Second law of thermodynamics

We go back to Joule's paddle wheel experiment, where work is done by lowering a weight to stir
the water in a container. This raises the temperature (energy) of the water, once the water is allowed
to come to rest. Heat is then transferred from the water to an ice bath, until the system (water)
comes back to its original temperature. In this cyclic process with identical initial and final states of
the system, we have

All the work done on the system is converted to heat and we can write

where the arrow indicates the direction of energy conversion, from work to heat.

In a reverse experiment, if we heat the water, and try to get work out of it, then not all the heat can
be converted into work.

We will have to supply more heat to the water than the work output and some of the heat has to be
rejected to bring the water (system) back to its initial state, to complete the cycle. In fact, this
reverse cycle is much more relevant to us, because of the very nature of engines (whether IC or gas
turbine) which add heat by burning fuel and try to extract as much mechanical work out of the gas.
The question of how much heat is to be added to get the desired amount of work and what is the
minimum amount of heat to be rejected are most important to an engineer.

We also note that the rejection of heat is not the same as heat leakage to the outside environment, or
the frictional losses within a machine that tend to heat up the gas. These losses are due to
irreversibilities in a system, as we will soon discuss. The requirement that some heat has to be
rejected is true for perfectly reversible processes, i.e. to say that heat cannot be completely
converted to work even in the best possible scenario of an idealized system with no losses.
Similarly, in a flow-through device, there has to be a continuous rejection of heat for the engine to
generate work from a continuous flow of the working fluid through its components.

Work is regarded as a high-grade energy transfer and heat is a low-grade energy transfer.
Complete conversion of high-grade to low-grade is possible, but the reverse conversion of low-
grade to high-grade is not entirely possible. Second law of thermodynamics is a generalization and
formalization of this idea. It tells us which processes are possible and which are not. For example,
heat transfer from a high temperature to a low temperature body is possible, just like fluid flows
from a high pressure to a low pressure region. The reverse processes do not happen spontaneously,
and additional work is required to make them happen.

Before we state the second law and look at its implications, we need to define two terms – a heat
engine and a heat pump – that are used extensively in the discussion of the second law. The heat
engine is an idealization, or an abstract form, of different kinds of engines that are operational in
real life. The heat pump is an idealization of refrigerator or an air-conditioner. Both the heat pump
and the heat engine are cyclic processes, and are inherent in the definition of the second law of
thermodynamics.

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HEAT ENGINE

A heat engine is defined as a system that operates on a cycle, where it takes up heat, does work and
rejects part of the heat. The thermodynamic cycle is called the heat engine cycle. The function of a
heat engine is to generate work continuously at the expense of heat input to the system.

For example, the gas enclosed in a piston-cylinder arrangement can be easily made to work as a
heat engine. First, heat Q1 is transferred to the system, which raises the temperature and pressure
inside the cylinder. The gas is then allowed to expand, and it does work W_E on the surrounding by
displacing the piston. Next, heat Q2 is rejected to the surroundings and compression work (W_c) is
done on the gas to bring the system back to its initial state.

A gas turbine engine also works in a similar way. It is a flow-through device, where we take a
parcel of air moving through the different components of the engine as our system. Ambient air is
first energised by doing compression work (W_c) on it. Fuel is added to the high pressure and high
temperature gas, and heat (Q1) is added in the combustor. The hot gas passes through a turbine
where the expansion work (W_E) is used to drive the compressor. The gas is further expanded in
the nozzle to produce thrust power, or equivalently, propulsive work (W_p). Finally, the gas and its
heat content (Q2) is rejected to the atmosphere.

It is called an open cycle, because the same fluid is not brought back to its initial state, as in a
complete cycle. In stead, the parcel of hot gas is rejected and an equivalent amount of freestream air
is taken into the engine. The ambient air that is taken in at the beginning of each engine cycle is at
the same temperature and pressure, making the starting point the same on a p-V diagram. This
effectively simulates the heat rejection step, if the same fluid was recycled back into the engine.
Reusing the air to burn more fuel is not very effective, and cannot be done infinitely to continuously
generate power. A fresh charge of fluid is required for all devices which involve combustion to heat
the gas directly. The engine is thus idealized as a cyclic process, even though the same mass of air
does not go through the entire cycle to come back to its initial state. Applying thermodynamic
analysis to a cyclic process is far easier than otherwise, as we will find out soon.

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The net work output of a heat engine is the difference between the work done by the system and the
work done on the system during the entire cycle, which is equal to W_E + W_P – W_C in the case
of a gas turbine engine. For other cases, W_P = 0 in land-based applications of the gas turbine
engine, as well as in the piston-cylinder example presented above. The net heat input to the system
is the difference between the heat added and the heat rejected to the surroundings in each turn of the
cycle. In the absence of a change in the internal energy or total energy of the gas working in a
thermodynamic cycle, we have

Also note that there are other applications of a gas turbine that do not involve generation of a high-
speed jet for aircraft propulsion. These include land-based power generation and naval applications
to power ships; small gas turbine engines are also used in battle tanks. (More details are available in
a document posted on moodle.) Naturally, these devices have a compressor, combustor and turbine,
and not the nozzle or diffuser, as in an aircraft engines. In such cases, W_p = 0 and the entire
amount of useful work is extracted by the turbine, whose job is to not only drive the compressor,
but also provide useful power for the specific purpose of the machine.

The efficiency of a heat engine is calculated as the ratio of the net work output to the heat input to
the system., i.e. what fraction of the heat added to the gas can be recovered back as useful work.

This is often called the thermal efficiency of an engine. There are other types of efficiencies, like
mechanical efficiency, propulsive efficiency, etc. that we will learn later.

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Finally, a heat engine is schematically shown as working between two reservoirs, a source at a
higher temperature T1 and a sink at a lower temperature T2. The system is represented by a
rectangular box and the circle inside the box indicates the cyclic nature of a heat engine. The arrows
into and out of the system, as usual, highlight the different heat and work interactions.

RESERVOIR

A reservoir is a large enough body which either supplies heat or absorbs the rejected heat from an
engine. It is assumed to have a large enough heat capacity that the amount of heat taken up the
engine or the amount rejected by the engine does not make any appreciable difference to its
temperature. An easy example is the ambient atmosphere, where the heat rejected in the form of
exhaust gases just gets diffused, without changing the properties of the atmosphere itself. Ofcourse,
there is the indirect effects via global warming that is definitely of concern. Heat addition by
burning fuel can also be considered as a reservoir, not because of its size, but due to the fact that we
are continuously injecting fuel, mixing it with the air and burning it to release heat. It is a un-ending
process and in a steady state, it can be assumed to maintain the temperature of the combustion
chamber, and thus simulate a constant temperature reservoir as the source of heat for an engine.

HEAT PUMP

A heat pump is a device, which operating in a thermodynamic cycle, extracts heat Q2 from a body
at lower temperature T2 and delivers heat Q1 to a body at higher temperature T1. The device
requires net external work W to be performed on the system to pump heat from a cooler to a hotter
body.

Schematically, it is very similar to the heat engine, but the direction of the heat flows Q1 and Q2
are now opposite. The work interactions are similar to a heat engine, in the sense that we need both
compression and expansion steps. The difference is that the compression work done on the system
is higher in magnitude than the expansion work extracted from the working fluid. Thus, there is a
net work input to the system, as opposed to a net work output in a heat engine.

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The most common example of a heat pump is a refrigerator, which operates between the outside
environment at a temperature T1 = 30 deg C and inside of the refrigerator maintained at a
temperature T2 = 0 deg C. The working fluid is called the refrigerant, which extracts heat Q2 from
the inside (air and the food items). This is equal to the heat lost from the refrigerator, by for
example, opening the door, and is achieved by evaporating the refrigerant. The vapor is then
compressed to a higher pressure and temperature – an amount of work W_C is done on the system.
Next, the refrigerant condenses at the higher temperature T1, rejecting heat Q2 to the ambient air in
the room. The liquid refrigerant is then expanded to reduce its temperature to T2 – the equivalent
expansion work is W_E – and the whole cycle repeats by evaporation at T2.

Applying first law of thermodynamics to the heat pump cycle, we get

where the absolute value notation is omitted for convenience. Thus, Q1 and Q2 represent the
magnitude of the heat interactions from the respective reservoir. The sign as per the sign convention
is applied separately and is not included in the Q's. The same thing is true for the work interactions
W_C and W_E and for the net work input to the system W_net. All are taken as positive numbers,
and the appropriate signs are assigned to them in the equation. On rearranging, we can write

It is now easy to see that for Q2 > 0 and W_net > 0 (which are always true),

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Other examples of heat pump include room air conditioner, which in a manner similar to a
refrigerator, pump heat from the cooler inside of a room to the hotter outside summer atmosphere.
An opposite example would be that of a device that heats a house during winter months, when the
outside temperature (sometimes well below 0 deg C) is much lower than the indoor air maintained
at say 25 deg C. For such a device, it is important to know how much heat is delivered inside the
house to keep it warm, for a given work input to the heat pump. In other words, what is the
maximum heating possible per unit work input, and a coefficient of performance of the heat pump
is defined as:

Unlike the efficiency of a heat engine that is always less than 1, the parameter COP is always
greater than one. A higher value corresponds to a more efficient heat pump. The definition of COP
for a heat pump is exactly the inverse of the efficiency for a heat engine.

Why always a cycle? Because many a times, the working fluid is not freely available, unlike air or
water, and it has to be recycled to repeatedly run in the machine. An example is the coolant in a
room air-conditioner or the refrigerant in a refrigerator.

Moodle questions:

What would happen to the working of an air conditioner if the outside temperature is below the
room temperature? Will it work as a heater?

Similarly, how will a refrigerator work if kept in a room with sub-zero temperature?

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Statement of Second law

The second law of thermodynamics for heat engines state that

it is impossible for a heat engine to produce net work in a complete cycle, if it exchanges
heat only with bodies at a single fixed temperature.

This is called the Kelvin-Planck statement of the second law, and it based purely on experience
and experimentation. Like the other laws of thermodynamics, this is also empirical and cannot be
proven.

For a heat engine defined earlier, we had seen that

If Q2 = 0, it will violate the second law statement presented above, i.e. to generate a net work by
taking up heat from the source at T1. This is called a perpetual motion machine of the second kind
(PMM2), and is not possible as per the second law.

What is a perpetual motion machine of the first kind (PMM1)?

An alternate form of the second law as applicable to heat pumps is called the Clausius statement:

it is impossible to construct a device which, operating in a cycle, will produce no effect

other than the transfer of heat from a cooler body to a hotter body.

Heat flows spontaneously from a body at higher temperature to another body at a lower
temperature. Reverse flow can only be achieved by a system at the cost of some external work done
on it. Once again, the statements is based purely on observations and nothing has been found to
contradict them.

The two statements of the second law are equivalent and it can be shown that violating one will
violate the other.

If we consider a situation where a heat pump (P) operates between a hot source at temperature T1
and a cold sink at a lower temperature T2. The heat and work interactions are Q'_1, Q'_2 and W', as
shown in the figure below. Let us start with violating Clausius statement for the pump, and assume
that the device operates without any work input, i.e. W' = 0. The heat taken up by the heat pump
from the cold body is therefore equal to the heat delivered to the hotter body, both equal to Q'_1.
We now operate a heat engine (H.E.) between the same reservoirs, and make sure that it follows the

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Kelvin-Planck statement. It is shown in the figure below in terms of the heat interactions Q1 and
Q2, with Q1 > Q2 and the net work output W = Q1 – Q2 > 0.

We now adjust the working fluid in the engine and its flow rate such that the heat delivered by the
pump Q'_1 is equal to the heat taken up by the engine Q1. We can therefore replace the hot
reservoir with just a conductor that transfers Q'_1 = Q1 from the heat pump directly to the heat
engine, with out storing any energy. Thus there is no heat exchange with the hot body and it is
effectivly eliminated from the operation of the heat pump and the heat engine. We now consider the
new device that is a combination of the heat pump and the original heat engine. This combined
device exchanges heat only with a single body, i.e. the cold reservoir. The net heat transfer is Q'_2-
Q2 = Q'_1 – Q2 = Q1 – Q2 > 0, taken up from the cold body, and is converted to work output W =
Q1 - Q2. The new device is therefore a heat engine (shown in part (b) of the figure below), but it
violates the Kelvin-Planck statement of the second law.

(a) (b)

In this case, we start with violating the Clausius statement and end up violating the Kelvin-Planck
statement. The reverse can also be proved, i.e. if we start with a violation of the Kelvin-Planck
statement, it will eventually result in a violation of the second law for heat pumps as well. We also
note that although the second law of thermodynamics itself is empirical and cannot be proven, it can
be used to prove why certain processes are possible and other are not possible. In that manner,
thermodynamics based on these laws has a bit of abstractness similar to mathematics.

Reversibility of a process

A reversible process is one in which the system can retrace the exact path, if the direction of the
fore or the potential is reversed. A reversible process is thus a quasi-static process (infinitely slow)
in which the system is in a state of thermodynamic (thermal, mechanical and chemical) equilibrium
at every intermediate point (between the end points) along the process. A reversible process is
carried out by infinitesimal changes in temperature, pressure and composition.

Irreversibility can be caused by, either a lack of equilibrium, due to finite temperature or pressure
difference or due to dissipative effects like friction, electric heating, etc. All processes in nature and
engineering devices have dissipative effects and/or have finite differences in the driving potential.
They do not occur over infinite time duration, and are therefore irreversible. Studying an equivalent
reversible process tells us about the best possible behavior of the system, in the limit of zero losses

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and a perfect performance. This often maximizes the output of the system and hence is an ideal
benchmark against which real systems can be compared.

The second law of thermodynamics enables us to identify which processes are reversible and which
are not. We consider two commonly encountered processes in propulsion application, to show that
the reverse processes violate the second law.

Heat transfer through a finite temperature difference

Let there be a source at temperature Ta and a sink at temperature Tb, such that Ta > Tb and an
amount of heat Qab flows spontaneously between them when connected via a conducting material.
We operate a heat engine between the two reservoirs, as per the Kelvin-Planck statement of the
second law of thermodynamics. It takes up Q1 amount of het from the source, delivers work W and
rejects heat Q2 to the sink. Let us assume that Q2 is identical in magnitude to Qab.

(a) (b)

If we now reverse the flow of heat Qab to Qba, keepting the magnitude the same, then the sink can
be eliminated by feeding the heat Q2 rejected in the engine cycle straight to Qba. The overall cycle
now exchanges heat Q1 with only one reservoir (at Ta) and produces work output W. It is therefore
in violation of the K-P statement of the second law, which implies that the reverse process of heat
flowing from the cooler body at Tb to the hotter body at temperature Ta is not possible. In other
words, heat transfer through a finite temperature difference is an irreversible process.

The same arguments cannot be made if the temperature difference between the source and the sink
was negligible. Thus, heat transferred across an infinitesimal temperature difference is reversible.

Flow caused by finite pressure difference

We consider an insulated container with two compartments separated by a thin diaphragm

containing a gas at two different pressures. When the diaphragm is ruptured, high pressure gas
spontaneously flows to the low pressure until the pressure equalizes in the whole container. To
prove that the reverse process is not possible, we set up a turbine between the two compartments
and extract work W from the flow set up from the high-pressure to the low-pressure side through
the turbine. The work is generated at the expense of the extra enthalpy of the gas stored in
compartment A.

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and work can be generated as long as the pressure p_A is higher than the pressure in compartment
B.

Let us assume that the reverse process of gas going from compartment B to compartment A is
possible by rupturing the diaphragm. Some amount of heat Q must be added to restore the gas back
to its original high-pressure state in compartment A, and a balance of energy shows that

The overall cycle represents a heat engine that absorbs heat from a source and delivers all of it as
work output. This is in violation of the K-P statement of second law. Therefore, the reverse flow
from low to high pressure is not possible. In other words, flow set up by a finite difference in
pressure is not reversible.

Similarly, it can be shown that the processes involving dissipative effects are not reversible. These
processes involve work done without equivalent increase in the potential or kinetic energy of the
system. The work done is generally converted into the internal energy and raises the temperature of
the body. If we assume the reverse processes to be feasible, then it would amount to violating the
second law of thermodynamics.

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