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KIL 2008 / KKEK2158 2nd Semester, 2017/18 Session

Tutorial 1 – Review of Thermodynamics

Submit questions no. 9 and 10 according to your groups.

1) Explain in detail, using thermodynamic principles, why the mixing of pure chemicals to form a
homogeneous mixture is a so called spontaneous process, while the separation of that mixture into
its pure (or nearly pure) species is not.

2) Compare the advantages and disadvantages of making separations using an ESA versus using an MSA.

3) Estimate the K-values of a vapor-liquid mixture of water and methane at 2 atm total pressure for
temperatures of 20°C and 80°C.

T (°C) 𝑷𝒔𝒂𝒕
𝑯𝟐 𝑶 (atm) H for CH4 (atm)
20 0.02307 3.76 × 104
80 0.4673 6.82 × 104

4) A water (1) – CO2 (2) solution in a vapor-liquid separation vessel at 20°C has a CO2 mole fraction of
0.01 in the liquid. Calculate:

a) The composition of the vapor at equilibrium with the liquid


b) The vessel pressure
c) The K-values of water and CO2

Henry’s law constant for CO2 in water at 20°C is 140 000 kPa and the vapor pressure of water is
given by the Antoine equation:

3800
ln 𝑃1𝑠𝑎𝑡 (𝑘𝑃𝑎) = 16.26 −
𝑇(℃) + 226.4

5) The partial pressure of CO2 in air is 1.333 × 104 Pa and the total pressure is 1.133 × 104 Pa. The gas
phase is in equilibrium with a water solution at 303 K. What is the value of 𝑥𝐴 for CO2 in equilibrium
in the solution? Henry’s law constant for CO2 in water at 303 K is 0.186× 10−4 atm/mol fraction.

6) At 303 K the concentration of CO2 in water is 0.90 × 10−4 kg CO2/kg water. What partial pressure of
CO2 must be kept in the gas to prevent the CO2 from vaporizing from the aqueous solution? Henry’s
law constant for CO2 in water at 303 K is 0.186× 10−4 atm/mol fraction.

7) For the system SO2-air-water, the total pressure is set at 1 atm abs and the partial pressure of SO2 in
the vapor is set at 0.20 atm.
a) Calculate the number of degrees of freedom
b) What variables are unspecified and hence can be arbitrarily set?

8) For the system NH3-water and only a vapor phase present,


KIL 2008 / KKEK2158 2nd Semester, 2017/18 Session

a) Calculate the number of degrees of freedom


b) What variables can be fixed?

9) Using the data for the system benzene (A) – toluene (B) below

a) Calculate yA and xA using Raoult’s law at 378.2 K


b) If a mixture has a composition of xA = 0.40 and is at 358.2 K and 101.32 kPa pressure, will it boil?
If yes, justify. If not, at what temperature will it boil and what will be the composition of the vapor
first coming off?

Mole fraction of
Vapor pressure (kPa)
T (°C) benzene at 101.325 kPa
Benzene Toluene xA yA
80.1 101.32 1.000 1.000
85 116.9 46.0 0.780 0.900
90 135.5 54.0 0.581 0.777
95 155.7 63.3 0.411 0.632
100 179.2 74.3 0.258 0.456
105 204.2 86.0 0.130 0.261
110.6 240.0 101.32 0 0

10) A stream containing 20 mol% ethanol (1) and 80 mol% iso-octane (2) is flashed at 50°C and 35 kPa and
separated into a vapor product and a liquid product. Calculate:

a) The fraction of the feed vaporized


b) Composition of the liquid and vapor products

The component vapor pressures at 50°C are 𝑃1𝑠𝑎𝑡 = 29.5 kPa and 𝑃2𝑠𝑎𝑡 = 19.5 kPa. The mixture is non-
ideal and can be represented using the Wilson model of activity coefficient. The Wilson coefficients
for this binary system are A12 = 0.0995 and A21 = 0.247.

𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
Use 𝐾𝑖 = 𝑃

Wilson model:
ln 𝛾𝑖 = − ln(𝑥𝑖 + 𝐴𝑖𝑗 𝑥𝑗 ) + 𝛽𝑖𝑗 𝑥𝑗

𝐴𝑖𝑗 𝐴𝑗𝑖
Where 𝛽𝑖𝑗 = 𝑥 +𝐴 −𝑥
𝑖 𝑖𝑗 𝑥𝑗 𝑗 +𝐴𝑗𝑖 𝑥𝑖