Thermodynamics

2. Entropy & the second law — Exercises

v.2024-11-12

Notes

ˆ Unless otherwise stated data is given in the MKSC system of units.

ˆ Unless otherwise stated numerical data with no decimal point should be assumed
to have 3 significant digits.

ˆ Unless otherwise stated it can be assumed that all processes proceed quasi-statically
and that all gases are ideal and perfect.

ˆ Some exercises may require the use of data given in the Appendix.

2. The second law — Exercises 1

Heat engines

2.1. (*)
A heat engine absorbs 200 J and rejects 160 J of heat per cycle. What is its efficiency?
Answer:
20%
Sol:

|W | Qh − |Qc |
ϵ= = = 40/200
Qh Qh

2.2. (*) DEMO

A steam engine with an efficiency of 0.30 absorbs 500 J of heat per cycle.
(a) How much work does it perform per cycle?
(b) How much heat does it reject per cycle?
Answer:
(a) 150 J (b) 350 J
Sol:
(a)
|W | = ϵ Qh = 0.30 × 500
(b)
|Qc | = Qh − |W | = 500 − 150

2.3. (**) HMWK

Calculate the thermal efficiency of the ABCDA cycle shown in the figure where V1 = 1 L,
V2 = 3 L, P1 = 2 atm, P2 = 4 atm. Assume all the heat transferred to the system is
provided at a cost and that all the heat given off by the system is rejected. The fluid is
an ideal diatomic gas.

2. The second law — Exercises 2

 Source: Adapted from Wkpd by PAR∼commonswiki
Answer:
12%
Sol:
The work done is
|W | = (P2 − P1 )(V2 − V1 ) = 4
The heat absorbed is in steps a (A → B) and d (D → A). Using the 1st law,

Cv 7
Qa = Cv (TB − TA ) + P2 (V2 − V1 ) = (P2 V2 − P2 V1 ) + P2 (V2 − V1 ) = P2 (V2 − V1 )
nR 2
where it has been used that Cv /(nR) = 5/2. Furthermore,
5
Qd = Cv (TA − TD ) = V1 (P2 − P1 )
2
The total heat is then
7 5
Q = Qa + Qd = P2 V2 − P1 V1 − P2 V1 = 33
2 2
The efficiency is the quotient,
|W | 4
ϵ= =
Q 33

2.4. (**)
Calculate the efficiency of a Stirling engine working with an ideal gas but without
regenerator, that is, assuming that the heat during the isochoric process that goes from
the cold temperature Tc up to the hot one Th is at a cost. Express the result in terms

2. The second law — Exercises 3

of the known variables, i.e., Tc , Th , the max and min volumes and the heat capacity of
the gas, which is diatomic.
Answer:
 −1
5ϵC
ϵC 1 +
2 log r
with ϵC = 1 − Tc /Th the efficiency of the ideal Stirling cycle with regenerator and
r = V2 /V4 the compression ratio.
Sol:

|Wh | − Wc nR(Th − Tc ) log(V2 /V4 )

ϵ= =
Qh + Q4 nRTh log(V2 /V4 ) + Cv (Th − Tc )
with Cv /(nR) = 5/2. This result can be rearranged to give the expression used for the
answer.

2.5. (***) HMWK

Assuming an ideal gas with constant heat capacities, show that the thermal efficiency
of an Otto cycle is given by
1
ϵ = 1 − γ−1
r
where r ≡ V1 /V2 is the engine compression ratio. In practice, r for a gasoline engine
cannot exceed a value of about 10 to prevent a rise in temperature upon compression
that would cause the spontaneous combustion of the gasoline-air mixture before the
discharge of the spark. This unwanted effect is called preignition—the engine “knocks”.
What is the theoretical max efficiency for r = 9.0 and γ = 1.4?
Answer:
58%
Sol:
Let us call (P1 , V1 , T1 ) the initial (known) state, with P1 = 1 atm and T1 the ambient
temp. After adiabatic compression (step1, with work W1 > 0) state (P2 , V2 , T2 ) is
reached. After isochoric compression (step2, heat input Q2 > 0) state (P3 , V2 , T3 ) is
reached. After adiabatic expansion (step3, with work W3 < 0) state (P4 , V1 , T4 ) is
reached. The last step4 takes the system to the initial conditions. All these states are
known, since the first one is and they are connected by known eqs. of transformation.
Thus, in step1,
P1 V1γ = P2 V2γ
which implies that state 2 is defined by
 γ
V1
P2 = P1
V2

2. The second law — Exercises 4

and  γ
P2 V2 P1 V1
T2 = = V2
nR nR V2

For step 2 to take the system to state 3 the relation (no work is done)

Cv (T3 − T2 ) = Q2

is used, giving T3 as
Q2
T3 = + T2
Cv
P3 is then  γ
nRT3 nRQ2 V1
P3 = = + P1
V2 Cv V2 V2

Step 3 is again an adiabatic, yielding

 γ  γ
V2 nRQ2 V2
P4 = P3 = + P1
V1 Cv V2 V1

and  γ−1
P4 V1 Q2 V2 P1 V 1
T4 = = +
nR Cv V1 nR

With all this we can now obtain the work,

" γ−1 #
P1 V 1 V1
W1 = Cv (T2 − T1 ) = Cv −1
nR V2
"  γ−1 # " γ−1 #
V2 P1 V1 V1
W3 = Cv (T4 − T3 ) = −Q2 1 − − Cv −1
V1 nR V2
The total work is thus
"  γ−1 #
V2
−W = −W1 − W3 = Q2 1 −
V1

and the efficiency  γ−1

|W | V2
ϵ= =1−
Q2 V1

2. The second law — Exercises 5

Reversibility

2.6. (*)
Consider the Joule’s experiment to measure the amount of mechanical work required
to produce a given amount of heat, that is, the mechanical equivalent of heat. Is this
process reversible or irreversible?
Answer:
Irreversible
Sol:
The process transforms external mechanical energy (i.e., external work) into internal
energy and, hence, it implies an external mechanical irreversibility.

Carnot cycle

2.7. (*)
A Carnot engine absorbs 100 J of heat from a reservoir at the temperature of the normal
boiling point of water and rejects heat to a reservoir at the temperature of the triple
point of water. Find (a) the heat rejected; (b) the work done by the engine; and (c) the
thermal efficiency.
Answer:
(a) 73.2 J (b) 26.8 J (c) 26.8%
Sol:
The efficiency is
Tc 273.16
ϵ=1− =1− = 26.8%
Th 373.15
The work done by the engine is then

W eng = ϵ Qh = 26.8% × 100

and the heat rejected is (since ∆U = 0)

−Qc = Qh − W eng

2. The second law — Exercises 6

2.8. (**) HMWK
Which is the more effective way to increase the thermal efficiency of a Carnot engine, to
increase Th a bit dT , keeping Tc constant; or to decrease Tc by the same amount −dT ,
keeping Th constant?
Answer:
Decrease Tc
Sol:
Considering the efficiency as a function of the two temps,
Tc
ϵ(Tc , Th ) = 1 −
Th
Its sensitivity to variations of each one of the variables is
∂ϵ −1
=
∂Tc Th
and
∂ϵ Tc 1 Tc ∂ϵ
= 2 = <
∂Th Th Th Th ∂Tc
which proves the point.

2.9. (***) HMWK

Consider the cycle shown in the figure, named “sadly-cannot”—see exercises in chapter
1—formed by a straight line from the state tagged ‘0’ to the state ‘1’ and an adiabatic
back to the initial state.

2. The second law — Exercises 7

The work W gas done by the fluid, assume for concreteness an ideal gas, is positive. Since
the change in internal energy in a cycle is nil, ∆U = 0, the total heat Q equals W gas .
During the adiabatic leg no heat is exchanged, so the heat Q > 0 has to be absorbed
during the straight segment. Overall, this cycle involves the absorption of some amount
of heat Q and the production of an equal amount of work W gas . It is thus a heat engine
with 100% efficiency! This is a flagrant violation of Carnot’s postulate, which asserts
that the max efficiency is (1 − Tc /Th ), always less than 1. Where is the flaw?
Sol:
This is not a cycle between two reservoirs. Implicit in the straight line there is first a
raise in temp, then a fall. So, along the straight line heat is absorbed, then rejected at
different T ’s. The total heat Q is the balance of the whole process, but only the heat
absorbed must be taken into account when calculating the efficiency. The heat rejected
is lost.

The second law

2.10. (*)
A heat engine works between a high temperature reservoir at 100◦ C and a low temper-
ature one at 0◦ C .
(a) What is the maximal efficiency that this engine can have?
(b) If the same engine works in reverse as refrigerator, what is its maximum CoP (i.e.,
efficiency) in this case?
Answer:
(a) 26.8% (b) 2.73
Sol:
(a)
ϵ = 1 − Tr
(b)
Tr
ϵ=
1 − Tr

2.11. (*)
An inventor claims to have developed an engine that takes in 100,000 kcal at a temper-
ature of 400 K, rejects 40,000 kcal at a temperature of 200 K, and delivers 59.5 kWh of

2. The second law — Exercises 8

work. Would you advise investing money to put this engine on the market?
Answer:
No way
Sol:
The claimed efficiency is
|W |
ϵclaim = = 51%
|Qh |
The max theoretical efficiency is
Tc
ϵ=1− = 50%
Th

2.12. (**) HMWK

The efficiency of a particular domestic freezer is 5.5. We put in 1 L of water at 10◦ C to
make ice cubes (the freezer indicates −20◦ C ). Calculate how much energy is consumed
from the electrical network in the process.
Data in the appendix (at 1 atm; assume heat capacities do not depend on the temper-
ature)

Answer:
21 Wh
Sol:
The mass is m = 1 kg. The heat extracted from the water or ice is obtained in 3
distinctive stages, namely, (i) water cooled down from +10◦ C to 0◦ C ; (ii) water freezing
into ice; and (iii) ice cooled down from +0◦ C to −20◦ C . Every stage involves a different
calculation for the heat, as follows,

|QcoolWater | = m cp,water |∆Twater | = 41.8 kJ

|Qfreeze | = m Lfusion = 334 kJ

|QcoolIce | = m cp,ice |∆Tice | = 40.0 kJ
The total heat extracted is then
|Q| = 416 kJ
The electrical energy is
|Q|
W = = 75.6 kJ = 21 Wh
ϵ

2. The second law — Exercises 9

2.13. (**) HMWK
A heat engine consumes 200 J from a high temperature reservoir at 373 K and rejects
152 J to a low temperature reservoir at 273 K. How much work is lost at each cycle due
to the irreversibility of the engine?
Answer:
5.62 J
Sol:
The max efficiency is
Tc |Wmax |
ϵ=1− =
Th |Qh |
But the net work actually produced by the engine is

|W | = |Qh | − |Qc |

The lost work is therefore

Tc
|Wlost | = |Wmax | − |W | = |Qc | − |Qh |
Th

2.14. (**) HMWK

On a winter day the interior of a house is kept at 22◦ C . A 1-kW heat pump with a CoP
of 3.5 operates between the exterior ground, whose temperature is 0◦ C , and the house.
Calculate,
(a) kWh of electrical energy required to generate 1 Mcal of heat.
(b) kWh that would be needed if the heat pump were an ideal reversible machine.
Answer:
(a) 0.33 kWh (b) 0.087 kWh
Sol:
The energy required is
|Qh |
|W | = = 332 Wh
ϵ
The max possible efficiency is
1
ϵmax = = 13.4 = 3.83 ϵreal
1 − Tr
Thus, the energy is reduced by this same factor.

2. The second law — Exercises 10

Entropy

2.15. (*) HMWK

Find the change of the entropy of the universe that takes place in a Joule (i.e., free and
adiabatic) expansion of one mole of an ideal gas when it doubles its volume.
Answer:
5.8 J/K
Sol:
An ideal gas does not change its T when expanded freely and adiabatically. Therefore,
V
∆S = nR log = nR log 2 = 5.76 J/K
V0

2.16. (**) HMWK

A mass of 1 kg of water at 30◦ C is mixed with 2 kg of water at 90◦ C at a constant
pressure of 1 atm in a thermally isolated container with negligible heat capacity. Calcu-
late the change of the entropy of the water once it has reached the equilibrium. Assume
that cp for water (see the Appendix for values) does not depend on the temperature.
Answer:
44.6 J/K
Sol:
The final temp of the mixture will be,
m1 T1 + m2 T2
Tf = = 343
m1 + m2
The change of entropy of the i-th mass (i = 1, 2) is
Z Tf Z Tf
δQrev dT Tf
∆Si = = mi cp = mi cp log
Ti T Ti T Ti

Therefore,
(m +m )
!
Tf 1 2
∆S = ∆S1 + ∆S2 = cp log = 44.56 J/K
T1m1 T2m2

2. The second law — Exercises 11

2.17. (*)
A 5-kg wooden block moving at 8 m/s slides across the floor until friction stops it.
Calculate the resulting change in entropy of the universe assuming that both the block
and the floor begin and end (once heat is dissipated to the surrounding air) at room
temperature, 20◦ C .
Answer:
0.546 J/K
Sol:
Since both block and floor begin and end in the same thermodynamic state, their varia-
tion of entropy is null. The only net effect is that some heat, equal to the kinetic energy
of the block, has been transferred to the heat reservoir of the air in the room. That
energy is
1
K = m v 2 = 160 J
2
Thus,
Qair
∆Suniv = ∆Sair = = 160/293 = 0.546
T

2.18. (**) DEMO

In each cycle a Carnot engine extracts heat from a reservoir at temperature Th , performs
some work W and rejects the residual heat to a colder reservoir at Tc . Calculate, for
one cycle and in terms of the two given temperatures and W , the change of entropy of...
(a) Hot reservoir
(b) Cold reservoir
(c) Universe.
Answer:
(a) −|W |/(Th − Tc ) (b) +|W |/(Th − Tc ) (c) 0
Sol:
The heat extracted from the hot reservoir is
|W | Th
|Qh | = = |W |
ϵ Th − Tc
and the heat dumped into the cold one is
Tc
|Qc | = |Qh | − |W | = |W |
Th − Tc
Therefore,
(a)
−|Qh | −|W |
∆Sh = =
Th Th − Tc

2. The second law — Exercises 12

(b)
+|Qc | +|W |
∆Sc = =
Tc Th − Tc
(c) The fluid is a cycle, so ∆Sfluid = 0 and, hence,

∆S = ∆Sh + ∆Sc + ∆Sfluid = 0

2.19. (**) HMWK

Draw the T S diagram (i.e., temperature in the ordinate vs entropy in the abscissa) for
the fluid of an engine running a Carnot cycle.
Sol:

Source: Wkpd by PAR∼commonswiki

2. The second law — Exercises 13

Appendix. Water properties

ˆ Sources: https://www.engineeringtoolbox.com and Wikipedia

ˆ Water specific heat capacities at constant (105 Pa, approx 1 atm) pressure:

cp (water) = 4.1844 J g−1 K−1 (at 20◦ C )

(See this page for other temperatures.)

cp (ice) = 2.000 J g−1 K−1 (at −10◦ C )

(See this page for other temperatures.)

cp (vapor) = 1.890 J g−1 K−1 (at 102◦ C )

(See this page for other temperatures.)

ˆ Water latent heats at 105 Pa, approx 1 atm:

L(fusion) = 334 J/g

L(evap) = 2265 J/g

ˆ Expansion and compressibility coefficients:

. Thermal expansion
 
1 ∂V
β≡ = 2.07 × 10−4 K−1 (at 20◦ C )
V ∂T P

(See this page for other temperatures.)

. Isothermal compressibility
 
1 ∂V
κ≡− = 5 × 10−10 Pa−1
V ∂P T

2. The second law — Exercises 14