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The zeroth law of thermodynamics states the transitivity of thermal equilibrium: if two systems each equilibrate thermally with a third, they equilibrate with one another. A reproducible thermometric property can therefore label their temperature. Its empirical numerical scale is not itself the complete thermodynamic content; reversible heat-engine relations establish an absolute temperature scale.

The first law of thermodynamics expresses energy conservation. For a closed system, $dU=\delta Q-\delta W$ when $\delta W$ is work done by the system. internal energy is a state function, while heat and work depend on the path. In reversible simple compressible motion, $\delta W=pdV$ and $dU=TdS-pdV$; an open system additionally needs the energies carried by transferred matter. An ideal gas can expand freely with $Q=W=0$ and unchanged internal energy. The first law alone does not decide whether the reverse spontaneous process occurs.

The Second law of thermodynamics introduces entropy and restricts direction. For a reversible path, $dS=\delta Q_{\mathrm{rev}}/T$; for an irreversible process the entropy balance includes nonnegative production. The entropy of an isolated system cannot decrease. In a cycle, the Clausius inequality is $\oint \delta Q/T\le 0$, using the appropriate boundary/reservoir temperatures. The Kelvin–Planck statement forbids a cyclic device whose sole effect is extracting heat from one reservoir and turning all of it into work; the Clausius statement forbids moving heat from cold to hot with no compensating effect. A refrigerator is allowed because it consumes work. A two-reservoir engine has $\eta \le 1-T_c/T_h$, with equality in the reversible limit. Work may be fully dissipated as heat without contradicting this one-way restriction.

The third law of thermodynamics constrains low-temperature entropy. An equilibrium perfect crystal with a nondegenerate ground state approaches zero entropy as $T\to 0$, fixing the conventional absolute entropy reference. Degenerate ground states or frozen nonequilibrium disorder require care when discussing residual entropy. Under regular equilibrium conditions the heat capacity must decrease sufficiently for $\int C/TdT$ to remain finite; a constant positive classical heat capacity cannot be extrapolated to zero temperature. The unattainability formulation states that absolute zero cannot be reached by a finite sequence of admissible cooling operations. These statements concern the limiting thermodynamic regime, rather than predicting that every substance stays in one classical phase during cooling.

The laws work together: conservation sets a device's energy budget, entropy production restricts the attainable budget, and constitutive equations give the properties of its working material. For fixed temperature and volume, Helmholtz free energy decreases toward equilibrium; at fixed temperature and pressure the corresponding potential is Gibbs free energy. Stable equilibrium, phase coexistence and Maxwell relations follow from these potentials with appropriate constraints. Calorimetry, mechanical-work measurements, thermometry and reversible-path comparisons test different parts of this framework. None of the laws by itself supplies a particular gas equation of state or microscopic heat capacity.

Suppose two distinct reversible adiabatic processes intersect at an equilibrium state $C$. Choose an isothermal process that meets the two branches at distinct states $A$ and $B$, forming a nonzero-area three-sided thermodynamic cycle. There is no heat exchange on $AC$ or $BC$, so the only net heat comes from the one heat reservoir on $AB$. Since $\Delta U=0$ around a cycle, $W_{\mathrm{cycle}}=Q_{AB}$.

Choose the direction in which this nonzero cycle delivers positive work. It would then convert heat from a single reservoir entirely into work, violating the Kelvin-Planck statement of the second law. Distinct reversible adiabats cannot intersect. Equivalently, their constant entropy labels cannot differ at one equilibrium state. The argument concerns an ordinary equilibrium family of reversible adiabats, not arbitrary irreversible insulated paths. The usual local uniqueness of an equilibrium adiabat excludes coincident segments described as distinct curves.

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.

In the Carnot cycle, let $1\to 2$ be reversible isothermal expansion at $T_h$, $2\to 3$ reversible adiabatic expansion, $3\to 4$ isothermal compression at $T_c$, and $4\to 1$ adiabatic compression. The pressure–volume curve is clockwise. The entropy–temperature figure below uses temperature on the horizontal axis and entropy on the vertical axis, literally an $S$–$T$ plot: isotherms are vertical and adiabats horizontal. The hot isotherm increases entropy by $\Delta S$ and absorbs $Q_h=T_h\Delta S$; the cold one rejects $Q_c=T_c\Delta S$. Thus $W=(T_h-T_c)\Delta S$ and ${\eta }_C=1-T_c/T_h$.

For the second engine, choose the working direction with heat addition during $A\to B$ at $p_1$ and rejection during $C\to D$ at $p_2$. A reversible ideal-gas adiabat obeys $T\propto p^{(\gamma -1)/\gamma }$. DefineThe two constant-pressure heat transfers are $Q_{\mathrm{in}}=c_p(T_B-T_A)$ and $Q_{\mathrm{out}}=c_p(T_C-T_D)=Q_{\mathrm{in}}/r$, where rejected heat is quoted positive. Therefore the Brayton cycle efficiency isfor $\gamma =5/3$. All heat-capacity amount conventions cancel in the ratio.

Since $T_B>T_A$ and $T_C=T_B/r$, $T_D=T_A/r$, the maximum is at B and the minimum at D. The Brayton-Carnot efficiency comparison isThe inequality is strict for a nondegenerate cycle with positive heat input. Although each process can be reversible, the isobaric heat transfer spans a range of temperatures; making the whole cycle reversible requires a succession of matched-temperature reservoirs, rather than just the hottest and coldest reservoirs.

For an ideal diatomic gas with active rotation and frozen vibration, $\gamma =7/5$ andHere $0<p_2/p_1<1$. This comparison holds at the same pressure ratio and assumes temperature-independent heat capacities in the stated mode regime. Frozen rotation or excited vibration would require their actual heat capacities.

A microstate specifies the microscopic state: classically the positions and momenta of all particles, or quantum mechanically an allowed many-body state. A macrostate specifies a few coarse variables such as energy, volume and particle number. Many microstates can give the same macrostate. A statistical ensemble is a probability assignment over hypothetical copies prepared with the same macroscopic constraints; it does not require a sample to be literally divided into many physical copies. An observable's ensemble mean is $⟨A⟩={\sum }_i{p}_i{A}_i$, with an integral replacing the sum in classical phase space.

For an isolated system at fixed $U,V,N$, the microcanonical ensemble assigns equal probability to accessible microstates in a narrow energy shell. If their number is $\Omega (U,V,N)$, the Boltzmann entropy is $S=k_B\ln \Omega$. Thermal contact between two initially isolated systems allows energy to be shared while their sum stays fixed. The most probable division maximizes $S_1(U_1)+S_2(U-U_1)$, so equilibrium requires equal $\partial S/\partial U$. This gives the statistical temperature definitionFor positive temperature, energy tends to flow from lower entropy slope to higher entropy slope until those slopes agree. The narrow energy-shell width represents macroscopic resolution; it must not exclude the physically accessible states.

For a small subsystem exchanging energy with a much larger bath, the bath has energy $U_{\mathrm{tot}}-E_i$ when subsystem microstate $i$ has energy $E_i$. Expanding its entropy gives $S_b(U_{\mathrm{tot}}-E_i)=S_b(U_{\mathrm{tot}})-E_i/T+\cdots$. Counting compatible bath states therefore yields the Boltzmann distribution and canonical ensemble:The exponential weights individual microstates. An energy level of degeneracy $g_j$ has total probability $g_j{e}^{-\beta E_j}/Z$; a more degenerate excited level can outweigh one ground-state level even though each of its microstates is less probable. The Gibbs entropy $-k_B{\sum }_i{p}_i\ln p_i$ gives $S=k_B\ln Z+U/T$. The equilibrium energy variance is $⟨(\Delta E{)}^2⟩=k_B{T}^2{c}_V$, linking measurable fluctuations to a macroscopic response.

If particle exchange is also allowed, a reservoir fixes $T$ and chemical potential $\mu$. The grand canonical ensemble weights a state by $e^{-\beta (E_i-\mu N_i)}/\Xi$, with $\Xi ={\sum }_{N,i}{e}^{-\beta (E_i-\mu N)}$. Mean particle number is $k_{B}T\partial \ln \Xi /\partial \mu$, while volume remains a constraint in this version. Thus the ensemble follows the physical exchange conditions: fixed energy, thermal contact, or thermal and particle contact.

In ordinary large short-range systems, relative fluctuations often decrease as $N^{-1/2}$ and the ensembles give the same bulk thermodynamics away from singular limits. Finite systems, critical fluctuations and long-range interactions require care. Interpreting a time average as an ensemble average additionally requires appropriate sampling or mixing dynamics; it is not guaranteed solely by naming an ensemble. thermal equilibrium probability assignments do not describe every driven or relaxing state.

For the entropy balance of a thermostatted resistor, electrical work becomes heat $Q=I^{2}Rt=2.0\times 10^7\mathrm{J}$. At fixed temperature the resistor has no net change of thermodynamic state; it exports this heat to its thermostat. Treating the electrical supply as a source of work,Entropy is produced by Joule heating even though it does not accumulate in the resistor. Additional entropy production inside a nonideal power supply is outside the specified model.

At coexistence, the two phases have equal chemical potential. For a single component, $d\mu =-sdT+vdp$, with entropy and volume measured on the same molar or mass basis. Equating the phase derivatives along coexistence gives $\Delta vdp=\Delta sdT$. Reversible latent heat satisfies $L=T\Delta s$, henceHere $p$ and $T$ are coexistence pressure and absolute temperature, $L$ is latent heat for transforming phase 1 to phase 2, and $\Delta v=v_2-v_1$ uses the same amount of material as $L$.

For vaporization, neglect liquid molar volume compared with ideal-vapour volume $RT/p$. The ideal-vapour Clausius-Clapeyron approximation becomesUsing the normal boiling reference $T_b=373.15\mathrm{K}$, $p_b=1.01325\times 10^5\mathrm{Pa}$ and the supplied constant $L_e$ givesThis deliberately constant-latent-heat extrapolation does not reproduce the supplied triple-point pressure exactly. It predicts the liquid-vapour branch, metastable against ice below the triple-point temperature; it is not a precision sublimation-pressure prediction.

The phase diagram has solid, liquid and vapour regions meeting at the triple point. The sublimation and vaporization boundaries have positive slopes, whereas the ordinary ice–water boundary slopes negatively because ice has larger specific volume. The liquid–vapour line terminates at a critical point; the original schematic below emphasizes topology and marks the supplied triple point.

For the melting-pressure estimate, Archimedes' principle gives ${\rho }_i=0.90{\rho }_w=900\mathrm{kg}{\mathrm{m}}^{-3}$, soConvert the molar evaporation heat using water molar mass $M\simeq 0.0180\mathrm{kg}\mathrm{mo}{\mathrm{l}}^{-1}$, rounded from the tabulated value $18.0153\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$.^[ref] An enthalpy cycle through vapour then givesThis uses the question's temperature-independent evaporation heat all the way to the triple point; no replacement experimental fusion heat is inserted. The melting pressure inferred from flotation and latent heats, on holding $L_f$ and $\Delta v$ constant, isusing $T_t=273.16\mathrm{K}$ and $T=270.15\mathrm{K}$. Linearizing the logarithm about the triple point gives $53.4\mathrm{MPa}$ instead of $53.7\mathrm{MPa}$. Both are estimates within the stated constant-property approximation; the negative melting slope makes a positive pressure necessary to lower the melting 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.

With the standard liquid-water approximation $\rho \simeq 10^3\mathrm{kg}{\mathrm{m}}^{-3}$, each portion has mass $100\mathrm{kg}$. The equal heat capacities give final temperature $T_f=310\mathrm{K}$ by energy conservation. For an insulated mixing process with no other changes,The reversible integrals $mc\int dT/T$ evaluate entropy differences between equilibrium states; the actual heat transfer is irreversible. These are two portions of the same substance, so there is no additional ideal-mixture compositional entropy.

Define $q=N_{+}-N_{-}$, where $N_{+}$ counts particles in the $+ϵ$ level. Then $N_{\pm }=(N\pm q)/2$, soThe binomial entropy of independent two-level particles follows from counting which of the $N$ independently labelled particles occupy each nondegenerate level. This is the usual distinguishable, or localized, two-level model; occupation constraints of a degenerate quantum gas would require different counting.

For large occupations, Stirling's approximation with $x=q/N$ givesAllowed $q$ runs from $-N$ to $N$ in steps of two. Entropy is largest near equal populations and is zero when all particles occupy one level; use $0\ln 0=0$ at the endpoints.

Phase equilibrium minimizes Gibbs free energy at specified temperature, pressure and composition. Coexisting phases have equal temperature, pressure and chemical potential. For a pure substance, a first-order transition has continuous equilibrium Gibbs free energy but a jump in its first derivatives, such as entropy or volume; the latent heat is $T\Delta S$. Continuous transitions lack that latent heat and can instead have singular or discontinuous higher responses.

The van der Waals molar equationcombines an excluded-volume correction with attractive interactions. Its inflection conditions giveBelow $T_c$, the oscillatory isotherm contains a mechanically unstable segment with $(\partial p/\partial v{)}_T>0$. Equilibrium instead replaces the loop by a constant-pressure coexistence line. Equality of chemical potentials gives the Maxwell construction,On isothermal compression the gas reaches saturation, then converts progressively into liquid at fixed pressure. The mean molar volume obeys $v=(1-x)v_{\ell }+x{v}_g$, where $x$ is the gas fraction. Metastable superheated or supercooled states can persist when nucleation is delayed; they are not the global equilibrium selected by this construction.

A pressure–temperature phase diagram contains coexistence curves separating solid, liquid and gas. Three phases meet at a triple point; the liquid–gas coexistence curve ends at a thermodynamic critical point, above which liquid and gas can be connected without crossing a first-order phase boundary. A generic solid–liquid line continues beyond the liquid–gas critical temperature. For one component the Gibbs phase rule is $F=3-P$, so a three-phase equilibrium fixes both temperature and pressure.

Along a two-phase coexistence curve, $d\mu =-sdT+vdp$ for each phase givesThis is the Clapeyron equation, valid with consistent molar or specific quantities. For vaporization, neglecting the liquid volume and treating the vapour as ideal gives $\Delta v\simeq RT/p$, hence $d\ln p/dT=L/(R{T}^2)$. With approximately constant molar latent heat,This Clausius–Clapeyron approximation explains the rapid rise of vapour pressure with temperature. It fails close to the thermodynamic critical point, where phase volumes converge, and is not a universal expression for melting. The sign of a melting-line slope depends on its volume change; water's denser liquid gives a familiar negative slope.

Suppose an engine were more efficient than a reversible Carnot engine between the same reservoirs. Couple it to a reversed Carnot engine, scaling the cycles to have equal work. With no net external work, their combined effect would be to transfer heat from the colder reservoir to the hotter one, contradicting the Second law of thermodynamics. No such engine can exceed ${\eta }_C=1-T_c/T_h$. Equivalently, the cyclic entropy inequality gives $-Q_h/T_h+Q_c/T_c\ge 0$, hence the same bound.

The reversible working substance changes entropy by $Q_h/T_h$ on its hot isotherm and $-Q_c/T_c$ on its cold isotherm, with zero change on the two reversible adiabats. Closure requires $Q_h/T_h=Q_c/T_c$. The substance has zero entropy change over a cycle, while the reservoirs have changes $-Q_h/T_h$ and $Q_c/T_c$. Thus $\Delta S_{\mathrm{universe}}=0$ for the complete Carnot cycle.

Put $P_{\ast }=p_1{V}_1=nR{T}_1$. For the specified ideal gas, $C_V=3nR/2$, $C_p=5nR/2$ and $\gamma =5/3$. Isobaric expansion doubles temperature, so $T_2=2T_1$. Reversible adiabatic closure gives $T{V}^{\gamma -1}=\mathrm{constant}$, henceThere is no heat input on that compression. The other stages giveTherefore $W_{\mathrm{net}}^{\mathrm{by}}=P_{\ast }-W_{31}^{\mathrm{on}}=0.44494P_{\ast }$ andThe hot reservoir changes entropy by $-Q_{12}/(2.5T_1)=-P_{\ast }/T_1$. The cold reservoir changes by $-Q_{23}/(0.5T_1)=4.11012P_{\ast }/T_1$. Since the gas completes a cycle,Although the mechanical paths can be quasistatic, heat flows across finite temperature differences in both contacts. This entropy generation explains why the efficiency is well below the Carnot value $1-0.5/2.5=80\%$ between these reservoirs.

For an isothermal final compression at $T_1$, the preceding constant-volume cooling must instead end at $T_3=T_1$; keeping the old state 3 would not close the cycle. Compression then requires work $P_{\ast }\ln 2$, while the heat input remains $5P_{\ast }/2$. Thuswhich is lower: this isothermal compression occurs at a higher temperature throughout than the original adiabat and consumes more work. It also rejects heat during compression.

Since ${\gamma }^{\prime }=d\gamma /dT<0$, the Maxwell relation gives $(\partial S/\partial A{)}_T=-{\gamma }^{\prime }>0$. Thus isothermal stretching increases the film's entropy.

At fixed area, $(\partial S/\partial T{)}_A=C_A/T$. ThereforeFor reversible adiabatic stretching, $dS=0$ andThe film cools, assuming positive heat capacity. Adiabaticity alone would not ensure constant entropy if the deformation were irreversible.

Substitute the entropy differential into the given first law:

After the photon has thermalized, its energy $E_{\gamma }=hc/\lambda$ belongs to the macroscopic body's internal energy. The body's heat capacity makes the resulting temperature change negligible. Its equilibrium entropy therefore increases byThe Boltzmann entropy $S=k_B\ln \Omega$ then gives the microstate multiplier from photon absorption:For scale, explicitly choosing a representative visible wavelength $\lambda =500\mathrm{nm}$ and room temperature $T=300\mathrm{K}$ gives $\Delta S=1.32\times 10^{-21}\mathrm{J}{\mathrm{K}}^{-1}$, or $\Delta S/k_B=95.9$, and a multiplier approximately $4.5\times 10^{41}$. These are illustrative choices, not additional supplied data: the exact multiplier depends exponentially on the particular visible wavelength and temperature. The exact Planck constant, speed of light, and Boltzmann constant fix the conversion.^[ref]

The Second law of thermodynamics restricts which energy-conserving processes can occur. In the Kelvin-Planck statement of the second law, no cyclic engine can have as its sole effect the extraction of heat from one reservoir and its complete conversion into work. In the Clausius statement of the second law, no process can have as its sole effect transferring heat from a colder reservoir to a hotter one. An engine or refrigerator combined with the reverse of a reversible device shows that a violation of either statement would violate the other.

A heat engine takes heat $Q_h>0$ from a reservoir at $T_h$, rejects $Q_c>0$ to one at $T_c<T_h$, and returns its working substance to the initial state. Energy conservation gives $W=Q_h-Q_c$ and efficiency $\eta =W/Q_h=1-Q_c/Q_h$. Carnot's theorem states that no engine between these reservoirs is more efficient than a reversible one, and that all reversible engines between them have the same efficiency. Otherwise, drive a reversible engine backwards with the work of a more efficient engine; the composite cycle transfers heat from cold to hot without external work, contradicting the Clausius statement.

A reversible Carnot cycle consists of two isotherms joined by two reversible adiabats. For an ideal gas, $Q_h=N{k}_B{T}_h\log (V_2/V_1)$ and $Q_c=N{k}_B{T}_c\log (V_3/V_4)$. The adiabats give $V_2/V_1=V_3/V_4$, soCarnot's theorem makes this independent of the working substance and defines the thermodynamic absolute-temperature scale consistently with ideal-gas temperature.^[ref]

For any reversible cycle, $\oint \delta Q_{\mathrm{rev}}/T=0$. This makes the integral between two equilibrium states independent of the reversible path, defining the state function entropy:Heat itself is path dependent; entropy is not. An irreversible change can be evaluated using any imagined reversible path between its equilibrium endpoints. For example, a fixed amount of ideal gas with constant $C_V$ has $\Delta S=C_V\log (T_B/T_A)+N{k}_B\log (V_B/V_A)$.

For a general cycle the Clausius inequality is $\oint \delta Q/T_{\mathrm{boundary}}\le 0$. The entropy balance for a process is $\Delta S\ge \int \delta Q/T_{\mathrm{boundary}}$, with equality for reversible heat exchange and no entropy production. The surroundings' entropy must be included, giving $\Delta S_{\mathrm{universe}}\ge 0$. A system's own entropy can decrease by exporting entropy; an isolated system's cannot.

The engine's reservoirs have net entropy change $Q_c/T_c-Q_h/T_h\ge 0$, sowith equality for a reversible engine. Friction, heat flow through a finite temperature difference and unrestrained expansion produce entropy and reduce usable work. Thus energy conservation fixes the balance of heat and work, while the second law fixes their direction and the attainable efficiency.^[ref]