PEF1006 Thermodynamics

Fall 2023

Exercise 9
Problem 1

A liquid mixture of acetonitril(1) and benzene(2) has mole fractions x1=0.398 and x2 =
0.602 at 45 ˚C. The saturation pressures at 45 ˚C are 27.778(1) and 29.819(2) kPa. The
activity coefficients are 1.43 and 1.18. Ideal gas is assumed.

a) Calculate y1, y2 and P assuming Raoults law (ideal liquid) (bubble point
calculation).
b) Calculate y1, y2 and P in the mixture.
c) It is assumed that the activity coefficients are valid for other compositions. Show
that in that case, x1, x2 and P can be calculated explicitly (without iteration).
d) Calculate PDEW, x1, x2.
e) Show a calculation procedure for calculation of the dew point at 45 ˚C if the activity
coefficients are known as a function of composition.

Problem 2

A PT flash with known feed of 3 components shall be calculated. Saturation pressures

are known, ideal gas law is assumed and activity coefficients can be calculated by lnγi =
Zi(1-xi) where all the Zi’s are known.

a) Write 3 independent material balance equations, 3 equilibrium equations and 2

summation equations. (It is recommended to avoid using ki (=yi/xi)).

b) What are the unknown variables?

c) Show that the number of equations equals the number of variables.

Problem 3

An equation of state can calculate the fugacity coefficient as a function of composition,

pressure and temperature. General expression lnφi = f(P, T, yi, PCi, TCi, ωi, kij)

a) Can this expression (in principle) be used to calculate the gas phase?
b) Can this expression (in principle) be used to calculate the liquid phase?
c) How many pure component parameters are there for each component?
d) How many binary parameters (for each binary pair) are there?
PEF1006 Thermodynamics
Fall 2023

Problem 4

We have 5 systems with both a liquid and a vapour phase:

1) An ethanol/water system at 1 bar (a)

2) A sulphuric acid /water system at 1 bar (a)
3) A propane /butane system at 1 bar (a)
4) A propane /butane system at 15 bar (a)
5) A nitrogen /heptane system at 10 bar (a)

We have 5 model (set)s available:

- Raoults law for liquid phase, ideal gas.
- Peng Robinson equation of state for both phases.
- Margules activity model with known parameters for liquid, ideal gas.
- Margules activity model with known parameters for liquid, Peng Robinson for gas.
- Eletrolyte NRTL (Non Random Two Liquid) activity model for liquid, ideal gas.

Select a suitable model (set) for all the 5 systems (use all the available sets).