MCL701 Advanced Thermodynamics

Problem Sheet 2

1. The pressure within a 23.3 m3 tank should not exceed 105 bar. Check the pressure within the
tank if filled with 1000 kg of water vapor maintained at 360o C using the
a) ideal gas equation of state.
b) van der Waals equation.
c) Redlich–Kwong equation.
d) compressibility chart.
e) steam tables.

2. A certain refrigerant vapor enters a steady-flow, constant-pressure condenser at 150 kPa, 70o
C, at a rate of 1.5 kg/s, and it exits as saturated liquid. Using Clapeyron equation, calculate
the rate of heat transfer from the condenser. It may be assumed that the vapor is an ideal gas
and also that at saturation, vf << vg. The following is known: ln𝑃𝑔 = 8.15 − 1000⁄𝑇; 𝐶𝑝𝑜 =
0.7 kJ/kg K, with pressure in kPa and temperature in K. The molecular mass of the refrigerant
is 100.

3. Develop an expression for the variation in temperature with pressure in a constant-entropy

4. Using the property relations for simple compressible systems, derive the Clapeyron equation
which quantifies the slope of the p-T curve during liquid-vapour phase change of a substance
at any temperature Tsat in terms of the enthalpy of vapourisation ℎ𝑓𝑔 , entropy of vapourisation
𝑠𝑓𝑔 and change is specific volume during vapourisation 𝑣𝑓𝑔 .

5. The following expression for the enthalpy departure is convenient for use with equations of
state that are explicit in pressure:
𝑣̅
̅̅̅
ℎ 𝑥 (𝑇) − ℎ̅(𝑇, 𝑣̅ ) 1 𝜕𝑝
= 𝑇𝑅 {1 − 𝑍 − ∫[𝑇( )𝑣 − 𝑝] 𝑑𝑣̅ }
𝑅̅𝑇𝑐 𝑅̅ 𝑇 𝜕𝑇
∞
a) Derive this expression.
b) Using the given expression, evaluate the enthalpy departure for a gas obeying the Redlich–
Kwong equation of state.
c) Using the result of part (b), determine the change in specific enthalpy, in kJ/kmol, for CO2
undergoing an isothermal process at 300 K from 50 to 20 bar.

6. A supplier delivers a 40 litre methane cylinder to your laboratory and assures that the cylinder
has 10 kg of methane. Your professor asks you to verify this claim. A Ph.D. Student in the
laboratory connects a regulator to the cylinder, whose pressure gauge reads 200 bar as the
pressure of gas in the cylinder. The ambient temperature is measured to be 27oC. He suggests
that we can consider methane to be an ideal gas and do the calculations.
a) Verify whether or not methane at this state can be treated as ideal gas.
b) As a student of MCL701, what would be your approach to complete the above task?
c) Taking specific enthalpy and specific entropy of methane at 1 bar and 273K to be zero,
compute the specific enthalpy and specific entropy of methane in the cylinder. You may use
the following data for methane: 𝑝𝑐 =4.6 MPa, 𝑇𝑐 =190.4 K, 𝐶𝑝,𝑜 = 2.254 kJ/kgK.

7. A Compressed Natural Gas (CNG) cylinder in a car has a volume of 0.1 m 3. When gas in this
cylinder is at 300 K and a pressure of 200 bar, compute the mass of CNG in the cylinder,
assuming CNG to be methane. Properties of methane can be taken as: Molecular mass
M=16.043, Critical temperature Tc=190.4 K, Critical pressure pc=4.6 MPa, Ideal gas specific
 heat Cpo=2.254 kJ/kgK. In case the gas is throttled adiabatically to ambient pressure, at which
it can be assumed to behave as ideal gas, compute the temperature of the gas after throttling.
For all calculations, use the generalized charts for compressibility and enthalpy correction.

8. One early attempt to improve on the van der Waals equation of state was an expression of the
form
𝑅𝑇 𝑎
𝑃= − 2
𝑣−𝑏 𝑣 𝑇
Solve for the constants a, b, and vc using the same procedure as for the van der Waals equation.

9. A 200-L rigid tank contains propane at 9 MPa, 280o C. The propane is allowed to cool to 50o
C as heat is transferred with the surroundings. Determine the quality at the final state and the
mass of liquid in the tank, using the generalized compressibility chart. Properties of propane
are M=44.094; Tc=369.8 K; pc=4.25 MPa; vc=0.00454 m3/kg.

10. A control mass of 10 kg butane gas initially at 80o C, 500 kPa is compressed in a reversible
isothermal process to one-fifth of its initial volume. What is the heat transfer in the process?
Use enthalpy departure chart. What is the percent deviation in the answer if ideal gas
assumption is used?

11. Consider an oxygen cylinder used for medical purposes, of internal volume 46.7 litres (1 litre
= 1000 cm3). When filled, the cylinder has a gauge pressure of 150 bar and a temperature of
30oC. Considering the gas to be pure oxygen and using its critical constants pc = 50.4 bar and
Tc = 154.6 K, compute the mass of oxygen in the cylinder, using the generalized
compressibility chart given in Figure 1, taking atmospheric pressure as 1 bar. If you use ideal
gas equation of state, what would be the calculated mass of oxygen?
 Figure 1 Generalized Compressibility Chart

12. 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 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 litres.
Answer the following questions with reference to this scenario. Property data are given in
table below
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?
13. 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 ¯v=0.5432 m 3 /kmol at this state for the
calculations.

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.