Course Code: CHM226 Course Title: Thermodynamics

Course Instructor: Dr. Prashant kumar

Academic Task No.: 02 Academic Task: VLE in distillation

Date of Allotment: 18/09/24 Date of submission: 19 /26/24

Student’s Roll no.:07 Student’s Reg. no: 12305182

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Learning Outcomes: Learnt about Novel heat conduction model for use in nanotechnology.

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Introduction

Vapor-liquid equilibrium (VLE) is a fundamental concept in thermodynamics and

chemical engineering describes the situation in which a liquid and its vapor live in
balance at a specific temperature and pressure. The compositions of the liquid and vapor
phases stay constant under these conditions, and the rates of vaporization and
condensation are equal. VLE is essential for comprehending and planning phase-change
processes, such distillation, which is utilized extensively in sectors ranging from
beverage manufacturing to petroleum refining. In order to forecast how mixtures will
behave under different circumstances and facilitate effective separation and purification
procedures, VLE research integrates thermodynamic concepts with experimental.
Phase equilibrium thermodynamics, namely Raoult's Law and Dalton's Law for ideal
mixes, as well as activity coefficients for non-ideal systems, regulate the fundamentals
of VLE. According to Raoult's Law, a component's partial pressure in the vapor phase
is directly proportional to both its vapor pressure and its mole fraction in the liquid
phase. Conversely, Dalton's Law states that the sum of the partial pressures of each
component is the total pressure of the vapor phase. Activity coefficients or equations of
state, which give a more accurate description of the interactions between molecules, are
used to account for deviations from ideal behavior in non-ideal mixtures.

Distillation processes, which depend on variations in component volatility for

separation, depend heavily on VLE in their design and operation. The combination is
heated in a distillation column to produce vapor, which rises to the top and interacts
with liquid that is descending. The lighter, more volatile components preferentially
concentrate in the vapor as a result of these interactions, while the heavier, less volatile
components stay in the liquid. Engineers can calculate the number of stages needed, the
energy input necessary, and the overall efficiency of the column by comprehending
VLE.

Beyond distillation, VLE is also used in environmental engineering, chemical synthesis,

and refrigeration. For example, VLE data is crucial for the separation of complex
hydrocarbon mixtures in the petrochemical industry. Similar to this, VLE principles
direct the elimination of contaminants while preserving desired flavors in the
manufacturing of alcoholic beverages. The idea is particularly essential for building
carbon capture and storage systems, which require exact control over gas-liquid
interactions.

In conclusion, VLE serves as the foundation for a large number of phase-change-related

industrial processes. Its concepts make it possible to forecast and control phase
behavior, which guarantees effective separation and purification system design. VLE is
a key component of developments in chemical engineering and related disciplines by
connecting thermodynamics with real-world engineering applications.

Fund..

Vapor-Liquid Equilibrium (VLE) Basics

The balance between a substance's or mixture's liquid and vapor phases at a specific
temperature and pressure is known as vapor-liquid equilibrium, or VLE. Since it
explains how components arrange themselves between the two phases under
equilibrium conditions, it serves as the foundation for many chemical engineering
activities, including distillation. Thermodynamics, phase behavior, and compositional
relationships are necessary to comprehend VLE.gg .

key Ideas:
1. Phase Equilibrium:
At equilibrium, the rate at which molecules move from
the
liquid phase into the vapor phase and the rate at which they return to the liquid
phase are equal. For both phases, this dynamic equilibrium guarantees constant
macroscopic characteristics including temperature, pressure, and composition.

2. Raoult’s law:
Raoult's Law establishes a connection between a component's
partial pressure in the vapor phase and its mole fraction in the liquid phase for ideal
mixtures:
𝑃 = 𝑥𝑖⋅𝑃𝑖
In this case, Pi is the partial pressure, P is the vapor pressure of the pure component at
the specified temperature, and xi is the mole fraction in the liquid phase.

3. Dalton’s law:
According to Dalton's Law, the sum of the partial
pressures of each component in the vapor phase determines the system's total pressure:

𝑃 total= ∑𝑦𝑖⋅𝑃

4. Non-Ideal Behavior:
 Real mixtures often deviate from ideality due to
molecular interactions. Activity coefficients (γi) quantify these deviations. The
modified Raoult’s Law accounts for non-ideal behavior:
Pi=xi⋅γi⋅Pi
5. Phase Diagrams:
VLE data is often visualized using phase diagrams.
o P-x-y Diagrams show the relationship between pressure and composition
at a constant temperature.
o T-x-y Diagrams display temperature-composition relationships at a fixed
pressure.
These diagrams indicate the boiling point of mixtures and help determine
bubble point (start of vaporization) and dew point (start of condensation).
2. Azeotropes
Azeotropes are unique mixtures where the vapor and liquid phases have identical
compositions. At azeotropic conditions, traditional distillation cannot separate
the components.
Thermodynamic Basis
At equilibrium, the chemical potential (μ) of each component is equal in both phases.
This condition ensures that the fugacity (pressure accounting for non-ideality) of a
component in the liquid phase equals its fugacity in the vapor phase.
fi(l) =fi(v)
Applications
VLE principles govern the design of separation processes like distillation and
absorption. By analyzing the VLE behavior of mixtures, engineers can predict the
number of distillation stages, reflux ratios, and operating conditions needed for efficient
separation.
In summary, the fundamentals of VLE lie in understanding the balance of phase
properties, thermodynamic laws, and real-mixture deviations. Mastery of these
principles enables the optimization of industrial separation processes.

Thermodynamic Models for Vapor-Liquid Equilibrium (VLE)

Models for Vapor-Liquid Equilibrium (VLE) in Hermodynamics

Thermodynamic models, which explain the link between temperature, pressure, and
phase composition, are essential for forecasting vapor-liquid equilibrium (VLE). The
distribution of components between the liquid and vapor phases at equilibrium is
determined by these models using thermodynamic concepts, such as the equality of
chemical potentials or fugacities. Depending on whether the system exhibits ideal or
non-ideal behavior, VLE modeling often employs two different methodologies:
equations of state (EOS) and activity coefficient models.
For systems, like hydrocarbon mixtures, where both phases show notable non-idealities,
equations of state (EOS) work very well. An EOS predicts phase behavior by
establishing a relationship between a substance's molar volume, temperature, and
pressure. Because of their accuracy in predicting vapor pressures and densities, the
Peng-Robinson and Soave-Redlich-Kwong equations are common EOS models that are
frequently employed for hydrocarbon and high-pressure systems. These models use
parameters derived from crucial characteristics to account for intermolecular forces and
the finite size of molecules. In order to determine the interaction parameters between
various components, EOS frequently uses mixing rules for mixtures, such as the van
der Waals or quadratic mixing rules.
On the other hand, non-ideal liquid-phase systems—especially those with polar or
highly associating components like water or alcohols—are better suited for activity
coefficient models. Activity coefficients are used in these models to characterize the
liquid phase's departure from ideality. Wilson, NRTL (Non-Random Two-Liquid), and
UNIQUAC (Universal Quasi-Chemical) are examples of popular models. These
molecular interaction-based models offer parameters to measure the contributions of
entropy and enthalpy to phase behavior. For example, the NRTL model works well for
systems with azeotropes or high polarity because it includes non-randomness elements
to manage strong interactions between dissimilar molecules.
A key component of these models is the thermodynamic consistency of VLE data,
which guarantees conformity with the Gibbs phase rule. Each component's fugacity in
the liquid phase must match its fugacity in the vapor phase for phase equilibrium to
occur. Activity coefficients are utilized for the liquid phase and fugacity coefficients
obtained from an EOS for the vapor phase in non-ideal systems. Methods such as the
gamma-phi approach, in which an EOS manages the vapor phase and activity
coefficient models describe the liquid phase, can be used to merge the models.
Predictive models such as UNIFAC (Universal Functional Activity Coefficient) and
COSMO-RS (Conductor-like Screening Model for Real Solvents) are extremely useful
for systems for which there is a dearth of experimental data. COSMO-RS predicts phase
behavior without requiring a lot of data by using quantum chemical computations,
whereas UNIFAC calculates activity coefficients based on group contributions. When
creating new separation procedures or researching systems with intricate or unusual
combinations, these prediction tools are especially helpful.

In general, the type of system, the operating environment, and the information at hand
all influence the choice of VLE thermodynamic model. Activity coefficient models are
excellent at managing less-than-ideal liquid mixes, whereas equations of state are
preferred for high-pressure and hydrocarbon systems. The precision and usefulness of
VLE forecasts have been further improved by developments in computational
techniques and hybrid models, allowing for effective process designing.

Measurement and Correlation of VLE Data

The design and optimization of separation processes including distillation, absorption,

and extraction depend heavily on the precise measurement and correlation of vapor-
liquissd equilibrium (VLE) data. The construction and validation of thermodynamic
models are based on experimental VLE data, which allows engineers to forecast phase
behavior in a variety of scenarios. In order to describe the equilibrium relationships
between the vapor and liquid phases, VLE data must be measured and correlated using
experimental methods, data analysis, and mathematical modeling.

Evaluation of VLE Information

The compositions of the liquid and vapor phases at certain temperatures and pressures
are ascertained through experimental VLE measurements. VLE data is obtained using
a variety of techniques, which can be categorized as flash equilibrium, isothermal, or
isobaric (constant temperature) methods, based on the conditions maintained during the
experiment.
Using static methods, a combination is put in a sealed container and left to come to
equilibrium. Following equilibrium composition analysis, samples are taken. Systems
that need precise pressure control or have low volatility can benefit from this approach.
Dynamic methods make use of continuous flow systems that permit dynamic interaction
between the liquid and vapor phases. These techniques are more rapid and frequently
applied to highly volatile systems.
The phase compositions must be analyzed using analytical techniques like gas
chromatography (GC) or infrared (IR) spectroscopy. To guarantee accurate VLE data,
these methods must be precise.
Frequently, mathematical models are used to connect experimental data in order to
produce smooth and continuous representations of phase behavior. The method of
correlation entails fitting experimental data.
Raoult's and Dalton's laws are frequently used to illustrate ideal systems. These rules
apply to simple systems like hydrocarbons because they assume optimal mixing
behavior.

Activity coefficient models (such as Wilson, NRTL, and UNIQUAC) are necessary for
non-ideal systems in order to take into consideration molecular interactions and liquid
phase deviations from ideality. Regression analysis is used in these models to extract
interaction parameters from experimental data.
The error between experimental and anticipated data is reduced by regression
techniques. For parameter estimation, techniques like least squares fitting are frequently
employed.
Testing for Thermodynamic Consistency To guarantee their dependability, VLE data
must meet thermodynamic consistency requirements. Tests of consistency, such the
Gibbs-Duhem integration, confirm if the measured data adhere to thermodynamic laws.
Data that doesn't pass these standards could need to be rejected or refined further.
Predictive Model Utilization
Predictive models such as UNIFAC or COSMO-RS
can estimate VLE behavior based on molecular structure or group contributions for
systems with scarce experimental data. These models are useful for preliminary process
design and screening, even though they are not as exact as experimental data.

The Value of the VLE Correlation

The validation of thermodynamic models, the creation of effective separation apparatus,
and the improvement of industrial processes are all made possible by precisely
measured and correlated VLE data. Additionally, high-quality VLE data improve
process efficiency and safety while assisting in the creation of new chemical processes.

In conclusion, two essential steps in applying thermodynamics to real-world

engineering challenges are measuring and correlating VLE data. Developments in
computational tools and experimental methodologies keep enhancing the precision and
reach of VLE data, enabling better decision-making in chemical process design.

Applications of Vapor-Liquid Equilibrium (VLE) in Distillation

A fundamental idea in the construction and functioning of distillation columns,

one of the most used separation techniques in the chemical and petroleum
industries, is vapor-liquid equilibrium, or VLE. VLE offers the essential
framework for comprehending how components distribute themselves between
the vapor and liquid phases at equilibrium, which is crucial for distillation, which
depends on the variations in the volatilities of mixture constituents. In order to
guarantee the efficacy and efficiency of the separation process, engineers can
ascertain the reflux ratio, the number of distillation stages, and other crucial
operational parameters by examining VLE data.
The connection between the composition of the liquid and vapor phases at a specific
temperature and pressure is governed by VLE in distillation. Since the liquid and vapor
phases are in equilibrium at any given point in the distillation column, the composition
of the vapor and the liquid are directly correlated through VLE. A key factor in
influencing the ease of separation is the idea of relative volatility, which is the ratio of
the two components' vapor pressures. It is easier to separate the components by
distillation when the relative volatility is higher.

VLE is used in continuous distillation column design to determine how many theoretical
stages are needed for a particular separation. The McCabe-Thiele method is a graphical
technique that allows engineers to predict the number of stages required for a specific
separation by creating an operating line and an equilibrium line using VLE data. This
approach depends on understanding the equilibrium composition at various column
stages, which is obtained via VLE data. Another crucial factor impacted by VLE data is
the reflux ratio, which is the ratio of the liquid product removed from the column to the
liquid returned to it. Although a larger reflux ratio usually leads to a more effective
separation, it also uses more energy.
VLE is as significant in batch distillation, which is employed for variable-feed or
smaller-scale separations. It directs the operational strategy, including the cut points for
separating various components, and aids in determining how the composition varies
over time as the distillation process advances. Based on the mixture's VLE behavior,
batch distillation frequently necessitates exact temperature and pressure control to
provide the required separation.
Case Studies in VLE
The practical application of vapor-liquid equilibrium (VLE) principles is central to the
design, optimization, and troubleshooting of distillation processes in various industries.
Case studies provide insights into how VLE is applied in real-world scenarios to solve
complex separation challenges and improve operational efficiency. Below are examples
of case studies illustrating the role of VLE in industrial and research settings.
One prominent case study involves the ethanol-water distillation system, a classical
example of azeotropic separation. Ethanol and water form a minimum boiling azeotrope
at approximately 95.6% ethanol by weight under atmospheric pressure, meaning
conventional distillation cannot achieve pure ethanol. In the beverage and fuel
industries, breaking this azeotrope is crucial for producing high-purity ethanol.
Engineers often employ azeotropic distillation using entrainers like benzene or
cyclohexane, which alter the relative volatility of the components by forming a ternary
azeotrope. Alternatively, pressure-swing distillation exploits the fact that the
azeotropic composition shifts with changes in pressure. VLE models, such as NRTL or
UNIQUAC, are critical for simulating these systems and designing effective separation
units.
Another case study examines the petrochemical industry, particularly the separation
of hydrocarbons in crude oil distillation. In this process, crude oil is separated into
fractions like naphtha, kerosene, and diesel based on boiling points. Given the
complexity of hydrocarbon mixtures, accurate VLE data is essential for determining the
number of stages, feed location, and reflux ratio in distillation columns. Advanced
thermodynamic models, such as Peng-Robinson EOS or Soave-Redlich-Kwong, are
often used to handle the non-idealities of hydrocarbon systems. A specific example is
the separation of propane and propylene, which have close boiling points and require
precise VLE modeling to achieve high purity. The use of predictive tools like Aspen
Plus and data from experimental VLE measurements ensures efficient column design
and operation.
In the pharmaceutical industry, a case study on solvent recovery highlights the
application of VLE in green chemistry initiatives. Solvent recovery via distillation is a
key step in reducing waste and recycling resources in drug manufacturing. For example,
the separation of methanol from water in a pharmaceutical process requires detailed
VLE data to optimize energy consumption and ensure the desired purity of recovered
methanol. Activity coefficient models like UNIQUAC or NRTL are commonly used to
account for the polar nature of such mixtures.
Another example is the separation of carbon dioxide and methane in the natural
gas processing industry. This separation is vital for purifying natural gas for
commercial use and reducing greenhouse gas emissions. VLE principles are used
to design distillation units operating at cryogenic temperatures, where phase
behavior is highly sensitive to temperature and pressure. Thermodynamic models
like the Peng-Robinson EOS and experimental VLE data are crucial for
accurately predicting phase behavior and optimizing separation efficiency.
In the chemical manufacturing sector, the separation of acetic acid and water
in the production of acetic acid via methanol carbonylation demonstrates VLE’s
importance. This system exhibits high non-ideality, requiring advanced
thermodynamic models to predict phase equilibria. Engineers utilize hybrid
separation techniques, such as extractive distillation or reactive distillation,
guided by VLE principles to enhance product purity and minimize energy costs.
These case studies illustrate the indispensable role of VLE in addressing
separation challenges across industries. By combining experimental data,
thermodynamic models, and simulation tools, engineers can design and
optimize processes that meet industrial demands while maintaining efficiency
and sustainability.
Conclusion

A key idea in chemical engineering, vapor-liquid equilibrium (VLE) serves as the

foundation for the planning, development, and use of separation techniques like
distillation. VLE provides the essential information needed to comprehend and forecast
phase behavior in mixes by characterizing the distribution of components between the
vapor and liquid phases at equilibrium. It is significant for a variety of industries, such
as environmental engineering, chemical production, medicines, and petroleum refining.
Effective separation procedures, improved energy use, and product quality are all made
possible by the use of VLE principles into industrial applications.

The fundamental ideas of VLE, which are based on thermodynamic rules, guarantee
that phase equilibrium is reached when each component's fugacity or chemical potential
in both phases is equal. Equations of state (EOS) for the vapor phase and activity
coefficient models for the liquid phase are mathematical representations of these
concepts that enable engineers to precisely characterize phase behavior under a range
of operating circumstances. To improve these predictions, however, sophisticated
models and experimental data are frequently required due to the complexity of real-
world systems, especially those that display azeotropes or non-ideal behavior.
The most obvious uses of VLE are probably in distillation procedures, where it helps
determine important factors like column design, reflux ratio, and stage count. The
McCabe-Thiele approach, for instance, uses VLE data in continuous distillation to
visually ascertain the number of theoretical steps needed for a particular separation.
VLE principles guide the timing of product cuts in batch distillation to get the required
purities. Additionally, to overcome the difficulties presented by azeotropes and closely
boiled components, specialist methods such as extractive distillation and azeotropic
distillation mostly depend on precise VLE data.

Notwithstanding its crucial function, a number of obstacles prevent VLE applications

from reaching their full potential. Due to the lack of experimental data, modeling
extremely non-ideal systems—particularly multi-component mixes with strong
intermolecular interactions—remains a major challenge.
Thanks to developments in computational tools, experimental methods, and sustainable
practices, VLE research and applications have a bright future. The estimation of VLE
behavior is being revolutionized by predictive models such as COSMO-RS and
machine learning techniques, which allow for precise predictions even for novel
combinations with sparse data. Reactive distillation and membrane-assisted distillation
are two examples of hybrid separation technologies that provide creative ways to
increase separation effectiveness while lowering energy usage. Furthermore, initiatives
to include renewable energy sources, create eco-friendly solvents, and recycle process
streams in distillation operations have been sparked by the increased focus on
sustainability.

In summary, VLE remains an indispensable tool in process engineering, facilitating the

development of efficient, cost-effective, and sustainable separation processes. By
addressing current challenges and leveraging emerging technologies, VLE applications
are poised to play an even greater role in advancing industrial separation processes,
minimizing energy consumption, and contributing to global sustainability efforts
Research Articles:
1. "Development of Finite Volume Methods for Fluid Dynamics"
o Discusses the advancement of finite volume methods and their
applications in CFD.
2. "Simulation of Incompressible Flows Using OpenFOAM"
o Details the use of OpenFOAM for fluid flow problems, with case studies
on incompressible flow.
3. "CFD Analysis of Pipe Flow and Heat Transfer"
o Explores pipe flow dynamics and heat transfer simulations, relevant for
analyzing horizontal pipe flow.

Online Resources:
1. ANSYS Fluent Tutorials
o Available on the ANSYS website or YouTube, providing step-by-step
guidance on CFD analysis.
2. OpenFOAM Documentation
o Comprehensive documentation and examples for performing CFD
simulations with OpenFOAM: https://openfoam.org.
3. NASA CFD Resources
o Offers a range of CFD-related materials: https://www.nasa.gov.
4. CFD Online
o A community forum and resource site for CFD practitioners:
https://www.cfd-online.com.