The kinetic theory of gases provides a microscopic explanation for the macroscopic behavior of gases, such as pressure and temperature.
Origin of Pressure in a Gas
Pressure arises from the collisions of gas molecules with the walls of their container.
Each collision exerts aforce on the wall, and the cumulative effect of countless collisions results in pressure.
Note
Pressure is defined as the force exerted per unit area: $$P = \frac{F}{A}$$
Deriving the Pressure Equation
Note
Further derivation assumes an ideal gas, where molecules are point particles that undergo elastic collisions and experience no intermolecular forces.
To relate pressure to molecular motion, consider a cube of side $L$ containing $N$ molecules, each of mass $m$.
Assume the moleculesmove randomly with velocity components $v_x$, $v_y$, and $v_z$.
Momentum Change in a Collision:
A molecule moving with velocity $v_x$ along the x-axis collides elastically with a wall.
Before the collision, its momentum is $mv_x$, after the collision, it is $-mv_x$.
The change in momentum is $2mv_x$.
Time Between Collisions:
The molecule travels a distance $2L$ (to the wall and back) in time $t = \frac{2L}{|v_x|}$.
Force Exerted by the Molecule:
The average force exerted on the wall is given by the rate of change of momentum: $$F = \frac{2m|v_x|}{\frac{2L}{|v_x|}} = \frac{mv_x^2}{L}$$
Total Pressure from All Molecules:
For $N$ molecules, the total pressure is the sum of the forces exerted by each molecule.
Using the root mean square speed $v_{\text{rms}}$, where $v_{\text{rms}}^2 = \frac{1}{N}\sum_{i=1}^{N} v_i^2$ and $\langle v_x^2 \rangle = \frac{1}{3} v_{\text{rms}}^2$, the pressure is: $$P = \frac{1}{3} \rho v_{\text{rms}}^2$$
Here, $\rho = \frac{Nm}{V}$ is the density of the gas.
Tip
The factor $\frac{1}{3}$ arises because the molecules move in three dimensions, and only one-third of their velocity contributes to motion along any single axis.
Temperature Measures Average Kinetic Energy
Comparing the two expressions for $PV$ links molecular motion directly to temperature.
Since $PV = \frac{1}{3}Nmv_{\text{rms}}^2$ and $PV = Nk_BT$, it follows that: $$\frac{1}{2}mv_{\text{rms}}^2 = \frac{3}{2}k_BT$$
So the average translational kinetic energy of a single molecule depends only on the absolute temperature: $$\bar{E}_k = \frac{3}{2}k_BT$$
Absolute temperature is a direct measure of the average translational kinetic energy of gas molecules.
Internal Energy of an Ideal Gas
Definition
Internal energy
Internal energy is the sum of kinetic energy and potential energy of a substance and is the result of the motion of the particles which make up the substance.
The internal energy of an ideal gas is the total kinetic energy of its molecules.
Note
For a monatomic ideal gas, this energy depends only on temperature.
Expression for Internal Energy
The internal energy $U$ of an ideal gas is given by: $$U = \frac{3}{2} Nk_B T \quad \text{or} \quad U = \frac{3}{2} nRT$$ where:
$N$ is the number of molecules.
$n$ is the number of moles.
$k_B$ is the Boltzmann constant ($1.38 \times 10^{-23} \, \text{J K}^{-1}$).
$R$ is the universal gas constant ($8.31 \, \text{J K}^{-1} \text{mol}^{-1}$).
$T$ is the absolute temperature in kelvin.
Note
In an ideal gas, internal energy is purely kinetic.
There is no potential energy because intermolecular forces are negligible.
Example question
Calculate the internal energy of 2 moles of helium gas at $300 \, \text{K}$.