Raoult's Law Mixture Calculator

Calculate vapor pressure of ideal liquid mixtures using Raoult's law.

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What Raoult’s Law Assumes

Raoult’s law states that each component of a liquid mixture contributes vapour pressure in proportion to its mole fraction. Its underlying assumption is strong and worth stating plainly: a molecule of A is surrounded by neighbours it finds indistinguishable from its own kind.

Ptotal = x1P1* + x2P2*

That holds only when A–A, B–B and A–B intermolecular forces are essentially equal. Benzene and toluene satisfy this almost perfectly — both are non-polar aromatics of similar size — which is why they are the standard textbook example of an ideal mixture.

TermMeaningNote
x1Mole fraction in the liquidNot mass fraction, and not the vapour composition
P1*Vapour pressure of pure component 1Strongly temperature dependent
PtotalTotal vapour pressure above the mixtureSum of partial pressures

Deviations and What They Mean

BehaviourA–B forcesObserved PExampleΔHmix
IdealEqual to A–A and B–BMatches RaoultBenzene / toluene~0
Positive deviationWeaker than pureHigher than predictedEthanol / waterEndothermic
Negative deviationStronger than pureLower than predictedAcetone / chloroformExothermic

The logic is direct. If A and B attract each other less strongly than they attract their own kind, molecules escape into the vapour more readily than expected — pressure comes out high. Ethanol and water behave this way because mixing disrupts ethanol’s hydrogen-bonded network. Acetone and chloroform do the opposite: they form a new hydrogen bond between the chloroform proton and the acetone carbonyl, holding both more tightly in the liquid.

Large deviations produce azeotropes — compositions where liquid and vapour have identical composition, so distillation cannot separate them further. The ethanol–water azeotrope at 95.6% ethanol is why absolute alcohol cannot be produced by simple distillation.

Why the Vapour Is Richer in the Volatile Component

The vapour composition is not the same as the liquid. Each component’s share of the vapour is its partial pressure divided by the total, which favours whichever component has the higher pure vapour pressure. That enrichment is the entire basis of fractional distillation — each theoretical plate repeats the enrichment step.

Worked Examples

Example 1: Benzene/toluene x_benz=0.4, P*=96/29 mmHg
P=0.4x96+0.6x29
Result: P=38.4+17.4=55.8 mmHg
Ideal mixture - no intermolecular interactions
Example 2: Ethanol/water: positive deviation expected
Actual P > Raoult prediction
Result: Indicates weaker interactions in mixture than pure components
Non-ideal: use activity coefficients
Example 3: Vapour composition
Benzene/toluene, xbenz = 0.4, P* = 96 and 29 mmHg
Result: ybenz = 38.4/55.8 = 0.688
The liquid is 40% benzene but the vapour is 69% benzene. That enrichment in a single step is what fractional distillation multiplies.
Example 4: Negative deviation
Acetone/chloroform, 50:50 mixture
Result: Observed P lower than Raoult predicts
A hydrogen bond forms between the chloroform C–H and the acetone C=O. Both components are held more tightly, so fewer escape and mixing is exothermic.
Example 5: The azeotrope limit
Ethanol/water at 95.6% ethanol by mass
Result: Liquid and vapour compositions identical
No further enrichment is possible by distillation. Producing absolute ethanol requires a different method such as molecular sieves or azeotropic distillation with a third component.

Common Mistakes

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Using mass fraction instead of mole fraction

Raoult’s law is written in mole fractions. Converting from mass requires dividing by molar masses first, and the two differ substantially when the components have different molecular weights.

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Assuming vapour composition equals liquid composition

The vapour is always richer in the more volatile component. Confusing the two makes distillation impossible to understand and gives wrong answers on any vapour-phase question.

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Applying the law to strongly interacting mixtures

Raoult’s law is an idealisation. Ethanol/water deviates so strongly that it forms an azeotrope, and predictions from the ideal equation are simply wrong there.

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Forgetting that P* depends on temperature

Pure vapour pressures rise steeply with temperature via the Clausius–Clapeyron relation. Using values from the wrong temperature invalidates the whole calculation.

Frequently Asked Questions

Ideal vs non-ideal mixtures?
Raoult's law holds for ideal mixtures (similar molecules, same intermolecular forces). Positive deviation (P>Raoult): different molecules repel each other. Negative deviation (P
Distillation connection?
Raoult's law predicts enrichment of more volatile component in vapor. Each distillation stage enriches vapor by factor alpha=P1*/P2* (relative volatility). Higher alpha = easier separation.
What does Raoult’s law assume?
That all intermolecular forces in the mixture are equal — A–A, B–B and A–B alike. Mixtures of chemically similar molecules such as benzene and toluene approximate this well.
What causes positive deviation?
A–B attractions weaker than the pure-component attractions. Molecules escape more readily than predicted, raising vapour pressure. Mixing is endothermic and often causes slight cooling.
Why is the vapour richer in the volatile component?
Because each component’s share of the vapour is its partial pressure over the total, and the more volatile component contributes disproportionately. This is what makes distillation work.
What is an azeotrope?
A composition at which liquid and vapour have identical composition, so distillation cannot separate the components further. Ethanol/water forms one at 95.6% ethanol.
Can Raoult’s law be used for solutions of solids?
In the dilute limit yes — it underlies vapour pressure lowering and the colligative properties. The solute is assumed non-volatile and simply dilutes the solvent.

Formula Explorer connections

Interpretation: This relationship connects pressure, volume, temperature, amount or phase composition for gases and volatile mixtures. Assumption: Use absolute temperature and compatible pressure-volume units. Ideal behavior weakens at high pressure, low temperature, strong intermolecular attraction or near phase change.