Faculty of Agriculture, Engineering & Natural Sciences
School of Engineering & the Built Environment
Department of Mechanical & Metallurgical Engineering
Metallurgical Thermodynamics
(I3611TT)
Tutorial 4: Second Law of Thermodynamics
Lecturer/Tutor: Mr. Thomas Moongo
Date: 8th May 2023
Tutorial Instructions:
1. All students should answer all the tutorial questions.
2. The students should be prepared to share their answers during the tutorial session.
3. Students are expected to discuss/explain solutions and give their suggestions.
4. No spoon feeding! Students will not be given the tutorial memo. Students should
develop their own memo.
5. Students may verify their answers to some questions with the lecturer/tutor provided
they have made an attempt on the question and they can show what they have done.
6. Feel free to write down solutions from other students during the tutorial session.
7. Team work is allowed during the tutorial session. You can help each other during the
tutorial session.
8. Students are allowed to refer to the notes, textbooks, internet and other sources
during the tutorial session.
9. The lecturer/tutor will only be facilitating and coordinating the tutorial session.
Students will lead/drive the entire tutorial session.
10. The lecturer/tutor will randomly choose questions to be discussed/answered during
the tutorial questions without the awareness of students and also the student(s) that
should answer them.
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SECTION A: THE SECOND LAW OF THERMODYNAMICS
1. 1 kg of steam at 7 bar, entropy 6.5 kJ/kg K, is heated reversibly at constant pressure
until the temperature is 250℃. Calculate the heat supplied, and show on a T-s diagram
the area which represents the heat flow.
2. A rigid cylinder of volume 0.025 m3 contains steam at 80 bar and 350℃. The cylinder
is cooled until the pressure is 50 bar. Calculate the state of the steam after cooling and
the amount of heat rejected by the steam. Sketch the process on a T-s diagram
indicating the area which represents the heat flow.
3. Air at 15℃ and 1.05 bar occupies 0.02 m3. The air is heated at constant volume until
the pressure is 4.2 bar, and then cooled at constant pressure back to the original
temperature. Calculate the net heat flow to or from the air and the net entropy
change. Sketch the process on a T-s diagram.
4. Dry saturated steam at 100 bar expands isothermally and reversibly to a pressure of
10 bar. Calculate the heat supplied and the work done per kilogram of steam during
the process.
5. 0.03 m3 of nitrogen (molar mass 28 kg/kmol) contained in a cylinder behind a piston
is initially at 1.05 bar and 15℃. The gas is compressed isothermally and reversibly until
the pressure is 4.2 bar. Calculate the change of entropy, the heat flow, and the work
done, and sketch the process on a p-v and T-s diagram. Assume nitrogen to act as a
perfect gas.
6. Steam at 100 bar, 375℃ expands isentropically in a cylinder behind a piston to a
pressure of 10 bar. Calculate the work done per kilogram of steam.
7. In a reciprocating compressor of a refrigeration plant the refrigerant is dry saturated
at 2.01 bar at the beginning of compression and is compressed reversibly according to
a polytropic law pv1.1 = constant to a pressure of 10 bar. Calculate the change of
specific entropy during the process using the table of properties of refrigerant given
below, interpolating where necessary.
Saturation values Superheated values at 10 bar
pg vg sg v s
3 3
(bar) (m /kg) (kJ/kg K) (m /kg) (kJ/kg K)
2.01 0.0978 1.7189 0.0222 1.7564
10 0.0202 1.7033 0.0233 1.7847
8. Calculate the change of entropy of 1 kg of air expanding polytropically in a cylinder
behind a piston from 6.3 bar and 550℃ to 1.05 bar. The index of expansion is 1.3.
9. 0.05 kg of carbon dioxide (molar mass 44 kg/kmol) is compressed from 1 bar, 15℃,
until the pressure is 8.3 bar, and the volume is then 0.004 m3. Calculate the change of
entropy. Take Cp for carbon dioxide as 0.88 kJ/kg K, and assume carbon dioxide to be
a perfect gas.
10. Steam at 7 bar, dryness fraction 0.96, is throttled down to 3.5 bar. Calculate the
change of entropy per unit mass of steam.
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SECTION B: THE HEAT ENGINE CYCLE
1. What is the highest possible theoretical efficiency of a heat engine operating with a
hot reservoir of furnace gases at 2000℃ when the cooling water available is at 10℃?
2. A hot reservoir at 800℃ and a cold reservoir at 15℃ are available. Calculate the
thermal efficiency and the work ratio of a Carnot cycle using air as the working fluid,
if the maximum and minimum pressures in the cycle are 210 bar and 1 bar.
3. In a gas turbine unit air is drawn at 1.02 bar and 15℃, and is compressed to 6.12 bar.
Calculate the thermal efficiency and the work ratio of the ideal constant pressure
cycle, when the maximum cycle temperature is limited to 800℃.
4. Calculate the ideal air standard cycle efficiency based on the Otto cycle for a petrol
engine with a cylinder bore of 50 mm, a stroke of 75 mm, and a clearance volume of
21.3 cm3.
5. A diesel engine has an inlet temperature and pressure of 15℃ and 1 bar respectively.
The compression ratio is 12/1 and the maximum cycle temperature is 1100℃.
Calculate the air standard thermal efficiency based on the diesel cycle.
6. An oil engine takes in air at 1.01 bar, 20℃ and the maximum cycle pressure is 69 bar.
The compressor ratio is 18/1. Calculate the air standard thermal efficiency based on
the dual-combustion cycle. Assume that the heat added at constant volume is equal
to the heat added at constant pressure.
7. Calculate the mean effective pressure for the cycle for question 6.
SECTION C: FREE ENERGY FUNCTION
1. Determine the Gibbs free energy for the below reaction
<NiO> + (H2) = <Ni> + (H2O)
Given that:
<NiO> = <Ni> + ½(O2) Δ𝐺2980 = 50,786 cal
(H2O) = (H2) + ½(O2) Δ𝐺2980 = 54,996 cal
2. Calculate the standard free energy change of the reaction
<MoO3> + 3(H2) = <Mo> + 3H2O)
At 727°C (1000K) and 1 atm pressure from the following data:
Δ𝐺01000,<𝑀𝑜𝑂 >0 = −120,000 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
3
Δ𝐺01000,<𝐻 𝑂>0 = −45,500 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
2
3. Given the following data, determine which metal has the greater probability of oxidation in
steam at 827°C (1100 K) and 1 atm pressure.
<NiO> + (H2) = <Ni> + (H2O) Δ𝐺0 = -550 – 10.18T cal
1/3 <Cr2O3> + (H2) = 2/3 <Cr> + (H2O) Δ𝐺0 = 30,250 – 7.33T cal
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4. Calculate the standard free energy change of the reaction
<Ni> + ½ (O2) = <NiO>
At 372°C (600K) from the following data:
Δ𝐻298,<𝑁𝑖𝑂>0=−57,500 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝑆298,<𝑁𝑖>0=7.12 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝑆298,(𝑂2)0=49.02 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝑆298,<𝑁𝑖𝑂>0=9.10 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝐶𝑝,<𝑁𝑖>=6.03−2.5 𝑥 10−3𝑇+10.44 𝑥 10−6𝑇2 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝐶𝑝,(𝑂2)=7.16+1.0 𝑥 10−3𝑇−0.4 𝑥 105𝑇−2 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
𝐶𝑝,<𝑁𝑖𝑂>=12.91 𝑐𝑎𝑙/𝑚𝑜𝑙𝑒
5. Calculate the entropy change of the system and the surroundings for the isothermal
freezing of one mole of supercooled liquid copper at 900°C (1,173 K) when the
surroundings are also at the same temperature. Assume that Cp for liquid copper also
holds good for supercooled liquid copper.
Given: Melting point of copper = 1,083°C (1,356 K)
Heat of fusion of copper at m.p. = 3,100 cal/mole
𝐶𝑝,<𝐶𝑢>= 5.41 + 1.50 x 10-3 T cal/deg/mole
6. Determine which of the following metals can be produced by the reduction of metal
sulphides with metal oxide at 1000°C (1273 K) and 1 atm pressure (101,325 N/m 2).
Given that:
Cu2S + 2Cu2O = 6Cu + SO2 Δ𝐺0 = 28,530 + 14.06 𝑇log𝑇−70.43 𝑇 𝑐𝑎𝑙
PbS + 2PbO = 3Pb + SO2 Δ𝐺0 = 98,440 +16.1 𝑇log𝑇−121.14 𝑇 𝑐𝑎𝑙
Ni3S2 + 4NiO = 7 Ni + 2SO2 Δ𝐺0 = 139,800 − 98.59 𝑇 𝑐𝑎𝑙
7. Chromium and carbon present in stainless steel form chromium carbide at 600°C (873 K).
Show by thermodynamic calculation which of the metals among Si, Ti and V should be alloyed
to stainless steel, so as to prevent the formation of chromium carbide. Given that:
3Cr + 2C = Cr3C2 Δ𝐺0 = −20,800 −4.0 𝑇 𝑐𝑎𝑙
Si + C = SiC Δ𝐺0 = −12,770 +1.66 𝑇 𝑐𝑎𝑙
V + C = VC Δ𝐺0= −20,000 +1.6 𝑇 𝑐𝑎𝑙
Ti + C = TiC Δ𝐺0 = −45,000 +2.8 𝑇 𝑐𝑎𝑙
8. Calculate the change in freezing point of water at 0°C per atm change of pressure,
given that the heat of fusion of ice is 335 J/g, the density of water is 0.9998 g/cm3, and
the density of ice is 0.9168 g/cm3.
9. The vapour pressure of liquid titanium at 2227°C is 1.503 mm Hg (200 N/m2). The heat
of vaporisation at the normal boiling point of titanium is 104 kcal/mole. Calculate its
normal boiling point.
10. The melting point of gallium is 30°C at 1 atm (101,226 N/m2). The densities of solid
and liquid gallium are 5.885 and 6.08 g/cm3, respectively. The heat of fusion of gallium
is 18.5 cal/g. Calculate the change in melting point of gallium for an increase of
pressure of 1 atm.
11. The normal boiling point of zinc is 907°C. Calculate its vapour pressure at 800°C, assuming that
zinc follows Trouton’s rule.
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