same temperature and have the same number of
molecules, then we can also write Boyle’s law as

𝑝1 𝑉1 = 𝑝2 𝑉2. (18.3)

Charles’s Law

Charles’s law states that when the pressure and number molecules of a gas are kept constant, the
volume of the gas is directly proportional to its absolute temperature:

𝑉 ∝ 𝑇, (18.4)

or,
𝑉
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
𝑇
(18.5)

Given two states with the same pressure and number of molecules, Charles’s law can also be written as
𝑉1 𝑉
𝑇1
= 𝑇2. (18.6)
2

Gay-Lussac’s Law

Gay-Lussac’s law, or Amonton’s law, states that the absolute pressure and absolute temperature are
directly proportional to each other at constant volume and number of molecules:

𝑝 ∝ 𝑇, (18.7)

or,
𝑝
𝑇
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
(18.8)

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 Thermal II 2

Given two states with the same volume and number of molecules, the above equation can also be
written as
𝑝1 𝑝2
𝑇1
= 𝑇2
. (18.9)

Combined Gas Law

Combining the three gas laws above, we can see that for a constant number of molecules, the absolute
pressure and volume of a gas are inversely proportional to each other and directly proportional to the
absolute temperature. That is, combining equations (18.2), (18.5), and (18.8) gives
𝑝𝑉
𝑇
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡. (18.10)

Rewriting the above equation for two states with the same number of molecules:
𝑝1 𝑉1 𝑝2 𝑉2
𝑇1
= 𝑇2
. (18.11)

This is commonly referred to as the combined gas law, or combined gas equation.

Ideal Gas Law

In equation (18.10), the product of the absolute pressure and volume of a gas, divided by the absolute
temperature, is a constant. Experimental results show that for gases at low density (such that the total
volume of the gas is much less than the volume of its container) and at temperatures above the boiling
point, the above relationships between the state variables hold to a good approximation. Moreover,
the constant of proportionality in equation (18.10) is independent of the composition of the gas, and the
equation applies in the limit of low density and high temperature. A gas at this limit is called an ideal
gas, and it obeys the ideal gas law, which is the equation of state of an ideal gas.

The ideal gas law states that

𝑝𝑉 = 𝑛𝑅𝑇, (18.12)

where p is the absolute pressure of a gas, V is the volume that the gas occupies, n is the number of
moles in the gas, and T is its absolute temperature. The constant R is called the gas constant and is
equal to 8.314 J/mol·K. It is also equal to 0.0821 L·atm/mol·K.

The number of moles in a gas is related to the total mass of the gas by the relation:

𝑚𝑡𝑜𝑡 = 𝑛𝑀, (18.13)

where mtot is the total mass of the gas, n is the number of moles, and M is the molar mass. Substituting
(18.13) into (18.12), we get
𝑚𝑡𝑜𝑡
𝑝𝑉 = 𝑀
𝑅𝑇. (18.12)

Noting that the density of the gas is equal to the ratio of the total mass of the gas to the total volume,
we find the density of an ideal gas to be
𝑝𝑀
𝜌= 𝑅𝑇
. (18.13)

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One mole is defined as the amount of substance that contains 6.02 x 1023 molecules. The number of
molecules in a mole of substance is called Avogadro’s number. Numerically, we write

𝑁𝐴 = 6.02 × 1023 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠/𝑚𝑜𝑙. (18.14)

In terms of Avogadro’s number, the molar mass of a substance is equal to M=NAm, where m is the mass
of a molecule of the substance. The number of molecules in a substance is also related to Avogadro’s
number by

𝑁 = 𝑁𝐴 𝑛. (18.15)

Writing equation (18.12) using equation (18.15), the ideal gas equation becomes
𝑁
𝑝𝑉 = 𝑅𝑇. (18.16)
𝑁𝐴

We define the ratio of the gas constant R and Avogadro’s number NA as the Boltzmann constant, kB,
which has the value 1.38 x 10-23 J/K. Thus, the ideal gas equation can be written in terms of the number
of molecules in a gas as

𝑝𝑉 = 𝑁𝑘𝐵 𝑇. (18.17)

Kinetic-Molecular Model of an Ideal Gas

The previous section discussed the relationship between the state variables based on their macroscopic
definitions. Here, we relate the macroscopic properties of gases to the motion of the molecules they
consist of.

To relate the microscopic and macroscopic quantities of an ideal gas, let us consider an ideal gas in a
rigid container. First, we make assumptions about the molecules in an ideal gas and their behaviour in
the container:

1. There is a very large number (N) of molecules in an ideal gas, all are identical with mass m.
2. The molecules obey Newton’s laws and are in continuous motion, which is random and
isotropic.
3. The molecules are much smaller than the average distance between them, so their total volume
is much less than that of their container (which has volume V).
4. The molecules make perfectly elastic collisions with each other and with the walls of the
container. The container walls are rigid and infinitely massive, and so they do not move when
molecules collide with them.

There are other assumptions that we can make that will simplify calculations but not affect the result,
such as the container being a rectangular box. We also initially consider monatomic gases (molecules
consisting of single atoms), and then consider the diatomic and polyatomic gases later. Finally, we can
assume that the atoms have no energy except their translational kinetic energy.

Consider a gas colliding with the wall of the container. If the x- and y-axes are perpendicular and parallel
to the wall, respectively, then the component of the velocity along the x-axis reverses after collision
while the y-component of the velocity remains unchanged. Thus, the change in the molecule’s
momentum is equal to

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∆𝑝𝑥 = 𝑚∆𝑣𝑥 = 2𝑚|𝑣𝑥 |.

(18.18)

Using the impulse-momentum theorem, the force

exerted on the molecule by the wall is
2𝑚|𝑣𝑥 |
𝐹= ∆𝑡
, (18.19)

where t is the average time between collisions of

the molecule and the wall. If the length of the box
along the x-direction is L, then t is the time that the
molecule would take to go from one wall of the box
to the other and then back (a distance of 2L) at a
2𝐿
speed vx, or ∆𝑡 = . The expression for the force on
𝑣𝑥
the molecule becomes
𝑚|𝑣𝑥 |2
𝐹= . (18.20)
𝐿

Note that the above equation is the force exerted on the molecule by the box wall. According to
Newton’s third law, the magnitude of the force exerted by the molecule on the wall is the same. If there
are N molecules colliding with the box, then the total force exerted on the box is the sum of the force
exerted by each molecule on the wall:
𝑚|𝑣𝑖,𝑥 |2 𝑚 𝑁 𝑚
𝐹𝑡𝑜𝑡 = ∑𝑁
𝑖=1 𝐿
= ∑ |𝑣 |2
𝐿 𝑖=1 𝑖,𝑥
=𝑁 𝐿
(𝑣𝑥 2 )𝑎𝑣 . (18.21)

Noting that the square of the speed is equal to the sum of the squares of the velocity components, and
also noting the assumption of isotropy, we can write

(𝑣 2 )𝑎𝑣 = 3(𝑣𝑥 2 )𝑎𝑣 (18.22)

and equation (18.21) gives

𝑚
𝐹𝑡𝑜𝑡 = 𝑁 (𝑣 2 )𝑎𝑣 . (18.23)
3𝐿

The pressure on the wall of the box is equal to the total force on the wall divided by the area of the wall:
𝑚
𝑝 = 𝑁 3𝐴𝐿 (𝑣 2 )𝑎𝑣 . (18.24)

Noting that the volume of the box is given by the product AL, we arrive at the following result:
1
𝑝𝑉 = 3 𝑁𝑚(𝑣 2 )𝑎𝑣 . (18.24)

Combining this with the ideal gas equation (18.17), we can write the average translational kinetic energy
of a single molecule as:
1 3
2
𝑚(𝑣 2 )𝑎𝑣 = 2 𝑘𝐵 𝑇, (18.25)

and for the ideal gas (consisting of N molecules):

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1 3
𝐾𝑡𝑟 = 𝑁 2 𝑚(𝑣 2 )𝑎𝑣 = 2 𝑁𝑘𝐵 𝑇. (18.26)

In terms of the gas constant, the average translational kinetic energy of an ideal gas is
1 3
𝐾𝑡𝑟 = 𝑁 2 𝑚(𝑣 2 )𝑎𝑣 = 2 𝑛𝑅𝑇. (18.27)

Molecular Speeds

From equation (18.25), we can solve for the speed of a molecule of an ideal gas in terms of the absolute
temperature to determine what is known as the root-mean-square (rms) speed of the molecule:

3𝑘𝐵 𝑇 3𝑅𝑇
𝑣𝑟𝑚𝑠 = √(𝑣 2 )𝑎𝑣 = √ 𝑚
=√ 𝑀
. (18.28)

Mean Free Path and Mean Free Time

The mean free path, , is the average distance that a molecule travels between collisions with other
molecules, while the mean free time, tmean, is the average time between collisions of a molecule. If we
assume that there are N molecules of a gas occupying a container of volume V, and each molecule is a
sphere with radius r, then the mean free path is given by
𝑉
𝜆=4 . (18.29)
√2𝜋𝑟 2 𝑁

For an ideal gas, the mean free path is related to the absolute pressure and absolute temperature by:
𝑘𝐵 𝑇
𝜆=4 . (18.30)
√2𝜋𝑟 2 𝑝

The mean free time is simply the mean free path divided by the rms speed:
𝑘𝐵 𝑇
𝑡𝑚𝑒𝑎𝑛 = 4 . (18.31)
√2𝜋𝑟 2 𝑝𝑣𝑟𝑚𝑠

Heat Capacities
Recall that the quantity of heat required to raise the temperature of a substance is given by

𝑄 = 𝑛𝐶Δ𝑇, (18.32)

where n is the number of moles of the substance, C is the molar heat capacity of the substance, and T
us the change in temperature. An increase in temperature can be achieved by different paths. Here we
consider two processes: isovolumetric (constant volume) and isobaric (constant pressure).

Isovolumetric Process

The heat required to raise the temperature at constant volume is given by

𝑄 = 𝑛𝐶𝑉 Δ𝑇, (18.33)

where CV is the molar heat capacity at constant volume. Note that for a constant volume process, there
is no work done on the system, and the heat flow is equal to the change in average translational kinetic
energy. Equating (18.33) to (18.27), we find the molar heat capacity for an ideal gas:

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3
𝐶𝑉 = 2
𝑅 = 12.47 𝐽/𝑚𝑜𝑙 ∙ 𝐾. (18.34)

Degrees of Freedom

The 3 in the numerator of equations (18.34), (18.26), and (18.27) come from the fact that we assumed
the molecules to be point particles able to move in three dimensions (x, y, z). A degree of freedom is
defined as an independent possible motion of a molecule.

For a monatomic molecule, the number of degrees of freedom is 3, so the molar heat capacity at
constant volume is given by (18.34).

For a diatomic molecule (consisting of two atoms), in addition to the three possible directions for
translational motion there are also two possible directions of rotation. Thus, the number of degrees of
freedom for a diatomic molecule is 5, and the molar heat capacity at constant volume is given by
5
𝐶𝑉 = 𝑅. (diatomic molecule) (18.35)
2

Isobaric Process

The heat required to raise the temperature at constant pressure is given by

𝑄 = 𝑛𝐶𝑃 Δ𝑇, (18.36)

where CP is the molar heat capacity at constant pressure. For an isobaric process, a change in
temperature corresponds to a change in volume; hence work (equal to -pV) is done on the system.
Then, the sum of the heat required to change the temperature and the work done due to the change in
volume is equal to the change in average translational kinetic energy:

∆𝐾𝑡𝑟 = 𝑛𝐶𝑃 Δ𝑇 − 𝑝∆𝑉,

(18.37)

or

𝑛𝐶𝑉 Δ𝑇 = 𝑛𝐶𝑃 Δ𝑇 − 𝑝∆𝑉. (18.38)

Using the equation of state for an ideal gas, we get

𝐶𝑉 = 𝐶𝑃 − 𝑅. (18.39)

Thus, the molar heat capacity at constant pressure for monatomic and diatomic gases are (5/2)R and
(7/2)R, respectively.

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