Part of JTHERM-02 — Kinetic Theory of Gases

Pressure from Kinetic Theory

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The kinetic theory derivation of pressure considers NN molecules in a cubic container of side LL. Each molecule with x-component of velocity vxv_x transfers momentum 2mvx2mv_x per wall collision, with collision frequency vx/(2L)v_x/(2L) on one wall. Summing over all molecules and averaging over three directions (isotropy: vx2=vy2=vz2=v2/3\overline{v_x^2} = \overline{v_y^2} = \overline{v_z^2} = \overline{v^2}/3) gives P=13Nmv2V=13ρv2P = \frac{1}{3}\frac{Nm\overline{v^2}}{V} = \frac{1}{3}\rho\overline{v^2}.

Rewriting: P=23NVKEP = \frac{2}{3}\frac{N}{V}\overline{KE} where KE=12mv2\overline{KE} = \frac{1}{2}m\overline{v^2} is the average translational KE per molecule. This shows pressure is proportional to the kinetic energy density (kinetic energy per unit volume). Substituting KE=32kBT\overline{KE} = \frac{3}{2}k_BT recovers PV=NkBT=nRTPV = Nk_BT = nRT.

Dalton's law follows naturally: in a mixture, each species contributes independently to pressure. Ptotal=Pi=NikBT/VP_{\text{total}} = \sum P_i = \sum N_i k_BT/V. Crucially, at the same TT and VV, equal numbers of molecules of different gases exert equal pressure — pressure does not depend on molecular mass (Avogadro's insight).

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