Carnot theorem

22nd August 2016

Carnot theorem states that: Of all heat engines operating between a given constant
temperature source and a given constant temperature sink, none has a higher efficiency than
a reversible engine.

In other words, Carnot’s engine is the most efficient of all heat engines operating between
two given fixed-temperature reservoirs. Carnot’s cycle can operate as a heat engine or a heat
pump, as described above, and the cycle consists of four reversible steps. It turns out that
Carnot’s engine is the only perfectly reversible engine that can operate the scenario described
by his theorem. This is because the only perfectly reversible heat transfer interaction
(addition/rejection) with a fixed-temperature reservoir has to be a constant-temperature
(isothermal) process. Replacing the isothermal heat addition and isothermal heat rejection
steps in a Carnot cycle by any other process, like, constant pressure, constant volume, etc.
makes it irreversible. This is due to the fact that heat transfer across finite temperature
difference is not reversible, as proved earlier. A non-isothermal step will either involve heat
transfer across non-negligible temperature difference or will involve a source/sink with
varying temperature, either way violating Carnot’s theorem.

Before we delve into the details of Carnot’s theorem, its implication and a proof of the
theorem, we will discuss a bit of historical development of steam engines, and how it set the
stage for Carnot’s theorem. It will bring out the importance of this crucial idea from Sadi
Carnot and how it then led to the development of thermodynamics.

Historical development leading to Carnot’s theorem

The invention of the steam engine was crucial to development of thermodynamics.

Historically it was very important, as it drove the industrial revolution in England and the rest
of Europe. It was also responsible for the developmet of the entire branch of science that we
call thermodynamics, which was used to understand the working of the steam engine and to
make it better. Interestingly, the birth of steam engine preceded the ideas of thermodynamics
by more than a century, as we will see below.

The first engine by Newcomen in 1712, and a sketch of the same is shown above. They key
components of this engine are boiler, piston-cylinder, wooden beam, weighted pump rod
going down to the mines. They used the boiler to convert water into steam; it fills the
cylinder; piston moves up under the weight of the weighted pump rod. Spray water into the
steam to make it condense immediately. Pressure drops inside the cylinder, and the piston
moves down, the pump moves up and gets water out of the mines. The outside atmospheric
pressure pushes the piston done. Actually it was an Atmospheric engine, and not really a
steam engine, as the steam never did the work in driving the piston.

Some of the early developments were published in a booklet called “The Miners Friend: an
engine to raise water by fire”. The steam engines were actually called fire engine. Before this,
water wheels were used extensively to generate “power”. Who would get the water up to the
tank to run the water wheel? Animals like horses (commonly used unit: horsepower) or
manual labor were used.

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Watt’s engine in 1769 was a significant improvement. Construction was similar to the
Newcomen engine: Boiler, piston-cylinder, wooden beam, weighted pump rod going down to
the mines. Two key differences. First, he introduced a separate condensing chamber, so that
the cylinder itself was not cooled, and then reheated in every cycle. Water was sprayed in the
condenser unit, which cooled the steam and the pressure dropped in the condenser and the
main cylinder. The condenser was kept cold all the time, and the cylinder remained
permanently hot, thus resulting in a significant saving in steam and fuel.

Second, in addition to filling the cylinder with steam, he also injected steam above the piston.
When the pressure in the cylinder dropped because of the cooling spray in the condense, the
hot steam pushed the piston down, in stead of the atmospheric air doing the same job in the
Newcomen engine. This way, the idea was closer to our notion of heat engine, where we add
heat to the system (boil water to make steam) and then the high energy steam (steam) pushes
the piston to do work. It was technically the first steam engine in history.

The interesting thing was that the steam pressure was only slightly higher than ambient
pressure. It was still the sudden cooling of the steam in the condenser, and the resulting drop
in pressure that was really the main driving force behind moving the piston. James Watt was
hugely successful in making efficient engines, but he kept the working details of his steam
engine secret for many many years. Until someone could make an engine that could operate
with much higher pressure of the steam. This eliminated the condenser that was the crucial
component of Watt’s engine.

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The steam engines were often used for pumping water out of mines, and other applications.
They were very large in size, compared to the engines that we see around these days. A
typical heat engine would be like a two- to three-storey building, with a large boiler and a
long cylinder. A large wooden beam connecting the engine with the mine pump was possibly
the most conspicuous part seen in many sketches of the so-called fire engines of that era. The
steam engine was the new machine to generate power and as expected, and much of the
initial development was in England and Scotland, staring with Newcomen engine in 1712 to
Watt’s engine in 1769. They had a monopoly until about 1800.

While the British and the Scottish were making their steam engines, the French were busy
with their revolution and the wars of Napolean. As a result, the initial development and
deployment of steam engines in France was very much delayed. But it was the French who
did some excellent work in understanding and analyzing these “new” engines – how they
work, how to make them more efficient, and so on. In fact, it is the work of Sadi Carnot in
1824 that marks the beginning of this new field of study that we call thermodynamics. He
gave the ideas of the ideal engine, which later became the fundamental concepts used in the
second law of thermodynamics.

It turns out that Carnot’s work in 1824 went unnoticed by the majority of the people. Carnot’s
ideas were reworked and republished by another French engineer, Clayperon in 1834, but
these were also ignored for another decade, until came William Thomson, again from
Scotland, who used Carnot’s ideas to develop the absolute temperature scale, which we will
discuss shortly. Carnot’s ideas were further developed by a German physicist by the name of
Clausius, and it is the work of Thomson (later Lord Kelvin) and Clausius and others that gave

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birth to the new science of thermodynamics in the 1850s. By then the fire engine, either in the
form of Newcomen’s atmospheric engine or Watt’s steam engine, has already been around
for more than a century!!

Proof of Carnot theorem

The theorem can be proven by contradiction. Consider two heat engines, Ei and Er, operating
between two reservoirs (a source at temperature T1 and a sink at temperature T2). Engine Ei
is not reversible, whereas engine Er is reversible. The heat and work interactions are
identified as per the norm followed for heat engines before, with an extra subscript i or r to
denote the irrreversible or the reversible engine. Once again, the Q and W symbols represent
the magnitude of the heat and work interactions, and the usual relations hold.

To contradict Carnot theorem, we assume that the irreversible engine is more efficient than
the reversible one.

which implies that the work output W_i is larger than W_r for the same heat input, i.e. Q_1i
= Q_1r. The two engines chosen can be assumed to take up the same amount of heat from the
source, without loss of generality. This can be achieved, for example, by controlling the mass
flow rate of an engine operating as a flow-through device. Also, the more efficient
irreversible engine rejects less heat than the reversible one, i.e. Q_2i < Q_2r.

Now, if we reverse each step of the reversible heat engine (Er), we get an ideal heat pump
(P_r), which takes up heat Q_2r from the reservoir at lower temperature and delivers Q_1r to

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the hotter body. The magnitudes of the heat transfers remain unchanged, only their directions
are reversed. The same is true for the work interaction, which now becomes an input to the
heat pump, unlike the work output of the reversible heat engine.

Let us then create a new device by combining the irreversible engine E_i and the reversed
heat pump P_r. The combined device (shown by the red box in the figure) produces a net
work W_i – W_r (since W_i > W_r > 0), and hence operates as a heat engine. An amount of
heat equal to Q_2r – Q_2i is taken up from the reservoir at temperature T2, but there is no net
heat transfer to the other body at T1. In fact, we can replace the hot reservoir by a conducting
material to transfer the heat Q_1r delivered by the pump directly to the irreversible heat
engine as Q_1i, as both are equal in magnitude and opposite in direction. This is shown by
the bold line in the figure.

The new combined heat engine, thus, interacts with only one reservoir (the so called sink at
T2) and delivers net work output, which is equal to the heat input to the device. It therefore
violates the second law, which implies that our original assumption about the efficiencies is
not valid. Thus, proving Carnot's theorem, i.e.

The efficiency of the irreversible heat engine has to be lower than the efficiency of the
reversible engine, and equality holds only if the two engines are both reversible, as shown
below.

23rd August 2016

Efficiencies of reversible engines operating between the same source and sink

A corollary of Carnot theorem is that the efficiencies of all reversible heat engines operating
between the same fixed-temperature source and a fixed-temperature sink are identical.

This can be easily proven by an extension of the idea presented above. If you have two
reversible engines Ea and Eb, drawing heat from a source at T1 and a sink at T2, then the
earlier arguments can be advanced again to flip Eb into a reverse cycle representing an ideal
heat pump Pb; see part (a) of the figure below. If we assume

and follow the arguments used for Ei and Pr, it will lead to a contradiction of the second law
for the new device obtained by combining Ea and Pb, i.e.

which produces net positive work Wa-Wb, which is equal to the net heat input from the
reservoir at temperature T2. This would then imply that

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(a)

(b)

The fact that the first engine is also reversible can be used to flip Ea and get a heat pump Pa,
while keeping the second engine Eb as it is. This is shown in part (b) of the figure. The same
arguments can then be applied for the new device obtained by combining Pa and Eb to show
that

The two relations can only be satisfied for the special case, when eta_a = eta_b. In other
words, if there are two reversible heat engines and either one can be reversed into a pump,
then both engines have to have the same efficiency.

To give a realistic picture, one of the engines can be the ideal gas in a piston-cylinder device
we discussed earlier. The other engine can be thought of working with a water-steam mixture,
involving evaporation and condensation processes. As long as they are made to operate
between the same fixed temperatures, both will have the same efficiency. Their efficiency do
not depend on what is the working fluid inside, or how the heat and work interactions are
taking place. In one case, it could be the expansion work extracted from the steam in running
a turbine, and in the other engine, it is the high-pressure gas pushing a piston. Similarly, heat
addition can be by conduction to an ideal gas, or by evaporation of water as the working fluid
into steam.

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Does that mean that the two engines will draw the same amount of heat from the source
and reject identical quantity to the sink and produce exactly the same magnitude of
work output?

Are there other heat engines which are also reversible, but have lower efficiencies?
Do the other heat engines working on Otto cyle, Brayton cycle, etc have the same efficiency?

Absolute temperature scale

The fact that the efficiency of a Carnot cycle depends only on the temperature of the source
and the sink, is used to define a new temperature scale. This scale is independent of the
material or the working fluid used in the device, unlike most other scales that use one or the
other property of a material to measure temperature. For example, a mercury thermometer
relies upon the volumetric expansion of mercury with temperature …

Let us consider a Carnot engine E1 working between a source at T1 and a reservoir at T2

(with T1>T2), drawing heat Q1 from the former and rejecting heat Q2 to the latter and
producing a net work W1 = Q1 – Q2 as output. Then as per Carnot’s theorem, the efficiency
eta_1 is a function of T1 and T2, which can be rewritten in terms of the ratio of heats

Another Carnot engine E2 is set up such that it draws heat Q2 from the reservoir at T2 and
rejects heat Q3 to a third body at T3. The net work output in this case is W2 = Q2-Q3, and
the efficiency is a function of T2 and T3. The ratio of heats taken to rejected can, once again,
be written as

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Now, a third heat engine E3 can be constructed by combining E1 and E2, with a total work
output of W1+W2, heat input of Q1 from the source at T1 and it rejects Q3 to the sink at T3.
The intermediate reservoir can be eliminated and the heat rejected by E1 can be directly
transferred delivered as input to E2. We can then apply Carnot theorem to the combined
engine E3 and write

The above heat ratios can be rearranged to show that

where the left hand side is a function of T1 and T2 alone, and is independent of T3. So, the
functional dependence on T3 should drop out of the right hand side of the equation as well.
This is only possible if the function F is of the form

where phi(T) is any arbitrary function. A similar form holds true for F(T2,T3) and F(T1,T3).
We can substitute these into the earlier equation and verify that the right hand side indeed
becomes independent of T3 as well.

If we employ a change of notation and write the function phi(T) as T’(T), and denote the
value of the function T’(T1) by T’1 and T’(T2) by T’_2. Then

Q1/Q2 = F(T1,T2) = T’1/T’2

This relation between the heats taken up and rejected by a Carnot engine is then used to
define a new temperature scale T’. If we are operating a heat engine between two reservoirs,
then the heat taken up and the heat rejected by the engine are always in this ratio. Of course,
we have to have a Carnot engine for this to be true. But, if it is a Carnot engine, the ratio of
heats will not depend on whether we have air as a perfect gas, or water-steam combination, or
any thing else as the working fluid. The ratio in independent of the nature of the fluid and its
properties. This is a big advantage over all the other thermometers which rely on the thermal
property of the liquid or gas to measure temperature. This is why this temperature scale is
called the Absolute temperature scale.

The Kelvin and Rankine scales

We will present two absolute scales of temperature – the Kelvin scale and the Rankine scale.
Let us consider two reservoirs at temperatures that are familiar to us – one with boiling water,
and the second with freezing water. If we operate a Carnot engine between these two
reservoirs, and conduct an experiment to measure the heat and work interactions, it turns out
that the ratio of heat taken up to the heat rejected comes out to be

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 Q2/ Q1 = 0.732 = T’2/T’1.

This gives us a ratio of the two temperatures of the new scale. Now, if we say that there are
100 degrees (like the centigrade scale) between the boiling and freezing points of water, then

T’1 – T’2 = 100

We can now solve for the two temperatures, and we get the absolute temperature
corresponding to the Centigrade scale, where

T’1 = 373.15 and T2 = 273.15

And call this as the Kelvin scale. A similar exercise for the Farenheit scale, with

T’1 – T2 = 212 – 32 = 180

Gives us the Rankine scale of absolute temperature.

T’1 = 672 deg R and T2 = 492 deg R

The conversions between the regular and the absolute scales are thus given by

C + 273.15 = K and F + 460 = R

The experiment described above is a perfect way to determine the absolute scale, at least in
principle. However, practical difficulties in creating a perfect Carnot engine makes this
method inaccurate. There are alternate ways to use the ideas of second law of
thermodynamics to arrive at the absolute scale, but they are outside the scope of the current
level of discussion in this course.

25th August 2016

Creating the absolute temperature scale

Once we have the two markers of absolute temperature, namely, boiling point of water at 373
K or 672 R and the melting point of ice at 273 K or 492 R, we go on to create the entire scale
in terms of the sub-divisions. There weould be 100 sub-divisions on the Kelvin scale and 180
of them o nth Rankine scale.

To achieve this, we set up a series of heat engines, such that the heat rejected by the first is
taken up by the second, and the heat rejected by the second is taken up by the third, and so
on. Also, we pick the engines such that they have identical work output, i.e.

W = Q1 – Q2 = Q2 – Q3 = …

For each engine, we can write the ratios of heat taken up to that rejected in terms of the
abosolute temperatures at which the heat addition and rejection takes place for each engine.

Q1/Q2 = T’1/T’2, Q2/Q3 = T’2/T’3 , etc.

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We can rearrange this to get

Q1/T’1 = Q2/T’2 = Q3/T’3 = …

Essentially, we have Q_i = const. x T_i, which when substituted in the work relation above
gives

T’1 – T’2 = T’2 – T’3 = … = Delta T’

In other words, the temperature difference across each engine is identical. Now, if we have
100 such small engines set up in series between the two temperature markers of 373 K and
273 K, then essentially we created the Kelvin scale with 100 divisions that we started out to
do.

The question now is whether each degree of the Kelvin scale matches up with the
corresponding increment of the Celsius scale, on which it is based. There is no guarantee of
that, even though we can say for sure that the two temperature markers we set definitely
match up on the two scales. The calibration of the Celsius scale is based on the coefficient of
thermal expansion of mercury, where as the calibration of the Kelvin scale is based on the
measurement of work output by each small engine put in series. The work output can be
interpreted as raising a weight against gravity, as shown in the figure below. Fortunately,
there is negligible difference between the Kelvin and Celsius scales, and they can be used
interchangeably using the formula presented above.

The fact that the absolute scale is based measurement of mechanical work turned out to be a
great advantage, especially at a time in history that scientists were struggling to identify

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which temperature scale and which thermometer is the best or most accurate. Different
thermometers were constructed using distilled water, purified alcohol, various gases, and
even oil extracted from whales. However, the measurements were inherently determined by
the thermal properties of the material used in each thermometer. In addition, there was
enough confusion about the very nature of heat and the calorific values of different materials.

It was therefore a significant achievement to bypass all these uncertainties, and create a
temperature measurement solely based on mechanical work. The nature of mechanical work
and changes in potential and kinetic energies were much better understood at that time,
thanks to the well-established Newton’s laws of motion. All we have to do is to make sure
that each engine raises the same weight by the same height, and we have equal increments on
the absolute temperature scale between the two markers of boiling and melting points of
water/ice.

Kelvin (or William Thomson) came up with this idea of an absolute scale of temperature in
1845, soon after he finished his undergraduate studies at ???. It is reported that he was trying
out things even before he graduated, with experiments conducted in his undergraduate
laboratories.

The question remains whether this scale is linear or not !! Possibly it is, because unlike
other thermometers based on mercury, etc., here we DO NOT rely on the assumption that the
thermal property of the material to vary linearly with temperature.

Absolute zero temperature

In the experiment that we proposed to construct the absolute scale of temperature, let us say
that we start with an amount of heat Q1 taken from the reservoir at temperature T’1, some of
it is converted to work and the remaining transferred to the next engine as Q2. We thus have

Q2 = Q1 – W

As earlier, if we start with a reservoir at T’1 = 100 deg C = 373 K, and operate a heat engine
with work output such that there is a drop of 1 deg across the engine. For a number of
identical engines put in series, we have

Q3 = Q2 – W = Q1 – 2W
Q4 = Q3 – W = Q1 – 3W
……
Qn = Q1 – (n-1)*W

The work output of a set of n engines will be nW, and it is easy to see that

Q1 > Q2 > Q3 > Q4 > …

Now, if we continue this process, until all the initial amount of heat Q1 is exhausted, i.e. nW
= Q1. In other words, we have 373 of such engines lined up in series, then Qn+1 = 0. The
engine obtained by combining all the individual Carnot engines E1, E2, … En would have a
heat input of Q1, a work output of nW and a zero heat rejection. This would qualify as a

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perpetual motion motion of the second type, and hence is not possible as per the second law
of thermodynamics. It is interesting to note that the last engine in the series that takes up

Q_n = Q1 – (n-1)*W = W

amount of heat and gives an equal amount of work output W is NOT POSSIBLE. All the
other engines prior to the last one DO NOT violate the second law.

The efficiency of the combined Carnot engine will be 1, as all the heat input is converted into
work, and no heat is rejected. In terms of absolute temperature scale, this is given by

Eta = W/Q1 = 1 – Q_n+1/Q1 = 1 – T’n+1/T’1

The same is true for the last engine in the series.

Eta_n+1 = W/Q_n = 1 – Q_n+1/Q_n = 1 – T’_n+1/T’_n

In the limit of the heat rejected going to zero, the temperature T’n+1 tends to zero. It is the
only way we can satisfy the relations

Q1/T’1 = Q2/T’2 = Q3/T’3 = … = Qn+1/T’n+1

for every engine in the series, as well as the combined Carnot engine.

Thus, the zero temperature on the absolute scale cannot be reached by any process, without
violating second law of thermodynamics. It represents the lowest temperature that can only
be approached in a limit, and is the absolute bottom of the temperature scale. It is a
temperature where all molecular activity ceases, and NO temperature below this is possible.
This is one more reason to call the new temperature scale the absolute temperature scale.

This leads us to the Third law of thermodynamics, which states that it is impossible by any
procedure, no matter how idealized, to reduce a system to absolute zero temperature in a
finite number of operations. The third law is primarily applicable to problems of chemical
equilibrium, which is not the focus of the current text.

Ideal gas temperature vs. Absolute temperature

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Let us come back to the Carnot cycle example which has an ideal gas filled inside a piston
cylinder arrangement, operating between two reservoirs at temperatures Ta and Tb. Note that
we are back to the normal temperature scale, and not using the absolute scale defined above.
The cycle in terms of the four well-defined processes is shown on a p-V diagram, where a-d
are the four states corresponding to the beginning and end points of the four processes.

For the isothermal heat addition and isothermal heat rejection steps, we had shown earlier
that

Noting that Vb > Va and Vc > Vd, we have

such that

Now, considering the reversible adiabatic work step b-c, we can write

which along with the perfect gas law (pv = RT) gives

On integration from b to c, we get

A similar development for the reversible adiabatic compression step d-a gives us

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The above two relations can be compared to get

which then directly leads to

Here the last equality is a result of the definition of the absolute scale based on the ideas of
Carnot cycle. We can thus say that the temperature T that we have been using in the ideal gas
law is proportional to the absolute temperature derived from the second law of
thermodynamics. Fixing a common point on the two scales then will make them identical.
The common point is usually taken as the triple point of water, Tref = T’ref = 273.15 K,
which renders the ideal gas temperature identical to the absolute temperature on the Kelvin or
Rankine scales. The fact that the two scales are numerically equal makes it possible to
directly measure the absolute temperature using a gas thermometer.

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