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Co-distillation is the vaporization and collection of multiple components together during distillation. A component can enter the collected vapor alongside another volatile substance instead of being isolated as a pure vapor. Steam distillation is the case in which water supplies a volatile carrier; co-distillation is not restricted to water.

The result depends on vapor-liquid equilibrium. In an ideal, fully mixed binary liquid at a specified temperature, Raoult's law gives $p_A=x_A{p}_A^{\ast }$ and $p_B=x_B{p}_B^{\ast }$. The vapor fraction is $y_A=p_A/(p_A+p_B)$. The McMaster distillation manual uses liquid/vapor composition diagrams to explain why the vapor can be enriched in one component while still containing both.^[ref]

For original hypothetical data, let $x_A=0.25$, $p_A^{\ast }=80\mathrm{kPa}$ and $p_B^{\ast }=20\mathrm{kPa}$. Then $p_A=20$ and $p_B=15\mathrm{kPa}$, giving $y_A=20/35\approx 0.571$. Both components co-distil, but the vapor is richer in $A$ than the starting liquid. These are equilibrium pressures at the stated temperature; boiling additionally requires their sum to match the external pressure.

With two persistent immiscible liquid phases, a different limiting model uses the pure-component vapor pressures directly, rather than multiplying each by its fraction of a homogeneous mixture. An azeotrope is another special equilibrium situation. Specify the phase behavior before assigning a distillate composition, and use a distillation material balance to distinguish enrichment from total recovery. Collecting a component together with a carrier does not itself establish complete separation from every impurity.

The first-order combination of the Kelvin equation and Raoult's law for a chemical solution droplet with $A/r\ll 1$ and $B/r^3\ll 1$. Its maximum is at $r_c=\sqrt{3B/A}$, with $S_c-1=2A/(3r_c)$. For ambient saturation ratio $1<S<S_c$, the smaller equilibrium radius is stable and the larger is unstable: the sign of condensational growth is the sign of $S-S_{\mathrm{eq}}(r)$. In particular, exceeding $r_c$ alone need not activate continued growth at subcritical atmospheric supersaturation.

François-Marie Raoult is associated with quantitative relations between chemical solution composition and physical properties. Raoult's law relates a component's partial vapor pressure in an ideal liquid mixture to its mole fraction and the pure component's vapor pressure at the same temperature. It provides a reference model against which nonideal solution behaviour can be compared.^[ref]

Chemist.

Biographical sketch: www2.chem.umd.edu/thermobook/v10-screen.pdf

For the stipulated A/B ideal solution, put $x=x_A$. At the fixed temperature $300\mathrm{K}$, Raoult's law reduces toThe relative volatility is $\alpha =p_A^{\ast }/p_B^{\ast }=4$. For $0<x<1$,Hence every interior vapor-liquid equilibrium pair in this chosen model has A-enriched vapor; neither pure endpoint is enriched. Conversely,For example, $y_A=1/2$ corresponds to $x_A=1/5$, $p_A=p_B=16\mathrm{kPa}$ and $P=32\mathrm{kPa}$. Equal vapor mole fractions therefore need not mean equal liquid mole fractions.

These are fixed-temperature predictions. During boiling at a specified external pressure, the temperature instead adjusts until ${\sum }_i{x}_i{p}_i^{\ast }(T)=P_{\mathrm{external}}$. The two stipulated vapor pressures specify only one temperature; they provide no boiling-temperature curve.

An ideal solution is a chemical solution whose component chemical potentials depend on composition throughHere $n_i$ is an amount of substance, $x_i$ its mole fraction, $R$ the molar gas constant, and ${\mu }_i^{\ast }$ the pure-component liquid reference at the same temperature $T$ and pressure $P$. This model applies to every component across the composition range; it is stronger than an approximation valid only near a pure solvent.^[ref]

With this pure-liquid standard state convention, the thermodynamic activity satisfies ${\mu }_i={\mu }_i^{\ast }+RT\ln a_i$, so an ideal solution has $a_i=x_i$, or activity coefficient ${\gamma }_i=a_i/x_i=1$.^[ref] This statement concerns the liquid. Assuming that a coexisting vapor is an ideal gas mixture is an additional approximation. Its mole fractions $y_i$ generally differ from the liquid mole fractions $x_i$.

For an original two-component example, stipulate $T=300\mathrm{K}$ and pure-component vapor pressures $p_A^{\ast }=80\mathrm{kPa}$ and $p_B^{\ast }=20\mathrm{kPa}$. A and B are invented distinguishable components; these numbers are chosen model inputs, not material data. Combine an ideal solution with an ideal gas vapor, neglect the pure-liquid reference's pressure correction, and exclude other gases. At liquid mole fractions $x_A=0.4$ and $x_B=0.6$, Raoult's law and addition of partial pressures giveThus the coexisting vapor contains about $72.73\%$ A by amount of substance, although the liquid contains only $40\%$. The total pressure is neither pure-component vapor pressure, and $x_A$ cannot be substituted for $y_A$. This enrichment is the basis of distillation.

The usefulness of the ideal solution is that one composition law connects chemical potentials, vapor-liquid equilibrium, entropy of mixing and Gibbs free energy of mixing. Its liquid components can interact strongly: the defining condition is their composition dependence, rather than the absence of all interactions as in an ideal gas model.

The Mixture measurements and the Gibbs-Duhem constraint article describes the inspected acetone–chloroform preparation, apparatus, paired readouts, controls and sampling limits.^[ref]

That existing apparatus account supplies the experimental controls and limitations. Its refractive index calibration yields mass fractions, which must be converted to mole fractions. For a measured component-A mass fraction $w_A$ and component molar masses $M_A,M_B$,Apply this conversion separately to the flask sample and to completely condensed vapor to obtain $x_A$ and $y_A$. Comparing $y_{i}P$ with $x_i{p}_i^{\ast }(T)$ tests Raoult's law at the measured temperature; using the changing temperature at each composition is essential. The chosen A/B values above are unrelated to the protocol's substances.

The more general diagnostic, retaining an ideal gas vapor and negligible pure-liquid pressure correction, isThis follows by replacing $\ln x_i$ with $\ln (x_i{\gamma }_i)$ in the chemical potential subtraction used for Raoult's law. A reproducible discrepancy from ${\gamma }_i=1$ can expose failure of the ideal solution approximation, but interpreting it requires checking measurement uncertainty, representative paired sampling and the ideal gas approximation. Apparent agreement within uncertainty supports an approximation over the tested conditions; it cannot establish exact ideality at every composition.

Positive or negative deviations of component partial pressures require activity coefficients different from one under these assumptions. An azeotrope is also absent from the chosen unequal-vapor pressure model: the explicit inequality in ideal binary vapor composition gives $y_A>x_A$ throughout $0<x_A<1$. An interior equality would require $p_A^{\ast }=p_B^{\ast }$; in that degenerate case every composition has $y_A=x_A$, rather than an isolated enrichment reversal. Neither an azeotrope nor liquid phase separation should be inferred from the ideal curves.

$S=e/e_s^l$ is the ambient saturation ratio over a flat liquid-water surface; $S-1$ is the liquid atmospheric supersaturation. Curvature increases the surface equilibrium vapour pressure, producing the Kelvin penalty $A/r$, while dissolved solute lowers it and gives the opposing Raoult contribution $B/r^3$. Thus the dilute Köhler equilibrium curve is $S_{\mathrm{eq}}-1=A/r-B/r^3$, and the numerator is the atmospheric supersaturation available to drive growth beyond surface equilibrium.

$F_d^l$ describes the resistance of vapour diffusion through the surrounding air. $F_k^l$ describes the thermal-conduction resistance to removing latent heat released by condensation: a warmed droplet surface has a higher equilibrium vapour pressure and hence a weaker mass-transfer drive. Common continuum approximations are $F_d^l\simeq R_{v}T/(D_v{e}_s^l)$ and $F_k^l\simeq L_v[k_{\mathrm{air}}T{]}^{-1}[L_v/(R_{v}T)-1]$, showing the roles of diffusivity, conductivity, saturation pressure and latent heat. Both resistances have the supplied units $\mathrm{s}\mathrm{m}\mathrm{k}{\mathrm{g}}^{-1}$ and add for this coupled transport problem.

For a spherical droplet of constant density, $m=4\pi \rho r^3/3$. Multiplying the radius equation by $4\pi \rho r$ givesAt sufficiently large radius, curvature and solute corrections are negligible, soThis limit also requires sustained positive atmospheric supersaturation. It need not describe the earliest submicrometre stage or an unactivated haze particle.

A rising parcel cools, lowering the saturation pressure. Once its water vapor supply exceeds that value, atmospheric supersaturation develops. Homogeneous nucleation of pure water is strongly inhibited at the small atmospheric supersaturations typical of clouds; existing aerosol particles provide cloud condensation nuclei. Their dry sizes and composition, together with the parcel's ascent rate, determine how many cloud droplets activate.

Köhler theory combines the Kelvin equation, which raises equilibrium vapor pressure over a curved surface, with Raoult's law, which lowers it for a chemical solution. In a dilute diameter convention, with dry diameter $D_d$ and wet diameter $D$,Here $s=e_v/E(T)-1$ is atmospheric supersaturation, ${\sigma }_w$ is surface tension, and ${\kappa }_h$ measures aerosol hygroscopicity, not the dry-adiabatic process exponent. The maximum of the Köhler curve is the critical supersaturation. Larger or more hygroscopic particles generally have lower thresholds. Cloud-droplet activation requires overcoming that maximum; total aerosol number is not the activated number.

Given an observed aerosol number size distribution $n_j(D_d)=d{N}_j/d\ln D_d$ for composition classes $j$, first assign each class a hygroscopicity and compute its critical supersaturation. If the parcel reaches maximum atmospheric supersaturation $s_{\max }$, the equilibrium-threshold estimate isFor each fitted lognormal distribution, this is its upper-tail integral; it can be evaluated analytically with an error function or numerically from measured bins.

The value $s_{\max }$ must be calculated, not guessed from the aerosol distribution alone. Prescribe parcel upward velocity $w$, initial pressure, temperature and humidity, then integrate expansion cooling, latent heat release, conservation of total water, and diffusional cloud droplet growth. Schematically,where $a_s,b_s>0$, $G$ includes water vapor diffusion and thermal conduction, and $q_l$ is liquid mass fraction. Rising motion produces atmospheric supersaturation; growing particles consume it. Their competition selects the peak and which particles cross their activation barriers. Assume a well-mixed closed parcel, liquid water, soluble spherical particles, specified mixing state, and negligible collision-coalescence and fallout during activation. Slow kinetic growth, weakly soluble particles or entrainment require a more detailed treatment than the threshold integral.

The dilute Köhler curve follows because the Kelvin equation multiplies the planar-solution saturation pressure by the curvature correction. Combining it with Raoult's law therefore givesFor a dilute chemical solution and a small curvature correction, $B/r^3\ll 1$ and $A/r\ll 1$. A first-order Taylor expansion givesThus the simplified Köhler theory relation isThe curvature term raises the required ambient vapor pressure; the solute term lowers it. These laws combine multiplicatively before linearization, so the displayed simplified relation is an approximation, not an exact identity.

In the ideal solution and ideal gas vapor approximation, each component's partial pressure equals its liquid mole fraction times its pure-component vapor pressure at the same temperature:These pressure formulas neglect the change in the pure-liquid reference between its saturation pressure and $P$; appreciable real gas behavior also requires a more general treatment. The ideal solution definition in terms of chemical potentials does not require either approximation.^[ref]

A short derivation explains the reference choice. At vapor-liquid equilibrium, each component has the same chemical potential in the liquid and vapor. For an ideal gas mixture, chemical potential of an ideal gas giveswhere $p^{\circ }$ is a reference pressure. Approximate ${\mu }_i^{\ast }(T,P)$ by ${\mu }_i^{\ast }(T,p_i^{\ast })$ and subtract the pure-component equation from the mixture equation:Taking the exponential function gives Raoult's law. Summing partial pressures and normalizing gives $P$ and $y_i$; this last step uses the ideal gas vapor assumption separately from the liquid model.

The law is named after François-Marie Raoult, who measured vapor pressures and freezing behavior of chemical solutions.^[ref]

Water activity measures the chemical potential of water relative to a chosen pure-water standard state. Under ideal-vapour conditions above a flat solution, it is the equilibrium vapour pressure divided by that above pure liquid water at the same temperature. Dissolved solute usually lowers activity. Raoult's law gives the ideal dilute-solution limit; nonideal interactions require an activity model.