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Use $c_p,c_V$ for the heat capacities of the entire $n$-mole sample. For a stable simple compressible gas, a Maxwell relation giveswhere ${\alpha }_V=V^{-1}(\partial V/\partial T{)}_p$ and ${\kappa }_T=-V^{-1}(\partial V/\partial p{)}_T>0$. This heat-capacity difference and mechanical stability explains the sign without assuming the internal energy depends only on temperature. It is strictly positive for an ordinary expanding gas; the unrestricted word “always” needs the qualification that equality is possible when thermal expansion vanishes.

For an ideal gas, thermodynamic consistency givesConsequently $U=U(T)$, while $H=U+pV=U+nRT$. Differentiating gives $c_p-c_V=nR$: at fixed pressure extra supplied heat permits expansion work in addition to the internal-energy increase.

Differentiate the supplied entropy at fixed $n$:Thus $U=5nRT/2$, consistently recovering $pV=nRT$, andThe coefficient in this entropy corresponds to five active quadratic thermal degrees of freedom per molecule. It should not be replaced by the monatomic value. Reference scales needed to make logarithms dimensionless are absorbed into the entropy constant and do not affect these derivatives.

With open windows the house equilibrates mechanically at approximately the same atmospheric pressure before and after heating. It is an open system: its mole number is not fixed. The isobaric ideal-gas internal-energy density isAt a fixed house volume, $n_{300}/n_{273}=273/300=0.91$: fewer molecules occupy the house, each with greater mean energy. Heating energy can enter while enthalpy leaves with escaping air. Treating the room as a sealed fixed-$n$ gas would give the wrong energy-density comparison.

Keep the problem's one-mole convention throughout. The excluded-volume parameter $b$ represents the loss of available translational volume due to short-range repulsion; it is an effective covolume, not simply the literal molecular material volume. The attraction parameter $a$ reduces the pressure below its purely repulsive value. In a mean-field picture, interaction energy is proportional to pair density, so the attractive free-energy contribution scales as $-a/V$ for one mole and the pressure correction as $-a/V^2$. Equivalently, molecular cohesive forces and the number striking a wall each supply a density factor. These parameters approximate microscopic correlations rather than measuring every pair potential exactly.

At fixed temperature, $dF=-pdV$. Substituting $p=RT/(V-b)-a/V^2$ and integrating gives the isothermal free-energy change of a Van der Waals gasThe arbitrary temperature-only term cancels. The internal-energy derivative is insteadExpansion raises the attractive internal energy toward zero. As a check, the entropy change is $R\ln [(V_2-b)/(V_1-b)]$, so $\Delta F=\Delta U-T\Delta S$. Constant $a,b$ and a homogeneous branch with $V>b$ are assumed. If a subcritical equilibrium path crosses coexistence, a Maxwell construction replaces the unstable homogeneous continuation; the displayed integral is the direct equation-of-state result, not a claim that such a continuation is physically stable.

At the Van der Waals critical point, the critical isotherm has a stationary inflection:Equating the resulting expressions for $R{T}_c$ gives $2V_c=3(V_c-b)$, henceIn reduced variables $x=V/V_c$, the critical curve is $p/p_c=8/(3x-1)-3/x^2$: it decreases through $(1,1)$ with zero first and second derivative, rather than having separate liquid/gas turning points at the critical temperature.

For a simple compressible one-component equilibrium system, the fundamental thermodynamic relation isThe internal energy has natural variables $(S,V,N)$: its derivatives give $T$, $-p$ and chemical potential $\mu$. The natural variables of a thermodynamic potential identify the independent arguments whose conjugates appear directly in a potential's differential. A Legendre transform exchanges a variable for its conjugate, giving potentials suited to different controlled conditions:

For fixed composition and the appropriate closed-system constraints, equilibrium minimizes $U$ at fixed $S,V$, $H$ at fixed $S,p$, $F$ at fixed $T,V$, or $G$ at fixed $T,p$, with other allowable internal variations understood. Enthalpy is useful for constant-pressure heat exchange with only pressure–volume work. Helmholtz free energy is suited to fixed-temperature, fixed-volume systems, and Gibbs free energy to fixed-temperature, fixed-pressure phase or chemical equilibrium. Coexisting phases of one substance have equal chemical potentials.

Where a potential is twice continuously differentiable, equality of mixed derivatives gives Maxwell relations. At fixed $N$, the four usual forms areThe fixed subscripts and signs follow from the chosen natural variables. Derivatives through a nonsmooth phase boundary require separate phase descriptions rather than automatic use of the smooth single-phase formulas.

As an application, the Helmholtz relation turns pressure data into an isothermal entropy change. For an ideal gas, $(\partial p/\partial T{)}_V=nR/V$, givingCombining the same relation with $dU=TdS-pdV$ yields $(\partial U/\partial V{)}_T=T(\partial p/\partial T{)}_V-p$, which vanishes for an ideal gas and reveals attractive-energy effects for a van der Waals gas. Thermodynamic potentials organize equilibrium constraints, while Maxwell relations convert difficult entropy derivatives into measurable response derivatives.

For speed distribution $f(v)$ normalized to one and isotropic directions, the incident number flux isThe positive normal velocity weights the population reaching the wall. Consequently its mean translational energy isThe bulk value $3k_{B}T/2$ would omit the arrival weighting.

For the two vessels, let $r=\sqrt{T_1/T_0}$, with subscripts h and c for hot and cold. Equal opposing effusion rates give $p_h/\sqrt{T_1}=p_c/\sqrt{T_0}$. Number conservation in equal, fixed volumes adds $p_h/T_1+p_c/T_0=2p_0/T_0$. HenceBoth final pressures must be determined; holding the cold temperature fixed does not hold its particle number fixed.

For aperture area $A_h=\pi d^2/4$, the common one-way flux is $J=p_c/\sqrt{2\pi m{k}_B{T}_0}$. The translational heat transfer from hot to cold is thereforeThis is the total heat transfer for a monatomic gas with no active internal modes, neglecting radiation and conduction through vessel walls. For a molecular gas, add $A_{h}J[u_{\mathrm{int}}(T_1)-u_{\mathrm{int}}(T_0)]$ for its internal energy per molecule. The maintained unequal temperatures describe a stationary nonequilibrium state even though the net particle current is zero.

A thermodynamic potential packages the equilibrium state in variables suited to the imposed constraints. For a simple fluid, $U(S,V,N)$ has differential $dU=TdS-pdV+\mu dN$. Legendre transforms give $H=U+pV$, $F=U-TS$ and $G=U+pV-TS$, with natural variables of a thermodynamic potential $(S,p,N)$, $(T,V,N)$ and $(T,p,N)$ respectively. At fixed particle number, Helmholtz free energy is minimized at fixed $T,V$; Gibbs free energy at fixed $T,p$.

A flow vessel is an open control volume, even if its walls are enclosed. For each inlet, pressure forces carry flow work $pdV$ in addition to internal energy. The steady first-law balance isWith no heat exchange, shaft work, or significant kinetic and gravitational energy differences, the enthalpy fluxes are equal. Mass flow must also balance. This equality concerns mass-flow-weighted specific enthalpies, not an unweighted sum over pipes.

Use the liquefaction yield with separate warm-gas and liquid outlets. The wording specifies that the outgoing gas is at 14 K; it does not require the outgoing liquid to have that temperature. The two outlet streams need not be in mutual thermal equilibrium. Taking $H$ as the printed specific enthalpy, the steady-flow energy balance givesFor fixed outlet enthalpies the greatest yield occurs at the smallest inlet enthalpy. Among the tabulated pressures this is 30 atm. Approximating the atmospheric-pressure gas enthalpy by the tabulated zero-pressure limiting value givesThis uses a low-pressure approximation: $p_0=1$ atm is not literally the zero-pressure table entry. Linear interpolation to 1 atm would instead give $H(p_0)\simeq 8.651\times 10^4\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$ and $\alpha \simeq 0.193$. The sparse table does not determine an exact continuous optimum between entries.

Atmospheric-pressure liquid helium must be much colder than the 14 K gas outlet: its normal boiling point is about 4.224 K.^[ref] A counterflow heat exchanger can return cold gas through the incoming stream before that gas leaves the overall control volume, while the collected liquid leaves separately at the cold end. This is a possible interpretation of the whole apparatus, rather than an extra diagram specified by the question. The enthalpy calculation needs only the stated inlet and outlet properties; it does not assume one equilibrium vessel containing both phases at 14 K. In particular, $H(p_0)-H_{\ell }$ is an outlet-stream enthalpy difference, not the latent heat of vaporization at one common temperature.

Reading the approximately straight trend in the supplied graph gives $\gamma (330\mathrm{K})\simeq 22\mathrm{mN}{\mathrm{m}}^{-1}$ and ${\gamma }^{\prime }\simeq -0.13\mathrm{mN}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$. These are graph-read estimates, not more precise material constants. For $\Delta A=10^{-4}{\mathrm{m}}^2$, reversible isothermal stretching givesBoth are positive: stretching does mechanical work on the film and requires heat input to prevent cooling. Its internal energy increases by about $6.5\mu \mathrm{J}$.

Write $\gamma =\alpha -\beta T$, with $\beta =-{\gamma }^{\prime }\simeq 1.3\times 10^{-4}\mathrm{J}{\mathrm{m}}^{-2}{\mathrm{K}}^{-1}$. Constant $C_A$ then makes the reversible adiabatic conditionwhere $T_{\ast }$ is an arbitrary fixed reference temperature; absorbing it into the constant gives the requested logarithm convention. HenceHere $C_A=0.070\mathrm{J}{\mathrm{K}}^{-1}$. Since $\gamma -T{\gamma }^{\prime }=\alpha$, integration gives $\Delta U=C_A(T_f-T_i)+\alpha \Delta A$. To first order this isThere is no heat exchange on this reversible adiabat. Cooling and increasing internal energy are compatible: positive area work more than offsets the decrease of the temperature-dependent energy term.

Molecules. In a dilute classical gas, collisions establish a Maxwell-Boltzmann distribution. The normalized speed distribution and its first two moments areMomentum transfer to a wall gives $p=nm\overline{v^2}/3=n{k}_{B}T$. Translational internal energy is $U=3N{k}_{B}T/2$; rotational and vibrational degrees of freedom add energy when thermally populated, without changing the dilute ideal-gas pressure law. Classical equipartition gives $k_{B}T/2$ per quadratic contribution, but quantum level spacing can freeze out modes.

Only the molecules moving towards a surface contribute to its one-sided number flux:For an effusive molecular energy flux, faster molecules are preferentially sampled, giving mean translational energy $2k_{B}T$ per crossing molecule and $F_E=2k_{B}TJ$. This differs from multiplying $J$ by the bulk mean $3k_{B}T/2$. Collisions and finite molecular interactions produce transport and departures from the ideal-gas equation of state.

Photons. All photons travel at $c$ in vacuum, so their thermal distribution is over frequency, not over a range of speeds. The two polarizations and Bose-Einstein occupation with zero chemical potential giveHere the spectral quantity is $u_{\nu }$ and the total energy density is $u$. Momentum flux gives $p=u/3$, while isotropic angular averaging gives the one-sided energy flux $F_E=cu/4={\sigma }_{\mathrm{SB}}{T}^4$ through a small aperture of a black-body cavity. The photon number flux is similarly $c{n}_{\gamma }/4$.

Both pressures arise from momentum transfer, but their equations of state differ: a classical molecular gas has $pV=N{k}_{B}T$ with fixed molecule number, whereas a photon gas has $pV=U/3$, $U=a_{R}V{T}^4$ and an equilibrium photon number that changes with temperature. Photon creation and absorption by the walls are essential to the zero-chemical-potential equilibrium description.

To obtain the maximum work from two finite heat reservoirs, operate a reversible heat engine between the bodies until their temperatures coincide. Include the work store in the isolated total system: no heat enters from outside, while the bodies can transfer energy to that store. With the stated constant heat capacities, reversibility requiresNumerically, $T_f=450^{5/8}273^{3/8}=373.094\mathrm{K}$. The decrease of the bodies' internal energy isDirect thermal equilibration without an engine would instead reach the arithmetic heat-capacity-weighted temperature $383.625\mathrm{K}$ and deliver no work. entropy production can only raise the final common temperature above the value for zero entropy production and reduce extractable work.

Use heat into the gas as positive. The two adiabatic stages have $Q_{12}=Q_{34}=0$. During constant-pressure heating and constant-volume cooling,The first law over a complete cycle gives $W_{\mathrm{out}}=Q_{23}+Q_{41}$, since the internal energy returns to its initial value. ThereforeSubstitute the temperatures:HenceEquivalently, define compression ratio $r=V_1/V_2$ and cutoff ratio $\rho =V_3/V_2$:These formulas use the ideal constant-heat-capacity model and reversible adiabatic strokes. The heat-addition and heat-rejection strokes occur over changing gas temperatures, unlike the isothermal heat exchanges of a Carnot engine.

Start with the fundamental relation at fixed material amount, $dU=TdS-pdV$, and expand entropy in independent variables $T,V$:The last equality uses the supplied Maxwell relation. ConsequentlyFor the excluded-volume ideal gas, $(\partial p/\partial T{)}_V=R/(V-b)=p/T$, so the bracket vanishes:Once $U$ depends only on temperature, $C_V=dU/dT$ cannot depend on volume either. Its stipulated temperature independence therefore makes it a constant, giving $U=C_{V}T+U_{\ast }$ with arbitrary energy reference $U_{\ast }$. Excluded volume changes the pressure without adding the volume-dependent attractive internal energy that a more general interacting-gas model might have.

An equation of state relates equilibrium state variables such as pressure, volume, temperature and material amount. At fixed composition, it reduces the number of independent thermodynamic variables. It does not by itself specify all caloric properties: information such as heat capacity or internal energy is also needed.

At a liquid-gas first-order transition, an equilibrium isotherm can contain a constant-pressure interval in which changing total volume changes the phase fractions. A metastable single-phase extrapolation can instead show a region with $(\partial p/\partial V{)}_T>0$; that region has negative isothermal compressibility and is mechanically unstable. Thermodynamic phase coexistence requires equal temperature, pressure and chemical potential, and a consistent free-energy description replaces the unstable region by coexistence. For an appropriate analytic fluid equation of state, a liquid-gas critical point occurs where $(\partial p/\partial V{)}_T=({\partial }^{2}p/\partial V^2{)}_T=0$.

These tests diagnose the phase behaviour represented by that equation of state. They do not guarantee detection of every possible transition involving an additional order parameter which the mechanical equation omits.

For the specified increment,Using the adiabat, or its first-order Taylor expansion,This is a very small cooling, about $61\mu \mathrm{K}$. There is no heat exchange, and the film is stretched against positive surface tension, so the internal energy increases, withThe cooling does not contradict this increase. In the linear model, $\gamma -T{\gamma }^{\prime }={\gamma }_0\simeq 0.065\mathrm{J}{\mathrm{m}}^{-2}$, soCreation of surface raises the internal energy more than the cooling lowers its temperature-dependent part. The change in surface tension during this tiny temperature fall changes the work only at a negligible higher order.

Write ${\gamma }^{\prime }=d\gamma /dT<0$. The Maxwell relation givesThus isothermal stretching increases the entropy. For an infinitesimal increase, $dS=-{\gamma }^{\prime }dA$; if the derivative is independent of area, this integrates to $\Delta S=-{\gamma }^{\prime }\Delta A$ at fixed temperature. Mechanical energy used to create extra surface is not, in general, identical to the increase of internal energy at fixed temperature, because the stretching can also absorb heat.

Substitute the entropy differential into the fundamental relation:ThereforeThe coefficient of $dA$ is the change of internal energy per added area at fixed temperature, whereas $\gamma$ is the change of Helmholtz free energy per added area. Their difference $-T{\gamma }^{\prime }$ is the heat absorbed per added area in a reversible isothermal stretch. Both $\gamma$ and $T{\gamma }^{\prime }$ have units $\mathrm{J}{\mathrm{m}}^{-2}=\mathrm{N}{\mathrm{m}}^{-1}$.

Treat the film at fixed material content, with area $A$ the coordinate conjugate to the surface tension in the stated work term. The Helmholtz free energy is a Legendre transform of the internal energy:Its natural independent variables are therefore $T,A$, soEquality of mixed second partial derivatives gives the Maxwell relation for the thermodynamics of a liquid film:The area convention matters: the supplied fundamental relation already specifies the coefficient of $dA$. There is no additional factor of two unless one changes from total interfacial area to a projected film area and changes the work term consistently.

Origin of diffusion. In a material near local thermal equilibrium, microscopic carriers transfer energy from hotter regions to colder regions. On distances long compared with their mean free path and times long compared with relaxation times, the local constitutive law is Fourier's law,Combining this temperature-gradient-driven flux with local conservation of energy produces a diffusion equation. This description assumes diffusive thermal conduction; it is not generally valid for ballistic transport, and flow would add advective transport.

Energy balance with heating. Choose any fixed volume $V$, let $c$ be its uniform volumetric heat capacity and $H$ its heat generation rate per unit volume. The rate of increase of internal energy equals heat generation minus outward heat flux:Since $V$ is arbitrary, for constant thermal conductivityThe ratio $\kappa /c$ is the thermal diffusivity in ${\mathrm{m}}^2{\mathrm{s}}^{-1}$. Here $c$ is in $\mathrm{J}{\mathrm{m}}^{-3}{\mathrm{K}}^{-1}$, $\kappa$ in $\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$ and $H$ in $\mathrm{W}{\mathrm{m}}^{-3}$, so both right-hand terms have units $\mathrm{K}{\mathrm{s}}^{-1}$. If thermal conductivity varies with position or temperature, the divergence $\nabla \cdot (\kappa \nabla T)$ must be retained rather than replacing it by $\kappa {\nabla }^{2}T$.

Initially and finally the block and lake are at the same temperature. After the falling block has come to rest, its lost gravitational potential energy has dissipated into internal energy of the lake and surroundings. In the idealization that all $mgh$ is ultimately thermalized in the lake at $T_0=283.15\mathrm{K}$,The block returns to its original thermal state, so its net entropy change is zero. Mechanical potential energy carries no thermal entropy that must be subtracted. ThusUse of $g=9.80\mathrm{m}{\mathrm{s}}^{-2}$ gives the same three-significant-figure answer. Splashing and any temporary heating do not change this final-state balance if their mechanical energy is eventually dissipated in the same reservoir.

Pressure and its physical terms. Solving the molar Van der Waals equation for pressure givesThe excluded-volume parameter $b$ reduces the volume available for translational motion, raising the kinetic pressure relative to $RT/V$. The attraction parameter $a$ lowers the pressure because attractive interactions reduce the momentum transferred to the boundary. This mean-field model treats $a,b$ as temperature-independent material constants. For one mole, $V$ is the sample volume with the molar amount already fixed; $b$ has units of that volume and $a$ of pressure times volume squared.

volume dependence of entropy. The Helmholtz free energy has differential $dF=-SdT-PdV$. Equality of mixed derivatives yields the Maxwell relationFor $a=0$ this derivative is $R/(V-b)$, givingEquivalently, $S=R\ln (V-b)+f(T)$ with a common reference volume understood inside the logarithm. The equation of state fixes this volume dependence, not the otherwise unspecified function of temperature.

Excess entropy at fixed volume and temperature. The ideal gas has $(\partial S_{\mathrm{id}}/\partial V{)}_T=R/V$. ThereforeIntegrate from infinite volume, where the entropy difference is specified to vanish:It is negative because excluding configurations reduces the accessible state count. It tends to zero as $V\to \infty$ and has leading dilute limit $-Rb/V$. This is the entropy excess of a van der Waals gas.

Effect of attraction. Restoring a temperature-independent $a$ changes the pressure by $-a/V^2$, but not its derivative with respect to temperature. With the same infinite-volume entropy reference, it therefore does not change $\Delta S^{\mathrm{ex}}$ at fixed $V,T$. This can also be seen fromThe attraction affects internal energy and the equilibrium volume, so it can affect entropy indirectly when different state points are compared. If $a$ were temperature dependent, its derivative would contribute directly to the entropy; that is outside the stipulated constant-parameter model.

Coexistence isotherm. Below the Van der Waals critical point, the formal homogeneous isotherm has a local minimum and maximum. Its middle branch has $\partial P/\partial V>0$, hence negative isothermal compressibility, and is mechanically unstable. Portions of the negative-slope branches can be metastable rather than globally stable. The equilibrium isotherm replaces the loop between liquid volume $V_l$ and vapour volume $V_g$ by a constant saturation pressure $P_s$. The two volume are fixed byThe Maxwell equal-area construction expresses equality of the two phases' chemical potentials. Intermediate total volume are mixtures: changing the vapour fraction changes total volume at the same pressure, rather than following the unstable homogeneous curve. The spinodals are the turning points of the formal isotherm; they are distinct from the coexistence endpoints.

Dense-phase volume at low temperature. At a general subcritical temperature, the two coexistence equations above must be solved together. For this equation of state the area condition is explicitlyThis supplies an exact implicit determination of the liquid volume even when a simple closed form is unavailable.

For the asymptotically low-temperature limit, put $\tau =RTb/a\ll 1$. The liquid is dense, $V_l\simeq b$, while the vapour is dilute, $P_s{V}_g\simeq RT$ and $V_g\gg V_l$. The area condition then givesThus the vapour volume grows exponentially in $1/\tau$, and the saturation pressure is exponentially small. It is consequently consistent to neglect $P_s$ in the liquid equation to algebraic order in $\tau$:Choose the root near $b$, not the large-volume zero-pressure root:Expanding gives the leading requested dense-phase behavior,This is the low-temperature liquid volume of a van der Waals gas. Setting $P_s=0$ is an asymptotic approximation, not an exact coexistence condition at every temperature below $T_c$. The figure illustrates generic subcritical coexistence; its finite-temperature liquid volume is determined by the full equal-area equations. The van der Waals liquid also ceases to be a realistic description at sufficiently low physical temperature, where other phases or quantum effects can matter.

Configuration count. Choose the end-to-end direction as positive and let $N_R,N_L$ count rightward and leftward links. ThenA configuration is determined by choosing the positions of its leftward links, soThe counts must be nonnegative integers; in particular, allowed signed extensions occur in steps of $2a$. If distance means $|L|$ with neither direction selected, there are two corresponding sets for $L>0$, adding a factor of two. That constant does not affect the tension. There is no excluded-volume penalty in this one-dimensional idealized count.

Entropy from the multiplicity. Put $x=L/(Na)$, so $|x|<1$. Applying the leading Stirling's approximation to all three large factorials givesTerms subleading in $N$, including logarithmic factorial prefactors, have been omitted consistently. Expanding near zero extension givesStretching reduces the number of available configurations and hence the entropy.

Tension and the range of Hooke's law. The model assigns no extension-dependent internal energy. At fixed temperature, the externally applied tension is $\mathcal{F}=(\partial F/\partial L{)}_T=-T(\partial S/\partial L{)}_T$. Differentiating the full leading entropy givesIt is the external force needed to oppose the chain's restoring entropic force. Only when $|L|\ll Na$ can one put $\mathrm{artanh}x\simeq x$, yieldingThe paper's displayed linear law therefore requires this small-extension approximation, which is not explicitly stated in its premise $L<L_0$. It is not the exact force law up to full extension. The entropic spring constant grows with temperature because stronger thermal disorder makes a given reduction in configurational entropy cost more free energy. This is the one-dimensional entropic chain force-extension relation.

A sparse number of backward links. Write $q=N_L\ll N$, so $N_R=N-q$ and $L=a(N-2q)$. Exactly,For fixed $q$ and large $N$, each numerator factor approaches $N$, givingMore precisely, the logarithm of the product is $-q(q-1)/(2N)+O(q^3/N^2)$. A small relative error in the multiplicity requires $q^2/N\ll 1$; merely $q/N\ll 1$ need not make the omitted product close to one. The weaker sparse-link condition does suffice for the leading entropy density and leading high-extension tension. These are sparse backward links near full chain extension.

Tension in that limit. In the overlap regime $1\ll q\ll N$, use Stirling also for $q!$:ThusThe full leading entropy would give $(k_{B}T/(2a))\ln [(N-N_L)/N_L]$, which has the same dominant logarithm when $N_L/N\to 0$.

Approaching full extension. The continuum force law diverges logarithmically as $N_L\to 0$, or $L\to Na$. One must not literally apply Stirling to a zero factorial: at the discrete endpoint there is exactly one directed configuration, $\Omega =1$, and its entropy is zero. A continuous fixed-extension derivative is not defined at that endpoint.

An independent force-ensemble calculation makes the limiting physical statement precise. For applied tension $\mathcal{F}$, a link has partition function $z=2\cosh (\beta \mathcal{F}a)$, giving the exact mean extensionIt approaches $Na$ only as $\mathcal{F}\to \infty$ at positive temperature, and inversion reproduces the logarithmic force law for mean extension. In a real chain, bond extension or failure eventually replaces the ideal inextensible-link model.

The internal energy is the canonical mean of the energy:Holding the external mechanical parameters fixed, so that the spectrum and degeneracies do not change when differentiating with respect to $\beta$, givesComparison yieldsAn explicitly temperature-dependent effective Hamiltonian would require care: differentiating its partition sum would also differentiate the assigned energy levels. The stated result uses the fixed physical spectrum of the canonical system.