Study Guide on Engineering Thermodynamics 1

Unit 4: Second Law of Thermodynamics

Time Frame: 6 hours

Unit 4
SECOND LAW OF THERMODYNAMICS

Learning Objectives
 Introduce the second law of Thermodynamics and Entropy.
 Discuss thermal energy reservoirs, reversible and irreversible processes, heat engines, refrigerators and heat
pumps.
 Discuss the concepts of perpetual-motion machines.
 Apply the second law of thermodynamics to cycles and cyclic devices.

Content Outline

4.1 Introduction to the Second Law

4.2 Thermal Energy Reservoirs
4.3 Heat Engines
4.4 Thermal Efficiency
4.5 Statements of the Second Law of Thermodynamics
4.6 Refrigerator and Heat Pump
4.7 Perpetual Motion Machines
4.8 Reversible and Irreversible Process
4.9 The Carnot Cycle
4.10 Entropy

4.1 Introduction to the Second Law

To this point, we have focused our attention on the first law of thermodynamics, which requires that
energy be conserved during a process. In this topic, we introduce the second law of thermodynamics, which
asserts that process occurs in a certain direction and that the energy has a quality as well as quantity.

 No process is known to have taken place in violation of the First Law of Thermodynamics (Process must
satisfy the first law to occur), however, satisfying the first law alone does not ensure that the process
will actually take place. It must also satisfy the Second Law.

 Processes proceed in a CERTAIN DIRECTION and not in the reverse direction. Example: A cup of
coffee, as shown in Figure 1, does not get hotter in a cooler room. The direction of heat transfer is
from hotter body to cooler body. Also, transferring heat to a paddle wheel, Figure 2, will not cause it to
rotate.

Figure 1 Figure 2

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

 The inadequacy of the first law to identify whether a process can take place is remedied by introducing
the second law of thermodynamics.
 The second law asserts that energy has a quality as well as quantity.
 More of high temperature energy can be converted into work (by the use of heat engines) than the
same amount of energy at a lower temperature. Hence, High temperature energy is energy of high
quality than low temperature energy.
 The second law of thermodynamics is also used in determining the theoretical limits for the performance
of commonly used engineering systems such as heat engines and refrigerators.

4.2 Thermal Energy Reservoirs

Thermal Energy Reservoir – a hypothetical body with a relatively large thermal energy capacity (Mass x
Specific Heat) that can supply or absorb finite amounts of heat without undergoing a temperature change.

Heat Source or simply Source – reservoir that supplies energy in the form of heat
Heat Sink or simply Sink – reservoir that absorbs energy in the form of heat

4.3 Heat Engines

Heat Engine – device that converts fraction of the heat supplied into work.

Note: Work can be directly and completely converted into heat but heat can only be converted into work
by the use of heat engine.

Common Characteristics of Heat Engines:

1. Receives heat from a high temperature source. ( Solar Energy, Furnace, Nuclear Reactor, Etc.)
2. Converts part of the heat received into Work. ( Usually in the form of rotating shaft)
3. Rejects the remaining waste heat to a low-temperature sink. ( atmosphere, river, etc.)
4. Operates on cycle.

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Working Fluid – is the fluid used in a heat engine or other cyclic device in which heat is transferred to or
from during the series of processes.

Cycle or Cyclic Process – a series of processes (usually two or more processes) that returns to its initial
state/condition. This topic will be discussed thoroughly in the later part of our course.

The figure below shows a schematic diagram of the cyclic process of a steam power plant.

where:

– net work output of the power plant is simply the difference between the total work output of the
plant and the total work input.

Using energy balance in the cycle, we can get

4.4 Thermal Efficiency

Thermal efficiency is a measure of performance of the heat engine.

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

The desired output of the heat engine is the net work produce by the engine and the required input is the
heat added/supplied to the engine.

4.5 Statements of the Second Law of Thermodynamics

Some significant statements of second law are:

 Kelvin-Planck. It is impossible to construct a heat engine which, while operating in a cycle produces
no effects except to do work and exchange heat with a single reservoir.
 Clausius. It is impossible for a self-acting machine unaided by an external agency to move heat from
one body to another at a higher temperature.
 All spontaneous processes results in a more probable state. The natural trend of events is from
less probable to a more probable state.
 The entropy of an isolated system never decreases. If all processes that occur within the system
are reversible, its entropy remains the same; otherwise, its entropy increases.
 No actual or ideal heat engine operating in cycles can convert into work all the heat supplied
to the working substance; it must reject some heat. This statement highlights the important
concepts of the degradation of energy as it passes from a high temperature state to one of lower
temperature.

4.6 Refrigerator and Heat Pump

Devices that transfer heat from a low temperature medium to a high-temperature one are refrigerator and
heat pump. Refrigerator and heat pump operate in same cycle but differ in their objective.

Refrigerator – maintains the refrigerated space at a low temperature by removing heat from it.
Discharging this heat to a higher temperature medium is merely necessary part of the operation, not the
purpose.

Heat pump – maintains a heated space at high temperature.

Coefficient of Performance – the measure of performance of refrigerator and heat pump.

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Refrigerator

Heat Pump

Relation of and :

4.7 Perpetual Motion Machines

There is no known working device that violates the first and second law of thermodynamics. Any device
that violates either law of thermodynamics is called Perpetual Motion Machine (PMM). In particular, if a
device violates the second law of thermodynamics it is called Perpetual Motion Machine of the second
kind.

4.8 Reversible and Irreversible Process

Reversible Process – process that can be reversed without leaving any trace on the surroundings. A
processes that are not reversible are called irreversible processes.

Irreversibilities – the factors that cause a process to be irreversible; among them are:

 Friction
 Unrestrained expansion of a gas
 Heat transfer to a finite temperature difference

Internally Reversible – no irreversibilities that occur within the boundaries of the system during the
process. In this process the system proceeds through a series of equilibrium states, and when the process
is reversed, the system passes through exactly the same equilibrium states while returning to its initial
states. One example of this process is the quasi-equilibrium process.

Externally Reversible – no irreversibilities occur outside the system boundaries during the process.

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Total Reversible or simple Reversible – no irreversibilities within the system or its surroundings.

4.9 The Carnot Cycle

The Carnot cycle is the most efficient thermodynamic cycle. It consists of two isothermal and two
isentropic processes. (Note: Processes of fluids, particularly ideal gas, and cycle or cyclic process
will be discussed in detail on the succeeding topics)

Pressure-Volume Diagram of Carnot Cycle

Reversed Carnot cycle:

The Carnot heat-engine cycle is a totally reversible cycle. Therefore, all processes that comprise it can
be reversed, in which case it becomes the Carnot Refrigeration cycle.

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Pressure-Volume Diagram of Reversed Carnot Cycle

Carnot Principles:

Thermal Efficiency of Carnot Cycle:

It is clear in the formula of thermal efficiency that if the low temperature is held constant more
of the high temperature thermal energy can be converted to work. Therefore, the higher the
temperature, the higher the quality of the energy. Also, the greater the difference of high temperature
(source) and low temperature (sink), the greater the amount of thermal energy converted into work.

4.10 Entropy

Entropy: S
 Consequence of the second law of thermodynamics
 Entropy is a measure of randomness or disorder of the molecules of a substance

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

 An abstract property, best understood by studying its uses in commonly encountered engineering
processes.

Clausius Inequality: [by German physicist R.J.E. Clausius (1822 – 1888)]

- An important inequality that has a major consequences in thermodynamics

The cyclic integral of is less than or equal to zero.

- For totally or internally reversible process/cycle:

- Clausius realized in 1865 that he had discovered a new thermodynamic property, and he chose to name
this property entropy. It is designated by symbol S and is defined as

- The entropy change of a system during a process is found by integrating dS:

Special case : Internally reversible constant temperature process

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Increase of Entropy principle:

From Clausius Inequality,

The second integral in equation above is recognized as entropy change . Therefore,

Which can be arrange as

It can also be expressed in differential form as

The equality holds for internally reversible process and the inequality for irreversible process.

The quantity represents the entropy change of the system. If the process is internally
reversible then

- The inequality sign in the preceding relations is a constant reminder that entropy change of a
closed system during an irreversible process is always greater than the entropy transfer. That is,
some entropy is generated or created during an irreversible process, and this generation is due
entirely to the presence of irreversibilities.

The entropy generated during a process is called entropy generation and is denoted by .
Note: Entropy generation is always a positive
quantity or zero.

Entropy Increase principle:

- The entropy of an isolated system during a process always increase or, in limiting case of
reversible process, remains constant

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Some remarks about entropy:

1. Processes can occur in a certain direction, not in any direction. A process can occur in the
direction that complies with the increase of entropy principle.
2. Entropy is a nonconserved property. There is no such thing as conservation of entropy
principle.
3. The performance of engineering system is degraded by the presence of irreversibilities, and
entropy generation is a measure of the magnitudes of the irreversibilities present during that
process.

Isentropic process – internally reversible adiabatic (Q =0, no heat transfer) process. It is a constant
entropy process.

Property Diagram involving Entropy :

Temperature – Entropy (T-S) Diagram

Note: The area under the curve of T-S diaram represents the heat transfer for internally reversible
process.

- Another diagram that involves entropy is the h-s (Specific enthalpy vs. specific entropy) diagram.
This diagram is also called Mollier Diagram named after German scientist R. Mollier (1863 – 1935).

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Mollier Diagram

The T ds Relations:

The differential form of the conervation of energy for a closed system containing a simple
compressible substance can be expressed for an internally reversible process as

This is known as T ds, or Gibbs, equation.

Also, from
(specific enthalpy)

so

Explicit relations for differential changes in entropy are obtained by solving for ds:

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Study Guide on Engineering Thermodynamics 1
Unit 4: Second Law of Thermodynamics

Entropy Balance:

- The second law of thermodynamics state that entropy can be created but it cannot be destroyed.
Therefore, the entropy change of a system is greater than the entropy transfer by an amount equal
to the entropy generated during the process within the system, the increase of entropy principle for
any system is expressed as,

Mechanism of Entropy Transfer for control volume:

1) Heat and 2) Mass

Exercises 4.1

Solve/Answer the following problems:

1. An inventor proposes a heat engine that receives heat (160 kJ/min) at 800 K. For a sink
temperature of 500 K, he claims that 65 kJ/min of work are delivered. Do you think that his claim is
justifiable? Is any thermodynamics principle violated?
2. State the third law of thermodynamics.
3. There are transferred 500 kJ of heat from reservoir A (at 1000 K) to reservoir B ( at 500 K); in each
case the reservoirs remain at constant temperature. According to the second law, what is the net
change of entropy of the two reservoirs?
4. The entropy of a hot baked potato decreases as it cools. Is this a violation of the increase of
entropy principle?
5. Is it possible to create entropy? Is it possible to destroy it?
6. During the isothermal heat rejection process of a Carnot cycle, the working fluid experiences an
entropy change of -0.7 Btu/R. If the temperature of the heat sink is 95OF, determine (a) the amount
of heat transfer, (b) the entropy change of the sink, and (c) the total entropy change for this
process.
7. Expound the statement of the second law “Entropy of an isolated system never decreases”.

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