Past exam of the physics B course of the University of Cambridge / 2017 / Paper 2 / Section C / C13

Molecular transport across gradients. A gas can transport momentum, thermal energy and species abundance even when its average bulk velocity is zero. Molecules arriving at a point carry properties acquired near their preceding collisions. A small gradient makes the populations arriving from opposite sides slightly different, producing transport from larger to smaller values of the carried property. A continuum transport law requires a mean free path $\lambda$ small compared with the gradient length, and relaxation times short compared with the observation time.

For a dilute hard-sphere gas,where $d$ is molecular collision diameter. Both speed and collision distance matter: high speed alone does not determine a transport coefficient.

A simple kinetic estimate makes the common structure explicit. For a quantity $a(y)$ carried per particle, a molecule moving at angle $\theta$ to $+y$ brings approximately $a(y-\lambda \cos \theta )$. Expanding to first order and averaging an isotropic velocity distribution givessince $⟨\cos \theta ⟩=0$ and $⟨{\cos }^2\theta ⟩=1/3$. This mean-free-path argument estimates the coefficients; a detailed collision calculation changes their numerical prefactors and distinguishes different relaxation rates.

Momentum transport and viscosity. For a shear flow with mean velocity $U_x(y)$, the transported directed momentum per molecule is $m{U}_x$. The net flux of $x$ momentum in the $+y$ direction isHere $\eta$ is dynamic viscosity in $\mathrm{Pa}\mathrm{s}$. The associated shear stress on a material surface has the corresponding traction sign convention; the flux carries momentum from the faster-moving layer towards the slower-moving one. The kinematic viscosity is $\nu =\eta /(nm)$, with units ${\mathrm{m}}^2{\mathrm{s}}^{-1}$. Viscosity smooths velocity gradients, and the lost ordered mechanical energy becomes heat.

Heat transport. Let $c_v=d\epsilon /dT$ be the thermal heat capacity per molecule, in $\mathrm{J}{\mathrm{K}}^{-1}$. Substituting $a=\epsilon (T)$ gives Fourier's law,Thermal conductivity has units $\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$. For a monatomic gas, translational equipartition gives $c_v=3k_B/2$. Rotational or vibrational excitations in other gases can increase the energy carried per molecule, while collisions govern how those modes exchange energy. A temperature gradient can therefore be transported differently from directed momentum even when the dimensional estimates look similar.

Species transport. For a dilute tracer or a mixture with prescribed total density and negligible bulk flow, molecules diffuse down concentration gradients. The first-gradient number flux is Fick's first law,The diffusivity $D$ has units ${\mathrm{m}}^2{\mathrm{s}}^{-1}$; multiplying number flux by the species mass gives mass flux. More generally one uses diffusion flux relative to the mixture's bulk velocity and specifies mass or mole fractions. The approximation is not a claim that an arbitrary pure-gas pressure gradient can remain at rest while only a Fick flux acts. In a mixture, collision cross-sections and relative molecular speeds, including the reduced mass, determine the species diffusivities.

Dependence on density and temperature. The kinetic estimates of gas transport coefficients predict, for fixed collision diameter and molecular heat capacity,Thus dynamic viscosity and thermal conductivity are approximately density independent in the dilute continuum regime. Reducing density reduces the number of carriers but increases their mean free path in the same proportion. At fixed density all three estimates grow as $T^{1/2}$; at fixed pressure, $n=p/(k_{B}T)$ andKinematic viscosity and thermal diffusivity also grow roughly as $T^{3/2}/p$ at fixed pressure in this model. Real interaction potentials make effective collision cross-sections temperature dependent, and internal excitations change $c_v$. Dense-gas correlations and boundaries invalidate the simple cancellation. In particular, when the mean free path approaches the apparatus scale, transport becomes free molecular; it cannot be described by extending the same local, pressure-independent Fourier and viscosity coefficients indefinitely.

Heat diffusion equation. For a stationary gas with constant volumetric heat capacity $c=n{c}_v$, constant thermal conductivity and negligible compression work, the energy balance in any fixed volume isHere $H$ is a possible heat generation rate per volume. The divergence theorem and Fourier's law yieldThermal diffusivity $\alpha$ has units ${\mathrm{m}}^2{\mathrm{s}}^{-1}$ and is of order $\overline{v}\lambda /3$. In a moving or compressing gas, the material derivative, pressure-volume work and viscous heating must also enter the internal-energy equation. The displayed pure diffusion equation describes the approximation in which those effects are absent or negligible.

Representative solutions. With no source, a steady one-dimensional slab between temperatures $T_a,T_b$ at $x=0,L$ has $T=T_a+(T_b-T_a)x/L$ and uniform heat flux $-\kappa (T_b-T_a)/L$. Thus a constant spatial gradient transports heat without changing local temperature in time when the boundaries continually supply and remove it.

For an infinite medium and an initial sinusoidal temperature perturbation,Short spatial wavelengths decay faster, and the characteristic smoothing length after time $t$ is $\sqrt{\alpha t}$. A finite slab with both ends held at $T_b$ has a sine expansion with factors $e^{-\alpha (n\pi /L{)}^{2}t}$; its slowest relaxation time is $L^2/({\pi }^2\alpha )$.

An instantaneous heat input $Q_A$ per unit transverse area at $x=0$ in an otherwise uniform infinite medium gives the Gaussian solutionIts integral $\int c(T-T_b)dx=Q_A$ conserves the deposited heat. The peak falls as $t^{-1/2}$ while its width grows as $\sqrt{t}$; diffusion redistributes energy instead of transporting a sharp front at a single velocity.

Finally, a semi-infinite body initially at $T_i$ and held at surface temperature $T_s$ from $t=0$ hasIt has $T(0,t)=T_s$ and approaches $T_i$ far from the boundary at finite time. These solutions demonstrate steady conduction, mode decay, spreading of localized heat and boundary-driven diffusion. Their idealized behaviour at extremely short times or arbitrarily long distances must be interpreted within the continuum regime rather than as an assertion of instantaneous microscopic communication.