Module 2: Equations of State

Introduction
This module focuses on equations of state (EOS), which are mathematical relationships
between pressure, volume, temperature, and sometimes composition for a substance or
mixture. Equations of state are fundamental tools for predicting thermodynamic
properties and phase behavior of fluids, making them essential for analyzing and
designing processes involving fluid phase equilibria.

Learning Outcomes
1. Classify and formulate equations of state (EOS) for ideal and real fluids, including
cubic models such as van der Waals, Redlich-Kwong, Soave-Redlich-Kwong, and
Peng-Robinson.

2. Apply EOS to analyze phase behavior and phase equilibria, including

calculation of critical points, phase boundaries, and fugacity for equilibrium
conditions.

3. Use the Corresponding States Principle (CSP) and generalized charts to estimate
thermodynamic properties of fluids.

Key Concepts

Introduction to Equations of State

An equation of state relates the pressure (P), volume (V), and temperature (T) of a
substance, allowing us to predict how these properties change under different
conditions. The simplest equation of state is the ideal gas law:

PV = nRT

Where: - P is pressure - V is volume - n is the number of moles - R is the universal gas

constant - T is absolute temperature

The ideal gas law assumes that gas molecules have negligible volume and no
intermolecular forces. While this is a good approximation at low pressures and high
temperatures, it fails to accurately predict behavior at high pressures or low
temperatures where molecular interactions become significant.

Compressibility Factor

The compressibility factor (Z) is a dimensionless quantity that measures the deviation of
a real gas from ideal gas behavior:

Z = PV/nRT

For an ideal gas, Z = 1. For real gases: - Z < 1 indicates attractive forces dominate
(common at moderate pressures) - Z > 1 indicates repulsive forces dominate (common at
very high pressures)

The compressibility factor can be expressed as a function of reduced properties using

the principle of corresponding states:

Z = f(Pr, Tr)

Where: - Pr = P/Pc (reduced pressure) - Tr = T/Tc (reduced temperature) - Pc and Tc are

the critical pressure and temperature

Corresponding States Principle

The corresponding states principle (CSP) states that all fluids, when compared at the
same reduced conditions (Tr, Pr), have approximately the same compressibility factor
and behave similarly. This principle allows us to use generalized charts and correlations
to estimate properties of various fluids.

The principle is based on the observation that when properties are normalized by their
critical values, many fluids follow similar patterns of behavior. The principle works best
for simple molecules with similar structures.

For more complex molecules, the acentric factor (ω) is introduced as a third parameter:

Z = f(Pr, Tr, ω)

The acentric factor is defined as:

ω = -log10(Pr^sat at Tr = 0.7) - 1.0

Where Pr^sat is the reduced vapor pressure at a reduced temperature of 0.7.

Cubic Equations of State

Cubic equations of state are called "cubic" because they can be arranged as cubic
polynomials in terms of volume. They account for both molecular attractions and
repulsions, making them more accurate than the ideal gas law for real fluids.

Van der Waals Equation

The van der Waals equation was the first cubic EOS to account for both molecular
attraction and repulsion:

P = RT/(V-b) - a/V²

Where: - a accounts for intermolecular attraction forces - b represents the finite volume
occupied by molecules

The parameters a and b are related to critical properties: - a = 27R²Tc²/64Pc - b = RTc/8Pc

Redlich-Kwong Equation

The Redlich-Kwong equation improved upon the van der Waals model by introducing
temperature dependence in the attraction term:

P = RT/(V-b) - a/(T^(1/2)V(V+b))

With parameters: - a = 0.42748R²Tc^(5/2)/Pc - b = 0.08664RTc/Pc

This modification significantly improved predictions for non-polar substances.

Soave-Redlich-Kwong Equation

The Soave-Redlich-Kwong (SRK) equation further refined the temperature dependence

of the attraction parameter by incorporating the acentric factor (ω):

P = RT/(V-b) - a(T)/V(V+b)

Where: - a(T) = a₀·α(T,ω) - a₀ = 0.42748R²Tc²/Pc - b = 0.08664RTc/Pc - α(T,ω) = [1 + m(1-

√(Tr))]² - m = 0.480 + 1.574ω - 0.176ω²

This equation provides good accuracy for many hydrocarbon systems.

Peng-Robinson Equation

The Peng-Robinson equation modified the volume dependence of the attraction term to
improve liquid density predictions:

P = RT/(V-b) - a(T)/[V(V+b) + b(V-b)]

With parameters: - a(T) = a₀·α(T,ω) - a₀ = 0.45724R²Tc²/Pc - b = 0.07780RTc/Pc - α(T,ω) =
[1 + κ(1-√(Tr))]² - κ = 0.37464 + 1.54226ω - 0.26992ω²

The Peng-Robinson EOS is widely used in the petroleum and chemical industries due to
its accuracy across a broad range of conditions.

Mixing Rules for Equations of State

For mixtures, the parameters in cubic equations of state must be calculated using mixing
rules. The most common are the van der Waals one-fluid mixing rules:

a_mix = Σᵢ Σⱼ xᵢxⱼaᵢⱼ b_mix = Σᵢ xᵢbᵢ

Where: - xᵢ and xⱼ are mole fractions - aᵢⱼ is typically calculated as aᵢⱼ = √(aᵢaⱼ)(1-kᵢⱼ) - kᵢⱼ is a
binary interaction parameter that accounts for deviations from the geometric mean rule

Fugacity Calculation from Equations of State

Fugacity is a key concept in phase equilibria, representing the "effective pressure" of a

component in a mixture. For pure components, the fugacity coefficient (φ = f/P) can be
calculated from an equation of state using:

ln(φ) = ∫[(Z-1)/P]dP from 0 to P

For cubic equations of state, this can be expressed as:

ln(φ) = Z - 1 - ln(Z - B) - (A/B)ln[(Z + B)/Z]

Where A and B are dimensionless parameters derived from the equation of state.

For mixtures, the fugacity coefficient of component i is:

ln(φᵢ) = (∂(nZ)/∂nᵢ)T,P,nⱼ≠ᵢ - ln(Z)

Critical Properties and Phase Behavior

Equations of state can be used to predict critical properties and phase behavior:

· Critical point: The point where (∂P/∂V)T = 0 and (∂²P/∂V²)T = 0

· Phase boundaries: Determined by the equal fugacity criterion (fᵢᵛ = fᵢˡ)
· Phase stability: Analyzed using the tangent plane distance method
Applications of Equations of State

Vapor-Liquid Equilibrium Calculations

Equations of state are widely used for vapor-liquid equilibrium (VLE) calculations:

1. Flash calculations: Determining the amounts and compositions of vapor and liquid
phases in equilibrium
2. Bubble point calculations: Finding the temperature or pressure at which the first
vapor bubble forms
3. Dew point calculations: Finding the temperature or pressure at which the first
liquid droplet forms

Property Estimation

Equations of state can be used to estimate various thermodynamic properties:

1. Enthalpy and entropy departures from ideal gas behavior

2. Heat capacities
3. Joule-Thomson coefficients
4. Compressibility factors

Process Design Applications

In chemical engineering, equations of state are essential for:

1. Distillation column design

2. Flash drum sizing
3. Compressor and expander calculations
4. Pipeline transport of gases and liquids

Example Problems

Problem 1: Compressibility Factor Calculation

Question: Calculate the compressibility factor of methane at 250 K and 50 bar using the
Peng-Robinson equation of state. Given: - Critical temperature (Tc) = 190.6 K - Critical
pressure (Pc) = 46.0 bar - Acentric factor (ω) = 0.011

Solution: Step 1: Calculate reduced temperature and pressure Tr = T/Tc = 250/190.6 =

1.311 Pr = P/Pc = 50/46.0 = 1.087
Step 2: Calculate Peng-Robinson parameters κ = 0.37464 + 1.54226ω - 0.26992ω² =
0.37464 + 1.54226(0.011) - 0.26992(0.011)² = 0.3916 α = [1 + κ(1-√Tr)]² = [1 + 0.3916(1-
√1.311)]² = [1 + 0.3916(1-1.145)]² = [1 - 0.0568]² = 0.8877

a = 0.45724(R²Tc²/Pc) = 0.45724(R²(190.6)²/46.0) = 3.5796R² b = 0.07780(RTc/Pc) =

0.07780(R(190.6)/46.0) = 0.0323R

A = aαP/(RT)² = 3.5796R²(0.8877)(50)/(R²(250)²) = 0.2540 B = bP/RT = 0.0323R(50)/(R(250))

= 0.0646

Step 3: Solve cubic equation for compressibility factor Z Z³ - (1-B)Z² + (A-3B²-2B)Z - (AB-
B²-B³) = 0 Z³ - (1-0.0646)Z² + (0.2540-3(0.0646)²-2(0.0646))Z - (0.2540)(0.0646)-(0.0646)²-
(0.0646)³ = 0 Z³ - 0.9354Z² + 0.1167Z - 0.0172 = 0

Using numerical methods (or a calculator), the largest real root is Z = 0.8253

Therefore, the compressibility factor of methane at these conditions is 0.8253.

Problem 2: Fugacity Coefficient Calculation

Question: Using the results from Problem 1, calculate the fugacity coefficient and
fugacity of methane at 250 K and 50 bar.

Solution: From Problem 1, we have: Z = 0.8253 A = 0.2540 B = 0.0646

The fugacity coefficient can be calculated as: ln(φ) = Z - 1 - ln(Z-B) - (A/B)ln[(Z+B)/Z] ln(φ)
= 0.8253 - 1 - ln(0.8253-0.0646) - (0.2540/0.0646)ln[(0.8253+0.0646)/0.8253] ln(φ) =
-0.1747 - ln(0.7607) - 3.9320ln(1.0783) ln(φ) = -0.1747 - (-0.2736) - 3.9320(0.0753) ln(φ) =
-0.1747 + 0.2736 - 0.2961 ln(φ) = -0.1972

Therefore, φ = e^(-0.1972) = 0.8210

The fugacity is: f = φP = 0.8210 × 50 = 41.05 bar

Problem 3: Binary Mixture Parameters

Question: Calculate the a and b parameters for the Peng-Robinson equation of state for
an equimolar mixture of ethane (1) and propane (2) at 350 K. Given: - For ethane: Tc₁ =
305.4 K, Pc₁ = 48.8 bar, ω₁ = 0.099 - For propane: Tc₂ = 369.8 K, Pc₂ = 42.5 bar, ω₂ = 0.152 -
Binary interaction parameter: k₁₂ = 0.011

Solution: Step 1: Calculate pure component parameters For ethane: κ₁ = 0.37464 +

1.54226ω₁ - 0.26992ω₁² = 0.37464 + 1.54226(0.099) - 0.26992(0.099)² = 0.5242 α₁ = [1 +
κ₁(1-√(T/Tc₁))]² = [1 + 0.5242(1-√(350/305.4))]² = [1 + 0.5242(1-1.0711)]² = [1 - 0.0372]² =
0.9263 a₁ = 0.45724(R²Tc₁²/Pc₁) = 0.45724(R²(305.4)²/48.8) = 8.7721R² a₁(T) = a₁α₁ =
8.7721R² × 0.9263 = 8.1257R² b₁ = 0.07780(RTc₁/Pc₁) = 0.07780(R(305.4)/48.8) = 0.0487R

For propane: κ₂ = 0.37464 + 1.54226ω₂ - 0.26992ω₂² = 0.37464 + 1.54226(0.152) -

0.26992(0.152)² = 0.6031 α₂ = [1 + κ₂(1-√(T/Tc₂))]² = [1 + 0.6031(1-√(350/369.8))]² = [1 +
0.6031(1-0.9732)]² = [1 + 0.0161]² = 1.0324 a₂ = 0.45724(R²Tc₂²/Pc₂) = 0.45724(R²(369.8)²/
42.5) = 14.6118R² a₂(T) = a₂α₂ = 14.6118R² × 1.0324 = 15.0850R² b₂ = 0.07780(RTc₂/Pc₂) =
0.07780(R(369.8)/42.5) = 0.0677R

Step 2: Calculate cross-interaction parameter a₁₂ = √(a₁(T)a₂(T))(1-k₁₂) = √(8.1257R² ×

15.0850R²)(1-0.011) = √(122.5761R⁴)(0.989) = 11.0124R²

Step 3: Calculate mixture parameters using van der Waals mixing rules a_mix = Σᵢ Σⱼ xᵢxⱼaᵢⱼ
= x₁²a₁(T) + 2x₁x₂a₁₂ + x₂²a₂(T) a_mix = (0.5)²(8.1257R²) + 2(0.5)(0.5)(11.0124R²) +
(0.5)²(15.0850R²) a_mix = 2.0314R² + 5.5062R² + 3.7713R² = 11.3089R²

b_mix = Σᵢ xᵢbᵢ = x₁b₁ + x₂b₂ = 0.5(0.0487R) + 0.5(0.0677R) = 0.0582R

Summary
Module 2 covers the essential concepts of equations of state and their applications to
phase equilibria:

1. Equations of state relate pressure, volume, and temperature, allowing prediction of

thermodynamic properties and phase behavior.

2. The compressibility factor quantifies deviations from ideal gas behavior and can be
estimated using the principle of corresponding states.

3. Cubic equations of state (van der Waals, Redlich-Kwong, Soave-Redlich-Kwong,

and Peng-Robinson) account for molecular interactions and provide improved
accuracy for real fluids.

4. For mixtures, mixing rules are used to calculate equation of state parameters.

5. Fugacity, a key concept in phase equilibria, can be calculated from equations of

state and used to determine equilibrium conditions.

These concepts form the foundation for the more advanced phase equilibria calculations
covered in Module 3.