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The Clapeyron equation connects the slope of a phase coexistence curve to the latent heat and the change in volume during a first-order phase transition. A steep boundary can indicate a large latent heat, a small change in volume, or both. This lets a measured boundary constrain caloric properties and predicts how changing pressure shifts a melting temperature.

For a pure substance in bulk phase coexistence, label the initial and final thermodynamic phases $\alpha$ and $\beta$. Both have the same absolute temperature $T$, pressure $p$, and chemical potential. With $s$, $h$, and $v$ denoting entropy, enthalpy, and volume on one common basis, define $\Delta s=s_{\beta }-s_{\alpha }$, $\Delta h=h_{\beta }-h_{\alpha }$, and $\Delta v=v_{\beta }-v_{\alpha }$. ThenThe derivative follows the phase coexistence curve; it is not a partial derivative within one thermodynamic phase. Use molar volume $v_m$ with molar latent heat $L_m$ in $\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}$, or specific volume $v$ with latent heat $L$ in $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$. Both give $dp/dT$ in $\mathrm{Pa}{\mathrm{K}}^{-1}$. For molar mass $M$, $L_m=ML$ and $\Delta v_m=M\Delta v$, so the predicted slope is independent of the chosen basis. This formulation assumes a simple compressible system, fixed composition, and negligible interface contributions; a curved interface can instead require the Young–Laplace equation.

For positive latent heat in the stated conversion direction, the sign of the slope is the sign of $\Delta v$. Converting liquid to gas normally increases volume and gives a positive slope. The negative melting-point slope of water illustrates the opposite sign. At a thermodynamic critical point, the coexisting gas and liquid merge: both $L$ and $\Delta v$ vanish, so their ratio needs a limiting analysis rather than substitution of zero into the Clapeyron equation.^[ref]

A short derivation uses the molar Gibbs free energy $g_m$, equal to the chemical potential for a pure substance. Equality persists along the boundary, so $d{g}_{m,\alpha }=d{g}_{m,\beta }$ with $d{g}_m=-s_{m}dT+v_{m}dp$. Therefore $-\Delta s_{m}dT+\Delta v_{m}dp=0$. Equality of $g_m=h_m-T{s}_m$ also gives $\Delta h_m=T\Delta s_m$. Eliminating $\Delta s_m$ yields the Clapeyron equation.

Consider two hypothetical parcels at the same temperature $300\mathrm{K}$, kept separated with negligible partition mass and excluded container volume. Parcel A has mass $2\mathrm{kg}$ and volume $0.002{\mathrm{m}}^3$; parcel B has mass $3\mathrm{kg}$ and volume $0.006{\mathrm{m}}^3$. They may be different materials. Their individual mass densities and the composite mass density areThe composite mass density is total material mass divided by total occupied volume; it need not be the local mass density anywhere. Equal temperature does not make these parcels replicas. In particular, the unweighted average $750\mathrm{kg}{\mathrm{m}}^{-3}$ is wrong. The volume fractions are $1/4$ and $3/4$, givingWith mass fractions $2/5$ and $3/5$, the equivalent rule is a weighted harmonic mean:This follows directly by writing $V_i=m_i/{\rho }_i$ and dividing total volume by total mass; it is also the mass-weighted average of specific volumes. An unweighted average of mass densities is valid when the parcel volume values are equal, not merely when their temperatures are equal.

If a partition is removed and different substances mix, the final volume need not equal the sum of initial volume values. A new temperature, thermodynamic phase or composition may also change the local mass density. Use the actual final volume in $\rho =m/V$; the pre-mixing weighted identity cannot supply it. Even unchanged temperature alone does not guarantee unchanged volume.

The liquid phase of water. Its density is much greater than that of dilute water vapor, allowing the liquid's specific volume to be neglected in the usual integrated Clausius-Clapeyron relation.

For a local illustrative ice–water melting calculation, stipulate $T_m=273.15\mathrm{K}$, latent heat of fusion $L=334\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}$, solid mass density ${\rho }_s=917\mathrm{kg}{\mathrm{m}}^{-3}$, and liquid mass density ${\rho }_l=1000\mathrm{kg}{\mathrm{m}}^{-3}$. These are explicitly stipulated rounded inputs, not measurements made here. The specific volume change on melting isThe common-pressure melting-point slope therefore givesA small $1\mathrm{MPa}$ increase in the common pressure thus lowers the melting temperature by about $0.074\mathrm{K}$ in this local model. Positive latent heat does not force a positive phase coexistence curve slope: ice contracts on conversion to liquid water. Increasing pressure favors the smaller specific volume. This calculation compares equilibrium states of the same two thermodynamic phases; extending its tangent to large pressures would require updated mass densities, latent heat of fusion, and the relevant ice phase diagram.

Dividing two extensive quantities with the same replication factor produces an intensive quantity:Division by volume gives a density, such as mass density $\rho =m/V$ or energy density $U/V$. Division by mass gives a specific quantity, such as specific internal energy $u=U/m$ or specific volume $v=V/m$. Division by amount of substance gives a molar quantity, such as molar volume $V_m=V/n$. Their units are respectively $\mathrm{kg}{\mathrm{m}}^{-3}$, $\mathrm{J}{\mathrm{m}}^{-3}$, $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$, ${\mathrm{m}}^3\mathrm{k}{\mathrm{g}}^{-1}$ and ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. The denominator must be stated: “per particle”, “per mole” and “per unit mass” are different normalizations.

For a hypothetical uniform parcel with mass $2\mathrm{kg}$, volume $0.002{\mathrm{m}}^3$ and internal energy $40\mathrm{kJ}$ relative to a specified reference, $u=20\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}$ and $\rho =1000\mathrm{kg}{\mathrm{m}}^{-3}$. Three independent copies have $6\mathrm{kg}$, $0.006{\mathrm{m}}^3$ and $120\mathrm{kJ}$; both ratios remain unchanged. This permits comparison of materials without confusing the amount tested with the state tested.

If $X$ and $Y$ are additive but the parcels have different $r_i=X_i/Y_i$, their composite ratio is a weighted arithmetic mean:The denominator supplies the weights: specific internal energy uses mass weights, while mass density uses volume weights. This identity is accounting for the specified subsystems; predicting a new state after mixing also needs the relevant equation of state.

The entropy form of dry potential temperature follows from its parcel definition. The potential temperature is the temperature a parcel would reach if brought reversibly and adiabatically to a reference pressure $p_0$. For dry air of fixed composition, treated as an ideal gas with constant specific heat capacity,Per unit mass, the first law of thermodynamics, together with $\alpha =R_{d}T/p$ for specific volume, gives $\delta q=c_{p}dT-\alpha dp$. The reversible form of the Second law of thermodynamics then givesHence dry reversible adiabatic motion has $D\theta /Dt=0$. Pressure changes cause expansion cooling or compression warming, while the pressure factor in theta compensates exactly. Adiabaticity alone is insufficient if irreversible mixing or viscous dissipation produces entropy. Condensation or freezing supplies latent heating, so ordinary dry potential temperature need not be conserved in a moist adiabatically moving parcel.

At a stated external pressure, the boiling point of a pure liquid is the temperature at which its saturation vapor pressure equals that pressure. A vapour bubble inside the liquid must also withstand the hydrostatic head and any capillary pressure; the simple free-surface boiling-point rule neglects those small local corrections.

Increasing external pressure raises the usual boiling point, while lowering it lowers the boiling point. The Clapeyron equation explains the direction:for ordinary vaporization with positive latent heat $L$ and a larger vapour specific volume. Consequently water can boil below its usual open-vessel temperature at altitude or under partial vacuum, and above it in a sufficiently pressurized vessel.

Composition also matters. A nonvolatile dissolved solute generally lowers the solvent's vapour pressure and produces boiling-point elevation at fixed external pressure. A volatile second component can instead raise or lower the boiling temperature according to the mixture's phase equilibrium; an azeotrope is a useful warning against applying the nonvolatile-solute rule to every mixture.

Finally, distinguish the equilibrium boiling point from the observed onset of bubbles. A smooth clean vessel or a shortage of nucleation sites can permit superheating; agitation or suitable existing sites can make boiling begin nearer equilibrium. Heating power mainly controls the rate of sustained boiling under otherwise fixed conditions, rather than setting an arbitrary new equilibrium boiling point. A thermometer must be placed to measure the intended liquid or saturated vapour region, rather than a locally overheated wall.

First estimate the excess pressure as weight divided by contact area:For the equilibrium estimate, use the Clapeyron equation for melting. The specific volume change on melting is $\Delta v=1/{\rho }_w-1/{\rho }_i$, and the latent heat of fusion $L$ gives $\Delta s=L/T_m$. Thus the common-pressure melting-point slope isTake $T_m\simeq 273.15\mathrm{K}$ and the usual rounded water density ${\rho }_w\simeq 1000\mathrm{kg}{\mathrm{m}}^{-3}$, in addition to the supplied ${\rho }_i=920\mathrm{kg}{\mathrm{m}}^{-3}$ and $L=3.3\times 10^5\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$. ThensoThe sign is negative because ice contracts on melting. This is a linear equilibrium estimate treating the load as a common local pressure on coexisting ice and water. The actual contact stress is nonuniform, and frictional heating, deformation and drainage also affect skating; the estimate is not a complete account of the lubricating water film.

Notation. The source uses $p_s$ for both the hypothetical dry surface pressure and the actual surface pressure after evaporation. Distinguish them as $P_d$ and $P$, respectively, and interpret the specified pressure thickness $\Delta p$ as fixed. This conserves the original hydrogen inventory and permits $P$ to vary. Reading both occurrences as one fixed number would be inconsistent with adding water vapor to a closed atmospheric column mass budget.

Let $E(T)$ denote the saturation pressure of water, let $x$ be the mole fraction of water vapor in the mixed layer, and let $M_d,M_v$ be the molar masses of hydrogen and water. Surface phase equilibrium and the ideal gas law giveBecause the layer has constant temperature, its relative humidity isThus every level strictly above the surface is subsaturated: hydrostatic balance makes $p<P$, whereas the saturation pressure stays constant. The result does not require a dilute water vapor approximation.

The Clausius-Clapeyron relation, neglecting the specific volume of liquid water and treating the water vapor as an ideal gas, givesHere $T_t,E_t$ are the triple point values, $L_v$ is the specific latent heat, and $R$ is the molar gas constant. All temperatures in these expressions are absolute. As throughout the question, this is a constant-latent heat, ideal gas model, not an extrapolation valid through the real critical point of water.

For a well-mixed ideal gas mixture, its mean molar mass and water vapor mass fraction areBy hydrostatic balance, the mixed layer has total mass per unit area $\Delta p/g$, of which $w_v\Delta p/g$ is water vapor. The remaining atmosphere contains no water vapor. Consequently conservation of hydrogen mass givesEquivalently the requested quadratic equation isFor each $T_s$, calculate $E$, take the positive root of this quadratic equation, and retain it only if $0\le x<1$ and $P>\Delta p$. The last condition leaves a nonempty dry layer. In particular the dry constituent's surface partial pressure is not generally $P_d$: $P_d$ measures its column weight, and the hydrogen and water vapor have different molar masses.

A concrete experiment turns the phase coexistence curve into pairs of temperature and saturation pressure. A 1969 paper reports water measurements made in 1942 and 1947–1949 using a boiler and precision mercury manometer. Platinum resistance thermometers read the boiler temperature through a resistance bridge. The pressure-transfer line passed through an ice-water condenser and a dry-ice trap; helium filled connecting sections. Corrected mercury column height gave the pressure at the thermometer coils, including hydrostatic pressure contributions from water vapor, helium, mercury, and mercury vapor.^[ref]

Controls included normal/reversed-lead readings, readings at two thermometer electric currents extrapolated to zero current to remove self-heating, repeated bridge calibration, and daily triple point thermometer calibration checks. Cellar temperature measurements corrected fluid-column and gauge-block thermal expansion. One measurement series was excluded because a trapped gas bubble was suspected of corrupting the mercury head. The paper adjusted measurements to round temperatures using previously tabulated slopes; those adjusted values therefore are not independent measurements of those slopes.^[ref]

The thermodynamic inference requires liquid and gas in phase coexistence, a well-defined common temperature, and a pressure corrected to that same location. Leaks, contamination, or a temperature gradient can spoil that interpretation. A separate calorimetry measurement of latent heat, together with the two specific volumes, allows a test of the full Clapeyron equation. Converting a measured phase coexistence curve slope directly into latent heat instead assumes that equation; it is not an independent test.

The volume per unit mass; for a uniform substance it is the reciprocal of mass density. The Clapeyron equation pairs a difference of specific volumes with latent heat per unit mass.

The volume divided by the positive number of particles $N$. The Van der Waals equation uses this convention for $v$, whereas specific volume divides by mass and molar volume divides by the amount of substance. With the Avogadro constant $N_A$, the molar volume is $v_m=N_{A}v$.