Equations of State Models

PENG-ROBINSON EQUATION & SOAVE-REDLICH-KWONG EQUATION

Pratham Kingar | CL 260 | 31.03.2024

200040075
Contents
Topic/Problem Statement ................................................................................................................................. 2
Introduction to Equation of State Models:....................................................................................................... 3
Introduction to Equation of State (EOS) Models ......................................................................................... 3
Historical Development of EOS Models: ...................................................................................................... 3
Fundamental Principles: ................................................................................................................................... 4
Commonly Used EOS Models: .......................................................................................................................... 5
Peng-Robinson Equation:.............................................................................................................................. 5
Soave-Redlich-Kwong Equation:................................................................................................................... 5
Strengths: ....................................................................................................................................................... 6
Limitations: .................................................................................................................................................... 6
Applicability: .................................................................................................................................................. 6
Derivation and Parameterization: .................................................................................................................... 6
The Peng-Robinson Equation of State: ......................................................................................................... 6
The Soave-Redlich-Kwong (SRK) equation .................................................................................................. 7
Applications in Chemical Engineering: ............................................................................................................ 8
Implementation and Computational Tools: ..................................................................................................... 9
Challenges and Future Directions: ................................................................................................................... 11
Conclusion: ....................................................................................................................................................... 12
References: ........................................................................................................................................................ 12

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Topic/Problem Statement
Understanding and Application of Equation of State Models in Chemical Engineering Processes

Chemical engineering processes heavily rely on accurate thermodynamic models for the prediction of
phase behaviour, mixture properties, and process design. Among these models, Equation of State (EOS)
models play a pivotal role due to their ability to describe the thermodynamic properties of fluids and
fluid mixtures with varying complexities. The objective of this literature review is to comprehensively
explore the theory, application, and computational implementation of EOS models in chemical
engineering.

EOS models are mathematical representations of the relationship between thermodynamic variables,
such as pressure, temperature, and volume, which govern the behaviour of fluids. They are derived from
fundamental principles of statistical mechanics or empirical correlations. However, the selection and
parameterization of EOS models require careful consideration of factors such as molecular interactions,
phase behaviour, and computational efficiency.

This literature review will begin by providing an introduction to EOS models, elucidating their
significance in chemical engineering and outlining the scope of the review. Subsequently, it will delve
into the fundamental principles underlying EOS models, including the ideal gas law, intermolecular
forces, and molecular interactions. The review will then explore commonly used EOS models, focusing on
the Peng-Robinson equation and the Soave-Redlich-Kwong equation, discussing their mathematical
formulations, assumptions, and range of applicability.

Furthermore, the review will address the derivation and parameterization of EOS models, highlighting
methods for estimating model parameters from experimental data or molecular simulations. It will also
investigate the applications of EOS models in chemical engineering, with a particular emphasis on their
role in process design, simulation, and optimization. Additionally, the review will discuss the
implementation of EOS models in computational tools commonly used by chemical engineers, such as
Aspen/DW-SIM and MATLAB, elucidating the algorithms and numerical methods employed for solving
EOS equations.

Validation of EOS models against experimental data or benchmark calculations will be examined, along
with techniques for assessing the accuracy and reliability of thermodynamic predictions. Furthermore,
the review will identify current challenges and limitations in EOS modelling, such as the treatment of
complex mixtures and extreme conditions, and propose potential research directions for overcoming
these challenges.

In conclusion, this literature review aims to provide a comprehensive understanding of EOS models in
chemical engineering, emphasizing their significance, applications, challenges, and future directions.

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Introduction to Equation of State Models:
INTRODUCTION TO EQUATION OF STATE (EOS) MODELS
EOS models are foundational in chemical engineering, offering precise mathematical descriptions of fluid
and fluid mixture thermodynamics. Crucial for predicting phase equilibria, vapor-liquid equilibria, and
other key properties, these models are indispensable across diverse chemical engineering processes. By
accurately capturing molecular interactions, EOS models empower engineers to optimize processes,
minimize energy consumption, and ensure product quality in industries such as petroleum refining and
pharmaceuticals. Thus, they serve as essential tools for scientific inquiry and practical application in
chemical engineering endeavors.

HISTORICAL DEVELOPMENT OF EOS MODELS:

The roots of modern Equation of State (EOS) models can be traced back to seminal works such as the
ideal gas law (PV = nRT), revered for its simplicity but limited applicability. Over the years, significant
strides have been made towards developing more robust and versatile EOS models, covered by John M.
Prausnitz and discussed in a seminal 1983 study.

Prausnitz anticipated several advancements, including (semi) theoretical EOS for complex mixtures,
abandonment of quadratic mixing rules, and specialized EOS for petroleum fractions and polymers. He
also foresaw the incorporation of scaling laws for the critical region and the development of
comprehensive frameworks for multicomponent mixtures containing aqueous electrolyte solutions.

In his 1983 manuscript, Prausnitz expressed the hope for model consolidation, envisioning a future where
a single, universal model could cover a wide range of applications in chemical engineering. However,
despite progress, achieving a singular model remains a challenge.

EOS models have evolved into distinct categories, including virial equations, cubic equations of state, and
advanced molecular EOS such as the Statistical Associating Fluid Theory (SAFT). While each category
offers unique advantages, only a few, like cubic EOS and molecular EOS, possess the potential for broad
applicability.

The development of multi-parameter EOS, such as those for CO2 by Span and Wagner, and extensions
for mixtures by Kunz and Wagner, showcases advancements tailored to specific systems. Yet, challenges
persist, including computational complexities and limitations in modelling polar and associating
compounds.

Industries continue to employ diverse EOS models, often within the same company. Despite the
proliferation of models, the quest for a unified, all-encompassing EOS model remains a tantalizing
prospect, propelling ongoing research and innovation in the field.

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Fundamental Principles:
Assuming an equilibrium state, the three properties needed to completely define the state of a system are
pressure (P), volume (V), and temperature (T). Hence, we should be able to formulate an equation
relating these 3 variables, of the form f (P, T, V) =0.

An equation of state (EOS) is a functional relationship between state variables — usually a complete set
of such variables. Most EOS are written to express functional relationships between P, T and V. It is also
true that most EOS are still empirical or semi-empirical. Hence, the definition:

An Equation of State (EOS) is a semi-empirical functional relationship between pressure, volume and
temperature of a pure substance. We can also apply an EOS to a mixture by invoking appropriate mixing
rules.

The functional form of an EOS can be expressed as:

𝑓(𝑃, 𝑉, 𝑇, 𝑎𝑘 = 1, 𝑛𝑝 ) = 0

Where ak = EOS parameters.

The development of cubic Equation of State (EOS) models traces back to van der Waals' pioneering work,
emphasizing the molecular origins and practical significance of his equation. Despite early skepticism,
van der Waals' optimism regarding the predictive power of his equation resonates with the subsequent
evolution of cubic EOS models.

Cubic EOS models, embodying the Corresponding States Principle and accounting for both entropic and
energetic effects, offer versatile representations of intermolecular interactions and phase behavior.
However, thorough evaluation of cubic EOS models requires meticulous attention to parameter
estimation methodologies, as the choice of data and techniques can significantly impact model
performance.

One approach to comprehend cubic Equation of State (EOS) models and their mixing rules involves
examining and scrutinizing the excess Gibbs (GE) or Helmholtz (AE) energies and activity coefficient
expressions derived from them. In the context of GE or AE expressions, these formulations are general
and do not entail mixing or combining rules. Conversely, activity coefficient expressions rely on the
application of mixing and combining rules. For instance, the van der Waals EOS, when employing the
classical vdW1f mixing and combining rules (with all interaction parameters set to zero), can be
expressed as (assuming zero excess volume, as detailed in Kontogeorgis and Economou (2010):

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where γ is the activity coefficient, ψ the volume fraction, x the molar fraction, V the volume, while b and
a are the equation of state parameters

In summary, while cubic EOS models represent significant advancements in thermodynamic modeling,
careful consideration of parameter estimation methodologies is crucial for realizing their potential in
practical applications

Commonly Used EOS Models:

In the realm of thermodynamic modelling, two prominent Equation of State (EOS) models widely used in
chemical engineering are the Peng-Robinson (PR) equation and the Soave-Redlich-Kwong (SRK)
equation. These models serve as essential tools for predicting phase behaviour, vapour-liquid equilibria,
and other thermodynamic properties of fluids and fluid mixtures. Let's delve into a detailed discussion of
each model and then compare and contrast their characteristics:

PENG-ROBINSON EQUATION:
The Peng-Robinson equation, proposed by Peng and Robinson in 1976, is a cubic EOS model designed to
capture the behaviour of both pure components and mixtures. Its mathematical formulation is as follows:

𝑅𝑇 𝑎𝛼
𝑃= − 2
𝑉 − 𝑏 𝑉 + 2𝑏𝑉 − 𝑏 2
Where: P is the pressure, T is the temperature, V is the molar volume, R is the gas constant, a and b are
adjustable parameters specific to each substance, α is a parameter related to the repulsion between
molecules.

The PR equation is based on the van der Waals mixing rule for the attractive parameter

a and the original van der Waals volume correction term.

SOAVE-REDLICH-KWONG EQUATION:
The Soave-Redlich-Kwong equation, proposed by Soave in 1972 as an improvement to the original
Redlich-Kwong equation, is another widely used cubic EOS model. Its mathematical formulation is given
by:

𝑅𝑇 𝑎𝛼
𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)

where the terms are similar to those in the PR equation, with the addition of a factor V+b in the
denominator of the second term. The PR model employs the van der Waals mixing rule for the attractive
pressure term (a) and the original volume correction (b). The SRK equation incorporates a modification
in the denominator of the second term using a temperature-dependent term (1 + √(T/Tc)), where Tc is
the critical temperature.

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STRENGTHS:
− Computational Efficiency: Compared to more complex EOS models, both PR and SRK offer
relative simplicity and computational efficiency, making them favourable for various engineering
applications.

− Phase Equilibria Prediction: These models exhibit good accuracy in predicting phase behaviour
and VLE for a broad spectrum of systems, encompassing pure components and mixtures.

− Accessibility and Implementation: The PR and SRK models are widely implemented in process
simulation software and extensively documented, facilitating their use by engineers and
researchers.

LIMITATIONS:
− Critical Point and Extreme Conditions: Both models might encounter limitations in accurately
predicting properties near critical points or under extreme pressure-temperature conditions
where significant deviations from ideal gas behaviour occur.

− Pressure Prediction: The PR model may overestimate pressures, particularly for polar or
associating fluids. Conversely, the SRK model might underestimate pressures and exhibit lower
accuracy for highly non-ideal systems or mixtures with strong associative interactions.

APPLICABILITY:
The PR and SRK EOS models find application in a wide range of chemical engineering processes,
including: Process Design, Simulation, Optimization.

They are particularly well-suited for systems involving hydrocarbons, natural gas, and other non-polar
substances. However, their efficacy diminishes for systems containing polar or associating compounds,
where more sophisticated EOS models might be necessary.

Derivation and Parameterization:

THE PENG-ROBINSON EQUATION OF STATE:
The Peng-Robinson (PR) equation of state, introduced in 1976, aimed to address several key
considerations in fluid property prediction for chemical engineering applications. The developers, Peng
and Robinson, sought an equation where:

1. Parameters could be derived from critical properties and acentric factors.

2. The model offered good accuracy near the critical point, particularly for compressibility factor and
liquid density calculations.
3. Mixing rules required only one temperature, pressure, and composition independent binary
interaction parameter.
4. The equation could be applied to various fluid property calculations in natural gas processing.

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The PR equation is expressed as:

In polynomial form

Key Considerations:

The PR equation exhibits performance comparable to the Soave equation, but generally excels in
predicting liquid densities, especially for non-polar materials. Extensive evaluations of the original PR
equation's performance for density, thermal properties, and phase equilibria have been documented.
These evaluations indicate that the original form has deviations in vapor pressure and phase equilibria
roughly three times larger than those observed in updated implementations.

THE SOAVE-REDLICH-KWONG (SRK) EQUATION

The Soave-Redlich-Kwong (SRK) equation of state (EOS) builds upon the Redlich-Kwong (RK) EOS to
improve fluid property prediction, particularly for non-polar fluids. Here's a breakdown of its derivation
and parametrization:

Derivation:

Modification of the RK term: The original RK equation has a constant term (b) for volume correction. The
SRK EOS replaces this with a temperature and acentric factor (ω) dependent term, α (T, ω). This
modification aims to improve accuracy near the critical point.

Reduced form: Similar to other cubic EOS, the SRK equation can be expressed in reduced form using
reduced pressure (P*) and reduced temperature (T*). This allows for a single equation applicable to
various substances.

Cubic form: The final form of the SRK EOS is a cubic equation in terms of reduced pressure:

0 = Z3-Z2+Z (A-B-B2)-AB

Where:

Z - Compressibility factor (PV/RT*) A - a temperature and acentric factor dependent term B - co-volume
parameter

Parametrization:

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The key aspect of parametrization is determining the values of A* and B for a specific substance. The SRK
equation uses the following:

Critical properties (temperature, pressure, volume)

Acentric factor (ω) - a measure of a molecule's non-sphericity

Important points:

The introduction of α (T, ω) improves the SRK EOS compared to the original RK equation, especially for
non-polar fluids.

The parametrization relies on critical properties and acentric factor, requiring reference data for each
substance.

While offering good performance for hydrocarbons, the SRK EOS might not be as accurate for highly
polar or associating fluids.

Applications in Chemical Engineering:

Equation of State (EOS) models play a pivotal role in various chemical engineering processes, offering
predictive insights into phase equilibria, vapour-liquid equilibria, and other essential thermodynamic
properties. Let's explore some key applications where EOS models have been utilized:

Process Design and Optimization:

− EOS models are integral to the design and optimization of chemical processes, providing critical
thermodynamic data required for equipment sizing, heat and mass transfer calculations, and
overall process performance assessment.

− Engineers rely on EOS models to predict phase behaviour and determine optimal process
conditions, ensuring efficient operation and maximizing product yields.

− In industries such as petroleum refining, EOS models are used to design separation processes,
such as distillation and extraction, to achieve desired product specifications while minimizing
energy consumption and operating costs.

Simulation and Modelling:

− Process simulation software, such as Aspen Plus and HYSYS, leverage EOS models to simulate
complex chemical processes and predict system behaviour under varying operating conditions.

− EOS models enable engineers to simulate multiphase systems, such as gas-liquid or liquid-liquid
systems, and accurately predict phase compositions, densities, and other thermodynamic
properties.

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 − By integrating EOS models into simulation tools, engineers can assess the performance of
different process configurations, evaluate alternative feedstock or operating conditions, and
optimize process designs before implementation.

Thermodynamic Property Prediction:

− EOS models serve as reliable tools for predicting thermodynamic properties of pure components
and mixtures, including enthalpies, entropies, and fugacity coefficients.

− Engineers use EOS models to estimate critical properties, such as critical temperature and
pressure, which are crucial for process safety analysis, equipment design, and product stability
assessment.

− In the pharmaceutical industry, EOS models are employed to predict solubility behaviour,
crystallization kinetics, and other thermodynamic properties relevant to drug formulation and
process development.

Advanced Process Control:

− EOS models are integrated into advanced process control strategies to optimize process
performance in real-time and ensure consistent product quality.

− By incorporating EOS-based thermodynamic models into control algorithms, engineers can

maintain process stability, minimize deviations from set point conditions, and maximize overall
process efficiency.

In essence, Equation of State models serve as indispensable tools in chemical engineering, enabling
engineers and researchers to design, simulate, and optimize processes with precision and confidence.
From process design to operation and control, the predictive capabilities of EOS models are instrumental
in driving innovation and efficiency across diverse chemical engineering applications.

Implementation and Computational Tools:

Peng-Robinson Equation of State

Flow Chart

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The Soave-Redlich-Kwong (SRK) equation

Flowchart

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Challenges and Future Directions:
Treatment of Complex Mixtures and Extreme Conditions:

 EOS models face challenges in accurately describing phase behaviour and thermodynamic
properties of complex mixtures, including those containing polar or associating compounds.

 Extreme conditions, such as high pressures or temperatures, can lead to deviations from ideal
behaviour, necessitating improvements in EOS formulations to enhance predictive accuracy.

Development of Advanced Mixing Rules:

 Research efforts focus on refining mixing rules within EOS models to better capture the
effects of molecular interactions in complex mixtures.

 Advanced mixing rules aim to incorporate additional parameters or empirical correlations to

account for non-ideal behaviour, particularly in systems with strong associating interactions.

Incorporation of Molecular Simulation Data:

 Integration of molecular simulation data into EOS models offers opportunities to improve
parameter estimation and validate model predictions.

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  By leveraging molecular simulation techniques such as Monte Carlo or molecular dynamics
simulations, researchers can refine EOS formulations and enhance their predictive capabilities
for a wide range of chemical systems.

In summary, addressing challenges in EOS modelling requires innovative approaches, including the
development of advanced mixing rules and the incorporation of molecular simulation data. These
research directions hold promise for advancing the accuracy and applicability of EOS models in
predicting phase behaviour and thermodynamic properties across diverse chemical engineering
applications.

Conclusion:
In conclusion, this literature review provides valuable insights into the applications of Equation of State
(EOS) models in chemical engineering. Through an examination of various EOS models such as the Peng-
Robinson and Soave-Redlich-Kwong equations, key findings have been elucidated.

EOS models play a crucial role in advancing our understanding of thermodynamic behaviour in chemical
engineering systems. They serve as indispensable tools for predicting phase equilibria, vapour-liquid
equilibria, and other essential thermodynamic properties. From process design and simulation to
optimization and control, the predictive capabilities of EOS models contribute significantly to the
efficiency and effectiveness of chemical engineering processes.

Overall, this review underscores the significance of EOS models in facilitating research and innovation in
chemical engineering, driving progress towards more sustainable and efficient industrial practices.

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PT Behavior and Equations of State (EOS), Part II
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