Exercises of the thermodynamic second law
1 A block of copper of mass 2.00 kg (Cp,m = 24.44 J K−1 mol−1) and temperature 0°C is introduced into an
insulated container in which there is 1.00 mol H2O(g) at 100°C and 1.00 atm. (a) Assuming all the steam is
condensed to water, what will be the final temperature of the system, the heat transferred from water to
copper, and the entropy change of the water, copper, and the total system? (b) In fact, some water vapour is
present at equilibrium. From the vapour pressure of water at the temperature calculated in (a), and assuming
that the heat capacities of both gaseous and liquid water are constant and given by their values at that
temperature, obtain an improved value of the final temperature, the heat transferred, and the various
entropies. (Hint. You will need to make plausible approximations.)
2- A Carnot cycle uses 1.00 mol of a monatomic perfect gas as the working substance from an initial state of
10.0 atm and 600 K. It expands isothermally to a pressure of 1.00 atm (Step 1), and then adiabatically to a
temperature of 300 K (Step 2). This expansion is followed by an isothermal compression (Step 3), and then
an adiabatic compression (Step 4) back to the initial state. Determine the values of q, w, ΔU, ΔH, ΔS, ΔStot,
and ΔG for each stage of the cycle and for the cycle as a whole. Express your answer as a table of values.
3- A block of copper of mass 500 g and initially at 293 K is in thermal contact with an electric heater of
resistance 1.00 kΩ and negligible mass. A current of 1.00 A is passed for 15.0 s. Calculate the change in
entropy of the copper, taking Cp,m = 24.4 J K−1 mol−1. The experiment is then repeated with the copper
immersed in a stream of water that maintains its temperature at 293 K. Calculate the change in entropy of
the copper and the water in this case.
4- Calculate the change in the entropies of the system and the surroundings, and the total change in entropy,
when the volume of a sample of argon gas of mass 21 g at 298 K and 1.50 bar increases from 1.20 dm3 to 4.60
dm3 in (a) an isothermal reversible expansion, (b) an isothermal irreversible expansion against pex = 0, and (c)
an adiabatic reversible expansion.
5-A normal breath has a volume of about 1 L. The pressure exerted by the lungs to draw air in is about 758
torr. If the surrounding air is at exactly 1 atm (5 760 torr), calculate the change in entropy exerted on a breath
of air due to its being inhaled into the lungs. Assume a temperature of 22.0°C. (Hint: You will have to
determine the number of moles of gas involved.)
6-An automobile tire contains 15.6 L of air at 46.0 psi (absolute) and 22.0°C. After driving around a while, the
tire’s temperature warms to 85.0°C. What is the entropy change of the air? Assume a constant-volume heat
capacity of 20.79 J/mol-K for air.
7-The protein lysozyme unfolds at a transition temperature of 75.5°C and the standard enthalpy of transition
is 509 kJ mol−1. Calculate the entropy of unfolding of lysozyme at 25.0°C, given that the difference in the
constant pressure heat capacities upon unfolding is 6.28 kJ K−1 mol−1 and can be assumed to be independent
of temperature. Hint. Imagine that the transition at 25.0°C occurs in three steps: (i) heating of the folded
protein from 25.0°C to the transition temperature, (ii) unfolding at the transition temperature, and (iii) cooling
of the unfolded protein to 25.0°C. Because the entropy is a state function, the entropy change at 25.0°C is
equal to the sum of the entropy changes of the steps.
