compare pV = 31Nm<c2> with pV = NkT to deduce that the average translational kinetic energy of a molecule is 23 kT, and recall and use this expression

Kinetic Theory of Gases – Cambridge IGCSE/A‑Level (9702)

Learning Objectives

  • State the five basic assumptions of the kinetic‑theory model.
  • Derive the kinetic‑theory form of the ideal‑gas equation


    pV = \(\dfrac13 N m \langle c^{2}\rangle\).

  • Compare this microscopic equation with the macroscopic ideal‑gas law

    pV = N k T (and the molar form pV = n R T) and deduce


    \(\langle E_{\text{trans}}\rangle = \dfrac32 kT\) and \(U = \dfrac32 n R T\).

  • Use the result to calculate rms speed, internal energy, and the change in internal energy

    \(\Delta U = \dfrac32 n R \Delta T\) for a monatomic ideal gas.

  • recognise how the expression will be used later in the thermodynamics section (Section 16).

Key Assumptions of the Kinetic Theory

  • The gas consists of a very large number of identical, point‑like molecules (size ≪ mean free path).
  • Molecules move randomly in straight lines between instantaneous, perfectly elastic collisions.
  • No intermolecular forces act except during collisions.
  • Collisions with the container walls are elastic and give rise to pressure.
  • The time‑averaged kinetic energy is the same in the three orthogonal directions (isotropy).

Derivation of the Kinetic‑Theory Equation

  1. Consider a cubic container of side L (volume \(V = L^{3}\)) containing N molecules of mass m.
  2. For a single molecule with velocity components \((cx,cy,c_z)\) the change in momentum when it strikes a wall perpendicular to the x-axis is

    \[

    \Delta p = 2 m c_x .

    \]

  3. The molecule travels a distance \(2L\) (to the opposite wall and back) between successive impacts, so the number of collisions with that wall per second is

    \[

    \frac{c_x}{2L}.

    \]

  4. Force on the wall due to this molecule:

    \[

    F = \frac{\Delta p}{\Delta t}= \frac{2 m cx}{2L/cx}= \frac{m c_x^{2}}{L}.

    \]

  5. Summing over all molecules and using \(p = F/A\) with wall area \(A = L^{2}\):

    \[

    p = \frac{1}{L^{3}}\,m\sum{i=1}^{N}c{x,i}^{2}

    = \frac{N m\langle c_x^{2}\rangle}{V}.

    \]

  6. Because the motion is isotropic,

    \[

    \langle cx^{2}\rangle = \langle cy^{2}\rangle = \langle c_z^{2}\rangle,

    \qquad

    \langle c^{2}\rangle = \langle cx^{2}\rangle+\langle cy^{2}\rangle+\langle cz^{2}\rangle = 3\langle cx^{2}\rangle .

    \]

  7. Substituting gives the kinetic‑theory form of the ideal‑gas equation:

    \[

    pV = \frac13 N m \langle c^{2}\rangle .

    \]

Comparison with the Macroscopic Ideal‑Gas Law

Both expressions describe the same state of an ideal gas, so their right‑hand sides are equal:

\[

\frac13 N m \langle c^{2}\rangle \;=\; N k T .

\]

Cancel the common factor N and multiply both sides by \(\tfrac32\):

\[

\frac12 m \langle c^{2}\rangle \;=\; \frac32 k T .

\]

The left‑hand side is the average translational kinetic energy of a single molecule, therefore

\[

\boxed{\langle E_{\text{trans}}\rangle = \frac12 m \langle c^{2}\rangle = \frac32 k T } .

\]

For a mole of gas (\(N = n N{A}\) where \(N{A}=6.022\times10^{23}\,\text{mol}^{-1}\)) the total translational kinetic energy (the internal energy of a monatomic ideal gas) is

\[

U = N\langle E_{\text{trans}}\rangle = \frac32 N k T = \frac32 n R T ,

\]

and the change in internal energy on heating or cooling is

\[

\boxed{\Delta U = \frac32 n R \,\Delta T } .

\]

Key Symbols

SymbolQuantityUnits
pPressurePa (N m⁻²)
VVolume
NNumber of molecules
nNumber of molesmol
N_{A}Avogadro’s constant6.022 × 10²³ mol⁻¹
mMass of one moleculekg
cSpeed of a moleculem s⁻¹
\(\langle c^{2}\rangle\)Mean‑square speed(m s⁻¹)²
\(\langle E_{\text{trans}}\rangle\)Average translational kinetic energy per moleculeJ
kBoltzmann constant = \(1.38\times10^{-23}\) J K⁻¹J K⁻¹
RUniversal gas constant = \(N_{A}k = 8.31\) J mol⁻¹ K⁻¹J mol⁻¹ K⁻¹
TAbsolute temperatureK

Consequences for a Monatomic Ideal Gas

  • Average translational kinetic energy per molecule:

    \(\displaystyle \langle E_{\text{trans}}\rangle = \frac32 k T\).

  • Root‑mean‑square speed:

    \(\displaystyle c_{\text{rms}} = \sqrt{\langle c^{2}\rangle}= \sqrt{\frac{3kT}{m}}\).

  • Internal energy (per mole):

    \(\displaystyle U = \frac32 n R T\).

  • Change in internal energy:

    \(\displaystyle \Delta U = \frac32 n R \Delta T\) – this formula is used in the thermodynamics section (Section 16) when applying the first law.

Cross‑Reference

The expression \(U = \tfrac32 nRT\) and its differential form \(\Delta U = \tfrac32 nR\Delta T\) are required in Section 16 – Thermodynamics for solving first‑law problems involving ideal gases.

Worked Example 1 – Average Translational Kinetic Energy

Given: \(N = 2.0\times10^{23}\) helium atoms at \(T = 300\) K.

  1. Energy per molecule:

    \[

    \langle E_{\text{trans}}\rangle = \frac32 k T

    = \frac32 (1.38\times10^{-23})(300)

    = 6.21\times10^{-21}\,\text{J}.

    \]

  2. Total translational kinetic energy:

    \[

    U = N\langle E_{\text{trans}}\rangle

    = (2.0\times10^{23})(6.21\times10^{-21})

    = 1.24\times10^{3}\,\text{J}.

    \]

Worked Example 2 – RMS Speed of Oxygen

Given: 1 mol O₂ at 298 K. Molar mass \(M = 32.0\) g mol⁻¹.

Molecular mass \(m = \dfrac{M}{N_{A}} = \dfrac{32.0\times10^{-3}}{6.022\times10^{23}} = 5.31\times10^{-26}\) kg.

\[

c_{\text{rms}} = \sqrt{\frac{3kT}{m}}

= \sqrt{\frac{3(1.38\times10^{-23})(298)}{5.31\times10^{-26}}}

= 4.8\times10^{2}\,\text{m s}^{-1}.

\]

Worked Example 3 – Change in Internal Energy

Given: 2.0 mol of a monatomic gas is heated from 300 K to 350 K.

\[

\Delta U = \frac32 n R \Delta T

= \frac32 (2.0)(8.31)(350-300)

= 1.25\times10^{3}\,\text{J}.

\]

Common Pitfalls (Cambridge Mark‑Scheme Tips)

  • Do not replace \(\langle c^{2}\rangle\) by \((\langle c\rangle)^{2}\); the two are equal only for a degenerate (single‑speed) distribution.
  • Remember that \(\langle E{\text{trans}}\rangle\) is *per molecule*; use the Boltzmann constant \(k\). For quantities per mole replace \(k\) by \(R\) and \(N\) by \(n\) (using \(N = n N{A}\)).
  • When a question asks for internal energy of a monatomic gas, use \(U = \tfrac32 nRT\). For diatomic gases at room temperature you must add the rotational contribution \(\tfrac12 RT\) per mole (later in the syllabus).
  • In algebraic manipulations, show the cancellation of the common factor \(N\) (or \(n\)) and the rearrangement steps; examiners award marks for clear working.

Summary

  • The kinetic‑theory equation \(pV = \frac13 N m \langle c^{2}\rangle\) links macroscopic pressure to microscopic molecular motion.
  • Equating it with the ideal‑gas law \(pV = N k T\) (or \(pV = n R T\)) gives the fundamental result

    \(\displaystyle \langle E_{\text{trans}}\rangle = \frac32 k T\) and, per mole, \(U = \frac32 n R T\).

  • This result underlies calculations of rms speed, internal energy, and the change in internal energy \(\Delta U = \frac32 n R \Delta T\) for monatomic ideal gases, and it is a cornerstone for later thermodynamics topics.

Suggested diagram: a rectangular container showing many small arrows (random molecular velocities) striking the walls; the arrows illustrate momentum transfer that produces pressure.