CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr.

Pranava Chaudhari

HBTU KANPUR — Department of Chemical Engineering

LECTURE NOTES

Vapour-Liquid Equilibria (VLE)

Raoult's Law · Modified Raoult's Law · Bubble Point · Dew Point

Dr. Pranava Chaudhari

Assistant Professor, Department of Chemical Engineering
[Link] Chemical Engineering | 2nd Year | HBTU Kanpur | Session 2025–26

📌 Course Context
These notes cover VLE — a core topic in Chemical Engineering Thermodynamics. Understanding phase
equilibria is essential for designing distillation columns, absorption towers, extraction processes, and
flash separators. Master these concepts and calculation procedures thoroughly.

SECTION 1: FUNDAMENTALS OF PHASE EQUILIBRIUM

1.1 What is Phase Equilibrium?

A system is in phase equilibrium when two or more phases coexist with no net transfer of mass or energy
between them. For a vapour-liquid system, the rate of evaporation equals the rate of condensation at every
point.
Three conditions must hold simultaneously:
● Thermal Equilibrium: T_vapour = T_liquid
● Mechanical Equilibrium: P_vapour = P_liquid
● Chemical Equilibrium: Chemical potential of each component i must be equal in both phases: μᵢ(L) =
μᵢ(V)

1.2 Gibbs Phase Rule

The Gibbs Phase Rule relates the degrees of freedom F to the number of components C and phases P:

F = C − P + 2
Phase Rule
F = degrees of freedom (intensive variables that can be independently varied)

For a binary (C=2), two-phase (P=2) VLE system: F = 2. Specifying T and P completely determines all
compositions.

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

1.3 Vapour Pressure — The Antoine Equation

Vapour pressure P*ᵢ(T) of pure component i is temperature-dependent. The Antoine equation is the most widely
used correlation:

log₁₀(P*) = A − B / (T + C)
Antoine Equation A, B, C = Antoine constants; T in °C (usually); P* in mmHg, kPa, or bar — check the
source

📌 CAUTION — Units Matter

Before using any Antoine constants, always verify: (1) temperature units (°C or K), (2) pressure units
(mmHg, kPa, bar, atm). Mixing units is the most common source of error in VLE calculations.

SECTION 2: RAOULT'S LAW — IDEAL VAPOUR-LIQUID EQUILIBRIA

2.1 Statement and Equation

"For an ideal solution, the partial pressure exerted by component i is equal to its pure-component vapour
pressure multiplied by its mole fraction in the liquid phase."

yᵢ · P = xᵢ · P*ᵢ(T)
Raoult's Law xᵢ = liquid mole fraction, yᵢ = vapour mole fraction, P = total pressure, P*ᵢ = sat. vapour
pressure

K-value (Equilibrium Ratio): Defined as Kᵢ = yᵢ / xᵢ

K-value (Raoult's Kᵢ = yᵢ / xᵢ = P*ᵢ(T) / P

Law) Kᵢ > 1 → more volatile (prefers vapour); Kᵢ < 1 → less volatile (prefers liquid)

2.2 Assumptions & Validity

Raoult's Law is valid when:
● Liquid phase is ideal — molecules have similar size, shape, and intermolecular forces
● Activity coefficient γᵢ = 1 for all components
● Vapour phase behaves as an ideal gas (valid at low to moderate pressures)

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

Binary System Why Nearly Ideal

Benzene – Toluene Similar aromatic structure, comparable molecular size

n-Hexane – n-Heptane Homologous series, very similar van der Waals forces
Chlorobenzene – Similar polarity and molecular geometry
Bromobenzene

Methanol – Ethanol Both short-chain alcohols with similar H-bonding

2.3 P-x-y Diagram (Isothermal, Constant T)

Bubble point line (liquid to two-phase boundary):

Bubble Point P P_bubble = Σᵢ xᵢ · P*ᵢ(T)

(Raoult) Linear in liquid composition for binary systems

Dew point line (vapour to two-phase boundary):

Dew Point P 1/P_dew = Σᵢ yᵢ / P*ᵢ(T) → P_dew = 1 / Σᵢ(yᵢ/P*ᵢ)

(Raoult) Hyperbolic in vapour composition

📌 Reading P-x-y Diagrams

Region ABOVE bubble-point line = subcooled liquid (single phase). Region BELOW dew-point line =
superheated vapour (single phase). Region BETWEEN the two lines = two-phase VLE envelope.

2.4 T-x-y Diagram (Isobaric, Constant P)

● Bubble point locus lies below the dew point locus in a T-x-y diagram
● More volatile component (lower boiling point) has Kᵢ > 1, so yᵢ > xᵢ — vapour is enriched in it
● For binary ideal system, T-x (bubble) and T-y (dew) curves are related by the same VLE equation

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

SECTION 3: MODIFIED RAOULT'S LAW — NON-IDEAL SYSTEMS

3.1 Activity Coefficient γᵢ

The activity coefficient γᵢ captures the deviation of the liquid phase from ideal behaviour. It is defined through
the chemical potential as:

γᵢ = (fugacity in non-ideal mixture) / (fugacity in

Activity Coefficient ideal mixture at same T, P, x)
γᵢ → 1 as xᵢ → 1 (Lewis-Randall rule — becomes pure liquid)

Condition Meaning & Example

γᵢ = 1 (ideal) Raoult's Law holds. Benzene-Toluene.
γᵢ > 1 (positive deviation) Unlike interactions weaker than like. System tends to demix. e.g.,
Ethanol–Water, Acetone–Hexane.
γᵢ < 1 (negative deviation) Unlike interactions stronger than like. Strong cross-association. e.g.,
Acetone–Chloroform.

3.2 Modified Raoult's Law

yᵢ · P = xᵢ · γᵢ · P*ᵢ(T)
Modified Raoult's
γᵢ = liquid-phase activity coefficient for component i at composition {xᵢ} and
Law
temperature T

K-value (Modified Kᵢ = yᵢ / xᵢ = γᵢ · P*ᵢ(T) / P

Raoult)

3.3 Activity Coefficient Models

Margules Equations
For a binary system (1-2):

ln γ₁ = A·x₂² ; ln γ₂ = A·x₁²
One-suffix Margules
Single constant A. Use for nearly symmetric systems.

ln γ₁ = x₂²[A₁₂ + 2(A₂₁−A₁₂)·x₁] ln γ₂ = x₁²[A₂₁ +

Two-suffix Margules 2(A₁₂−A₂₁)·x₂]
A₁₂ ≠ A₂₁ for asymmetric systems

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

van Laar Equations

ln γ₁ = A'₁₂ / [1 + (A'₁₂·x₁)/(A'₂₁·x₂)]² ln γ₂ = A'₂₁ /
van Laar [1 + (A'₂₁·x₂)/(A'₁₂·x₁)]²
Good for systems with large deviations from ideality

Wilson Equation
ln γ₁ = −ln(x₁+Λ₁₂x₂) + x₂[Λ₁₂/(x₁+Λ₁₂x₂) −
Λ₂₁/(x₂+Λ₂₁x₁)] ln γ₂ = −ln(x₂+Λ₂₁x₁) − x₁[Λ₁₂/(x₁+Λ₁₂x₂)
Wilson Equation
− Λ₂₁/(x₂+Λ₂₁x₁)]
Λ₁₂, Λ₂₁ = Wilson parameters. Cannot predict LLE (liquid-liquid separation).

Model Characteristics

One-suffix Margules Symmetric. One parameter. Quick estimate.

Two-suffix Margules Asymmetric. Two parameters. Most common for binaries.
van Laar Two parameters. Good for large deviations.
Wilson Two parameters. Excellent for polar/miscible. Cannot handle LLE.
NRTL Three parameters. Handles VLE + LLE.
UNIQUAC Multi-component capable. Used in process simulators (Aspen, HYSYS).

3.4 Azeotropes
An azeotrope is a constant-boiling mixture where xᵢ = yᵢ for all i. At the azeotrope:

Azeotrope P = γᵢ · P*ᵢ(T) for every component i

Condition This yields: γᵢ = P / P*ᵢ(T) at the azeotrope — useful for back-calculating parameters

Type Characteristics
Maximum-pressure γᵢ > 1 (positive deviation). P-x shows max; T-x shows min. Example:
(minimum-boiling) Ethanol–Water (95.6 mol% EtOH, 78.1°C, 1 atm).
Minimum-pressure γᵢ < 1 (negative deviation). P-x shows min; T-x shows max. Example:
(maximum-boiling) Acetone–Chloroform.

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

SECTION 4: BUBBLE POINT CALCULATIONS

4.1 Definition
Bubble Point: The condition at which the first infinitesimal bubble of vapour forms from a liquid of known
composition {xᵢ} at equilibrium. The vapour bubble is in equilibrium with the bulk liquid.

📌 Key Condition at Bubble Point

Σᵢ yᵢ = 1 ⟹ Σᵢ Kᵢ·xᵢ = 1 ⟹ Σᵢ [γᵢ·P*ᵢ(T)/P]·xᵢ = 1

4.2 Bubble Point Pressure (Given T and {xᵢ})

P_b = Σᵢ xᵢ · P*ᵢ(T)
Bubble Pt. P — Ideal
Direct calculation. No iteration needed.

Bubble Pt. P — P_b = Σᵢ xᵢ · γᵢ(x) · P*ᵢ(T)

Modified Raoult γᵢ evaluated at given {xᵢ} — still direct, no iteration.

Vapour yᵢ = xᵢ · γᵢ · P*ᵢ(T) / P_b

Composition Verify: Σyᵢ must equal 1.00

4.3 Bubble Point Temperature (Given P and {xᵢ})

Since P*ᵢ depends on T non-linearly, this is an iterative calculation:
1. Guess initial T (e.g., mole-fraction-weighted average of pure boiling points at P)
2. Compute P*ᵢ(T) from Antoine equation
3. Compute S = Σᵢ xᵢ·γᵢ·P*ᵢ(T)
4. Compare S to P: if S > P → T too high; if S < P → T too low
5. Update T and repeat until |S − P|/P < 10⁻⁵ (tolerance)
6. yᵢ = xᵢ·γᵢ·P*ᵢ/P_b once converged

4.4 Worked Example — Bubble Point Pressure (Benzene–Toluene at 100°C)

Problem: Binary mixture of benzene (1) and toluene (2). T = 100°C, x₁ = 0.40. Assume Raoult's Law.

Antoine Constants (log₁₀P in mmHg, T in °C):

Component A B C

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

Benzene (1) 6.8941 1203.53 219.888

Toluene (2) 6.9533 1343.94 219.377

Step 1: Vapour pressures at 100°C

log₁₀(P*₁) = 6.8941 − 1203.53/(100+219.888) = 6.8941 − 3.7622 = 3.1319
P*₁ = 10^3.1319 = 1354.9 mmHg
log₁₀(P*₂) = 6.9533 − 1343.94/(100+219.377) = 6.9533 − 4.2059 = 2.7474
P*₂ = 10^2.7474 = 559.0 mmHg

Step 2: Bubble point pressure

P_b = x₁·P*₁ + x₂·P*₂ = (0.40)(1354.9) + (0.60)(559.0) = 541.96 + 335.40 = 877.4 mmHg

Step 3: Vapour compositions

y₁ = x₁·P*₁/P_b = (0.40)(1354.9)/877.4 = 0.618
y₂ = 1 − y₁ = 0.382 [Check: Σyᵢ = 1 ✓]

📌 Result
T = 100°C, x₁ = 0.40 (Benzene-Toluene): Bubble Pressure P_b = 877.4 mmHg (≈ 1.155 atm). Vapour
compositions: y₁ = 0.618, y₂ = 0.382. As expected, vapour is enriched in more volatile benzene (Kbenzene
= 1354.9/877.4 = 1.545 > 1).

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

SECTION 5: DEW POINT CALCULATIONS

5.1 Definition
Dew Point: The condition at which the first infinitesimal drop of liquid forms from a vapour of known
composition {yᵢ} at equilibrium.

📌 Key Condition at Dew Point

Σᵢ xᵢ = 1 ⟹ Σᵢ yᵢ/Kᵢ = 1 ⟹ Σᵢ yᵢ·P/(γᵢ·P*ᵢ) = 1

5.2 Dew Point Pressure (Given T and {yᵢ})

P_d = 1 / Σᵢ [yᵢ / P*ᵢ(T)]
Dew Pt. P — Ideal
Direct calculation. No iteration needed for ideal systems.

xᵢ = yᵢ · P_d / P*ᵢ(T)
Liquid Composition
Verify: Σxᵢ must equal 1.00

Dew Pt. P — P_d = 1 / Σᵢ [yᵢ / (γᵢ(x) · P*ᵢ(T))]

Modified Raoult γᵢ depends on unknown {xᵢ} — iteration required

5.3 Iterative Algorithm — Dew Point P (Non-Ideal)

7. Start: assume γᵢ = 1 for all i. Compute initial P_d⁽⁰⁾ = 1/Σ(yᵢ/P*ᵢ)
8. xᵢ⁽⁰⁾ = yᵢ·P_d⁽⁰⁾ / P*ᵢ(T)
9. Normalise: xᵢ = xᵢ⁽⁰⁾ / Σxᵢ⁽⁰⁾
10. Recalculate γᵢ using activity coefficient model at updated {xᵢ}
11. P_d = 1 / Σᵢ[yᵢ/(γᵢ·P*ᵢ)]
12. Recalculate xᵢ = yᵢ·P_d/(γᵢ·P*ᵢ). Check |ΔP_d| < tolerance.
13. If not converged, return to step 3

5.4 Dew Point Temperature (Given P and {yᵢ})

Requires iterative solution because P*ᵢ = f(T):
14. Guess initial T_d
15. Compute P*ᵢ(T) from Antoine equation
16. S = Σᵢ yᵢ/P*ᵢ(T) [ideal] or S = Σᵢ yᵢ/(γᵢ·P*ᵢ) [non-ideal]
17. Converged when S = 1/P. If S > 1/P, T too low; if S < 1/P, T too high

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

18. Update T and repeat

5.5 Worked Example — Dew Point Pressure (Benzene–Toluene at 100°C)

Problem: Same system. T = 100°C, y₁ = 0.60. Raoult's Law. P*₁ = 1354.9 mmHg, P*₂ = 559.0 mmHg.

Step 1: Dew point pressure

1/P_d = y₁/P*₁ + y₂/P*₂ = 0.60/1354.9 + 0.40/559.0
1/P_d = 4.428×10⁻⁴ + 7.157×10⁻⁴ = 1.1585×10⁻³ mmHg⁻¹
P_d = 863.2 mmHg

Step 2: Liquid compositions

x₁ = y₁·P_d/P*₁ = (0.60)(863.2)/1354.9 = 0.382
x₂ = y₂·P_d/P*₂ = (0.40)(863.2)/559.0 = 0.618
Check: x₁ + x₂ = 0.382 + 0.618 = 1.000 ✓

📌 Result & Comparison

P_d = 863.2 mmHg < P_b = 877.4 mmHg for T=100°C and same overall composition z₁=0.60≈y₁ basis. The
dew point pressure is always less than or equal to the bubble point pressure at the same temperature.
The liquid phase is richer in less volatile toluene (x₂ = 0.618), as expected.

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

SECTION 6: FLASH CALCULATIONS & RACHFORD-RICE EQUATION

6.1 Flash Problem Definition

A flash calculation determines how a feed of composition {zᵢ} splits into vapour {yᵢ} and liquid {xᵢ} at given T and
P. The vapour fraction ψ = V/F is the key unknown.

Overall Material F = L + V ; F·zᵢ = L·xᵢ + V·yᵢ

Balance ψ = V/F = vapour fraction (0 < ψ < 1 for two-phase system)

Substituting yᵢ = Kᵢ·xᵢ and L = F(1−ψ):

Rachford-Rice Σᵢ zᵢ(Kᵢ−1) / [1 + ψ(Kᵢ−1)] = 0

Equation Solved for ψ by bisection or Newton-Raphson. Then xᵢ and yᵢ follow directly.

6.2 Flash Calculation Procedure

19. Compute Kᵢ = γᵢ·P*ᵢ(T)/P. For ideal: Kᵢ = P*ᵢ/P
20. Check: if all Kᵢ·zᵢ > 1 → all vapour (ψ=1); if all zᵢ/Kᵢ > 1 → all liquid (ψ=0)
21. Solve Rachford-Rice for ψ (bracket between 0 and 1)
22. xᵢ = zᵢ / [1 + ψ(Kᵢ−1)] ; yᵢ = Kᵢ·xᵢ
23. Normalise and verify Σxᵢ = Σyᵢ = 1
24. For non-ideal, update γᵢ at new {xᵢ} and iterate

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

SECTION 7: SUMMARY, FORMULAE & EXAM PREPARATION

7.1 Comparison: Bubble Point vs Dew Point

Aspect Bubble Point Dew Point
Starting phase Liquid {xᵢ} Vapour {yᵢ}

Condition Σᵢ Kᵢ·xᵢ = 1 (Σyᵢ = 1) Σᵢ yᵢ/Kᵢ = 1 (Σxᵢ = 1)

Find Pressure P_b = Σxᵢ·γᵢ·P*ᵢ (direct) P_d = 1/Σ(yᵢ/γᵢP*ᵢ) (direct if γ=1)

Find Temperature Iterative (S = ΣxᵢγᵢP*ᵢ = P) Iterative (S = ΣyᵢP/γᵢP*ᵢ = 1)

Physical event First bubble of vapour forms First drop of liquid condenses

Distillation analogy Liquid entering reboiler Vapour entering condenser

7.2 Master Formula Sheet

Raoult's Law yᵢ · P = xᵢ · P*ᵢ(T)

Modified Raoult's yᵢ · P = xᵢ · γᵢ · P*ᵢ(T)

Law

K-value Kᵢ = yᵢ/xᵢ = γᵢ·P*ᵢ(T)/P

Bubble Point P_b = Σᵢ xᵢ·γᵢ·P*ᵢ ; yᵢ = xᵢ·γᵢ·P*ᵢ/P_b

Pressure

Dew Point Pressure P_d = 1/Σᵢ[yᵢ/(γᵢ·P*ᵢ)] ; xᵢ = yᵢ·P_d/(γᵢ·P*ᵢ)

log₁₀(P*) = A − B/(T+C) [T in °C, P in mmHg

Antoine Equation
typical]

Rachford-Rice Σᵢ zᵢ(Kᵢ−1)/[1+ψ(Kᵢ−1)] = 0

Phase Rule F = C − P + 2

7.3 Common Mistakes & How to Avoid Them

● Confusing xᵢ with yᵢ: x = liquid, y = vapour. Always label clearly.
[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide
CEN-201: Thermodynamics & VLE | HBTU Kanpur Dr. Pranava Chaudhari

● Antoine unit mismatch: Check temperature (°C vs K) and pressure units from your data source before
every calculation.
● Ignoring γᵢ for polar systems: Ethanol-water, acetone-water deviate massively from Raoult. Always use
Modified Raoult.
● Not iterating for Tdew/Tbubble: P and T searches require iteration. One step is never enough.
● Forgetting to verify Σxᵢ = Σyᵢ = 1: This is your error-check. If it fails, find the bug before reporting the
answer.
● Assuming ideal vapour at high P: Above ~10 bar, use fugacity corrections (Poynting). For exam
problems unless stated, ideal vapour is assumed.

7.4 Practice Problems

Problem 1. n-Heptane (1) / n-Octane (2) at 100°C, x₁ = 0.40. Using Antoine constants from Perry's, find (a)
bubble point pressure, (b) vapour composition. Assume ideal.
Problem 2. Acetone (1) / Water (2) at 1 atm, y₁ = 0.30. Given γ₁ = 3.5, γ₂ = 1.1 (initial), find dew point
temperature by iteration.
Problem 3. Feed of z₁ = 0.50 benzene-toluene at T = 100°C, P = 760 mmHg. Using K-values from Section 4
example, solve Rachford-Rice to find ψ, {xᵢ}, {yᵢ}.
Problem 4. Ethanol (1) / Water (2) forms a minimum-boiling azeotrope at 78.15°C, x₁ = 0.894 (mol fraction), P =
760 mmHg. Calculate γ₁ and γ₂ at the azeotrope.
Problem 5. Derive the Rachford-Rice equation starting from overall and component material balances.

7.5 References
● Smith, J.M., Van Ness, H.C., Abbott, M.M. — Introduction to Chemical Engineering Thermodynamics, 8th
ed., McGraw-Hill (Primary textbook)
● Prausnitz, J.M., Lichtenthaler, R.N., de Azevedo, E.G. — Molecular Thermodynamics of Fluid-Phase
Equilibria, 3rd ed., Prentice Hall
● Perry's Chemical Engineers' Handbook, 9th ed. — Section 4 (Thermodynamics) and Section 13
(Distillation)
● Seader, J.D., Henley, E.J., Roper, D.K. — Separation Process Principles, 3rd ed., Wiley
● NIST WebBook: [Link] — Antoine constants and thermodynamic properties

Prepared by Dr. Pranava Chaudhari

Assistant Professor, Chemical Engineering, HBTU Kanpur | Session 2025–26
For academic use only. Unauthorised reproduction not permitted.

[Link] Chemical Engineering — 2nd Year See Table of Contents for section guide