82 3 The Second and Third Laws
value of the entropy of a system, whereas the thermodynamic
Energy Allowed states
(a)
Energy
Allowed states
(b)
Figure 3A.5 When a container expands from (b) to (a), the
translational energy levels of gas molecules in it come closer
together and, for the same temperature, more become accessible
to the molecules. As a result the number of ways of achieving the
same energy (the value of W ) increases, and so therefore does
the entropy.
The molecular interpretation of entropy helps to explain
why, in the thermodynamic definition given by eqn 3A.1, the
entropy change depends inversely on the temperature. In
a system at high temperature the molecules are spread out
over a large number of energy states. Increasing the energy
of the system by the transfer of heat makes more states ac-
cessible, but given that very many states are already occu-
pied the proportionate change in W is small (Fig. 3A.6). In
contrast, for a system at a low temperature fewer states are
occupied, and so the transfer of the same energy results in a
proportionately larger increase in the number of accessible
states, and hence a larger increase in W. This argument sug-
gests that the change in entropy for a given transfer of energy
as heat should be greater at low temperatures than at high, as
in eqn 3A.1a.
There are several final points. One is that the Boltzmann
definition of entropy makes it possible to calculate the absolute
Heat Heat
(a) High temperature (b) Low temperature
Figure 3A.6 The supply of energy as heat to the system results
in the molecules moving to higher energy states, so increasing
the number of microstates and hence the entropy. The increase
in the entropy is smaller for (a) a system at a high temperature
than (b) one at a low temperature because initially the number of
occupied states is greater.
definition leads only to values for a change in entropy. This
point is developed in Focus 13 where it is shown how to re-
late values of S to the structural properties of atoms and mol-
ecules. The second point is that the Boltzmann formula cannot
readily be applied to the surroundings, which are typically far
too complex for W to be a meaningful quantity.
3A.3 The entropy as a state function
Entropy is a state function. To prove this assertion, it is nec-
essary to show that the integral of dS between any two states
is independent of the path between them. To do so, it is suf-
ficient to prove that the integral of eqn 3A.1a round an arbi-
trary cycle is zero, for that guarantees that the entropy is the
same at the initial and final states of the system regardless of
the path taken between them (Fig. 3A.7). That is, it is necessary
to show that
dqrev
!∫ d S = !∫ T
=0 (3A.5)
where the symbol ! ∫ denotes integration around a closed path.
There are three steps in the argument:
1. First, to show that eqn 3A.5 is true for a special cycle
(a ‘Carnot cycle’) involving a perfect gas.
2. Then to show that the result is true whatever the working
substance.
3. Finally, to show that the result is true for any cycle.
(a) The Carnot cycle
A Carnot cycle, which is named after the French engineer
Sadi Carnot, consists of four reversible stages in which a gas
(the working substance) is either expanded or compressed in
Final state
Pressure, p
Initial state
Volume, V
Figure 3A.7 In a thermodynamic cycle, the overall change in a
state function (from the initial state to the final state and then
back to the initial state again) is zero.
 3A Entropy 83

Hot A
Stage 4
Pressure, p

Pressure, p
Stage 1 1 Isotherm Adiabat

D
B
Cold
Stage 3 Adiabat
2
Stage 2 Isotherm 3
C

Volume, V Volume, V

Figure 3A.8 The four stages which make up the Carnot cycle.
In stage 1 the gas (the working substance) is in thermal contact
with the hot reservoir, and in stage 3 contact is with the cold
reservoir; both stages are isothermal. Stages 2 and 4 are
adiabatic, with the gas isolated from both reservoirs.
Figure 3A.9 The basic structure of a Carnot cycle. Stage 1 is the
isothermal reversible expansion at the temperature Th. Stage 2 is
a reversible adiabatic expansion in which the temperature falls
from Th to Tc. Stage 3 is an isothermal reversible compression at Tc.
Stage 4 is an adiabatic reversible compression, which restores the
system to its initial state.

various ways; in two of the stages energy as heat is transferred How is that done? 3A.1 Showing that the entropy is a
to or from a hot source or a cold sink (Fig. 3A.8).
Figure 3A.9 shows how the pressure and volume change in state function for a perfect gas
each stage: First, you need to note that a reversible adiabatic expansion
(stage 2 in Fig. 3A.9) takes the system from Th to Tc. You can
1. The gas is placed in thermal contact with the hot source
then use the properties of such an expansion, specifically VT c
(which is at temperature Th) and undergoes reversible
= constant (Topic 2E), to relate the two volumes at the start
isothermal expansion from A to B; the entropy change is
and end of the expansion. You also need to note that energy as
qh/Th, where qh is the energy supplied to the system as
heat is transferred by reversible isothermal processes (stages 1
heat from the hot source.
and 3) and, as derived in Example 3A.1, for a perfect gas
2. Contact with the hot source is broken and the gas then
stage 1 stage 3
undergoes reversible adiabatic expansion from B to C. No !##"##$ !##"## $
energy leaves the system as heat, so the change in entropy V V
qh = nRTh ln B qc = nRTc ln D
is zero. The expansion is carried on until the temperature VA VC
of the gas falls from Th to Tc, the temperature of the cold
Step 1 Relate the volumes in the adiabatic expansions
sink.
For a reversible adiabatic process the temperature and volume
3. The gas is placed in contact with the cold sink and then are related by VT c = constant (Topic 2E). Therefore
undergoes a reversible isothermal compression from C
to D at Tc. Energy is released as heat to the cold sink; the for the path D to A (stage 4): VAT hc = VDT cc
change in entropy of the system is qc/Tc; in this expression for the path B to C (stage 2): VCT cc = VBT hc
qc is negative.
4. Finally, contact with the cold sink is broken and the gas Multiplication of the first of these expressions by the second
then undergoes reversible adiabatic compression from gives
D to A such that the final temperature is Th. No energy VAVCT hcT cc = VDVBT hcT cc
enters the system as heat, so the change in entropy is zero.
which, on cancellation of the temperatures, simplifies to
The total change in entropy around the cycle is the sum of the VD VA
changes in each of these four steps: =
VC VB
qh qc Step 2 Establish the relation between the two heat transfers
!∫ d S = T +
Tc
h
You can now use this relation to write an expression for
The next task is to show that the sum of the two terms on the energy discarded as heat to the cold sink in terms of VA and VB
right of this expression is zero for a perfect gas and so confirm- VD V V
qc = nRTc ln = nRTc ln A = − nRTc ln B
ing, for that substance at least, that entropy is a state function. VC VB VA
84 3 The Second and Third Laws

It follows that
Th
qh nRTh ln(VB /VA ) T
= =− h Hot source
qc −nRTc ln(VB /VA ) Tc
Note that qh is negative (heat is withdrawn from the hot 20

source) and qc is positive (heat is deposited in the cold sink), so qh

their ratio is negative. This expression can be rearranged into w
5
qh qc
+ =0 (3A.6)
Th Tc 15

qc
Because the total change in entropy around the cycle is
qh /Th + qc /Tc , it follows immediately from eqn 3A.6 that, for a Tc
Cold sink
perfect gas, this entropy change is zero.

Figure 3A.10 In a heat engine, an energy qh (for example, |qh| =

20 kJ) is extracted as heat from the hot source and qc is discarded
Brief illustration 3A.2 into the cold sink (for example, |qc| = 15 kJ). The work done by the
engine is equal to |qh| − |qc| (e.g. 20 kJ − 15 kJ = 5 kJ).
The Carnot cycle can be regarded as a representation of the
changes taking place in a heat engine in which part of the
energy extracted as heat from the hot reservoir is converted
into work. Consider an engine running in accord with the
Brief illustration 3A.3
Carnot cycle, and in which 100 J of energy is withdrawn from
the hot source (qh = −100 J) at 500 K. Some of this energy is
A certain power station operates with superheated steam at
used to do work and the remainder is deposited in the cold
300 °C (Th = 573 K) and discharges the waste heat into the
sink at 300 K. According to eqn 3A.6, the heat deposited is
environment at 20 °C (Tc = 293 K). The theoretical efficiency
Tc 300K is therefore
qc = − qh × = − (−100J) × = + 60J
Th 500K 293K
η = 1− = 0.489
This value implies that 40 J was used to do work. 573K
or 48.9 per cent. In practice, there are other losses due to
mechanical friction and the fact that the turbines do not
It is now necessary to show that eqn 3A.5 applies to any ma- operate reversibly.
terial, not just a perfect gas. To do so, it is helpful to introduce
the efficiency, η (eta), of a heat engine:
Now this conclusion can be generalized. The Second Law
work performed w Efficiency of thermodynamics implies that all reversible engines have the
η= = (3A.7)
heat absorbed from hot source qh [definition]
same efficiency regardless of their construction. To see the truth
of this statement, suppose two reversible engines are coupled
Modulus signs (|…|) have been used to avoid complications together and run between the same hot source and cold sink
with signs: all efficiencies are positive numbers. The defini- (Fig. 3A.11). The working substances and details of construc-
tion implies that the greater the work output for a given supply tion of the two engines are entirely arbitrary. Initially, suppose
of heat from the hot source, the greater is the efficiency of the that engine A is more efficient than engine B, and that a setting
engine. The definition can be expressed in terms of the heat of the controls has been chosen that causes engine B to acquire
transactions alone, because (as shown in Fig. 3A.10) the energy energy as heat qc from the cold sink and to release a certain
supplied as work by the engine is the difference between the quantity of energy as heat into the hot source. However, be-
energy supplied as heat by the hot source and that returned to cause engine A is more efficient than engine B, not all the work
the cold sink: that A produces is needed for this process and the difference
can be used to do work. The net result is that the cold reservoir
qh − qc q is unchanged, work has been done, and the hot reservoir has
η= = 1− c (3A.8)
qh qh lost a certain amount of energy. This outcome is contrary to
the Kelvin statement of the Second Law, because some heat has
It then follows from eqn 3A.6, written as |qc|/|qh| = Tc/Th that
been converted directly into work. Because the conclusion is
Tc contrary to experience, the initial assumption that engines A
η = 1− Carnot efficiency (3A.9)
and B can have different efficiencies must be false. It follows
Th
 3A Entropy 85

purple line. The entropy change around each individual

cycle is zero (as already demonstrated), so the sum of entropy
Hot source Th Hot source Th changes for all the cycles is zero. However, in the sum, the en-
tropy change along any individual path is cancelled by the en-
qh qh’ qhh – qh’ qh ’ tropy change along the path it shares with the neighbouring
cycle (because neighbouring paths are traversed in opposite
directions). Therefore, all the entropy changes cancel except
A B A B
qc w qc qc w qc for those along the perimeter of the overall cycle and therefore
the sum qrev/T around the perimeter is zero.
The path shown by the purple line can be approximated more
Cold sink Tc Cold sink Tc closely by using more Carnot cycles, each of which is much
smaller, and in the limit that they are infinitesimally small
(a) (b) their perimeter matches the purple path exactly. Equation 3A.5
(that the integral of dqrev/T round a general cycle is zero) then
Figure 3A.11 (a) The demonstration of the equivalence of the follows immediately. This result implies that dS is an exact dif-
efficiencies of all reversible engines working between the same ferential and therefore that S is a state function.
thermal reservoirs is based on the flow of energy represented in
this diagram. (b) The net effect of the processes is the conversion
of heat into work without there being a need for a cold sink. This (b) The thermodynamic temperature
is contrary to the Kelvin statement of the Second Law.
Suppose an engine works reversibly between a hot source at a
temperature Th and a cold sink at a temperature T, then it fol-
lows from eqn 3A.9 that
that the relation between the heat transfers and the tempera-
tures must also be independent of the working material, and T = (1 − η)Th (3A.10)
therefore that eqn 3A.9 is true for any substance involved in a
Carnot cycle. This expression enabled Kelvin to define the thermodynamic
For the final step of the argument note that any reversible temperature scale in terms of the efficiency of a heat engine:
cycle can be approximated as a collection of Carnot cycles. construct an engine in which the hot source is at a known tem-
This approximation is illustrated in Fig. 3A.12, which shows perature and the cold sink is the object of interest. The tem-
three Carnot cycles A, B, and C fitted together in such a way perature of the latter can then be inferred from the measured
that their perimeter approximates the cycle indicated by the efficiency of the engine. The Kelvin scale (which is a special
case of the thermodynamic temperature scale) is currently
defined by using water at its triple point as the notional hot
a1 source and defining that temperature as 273.16 K exactly.4

b1
(c) The Clausius inequality
Pressure, p

a2 c1
A To show that the definition of entropy is consistent with the
a4 b2
B c2 Second Law, note that more work is done when a change is
b4
a3 C reversible than when it is irreversible. That is, |dwrev| ≥ |dw|.
c4
Because dw and dwrev are negative when energy leaves the sys-
b3 tem as work, this expression is the same as −dwrev ≥ −dw, and
c3 hence dw − dwrev ≥ 0. The internal energy is a state function,
Volume, V so its change is the same for irreversible and reversible paths
between the same two states, and therefore
Figure 3A.12 The path indicated by the purple line can be
approximated by traversing the overall perimeter of the area
created by the three Carnot cycles A, B, and C; for each individual
dU = dq + dw = dqrev + dwrev
cycle the overall entropy change is zero. The entropy changes
along the adiabatic segments (such as a1–a4 and c2–c3) are zero, and hence dqrev − dq = dw − dwrev. Then, because dw − dwrev ≥ 0,
so it follows that the entropy changes along the isothermal it follows that dqrev − dq ≥ 0 and therefore dqrev ≥ dq. Division
segments of any one cycle (such as a1–a2 and a3–a4) cancel. The 4
The international community has agreed to replace this definition by
entropy change resulting from traversing the overall perimeter of another that is independent of the specification of a particular substance, but
the three cycles is therefore zero. the new definition has not yet (in 2018) been implemented.