Thermodynamics and

Fluid-Phase Equilibria
Topic 1

ChE 315 - Computer Applications

Topic 2 - Week 3 1
in ChE
Objectives
• At the end of this chapter you should be able to
• Estimate the vapor pressure of pure components.
• Determine boiling point and dew point of a mixture.
• Calculate relative volatility.
• Estimate the molar volume using equation of state.(EOS).
• Plot the effect of temperature on density.
• Use DWSIM and MS Excel software to estimate physical properties.

ChE 315 - Computer Applications

Topic 2 - Week 3 2
in ChE
Boiling Point Calculations
• When Raoult’s Law and Dalton’s law hold for the mixture, the K
factor is defined as the ration of the vapor pressure to the total
pressure of the system.
𝑃𝑣,𝑖
𝐾𝑖 =
𝑃

ChE 315 - Computer Applications

Topic 2 - Week 3 3
in ChE
Dew point calculations
• The dew point is the temperature at which a given parcel of air
must be cooled, at constant barometric pressure, for water vapor to
condense into water. The condensed water is called dew. Dew
point is a saturation point.
• The basic equation for the dew point is as follows:
𝑛 𝑛
𝑦𝑖
෍ 𝑥𝑖 = ෍ = 1.0
𝐾𝑖
𝑖=1 𝑖=1

ChE 315 - Computer Applications

Topic 2 - Week 3 4
in ChE
Vapor Pressure Correlations
• One of the most successful correlations is called Antoine equation which uses
three coefficients, A, B, and C which depend on the substance being
analyzed.
• Antoine equation is as follows:

𝐵
log 𝑃𝑣 = 𝐴 −
𝑇+𝐶

• If Raoult’s law and Dalton’s law hold, valuesof Ki can be calculated from the
vapor pressure (Pv) and the total pressure (P) of the system.

𝑃𝑣
𝐾𝑖 =
𝑃

ChE 315 - Computer Applications

Topic 2 - Week 3 5
in ChE
Relative Volatility
• The K factors are strongly temperature dependent because of the
change in pressure, but the relative volatility of K for two
components change only moderately with temperature. The ratio
of K factors is the same as the relative volatility (𝛼𝑖𝑗 ) of the
components.
𝑦𝑖
𝑥𝑖 𝐾𝑖
𝛼𝑖𝑗 = 𝑦 =
𝑗 𝐾𝑗
𝑥𝑗
• When Raoult’s law applies:
𝑃𝑣,𝑖
𝛼𝑖𝑗 =
𝑃𝑣,𝑗

ChE 315 - Computer Applications

Topic 2 - Week 3 6
in ChE
Example 1-1
• Find the bubble-point temperature for a mixture of 35 mol% n-
hexane, 30% n-heptane, 25% n-octane, and 10% n-nonane at 1.5
atm total pressure.

ChE 315 - Computer Applications

Topic 2 - Week 3 7
in ChE
Example 1-1
• Hand calculation:
• Assume the temperature, calculate the vapor pressure using Antoine equation, and then
calculate the summation of yi; if the summation is 1, then temperature is the boiling point
temperature, and if not, consider other temperatures.

• At 110°C the summation of ∑Kixi = 1.127 and at T = 100°C ∑Kixi = 0.862; by interpolation at ∑Kixi =
1.0, the bubble point is 105.2°C.

ChE 315 - Computer Applications

Topic 2 - Week 3 8
in ChE
Example 1-1
• Using Excel

ChE 315 - Computer Applications

Topic 2 - Week 3 9
in ChE
Example 1-1
• Solution using DWSIM
• The easy way to estimate the bubble-point temperature with DWSIM is to build a simple
mixing process with feed stream S1 and exit stream S2. The property estimation method is
Peng–Robinson. Double click on S1 and fill in pressure and composition. Since the bubble-
point temperature is to be determined, the vapor to-phase ratio is set to 0. The system is
ready to run. The bubble-point temperature is 379.7 (106.564°C)

ChE 315 - Computer Applications

Topic 2 - Week 3 10
in ChE
Example 1-1

ChE 315 - Computer Applications

Topic 2 - Week 3 11
in ChE
Example 1-1

ChE 315 - Computer Applications

Topic 2 - Week 3 12
in ChE
Example 1-2
• Find the dew-point temperature for a mixture of 35 mol% n-hexane,
30% n-heptane, 25% n-octane, and 10% n-nonane at 1.5 atm total
pressure.

ChE 315 - Computer Applications

Topic 2 - Week 3 13
in ChE
Example 1-2
• Hand Calculation
• Assume the temperature, calculate the vapor pressure using Antoine equation, and then
calculate summation of xi; if the summation is 1, then temperature is the dew-point
temperature, and if not, consider other temperatures. To make use of the previous assumed
temperature, assume T = 110°C (Table 1.3). The assumed temperature should be increased,
and hence assume T = 130°C (Table 1.4). By interpolation, the dew point is 127.27°C.

ChE 315 - Computer Applications

Topic 2 - Week 3 14
in ChE
Example 1-2
• Solution using DWSIM
• The property estimation method is Peng–Robinson. Double click on S1 and fill in
pressure and composition. Since the dew-point temperature is to be determined,
the vapor-to-phase ratio is set to 1. The system is ready to run. The bubble-point
temperature is 399 K (~126°C).

ChE 315 - Computer Applications

Topic 2 - Week 3 15
in ChE
Example 1-3
• Find the vapor pressure of the pure components and the mixture of
35 mol% n-hexane, 30% n-heptane, 25% n-octane, and 10% n-
nonane at 130°C.

ChE 315 - Computer Applications

Topic 2 - Week 3 16
in ChE
Example 1-3
• Hand Calculation
• Using Antoine equation, for n-hexane,

ChE 315 - Computer Applications

Topic 2 - Week 3 17
in ChE
Example 1-3
• Solution using DWSIM
• To calculate the vapor pressure of pure n-hexane at 130°C, set the vapor fraction to 0. The
vapor pressure of pure n-hexane is 4.96045 atm.
To calculate the vapor pressure of gas mixture at 130°C, set the vapor fraction to 0. The
vapor pressure is 2.65448 atm

ChE 315 - Computer Applications

Topic 2 - Week 3 18
in ChE
Example 1-3

ChE 315 - Computer Applications

Topic 2 - Week 3 19
in ChE
Equations of State (EOS)
• An expression is required for gases that relate specific volume to
temperature and pressure.
• EOS
• relates molar quantity and volume of a gas to T and p.
• Used to predict p, V, n, and T for real gases, pure components, or mixtures
• Simplest example: Ideal gas law
• Formulated by collecting experimental data and calculating coefficients in
a proposed equation by statistical fitting
• Other EOS proposed in literature contains 2 or more coefficients
• Cubic EOS such as Redlich-Kwong, Soave-Redlich-Kwong, and Peng-
Robinson can have an accuracy of 1-2% over a large range of conditions of
many compounds.

ChE 315 - Computer Applications

Topic 2 - Week 3 20
in ChE
Equations of State (EOS)
• In solving for n or V, one must solve a cubic equation that might have more than one real root. Example:
Peng-Robinson EOS can easily be solved for p if V and T are given.
𝑅𝑇 𝑎
𝑝= −
𝑉 − 𝑏 𝑉 𝑉 + 𝑏 + 𝑏(𝑉 − 𝑏)
• The constants a, b are determined as follows:

1
𝑅2 𝑇𝑐2
𝑎 = 0.45724 1+𝑚 1− 𝑇𝑟2
𝑝𝑐
𝑅𝑇𝑐
𝑏 = 0.07780
𝑝𝑐

𝑚 = 0.37464 + 1.54226𝜔 − 0.26992𝜔2

𝑇
𝑇𝑟 =
𝑇𝑐

• 𝜔=acentric factor, where 𝑇𝑐 and 𝑝𝑐 are critical temperature and critical pressure, respectively. V is the specific volume

ChE 315 - Computer Applications

Topic 2 - Week 3 21
in ChE
Physical Properties
• Liquid Density
• For saturated-liquid molar volume, the Gunn and Ymada method is used[1].
𝑉
= 𝑉𝑟0 1 − 𝜔Γ
𝑉𝑠𝑐
• Where V is the liquid specific volume and 𝑉𝑠𝑐 is the scaling parameter that is defined in
terms of the volume at 𝑇𝑟 =0.6.
𝑉0.6
𝑉𝑠𝑐 =
0.3862−0.0866

• Where V0.6 is the saturated-liquid molar volume at a reduced temperature of 0.6. If V0.6 is
not available, then approximately Vsc can be estimated by:

𝑅𝑇𝑐
𝑉𝑠𝑐 = (0.2920 − 0.0967𝜔)
𝑃𝑐

ChE 315 - Computer Applications

Topic 2 - Week 3 22
in ChE
Physical Properties
• Liquid Density
• In most cases, Vsc is close to VC. However, if the saturated-liquid molar volume is available at
any temperature, VSC can be eliminated as shown in the next equation. In the next
equation, Vr(0) and Γ are functions of reduced temperature and 𝜔 is the acentric factor.
• For 0.2≤ 𝑇𝑟 ≤ 0.8
(0)
𝑉𝑟 = 0.33593 − 0.33593𝑇𝑟 + 1.51941𝑇𝑟2 − 2.02512𝑇𝑟3 + 1.11422𝑇𝑟4

• For 0.8< Tr <1.0

(0) 1/2 log 2
𝑉𝑟 = 1 + 1.3 1 − 𝑇𝑟 1 − 𝑇𝑟 − 0.50879 1 − 𝑇𝑟 − 0.91534 1 − 𝑇𝑟

• For 0.2≤ 𝑇𝑟 <1.0

Γ = 0.29607 − 0.09045Tr − 0.04842Tr2

Where: 𝑇𝑟 = 𝑇/𝑇𝑐

ChE 315 - Computer Applications

Topic 2 - Week 3 23
in ChE
Physical Properties
• In the absence of data, one may assume volume or mass additivity
to calculate the mixture densities from those of pure components.
𝑛

𝜌ҧ = ෍ 𝑥𝑖 𝜌𝑖
𝑖=1

𝑛
1 𝑥𝑖
=෍
𝜌 𝜌𝑖
𝑖=1

• This equation is more accurate than the equation above.

ChE 315 - Computer Applications

Topic 2 - Week 3 24
in ChE
Example 1-4
• Estimate the specific molar volume of n-hexane at 1 atm and 25°C.

ChE 315 - Computer Applications

Topic 2 - Week 3 25
in ChE
Example 1-4
• Set the stream conditions with pure n-hexane. Physical properties were determined
with Peng–Robinson. The specific molar volume is the inverse of the molar density (mass
density divided by molecular weight of n-hexane) is found from the generated text
report as shown below.

ChE 315 - Computer Applications

Topic 2 - Week 3 26
in ChE
Example 1-5
• Estimate the density of benzene as a function of temperature at 1
atm pressure and 25°C.

ChE 315 - Computer Applications

Topic 2 - Week 3 27
in ChE
Example 1-5
• Solution using polymath

ChE 315 - Computer Applications

Topic 2 - Week 3 28
in ChE
Example 1-5
You can export the code to Excel.

ChE 315 - Computer Applications

Topic 2 - Week 3 29
in ChE
Example 1-5

Create a table solving for the

temperature dependence of the
density, then plot.

ChE 315 - Computer Applications

Topic 2 - Week 3 30
in ChE
Example 1-5
• Solution using DWSIM
• Create a new process simulation. Choose benzene as the compound.
Choose PR as the property package. Input the properties for the inlet
stream.

ChE 315 - Computer Applications

Topic 2 - Week 3 31
in ChE
Example 1-5
• Using Sensitivity Study, input the independent variable:
(Temperature of inlet stream. From 0 to 70 deg C, with 7 data
points). For dependent variables, choose Density for the outlet
stream. Then proceed to Results Tab then Start Sensitivity Study. Go
to Chart tab to Draw graph.

ChE 315 - Computer Applications

Topic 2 - Week 3 32
in ChE
Example 1-5

ChE 315 - Computer Applications

Topic 2 - Week 3 33
in ChE
Example 1-6
• The density of 50 wt% H2SO4 in water at 25°C and 1 atm is 1.39
g/cm3. Estimate the density of the liquid mixture using the following
densities of pure H2SO4 and water, and compare it with the
experimentally obtained value.
Density of H2SO4 at 25°C = 1.834 g/cm3
Density of H2O at 25°C = 0.998 g/cm3

ChE 315 - Computer Applications

Topic 2 - Week 3 34
in ChE
Example 1-6
• Hand Calculations
• The density of liquid mixture (method 1)

• The density of liquid mixture (method 2)

ChE 315 - Computer Applications

Topic 2 - Week 3 35
in ChE
Example 1-6
• Using DWSIM
• In a new case in DWSIM, add the two components (H2SO4 and water) and
select PRSV for the property estimation. Select the material stream, specify
the temperature as 25°C, and set the pressure to 1 atm. The basis of
assumption is 1 kmol/h of mixture.

ChE 315 - Computer Applications

Topic 2 - Week 3 36
in ChE
Example 1-6

ChE 315 - Computer Applications

Topic 2 - Week 3 37
in ChE
Example 1-7
• A gas containing 1.00 mol% of ethane and the remaining being
nitrogen is contacted with water at 20.0°C and 20.0 atm. Estimate
the mole fraction of dissolved ethane.

ChE 315 - Computer Applications

Topic 2 - Week 3 38
in ChE
Example 1-7
• Hand Calculations
• Hydrocarbons are relatively insoluble in water, and so the solution of ethane
is likely to be very dilute. We should therefore assume that Henry’s law
applies , and look up Henry’s constant for ethane in water:

ChE 315 - Computer Applications

Topic 2 - Week 3 39
in ChE
Example 1-7
• Using DWSIM
• In a new case in DWSIM, add the components ethane, nitrogen, and water,
and select Peng–Robinson as the appropriate fluid package. Connect two
feed streams to a mixer and the outlet stream to a flash unit.

Stream 1

ChE 315 - Computer Applications

Topic 2 - Week 3 40
in ChE
Example 1-7

Stream 2

ChE 315 - Computer Applications

Topic 2 - Week 3 41
in ChE
Example 1-7

ChE 315 - Computer Applications

Topic 2 - Week 3 42
in ChE
Example 1-8
• An equimolar liquid mixture of benzene and toluene is in equilibrium
with its vapor at 30.0°C. What is the system pressure and the
composition of the vapor?

ChE 315 - Computer Applications

Topic 2 - Week 3 43
in ChE
Example 1-8
• Hand Calculations
• Assuming Raoult’s law applies, the vapor pressure of benzene, p B *

ChE 315 - Computer Applications

Topic 2 - Week 3 44
in ChE
Example 1-8
• Using DWSIM
• In a new case in DWSIM, add benzene and toluene components and select
the appropriate fluid package. Select Peng–Robinson EOS as a proper fluid
package for hydrocarbons.

ChE 315 - Computer Applications

Topic 2 - Week 3 45
in ChE
Example 1-8

ChE 315 - Computer Applications

Topic 2 - Week 3 46
in ChE