MCE 311 Thermodynamics II 2 Credits

Course Outline:
Review of the Basic Concepts of Thermodynamics including first and second law. The second
law of thermodynamics and its applications; Entropy; Exergy; Fuels and Combustion. Engine
cycles, heat pump and refrigeration cycles. Gaseous mixtures.

Course Description
Thermodynamics is the aspect of thermal systems engineering (i.e thermodynamics, heat transfer,
and fluid mechanics). It involves the transfer of mass and energy (e.g work and heat). It is the study
of the basic laws that govern energy and entropy transfers and the ways these interactions presents
itself in system behavior. The objective of this course is to provide an avenue for understanding of
thermodynamics in order to facilitate efficient engineering design and analysis of energy systems,
and also to provide a basis for further study and research in energy conversion systems.

Course Objective
The specific objectives of this course are:
1. To present fundamental principles and laws of thermodynamics, and to explore the
effects of these principles in system behavior.
2. To study and analyze energy systems through the application of thermodynamic
principles.
3. To develop problem-solving skills essential in thermodynamics systems.

Reference:
1. Moran, Michael J., Shapiro, Howard N., Munson, Bruce R. and DeWitt, David P. (2003),
Introduction to Thermal Systems Engineering: Thermodynamics, Fluid Mechanics, and
Heat Transfer, John Wiley & Sons, Inc., USA.

2. Cengel, Y. A. and Boles, M. A. (2006). Thermodynamics: An Engineering Approach, 5th

Edition, McGraw Hill.

3. U. S. DOE (1992), Thermodynamics, Heat Transfer, and Fluid Flow-Department of

Energy Fundamentals Handbook, Washington, D.C.

4. Rajput, R. K. (2006). Thermal Engineering, Laxmi Publications (P) Ltd., New Delhi.

5. Roger, G. F. C. and Mayhew, Y. R. (1992). Engineering Thermodynamics: Work and

Heat Transfer, Longman Group Limited, 4th Edition, UK.

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 CHAPTER ONE
FUNDAMENTAL CONCEPTS OF THERMODYNAMICS
Intended Learning Outcomes (ILO)
At the end of this chapter, students should be able:
 To identify and explain the fundamental concepts and definitions used in the study of
thermodynamics.
 Apply the basic concepts of thermodynamics to energy systems

1.1 Introduction
The word thermodynamics stems from the Greek words therme (heat) and dynamis
(force). Although various aspects of what is now known as thermodynamics have been of
interest since antiquity, the formal study of thermodynamics began in the early nineteenth
century through consideration of the motive power of heat: the capacity of hot bodies to produce
work. Today the scope is larger, dealing generally with energy and with relationships among the
properties of matter.

1.2 Defining Systems

1. System: The system is whatever we want to study. It may be as simple as a free body or
as complex as an entire chemical refinery. We may want to study a quantity of matter
contained within a closed, rigid-walled tank, or we may want to consider a pipeline
through which natural gas flows.
2. Surroundings: Everything external to the system is considered to be part of the system’s
surroundings.
3. Boundary: The system is distinguished from its surroundings by a specified boundary,
which may be at rest or in motion. You will see that the interactions between a system
and its surroundings, which take place across the boundary, play an important part in
thermal systems engineering.

4. Types of Systems: Two basic kinds of systems are distinguished from each other. These
are referred to, respectively, as closed systems and control volumes. A closed system

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 refers to a fixed quantity of matter, whereas a control volume is a region of space through
which mass may flow.
5. Closed system: A closed system is defined when a particular quantity of matter is under
study. A closed system always contains the same matter. There can be no transfer of mass
across its boundary.
6. Isolated system: A special type of closed system that does not interact in any way with
its surroundings is called an isolated system.

Figure 1.1: Closed system: A gas in a piston–cylinder assembly

Figure 1.1 shows a gas in a piston–cylinder assembly. When the valves are closed, we can
consider the gas to be a closed system. The boundary lies just inside the piston and cylinder
walls, as shown by the dashed lines on the figure. The portion of the boundary between the gas
and the piston moves with the piston. No mass would cross this or any other part of the
boundary.

1.3 Describing Systems and Their Behavior

1. Macroscopic and microscopic approaches
Systems can be studied from a macroscopic or a microscopic point of view. The
macroscopic approach is concerned with the gross or overall behavior of matter. No model of the
structure of matter at the molecular, atomic, and subatomic levels is directly used. Although the

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behavior of systems is affected by molecular structure, the macroscopic approach allows
important aspects of system behavior to be evaluated from observations of the overall system.
The microscopic approach is concerned directly with the structure of matter. The objective is to
characterize by statistical means the average behavior of the particles making up a system of
interest and relate this information to the observed macroscopic behavior of the system. For the
great majority of thermal systems applications, the macroscopic approach not only provides a
more direct means for analysis and design but also requires far fewer mathematical
complications.
2. Property, state, processes and thermodynamic cycle
(1) Property: A property is a macroscopic characteristic of a system such as mass, volume,
energy, pressure, and temperature to which a numerical value can be assigned at a given
time without knowledge of the previous behavior (history) of the system. Many other
properties are considered during the course of our study.
(2) State: The word state refers to the condition of a system as described by its properties.
Since there are normally relations among the properties of a system, the state often can be
specified by providing the values of a subset of the properties. All other properties can be
determined in terms of these few.
(3) Process: When any of the properties of a system change, the state changes and the
system is said to have undergone a process. A process is a transformation from one state
to another. However, if a system exhibits the same values of its properties at two different
times, it is in the same state at these times.
(4) Steady state: A system is said to be at steady state if none of its properties changes with
time.
(5) Thermodynamic cycle: A thermodynamic cycle is a sequence of processes that begins
and ends at the same state. At the conclusion of a cycle all properties have the same
values they had at the beginning.
(6) Isothermal process: A process occurring at constant temperature is an isothermal
process.
(7) Isobaric process: A process occurring at constant pressure is an isobaric process.
(8) Isometric process: A process occurring at constant volume is an isometric process.

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(9) Adiabatic process: A process in which there is no energy transfer by heat is an adiabatic
process.
(10) Polytropic process: The relationship between pressure and volume during an
expansion or compression process also can be described analytically. An example is

provided by the expression pV n  constant , where the value of n is a constant for the
particular process. A quasiequilibrium process described by such an expression is called a
polytropic process. Additional analytical forms for the pressure–volume relationship also
may be considered.

2. Extensive and Intensive Properties

Thermodynamic properties can be placed in two general classes: extensive and intensive.
(1) Extensive property: A property is called extensive if its value for an overall system is
the sum of its values for the parts into which the system is divided. Mass, volume,
energy, and several other properties introduced later are extensive. Extensive properties
depend on the size or extent of a system.
(2) Intensive property: The extensive properties of a system can change with time;
Intensive properties are not additive in the sense previously considered. Their values are
independent of the size or extent of a system and may vary from place to place within the
system at any moment. Thus, intensive properties may be functions of both position and
time, whereas extensive properties vary at most with time. Specific volume, pressure, and
temperature are important intensive properties; several other intensive properties are
introduced in subsequent chapters.

3. Phase and Pure Substance

(1) Phase: The term phase refers to a quantity of matter that is homogeneous throughout in
both chemical composition and physical structure. Homogeneity in physical structure
means that the matter is all solid, or all liquid, or all vapor (or equivalently all gas). A
system can contain one or more phases. For example, a system of liquid water and water
vapor (steam) contains two phases. When more than one phase is present, the phases are
separated by phase boundaries.

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 (2) Pure substance: A pure substance is one that is uniform and invariable in chemical
composition. A pure substance can exist in more than one phase, but its chemical
composition must be the same in each phase. For example, if liquid water and water
vapor form a system with two phases, the system can be regarded as a pure substance
because each phase has the same composition. A uniform mixture of gases can be
regarded as a pure substance provided it remains a gas and does not react chemically.

4. Equilibrium
(1) Equilibrium: Thermodynamics places primary emphasis on equilibrium states and
changes from one equilibrium state to another. Thus, the concept of equilibrium is
fundamental. In mechanics, equilibrium means a condition of balance maintained by an
equality of opposing forces. In thermodynamics, the concept is more far-reaching,
including not only a balance of forces but also a balance of other influences. Each kind of
influence refers to a particular aspect of thermodynamic, or complete, equilibrium.
Accordingly, several types of equilibrium must exist individually to fulfill the condition
of complete equilibrium; among these are mechanical, thermal, phase, and chemical
equilibrium.
(2) Equilibrium state: We may think of testing to see if a system is in thermodynamic
equilibrium by the following procedure: Isolate the system from its surroundings and
watch for changes in its observable properties. If there are no changes, we conclude that
the system was in equilibrium at the moment it was isolated. The system can be said to be
at an equilibrium state.

1.4 Actual and Quasiequilibrium Processes

There is no requirement that a system undergoing an actual process be in equilibrium
during the process. Some or all of the intervening states may be nonequilibrium states. For many
such processes we are limited to knowing the state before the process occurs and the state after
the process is completed. Processes are sometimes modeled as an idealized type of process called
a quasiequilibrium (or quasistatic) process. A quasiequilibrium process is one in which the
departure from thermodynamic equilibrium is at most infinitesimal.

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1.5 Energy and the First Law of Thermodynamics
1.5.1 Sign convention and notation for energy transfer by work
Engineering thermodynamics is frequently concerned with devices such as internal
combustion engines and turbines whose purpose is to do work. Hence, it is often convenient to
consider such work as positive. That is,
W  0 : work done by the system
W  0 : work done on the system
To reduce the possibility of misunderstanding in any such case, the direction of energy transfer is
shown by an arrow on a sketch of the system, and work is regarded as positive in the direction of
the arrow. The value of W depends on the details of the interactions taking place between the
system and surroundings during a process and not just the initial and final states of the system.
The amount of energy transfer by work for a process is given by the integral
2
W   W (1.1)
1

It follows that work is not a property of the system or the surroundings. In addition, the limits on
the integral of Eq. 1.1 mean “from state 1 to state 2” and cannot be interpreted as the values of
work at these states. The notion of work at a state has no meaning, so the value of this integral
and should never be indicated as W2  W1 .
1.5.2 Power
Many thermodynamic analyses are concerned with the time rate at which energy transfer
occurs. The rate of energy transfer by work is called power and is denoted by W . When a work
interaction involves an observable force, the rate of energy transfer by work is equal to the
product of the force and the velocity at the point of application of the force
W  F  V (1.2)
1.5.3 Modeling expansion or compression work

Figure 1.2: Expansion or

compression of a gas or liquid

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Let us evaluate the work done by the closed system shown in Fig. 1.2 consisting of a gas (or
liquid) contained in a piston-cylinder assembly as the gas expands. During the process the gas
pressure exerts a normal force on the piston. Let p denote the pressure acting at the interface
between the gas and the piston. The force exerted by the gas on the piston is simply the product
pA, where A is the area of the piston face. The work done by the system as the piston is
displaced a distance dx is
W  pAdx (1.3)
The product A dx in Eq. 1.3 equals the change in volume of the system, dV. Thus, the work
expression can be written as
W  pdV (1.4)
Since dV is positive when volume increases, the work at the moving boundary is positive when
the gas expands. For a compression, dV is negative, and so is work found from Eq. 1.4. These
signs are in agreement with the previously stated sign convention for work. For a change in
volume from V1 to V2, the work is obtained by integrating Eq. 1.4.
V2
W   pdV (1.5)
V1

Although Eq. 1.5 is derived for the case of a gas (or liquid) in a piston-cylinder assembly, it is
applicable to systems of any shape provided the pressure is uniform with position over the
moving boundary.

Example 1.1: Evaluating Expansion Work

A gas in a piston–cylinder assembly undergoes an expansion process for which the relationship

between pressure and volume is given by pV n  constant . The initial pressure is 3 bar, the initial
volume is 0.1 m3, and the final volume is 0.2 m3. Determine the work for the process, in kJ, if
(a) n = 1.5, (b) n = 1.0, and (c) n = 0.
Solution
Known: A gas in a piston–cylinder assembly undergoes an expansion for which

pV n  constant .
Find: Evaluate the work if (a) n = 1.5, (b) n = 1.0, (c) n = 0.
Schematic and Given Data: The given p–V relationship and the given data for pressure and
volume can be used to construct the accompanying pressure–volume diagram of the process.

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 Figure E 1.1: Expansion or compression
of a gas or liquid
Assumptions:
1. The gas is a closed system.
2. The moving boundary is the only work mode.
3. The expansion is a polytropic process.
Analysis: The required values for the work are obtained by integration of Eq. 1.5 using the given
pressure–volume relation.

(a) Introducing the relationship p  constant/V n into Eq. 1.5 and performing the integration

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Comments:
1. In each case, the work for the process can be interpreted as the area under the curve
representing the process on the accompanying p–V diagram. Note that the relative areas
are in agreement with the numerical results.
2. The assumption of a polytropic process is significant. If the given pressure–volume
relationship were obtained as a fit to experimental pressure–volume data, the value of

 pdV would provide a plausible estimate of the work only when the measured pressure
is essentially equal to that exerted at the piston face.
3. Observe the use of unit conversion factors here and in part (b).
4. It is not necessary to identify the gas (or liquid) contained within the piston–cylinder
assembly. The calculated values for W are determined by the process path and the end
states. However, if it is desired to evaluate other properties such as temperature, both the
nature and amount of the substance must be provided because appropriate relations
among the properties of the particular substance would then be required.

1.5.4 Change in total energy of a system

In engineering thermodynamics the change in the total energy of a system is considered
to be made up of three macroscopic contributions. One is the change in kinetic energy,
associated with the motion of the system as a whole relative to an external coordinate frame.
Another is the change in gravitational potential energy, associated with the position of the system

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as a whole in the earth’s gravitational field. All other energy changes are lumped together in the
internal energy of the system. Like kinetic energy and gravitational potential energy, internal
energy is an extensive property of the system, as is the total energy.
Internal energy is represented by the symbol U , and the change in internal energy in a
process is U 2  U 1 . The specific internal energy is symbolized by u or u respectively, depending
on whether it is expressed on a unit mass or per mole basis. The change in the total energy of a
system is
E 2  E1  ( KE 2  KE1 )  ( PE 2  PE1 )  (U 2  U1 ) (1.6)
or
E  KE  PE  U (1.7)

1.5.5 Sign convention and notation for energy transfer by heat

The symbol Q denotes an amount of energy transferred across the boundary of a system
in a heat interaction with the system’s surroundings. Heat transfer into a system is taken to be
positive, and heat transfer from a system is taken as negative.
Q  0 : heat transfer to the system
Q  0 : heat transfer from the system
As was indicated for work, it is sometimes convenient to show the direction of energy transfer by
an arrow on a sketch of the system. Then the heat transfer is regarded as positive in the direction
of the arrow. In an adiabatic process there is no energy transfer by heat. The value of a heat
transfer depends on the details of a process and not just the end states. Thus, like work, heat is
not a property, and its differential is written as Q . The amount of energy transfer by heat for a
process is given by the integral
2
Q   Q (1.8)
1

where the limits mean “from state 1 to state 2” and do not refer to the values of heat at those
states. Just as for work, the notion of “heat” at a state has no meaning, and the integral should
never be evaluated as Q2  Q1 .

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1.5.6 The first law of thermodynamics
The first law of thermodynamics, also known as the conservation of energy principle,
provides a sound basis for studying the relationships among the various forms of energy and
energy interactions. Based on experimental observations, the first law of thermodynamics states
that energy can be neither created nor destroyed during a process; it can only change forms.
Therefore, every bit of energy should be accounted for during a process. These considerations
are summarized in words as follows:
change in the amount  net amount of energy  net amount of energy 
of energy contained   transferre d in across   transferre d out across
     
 within the system    the system boundary by   the system boundary 
     
during some time  heat trans fer during  by work during the 
interval   the time interval   time interval 

This word statement is just an accounting balance for energy, an energy balance. It requires that
in any process of a closed system the energy of the system increases or decreases by an amount
equal to the net amount of energy transferred across its boundary. The energy balance can be
expressed in symbols as
E 2  E1  Q  W (1.9)
Introducing Eqs. 1.6 and 1.7, an alternative form is
KE  PE  U  Q  W (1.10)

Example 1.2: Cooling a Gas in a Piston-Cylinder

Four kilograms of a certain gas is contained within a piston–cylinder assembly. The gas

undergoes a process for which the pressure–volume relationship is pV 1.5  constant .The initial
pressure is 3 bar, the initial volume is 0.1 m3, and the final volume is 0.2 m3. The change in
specific internal energy of the gas in the process is u2  u1  4.6 kJ/kg . There are no

significant changes in kinetic or potential energy. Determine the net heat transfer for the process,
in kJ.
Solution
Known: A gas within a piston–cylinder assembly undergoes an expansion process for which the
pressure–volume relation and the change in specific internal energy are specified.
Find: Determine the net heat transfer for the process.

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Schematic and Given Data:

Figure E 1.2: Expansion or compression

of a gas or liquid

The value of the work for this process is determined in the solution to part (a) of Example 1.1 as:
W = +17.6 kJ. The change in internal energy is obtained using given data as

Comments:
1. The given relationship between pressure and volume allows the process to be represented
by the path shown on the accompanying diagram. The area under the curve represents the
work. Since they are not properties, the values of the work and heat transfer depend on
the details of the process and cannot be determined from the end states only.

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 2. The minus sign for the value of Q means that a net amount of energy has been transferred
from the system to its surroundings by heat transfer.
1.5.7 Energy balance
In the light of the preceding discussions, the conservation of energy principle can be
expressed as follows: The net change (increase or decrease) in the total energy of the system
during a process is equal to the difference between the total energy entering and the total energy
leaving the system during that process. That is,
 Total energy   Total energy   Change in the total 
       
 entering the system  leaving the system  energy of the system
or
Ein  Eout  Esystem (1.11)

This relation is often referred to as the energy balance and is applicable to any kind of system
undergoing any kind of process. The successful use of this relation to solve engineering
problems depends on understanding the various forms of energy and recognizing the forms of
energy transfer.
1.5.8 Energy conversion efficiencies
Efficiency is one of the most frequently used terms in thermodynamics, and it indicates
how well an energy conversion or transfer process is accomplished. Efficiency is also one of the
most frequently misused terms in thermodynamics and a source of misunderstandings. This is
because efficiency is often used without being properly defined first. Performance or efficiency,
in general, can be expressed in terms of the desired output and the required input as
Desired output
Efficiency  (1.12)
Required input
For example the efficiency of a cooking appliance represents the fraction of the energy supplied
to the appliance that is transferred to the food. If the energy supplied to a cooking appliance is
5kW and the energy used for cooking is 3 kW. The efficiency of the cooking appliance is
Energy utilized
Efficiency 
Energy supplied to the appliance
3kW
  0.6 or 60%
5kW

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This indicates that the unutilized energy is 2kW or 40% of energy supplied to the appliance,
which was likely lost to the environment as heat.

LIMITATIONS OF FIRST LAW OF THERMODYNAMICS

First law of thermodynamics based on law of energy conservation has proved to be a powerful
tool for thermodynamic analysis. But over the period of time when it was applied to some real
systems, it was observed that theoretically first law stands valid for the processes which are not
realizable practically. It was then thought that there exist certain flaws in first law of
thermodynamics and it should be used with certain limitations.
Say for example let us take a bicycle wheel and paddle it to rotate. Now apply brake to it. As a
result of braking wheel comes to rest upon coming in contact with brake shoe. Stopping of wheel
is accompanied by heating of brake shoe. Examining the situation from Ist law of
thermodynamics point of view it is quite satisfying that rotational energy in wheel has been
transformed into heat energy with shoe, thus causing rise in its temperature:
Now, if we wish to introduce the same quantity of heat into brake shoe and wish to restore wheel
motion then it is not possible simply, whereas theoretically first law permits the conversion from
heat to work (rotation of wheel in this case) as well. Therefore, it is obvious that Ist law of
thermodynamics has certain limitations as given below:
(i) First law of thermodynamics does not differentiate between heat and work and assures full
convertibility of one into others, whereas full conversion of work into heat is possible but the
vice-versa is not possible.
(ii) First law of thermodynamics does not explain the direction of a process. Such as theoretically
it shall permit even heat transfer from low temperature body to high temperature body which is
not practically feasible. Spontaneity of the process is not taken care of by the first law of
thermodynamics.
Perpetual motion machine of the first kind (PMM-I) is a hypothetical device conceived, based on
violation of First law of thermodynamics.

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Problem Set 1
1. One-half kg of a gas contained within a piston–cylinder assembly undergoes a constant-
pressure process at 4 bar beginning at v1 = 0.72 m3/kg. For the gas as the system, the
work is -84 kJ. Determine the final volume of the gas, in m3. (0.15m3)
2. A gas expands from an initial state where p1 = 500 kPa and V1 = 0.1 m3 to a final state
where p2 = 100 kPa. The relationship between pressure and volume during the process is
pV = constant. Sketch the process on a p–V diagram and determine the work, in kJ.
(80.47 kJ)
3. Air undergoes two processes in series: Process 1–2: polytropic compression, with n =
1.3, from p1 = 100 kPa, v1 = 0.04 m3/kg to v2 = 0.02 m3/kg. Process 2–3: constant–
pressure process to v3 = v1. Sketch the processes on a p–v diagram and determine the
work per unit mass of air, in kJ/kg. (1.8426 kJ/Kg)
4. Each line in the following table gives information about a process of a closed system.
Every entry has the same energy units. Fill in the blank spaces in the table.

5. A gas expands in a piston–cylinder assembly from p1 = 8.2 bar, V1 = 0.0136 m3 to p2 =

3.4 bar in a process during which the relation between pressure and volume is
pV1.2 = constant. The mass of the gas is 0.183 kg. If the specific internal energy of the gas
decreases by 29.8 kJ/kg during the process, determine the heat transfer, in kJ. Kinetic and
potential energy effects are negligible. (2.197 kJ)
6. A closed system of mass 2 kg undergoes a process in which there is heat transfer of
magnitude 25 kJ from the system to the surroundings. The elevation of the system
increases by 700 m during the process. The specific internal energy of the system
decreases by15 kJ/kg and there is no change in kinetic energy of the system. The
acceleration of gravity is constant at g = 9.6 m/s2. Determine the work, in kJ. (-8.4 kJ)
7. A closed system of mass 3 kg undergoes a process in which there is a heat transfer of 150
kJ from the system to the surroundings. The work done on the system is 75 kJ. If the

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 initial specific internal energy of the system is 450 kJ/kg, what is the final specific
internal energy, in kJ/kg? Neglect changes in kinetic and potential energy. (425 kJ/Kg)
8. Air is contained in a vertical piston–cylinder assembly by a piston of mass 50 kg and
having a face area of 0.01 m2. The mass of the air is 4 g, and initially the air occupies a
volume of 5 liters. The atmosphere exerts a pressure of 100 kPa on the top of the piston.
Heat transfer of magnitude 1.41 kJ occurs slowly from the air to the surroundings, and
the volume of the air decreases to 0.0025 m3. Neglecting friction between the piston and
the cylinder wall, determine the change in specific internal energy of the air, in kJ/kg.
Note: 1000 liters = 1 m3
9. Measured data for pressure versus volume during the expansion of gases within the
cylinder of an internal combustion engine are given in the table below. Using data from
the table, complete the following:
(a) Determine a value of n such that the data are fit by an equation of the form, pVn = constant.
V2
(b) Evaluate analytically the work done by the gases, in kJ, using W   pdV along with the
V1

result of part (a).

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