Clausius theorem
The Clausius theorem (1855) states that for a system
exchanging heat with external reservoirs and undergoing
a cyclic process (i.e. a process which ultimately returns a
system to its original state):
I
Q
0,
T Q
where Q is the amount of heat absorbed by the system
from the reservoir and T is the temperature of the exter-
nal reservoir at a particular instant. The equality holds in
the reversible case[1] and the inequality holds in the irre-
versible case. The reversible case is used to introduce the
entropy state function. This is because in cyclic process
the variation of a state function is zero.
1 History
The Clausius Theorem is a mathematical explanation of
the Second Law of Thermodynamics. Also referred to as
the Inequality of Clausius, the theorem was developed
by Rudolf Clausius who intended to explain the relation-
ship between the heat ow in a system and the entropy
of the system and its surroundings. Clausius developed
this in his eorts to explain entropy and dene it quan-
titatively. In more direct terms, the theorem gives us a
way to determine if a cyclical process is reversible or ir-
reversible. The Clausius Theorem provides a quantitative
formula for understanding the second law.
Clausius was one of the rst to work on the idea of entropy
and is even responsible for giving it that name. What is
now known as the Clausius Theorem was rst published
in 1862 in Clausius sixth memoir, On the Application
of the Theorem of the Equivalence of Transformations
to Interior Work. Clausius sought to show a proportional
relationship between entropy and the energy ow by heat-
ing (Q) into a system. In a system, this heat energy can
be transformed into work, and work can be transformed
into heat through a cyclical process. Clausius writes that
The algebraic sum of all the transformations occurring
in a cyclical process can only be less than zero, or, as an
extreme case, equal to nothing. In other words, the equa-
tion
I
Q exchanges heat. At each instant of the process, the system
=0
T
with Q being energy ow into the system due to heating Because of the Second Law of Thermodynamics, in each
and T being absolute temperature of the body when that innitesimal heat exchange process between the system
1
energy is absorbed, is found to be true for any process that
is cyclical and reversible. Clausius then took this a step
further and determined that the following equation must
be found true for any cyclical process that is possible, re-
versible or not. This equation is the Clausius Inequality.
I
0
T
Now that this is known, there must be a relation devel-
oped between the Clausius Inequality and entropy. The
amount of entropy S added to the system during the cycle
is dened as
I
Q
S=
T
It has been determined, as stated in the second law of
thermodynamics, that the entropy is a state function: It
depends only upon the state that the system is in, and not
what path the system took to get there. This is in contrast
to the amount of energy added as heat (Q) and as work
(W), which may vary depending on the path. In a cyclic
process, therefore, the entropy of the system at the be-
ginning of the cycle must equal the entropy at the end of
the cycle. In the irreversible case, entropy will be created
in the system, and more entropy must be extracted than
was added (S < 0) in order to return the system to its
original state. In the reversible case, no entropy is created
and the amount of entropy added is equal to the amount
extracted (S = 0) .
If the amount of energy added by heating can be mea-
sured during the process, and the temperature can be
measured during the process, the Clausius inequality can
be used to determine whether the process is reversible or
irreversible by carrying out the integration in the Clausius
inequality.
2 Proof
The temperature that enters in the denominator of the
integrand in the Clausius Inequality is actually the tem-
perature of the external reservoir with which the system
is in contact with an external reservoir.
2 5 EXTERNAL LINKS

I
and the reservoir, the net change in entropy of the uni- dSSys = 0
verse, so to say,is, dST otal = dSSys + dSRes 0 .
I I I
When the system takes in heat by an innitesimal amount dST otal = dSRes + dSSys 0
Q1 ( 0 ), for the net change in entropy dST otal1 in this
step to be positive, the temperature of the hot reservoir For a reversible cyclic process, there is no generation
THot needs to be slightly greater than the temperature of of entropy in each of the innitesimal heat transfer pro-
the system at that instant. If the temperature of the system cesses, and thus we would have the equality
is given by T1 at that instant, then dSSys1 = Q T1 , and
1

THot T1 forces us to have: I

Qrev
=0
T
Q1 Q1
dSRes1 = = dSSys1 Thus, the Clausius Inequality is a consequence of apply-
THot T1
ing the second law of thermodynamics at each innitesi-
This means the magnitude of the entropy loss from the mal stage of heat transfer, and is thus in a sense a weaker
reservoir, |dSRes1 | = TQ 1
Hot
is less than the magnitude of condition than the Second Law itself.
the entropy gain dSSys1 ( 0 ) by the system:
Similarly, when the system at temperature T2 expels heat
in magnitude Q2 ( Q2 0 ) into a colder reservoir 3 See also
(at temperature TCold T2 ) in an innitesimal step,
then again, for the Second Law of Thermodynamics to Introduction to entropy
hold, we would have, in an exactly similar manner:
Carnot heat engine

Q2 Q2
dSRes2 = = dSSys2 4 References
TCold T2
Here, the amount of heat 'absorbed' by the system is [1] Clausius theorem at Wolfram Research
given by Q2 ( 0 ), signifying that heat is transfer-
ring from the system to the reservoir, with dSSys2 0 Morton, A. S., and P.J. Beckett. Basic Thermo-
. The magnitude of the entropy gained by the reservoir, dynamics. New York: Philosophical Library Inc.,
dSRes2 = |Q 2|
Tcold is greater than the magnitude of the en- 1969. Print.
tropy loss of the system |dSSys2 |
Saad, Michel A. Thermodynamics for Engineers.
Since the total change in entropy for the system is 0 in a Englewood Clis: Prentice-Hall, 1966. Print.
cyclic process, if we add all the innitesimal steps of heat
intake and heat expulsion from the reservoir, signied by Hsieh, Jui Sheng. Principles of Thermodynamics.
the previous two equations, with the temperature of the Washington, D.C.: Scripta Book Company, 1975.
reservoir at each instant given by T , we would have, Print.
Zemansky, Mark W. Heat and Thermodynamics.
I I I 4th ed. New York: McGwaw-Hill Book Company,
Q
dSRes = dSSys = 0 1957. Print.
T
Clausius, Rudolf. The Mechanical Theory of Heat.
In particular.
London: Taylor and Francis, 1867. eBook

I
Q
T
0 5 External links
Hence, we proved the Clausius Theorem. Judith McGovern (2004-03-17). Proof of Clau-
We summarize the following, (the inequality in the third siuss theorem. Retrieved October 4, 2010.
statement below, being obviously guaranteed by the The Clausius Inequality And The Mathematical
second law of thermodynamics,which is the basis of our Statement Of The Second Law (PDF). Retrieved
calculation), October 5, 2010.
The Mechanical Theory of Heat (eBook). Retrieved
I
December 1, 2011.
dSRes 0
 3

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