explain how molecular movement causes the pressure exerted by a gas and derive and use the relationship pV = 31Nm<c2>, where < c2> is the mean-square speed (a simple model considering one-dimensional collisions and then extending to three dimensions

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

1. The mole, Avogadro’s constant and molecular mass

  • Mole (n): the amount of substance containing exactly Nₐ particles, where

    Nₐ = 6.022 × 10²³ mol⁻¹ (Avogadro’s constant).

  • Molar mass (M): mass of one mole of a substance (kg mol⁻¹).
  • Mass of a single molecule (m):

    \[

    m = \frac{M}{N_{\!A}}

    \]

    (e.g. for N₂, M = 28 g mol⁻¹ ⇒ m ≈ 4.65 × 10⁻²⁶ kg).

2. Ideal‑gas equation of state (syllabus 15.2)

The ideal‑gas law in the two common forms is

\[

pV = nRT \qquad\text{and}\qquad pV = Nk_{\!B}T,

\]

where

  • p = pressure (Pa),
  • V = volume (m³),
  • n = number of moles,
  • N = number of molecules ( N = n Nₐ ),
  • R = Nₐk_{\!B} = 8.314 J mol⁻¹ K⁻¹,
  • k_{\!B}=1.38 × 10⁻²³ J K⁻¹ (Boltzmann constant),
  • T = absolute temperature (K).

3. Fundamental assumptions of the kinetic‑theory model (syllabus 15.3.1)

AssumptionMeaning for the model
Large number of moleculesStatistical treatment is valid.
Point‑like particlesIndividual molecular volume is negligible compared with the container volume.
Random isotropic motionNo preferred direction; the three Cartesian components are statistically identical.
Elastic collisionsKinetic energy is conserved in collisions with walls and between molecules.
Negligible intermolecular forcesOnly brief forces during collisions are considered (ideal‑gas approximation).

4. One‑dimensional model – a single molecule

Consider a cubic container of side L (so V = L³) and a molecule of mass m moving only along the x-axis with speed cₓ.

  1. Time between successive impacts on the same wall

    \[

    \Delta t = \frac{2L}{c_{x}} .

    \]

  2. Momentum change in one impact (elastic reversal)

    \[

    \Delta p = 2m c_{x} .

    \]

  3. Average force on the wall**

    \[

    F = \frac{\Delta p}{\Delta t}

    = \frac{2m c{x}}{2L/c{x}}

    = \frac{m c_{x}^{2}}{L}.

    \]

  4. Pressure (force per unit area, \(A = L^{2}\))**

    \[

    p = \frac{F}{A}

    = \frac{m c_{x}^{2}}{L^{3}}

    = \frac{m c_{x}^{2}}{V}.

    \]

For N identical molecules all moving only in the x-direction we replace \(c{x}^{2}\) by the average \(\langle c{x}^{2}\rangle\):

\[

pV = N m \langle c_{x}^{2}\rangle \qquad (1)

\]

5. Extension to three dimensions – isotropy (syllabus 15.3.2)

In a real gas each molecule has independent velocity components \(c{x},c{y},c_{z}\). Random isotropic motion gives

\[

\langle c{x}^{2}\rangle = \langle c{y}^{2}\rangle = \langle c_{z}^{2}\rangle .

\]

The total mean‑square speed is the sum of the three orthogonal components:

\[

\langle c^{2}\rangle = \langle c{x}^{2}\rangle+\langle c{y}^{2}\rangle+\langle c_{z}^{2}\rangle

= 3\langle c_{x}^{2}\rangle .

\]

Substituting \(\langle c_{x}^{2}\rangle = \langle c^{2}\rangle/3\) into (1) yields the fundamental kinetic‑theory relation (syllabus 15.3.2):

\[

\boxed{\,pV = \frac{1}{3}\,N m \langle c^{2}\rangle\,} \qquad (2)

\]

6. Root‑mean‑square speed (syllabus 15.3.3)

\[

c_{\text{rms}} = \sqrt{\langle c^{2}\rangle } .

\]

Because \(\langle c^{2}\rangle\) appears directly in (2), the r.m.s. speed is the most convenient single number to characterise molecular motion.

7. Connection with temperature and average translational kinetic energy (syllabus 15.3.4)

Equating the kinetic‑theory result (2) with the ideal‑gas law \(pV = Nk_{\!B}T\) gives

\[

\frac{1}{3} N m \langle c^{2}\rangle = N k_{\!B} T .

\]

Cancel \(N\) and solve step‑by‑step:

\[

\langle c^{2}\rangle = \frac{3k_{\!B}T}{m},

\qquad

\frac{1}{2}m\langle c^{2}\rangle = \frac{3}{2}k_{\!B}T .

\]

Thus the average translational kinetic energy per molecule is a key formula the syllabus expects you to remember:

\[

\boxed{\,\langle E{\text{kin}}\rangle = \frac{1}{2}m\langle c^{2}\rangle = \frac{3}{2}k{\!B}T\,}.

\]

8. Internal energy of an ideal gas (link to Topic 16)

For a monatomic ideal gas the internal energy is purely translational:

\[

U = N\langle E{\text{kin}}\rangle = \frac{3}{2}Nk{\!B}T

= \frac{3}{2}nRT .

\]

For diatomic or polyatomic gases additional rotational (and at higher T, vibrational) contributions are added, but the translational part always remains \(\tfrac{3}{2}nRT\).

9. Practical determination of \(c_{\text{rms}}\) (syllabus 15.3.5 – practical skill)

A typical laboratory exercise:

  1. Measure the pressure \(p\), temperature \(T\) and volume \(V\) of a known amount of gas (e.g. 0.050 mol of He in a 0.010 m³ container).
  2. Use the ideal‑gas law to find the number of molecules \(N = nN_{\!A}\).
  3. Calculate \(\langle c^{2}\rangle\) from (2):

    \[

    \langle c^{2}\rangle = \frac{3pV}{Nm}.

    \]

  4. Take the square‑root to obtain \(c_{\text{rms}}\).

10. Limitations of the simple kinetic‑theory model (syllabus 15.3.5)

  • Finite molecular volume: at high pressures the “point‑like” assumption breaks down (real gases occupy a measurable fraction of the container).
  • Inter‑molecular forces: attractive forces become important near condensation; repulsive forces dominate at very high densities. These are ignored in the ideal‑gas derivation.
  • Quantum effects: at very low temperatures the classical description fails; molecules must be treated with quantum statistics (Bose–Einstein or Fermi–Dirac).
  • Non‑elastic collisions: in real gases some kinetic energy can be transferred to internal degrees of freedom (rotation, vibration), especially for polyatomic gases.

11. Worked examples

Example 1 – Pressure from a given \(\langle c^{2}\rangle\)

Find the pressure exerted by \(N = 2.5\times10^{25}\) molecules of nitrogen (\(\mathrm{N_{2}}\), \(M = 28\;\text{g mol}^{-1}\)) in a container of volume \(V = 0.010\;\text{m}^{3}\) when \(\langle c^{2}\rangle = (500\;\text{m s}^{-1})^{2}\).

  1. Mass of one molecule

    \[

    m = \frac{M}{N_{\!A}}

    = \frac{28\times10^{-3}\;\text{kg mol}^{-1}}{6.022\times10^{23}\;\text{mol}^{-1}}

    \approx 4.65\times10^{-26}\;\text{kg}.

    \]

  2. Pressure from (2)

    \[

    p = \frac{1}{3}\frac{Nm\langle c^{2}\rangle}{V}

    = \frac{1}{3}\frac{(2.5\times10^{25})(4.65\times10^{-26})(500^{2})}{0.010}

    \approx 9.2\times10^{4}\;\text{Pa}.

    \]

  3. Root‑mean‑square speed

    \[

    c_{\text{rms}} = \sqrt{\langle c^{2}\rangle}=500\;\text{m s}^{-1}.

    \]

  4. Average translational kinetic energy per molecule

    \[

    \langle E_{\text{kin}}\rangle = \tfrac12 m \langle c^{2}\rangle

    = \tfrac12 (4.65\times10^{-26})(500^{2})

    \approx 5.8\times10^{-21}\;\text{J}.

    \]

  5. Temperature from \(\langle E{\text{kin}}\rangle = \tfrac32 k{\!B}T\)

    \[

    T = \frac{2\langle E{\text{kin}}\rangle}{3k{\!B}}

    \approx \frac{2(5.8\times10^{-21})}{3(1.38\times10^{-23})}

    \approx 280\;\text{K}.

    \]

Example 2 – Pressure change when temperature rises (using the KE–temperature relation)

At constant volume, pressure is directly proportional to temperature:

\[

\frac{p{2}}{p{1}} = \frac{T{2}}{T{1}} .

\]

A sealed 2.0 L container holds air at 300 K and 1.0 atm. If the temperature is increased to 350 K, the new pressure is

\[

p{2}=p{1}\frac{T{2}}{T{1}}=1.0\;\text{atm}\times\frac{350}{300}=1.17\;\text{atm}.

\]

12. Quick reference – key formulas

ConceptFormula
Molecular mass\(m = \dfrac{M}{N_{\!A}}\)
Ideal‑gas law\(pV = nRT = Nk_{\!B}T\)
Kinetic‑theory pressure\(pV = \dfrac13 N m\langle c^{2}\rangle\)
r.m.s. speed\(c_{\text{rms}} = \sqrt{\langle c^{2}\rangle}\)
Average translational KE\(\langle E{\text{kin}}\rangle = \dfrac12 m\langle c^{2}\rangle = \dfrac32 k{\!B}T\)
Internal energy (monatomic)\(U = \dfrac32 nRT\)

13. Summary (aligned with syllabus objectives)

  • Assumptions: large number of point particles, random isotropic motion, elastic collisions, negligible forces.
  • Derivation: 1‑D model → \(pV = N m\langle c_{x}^{2}\rangle\); isotropy → \(pV = \frac13 N m\langle c^{2}\rangle\).
  • r.m.s. speed: \(c_{\text{rms}} = \sqrt{\langle c^{2}\rangle}\).
  • Link to temperature: \(\frac12 m\langle c^{2}\rangle = \frac32 k{\!B}T\); average translational kinetic energy per molecule = \(\tfrac32 k{\!B}T\).
  • Internal energy: for a monatomic ideal gas, \(U = \tfrac32 nRT\); translational part is the same for all gases.
  • Practical use: calculate any one of \(p, V, T, N, m, \langle c^{2}\rangle\) or \(c_{\text{rms}}\) when the others are known.
  • Limitations: finite molecular volume, intermolecular forces, quantum effects, and non‑elastic energy transfer.