Faculty of Agriculture, Engineering & Natural Sciences
School of Engineering & the Built Environment
Department of Mechanical & Metallurgical Engineering
Metallurgical Thermodynamics
(I3611TT)
Tutorial 5: Thermodynamics of Solutions
Lecturer/Tutor: Mr. Thomas Moongo
Date: 15th 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: THERMODYNBAMICS OF SOLUTIONS
1. The partial molar volume is defined as
𝜕(𝑛𝑉)
𝑉̅𝐼 ≡ [ 𝜕𝑛 ]
𝑙 𝑃,𝑇,𝑛𝐽
What physical interpretation can be given to this equation?
2. The need arises in a laboratory for 2000 cm3 of an antifreeze solution consisting of 30
mol-% methanol in water. What volumes of pure methanol and of pure water at 25°C
must be mixed to form the 2000 cm3 of antifreeze, also at 25°C? Partial molar volumes
for methanol and water in a 30 mol-% methanol solution and their pure-species molar
volumes, both at 25°C, are:
Methanol (1): 𝑉̅1 = 38.632 cm3∙mol-1 𝑉1 = 40.727 cm3∙mol-1
Water (2): 𝑉̅2 = 17.765 cm3∙mol-1 𝑉2 = 18.068 cm3∙mol-1
3. The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented
by the equation:
H = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 )
where H is in J∙mol–1. Determine expressions for 𝐻
̅1 and 𝐻
̅2 as functions of x1,
numerical values for the pure-species enthalpies H1 and H2, and numerical values for
̅1∞ and 𝐻
the partial enthalpies at infinite dilution 𝐻 ̅2∞ .
4. For H2O at a temperature of 300°C and for pressures up to 10,000 kPa (100 bar)
calculate values of fi and ɸi from data in the steam tables and plot them vs. P.
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5. Determine the fugacity coefficients for nitrogen and methane in a N 2(1)/CH4(2)
mixture at 200 K and 30 bar if the mixture contains 40 mol-% N2. Experimental virial-
coefficient data are as follows:
𝐵11 = - 35.2 𝐵22 = - 105.0 𝐵12 = - 59.8 cm3∙mol-1
6. Estimate the value for the fugacity of 1-butene vapor at 200°C and 70 bar.
7. Estimate the entropy change of mixing when 2.8 L of oxygen and 19.6 L of hydrogen
at 1 atm and 25°C are mixed to prepare a gaseous mixture.
8. An insulated rigid tank is divided into two compartments by a partition. One
compartment contains 5 kg of oxygen gas at 40°C and 100 kPa, and the other
compartment contains 7 kg of nitrogen gas at 20°C and 150 kPa. Now the partition is
removed, and the two gases are allowed to mix. Using ideal gas relation, determine
the mixture pressure after equilibrium?
9. The volume of a mixture of two organic liquids 1 and 2 is given by V = 110 – 17x1 –
2.5𝑥12 . Where V is the volume in m3 /mol at 1 bar and 300K. Find the expressions for
𝑉̅1 and 𝑉̅2.
10. The molar volume of a binary liquid mixture at T and p is given by v= 120 x 1 + 70x2 +
(15x1 + 8x2) x1x2.
(a) Find the expressions for the partial molar volume of species 1 and 2.
(b) Show that the expression satisfies the Gibbs – Duhem equation.
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