Chemical Engineering

Thermodynamics-2
B. Tech 4th sem Chemical Engg.
Lect-3 : VLE modeling by Raoult’s law

Dr. Sukanta Kumar Dash

SoET, PDPU
 Phase Equilibrium Analysis
Analysis of separation equipment often involves assumption of
phase equilibria in terms of Gibbs free energy (G), chemical
potentials (μ), fugacities (f), or activity coefficients (γ).

At equilibrium, the total Gibbs free energy for all phases is a

minimum, and the chemical potential of a particular species is
identical in all phases.

Chemical potential is generally expressed in terms of fugacity.

Partial fugacity of a species in a mixture is like a pseudo-pressure.
At equilibrium, the partial fugacity of a given species is identical in
all phases, and the temperatures and pressures of all the phases are
the same.

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 Models for VLE: Raoult’s law

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 Models for VLE : Raoult’s law

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 Apply for Bubble point calculations where the vapor phase compositions
are unknown.
For binary system

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 Dew point & Bubble point Calculation
Dew point and bubble point calculations are divided into four classes:
A. BUBL P: Calculate {yi} and P, given {xi} and T
B. DEW P: Calculate {xi} and P, given {yi} and T
C. BUBL T: Calculate {yi} and T, given {xi} and P
D. DEW T: Calculate {xi} and T, given {yi} and P
These calculations are generally iterative. Simplifying assumptions are
therefore generally made. Bubble point calculations are done as follows:

In a similar way, dew point calculation can be made as

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 Antoine Equation for calculating Vapour
pressure/Saturated pressure

𝑠𝑠𝑠𝑠𝑠𝑠
𝐵𝐵
𝑙𝑙𝑙𝑙𝑃𝑃 𝑘𝑘𝑘𝑘𝑘𝑘 = 𝐴𝐴 −
𝑇𝑇 𝐾𝐾 + 𝐶𝐶
A, B, C are known as component specific Antoine constant for
the calculation of saturated pressure and saturated temperature
(normally A and B are +ve and C is –ve )

The Antoine equation can also be transformed in a temperature-explicit form

with simple algebraic manipulations:

𝐵𝐵𝑖𝑖
𝑇𝑇𝑖𝑖𝑠𝑠𝑠𝑠𝑠𝑠 = - 𝐶𝐶𝑖𝑖
𝐴𝐴𝑖𝑖 −𝑙𝑙𝑙𝑙𝑙𝑙

1/11/2024 Prof. Sukanta Dash, PDPU 7

 Formulas frequently used

yi P = xi Pi sat ( Raoult ' s Law)

for binary system (x1 + x2 = 1, y1 + y2 = 1)
P P1sat
P =P2sat + ( P1sat − P2sat ) x1 =P 2
sat
(α ≡ sat )
x1α + x2 P2
P − P2sat
x1 = P
=1
sat
P( y1 + y2α )
( P1sat − P2sat )
Henry ' s law : yi P= xi Η i
( P andP calculated fromAntoine eq.)
sat sat
1 2
y1 P
Bi x1 =
ln Pi sat (kPa=
) Ai − or Η1
T ( K ) + Ci
Bi P = ∑ xiγ i pisat
Ti sat
= − Ci i
Ai − ln P
1
1 P=
P= yi
y1
+
y2 ∑i γ p sat
P1sat P2sat i i

x1 Pi sat
y1 =
P
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