Van der Waals molar equation ($p=RT/(v_m-b_m)-a_m/v_m^2$)

The molar volume $v_m=V/n_{\mathrm{mol}}$ is the volume per amount of substance, not the total container volume or the volume per particle. In the molar convention of the Van der Waals equation, take constant positive parametersThenor, for any fixed amount of substance,Both terms in the first equation are pressures. The total excluded volume is $n_{\mathrm{mol}}{b}_m$: using $V-b_m$ would subtract quantities with different units. Changing the sample size at fixed molar volume and temperature changes $V$ and $n_{\mathrm{mol}}$ proportionally, while leaving pressure unchanged. This is a useful unit and extensivity check before fitting a real gas.

For the molar Van der Waals critical point, differentiate with respect to molar volume at fixed temperature:Setting both to zero gives $R{T}_c=2a_m(v_{m,c}-b_m{)}^2/v_{m,c}^3$ and $R{T}_c=3a_m(v_{m,c}-b_m{)}^3/v_{m,c}^4$. Equating them and dividing by the nonzero factors yields $2v_{m,c}=3(v_{m,c}-b_m)$, soHere $v_{m,c}$ has units ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, $T_c$ has units $\mathrm{K}$, and $p_c$ has units $\mathrm{Pa}$. This is the molar version of the particle derivation below: $v_{m,c}=N_A{v}_c$, with the same physical $T_c$ and $p_c$. If one writes $v_c=3b$, $T_c=8a/(27Rb)$ and $p_c=a/(27b^2)$ without subscripts, then all of $v_c,b,a$ in those formulas must be molar quantities.

Now define the dimensionless reduced variables explicitly as $x=v_m/v_{m,c}$, $t=T/T_c$ and $q=p/p_c$. Substituting the three critical values cancels $a_m,b_m,R$ and givesBecause $v_m/v_{m,c}=v/v_c$, these are exactly the reduced variables in the Van der Waals isotherm discussion. The Van der Waals law of corresponding states is therefore independent of whether one starts with particle or molar units. It predicts a critical ratio $p_c{v}_{m,c}/(R{T}_c)=3/8$, providing a third check on any proposed parameter fit.

Choose a hypothetical fluid with molar constants $a_m=0.360\mathrm{Pa}{\mathrm{m}}^6\mathrm{mo}{\mathrm{l}}^{-2}$ and $b_m=4.00\times 10^{-5}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, using $R=8.314462618\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$. These stipulated constants are not a fit to carbon dioxide. The molar critical formulas giveAt $T=360\mathrm{K}$ and $v_m=240\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, first convert $v_m$ to $2.40\times 10^{-4}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. The repulsive-volume term and attractive correction areso $p=8.716033\mathrm{MPa}$. The ideal gas law would instead give $RT/v_m=12.471694\mathrm{MPa}$. The excluded volume raises pressure relative to that ideal value, but attraction more than offsets the increase here. Neither correction alone describes this example.

For $n_{\mathrm{mol}}=0.500\mathrm{mol}$, the same state occupies $V=n_{\mathrm{mol}}{v}_m=120\mathrm{c}{\mathrm{m}}^3$. The total-volume formula gives $n_{\mathrm{mol}}{b}_m=20\mathrm{c}{\mathrm{m}}^3$ and the same $8.716033\mathrm{MPa}$. Halving the sample has halved both its physical volume and its excluded volume, while retaining its pressure. Conversely, if the two critical measurements $T_c,p_c$ are used to determine model constants, inversion givesAn independent critical molar volume then tests the prediction $v_{m,c}=3R{T}_c/(8p_c)$; agreement with two fitted numbers does not ensure agreement with the third.

At $t=0.9$, the Van der Waals liquid-gas coexistence example below becomes $T\simeq 288.6537\mathrm{K}$, $p_{\ast }\simeq 5.391653\mathrm{MPa}$, $v_{m,l}\simeq 72.40823\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$ and $v_{m,g}\simeq 281.8611\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. For a mean molar volume of $120\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, the lever rule gives gas mole fraction $f_g\simeq 0.227219$. Its volume fraction is instead $f_g{v}_{m,g}/v_m\simeq 0.533703$: less than one quarter of the molecules occupy more than half the volume. The flat equilibrium pressure corresponds to changing these proportions. It does not describe a homogeneous sample sliding along the unstable loop.