Ideal-vapor Clausius-Clapeyron approximation ($d\ln p/dT\simeq L_m/(R{T}^2)$)

For liquid–gas phase coexistence, make two distinct approximations: the gas obeys the ideal gas law, $v_{m,g}=RT/p$, and its molar volume greatly exceeds the liquid molar volume, $v_{m,g}\gg v_{m,l}$. Here $R$ is the molar gas constant and $p$ is the saturation pressure of the pure substance. Substitution into the Clapeyron equation giveswhere $p_{\ast }>0$ is any fixed reference pressure, making the logarithm dimensionless. Constant latent heat is a further approximation, needed for the elementary Integrated Clausius-Clapeyron relation below.^[ref]

The neglected liquid molar volume has a transparent error estimate. If the gas is ideal but $ϵ=v_{m,l}/v_{m,g}$ is retained, thenThus ignoring the liquid molar volume underestimates this slope by a relative amount $ϵ$. This estimate does not bound errors from treating a real gas as ideal or from freezing $L_m(T)$. Near a thermodynamic critical point, the gas and liquid molar volumes approach each other and these dilute-vapor assumptions fail.

If the molar latent heat $L_m$ is approximately constant on the chosen temperature interval, the Ideal-vapor Clausius-Clapeyron approximation integrates toFor $L_m>0$, higher absolute temperature gives higher saturation pressure. A plot of $\ln (p/p_1)$ against inverse temperature $1/T$ is a straight line of slope $-L_m/R$. One reference pair $(T_1,p_1)$ fixes its intercept. On a per-unit-mass basis replace $L_m/R$ by $L/R_s$, with $R_s=R/M$ and $M$ the molar mass; using $L$ in $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$ with the molar $R$ would give incompatible units.

If only the constant-latent heat approximation is relaxed, the same ideal-vapor model instead givesConsequently an apparent straight-line fit across a broad temperature range need not represent a single material constant. The simple exponential also approaches a finite value as $T\to \infty$; this is a property of the stipulated formula, not a prediction that liquid–gas phase coexistence extends beyond a thermodynamic critical point.

Consider an unnamed model substance with molar latent heat $L_m=40.0\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ and saturation pressure $p_1=10.0\mathrm{kPa}$ at $T_1=300\mathrm{K}$. Stipulate the Ideal-vapor Clausius-Clapeyron approximation throughout $280\le T\le 340\mathrm{K}$, constant $L_m$, and $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$. These parameters define an illustrative model, not a measured dataset or a fit to water. At $T_2=330\mathrm{K}$,At the reference state the gas molar volume is $R{T}_1/p_1=0.24942{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, and the local slope is $dp/dT\simeq 0.5346\mathrm{kPa}{\mathrm{K}}^{-1}$. The tangent estimate $p_2\approx 10.0+30(0.5346)=26.04\mathrm{kPa}$ is much lower than the integrated result: a local derivative should not be extrapolated over this whole interval. By contrast, over a small temperature increment, the fractional sensitivity is $d\ln (p/p_1)/dT=L_m/(R{T}_1^2)\simeq 0.05346{\mathrm{K}}^{-1}$.

Within the Ideal-vapor Clausius-Clapeyron approximation, a local slope of the natural logarithm of saturation pressure against inverse temperature estimates the molar latent heat:In the stipulated vapor-pressure calculation, the slope is $-4811.16\mathrm{K}$, which recovers $40.0\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. For variable $L_m(T)$, a two-point estimate gives an average weighted by $T^{-2}$, rather than the latent heat at an arbitrary midpoint. Differentiating noisy pressure measurements amplifies their errors. Outside the ideal-vapor regime, use independently determined molar volumes in $L_m=T\Delta v_{m}dp/dT$; a straight-looking graph alone cannot establish that the gas is ideal.