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The Boltzmann entropy isThe thermodynamic definition of temperature givesHolding the other system parameters fixed, $E=(5N/2)k_{B}T$, so its heat capacity is $C=5N{k}_B/2$. The constants ${\Omega }_0$ and $E_0$ set an additive reference for entropy; neither affects this derivative or the resulting heat capacity.

Treat the lake as a large thermal reservoir at $T_f=283.15\mathrm{K}$, and take the copper's heat capacity $C=50\mathrm{J}{\mathrm{K}}^{-1}$ constant over the cooling interval from $T_i=783.15\mathrm{K}$. Although the actual cooling is irreversible, entropy is a state function, so its change can be calculated along a hypothetical reversible path:The lake receives $Q=C(T_i-T_f)=2.50\times 10^4\mathrm{J}$ at constant temperature, givingTherefore, neglecting other changes,The positive total is the entropy generated by transferring heat across a finite temperature difference. The copper's entropy decreases, but the colder lake gains a greater amount.

A Carnot cycle consists of four reversible stages: isothermal expansion at the hot-reservoir temperature $T_h$, adiabatic expansion to $T_c$, isothermal compression at $T_c$, and adiabatic compression back to the starting state. The adiabatic stages exchange no heat. For one mole of an ideal gas, the two isothermal stages have heats $Q_h=R{T}_h\ln (V_B/V_A)$ and $Q_c=R{T}_c\ln (V_C/V_D)$ in magnitude. The reversible adiabatic relations ensure $V_B/V_A=V_C/V_D$.

More generally, the total entropy change over any reversible cycle is zero. The two heat exchanges therefore satisfyWith work output $W=Q_h-Q_c$, its thermal efficiency isThe temperatures must be absolute. The second law makes this the maximum efficiency for an engine exchanging heat only with those two reservoirs; irreversible entropy production lowers the efficiency.

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.

For a reversible adiabatic change, $dS=0$, equivalently $C_{V}dT=-pdV$. Substitute $p=RT/(V-b)$:Integration, with fixed positive reference values $T_{\ast },W_{\ast }$, givesSince $T=p(V-b)/R$ and $\gamma =1+R/C_V$,The relation applies to the quasistatic reversible adiabat. Adiabatic heat isolation alone does not enforce it for an irreversible process which generates entropy. The shifted volume $V-b$, rather than $V$ itself, is the appropriate coordinate in this model.

Use absolute temperatures $T_c=278.15\mathrm{K}$ and $T_h=298.15\mathrm{K}$. Let ${\dot{Q}}_c$ be the heat extracted from the ground, ${\dot{Q}}_h$ the heat delivered indoors, and $P$ the electrical input power. For a reversible heat pump, the entropy transferred per unit time balances:Consequently the coefficient of performance isThe requested heat delivery is a rate, since the duration is unspecified:Of this, $13.9\mathrm{kW}$ comes from the ground and $1.0\mathrm{kW}$ from the electricity. A coefficient of performance greater than one is consistent with conservation of energy because the heat pump transports heat as well as converting electrical energy.

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.

The definition of heat capacity at constant area and the Maxwell relation give the entropy differentialFor a reversible adiabatic process, $dS=0$. Hencefor positive heat capacity $C_A$. Reversible adiabatic stretching cools the film. Reversibility, or negligible entropy production, is essential to this inference. Adiabatic isolation alone only sets the heat transfer to zero; an irreversible stretch can generate entropy, so its temperature change is not fixed by this isentropic derivative.

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 $\mathrm{J}{\mathrm{m}}^{-2}=\mathrm{N}{\mathrm{m}}^{-1}$.

Over the plotted range, approximate the surface tension by $\gamma (T)={\gamma }_0-\beta T$ with constant positive $\beta =-{\gamma }^{\prime }$, and take $C_A=70\mathrm{mJ}{\mathrm{K}}^{-1}=0.070\mathrm{J}{\mathrm{K}}^{-1}$. A reversible adiabat hasIntegrating givesThe arbitrary fixed reference temperature $T_{\ast }$ makes the logarithm dimensionless; changing it only shifts the integration constant. This is the dimensionally precise version of writing $C_A\ln T+\beta A$ as constant. Each term has units of entropy. Between two states,If the graph had substantial curvature, the entropy differential would still hold, but this particular constant-$\beta$ exponential would no longer follow.

Entropy at absolute zero. The third law of thermodynamics concerns the low-temperature limit of equilibrium states. In the zero-entropy formulation, the entropy of a perfect crystal with a nondegenerate ground state tends to zero as $T\to 0$. The statistical interpretation is $S=k_B\ln \Omega$: a unique accessible ground state has $\Omega =1$. The entropy-difference formulation of the third law of thermodynamics states that entropy differences associated with regular changes of mechanical parameters tend to zero as absolute zero is approached. These statements require equilibrium and appropriate ground-state assumptions; a frozen disordered material or a degenerate ground state can carry residual entropy.

For a phase of fixed composition and pressure,A finite limiting entropy constrains this integral. Ordinary equilibrium heat capacities therefore vanish as temperature approaches zero, with familiar examples $C\propto T^3$ for three-dimensional acoustic phonons and $C\propto T$ for a normal degenerate Fermi liquid. A constant positive heat capacity extrapolated to zero would give a logarithmically divergent entropy difference and is impossible in this regime. Discontinuous transitions and anomalous limits need separate treatment rather than extending a high-temperature approximation indefinitely.

Gibbs free energy. For fixed particle numbers,Thus, when $S\to 0$, the Gibbs free energy approaches its zero-temperature value with a horizontal tangent:The equality $G(0,p)=H(0,p)$ uses the enthalpy $H=U+pV$; neither limiting value needs to be zero. The low-temperature Gibbs free-energy expansion makes the approach quantitative. For $C_p=a{T}^r$ with $r>0$ and $S(0)=0$,The second derivative is ${\partial }_T^{2}G=-C_p/T\le 0$, although it need not tend to zero. For a reaction between such equilibrium phases, ${\partial }_T\Delta G=-\Delta S\to 0$, and $\Delta G$ and $\Delta H$ approach one another. If a genuine residual entropy $S_0$ is retained instead, $G=G(0,p)-S_{0}T+\cdots$ has limiting slope $-S_0$. A horizontal tangent cannot be asserted without the zero-entropy condition.

Why helium remains a liquid. Helium atoms attract each other weakly and are exceptionally light. Their zero-point energy is large compared with the binding that would localize them in a solid. Both helium-4 and helium-3 can therefore remain liquid down to the lowest temperatures at low pressure; substantial applied pressure is needed to solidify them. This is not a violation of the third law. A quantum liquid can have a unique low-entropy ground state, and zero-point motion does not itself imply thermal entropy. The third law does not require every substance to crystallize at atmospheric pressure.

A helium-4 atom has integer spin zero and is a boson. Below the lambda point near $2.17\mathrm{K}$ at saturated vapor pressure, its liquid is superfluid. Its strong interactions mean that it is not quantitatively an ideal Bose gas, and the condensate fraction need not equal the superfluid fraction. The two-fluid model of superfluidity separates an entropy-carrying normal component of a superfluid from the superfluid component, whose entropy is zero. At sufficiently low temperature the dominant thermal excitations are acoustic phonons: their linear dispersion in three dimensions gives $U-U_0\propto V{T}^4$, $C_V\propto V{T}^3$ and $S\propto V{T}^3$. Higher-energy rotons are exponentially suppressed. Thus the normal component of a superfluid and entropy disappear as $T\to 0$, while superfluid flow and quantum motion can persist.

A helium-3 atom has spin $1/2$ and is a fermion. Well below its Fermi temperature, but above its superfluid transition, liquid helium-3 is a degenerate interacting Fermi liquid. Only quasiparticles close to the Fermi surface are thermally excited, giving $C_V\propto T$ and $S\propto T$. At temperatures of order a millikelvin, helium-3 also becomes superfluid through formation of Cooper pairs of fermions. This is not Bose-Einstein condensation of individual helium-3 atoms. Pairing reorganizes the low-energy excitation spectrum; in the fully gapped bulk B phase, the fermionic quasiparticle contribution to heat capacity is exponentially suppressed at temperatures well below the pairing gap. Gapless collective modes can still give thermal terms following a power law. The entropy nevertheless tends to zero. The normal Fermi-liquid law cannot be extrapolated through its pairing transition unchanged.^[ref]

Helium-3 also illustrates the importance of nuclear spin entropy. Over an intermediate low-temperature range, localized spins in the solid can retain approximately $k_B\ln 2$ of entropy per atom, while the degenerate liquid has much less. Reversible conversion of liquid to the higher-entropy solid then absorbs heat; adiabatic compression along the melting curve can cool the sample. This is Pomeranchuk cooling. At still lower temperature, interactions between the nuclear spins remove this nearly free-spin entropy, so a constant $k_B\ln 2$ cannot be extrapolated to absolute zero.^[ref]

Liquefaction and cooling methods. A gas must be below its liquid-gas critical point to form a distinct liquid phase by compression. Compression above the critical temperature alone cannot achieve ordinary liquid-vapour coexistence. Practical liquefaction removes the compression heat, cools the compressed gas in a heat exchanger and uses expansion to lower its temperature further.

A throttling valve operates approximately at constant specific enthalpy when kinetic-energy changes and heat leakage are negligible. The Joule-Thomson coefficient isusing consistent molar quantities, or consistent total quantities for a fixed amount. A pressure drop cools the gas if ${\mu }_{\mathrm{JT}}>0$. An ideal gas has zero Joule-Thomson coefficient; real intermolecular interactions are essential. In particular, room-temperature helium warms on throttling, so it must first be brought into a region of positive Joule-Thomson coefficient. Expansion through an engine or turbine can instead remove work and produce approximately isentropic cooling.

A regenerative liquefier sends the cold returning gas through a counterflow heat exchanger to precool the incoming compressed gas before its next expansion. Expansion engines and external precooling can supply the initial cooling; repeated operation then produces liquid. Modern helium liquefaction commonly combines work-producing expansion with a final throttle. ^[ref]

Once liquid exists, pumping away vapour lowers its saturation pressure and boiling temperature. The escaping vapour carries latent heat away, cooling the remaining liquid. At still lower temperatures, a dilution refrigerator exploits the different entropy carried by helium-3 in concentrated and dilute helium mixtures; adiabatic demagnetization and Pomeranchuk cooling provide other routes.

Approaching zero. The unattainability formulation of the third law states that regular cooling operations with finite resources cannot reach absolute zero in finitely many stages. As the entropy available to remove becomes small and thermal couplings weaken, each method loses its ability to take the final step. An isentropic cooling trajectory starting at nonzero entropy cannot reach a common zero-entropy endpoint through regular finite changes of parameters. A fully general finite-time claim also requires assumptions about available controls and heat-transfer rates. Quantum liquids and refrigeration methods can approach $0\mathrm{K}$ while remaining consistent with vanishing equilibrium entropy; they do not provide a finite-operation route to absolute zero.

The units supplied for 130 indicate specific heat capacity, so the block's total heat capacity is $C=mc=0.5(130)=65\mathrm{J}{\mathrm{K}}^{-1}$. Treat it as constant, and the lake as a thermal reservoir at $T_0=283.15\mathrm{K}$. The initial block temperature is $T_i=373.15\mathrm{K}$.

Compute the block's entropy change using a reversible comparison path, even though the actual cooling is irreversible:The lake receives $Q=C(T_i-T_0)=5850\mathrm{J}$ at constant temperature, soThereforeThis is entropy generated by cooling a finite body in a reservoir. The positive total is consistent with the Second law of thermodynamics, although the cooling block's own entropy decreases.

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.

Three phase coexistence curves meet at the triple point, where ice, liquid water and water vapour have equal chemical potential. In the ordinary-pressure region, the low-temperature phase is ice, the high-pressure moderate-temperature phase is liquid, and the low-pressure high-temperature phase is vapour. The triple point is approximatelyBelow $p_t$, warming stable ordinary ice crosses the sublimation boundary directly into vapour; there is no intervening stable liquid. Above $p_t$, melting and then boiling can occur. The liquid–vapour curve terminates at the liquid-gas critical point, approximately $647.1\mathrm{K}$ and $22.06\mathrm{MPa}$, beyond which there is no liquid–vapour phase boundary.

The distinctive feature is the negative slope of the ordinary ice–water melting line. The Clapeyron equation givesMelting increases entropy but reduces volume because ordinary ice is less dense than liquid water, so $\Delta s>0$ and $\Delta v<0$. Increasing pressure consequently lowers the melting temperature locally. Sublimation and vaporization both increase volume and entropy, giving positive slopes. The following original schematic shows these signs; it is not a quantitative fit and omits the additional high-pressure ice polymorphs.

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.

Two equivalent second-law statements. The Clausius statement of the second law forbids a cyclic device whose sole net effect is transferring heat from a colder reservoir to a hotter one. A refrigerator can make that transfer when supplied with work, so the sole-effect qualification matters. The Kelvin-Planck statement of the second law forbids a cyclic device whose sole net effect is drawing heat from a single reservoir and converting all of it into work. A heat engine can produce work when it also rejects heat to a colder reservoir.

The two statements are equivalent by combining a supposed violating device with an ordinary reversible engine or refrigerator: one can cancel one reservoir exchange and obtain a violation of the other statement. The following original schematic shows the forbidden sole effects, with arrows indicating energy flow.

Microscopic fluctuations. The second law is a macroscopic statistical law. A finite fluctuation can transfer a small heat amount $Q$ from cold to hot, with reservoir entropy change $Q/T_h-Q/T_c<0$. Such an individual event does not imply that a cyclic engine can extract systematic useful work from equilibrium. Entropy-decreasing trajectories become exceedingly improbable when the entropy involved is large compared with $k_B$. Under suitable microscopic reversibility conditions, fluctuation relations quantify the relative probabilities of positive and negative entropy production and give nonnegative mean total entropy production. Thus a deterministic no-fluctuation reading has a limit at small scales or short times; the statistical second law remains applicable.

Maximum heating rate. Interpret the quoted $0.5\mathrm{kW}$ as the maximum work-input rate ${\dot{W}}_{\max }$ to an ideal reversible heat pump. This interpretation is needed to obtain a heating rate larger than its electrical input; the wording does not explicitly distinguish input power from delivered heat. A reversible cycle satisfiesTherefore the heating coefficient of performance isWith $T_h=293\mathrm{K}$ and $T_c=273\mathrm{K}$,The additional heat comes from the outdoor reservoir; it is not produced by converting work into more energy than was supplied.

Lowest outdoor temperature. Let $\Delta T=T_h-T_c>0$. The largest available heating rate is ${\dot{W}}_{\max }{T}_h/\Delta T$, while the house loses $\lambda \Delta T$. Equilibrium can be maintained whenAt the limiting outdoor temperature,HenceThis is the indoor-temperature limit of a Carnot heat pump. It assumes the ideal pump retains its stated input-power capability over the operating range. Real heat exchangers require finite temperature differences and incur irreversibility, so the reversible result is an ideal upper performance bound.

Conventional heater. At this limiting outdoor temperature, the required delivered heating power is simply the house's heat loss:This is heat delivered to the house. The fuel-input power would be $3.83/\eta \mathrm{kW}$ for heater efficiency $\eta$. At the earlier outdoor temperature of $273\mathrm{K}$, the required delivered heat would instead be $0.1(293-273)=2.00\mathrm{kW}$; the final question's reference temperature must be kept clear.

If $0.5\mathrm{kW}$ is read literally as a maximum delivered heat rate rather than a work-input rating, the alternative answers are ${\dot{Q}}_{h,\max }=0.5\mathrm{kW}$, $T_{c,\min }=293-0.5/0.1=288\mathrm{K}$, and a conventional heater delivering $0.5\mathrm{kW}$ at that limit. Such a pump could not balance the stated house loss at $273\mathrm{K}$. Both readings follow consistently once the ambiguous power rating is defined; the Carnot calculation above uses the work-input reading.

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.

Temperature as an equilibrium relation. Classical thermodynamics begins with the zeroth law of thermodynamics: thermal equilibrium is transitive. A thermometer can therefore assign a common empirical temperature to systems in mutual thermal equilibrium. Different thermometer properties initially give different monotone empirical scales; a resistance reading by itself does not define the absolute scale.

The Second law of thermodynamics provides a substance-independent thermodynamic scale. A reversible engine operating between reservoirs has a heat ratio depending only on their temperatures. One chooses absolute temperature so that $Q_h/Q_c=T_h/T_c$, with $Q_h,Q_c$ the positive heat magnitudes. Its reversible efficiency is $1-T_c/T_h$. Equivalently, reversible heat defines entropy through $dS=\delta Q_{\mathrm{rev}}/T$. For an equilibrium simple compressible system,Classical thermodynamics uses this relation without needing a microscopic account of entropy. A dilute-gas thermometer realizes an empirical scale approaching the thermodynamic scale after corrections for nonideal behavior.

Statistical meaning of the same derivative. In the microcanonical description, an equilibrium energy shell containing $\Omega (U,V,N)$ accessible states has $S=k_B\ln \Omega$. Its statistical temperature is consequentlyTo see why this is an equilibrium temperature, let two weakly coupled systems exchange a small energy while their total energy stays fixed. The combined multiplicity is ${\Omega }_A(U_A){\Omega }_B(U_{\mathrm{tot}}-U_A)$. Maximizing its logarithm giveswhich is equality of the two inverse temperatures. Stability requires the total entropy maximum, not only stationarity. The overwhelmingly dominant macrostate in a large system therefore realizes the thermodynamic equilibrium condition.

A large reservoir gives a small subsystem the canonical probabilities $p_i\propto e^{-\beta E_i}$, with $\beta =1/(k_{B}T)$. In that ensemble, $F=-k_{B}T\ln Z$ and $S=-k_B{\sum }_i{p}_i\ln p_i$ agree with macroscopic thermodynamic relations in their usual equilibrium regime. The equipartition identity for a classical dilute monatomic gas, $⟨p^2/(2m)⟩=3k_{B}T/2$, is a useful operational connection between microscopic motion and temperature, but is not a universal definition: quantum modes need not obey equipartition, and a system away from equilibrium need not have one temperature at all.

For finite systems one must specify the entropy convention and energy resolution; surface and fluctuation corrections can distinguish definitions that agree in the ordinary thermodynamic limit. Bounded-energy population-inverted systems can also have a negative entropy derivative and hence a negative statistical temperature. That possibility lies outside an ordinary positive-temperature ideal-gas thermometer; it does not mean temperature is merely an arbitrary average kinetic energy.

Obtaining the energy–temperature conversion. The Boltzmann constant connects entropy measured in $\mathrm{J}{\mathrm{K}}^{-1}$ with the dimensionless logarithm of a state count. Historically it could be determined from the ideal gas law $pV=N{k}_{B}T$: measure the molar gas constant $R$ and independently determine the Avogadro constant $N_A$, then obtain $k_B=R/N_A$. The independent particle-number determination matters; using $R$ alone would not fix energy per particle.

An electrical method uses Johnson-Nyquist noise. A resistor of resistance $R_e$ at known temperature has, in the classical range $hf\ll k_{B}T$, a one-sided open-circuit voltage-noise spectrum $S_V(f)=4k_{B}T{R}_e$. Over a calibrated flat bandwidth $\Delta f$,A practical measurement uses an equilibrium resistor, a calibrated low-noise amplifier and a known transfer function, subtracts or independently characterizes amplifier noise, and replaces a nominal bandwidth by the actual effective noise bandwidth. Varying temperature and fitting the mean-square voltage is more informative than treating one amplified voltage sample as the thermal variance. Other primary methods relate temperature to sound speed in a dilute gas or to calibrated particle diffusion and mobility.

There is a historically relevant unit-definition qualification: by the date of this exam, the revised SI had already taken effect on 20 May 2019. The kelvin is now defined by fixingThe same experiments now realize or compare thermodynamic temperatures using this fixed constant, whereas historically they measured the conversion constant on an independently defined temperature scale. The physical distinction between equilibrium temperature and microscopic state counting is unchanged.^[ref]

The third law of thermodynamics, in its perfect-crystal form, states that the entropy of a pure, perfectly ordered crystal with a unique ground state tends to zero as $T\to 0$. Its more general entropy-difference formulation says that the entropy difference between equilibrium states related by a finite change of a regular external control parameter tends to zero at absolute zero:The common limiting entropy is independent of $X$. Ground-state degeneracy or frozen disorder can produce residual entropy, so zero entropy is not an unconditional assertion about every sample.

In the usual regular thermodynamic setting, absolute zero cannot be attained from positive temperature by a finite sequence of cooling operations with finite resources. An entropy-temperature plot shows why a finite reversible adiabatic step cannot reach the common zero-temperature endpoint from a state with positive entropy above that endpoint: an isentropic process follows a horizontal line, while all the regular entropy curves meet only at $T=0$.

The figure illustrates this with two possible settings having $S-S_0=a_{1}T$ and $S-S_0=a_{2}T$, where $0<a_1<a_2$. First change the setting isothermally from the upper to the lower curve, rejecting heat; then change it reversibly and adiabatically back to the upper curve. Entropy conservation on the latter step givesfor every finite $n$. The staircase approaches the origin but reaches it only after infinitely many such stages. Irreversibility generates entropy and cannot improve on the reversible endpoint.

This is a thermodynamic illustration of unattainability of absolute zero, not a claim that every cooling apparatus has this particular linear entropy law. Its conclusion presumes regular equilibrium states and bounded control parameters; dynamical statements about finite cooling time additionally require physical assumptions about the available interactions and cooling rates.

The phase diagram must contain three coexistence curves meeting at the triple point: a solid-gas sublimation curve, a solid-liquid melting curve and a liquid-gas vaporization curve. The vaporization curve ends at a liquid-gas critical point; beyond it liquid and gas are continuously connected as a supercritical fluid.

The imposed contraction on freezing means $v_{m,s}<v_{m,l}$. Melting therefore has $\Delta v_m=v_{m,l}-v_{m,s}>0$ and $L_{\mathrm{fusion}}>0$. The Clapeyron equation then requiresThus raising the pressure raises the melting temperature. The liquid-gas and solid-gas slopes are also positive because the transformations into gas increase both entropy and volume. The liquid region lies between the positively sloping melting line and the vaporization curve, while gas occupies the low-pressure side. The figure is a qualitative solution sketch, not a reproduction or fit of the paper's vapor-pressure measurements; its axes are schematic.