 Liquid immiscibility

Liquid immiscibility is the failure of a mixture to form one homogeneous liquid at the specified composition and conditions. In a two-liquid phase equilibrium, each thermodynamic phase can contain some of both components, but their equilibrium compositions differ. “Immiscible” therefore need not mean that no molecules of either component dissolve in the other.

Hexane and water provide a concrete example of limited mutual solubility. A NIST-compiled experimental record describes overnight shaking, microsyringe sampling of an aqueous solution, and gas chromatography with flame-ionization detection to measure the dissolved hydrocarbon. Detecting a small dissolved amount does not imply that every bulk mixing ratio gives one liquid phase.^[ref]

An original lever rule example shows how phase amounts differ from phase compositions. Suppose a binary system at fixed temperature and pressure has coexisting liquid compositions $x_{\alpha }=0.1$ and $x_{\beta }=0.8$, where $x$ is the mole fraction of componentB. These stipulated values are not measurements of hexane/water. If the overall mole fraction is $z=0.4$, material balance givesHere $\lambda$ is the fraction of the total amount of substance in phaseβ. A100-mole sample therefore contains $300/7\simeq 42.86$ moles in phaseβ and $400/7\simeq 57.14$ moles in phaseα. The phase compositions stay0.8 and0.1; neither is the overall composition0.4.

Shaking the sample can create dispersed droplets without making a single molecularly homogeneous phase. Equilibration, temperature, pressure and composition must be stated when testing liquid-liquid equilibrium. The lever-rule fraction is a mole-amount fraction, not necessarily the fraction of vessel height or volume occupied by one layer.