SECOND LAW OF THERMODYNAMICS

20. A mole of monatomic ideal gas goes through a

reversible Carnot cycle, as indicated in the following
figure, with V1= 20 l, V2= 40 l, T1= 300 K and T3=200 K.
Calculate P, V, T, U, H, and S in each stage of
the cycle.
Sol.:
(1-2): -0.62 bar; 20 l; 0 K; 0; 0 ; R ln2;
(2-3): - 0.397 bar; 33.48 l; -100 K; -150 R; -250 R; 0;
(3-4): 0.226 bar; -36.7 4 l; 0; 0; -R ln2;
(4-1): 0.794 bar; -16.74 l; -100 K, 150 R, 250 R; 0.

21. A heat engine operates between a tank containing 1103 m3 of water and a river at a
constant temperature of 10ºC. If the initial temperature of the tank is 100ºC, what is
the maximum amount of work that the heat engine can do?
So l.: 4.93⋅1010 J.

22. A reversible heat engine operates between three reservoirs of temperatures T1 = 500 K,
T2 = 400 K and T3 = 300 K. If in one cycle it performs a work of 3616 kJ and from the
first reservoir it absorbs the amount of heat Q1 = 29 26 k J, calculate:
a) the amounts of heat exchanged with the other two reservoirs.
b) The efficiency of the cycle.
Sol .: a) Q2 = 9782.4 kJ; Q3 = -9092.4 kJ; b) 28%

23. A system has a constant heat capacity given by: Cv = AT2, where A = 0.0418 J/K3.
The system is initially at 200ºC and can be cooled down to 0 ºC through one or another
of the following processes:
a) by a direct contact with a reservoir at that temperature,
b) operating a reversible heat engine between the system and the reservoir.
Determine, in each case, the work obtained and the entropy changes of the system, the
reservoir and the Universe.
Sol.: a) 0;-3118.28 J/K; 4362.6 J/K; 1244.32 J/K; b) 339696.1 J; -3118.28 J/K;
3118.28 J/K; 0

24. Calculate the difference between the molar entropy of the supercooled liquid mercury
and that of the solid mercury, both at –50 ºC and a pressure of 1.013 bar. The melting
point of mercury is –39ºC and its enthalpy of fusion at this temperature is 2340.8 J/mol.
The molar heat capacity at constant pressure of liquid mercury is
cP(l)=29.68-6.6910-3 T J mol-1K-1 and that of solid mercury cP=26.75 J mol-1 K-1.
Sol.: -9.93 J /mol K

25. A hydrostatic system has isotherms given by pV2= Const. and an internal energy
given by U=pV/2. This system describes an A→B→C→A cycle in three stages, being
A→B an adiabatic reversible process, B→C an irreversible adiabatic process and C→A
an isothermal reversible process. Calculate the heat exchanged by the system and the
change of its entropy in each of the three processes, as a function of the coordinates of
each point.
Sol.: (A→B): 0; 0; (B→C): 0; (pAVA-pcVc)/2TA; (C→A): -(pAVA-pcVc)/2;
(pcVc-pAVA)/2TA
26. One mole of a monatomic ideal gas at a temperature of 399 K and a pressure of 4
bar, is enclosed in a cylinder with adiabatic walls provided with a non -heat-
conducting piston. Determine the entropy change of the gas when it expands suddenly
against an external pressure of 1 bar.
Sol.: 4.11 J/K

27. A vertical cylinder with adiabatic walls and a non-heat-conducting piston is divided by
a fixed and diathermal wall. The upper part contains 10 moles of an ideal gas while the
lower part contains a mixture in equilibrium at 1.013 bar of 100 g of water and 100 g of
ice. The piston is slowly introduced inward until the pressure of the gas is doubled.
What is the entropy variation of the gas, the mixture and the Universe in this process?
Sol.: -57.63 J/K; 57.63 J/K; 0 J/K.

28. A system undergoes the following reversible transformations:

a. From A to B, isothermal at 600 K with absorption of 1254 kJ.
b. From B to C, adiabatic up to 100 K.
c. From C to D, isothermal at 100 K with absorption of 2090 kJ.
d. From D to E, adiabatic up to 400 K.
e. From E to F, isothermal at 400 K with a release of 3344 kJ.
To turn back to the initial state, heat is only transferred isothermally at 350 K. What is the
amount of this heat?
Sol.: -5120.5 kJ

29. A closed cylindrical container, with adiabatic walls and a volume of 10 l, is divided into
two parts by an internal piston, also adiabatic, that can move without friction. In each
part there is the same amount of diatomic ideal gas, being both gases initially at the
same temperature (27 ºC) and pressure (71 cmHg). The left side has a heating device
that allows it to be slowly heated. This is brought into operation for a certain time
observing, as a consequence, the tripling of the pressure value in the system . Calculate:
a) The temperature and volume, in the final state, of each of the gases.
b ) the amount of heat absorbed by the gas on the left side.
c) the entropy change of the total system.
Sol.: a) TI =1389.6 K; TD= 410.7 K; VI = 7.72 l; VD = 2.28 l; b) 4732.64 J; c) 68.97 J/K

30. One mole of ideal gas expands isothermally, at 27ºC, from 20 a 40 l in three different
processes:
a. The first is carried out, reversibly, reducing slowly the pressure applied on the
piston until the final value pext is reached.
b. In the second, the pressure decreases sharply to its final value pext.
c. In the third, the gas occupying initially a volume of 20 l, suddenly and by
breaking a thin membrane, it is allowed to expand in vacuum to the remaining
20 l.
For each process, calculate Q, W,  U y S of the gas, the reservoir, and the total
adiabatically isolated system (gas + reservoir).

31. In an isolated recipient, 2 l of oxygen at 1 bar and 0ºC and 1 l of helium at 4 bar and
–5ºC are mixed. The final volume is 3 l. Calculate the entropy change in the process.
Assume ideal gases.
Sol.: 1.96 J/K
32. In a certain experiment, 5 g of liquid helium with a temperature of 0.5 K are brought
into contact, in an adiabatic container, with 100 g of paramagnetic salt of temperature Ts,
observing that in equilibrium the common final temperature is 0.04 K. Knowing that the
specific heat of the helium liquid can be expressed as cl = 0.02·T3 Jg-1K-1 and that of
the salt is cs = 10-4 T-2 Jg-1K-1, calculate the initial temperature of the salt (Ts) and the
entropy change of the Universe.
Sol.: 0.04 K; 0.035 J/K

33. A cylinder with adiabatic walls, provided with an adiabatic piston, is divided into two
compartments, I and II, by a fixed and diathermal wall, each containing one mole of
monatomic ideal gas. Initially, the piston is fixed in a position such tat VI = VII, with
PI = 5 bar and TI = 300 K. The piston is released expanding the gas II against an
external pressure of 1 bar. Determine:
a) The changes of the internal energy, enthalpy, and entropy of each of the gases in the
compartments.
b) The entropy change of the Universe.
Sol.:  U I = UII = -748.3 J;  HI= HII = -1247.1 J;  SI= -2.78 J/K;  SII = 8.74 J/K;
 SU = 5.96 J/K