Department of Chemical Engineering

CHPR4404 Advanced Thermodynamics

Semester 1, 2020
Assignment 4

DUE DATE:
This assignment is to be submitted on LMS by 22nd May.

INSTRUCTIONS:
Given a 0.75/0.25 by mole mixture of methane and heptane at 400 K and 5 MPa, determine
the following:

 Phase fractions and compositions

 Component fugacities
 Phase densities
You must use the SRK equation of state , and initially, assume a methane-heptane binary
interaction parameter (BIP) of zero. The formula you will need to implement the SRK EOS are
provided on the following page.
Performing this flash calculation using Multiflash RKS API Version model gives the following
phase densities:
Liquid Vapour
484.545 kg/m3 35.650 kg/m3
Tune the SRK EOS by adjusting the methane-heptane BIP such that the deviation of your
calculated results from these densities is minimized. Having done this, compare the phase
fractions, composition, densities and optimized BIP you obtain to those calculated by
Multiflash using the ‘RKS API Version’ model.
You must perform all calculations in the provided Excel workbook. This contains two
spreadsheets: the first, for calculations where the BIP is zero, and the second, being a copy
of the first wherein you have tuned the EOS.
The SRK EOS is given by:
𝑅𝑇 𝑎𝛼
𝑃= −
𝑉𝑚 − 𝑏 𝑉𝑚 (𝑉𝑚 + 𝑏)

Or, in cubic form:

𝑍 3 − 𝑍 2 + (𝐴 − 𝐵 − 𝐵 2 )𝑍 − 𝐴𝐵 = 0
Where:

𝑛 𝑛 𝑛

𝐴 = ∑ ∑ 𝑥 𝑖 𝑥𝑗 (1 − 𝑘𝑖𝑗 )√𝐴𝑖 𝐴𝑗 𝐵 = ∑ 𝑥 𝑖 𝐵𝑖
𝑖=1 𝑗=1 𝑖=1

𝑛 𝑛

𝑎𝛼 = ∑ ∑ 𝑥 𝑖 𝑥𝑗 (1 − 𝑘𝑖𝑗 )√(𝑎𝑖 𝛼𝑖 )(𝑎𝑗 𝛼𝑗)

𝑖=1 𝑖=1

For an individual component:

𝑃𝑟,𝑖 𝑃𝑟,𝑖
𝐴𝑖 = 0.42747𝛼𝑖 2 𝐵𝑖 = 0.08664
𝑇𝑟,𝑖 𝑇𝑟,𝑖

2
(𝑅𝑇𝑖𝐶 ) 𝑅𝑇𝑖𝐶
𝑎𝑖 = 0.42747 𝑏 𝑖 = 0.08664
𝑃𝑖𝐶 𝑃𝑖𝐶

2
𝑚𝑖 = 0.48508 + 1.55171𝜔𝑖 − 0.15613𝜔2𝑖 𝛼𝑖 = [1 + 𝑚𝑖 (1− √𝑇𝑟,𝑖 )]

Having solved the SRK EOS, the partial fugacity coefficient can be found using the following:
𝑁
𝐵𝑖 𝐴 𝐵𝑖 2 𝐵
ln𝜙 𝑖 = (𝑍 − 1) − ln(𝑍 − 𝐵) + [ − ∑ 𝑥𝑗(1 − 𝑘𝑖𝑗 )√ (𝑎𝑖 𝛼𝑖 )(𝑎𝑗 𝛼𝑗 )] ln (1 + )
𝐵 𝐵 𝐵 𝑎𝛼 𝑍
𝑗=1

Density can be found given the definition of compressibility factor:

𝑃
𝑍=
𝜌𝑅𝑇

Note that in the above formula, x and y are interchangeable depending on the phase for which
a calculation is being performed.
Note that comparison you make here is with model calculations rather than real experimental
data. Cubic EOS usually don’t perform well for densities when compared with actual
experimental values.