Carnot Engine

Introduction:
A Carnot heat engine is an engine that operates on the reversible Carnot cycle. The basic model
for this engine was developed by Nicolas Léonard Sadi Carnot in 1824. The Carnot engine
model was graphically expanded upon by Benoît Paul Émile Clapeyron in 1834 and
mathematically elaborated upon by Rudolf Clausius in 1857 from which the concept of entropy
emerged.
Every thermodynamic system exists in a particular state. A thermodynamic cycle occurs when
a system is taken through a series of different states, and finally returned to its initial state. In
the process of going through this cycle, the system may perform work on its surroundings,
thereby acting as a heat engine.
A heat engine acts by transferring energy from a warm region to a cool region of space and, in
the process, converting some of that energy to mechanical work. The cycle may also be
reversed. The system may be worked upon by an external force, and in the process, it can
transfer thermal energy from a cooler system to a warmer one, thereby acting as a refrigerator
or heat pump rather than a heat engine.

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Carnot's Diagram
In the adjacent diagram, from Carnot's 1824 work, Reflections on the Motive Power of Fire,
there are "two bodies A and B, kept each at a constant temperature, that of A being higher than
that of B. These two bodies to which we can give, or from which we can remove the heat
without causing their temperatures to vary, exercise the functions of two unlimited reservoirs
of caloric. We will call the first the furnace and the second the refrigerator.” Carnot then
explains how we can obtain motive power, i.e., “work”, by carrying a certain quantity of heat
from body A to body B.

Axial cross section of Carnot's heat engine. In this diagram, abcd is a cylindrical vessel, cd is
a movable piston, and A and B are constant–temperature bodies. The vessel may be placed in
contact with either body or removed from both (as it is here).
Modern Diagram

Carnot engine diagram (modern) - where an amount of heat QH flows from a high temperature
TH furnace through the fluid of the "working body" (working substance) and the remaining
heat QC flows into the cold sink TC, thus forcing the working substance to do mechanical work
W on the surroundings, via cycles of contractions and expansions.

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The previous image shows the original piston-and-cylinder diagram used by Carnot in
discussing his ideal engines. The figure at right shows a block diagram of a generic heat engine,
such as the Carnot engine. In the diagram, the “working body” (system), a term introduced by
Clausius in 1850, can be any fluid or vapor body through which heat Q can be introduced or
transmitted to produce work. Carnot had postulated that the fluid body could be any substance
capable of expansion, such as vapor of water, vapor of alcohol, vapor of mercury, a permanent
gas, or air, etc. Although, in these early years, engines came in a number of configurations,
typically QH was supplied by a boiler, wherein water was boiled over a furnace; QC was
typically supplied by a stream of cold flowing water in the form of a condenser located on a
separate part of the engine. The output work W here is the movement of the piston as it is used
to turn a crank-arm, which was then typically used to turn a pulley so to lift water out of flooded
salt mines. Carnot defined work as “weight lifted through a height”.
Carnot Cycle

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 Figure 1
The Carnot cycle when acting as a heat engine consists of the following steps:
1. Reversible isothermal expansion of the gas at the "hot" temperature, TH (isothermal
heat addition or absorption). During this step (A to B in Figure 1) the gas is allowed to
expand and it does work on the surroundings. The temperature of the gas does not
change during the process, and thus the expansion is isothermic. The gas expansion is
propelled by absorption of heat energy Q1 and of entropy ∆𝑺𝑯 = 𝑸𝑯 ⁄𝑻𝑯 from the
high temperature reservoir.

2. Isentropic (reversible adiabatic) expansion of the gas (isentropic work output). For this
step (B to C in Figure 1) the piston and cylinder are assumed to be thermally insulated,
thus they neither gain nor lose heat. The gas continues to expand, doing work on the
surroundings, and losing an equivalent amount of internal energy. The gas expansion
causes it to cool to the "cold" temperature, TC. The entropy remains unchanged.

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 3. Reversible isothermal compression of the gas at the "cold" temperature, TC. (isothermal
heat rejection) (C to D on Figure 1) Now the surroundings do work on the gas, causing
an amount of heat energy Q2 and of entropy ∆𝑺𝑪 = 𝑸𝑪 ⁄𝑻𝑪 to flow out of the gas to the
low temperature reservoir. (This is the same amount of entropy absorbed in step 1.)

4. Isentropic compression of the gas (isentropic work input). (D to A on Figure 1) Once

again the piston and cylinder are assumed to be thermally insulated. During this step,
the surroundings do work on the gas, increasing its internal energy and compressing it,
causing the temperature to rise to TH. The entropy remains unchanged. At this point the
gas is in the same state as at the start of step 1.

Carnot's Theorem
Carnot's theorem is a formal statement of this fact: No engine operating between two heat
reservoirs can be more efficient than a Carnot engine operating between the same reservoirs.

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real ideal engines (left) compared to the Carnot cycle (right). The entropy of a real material
changes with temperature. This change is indicated by the curve on a T-S diagram. For this
figure, the curve indicates a vapor-liquid equilibrium (See Rankine cycle). Irreversible systems
and losses of heat (for example, due to friction) prevent the ideal from taking place at every
step.

Explanation
This maximum efficiency η is defined as above:
W is the work done by the system (energy exiting the system as work),
QH is the heat put into the system (heat energy entering the system),
TC is the absolute temperature of the cold reservoir, and
TH is the absolute temperature of the hot reservoir.
A corollary to Carnot's theorem states that: All reversible engines operating between the same
heat reservoirs are equally efficient.
It is easily shown that the efficiency η is maximum when the entire cyclic process is a reversible
process. This means the total entropy of the total system consisting of the three parts: the
entropy of the hot furnace, the entropy of the "working fluid" of the Heat engine, and the
entropy of the cold sink. The total entropy of the system remains constant when the "working
fluid" completes one cycle and returns to its original state. (In the general case, the total entropy
of this combined system would increase in a general irreversible process).
Since the "working fluid" comes back to the same state after one cycle, and entropy of the
system is a state function; the change in entropy of the "working fluid" system is 0. Thus, it
implies that the total entropy change of the furnace and sink is zero, for the process to be
reversible and the efficiency of the engine to be maximum. This derivation is carried out in the
next section.
The Coefficient of Performance (COP) of the heat engine is the reciprocal of its efficiency.
Efficiency of Real Heat Engines

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In a complete cycle of Carnot’s heat engine, the gas traces the path abcd. The important
question is: what fraction of the heat supplied from the hot reservoir (along the top isotherm)
is turned into mechanical work? This fraction is called the efficiency of the engine.
The work output along any curve in the (P, V) plane is just ∫ 𝑃𝑑𝑉 the area under the curve, but
it will be negative if the volume is decreasing! So the work done by the engine during the hot
isothermal segment is the area abfh, then the adiabatic expansion adds the area bcef, but as the
gas is compressed back, the wheel has to do work on the gas equal to the area cdge as heat is
dumped into the cold reservoir, then dahg as the gas is recompressed to the starting point.
The bottom line is that:
the total work done by the gas is the area of the circuit abcd
that is, the area of the curved “parallelogram” in the (P, V) graph above.
We could compute this area by finding ∫ 𝑃𝑑𝑉 for each segment, but that is unnecessary on
completing the cycle, the gas is back to its initial temperature, so has the same internal energy.
Therefore, the work done by the engine must be just the difference between the heat supplied
at TH and that dumped at TC.
Now the heat supplied along the initial hot isothermal path ab is equal to the work done along
that leg, (from the paragraph above on isothermal expansion):

and the heat dumped into the cold reservoir along cd is

The difference between these two is the net work output. This can be simplified using the
adiabatic equations for the other two sides of the cycle:

Dividing the first of these equations by the second,

and using that in the preceding equation for QC,

So for the Carnot cycle the ratio of heat supplied to heat dumped is just the ratio of the absolute
temperatures!

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Remember this: it’ll be important in developing the concept of entropy.
The work done can now be written simply:

Therefore, the efficiency of the engine, defined as the fraction of the ingoing heat energy that
is converted to available work, is

These temperatures are of course in degrees Kelvin, so for example the efficiency of a Carnot
engine having a hot reservoir of boiling water and a cold reservoir ice cold water will be (1-
273/373) =0.27, just over a quarter of the heat energy is transformed into useful work. This is
the very same expression Carnot found from his water wheel analogy.
After all the effort to construct an efficient heat engine, making it reversible to eliminate
“friction” losses, etc., it is perhaps somewhat disappointing to find this figure of 27% efficiency
when operating between 0 and 100 degrees Celsius. Surely we can do better than that? After
all, the heat energy of hot water is the kinetic energy of the moving molecules, can’t we find
some device to channel all that energy into useful work? Well, we can do better than 27%, by
having a colder cold reservoir, or a hotter hot one. But there’s a limit: we can never reach
100% efficiency, because we cannot have a cold reservoir at TC=0K and, even if we did, after
the first cycle the heat dumped into it would warm it up!
Carnot Engine has maximum Efficiency(Prove)
For a real heat engine, the total thermodynamic process is generally irreversible. The working
fluid is brought back to its initial state after one cycle, and thus the change of entropy of the
fluid system is 0, but the sum of the entropy changes in the hot and cold reservoir in this one
cyclical process is greater than 0.
The internal energy of the fluid is also a state variable, so its total change in one cycle is 0. So
the total work done by the system W, is equal to the heat put into the system QH minus the heat
taken out QC.

……. (Eq. 1)
For real engines, sections 1 and 3 of the Carnot Cycle; in which heat is absorbed by the
"working fluid" from the hot reservoir, and released by it to the cold reservoir, respectively; no
longer remain ideally reversible, and there is a temperature differential between the temperature
of the reservoir and the temperature of the fluid while heat exchange takes place.

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During heat transfer from the hot reservoir at TH to the fluid, the fluid would have a slightly
lower temperature than TH, and the process for the fluid may not necessarily remain isothermal.
Let ∆𝑺𝑯 be the total entropy change of the fluid in the process of intake of heat.

where the temperature of the fluid T is always slightly lesser than TH, in this process.
So, one would get

Similarly, at the time of heat injection from the fluid to the cold reservoir one would have, for
the magnitude of total entropy change of the fluid in the process of expelling heat:

where, during this process of transfer of heat to the cold reservoir, the temperature of the fluid
T is always slightly greater than TC.
We have only considered the magnitude of the entropy change here. Since the total change of
entropy of the fluid system for the cyclic process is 0, we must have

The previous three equations combine to give:

……. (Eq. 2)
Equations (1) and (2) combine to give

Hence,

Where 𝜼 = 𝑾⁄𝑸𝑯 is the efficiency of the real engine, and ηI is the efficiency of the Carnot
engine working between the same two reservoirs at the temperatures TH and TC. For the Carnot
engine, the entire process is 'reversible', and Equation (2) is an equality.
Hence, the efficiency of the real engine is always less than the ideal Carnot engine.

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Equation (2) signifies that the total entropy of the total system (the two reservoirs + fluid)
increases for the real engine, because the entropy gain of the cold reservoir as QC flows into it
at the fixed temperature TC, is greater than the entropy loss of the hot reservoir as QH leaves it
at its fixed temperature TH. The inequality in Equation (2) is essentially the statement of the
Clausius theorem.
According to the second theorem, "The efficiency of the Carnot engine is independent of the
nature of the working substance".
Alternative Theorem
The Carnot engine or the Carnot cycle is important because it describes a heat engine that uses
reversible processes that can be handled theoretically.
The efficiency of a Carnot engine or any reversible heat engine is the greatest that is possible
to achieve. Call the efficiency of the Carnot engine ηC. Then suppose the efficiency of some
real heat engine, ηR, is greater than that of the Carnot engine,
ηR > ηC
Then we could use the real heat engine to power a Carnot cycle heat pump. If ηR > ηC, then the
net result would be the transfer of heat from a cold temperature to a high temperature. But this
violates the Second Law.

Qh is the heat absorbed from the high temperature by the real heat engine and Qh ' is the heat
expelled to the high temperature by the Carnot cycle heat pump. For this analysis, both Qh and
Qh ' are intrinsically positive.
ηR > ηC

W/Qh > W/Qh'

1/Qh > 1/Qh'

Qh < Qh'

Qh' > Qh

Qh-net = Qh' - Qh

Qh-net > 0

Since we believe the Second Law, that means our assumption that ηR > ηC is wrong.

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