The efficiency of the Carnot cycle with arbitrary gas equations of state

This article has been downloaded from IOPscience. Please scroll down to see the full text article.
2006 Eur. J. Phys. 27 719
(http://iopscience.iop.org/0143-0807/27/4/004)
Download details:
IP Address: 200.16.118.201
The article was downloaded on 08/03/2012 at 14:50
Please note that terms and conditions apply.
View the table of contents for this issue, or go to the journal homepage for more
Home Search Collections Journals About Contact us My IOPscience
INSTITUTE OF PHYSICS PUBLISHING EUROPEAN JOURNAL OF PHYSICS
Eur. J. Phys. 27 (2006) 719726 doi:10.1088/0143-0807/27/4/004
The efciency of the Carnot cycle with
arbitrary gas equations of state
Paulus C Tjiang and Sylvia H Sutanto
Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Katolik
Parahyangan, Bandung 40141, Indonesia
E-mail: pctjiang@home.unpar.ac.id and sylvia@home.unpar.ac.id
Received 25 January 2006
Published 2 May 2006
Online at stacks.iop.org/EJP/27/719
Abstract
The derivation of the efciency of the Carnot cycle is usually done by
calculating the heats involved in two isothermal processes and making use
of the associated adiabatic relation for a given working substances equation
of state, usually the ideal gas. We present a derivation of the Carnot efciency
using the same procedure with the RedlichKwong gas as a working substance
to solve calculation difculties raised by Agrawal and Menon (1990 Eur. J.
Phys. 11 8890). We also show that using the same procedure, the Carnot
efciency may be derived regardless of the functional form of the gas equation
of state.
1. Introduction
In any course of undergraduate thermodynamics, thermodynamical cycles and their efciencies
always play their part. The discussion of thermodynamical cycles is always followed by, or
carried out in parallel to, the discussion of the second law of thermodynamics. For a reversible
cycle between two single temperatures, it is well known that the efciency of such a cycle is
= 1
T
C
T
H
, (1.1)
where T
H
and T
C
are the absolute temperatures of hot and cold heat reservoirs. For an
irreversible cycle, since the total change of entropy is positive, the efciency of such a cycle
is less than (1.1).
There are many theoretical cycles that satisfy the efciency (1.1) [2], but the so-called
Carnot cycle is of interest because of the simple way in which it describes a reversible
cycle. The Carnot cycle consists of two isothermal processes and two adiabatic processes
as shown in gure 1. In most textbooks of either elementary physics or thermodynamics,
the Carnot efciency (1.1) is derived with the ideal gas as its working substance because
of its mathematical simplicity using the following procedure: calculate the heats involved
0143-0807/06/040719+08$30.00 c 2006 IOP Publishing Ltd Printed in the UK 719
720 P C Tjiang and S H Sutanto
Pressure p
Volume V
Isothermal expansion at
temperature TH
Isothermal compression at
temperature TC
Adiabatic expansion
Adiabatic
compression
1
2
3
4
Figure 1. The pV indicator diagram of a Carnot cycle 1-2-3-4, where T
C
< T
H
.
in isothermal expansion and compression in pV, VT or pT diagrams, then relate them
to the associated adiabatic relations. However, the second law of thermodynamics proves
that the efciency (1.1) should be independent of working substance [3], so it is natural to
question whether the Carnot efciency can be obtained from other equations of state using
the procedure above. Some attempt has been made to do the task above, among them is the
work of Agrawal and Menon [1] who used the van der Waals equation of state to derive the
Carnot efciency through the procedure above, and it turned out that their result agreed with
(1.1). Nevertheless, they pointed out that there were some calculation difculties arising when
the derivation was done for other real gas equations of state (such as the RedlichKwong gas
[2]) using the same procedure, and suggested deriving equation (1.1) through an innitesimal
cycle using a suitable Taylor expansion of thermodynamic variables about the initial state of
the cycle [1].
In this paper, we shall derive the Carnot efciency (1.1) with the RedlichKwong gas as a
working substance to solve the calculation difculties raised by Agrawal and Menon, and we
also show that using the customary procedure, we may obtain the efciency (1.1) regardless
of the functional form of the equation of state. We start with a brief review of the generalized
thermodynamic properties satised by any equation of state in section 2. Using the relations
discussed in section 2, we shall derive the Carnot efciency fromthe RedlichKwong equation
of state in section 3. In section 4, we present the derivation of the Carnot efciency using
the customary procedure without any knowledge of the substances equation of state. The
discussion will be concluded in section 5.
2. Generalized thermodynamic properties
In this section, we shall briey review the thermodynamic properties satised by any equation
of state.
2.1. Maxwell relations
An equation of state in thermodynamics may be written as
f (p, V, T ) = C, (2.2)
The efciency of the Carnot cycle with arbitrary gas equations of state 721
where p, V and T are the pressure, volume and absolute temperature of a substance,
respectively. Equation (2.2) yields the following relations:
p = p(V, T ), (2.3)
V = V(p, T ), (2.4)
T = T (p, V). (2.5)
However, the rst law of thermodynamics and the denition of entropy suggests that there is
another degree of freedom that should be taken into account, i.e. the entropy S, for
dU = T dS p dV U = U(S, V), (2.6)
where U is the internal energy of the substance. From equation (2.6), it is clear that
_
U
S
_
V
= T,
_
U
V
_
S
= p, (2.7)
which gives
_
T
V
_
S
=
_
p
S
_
V
(2.8)
according to the exactness condition of the internal energy U.
Using Legendre transformations [4], we may dene
H(p, S) = U(S, V) + pV, (2.9)
F(V, T ) = U(S, V) T S, (2.10)
G(P, T ) = H(p, S) T S, (2.11)
where H(p, S), F(V, T ) and G(p, T ) are the enthalpy, Helmholtz and Gibbs functions,
respectively. Differentiating equations (2.9), (2.10) and (2.11) gives
dH = T dS + V dp, (2.12)
dF = p dV S dT, (2.13)
dG = V dp S dT, (2.14)
which leads us to
_
T
p
_
S
=
_
V
S
_
p
, (2.15)
_
p
T
_
V
=
_
S
V
_
T
, (2.16)
_
V
T
_
p
=
_
S
p
_
T
(2.17)
due to the exactness of H(p, S), F(V, T ) and G(p, T ). The set of equations (2.8), (2.15),
(2.16) and (2.17) is called the Maxwell relations [2, 3].
2.2. General properties of entropy and internal energy
Now let us express the entropy U and internal energy S in terms of measurable quantities. Let
U = U(V, T ), then
dU =
_
U
T
_
V
dT +
_
U
V
_
T
dV
= C
v
dT +
_
U
V
_
T
dV, (2.18)
722 P C Tjiang and S H Sutanto
where C
v
is the heat capacity at a constant volume. Inserting equation (2.18) into
equation (2.6), we have
dS =
C
v
T
dT +
1
T
__
U
V
_
T
+ p
_
dV. (2.19)
Suppose S = S(T, V), then
dS =
_
S
T
_
V
dT +
_
S
V
_
T
dV
=
_
S
T
_
V
dT +
_
p
T
_
V
dV, (2.20)
where we have used equation (2.16). Comparing equations (2.20) and (2.19), we obtain
_
S
T
_
V
=
C
v
T
, (2.21)
_
U
V
_
T
= T
_
p
T
_
V
p. (2.22)
Substitution of equation (2.22) into equation (2.6) gives
dU = C
v
dT +
_
T
_
p
T
_
V
p
_
dV. (2.23)
Since dU is an exact differential, the following exactness condition must be fullled:
_
C
v
V
_
T
= T
_

2
p
T
2
_
V
. (2.24)
It is easy to see that equation (2.24) must also be satised to ensure the exactness of
equation (2.20). Equation (2.24) also tells us the isothermal volume dependence of C
v
.
2.3. General relations of isothermal and adiabatic processes
In an isothermal process, the change of internal energy is given by
dU =
_
T
_
p
T
_
V
p
_
dV, (2.25)
using equation (2.23). Using the rst law of thermodynamics dU = dQ p dV, the heat
involved in this process is
dQ = T
_
p
T
_
V
dV. (2.26)
In an adiabatic process, where no heat is involved, the rst law of thermodynamics,
together with equation (2.23), gives
C
v
dT = T
_
p
T
_
V
dV. (2.27)
Equations (2.26) and (2.27) will be used to obtain the Carnot efciency of the Redlich
Kwong gas in the next section.
The efciency of the Carnot cycle with arbitrary gas equations of state 723
3. Carnot efciency of the RedlichKwong equation of state
In this section, we shall derive the Carnot efciency (1.1) fromthe RedlichKwong gas, whose
equation of state is given by
p =
nRT
V b

n
2
a
T
1/2
V(V + b)
, (3.28)
where n is the number of moles of the gas, R 8.31 J mol
1
K
1
is the gas constant, and a
and b are constants evaluated from the critical state of the gas [2]. We shall follow the process
order of the Carnot cycle as shown in gure 1.
From equation (2.24), the volume dependence of the heat capacity of constant volume C
v
for the RedlichKwong gas is
_
C
v
V
_
T
=
3n
2
a
4T
3/2
V(V + b)
, (3.29)
which leads to the following functional form of C
v
:
C
v
(V, T ) =
3n
2
a
4bT
3/2
ln
V + b
V
+ f (T ), (3.30)
where f (T ) is an arbitrary function of temperature, since we do not have any information
about
_
C
v
T
_
V
.
Usingequations (2.26) and(3.28), we obtainthe involvedheat for the isothermal expansion
from states 1 to 2, as well as isothermal compression from states 3 to 4 as follows:
Q
12
= nRT
H
ln
V
2
b
V
1
b
+
n
2
a
2bT
1/2
H
ln
V
2
(V
1
+ b)
V
1
(V
2
+ b)
, (3.31)
Q
34
= nRT
C
ln
V
4
b
V
3
b
+
n
2
a
2bT
1/2
C
ln
V
4
(V
3
+ b)
V
3
(V
4
+ b)
. (3.32)
For the adiabatic process, equation (2.27) leads to the following differential form with the
help of equation (3.30):
M(V, T ) dT + N(V, T ) dV = 0, (3.33)
M(V, T ) =
3n
2
a
4bT
3/2
ln
V + b
V
+ f (T ), (3.34)
N(V, T ) =
nRT
V b
+
n
2
a
2T
1/2
V(V + b)
. (3.35)
It is clear that equation (3.33) is not an exact differential, which means that we have to nd a
suitable integrating factor in order to transform equation (3.33) to an exact differential. The
corresponding integrating factor (V, T ) for equation (3.33) is surprisingly simple:
(V, T ) (T ) =
1
T
. (3.36)
Multiplying (T ) to equation (3.33) gives

M(V, T ) dT +

N(V, T ) dV = 0, (3.37)

M(V, T ) =
3n
2
a
4bT
5/2
ln
V + b
V
+
f (T )
T
, (3.38)
724 P C Tjiang and S H Sutanto

N(V, T ) =
nR
V b
+
n
2
a
2T
3/2
V(V + b)
, (3.39)
whose general solution is
nRln(V b) +
n
2
a
2bT
3/2
ln
V
V + b
+ g(T ) = constant, (3.40)
where
g(T ) =
_
f (T )
T
dT. (3.41)
Using equation (3.40), we obtain the relation between states 2 and 3 connected by adiabatic
expansion as
nRln(V
2
b) +
n
2
a
2bT
3/2
H
ln
V
2
V
2
+ b
+ g(T
H
) = nRln(V
3
b) +
n
2
a
2bT
3/2
C
ln
V
3
V
3
+ b
+ g(T
C
).
(3.42)
The similar relation holds for adiabatic compression from states 4 to 1:
nRln(V
1
b) +
n
2
a
2bT
3/2
H
ln
V
1
V
1
+ b
+ g(T
H
) = nRln(V
4
b) +
n
2
a
2bT
3/2
C
ln
V
4
V
4
+ b
+ g(T
C
).
(3.43)
Equations (3.42) and (3.43) may be rewritten as
g(T
H
) g(T
C
) = nRln
V
3
b
V
2
b
+
n
2
a
2bT
3/2
C
ln
V
3
V
3
+ b

n
2
a
2bT
3/2
H
ln
V
2
V
2
+ b
(3.44)
and
g(T
H
) g(T
C
) = nRln
V
4
b
V
1
b
+
n
2
a
2bT
3/2
C
ln
V
4
V
4
+ b

n
2
a
2bT
3/2
H
ln
V
1
V
1
+ b
, (3.45)
respectively. Equating equations (3.44) and (3.45) and after doing some algebraic calculation,
we get
nRln
V
2
b
V
1
b
+
n
2
a
2bT
3/2
H
ln
V
2
(V
1
+ b)
V
1
(V
2
+ b)
= nRln
V
3
b
V
4
b
+
n
2
a
2bT
3/2
C
ln
V
3
(V
4
+ b)
V
4
(V
3
+ b)
. (3.46)
Now let us calculate the Carnot efciency of the RedlichKwong gas. From
equations (3.31) and (3.32), the efciency is
=
|Q
12
| |Q
34
|
|Q
12
|
= 1
|Q
34
|
|Q
12
|
= 1
T
C
_
nRln
V
3
b
V
4
b
+
n
2
a
2bT
3/2
C
ln
V
3
(V
4
+b)
V
4
(V
3
+b)
_
T
H
_
nRln
V
2
b
V
1
b
+
n
2
a
2bT
3/2
H
ln
V
2
(V
1
+b)
V
1
(V
2
+b)
_ 1
T
C
T
H
(3.47)
where we have used the adiabatic relation (3.46). It is clear that the Carnot efciency (3.47)
coincides with equation (1.1) in section 1 of this paper.
The efciency of the Carnot cycle with arbitrary gas equations of state 725
4. Derivation of the Carnot efciency of an arbitrary gas equation of state
The success of obtaining the Carnot efciency with the van der Waals gas in [1] and the
RedlichKwong gas in the previous section has tempted us to question whether we may
obtain equation (1.1) from any working substance using the same procedure mentioned in
section 1. Let the substances equation of state be in the form of equation (2.3). With the
volume dependence of C
v
given by equation (2.24), the functional form of C
v
is
C
v
(V, T ) = T
_ _

2
p
T
2
_
V
dV + f (T ), (4.48)
where f (T ) is an arbitrary function of temperature.
Using the same process order of the Carnot cycle as given in gure 1 and with the help
of equation (2.26), the heats involved in isothermal expansion from states 1 to 2, as well as
isothermal compression from states 3 to 4, are
Q
12
= T
H
_
V
2
V
1
_
p
T
_
V
dV T
H
[F(V
2
, T
H
) F(V
1
, T
H
)] , (4.49)
Q
34
= T
C
_
V
4
V
3
_
p
T
_
V
dV T
C
[F(V
4
, T
C
) F(V
3
, T
C
)] , (4.50)
respectively, where F(V, T ) =
_ _
p
T
_
V
dV.
In the adiabatic process, with the help of equation (2.24) it is easy to see that
equation (2.27) is not an exact differential. However, by multiplying equation (2.27) with a
suitable integrating factor, which turns out to be (V, T ) =
1
T
like that used in section 3, we
obtain
C
v
T
dT +
_
p
T
_
V
dV = 0. (4.51)
With the help of equation (4.48), it is easy to see that equation (4.51) is an exact differential,
whose general solution is
_ _
p
T
_
V
dV + g(T ) = constant F(V, T ) + g(T ) = constant, (4.52)
where g(T ) =
_
f (T )
T
dT is another arbitrary function of temperature. Using equation (4.52),
the relation between states 2 and 3 in the adiabatic expansion, and the relation between states
4 and 1 in the adiabatic compression are
g(T
H
) g(T
C
) = F(V
3
, T
C
) F(V
2
, T
H
), (4.53)
g(T
H
) g(T
C
) = F(V
4
, T
C
) F(V
1
, T
H
), (4.54)
respectively. Equating equations (4.53) and (4.54), we get
F(V
3
, T
C
) F(V
4
, T
C
) = F(V
2
, T
H
) F(V
1
, T
H
). (4.55)
Finally, the Carnot efciency is
= 1
|Q
34
|
|Q
12
|
= 1
T
C
|F(V
4
, T
C
) F(V
3
, T
C
)|
T
H
|F(V
2
, T
H
) F(V
1
, T
H
)|
1
T
C
T
H
(4.56)
using equation (4.55). It is just the same efciency as equation (1.1) given in section 1.
726 P C Tjiang and S H Sutanto
5. Summary and conclusion
In this paper, we have derived the Carnot efciency for the RedlichKwong gas as well as
for arbitrary gas equations of state using the procedure given in section 1. Both results are in
agreement with equation (1.1).
From the derivation using the RedlichKwong gas equation of state, we show that the
derivation procedure succeeds even if the specic heat at constant volume C
v
is a function
of volume and temperaturethe difculty encountered by Agrawal and Menon [1] while
deriving the Carnot efciency using an equation of state with
_
C
v
V
_
T
= 0. As shown by
equation (3.30), we may write the analytical form of C
v
(V, T ) with an unknown function of
temperature in it since we know only the volume dependence of C
v
through
_
C
v
V
_
T
. From
equation (3.46), it is clear that the equation of adiabatic relations among states 1, 2, 3 and 4
does not depend on that unknown function of temperature.
In contrast to Agrawal and Menons conclusion in [1] that it is difcult to apply the
procedure stated in section 1 for a nite Carnot cycle when the working substance is arbitrary,
our results in section 4 show that it is technically possible to derive the Carnot efciency
(1.1) from the general thermodynamic properties discussed in section 2. However, since the
thermodynamic properties are derived from Maxwells relations where the concept of entropy
is used, the results in section 4 are not surprising. Using equations (2.27), (4.49)(4.50) and
(4.55), it is easy to verify that the derivation given in section 4 is completely equivalent to
the condition of a reversible cycle
_
dS = 0 which also produces the Carnot efciency (1.1)
regardless of the working substance. The results in section 4 may answer students questions
concerning how the derivation of the Carnot efciency from any given working substance may
be carried out using the procedure stated in section 1 to produce equation (1.1) .
Acknowledgments
The authors would like to thank Professor B Suprapto Brotosiswojo and Dr A Rusli of the
Department of Physics, Institut Teknologi Bandung, Indonesia, for their helpful discussions
on the subject in this paper and their corrections.
References
[1] Agrawal D C and Menon V J 1990 Eur. J. Phys. 11 8890
[2] Ward K 1977 Thermodynamics 9th edn (New York: McGraw-Hill)
[3] Sears F W and Salinger G L 1975 Thermodynamics, Kinetic Theory and Statistical Thermodynamics 3rd edn
(Reading, MA: Addison-Wesley)
Zemansky M W and Dittman R H 1982 Heat and Thermodynamics 6th edn (New York: McGraw-Hill)
[4] Goldstein H 1980 Classical Mechanics 2nd edn (Reading, MA: Addison-Wesley) p 339