MODULE 4

BASIC THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

Terminologies related to Second Law
• Thermal Energy Reservoir: It is reservoir or a body with a relatively large thermal energy
capacity that can supply or absorb finite amounts of heat without undergoing any change in
temperature.
• Heat Source: It is a reservoir that supplies energy in the form of heat. It a reservoir at a higher
temperature.
• Heat Sink: It is a reservoir that absorbs energy in the form of heat and a reservoir at lower
temperature.
• Heat Engine: It is a device that converts heat to work. Work can easily be converted to other
forms of energy, but converting other forms of energy to work is not that easy. In heat engine,
heat is transferred from high temperature level to low temperature level. It requires special
devices called Heat Engine. E.g: Car engine, Gas turbine, Steam power plant.
• Reverse Heat Engine: In a reverse heat engine, heat is transferred from low temperature to high
temperature. E.g : Refrigerator, air conditioning etc.
• Heat Pump: It is also a device that transfers heat from a low-temperature medium to a high
temperature medium with the objective to maintain a heated space at a high temperature by
absorbing heat from a low-temperature source.
• Working Fluid: It is a fluid involve in heat engines and other cyclic devices, to and from which
heat is transferred while undergoing a cycle.
Refrigerator and Heat pump

Fig 1: Working of Heat Fig 2: A Refrigerator

Engine Fig 3: Heat Pump
 Characteristics of Heat Engines
• 1. They receive heat from a high-temperature source (solar energy, oil furnace, nuclear
reactor, etc.).
• 2. They convert part of this heat to work (usually in the form of a rotating shaft).
• 3. They reject the remaining waste heat to a low-temperature sink (the atmosphere, rivers,
etc.).
• 4. They operate on a cycle.
SECOND LAW OF THERMODYNAMICS
• The second law of thermodynamics may be defined in many ways, but the two
common statements according to Kelvin Planck statement and Clausius statement
are as follows:

1. Kelvin-Planck Statement: “It impossible for any device that operates on a

cycle process, to receive heat energy from a single thermal reservoir and
produce equivalent amount of work”.
In other words, no actual engine, working on a cyclic process, can convert whole of
the heat supplied to it, into mechanical work. It means that there is a degradation of
energy in the process of producing mechanical work form heat supplied. Thus, the
Kelvin Planck statement of the second law of thermodynamics is sometimes known
as law of degradation of energy.
 SECOND LAW OF THERMODYNAMICS CONT’D
• A heat engine which violates this statement of the second law of thermodynamics (i.e.
heat engine which converts whole of the heat energy into mechanical work) is known as
Perpetual Motion Machine of the second kind or 100 percent efficient machine which is
impossible to obtain in actual practice, because no machine can convert whole of the
heat energy supplied to it into its equivalent amount of work.

𝑊 =𝑄1

Fig 4: Perpetual Machine Fig 5: Heat Engine Fig 6: Even the most efficient heat
engines reject almost one-half of the
energy they receive as waste heat.
SECOND LAW OF THERMODYNAMICS CONT’D
• Thus for the satisfactory operation of a heat engine which is a device used for
converting heat energy into mechanical work, there should be at-least two
reservoirs of heat at a higher temperature and the other at a lower temperature as
shown in figure above. In this case, consider that heat energy (Q) from the high
temperature reservoir (or source) at temperature T 1 is supplied to the engine. A
part of this heat energy is rejected to the low temperature reservoir (or source) at
temperature T2. If Q2 is the heat rejected to the work, then the remaining heat
(i.e. Q1 – Q2) is converted into mechanical work. The ratio of the maximum
mechanical work obtained to the total heat supplied to the engine is known as
maximum thermal efficiency (of the engine. Mathematically,

= = 1 - = 1-
 SECOND LAW OF THERMODYNAMICS CONT’D
• Clausius Statement: According to Clausuis statement, “It is impossible for a self-
acting machine working in a cyclic process to transfer heat from a body at a lower
temperature to a body at a higher temperature without the aid of an external agency”.
In other words, heat cannot flow itself from a cold body to a hot body without the help
of an external agency (i.e. without the expenditure of mechanical work).

Fig 7: Perpetual motion machine of several kind

 SECOND LAW OF THERMODYNAMICS CONT’D
• In order to achieve the object of transferring heat from a cold body to a hot body, the
refrigerator and a heat pump, whole operating in a cyclic process, require an input
work, as shown in figures (8) and (9) respectively. Though there is no difference
between the cycle of operations of the refrigerator and a heat pump and achieve the
same overall objective, but the basic purpose of each is quite different. A refrigerator is
a device which operating in a cyclic process, maintains the temperature of a cold body
(refrigerated space) at a temperature lower than the temperature of the surroundings.
On the other hand, a heat pump is a device which operating in a cyclic process,
maintains the temperature of a hot body (heat space) at a temperature higher than the
temperature of the surroundings. In other words, a refrigerator works between the cold
body temperature and the atmospheric temperature whereas a heat pump operates
between the hot body temperature and the atmospheric temperature.
 SECOND LAW OF THERMODYNAMICS CONT’D

Fig 8: A Refrigerator Fig 9: A Heat pump

 SECOND LAW OF THERMODYNAMICS CONT’D

• The performance of refrigerator and heat pump is measure in terms of performance

which is defined as the ratio of the maximum heat transferred (i.e. heat taken from the
cold body) to the amount of work required to produce the desire effect.
Mathematically, maximum coefficient of performance for a refrigeration.

• And maximum coefficient of performance of a heat pump

= (C.O.P)R + 1
• We see that C.O.P of heat pump is greater than C. O.P of a refrigerator by unity.
 EQUIVALENCE OF KELVIN –PLANCK AND CLAUSIUS STATEMENTS

• Though Kelvin-Planck and Clausius statements of the second law of thermodynamics

appear to be different from each other, but these two statements are virtually
equivalent in all respects. The equivalence of the Kelvin –Planck and Clausuis
statements can be proved if it can be shown that the notation of Kelvin –Planck
implies the notation of Clausius statement and vice versa.

Fig 10: A Refrigerator (a) Powered by Heat Engine (b) Equivalent Refrigerator
• Consider the heat-engine-refrigerator combination shown in Fig.(a), operating between
the same two reservoirs. The heat engine is assumed to have, in violation of the Kelvin–
Planck statement, a thermal efficiency of 100 percent, and therefore it converts all the
heat QH it receives to work W. This work is now supplied to a refrigerator that removes
heat in the amount of QL from the low-temperature reservoir and rejects heat in the
amount of QL+QH to the high-temperature reservoir. During this process, the high
temperature reservoir receives a net amount of heat QL (the difference between QL+QH
and QH). Thus, the combination of these two devices can be viewed as a refrigerator, as
shown in Fig. (b), that transfers heat in an amount of QL from a cooler body to a warmer
one without requiring any input from outside. This is clearly a violation of the Clausius
statement. Therefore, a violation of the Kelvin–Planck statement results in the violation
of the Clausius statement.

• It can also be shown in a similar manner that a violation of the Clausius statement leads
to the violation of the Kelvin–Planck statement. Therefore, the Clausius and the Kelvin–
Planck statements are two equivalent expressions of the second law of thermodynamics.
 REVERSIBLE AND IRREVERSIBLE PROCESSES
• A reversible process is defined as a process that can be reversed without leaving any
trace on the surroundings. That is, both the system and the surroundings are returned to
their initial states at the end of the reverse process. This is possible only if the net heat
and net work exchange between the system and the surroundings is zero for the
combined (original and reverse) process.
Requirement for Reversibility

• The process obviously has to be a quasi-equilibrium process;

• No friction is involved in the process.
• Heat transfer occurs due to an infinitesimal temperature difference only.
• Unrestrained expansion does not occur.
• Irreversible processes: Processes that are not reversible are called irreversible
processes. In irreversible process, system passes through a series of non-equilibrium
states and when made to proceed in backward direction, its does not reach its original
state, It reach a new state.
The factor that cause a process to be irreversible:
• Friction
• Free Expansion
• Mixing of two fluids
• Heat transfer across a finite temperature difference
• Electric resistance
• Inelastic deformation of solids chemical reactions.

In Figure above, the process changes state from 1-2, but when taken in backward
direction, it does not return back to original state 1 but take a new state .
Example of irreversible process
• Relative motion with friction
• Combustion
• Diffusion of gases: mixing of dissimilar gasses
• Chemical reaction
• Free expansion and throttling process
• Plastic deformation
• Electricity flow through a resistance.