Problem # 4: Vapor-Liquid Equilibria

MA Termodinamika Teknik Kimia - Departemen Teknik Kimia FTUI, 22 April 2019, Instruktur: Kamarza Mulia, Ph.D.

Part 1: Raoult’s law

Gambar berikut menunjukkan plot T terhadap komposisi dari campuran biner N2 dan O2 fugasitas pada tekanan 1 bar.

Dengan mengacu pada gambar diatas, jawablah pertanyaan-pertanyaan berikut ini:

a. Jelaskanlah apa yang terjadi jika campuran ekuimolar N2 dan O2 diturunkan suhunya dari 90 K menjadi 74 K pada tekanan 1
bar?
b. Kurva yang manakah yang terletak dibagian atas daerah dua fasa, kurva titik gelembung (bubble point curve) atau kurva titik
embun (dew point curve)?.
c. Apakah benar bila suhu, tekanan, dan komposisi total diketahui seperti pada perhitungan p-T flash, maka fraksi uap jenuh dan
cairan jenuh serta komposisi kedua fasa tersebut dapat diketahui. Jika ya, tunjukkanlah secara grafis.
d. Apa yang dimaksud dengan bubble point?
e. Apa yang dimaksud dengan dew point calculation?
f. Gambar ulang plot T-xy tersebuty diatas dengan menggunakan hukum Raoult.
g. Jelaskanlah mengapa kesetimbangan cair-uap N2 dan O2 dapat diperkirakan menggunakan hukum Raoult.
h. Bagaimana jika anda ingin menggunakan hukum Raoult untuk campuran biner yang salah satu komponennya berada pada
keadaan superkritik?

Part 2: The case of ELPJI

Consider the 12 kg LPG produced by PERTAMINA. This product is marketed as ELPIJI and contains equal mass of propane and n-
butane (50:50 weight-%). Assume that vapor-liquid equilibrium is always maintained in the tank, and, the propane and n-butane
mixture behaves ideally.
a. If we assume that the ELPIJI tank is full of liquid and temperature is constant at 25 C, what is the pressure indicated on the
pressure gage?
b. You ran out of ELPIJI gas yesterday and you could hear a splashing sound when you shake the tank. You remember reading a
newspaper article stating that a significant amount of n-pentane is present in the ELPIJI. Do you think what you observed is
related to the article? Explain. Temperature is constant at 25 C
c. Consider the same ELPIJI tank is used in a location 800 m above the sea level and where it could be cold at night. Kalia, who
is a chemical engineering student, sent you an sms that read: “Our ELPIJI tank is full and its pressure is 55,7 psia, therefore, I
could estimate the temperature of gas inside the tank to be 10C”. Do you agree with Kalia’s estimation? Carry out calculations
to support your argument
d. Calculate the temperature and composition of a liquid in equilibrium with a gas mixture consisting of propane and n-butane
in 50:50 vol-% at pressure of 7 bar.

Part 3: Flash calculation

The stream from a gas well is a mixture containing 50-mol-% methane, 10-mol-% ethane, 20-mol-% propane, and 20-mol-% n-
butane. This stream is fed into a partial condenser maintained at a pressure of 17.24 bar, where its temperature is brought to
300.15 K (27°C). Prepare an algorithm that could be used to solve this problem and then use that algorithm to determine:
a. the molar fraction of the gas that condenses
b. the compositions of the liquid and vapor phases leaving the condenser
Assume that the mixture is an ideal mixture.

Part 4: VLE of a non-ideal mixture at low pressure

a. Explain why Raoult’s law is not suitable for analysis of P-x-y diagram of the chloroform-1,4 dioxane mixture, based your
explanation on the molecular structure and molecular interaction between the molecules
b. An equimolar chloroform-1,4 dioxane is mixed and the liquid mixture heated to 50C. The excess Gibbs energy is adequately
represented by
𝐺𝐸
= −𝑥1 𝑥2
𝑅. 𝑇
What is the composition of the vapor above the heated solution? Assume only a little bit of vapor is formed.
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Part 5: Data fitting using gamma approach
Amir were assigned to design a distillation column to separate binary mixture of methanol and ethyl acetate. The only
information available was that the distillation column will operate at 1 bar. From the internet he found the following diagram:

Amir knew that the first thing to do is to be able to reproduce the T-x/y diagram above. He used the Raoult’s law but the result
was not very good.
a. How could you describe a vapor-liquid mixture using phase diagram? Explain using two and three dimensional phase diagram.
Differentiate a bubble point, a dew point and a flash point.
b. Explain the procedure to carry out BublP, BublT, DewP, and DewT calculations using Raoult’s law.
c. Repeat what Amir has done
d. Give a definition for activity coefficient of component i (1) using your own words
e. Explain the procedure to carry out BublP using one of the activity coefficient models.
f. Obtain a much better fit (use the Margules equation)
g. Comments on the shape of the phase envelope shown above and based your explanation on the molecular structure and
molecular interaction between the molecules

Part 6: Fugacity and fugacity coefficient

a. Derive the given equation for ln():
 z + 2.414 B 
ln  = z − 1 − ln (z − B ) −
A a (T ) P bP
ln   , where A = and B = , by combining the following
2 2B  z − 0. 414 B  2
R T 2 R T
v  P 1
thermodynamic relationship ln  = z − 1 − ln z −   −  d v and the Peng-Robinson equation of state.
  R T V 
b. Use the working equation above to regenerate the fugacity and fugacity coefficient data points of H2O at 300C by writing a
suitable computer program (FORTRAN or Excell) and redraw the given plot. The requirement for liquid-vapor equilibrium of
a pure fluid is equality of fugacity (f) or fugacity coefficient (): fL=fV or L=V

c. Explain what is meant by fugacity and fugacity coefficient using the following plot of f and  as a function of pressure for H2O
at 300C.
d. At what pressure these requirements apply to water at a temperature of 300C? Is this pressure equal to the vapor pressure
given in the steam table?.

Part 7. VLE models available

List the advantages and disadvantages of using the activity coefficient approach. First of all, read the paper on VLE “Don’t
Gamble with Physical Properties for Simulations” by Eric C. Carlson, Chemical Engineering Progress, October 1996, p. 35-46. Is
your explanation in Part 5d and 6c consistent with what is in the paper?

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