MADAN MOHAN MALAVIYA UNIVERSITY OF TECHNOLGY

A Presentation on seminar topic

VAPOUR LIQUID EQUILIBRIUM
Presented by:
Nitin Kumar Jaiswal (2021061023)
Pawan Kumar Jaisal (2021061024)
Prachi Prajapati (2021061025)
Ratan Priya Gupta (2021061026) Under the guidance of:
Sachin Singh (2021061027) Dr. Jyoti
 • Introduction to Vapor Liquid Equilibrium (VLE)
• Vapour pressure
• Factors affecting vapour-liquid Equilibrium
• Types of Vapour-Liquid Equilibrium
• Phase Diagrams and Critical Points
•
Presentation •
Raoults law
Binary VLE Diagram: Txy Diagram, Pxy Diagram
Outline • Bubble point and Dew point curve
• Relative volatilities
• Ideal and Non-ideal system
• Azeotropes
• Industrial Application
• Result and Conclusion
• References.
Introduction to Vapor-Liquid
Equilibrium
Vapor-liquid equilibrium is a key concept in chemical
engineering, describing the distribution of a substance between
its vapor and liquid phases at equilibrium. Understanding this
phenomenon is crucial for various industrial processes, such as
evaporation, condensation, distillation and absorption. It
involves intricate intermolecular interactions and phase
transitions.
Introduction to
Vapor-liquid equilibrium is the condition where a liquid and its

Vapour-Liquid
vapor are in equilibrium with each other. This occurs at a
specific temperature and pressure, with both phases coexisting

Equilibrium
in a stable state. Fig.1 Representation of VLE
 Vapour Pressure

• Vapour is the pressure that a pure component exerts at a given temperature when
both liquid and vapour phases present.
• Vapour pressure is strongly temperature dependent.
• Liquids with higher vapor pressures (volatile liquids) have lower boiling points (and
vice versa).
• Vapor pressures can be determined by using Antoine Equation
𝑩
𝒍𝒐𝒈𝟏𝟎 𝑷 = 𝑨 − ……..(i)
𝑪+𝑻
where as P = Vapour pressure
T = Temperature(℃)
A,B and C = Antoine coefficients specific to the substance.
Factors affecting Vapour-liquid Equilibrium

• Temperature: The temperature affects the equilibrium by influencing the

vapor and liquid phase compositions.
• Pressure: Changes in pressure can impact the equilibrium and phase
behavior of the components.
• Intermolecular forces: The strength of intermolecular forces influences
the volatility of the components and the equilibrium state.
 Types of Vapour-Liquid Equilibrium

Single System Binary System Multicomponent

System
A system in which the
Consists of two components,
components do not chemically such as a liquid and its vapor Contains three or more
react with each other components interacting in
vapor-liquid equilibrium.
 Phase Diagram and Critical points

A phase diagram is a graph of pressure versus temperature that shows in which

phase a substance exists under different conditions of temperature and pressure.

Temperature and pressure control the phase of a substance.

A phase diagram typically has three regions, each representing a different

phase and three curves that separate each phase.

The points on the curves (the red, blue and yellow lines) indicate conditions
under which two phases coexist
 The critical point (B) indicates the
critical pressure and the critical
temperature above which a substance
cannot exist as a liquid

The triple point (A) is the

point on a phase diagram
that represents the
temperature and pressure at
which three phases of a
substance can coexist

The negative slope of the solid-

Fig.2 Phase Diagram of pure substance water liquid line in the phase diagram for
water indicates the solid floats on its
liquid
Raoults Law
• Raoult's law states that the partial pressure of each component of an ideal mixture of liquids is equal to
the vapor pressure of the pure component multiplied by its mole fraction in the mixture.
whereas; P = partial of component i
𝑷 = 𝑷′ 𝒙𝒊 𝑷′ = Vapour pressure of Pure i component at same temp.
𝒙𝒊 = mole fraction of component i in liquid.

•
.
Raoult's law has many limitations. It only applies to ideal solutions and the vapor should act like
ideal gas.

• Binary Vapour-Liquid Equilibrium is easily understandable by graphical representation of T-x-y

diagram and x-y diagram which is shown below.

• The VLE diagram provides valuable insights into the phase behavior of binary systems.
• Binary VLE Diagram
(Txy and x-y diagram at constant pressure)
Temperature is on y-axis
Lower curve shows the mole fraction more volatile component in liquid phase
Upper curve shows the mole fraction more volatile component in vapour phase

Fig.3.1 Variation of Temperature Vs Mole fraction. Fig .3.2 Variation of mole fraction in equilibrium diagram
Bubble Point and Dew Point Curve
• The lower curve is called the bubble point curve, there is
only a single subcooled liquid phase.
• It gives the mole fraction of benzene in the liquid phase (x).
• The upper curve is called the dew point. there is only a
saturated vapor phase.
• It gives the mole fraction of benzene in the vapor phase (y)
• In middle of curve mixture vapor and liquid present.

Bubble Point-It is the temperature (at a given pressure)

where the first bubble of vapor is formed when heating a
liquid consisting of two or more components.
Fig. 4 Bubble and dew point curve

The xy diagram can be generated from the Txy diagram by

Dew Point- It is the temperature (at a
drawing horizontal line between the bubble point curve and given pressure) where the first dew of
the dew point curve, thus we are able to read the mole liquid is formed when heating a liquid
fractions of binary mixture in equilibrium state consisting of two or more components.
Relative volatilities(α) and xy diagram
• The x=y line is usually drawn into the xy diagram
for comparison. It is also used, when determining
the steps needed for the desired distillation result.

• When α = 1, separation by distillation would be

not possible by simple distillation. Greater the
relative volatility, the easier is the separation by
distillation. α<1, separation is impossible.

• The greater is the value of α, the bigger is the

region between x=y line and the equilibrium line.
Fig. 5 x,y curves for different relative volatilities This region is called a separation area.
Ideal and Non-Ideal system
• The earlier benzene-toluene
mixture is a common example of
an ideal system.
• System is ideal when the
components are quite similar.
• If the components are
dissimilar, nonideal behavior
occurs. One example of a
nonideal system is the ethanol-
water mixture
• Equilibrium curve crosses the
x=y diagonal. This indicates the
presence of an azeotrope.

Fig.6 showing variation between ethanol in gas and liquid phase

Azeotropes • Azeotrope word has a meaning that “Boiling
without changing”

• An azeotrope is a composition at which the

liquid and vapor compositions are equals

• The vapor has the same proportions of

constituents as the unboiled mixture.

• When azeotrope formation will take place

i.e., value of α = 1 , separation cannot be
done by simple distillation, but can
separation can be done by Fractional
distillation

• Examples are Benzene and Toluene forms

suitable azeotrope when mixed with water.
Fig.7 Showing Azeotrope of propanol within liquid and vapor phase mixture
 Minimum Boiling Azeotrope
(Positive Azeotrope)
• The boiling point of this azeotrope is lower than the boiling
points of its constituents.
• This solution exhibits large positive deviation from Raoult's
law and large vapor pressure difference of components
• Example: Ethanol boils at 78.4°C,water boils at 100°C, but
the azeotrope boils at 78.2°C, which is lower than either of its
constituents.

Fig.7.1 Minimum Azeotrope

Maximum Boiling Azeotrope

(Negative Azeotrope)
• The boiling point of this azeotrope is higher than the boiling
points of its constituents
• The maximum boiling azeotrope occurs if the solution exhibits
negative deviation from ideality
• Example: Hydrogen chloride boils at -84°C and water at
100°C, but the azeotrope boils at 110°C, which is higher than
either of its constituents.
 Industrial Applications of VLE

Chemical Industry Pharmaceutical Petrochemical Environmental Food beverages

VLE is utilized in VLE plays a crucial role VLE is employed in air VLE is used in the
VLE is used in distillation
processes to separate different
solvent recovery in fractional distillation pollution control systems extraction of flavors
processes to separate processes used in the to remove pollutants from natural sources
components of a mixture based on
their boiling points. By
solvents from reaction petrochemical industry. from industrial exhaust such as fruits and herbs.
mixtures. By adjusting By controlling the gases. By utilizing VLE By controlling the
controlling the temperature and temperature and
the temperature and temperature and pressure, principles, harmful gases
pressure, the vapor and liquid pressure, volatile flavor
pressure, the solvent different hydrocarbon can be selectively
phases can be selectively compounds can be
can be evaporated and fractions can be absorbed into a liquid
separated, allowing for the selectively evaporated
recovered, while the separated, allowing to phase, effectively
purification and concentration of
desired products
desired product remains produce various reducing air pollution and recovered, resulting
in the liquid phase. petroleum products such and protecting the in the production of
as gasoline, diesel, and jet environment. concentrated and
fuel. natural flavors
 Results and Conclusion
After Study of vapor-liquid equilibrium, we concluded that-

• Vapor-liquid equilibrium (VLE) studies the phase equilibrium between a vapor phase and a liquid
phase.
• Vapor-liquid equilibrium is a fundamental concept in chemical engineering and thermodynamics,
playing a crucial role in the design and operation of separation processes.
• VLE is vital for optimizing processes in industries such as petrochemicals, pharmaceuticals, and
food processing
• Experimental data collected from VLE experiments typically involve measuring temperature and
pressure for different compositions of the liquid and vapor phases. This data is then used to construct
phase diagrams, such as T-x,y or P-x,y diagrams, which depict the conditions under which vapor and
liquid phases coexist in equilibrium.
• As binary Mixture (VLE), properties like viscosity and density changes on changing the temperature ,
thus our project is going under the VLE on the topic “ Measurement and modelling of viscosity for
binary Mixtures of Diisopropylether with n-alkanes (C7-C10).
 References
• Dutta, B. K. 2007. Principles of mass transfer and separation processes. New Delhi: Prentice-Hall, pp. 327-
340
• McCabe, W. L., Smith, J. C. & Harriott, P. 2005. Unit Operations of Chemical Engineering. 7th Edition.
New York: McGraw-Hill, pp. 737-740

• http://www.vle-calc.com/phase_diagram.html
• https://upload.wikimedia.org/wikipedia/commons/f/fa/VLEIsoropanolWaterAzeotrope.png
• https://en.wikipedia.org/wiki/Azeotrope#/media/File:Negative_Azeotrope.png
• https://en.wikipedia.org/wiki/Azeotrope#/media/File:Positive_Azeotrope.png
• https://researchspace.ukzn.ac.za/items/e8863387-194c-4d3c-979c-b30d2adefe55