Vapor liquid Equilibrium

Indian Institute of Technology Gandhinagar

Name: Rahul Kumar

Group Members: Dablu Kumar
Manish Jangir

HEAT TRANSFER AND THERMODYNAMICS LAB

Experiment No.: 8

VAPOR LIQUID EQUILLIBRIUM

2022
Date: 05 September

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 Vapor liquid Equilibrium

AIM:

• To determine the vapour liquid equilibrium data for the given binary system (A=more
volatile component, B= less volatile component)
• To check the dynamic consistency of the VLE data.

APPARATUS:

• The vapour liquid equilibrium still consists of the Vaporizer and Flash chamber or
Equilibrium chamber.
• The electrical heating coil in the vaporizer vaporizes the binary liquid mixture at a slow
rate. This vapour rises to the equilibrium chamber and finally vapour-liquid equilibrium
is established at the temperature and pressure of the chamber.
• A thermometer extends well inside the equilibrium chamber, which records the
equilibrium temperature. The pressure of the chamber is regulated by connecting
the vapor line to vacuum or pressure header.
• In the flash chamber, vapour and liquid phases separate from each other. The liquid
flows down through a liquid line via a water cooled joint to the feeder line, through
which the mixture again goes back to the vaporizer.
• The still may be drained through the feeder line and may be charged through either
the vapour or the liquid line.

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 Vapor liquid Equilibrium

Figure 1:- Experimetn Setup

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 Vapor liquid Equilibrium

[1] Figure 2: - Schematic of experimental setup for VLE data generation: A, glass balls
packing; B, drain holes; C, temperature sensor; D, vacuum jacket of equilibrium chamber; E,
magnetic stirrer; F, boiling vessel; G, Cottrell tube; H, vacuum jacket of Cottrell tube; I,
electric heating element; J, drain valve; K, mixing vessel; L, condenser; M, coolant inlet; N,
coolant outlet; O, mixture feed point; P, jacket for liquid return line and mixing vessel; Q,
cooling/heating medium inlet; R, cooling/heating medium outlet; S1, equilibrium liquid
sampling point; S2, equilibrium vapor sampling point; T, condensate receiver; U, vapor–
liquid equilibrium chamber.

PROCEDURE:
1. All the assembled apparatus and equipment required for the experiment were checked.
2. Open the cold-water valve need to opened because it’s necessary for the condensation
of vapor.
3. A mixture of 400 ml acetone and 100 ml benzene were prepared.
4. Voltage power supply (Rheostat) were opened and set voltage to 70 units.
5. The mixture was feuded in the boiling chamber.
6. Steady state temperature was noted once reached the steady state.
7. The liquid sample and vapor sample of mixture were collected in a glass tube.
8. The refractive index of both the sample were measured using the refractometer.
9. Now prepare 2 different mixtures first was 300ml acetone and 200ml benzene and
second was 200 ml acetone and 300 ml benzene and repeat the above step and take
reading.
10. All the switch and power supply were turned OFF after the experiment was done.

PRECAUTIONS:

• Wear full sleeve clothes and shoes during the experiment.

• The acetone and benzene used in this experiment is not suitable for health. Therefore,
avoid inhaling vapours. Also, avoid contacting the acetone with the skin or cloth.
• Make sure there are no open flames in the lab during the experiment.
• Make sure you wear the globs before touching anything during the experiment.
• Make sure you wear goggles when you see the condensed droplets of acetone or
during taking the reading of steady state temperature.
• Regulate the voltage power slowly and always keep it less than 90.
• Take the reading when a steady state has been achieved.
• Make sure the cold water is flowing continuously for condensation.
• Mixture should be prepared just before the feeding into the chamber as it may
evaporate and should be well stirred to make homogeneous.
• Before feeding the second mixture, clean the boiling chamber and the previous
sample totally.

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THEORY:

In engineering applications including distillation, environmental modelling, and general

process design, vapor-liquid equilibrium is crucial. When creating, using, and analysing such
separators, it is crucial to comprehend how different elements in a mixture interact with one
another. A useful method for connecting molecular interactions to mixture composition is the
activity coefficient.

Equilibrium is a static state in which a system's macroscopic properties do not alter over time.
liquid vapour When a liquid's vapour and itself are in equilibrium with one another, there is
no overall inter-conversion of vapour and liquid since the rate of evaporation is equal to the
rate of condensation at the molecular level.

[2] Figure :- Vapor-Liquid Equilibrium

𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑖𝑛 𝑣𝑎𝑝𝑜𝑟 𝑝ℎ𝑎𝑠𝑒

𝑦𝑖 =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑖𝑛 𝑣𝑎𝑝𝑜𝑟 𝑝ℎ𝑎𝑠𝑒

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 Vapor liquid Equilibrium

𝑚𝑜𝑙𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒

𝑋𝑖 =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒

In the chemical engineering the fugacity is concept which will tells us the interaction of
component in a mixture and also take into consideration of property of mixture as well as
component. In the vapor-liquid equilibrium the fugacity of vapor phase is equal to the
fugacity of the liquid phase means in both the phases the component interaction are same.

𝑓𝑖𝑣 (𝑇, 𝑃, 𝑦) = 𝑓𝑖𝐿 (𝑇, 𝑃, 𝑥)

𝐺 𝑅 (𝑇, 𝑃) − 𝐺 𝐼𝐺 (𝑇, 𝑃)
𝑓 = 𝑃 𝑒𝑥𝑝 ( )
𝑅𝑇

Where,

𝐺 𝑅 (𝑇, 𝑃) 𝑖𝑠 𝑡ℎ𝑒 𝑅𝑒𝑑𝑖𝑠𝑢𝑎𝑙 𝐺𝑖𝑏𝑏 ′ 𝑠 𝐸𝑛𝑒𝑟𝑔𝑦 𝑎𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇 𝑎𝑛𝑑 𝑝𝑟𝑒𝑠𝑠𝑟𝑢𝑒 𝑃

𝐺 𝐼𝐺 (𝑇, 𝑃) 𝑖𝑠 𝑡ℎ𝑒 𝐺𝑖𝑏𝑏 ′ 𝑠 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑖𝑑𝑒𝑎𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑎𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇 𝑎𝑛𝑑 𝑝𝑟𝑒𝑠𝑠𝑟𝑢𝑒 𝑃

For the vapor phase fugacity is written as

𝑓𝑖𝑣 = 𝑦𝑖 𝑓𝑖0𝑣 = 𝑦𝑖 𝑃 𝑤ℎ𝑒𝑟𝑒, 𝑓𝑖0𝑣 = 𝑝𝑢𝑟𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑣𝑎𝑝𝑜𝑟 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦

Liquid phase fugacity can we written in terms of activity coefficient

𝑓𝑖𝐿 = 𝛾 𝑥𝑖 𝑓𝑖0𝐿 𝑤ℎ𝑒𝑟𝑒, 𝑓𝑖0𝐿 = 𝑝𝑢𝑟𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐿𝑖𝑞𝑢𝑖𝑑 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦

The pure liquid component fugacity is equal to the saturation pressure.

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 Vapor liquid Equilibrium

𝑓𝑖0𝐿 = 𝑃𝑠𝑎𝑡

Now

𝑦𝑖 𝑃 = 𝛾 𝑥𝑖 𝑃𝑠𝑎𝑡

𝑓𝑖𝑣 = 𝛾 𝑥𝑖 𝑃𝑠𝑎𝑡

𝑦𝑖 𝑃 = 𝛾 𝑥𝑖 𝑃𝑠𝑎𝑡

Hence
𝑦𝑖 𝑃
𝛾 =
𝑥𝑖 𝑃𝑠𝑎𝑡

OBSERVATIONS:

• More volatile component (A)

• Less volatile component (B)

Table 1: - Properties of component from literature

Molecular Refractive
Density Boiling
Component Weight Index (R.I) at
(g/cm3) Point(°C)
(g/mol) 30°C

Acetone 0.7845 58.08 56 1.3588

Benzene 0.8765 78.114 80.1 1.4948

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 Vapor liquid Equilibrium

OBSERVATION TABLE:

R.I of
S No. T(°C) R.I of Liquid
Vapour
1. 57 1.4846 1.4874
2. 60 1.4868 1.4001
3. 63 1.4438 1.4237

CALCULATIONS:

𝑃𝐴 𝜌𝐴 𝑅𝑇
𝛾𝐴 = 𝑋 𝑤ℎ𝑒𝑟𝑒, 𝑃𝐴 =
𝑃 𝑜𝐴 𝐴 𝑀𝐴

𝑃𝐵 𝜌𝐵 𝑅𝑇
𝛾𝐵 = 𝑋 𝑤ℎ𝑒𝑟𝑒, 𝑃𝐵 =
𝑃𝑜 𝐵 𝐵 𝑀𝐵

• Calculate the Van Laar constants a and b from:

𝑋𝐵 𝑙𝑜𝑔𝛾𝐵 2
𝑎 = 𝑙𝑜𝑔𝛾𝐴 [1 + ]
𝑋𝐴 𝑙𝑜𝑔𝛾𝐴
𝑋𝐴 𝑙𝑜𝑔𝛾𝐴 2
𝑏 = 𝑙𝑜𝑔𝛾𝐵 [1 + ]
𝑋𝐵 𝑙𝑜𝑔𝛾𝐵
Where,
𝛾𝐴 = Activity coefficient of component A
𝛾𝐵 = Activity coefficient of component B
𝑋𝐴 = Composition of component A in liquid phase
𝑋𝐵 = Composition of component B in liquid phase
𝑌𝐴 = Activity coefficient of component B in vapor phase
𝑌𝐵 = Activity coefficient of component B in vapor phase
a = Van Laar Constant a
b = Van Laar Constant b

Note : - Find the calculation and graph in the excel

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 Vapor liquid Equilibrium

REFRACTIVE INDES AND MOLE FRACTION CORRELATION:

𝑅. 𝐼 = −0.1402 ∗ (𝑀𝑜𝑙𝑒 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛) + 1.4981

𝑅. 𝐼 𝑂𝐹 𝐿𝐼𝑄𝑈𝐼𝐷 = −0.1402 ∗ (𝑋𝐴 ) + 1.4981

𝑅. 𝐼 𝑂𝐹 𝑉𝐴𝑃𝑂𝑅 = −0.1402 ∗ (𝑋𝐵 ) + 1.4981

CALCULATION TABLE:

Table 1: - Properties of component from literature

R.I of R.I of P(A) (in P(B) (in
S No. T(°C)
T(K) Vapour Liquid atm) atm)
1 57 330.15 1.4846 1.4874 366.117762 304.1427734
2 60 333.15 1.4868 1.4001 369.4445931 306.9064514
3 63 336.15 1.4438 1.4237 372.7714242 309.6701295

Table 2: - Mole Fraction and Volatility

P°(A)
(in P°(B)
S No. X(A) Y(A) X(B) Y(B) α(AB) atm) (in atm)
1 0.076319544 0.096291013 0.923680456 0.903708987 1.289564723 1.02511 0.462911
2 0.699001427 0.080599144 0.300998573 0.919400856 0.037749561 1.13382 0.515309
3 0.530670471 0.387303852 0.469329529 0.612696148 0.559061549 1.25148 0.572332

Table 3: - Activity Coefficient

ln
S No. ϒ(A) ϒ(B) ln ϒ(A) ln ϒ(B) (ϒ(A)/ϒ(B))
1 27.25750453 606.8785052 3.305671625 6.408993127 0.515786421
2 227.7630467 179.2679811 5.428868708 5.189419849 1.04614174
3 158.0678774 253.9388609 5.063549555 5.537667702 0.914383063

Table 3: - Van Laar Constants

S No. T(°C) a b

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 Vapor liquid Equilibrium

1 57 1978.525135 6.966898678
2 60 10.81794032 61.03266877
3 63 19.59568509 22.90776443

RESULTS AND DISCUSSION:

• The steady state temperature at vapor-liquid equilibrium exits between the boiling
point of less volatile component and more volatile components. Here benzene is less
volatile component whose boiling point is 81 °C and acetone is more volatile
component whose boiling point is 56 °C.
• There is not significant change in Refractive Index when we change the composition
of mixture throughout the experiment.
• As we increase the benzene composition the steady state temperature increases
because benzene has more volatile that’s take more temperature to vaporised.
•

GRAPH:

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 Vapor liquid Equilibrium

CONCLUSION:

1. The boiling point of benzene and acetone is 81 °C and 56 °C respectively.

2. We can conclude that benzene is less volatile than acetone because as in the vapor
sample acetone is present in grater amount than benzene.
3. As be the composition of a component then the refractive index of that component
also increased.
4. From the graph we can calculate the refractive index of component at different
composition.

INDUSTRIAL APPLICATION:

[2] Vapor-liquid equilibrium data is useful for determining how liquid mixtures will separate.
Because the liquids have different boiling points, one liquid will boil into a vapor and rise in
the column, while the other will stay as a liquid and drain through the unit. Distillation is the
main method used to separate petroleum products in the petroleum industry. Crude oil is
distilled in a lot of oil refineries. Based on their different boiling temperatures, light

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hydrocarbons are distinguished from heavier constituents. Light substances like propane and
butane rise higher, while heavy substances like gas oils gather in the lower plates. Fuels made
of hydrocarbons, such as jet, diesel, and gasoline, are separated. To completely separate and
refine the products, this process is frequently performed numerous times. Efficiency is crucial
because refineries run these processes at steady state while continuously producing new
products at maximum capacity. Chemical engineers working on these procedures prioritise
maximising production effectiveness1.

REFERENCES:

[1] https://pubs.acs.org/doi/10.1021/acs.jced.8b00348

[2] https://www.jove.com/v/10425/vapor-liquid-equilibrium

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