VAPOR LIQUID EQUILIBRIA

Dr. Anteneh Mesfin Yeneneh

E-mail: anteneh@imco.edu.om
 Introduction

– The parameters for multicomponent equilibrium composition are more

difficult to predict compared with a simple binary case where you only
have A + B.

– The methods you learn in this chapter only gives you rough estimate
of parameters for more complicated systems in future.

– recall from thermodynamic; if there is no reaction: degree of freedom

in multicomponent phase = number of components.
 Self-Questioning
– Is the vapor pressure of liquid water at room condition (25 ̊C and
1atm), low or high?

– Compare the vapor pressure (evaporation speed) of pure water with

that of salty water at the same room condition.

3atm 1atm
In the solution the solute particles
G G obstruct, interfere the evaporation
of solvent particles, therefore the
L L vapor pressure will be less than that

Pure solvent Solvent mixed with of pure solvent.

non-volatile solute
 Vapor Pressure vs. Mole fraction

P˚solution = P˚pure solvent When X=1

1
Solution Vapor Pressure

0.8
(P˚solution)

0.6 =
0.4
0.2
0 Note that the original vapor
0 0.2 0.4 0.6 0.8 1
pressure of the solution can reduce
Mole fraction of solvent (X- by reducing the mole fraction of
solvent)
solvent (when Xsolvent <1).
 , where = and =

1atm

When it is mixed, each G

Even though blue and red particles are
substance lower the equally constitutes the solution (50%-
vapor pressure of the 50%), the vapor pressure of blue is
other substance as they higher than that of red, which means
obstruct each other’s the blue ones evaporates much easier).
L
evaporation.
Mixture of two volatile solvents
 Raoult’s Law vs. Henry’s Law

• Raoult’s: vapor pressure of and ideal solution is proportional to

the mole fraction for the solvent
• Solid in Liquid • xA: amount of A in Liquid phase
= • P̊A: vapor pressure of A (how
• Liquid in Liquid
much volatile A is)

Dreamstime, 2017
• yA: amount of A in gas phase
• Henry’s:
• Gas in Liquid • HA: Henry’s constant (can be
= found in Perry’s handbook)
CO2
(Amazon, 2017)

H2O can be described based on Raoult’s law

H2O CO2
CO2 can be described based on Henry’s law
 Example

• With the assumption that the air contains 4.5% water at room
temperature and 1 atm. Determine the content of Air in water.
(According to Perry’s handbook HAir = 7.71 x 104)
 Dalton’s Law

• Total pressure of a system = Sum of all components partial P

A with P̊A B with P̊ B

Where = and =
A+B
• Assume that A is solvent and B is a volatile solute

Where = and =

• Assume that A is solvent and B is a non-volatile solute

Because =
 Assignment No. 4
Q1. If we mix the 29 g of NH3 (as solute) in 250 ml of water (as solvent) with
the assumed vapour pressure of 24 torr, according to Raoult’s law
determine the new vapour pressure of the solution.

Q2. In a completely sealed container at room temperature, 150 g of ethanol

with the vapour pressure of 43.9 torr is mixed with 200 gr of acetone.
Determine the total vapour pressure of this mixture.

Q3. Calculate the amount glucose (C6H12O6) required to be mixed with 3 kg

of water at 65 ̊C to reduce the vapour pressure of solution with the size of
10 torr. Assume the vapour pressure of water at 65 ̊C is 188 torr.
 Antione Equation

• It is an empirical equation: derived from several experiments.

Form I (P˚ is in mm Hg and T is K) =

Form II (P˚ is in mm Hg and T is ˚C) =

• K1, K2 and K3 values can be found in tables or given in the question.

• P˚ (saturated vapor pressure) have to be expressed in the unit of mm Hg.

• T (Temperature) have to be expressed in the unit of ˚C or K.

• Antione equation is valid only for a limited range of T and P.

 Reidel Equation

• It is also an empirical equation derived from several

experiments. However, it is valid for lrange of T an P
=
 Reidel Equation

• If you are given vapor pressure of a substance at a certain temperature as

well as the critical point temperature and pressure (Tc and Pc), then you
should be able to predict the vapor pressure at any other temperature you
wish to.

• P (Pressure)have to be expressed in the unit of kN/m2.

• T (Temperature) have to be expressed in the unit of K.

=
 Assignment No. 5
Q1. A The vapour pressures of n-heptane and toluene at 373 K are 106 and 73.7 kN/m 2,
respectively. What are the mole fractions of n-heptane in the vapour and in the liquid phase at
373 K if the total pressure is 101.3 kN/m2? (Harker et al, 1990)
Q2. The constants in the Antoine equation are: 𝑥 𝐴= ( 𝑃 𝑡𝑜𝑡 − 𝑃 ° 𝐵
𝑃 ° 𝐴−𝑃 °𝐵 ) = , =

Benzene k1 = 6.90565 k2 = 1211.033 k3 = 220.790

Toluene k1 = 6.95334 k2 = 1343.943 k3 = 219.377

where P° is in mm Hg, T is in °C and log10 is used instead of loge. Determine the vapour phase
composition of a mixture in equilibrium with a liquid mixture of 0.5 mole fraction benzene
and 0.5 mole fraction of toluene at 338 °K. Will the liquid vaporise at a pressure of 101.3
kN/m2? (Harker et al, 1990)
Q3. The following data have been reported for acetone by Ambrose et al. Determine P° when T =
350.847 K using reduced form of the Riedel Equation. Pc =4700 kN/m2, Tc =508.1 K, P°1 =
100.666 kN/m2, T1 = 329.026 K. (Harker et al, 1990)
Most of separation processes (i.e Distillation, Evaporation and
Condensation) required well understanding of bubble and dew
points.

• Bubble point
The point where you have all liquid and the first
bubble of vapor is being created while boiling liquid.
Liquid

• Dew point
The point where you have all vapor and the first drop of
liquid is being created during condensation of the gas.
Gas
• 2-phase region
The region where you have both liquid and vapor
co-exist simultaneously.
Typical of Txy and Pxy equilibrium diagrams
for Benzene - Toluene
Superheated
Vapor Compressed
Liquid
Liq
uid
+V
ap
or
p or
Va
+
uid
Li q
Compressed
Liquid Superheated
Vapor
XB YB

• X is for Liquid
• Y is for Vapor
 Calculations of Bubble and Dew Points
Assumption of Idea Gas:
• Vapor is in ideal gas form
• Liquid follows Raoult’s Law

• Bubble point (xi and P̊ are known and yi is unknown)

𝑃=∑ 𝑃 𝑖=𝑥 𝐴 𝑃° 𝐴 (@𝑇 𝑏)+𝑥 𝐵 𝑃°𝐵 (@𝑇 𝑏)+…+𝑥𝑛 𝑃°𝑛 (@𝑇 𝑏) Xi = Liquid mole fraction
𝑃𝑖
𝑦 𝑖=
𝑃

• Dew point (yi and P̊ are known and xi is unknown)

∑ 𝑥𝑖=1𝑎𝑛𝑑𝑥𝑖 𝑃°𝑖 ( @𝑇 𝑑)=𝑦𝑖 𝑃 𝑥𝑖 =
𝑦𝑖 𝑃
𝑃 °𝑖
Yi= Vapor mole fraction

𝑦𝐴 𝑃 𝑦𝐵 𝑃 𝑦𝑛 𝑃
∑ 𝑥𝑖= + + …+ =1
 Relative Volatility
• The relationship between the vapor and liquid phase of
composition is vital in distillation column calculations.
𝑃 𝐴 𝑃𝐵
If 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐴=
𝑥𝐴 & 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐵 =
𝑥𝐵

Then

• The relation between the ratio A/B in vapor to the A/B in Liquid:
 Relative Volatility
• Plug in 1-yA for yB and 1-xA for xB:

To find out xA only from

component A and volatility
𝑥 𝐴=
(𝑦𝐴
α −( α −1) 𝑦 𝐴 )

• The relative volatility can be numerically expressed as ration of vapor pressure of components.
 Assignment No. 6
Q1. A liquid stream contains 10 mol % ethane (A) and 90 mol % n-hexane (B) at 25 °C.
The vapour pressure of ethane at 25 °C is 4150 kPa and the vapour pressure of n-hexane
at 25 °C is 16.1 kPa. If the pressure is such that this is a saturated liquid, determine the
total pressure and the composition of the first vapour to form.

Q2. The Table below shows the vapor pressure data for Benzene and Toluene, as
obtained from Perry’s Chemical Engineers’ Handbook, 6th edition.
Using these data, perform the following:
•Plot the Temperature vs Composition or T-x-y diagram for the mixture at atmospheric
conditions.
•Plot the x – y diagram for the system.
•Calculate the average relative volatility (α) for the system.
𝑥 𝐴=(𝑃 𝑡𝑜𝑡 − 𝑃 ° 𝐵
𝑃 ° 𝐴−𝑃 °𝐵 )
=

=
 References
• Amazon (2017). Coca Cola Icon, Retrieved 30 Oct 2017, from https://www.amazon.co.uk/Coca-Cola-330ml-Glass-Bottles/dp/B00ORZ5ZMW.
• Chanab. (2017). Glass of water with sugar, Retrieved 30 SEP 2017, from https://www.dreamstime.com/stock-photo-glass-water-sugar-image46451237.