Problem Sheet-4

1. 1 kmol of CO2 is kept in a vessel at a constant pressure and temperature of 5 bar and 2800 K.
The carbon dioxide dissociates according to the reversible reaction
CO2 ⇔ CO + ½ O2
and reaches equilibrium corresponding to the temperature and pressure of the vessel. Using the
Gibbs function of formation gfo(T) (kJ/kmol) data given in the table below, compute the fraction
of CO2 that would have dissociated.
Mol. Wt 2500 K 2700 K 2900 K
CO2 44.011 -396152 -395957 -395708
CO 28.01 -327245 -343519 -359661
O2 31.999 0 0 0
Assume all the species to behave as ideal gases. ℝ= 8.314 kJ/kmol K. Suppose the reaction
given above is written with reactants and products interchanged, i.e.,
CO + ½ O2 ⇔ CO2
what would be the relation of the new equilibrium constant with the one you calculated for the
original reaction? Explain.

2. Liquid water containing 5% ammonia by volume is kept in a closed vessel at a constant

pressure of 1 bar and 50oC, and allowed to attain phase equilibrium. If the liquid phase can be
assumed to be an ideal solution and vapour phase behaves as ideal gas, compute the mole
fractions of water and ammonia in the two phases.

3. Natural gas, containing 90% methane and 10% ethane by volume is filled in an evacuated rigid
adiabatic cylinder to 200 bar from a line at 300 bar, 20oC. Find the final temperature of the gas
in the cylinder. Use Kay's rule to treat natural gas as a pseudo-pure substance, with generalized
charts. Use the data in the table below and relevant charts.
Molecular Weight Specific Heat Critical Critical
(kJ/kmol K) Temperature (K) Pressure (bar)
Methane 16.043 36.156 191.1 46.4
Ethane 30.07 53.11 305.5 44.8

4. LPG is a mixture of 70% butane and 30% propane by volume. The mixture is compressed from
atmospheric pressure and temperature of 1 bar and 25oC to a pressure of 20 bar and 600 K in
order to bottle it in a cylinder. A compressor with a suction flow rate of 20 liters/sec is used for
the process, and the process can be assumed steady state, steady flow. If the motor efficiency is
0.75, find the power input needed to run the compressor, and the exergetic (II law) efficiency of
the compressor. Consider LPG as an ideal mixture of real gases (i.e., the constituent gases obey
real gas equations of state, and mixing does not alter constituent properties). Use generalized
compressibility, enthalpy and entropy correction charts for the constituent gases, taking the
critical temperatures and pressures of the gases as given below: Use the relevant charts.
Molecular Weight Specific Heat Critical Critical
(kJ/kmol K) Temperature (K) Pressure (bar)
Butane 58.124 99.74 425.2 38.0
Propane 44.094 74.03 369.8 42.5
What would be the answers if each constituent is treated as an ideal gas? Take Tamb=25oC.
5. Water gas shift reaction that happens in gasification systems for coal and biomass can be
written as
CO+ H 2 O ⇔CO2 + H 2
The reaction begins with an equimolar mixture of CO and H 2O and proceeds to equilibrium
at a pressure of 2 bar and 1500 K.
a. Determine the equilibrium composition.
b. If it is desired to increase the production of hydrogen in the equilibrium mixture, should
the temperature be increased or decreased?
c. If your colleague suggests that higher pressures would favour more hydrogen, what
would your response be?
Use the following table from a book: note that the reaction in the table is the reverse of the
above.
Equilibrium constant K o for the reaction CO2 + H 2 ⇔ CO+ H 2 O
Temperature 1000 1200 1400 1600 1800
log10 K o -0.159 0.135 0.333 0.474 0.577

6. A carbonated drink is fully charged with CO2 gas at 17o C and 600 kPa such that the
entire bulk of the drink is in thermodynamic equilibrium with the CO2 -water vapour
mixture. Now consider a 2 litre bottle of the drink, with no space for gas above the surface of
the liquid. If the CO2 gas in that bottle is entirely released and stored in a container at
25o C and 100 kPa, find the volume of container needed. Take saturation pressures of water
and CO at2 17o C as 1.938 kPa and 5.338 MPa respectively.
a
7. A gas obeys the van der Waals equation of state given as ( p+ )( v̄−b)=ℝ T . Derive an
v¯2
expression for ln f along an isotherm, where f is the fugacity of the gas.

8. 14.2 kg of LPG filled in a domestic LPG cylinder of volume 33 litres has a molar composition
of 80% n-butane and 20% propane. Compute the molar composition of LPG that would be
drawn by the gas stove at a typical winter room temperature of 290 K and a typical summer
room temperature of 310 K. At both these ambient temperatures, compute the pressure of gas in
the cylinder, and the volume occupied by the gas phase and liquid phase in the cylinder. What
are the masses of liquid and gas at these two states? State the assumptions made in the process
and justify the assumptions. Use the following data for saturated propane and butane:
Propane (M=44) N-Butane (M=58)
Temperature Psat (MPa) v¯f m3/kg v¯g m3/kg Psat (MPa) v¯f m3/kg v¯g m3/kg
(K)
290 0.7694 0.08734 2.6462 0.1877 0.0999 12.0453
310 1.2720 0.09328 1.5753 0.3472 0.1041 6.7114

9. Consider the water gas shift reaction given by CO2 + H 2 ⇔ CO+ H 2 O . The initial mixture has
2 moles of CO2 , 1 mole of H 2 , 1 mole of CO and 2 moles of H 2 O . The mixture is
allowed to attain chemical equilibrium at 1500 K. Find the equilibrium composition. Use the
following data for temperature variation of equilibrium constant for the above reaction.
Temperature (K) log10Ko
1400 0.333
1600 0.474
 10. Consider a natural gas with a molar composition of 92% methane, 5% ethane and 3% propane.
An intercooled compressor in the pumping station for CNG compresses the gas from 1 bar and
300K to a pressure of 300 bar, 320K. The heat removed by the intercooler is 875 kW when the
flow rate of natural gas is 0.4 kg/s. Compute the power input required to run the compressor, if
the heat losses other than that removed by the intercooler can be neglected. Also compute the
rate of exergy destruction in the intercooled compressor. Use the following data for the gases,
and use Kay's rule for the natural gas at the high pressure. Use the chart for enthalpy
correction.
Molecular Weight Critical Temperature (K) Critical Pressure (bar)
Methane 16.043 191.1 46.4
Ethane 30.07 305.5 44.8
Propane 44 370.0 42.6

11. In a CNG filling station, a cylinder in an automobile is being filled with CNG from a line. The
line supplies CNG, which can be considered to be a mixture of methane (CH4) and ethane (C2H6), in a
molar ratio of 4:1, at a pressure of 300 bar and temperature of 300 K. The cylinder in the automobile
initially has gas with the same composition at a pressure of 2 bar and 300 K. The filling happens
quickly, and the process can be assumed adiabatic, and the final pressure is 200 bar. The cylinder can
be assumed to be rigid. The volume of the cylinder is 40 liters. Answer the following questions with
reference to this scenario. Property data are given in table below.

Molecular Weight Specific Heat Critical Critical Pressure

(kJ/kmol K) Temperature (K) (bar)
Methane 16.043 36.156 191.1 46.4
Ethane 30.07 53.11 305.5 48.8
a) Write the equations for conservation of mass, first law and second law for this system
appropriately simplified.
b) What equation of state / model would you use to compute properties in the initial state,
inlet state and final state of gas mixture in the cylinder?
c) Which equation of state / model would you use to evaluate enthalpy / internal energy of
the mixture? Compute the final temperature and mass of gas in the cylinder. Do you
expect any phase change to happen at these states?

12. Compute the fugacity of pure nitrogen at 45 bar, 300 K, assuming nitrogen to obey the van
der Waal’s equation of state given below. Take v̄ =0.5432 m3/kmol at this state for the calculations
a
( p+ )( v̄−b)=R uT
v̄ 2
Hint: integrate from ideal gas state along an isotherm. Take reference state as 1 bar, 300 K at which
you can compute specific volume using ideal gas equation of state. Use Ru=8.314 kJ/kmol-K and
molecular mass of nitrogen = 28.

13. A mixture of 4 kmol of CO and 3 kmol of water vapour reacts to form an equilibrium mixture of
CO2, CO, H2O, and H2 at 1800 K, 1 atm. Given data of log10 K: at 1200 K: 0.135; at 2000 K: 0.656.
a) Compute the equilibrium composition of the mixture.
b) Will lowering the temperature increase or decrease the amount of H2 present? Explain.
c) Will decreasing the pressure while keeping the temperature constant increase or decrease the
amount of H2 present? Explain.