Past exam of the thermal and statistical physics course of the University of Cambridge / 2019 / Section B / 5

Availability and total entropy. The reservoir changes by $d{U}_R=-dU$ and $d{V}_R=-dV$. Its particle number and the system's particle number are fixed. The reservoir's first law of thermodynamics therefore givesAdd the system's entropy change. Because $T_R,p_R$ are constant,Thus define the availabilityAn additive constant in $A$ is immaterial; its value above the equilibrium reference is the exergy. The Second law of thermodynamics gives $\Delta S_{\mathrm{tot}}\ge 0$, hence $\Delta A\le 0$. A stable equilibrium maximizes total entropy over the allowed variations and therefore minimizes $A$. The environmental $T_R,p_R$ enter this definition even when the system has not yet reached their values. Because both thermal and mechanical exchanges are allowed, equilibrium here includes mechanical balance; equality of temperatures alone does not ensure the minimum.

Probability and curvature. For a fixed value of a macroscopic coordinate $x$, let $S(x)$ count the compatible system microstates. The product of the system and reservoir multiplicities isAll factors independent of $x$ enter a normalization constant, givingHere $A(x)$ is the constrained or effective availability for this coordinate, including the multiplicity of any eliminated variables. A nonuniform coordinate measure must likewise be retained or incorporated in that effective availability.

At a stable interior minimum, $A^{\prime }(x_0)=0$ and $A^{\prime \prime }(x_0)>0$. Its Taylor expansion givesKeeping the quadratic term yields a normal distribution,This is availability curvature and equilibrium fluctuations. The quoted fluctuation formula holds at quadratic order in the Gaussian fluctuation approximation; it is not an exact identity for an arbitrary nonlinear $A(x)$. Higher terms can shift the mean away from its most probable value $x_0$.

Bubble equilibrium. Keep the number of air molecules fixed and include the surface energy in the system's total internal energy. For constant surface tension $\Gamma$, this contribution is $\Gamma \Omega =\Gamma \alpha V^{2/3}$, with no surface entropy under the stated approximation. Its differential isHenceIndependent thermal and volume variations give $T=T_R$ andThe air pressure is evaluated at $V_0$; since the bubble is closed it generally depends on volume, so this equation is implicit until an air equation of state is supplied. For a sphere, $\alpha =(36\pi {)}^{1/3}$, $\Omega =4\pi R^2$, and the pressure jump becomes $2\Gamma /R$, the Young–Laplace equation for a single gas–liquid interface. There is no second surface as in a thin soap film.

Isothermal volume fluctuations. With the air maintained at $T_R$, eliminate its entropy in favor of its Helmholtz free energy:The identity $(\partial F_{\mathrm{air}}/\partial V{)}_{T,N}=-p_{\mathrm{air}}$ givesUsing the curvature result,These are the volume fluctuations of a closed gas bubble. Stability requires the denominator to be positive. The negative surface contribution reflects the concavity of $V^{2/3}$; gas compression supplies the positive restoring curvature. For ideal air, ${\kappa }_T^{-1}=p_{\mathrm{air}}$, and mechanical equilibrium reduces the denominator toThe units are consistent: $D$ is pressure, so $k_B{T}_R{V}_0/D$ has units ${\mathrm{m}}^6$, the units of a volume variance. Holding $p_{\mathrm{air}}$ externally fixed while varying $V$ would remove the gas-compression term and change this stability problem; that is not the fixed-particle-number situation here.

Numerical size of the fluctuations. The volume conversion is important:Use the specified $\alpha =4.84$, $\Gamma =0.072\mathrm{N}{\mathrm{m}}^{-1}$ and $p_R=10^5\mathrm{Pa}$. ThenWith the Boltzmann constant $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$,Thus the fractional root mean square fluctuation and fractional variance are respectivelyThe absolute root mean square fluctuation is $2.01\times 10^{-19}{\mathrm{m}}^3$. The very small fractional value supports the local Gaussian fluctuation approximation. This estimate neglects exchange of dissolved air, variations of surface tension, shape fluctuations and temperature fluctuations, consistently with the prescribed fixed-number, isothermal bubble model.