VLE Phase Diagram Simulator: T-xy Bubble & Dew Point Calculator

simulator beginner ~8 min
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T_bp = 78.2°C — y* = 0.623 at x = 0.40

For a methanol-water type system at 101.3 kPa with x = 0.40, the bubble-point temperature is 78.2°C and the equilibrium vapor composition is y = 0.623.

Formula

log₁₀(P^sat) = A − B/(C + T) (Antoine equation)
y_i = x_i · P_i^sat(T) / P (Raoult's law)
Σ x_i · P_i^sat(T_bp) = P (bubble-point condition)

The Phase Diagram

The T-xy diagram is the chemical engineer's map of vapor-liquid equilibrium. At any point on the diagram, you know the temperature, the composition of the liquid phase, and the composition of the vapor phase in equilibrium with it. Below the bubble-point curve, everything is liquid; above the dew-point curve, everything is vapor; between them lies the two-phase region where both phases coexist. Every distillation column operates within this lens-shaped region, separating mixtures by exploiting the composition difference between coexisting phases.

Bubble & Dew Points

The bubble-point temperature is the temperature at which the first tiny vapor bubble forms when a liquid is heated at constant pressure. Mathematically, it satisfies Σx_iP_i^sat(T) = P. The dew-point temperature is where the first liquid droplet condenses from a cooling vapor: Σy_i/K_i(T) = 1. The gap between these curves determines how effective a single equilibrium stage is — wider gaps mean greater enrichment per stage and easier separation.

Relative Volatility & Separation

The shape of the T-xy envelope encodes the ease of separation. When the two components have very different boiling points (wide envelope), relative volatility α is large and few distillation stages suffice. When boiling points are close (narrow envelope), α approaches 1 and separation becomes energy-intensive, requiring many stages and high reflux ratios. The simulation shows how adjusting the boiling points changes the envelope width and the resulting equilibrium compositions.

Pressure Effects

System pressure shifts the entire diagram vertically. Higher pressure raises boiling temperatures and generally narrows the VLE envelope because the ratio of vapor pressures P_A^sat/P_B^sat decreases as temperature increases (components become more similar in volatility). This is why vacuum distillation is preferred for close-boiling mixtures — reducing pressure increases relative volatility, widening the phase envelope and improving separation efficiency at the cost of larger column diameter to handle the increased vapor volume.

FAQ

What is a T-xy diagram?

A T-xy diagram plots temperature on the vertical axis against liquid composition (x) and vapor composition (y) on the horizontal axis at constant pressure. It shows two curves: the lower bubble-point curve (where liquid begins to boil) and the upper dew-point curve (where vapor begins to condense). The region between the curves is the two-phase zone where liquid and vapor coexist.

How do you read a tie line on a T-xy diagram?

A horizontal line at constant temperature in the two-phase region is called a tie line. Its left intersection with the bubble-point curve gives the liquid composition x; its right intersection with the dew-point curve gives the equilibrium vapor composition y. The overall feed composition z determines the relative amounts of liquid and vapor via the lever rule: V/F = (z−x)/(y−x).

What is the Antoine equation?

The Antoine equation log₁₀(P^sat) = A − B/(C+T) is an empirical correlation for pure-component vapor pressure as a function of temperature. Constants A, B, and C are tabulated for thousands of compounds. It is the standard method for estimating vapor pressures in VLE calculations and is accurate over moderate temperature ranges around the normal boiling point.

How does pressure affect the T-xy diagram?

Increasing system pressure shifts the entire T-xy diagram upward (higher boiling temperatures) and typically narrows the two-phase envelope because relative volatility decreases with pressure. At the critical pressure of one component, the envelope closes. Vacuum distillation lowers boiling temperatures and can improve separation for close-boiling or heat-sensitive mixtures.

Sources

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