ENGINEERING THERMODYNAMICS (EET 222)

Course Outline
1. Fundamental Concepts and Definitions
2. Laws of thermodynamics and consequences
3. Properties of pure substances and property relation for a perfect gas
4. Application of combined 1st and 2nd laws of thermodynamics to various systems and
processes.
Textbooks

1. Engineering Thermodynamics by G. F. C Rogers and Y. R. Mayhew

2. Thermodynamics – An Engineering Approach by Yunus A. Cengel and Michael A. Boles
3. Thermodynamics for Engineers – Theory and Problems – (Schaum’s Outline Series) by
Merle C. Potter, Graig W. Somerton

Required
 Property Tables – Thermodynamic and Transport Properties of Fluid (S. I. Units) by
Rogers and Mayhew
 Property Diagrams (P-v, T-v, P-T, T-s, P-h, P-v-T, etc.) and Property Charts, e.g. h-s or
Mollier Chart

CHAPTER 1. FUNDAMENTAL CONCEPTS AND DEFINITIONS

1.1 Introduction
Thermodynamics
Thermodynamics is the science of energy, the transformation from one form to another and the
transfer across a boundary in the form of heat or work, and the related changes in properties of
matter. Examples of processes that are based on thermodynamic principles include the following:
(a). Domestic processes, e.g. transformation of energy from hot gases emerging from a burner
to cooler water in a hot-water heater.
(b). Industrial processes, e.g. transformation of the thermal energy contained in the hot gases
in an automobile engine into mechanical energy, i.e. work at the wheels of the vehicle,
and transformation of the work into kinetic energy in the form of automobile
transportation; the conversion of electrical work into cooling air in air-conditioning
systems; conversion of the chemical energy contained in fuel into thermal energy in a
combustor or the conversion of calorific energy into heat and work in power plants, etc.
(c). Universal activities, e.g. conversion of the motion of gas, dust and the mass of moving
matter in space into the formation of astral bodies – stars, planets, etc.
Application Areas
Small Scale
Application in part or whole design of household utensils and appliances, such as electric or gas
range, the heating and air-conditioning system, refrigerator, humidifier, pressure cooker, water
heater, shower, iron and even the computer and television
Large Scale
Major tool in the design and analysis of automobile engine, rockets, jet engines, and conventional
or nuclear power plants.
Common Units of Quantities in Use
Some of the more common quantities in use in thermodynamics and their units include the
following:
Length: meter (m)
Mass: kilogram (k)g
Temperature: SI units: Celsius degree (oC), Kelvin (K); USCS units: Fahrenheit degree (oF), Rankine (R)
T(K) = T(oC) + 273; T(R) = T(oF) + 460
Pressure: N/m2; Bar, Paschal (Pa); kPa = 103 Pa; MPa = 106 Pa; atmosphere (atm)
1 N/m2 = 1 Pa; 1 bar = 105 Pa = 105 N/m2; 1 atm = 101325 Pa = 101325 N/m2 = 1.01325 bar

Energy & Work: J; kJ; MJ

1 kJ = 103 J; 1 MJ = 106 J
Power: J/s (W); kJ/s (kW); MJ/s (MW)
1 kJ/s (kW) = 103 J/s (W); 1 MJ/s (MW) = 106 J/s (W)

Approaches to the Study of Thermodynamics

The two fundamental approaches used in the thermodynamic analysis of phenomena are:
(a). Classical approach,
(b). Statistical approach
Classical or Macroscopic Approach
The classical approach is based on the continuum concept. It deals with the macroscopic or large-
scale analysis of substances or matter and does not require a knowledge of the behaviours or
actions of the individual particles called molecules, nor the structure of the matter to determine the
behaviour of the substance.
Statistical Approach or Microscopic Approach
In the statistical approach, the behaviour of individual molecules is taken into consideration. The
approach is based on statistical analysis and probability theory, dealing with average values of the
behaviours and structure of large groups of individual particles under consideration. The approach
is important in situations where the continuum assumption is not valid; for example, during re-
entry of satellites, which usually takes place at the very high altitude beginning upwards from
around the of the atmosphere.
1.2 Matter, Space and Time
Matter
Matter is every real, objectively existing thing from the smallest microscopic particle to the largest
bodies in the Universe. It is characterized by endless motion activity and endless processes of
transformation.
Properties of matter
Include the following: Infinity of extension and duration, transformability, non-creatability, non-
destructivity, unity of discontinuity and continuity.
Space
Space is a form of existence of matter that expresses or defines its extent and structure, the co-
existence and interaction of elements in various material systems.
Properties of space
Include dimension, infinity, connectedness, unity of discontinuity and continuity.
Time
It is a form of existence of matter that characterizes the duration of (and instant or point in) its
existence and the sequence of changes which it undergoes. The measure of the duration of the
existence of material system is a definite number of cyclical processes in the structure of subsystem
of which they are constituted or of layer systems.
The most convenient units of time (e.g. seconds, year, etc.) are used to express the cyclical
processes.
Properties of time
Some of the universal properties of time are duration, irreversibility (has direction), asymmetric,
non-cyclical character, unity of discontinuity and continuity, connectedness, infinity, and related
connections with motion, space and structural relation in systems, etc.

1.3 Thermodynamic System and Control Volume

System
A thermodynamic system is that portion of the Universe that is intended for study. It may be an
atom, a galaxy, a certain quality of matter or a certain volume in space.
Surroundings
Also known as environment, it is the mass or region all around and external to a system. The
surroundings may contain other systems, some of which may affect or may be affected by the
processes occurring within the system under investigation.
Boundary
This is the surface, real or imaginary, that separates a system from the surroundings. The boundary
of a system can be fixed or moving. The thermodynamic system, its surroundings and boundary
are illustrated in Figure 1.

Figure 1. System, surroundings, & boundary

Closed system, Open system, Isolated system

Closed System
A closed system, also known as a control mass, is a system in which there is no exchange of mass
with the surroundings across its boundaries, but energy may cross the boundaries. The volume of
a closed system does not have to be fixed, in which case, at least, one of the boundaries is a moving
boundary. Figure 2(a) illustrates the thermodynamic system, while Figure 2(b) shows the system
with a moving boundary.
Examples of a closed thermodynamic system include the piston-cylinder system, pressure cooker,
water coolant circuit system of an automobile radiator, refrigerant circuit system of a domestic
refrigerator (shown in Figure 3), and water/steam circuit system of a steam power plant.
Open System or Control Volume
An open system, also known as a control volume, is a system in which there is exchange of both
mass and energy with the environment across the boundaries.
A control volume can be fixed in size and shape as is common with most control volumes, e.g. as
in the case of a nozzle (Figure 4(a)), or it may involve a moving boundary (Figure 4(b)), as in the
cases of devices with only inlet and no outlet such as a pump, an inflating balloon, or during intake
stroke of a piston-cylinder system. The inner boundaries of a control volume are called control
surface, and they can be real, e.g. as the inner surface of a nozzle, or imaginary, as the entrance
and exit areas of the nozzle where there are no physical surfaces present. The control volume and
its characteristics are illustrated in Figure 4.
Other examples of an open thermodynamic system include flows through a bathroom water heater,
a nozzle, a compressor, a turbine, a condenser, a capillary tube.
Isolated System
If in addition to there not being exchange of mass with the surroundings across the boundary of a
system, energy (in the form of heat and work) is also not allowed to cross the boundary, the system
is called an isolated system. The isolated system should therefore have a rigid wall.
Examples include thermo-flask, food warmer or cooler, etc. Other approximating examples
include closed compartments with jacketed insulation walls such as refrigerator and freezer
compartments of an unplugged refrigerator or deep freezer.

(a). Closed system (b). Closed system with moving boundary

Figure 2. Characteristics of a closed thermodynamic system

Figure 3. The refrigerant circuit system of a domestic refrigerator

(a). Control volume with real (b). Control volume with fixed & (c). An open system, or a control
& imaginary boundaries moving boundaries, & one inlet volume, with one inlet and one exit
Figure 4. Characteristics of a control volume

Working Substance or Working Fluid

The working substance is the medium, usually fluid (liquid, gas or the mixture) employed in the
transfer and transformation of energy in thermodynamic systems. It is usually made up of
molecules and may sometime involve atoms (such as in reactive systems). Examples are steam in
a steam turbine, air in a compressor, fuel and air mixture in an engine, etc. A working substance
may be classified as a simple system and/or a pure substance.
Pure Substance
A pure substance, either an element or a compound, is one whose chemical composition is spatially
uniform or homogenous in all its phases. It may exist in more than one phase, but each phase must
have the same chemical composition. Examples include the following: Water, multiphase systems
such as a mixture of ice, liquid water, and its vapour, or the liquid water and vapour mixture. Each
of these mixtures have single chemical components or chemical composition, and are thus, also
pure substances. A mixture of pure substances, such as the ocean water, is not a pure substance,
since it contains spatially varying chemical composition, a non-uniform fraction of salt depending
on the depth. Air is also not a pure substance, as it is a mixture of various elements. Other examples
of pure substances include gases such as Nitrogen, Helium and, Carbon-dioxide.
Simple System
A simple system is a single-phase homogeneous (with properties such as density being uniform),
isotropic, and chemically inert system free from external effects such as magnetic, gravitational,
electromagnetic/electrical and surface effects. The system involves a single work mode. The state
of such a substance is defined by two independent intensive thermodynamic properties.
1.4 Thermodynamic Properties and Thermodynamic State of a System
Properties
Properties are characteristics by which the condition of a system is described. The condition of the
system as described by the properties is called the state of the system. Properties, thus, define the
thermodynamic state of the system. The property has a unique value when a system is in a
particular state. There are six common thermodynamic properties of a closed system, and they are
pressure P, temperature T, volume v, internal energy u, enthalpy h and entropy s. The other two,
useful when considering chemical reactions, are Helmholtz function f and Gibbs function g, also
called free energy, which together are combinations of the other properties.
Of the eight properties listed, only three: P, v and T, often referred to as primary or primitive
properties, are observable by the human senses and therefore directly measurable. The other
properties are not directly observable by the senses, and are, thus, determined in terms of the
primary properties.
The value of a thermodynamic property is independent of the path (process) through which the
fluid has passed in reaching the state. The thermodynamic property is, thus, not a path function,
but a state or point function.
From an experimental study done on a closed system, it has been found that only two of the
thermodynamic properties are necessary and adequate to determine the state of the closed system
containing a simple fluid. The two properties must, however, be intensive properties and be
independent of each other.
For an open system two additional properties: velocity (relative to a fixed boundary of the system)
and position (in the gravitational field), e.g. height above some datum level, called mechanical
properties, are required to determine the state of the system. The mechanical properties are
independent of one another, and are independent of the thermodynamic properties.
Other less familiar properties include density, mass (a primary property), viscosity, thermal
conductivity, modulus of elasticity, thermal coefficient of expansion, and electrical resistivity.
Intensive and Extensive Properties
Intensive Properties
These are properties which do not depend on the mass of the system. They are the same for the
entire system or for parts of the system. Examples include temperature, pressure, density, velocity,
viscosity, thermal conductivity, modulus of elasticity, thermal coefficient of expansion, and
electrical resistivity.
Extensive properties
These are properties which depend on the mass of the energy. Examples include volume, mass,
momentum, kinetic energy, internal energy, and enthalpy. The extensive property of two systems
brought together is the sum of the separate extensive properties of the original two systems.
When properties are expressed per unit mass, they are referred to as specific properties. Specific
properties are also intensive properties. Example: specific volume, v = V/m; specific enthalpy, h
= H/m, where V is total volume, H is total enthalpy and m is mass.

1.5 Thermodynamic Equilibrium, Equilibrium Stability and Thermodynamic Process

1.5.1 Thermodynamic Equilibrium
A condition of thermodynamic equilibrium is said to exist when the properties of a system can be
observed to be constant from point to point throughout the system domain and when there is no
tendency for change with time when the system is isolated from the surroundings. If there is a
sudden change in the property (e.g. changes in pressure due to turbulence at some point of the
system boundary, spontaneous redistribution occurs until all parts of the system are at the same
property. A single value can, thus, be assigned to a property of a system in thermodynamic
equilibrium that is valid throughout the system domain. There are three types of equilibrium, the
separate condition of each which must be satisfied for a thermodynamic system to be in
thermodynamic equilibrium. They are (i). Thermal equilibrium, (ii). Mechanical equilibrium, and
(iii). Chemical equilibrium. For a system involving two phases, a fourth type of thermodynamic
equilibrium is phase equilibrium.
Thermal Equilibrium
A system is in thermal equilibrium if the temperature is the same throughout the entire system.
That is there must be no temperature gradient throughout the system.
Mechanical Equilibrium
Mechanical equilibrium is equality of pressure. A system is in mechanical equilibrium if the
pressure is the same at any point of the system with time such that there are no unbalanced forces
within the system.
Chemical Equilibrium
Chemical equilibrium is related to the chemical potential of a system to undergo chemical reaction.
A system is in chemical equilibrium when its chemical composition does not change with time
throughout the system, that is, it does not undergo chemical reaction anywhere within the system.
Phase Equilibrium
Applies to a system involving two phases; it is when the mass of each phase remains constant and
does not change with time, e.g. as occur in dry superheated steam changing to wet vapour.
A system will only be in thermodynamic equilibrium when all the relevant equilibrium criteria of
the above are satisfied.
1.5.2 Equilibrium of Thermodynamic States
Stable equilibrium
The thermodynamic state of a system is said to be in stable equilibrium if when the system is
perturbed or disturbed from the original state, it returns back to the state when the source of
disturbance is removed. The stable equilibrium state represents the state with the lowest energy.
The normal thermodynamic states of a system as defined by the equation of state for the system
are stable equilibrium states. Stable equilibrium states for steam/liquid water, thus, include the
states on the P-v, T-v, P-T, or the P-v-T surface for the substance.
Metastable equilibrium
A metastable equilibrium state is one to which a system returns after a small perturbation is
imposed on it, but which moves to different state with lower energy at which the system is more
stable on application of a larger perturbation. Examples of stable equilibrium states include the
following: Water at the pressure of 100 kPa and a temperature of 105 oC and not boiling. Under
this condition, when impurities are added, the water would start to boil. Another example is a
mixture of gasoline and air. The mixture appears stable until it is ignited by a small spark by which
it is converted rapidly into products (a stable state with lower energy level), releasing energy that
is many thousand times that of the spark that initiated the combustion process. A third example is
supersaturated or supercooled vapour, which can occur in nozzles with very high superheated
steam flow speed.
Unstable equilibrium
An unstable equilibrium state is a state for which any infinitesimal disturbance will cause a major
change of state to a different state. The infinitesimal disturbance may be in the form of a tiny
droplet formed in or introduced into a vapour.
1.5.3 Thermodynamic Process
A thermodynamic process is the path of successive states through which a system passes when it
changes from one equilibrium state to another. Thus, if anyone or more properties of a system
changes, the system is said to have undergone a process, i.e. there has been a change of state. Some
of the common thermodynamic process are as follows:
Isothermal Process
This is a process during which a system temperature remains constant. In an isothermal
compression, heat must be removed continuously from the system in order to maintain the
temperature of the system constant, while in an isothermal expansion heat must be added
continuously to maintain the system at a constant temperature. Examples of an isothermal process
include the boiling (shown in Figure 5) and condensation processes of water, processes undertaken
in the boiler and condenser of a Carnot cycle, or the evaporator and condenser of a Carnot
refrigerator or domestic refrigerator.
Isobaric Process
The pressure remains constant during an isobaric process. The process is illustrated in Figure 6.
Examples include the processes in a boiler and condenser of a steam power plant, or the evaporator
and condenser of a domestic refrigerator. It also includes external combustion processes, and the
induction and exhaust processes of spark-ignition (S. I.) engines and compression-ignition (C. I.)
engines.
 Fixed stopper

Saturated steam Saturated steam

Liquid H2O Liquid H2O

(a). Boiling with unrestrained piston (b). Boiling with restrained piston
Figure 5. Boiling processes as examples of an isothermal process

Figure 6. Heating at constant pressure

Isometric Process
An isometric process, also known as isochoric process, is a constant-volume process (Figure 7).
Examples include a pressure-cooker under heating, combustion process of S. I. engines, heat
addition and heat rejection processes of an Otto cycle, heat rejection process of an ideal diesel
cycle.

Figure 7. Heating at constant volume

Adiabatic Process
An adiabatic process is a process during which heat does not cross the system boundaries. The
process is illustrated in (Figure 8).

Figure 8. An adiabatic process

Examples include the processes in nozzles, diffusers, turbines, and rotary compressors. The
process is also closely approximated by flow along a pipe that is insulated on the external surface
of the wall, e.g. the indoor-outdoor units connecting pipe of split air-conditioners.
Isentropic Process
This is a reversible adiabatic process. It is governed by equation of the form 𝑃𝑣 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡,
where  is the ratio of specific heat at constant pressure (cp) to that at constant volume (cv), i.e.  =
cp/cv. The ideal process occurs in nozzles, diffusers, turbines, and rotary compressors where the
processes are assumed reversible.
Polytropic Process
A polytropic process is governed by an equation of the form 𝑃𝒗𝒏 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕, where n is
polytropic index which depends on the method of expansion and compression of the system. Most
practical gas compression and expansion processes can be approximated as polytropic, e.g. that of
a vulcanizer’s compressor machine.
Free Expansion
Free expansion occurs when a system, e.g. a gas, undergoes an expansion that is not restrained in
any way by an opposing force. As an illustration, we consider two vessels 1 & 2 connected by a
short pipe through a closed valve and perfectly insulated thermally, as shown in Figure 9. Initial
vessel 1 contains a fluid at a certain pressure, while vessel 2 is completely evacuated. When the
valve is opened, the fluid in vessel 1 will expand rapidly to fill the two vessels, causing the pressure
in vessel 1 to decrease and raising the pressure in vessel 2. This process of expansion is called free
expansion. It is a highly irreversible process, since there is a lot of eddying motion of the fluid that
accompanies the expansion.
 Figure 9. Free expansion process

Reversible Process
A reversible process is one in which a system is imagined to pass through a continuous series of
equilibrium states and any heat transfer and work transfer between the system and surroundings
are by infinitesimally small temperature difference and infinitesimally small differences in the
opposing forces due to their pressures. In the process, all properties are uniform throughout the
system (as shown in Figure 10a). Extensive properties can, thus, be written as the product of the
masses and their specific values, e.g. total internal energy 𝑈 = 𝑚𝑢 and total volume 𝑉 = 𝑚𝑣,
where u and v are specific internal energy and specific volume, respectively. The process is an
infinitesimally slow process, which can be stopped and made to proceed in the reverse direction
to its initial state. A reversible process is usually sketched on appropriate coordinates by using a
solid line between the initial and final states as shown in Figure 11a.
Internally Reversible and Externally Reversible Process
A process would only be reversible if it is both internally and externally reversible. In an internally
reversible process, the system passes through a continuous series of equilibrium states between the
initial and final states, and passes through the exact same states when the process is reversed to the
initial state. For the process therefore, the paths of the forward and reverse processes coincide. In
an externally reversible process, heat transfer between the system and surroundings is by
infinitesimally small temperature difference, and work transfer is by infinitesimally small
difference in the opposing forces due to the pressures of the system and surroundings.
Irreversible Process
This is a process during which the system does not pass through a continuous series of equilibrium
states. As a result, the extensive properties cannot be written as the product of their specific
properties and their masses, e.g. 𝑈 ≠ 𝑚𝑢, because u is not uniform throughout the system (Figure
10b). An example is a cup of hot coffee which once it cools will not heat up to the initial state by
retrieving the heat it lost from the surroundings. A dashed curve between the initial and end states
is normally used to represent the process as shown in Figure 11b.
 (a). A reversible process (b). An irreversible process
Figure 10. Reversible process and an irreversible process

(a). Quasi-equilibrium or reversible process (b). Non-quasi-equilibrium or irreversible process

Figure 11. A reversible process and an irreversible process

Quasi-Equilibrium and Non-Quasi-Equilibrium Processes

When a system passes from one state to another such that the deviation from equilibrium is
infinitesimal, a quasi-equilibrium process (a very nearly reversible process) occurs and each state
in the process may be idealized as an equilibrium state. The compression and expansion of gases
in an internal combustion engine, can be approximated as quasi-equilibrium processes with no
significant loss of accuracy.
Like the reversible process, a quasi-equilibrium process is usually sketched on appropriate
coordinates by using a solid line between the initial and final states.
A non-quasi-equilibrium process (or an irreversible process) goes from one equilibrium state to
another through a series of non-equilibrium states, e.g. a combustion process. For the process, a
dashed curve (as used for an irreversible process) is used to represent the change from an initial
state to a final state. Figure 12 a illustrates a quasi-equilibrium process, while Figure 12b illustrates
a non-quasi-equilibrium process.

(a). Quasi-equilibrium process

 (b). Non-quasi-equilibrium process
Figure 12. Quasi-equilibrium and non-quasi-equilibrium process

1.5.4 Thermodynamic Cycle

When a certain mass of substance (system) in a particular state passes through a series of quasi-
equilibrium processes and returns to its original state, the system is said to have undergone a
thermodynamic cycle. An example is the process undergone by a gas in the piston -cylinder system
shown in Figure 13. Another example of a thermodynamic cycle is the combination of processes
1 – 2 – 3 – 4 – 1 undergone by a Carnot cycle, the P-v and T-s diagrams, shown in Figure 14.

(a). Initial state at P = 5 bar, T = 120 oC

(b). Intermediate state at P = 0.75 bar, T = 30 oC

(c). Final sate at P = 5 bar, T = 120 oC

Figure 13. Piston-cylinder system undergoing a thermodynamic cycle

(a). P-v diagram of Carnot cycle (b). T-s diagram of Carnot cycle
Figure 14. The thermodynamic cycle of a Carnot cycle
1.6 Energy Concept
Energy is the capacity to produce an effect. It is inherent in all matter and is responsible for the
transformation of matter from one form to another. The mass of substance is related to its total
energy by or according to the relativistic equation (𝑬 = 𝒎𝒄𝟐 ), where E is total energy and c is the
velocity or speed of light. In thermodynamics, the absolute value of total energy of a system is not
of much importance; what matters is the change in the energy.
1.6.1 Forms of Energy
The various forms of energy of a system include kinetic, potential, flow energy or pressure energy,
mechanical, internal energy, sensible energy, latent energy, thermal energy, chemical energy,
nuclear energy, magnetic energy, electric energy, and surface tension energy. The forms of energy
constitute the total energy of a system. They are referred to as the static forms of energy. The
dynamic forms or energy interactions, which are heat and work transfers, are those recognized at
the boundaries of a system.
Kinetic energy
This is the energy of a system as a result of its motion. The total kinetic energy, usually just referred
to as kinetic energy, is expressed as
1
𝐾. 𝐸 = 2 𝑚𝑣 2

and on per unit mass basis as

1
𝑘. 𝑒 = 2 𝑣 2 .

Potential energy
Potential energy is the energy of a system as a result of its position (elevation) in a gravitational
field. It is expressed as
𝑃. 𝐸 = 𝑚𝑔𝑧
On per unit mass basis, it is expressed as
𝑝. 𝑒 = 𝑔𝑧
where z is the elevation or height above certain datum.
Mechanical energy
It is the form of energy that can be converted to mechanical work completely and directly by an
ideal mechanical device such as an ideal turbine or an ideal pump. A pump transfers mechanical
energy to a fluid by raising its pressure, while a turbine extracts mechanical energy from a fluid
by dropping its pressure. Thermal energy is not mechanical energy. The various forms of
mechanical energy include kinetic energy, potential energies, and flow or pressure energy for a
flowing fluid.
In thermodynamics, the various forms of energy are grouped into those a system possesses as a
whole, in relation to motion and the influence of some external effects, with respect to some outside
reference frames, called macroscopic forms of energy, and those related to the molecular structure
of a system and the degree of the molecular activity and are independent of outside reference
frames, called microscopic forms of energy. The sum of the microscopic forms of energy is called
internal energy.
Macroscopic forms of energy
The macroscopic forms of energy refer to the energies a system has as a whole. They consist of
potential energy, kinetic energy, and energies due to influence of some external effects such as
magnetic, electric, and surface tension effects, usually significant in some specialized cases only.
The most significant are kinetic energy and potential energy.
Microscopic forms of energy
The microscopic forms of energy or internal energy consists of the sum of internal kinetic energies
and the sum of internal potential energies of a system. The microscopic kinetic energies include
the following:
(a). Kinetic energy of the molecules as they move through space, also called translational
energy
(b). Rotational kinetic energy of the molecules as they rotate about an axis
(c). Vibrational kinetic energy of the molecules about their common center of mass
(d). Translational energy of the electrons
(e). Rotational kinetic energy of the electrons about the nucleus
(f). Spin energy of the electrons about their axes
(h). Nuclear spin energy
The portion of the internal energy of a system associated with the kinetic energies of the molecules
is called the sensible energy. It comprises all the microscopic kinetic energies: the molecular
translation, molecular rotation, molecular vibration, electron translation, electron rotation, electron
spin, and nuclear spin energies.
The microscopic potential energies include the following:
(a). The binding or bonding forces between the molecules of a substance, associated with
phase change. The internal energy associated with the phase of a system is called the
latent energy. It is the energy by which the intermolecular forces between the molecules
of a system, which bind the molecules to each other, are overcome to cause a change from
one phase of the system to another.
(b). The binding forces between the atoms within a molecule
(c). The binding forces between the sub-atomic particles, within an atom and its nucleus
(neutrons and positively charge protons in the nucleus, and negatively charged electrons
orbiting the nucleus).
(d). Nuclear binding forces
The internal energy associated with the atomic bonds in a molecule is called chemical energy (e.g.
as encountered during a chemical reaction such as combustion), while that associated with the
tremendous amount of energy associated with the strong bonds within the nucleus of the atom
itself is called nuclear energy. In thermodynamics, the sensible and latent forms of internal energy
are often referred to as thermal energy.
It is to be noted that mechanical energy is the sum of kinetic energy, potential energy, and flow
or pressure energy, while thermal energy is the sum of internal energy and sensible energy.
The sum of all the forms of energy is the total energy of a system. In the absence of external effects
such as magnetism, electricity and surface tension effects, which is the case in most instances, the
total energy (E) of a system, thus, consists of kinetic energy (KE), potential energy (PE), and
internal energy (U) and is often expressed, with unit in kJ, as
𝐸 = 𝑈 + 𝐾𝐸 + 𝑃𝐸
1
= 𝑈 + 2 𝑚𝑣 2 + 𝑚𝑔𝑧 (1.2)

On a per unit basis with unit in kJ/kg called specific energy, it is expressed as
𝑒 = 𝑢 + 𝑘𝑒 + 𝑝𝑒
1
= 𝑢 + 2 𝑣 2 + 𝑔𝑧 (1.3)

Stationary System
A stationary system is a system which experiences no change in its kinetic and potential energy
during a process. The change in the total energy of the system is, thus, equal to the change in its
internal energy, i.e. ∆𝐸 = ∆𝑈. Most closed systems are stationary systems.

1.7 Modes of Energy Transfer - Heat and Work Transfer

1.7.1 Concept of Heat
Heat is an energy interaction between two systems or between a system and its surroundings that
takes place because of a temperature difference. In thermodynamics, heat and energy are different.
Energy is a property, heat is not. Heat is a path function. Energy is associated with a state; heat is
associated with a process. A body contains energy, but not heat. Heat is energy interaction. It is
recognized only as it crosses the boundary.
As a form of energy transfer, heat also has energy unit (kJ or Btu). Heat is a directional quantity.
The heat transferred to a system increases the energy of the system, while that transferred from a
system decreases the energy of the system. The universally adopted sign convention for heat is,
thus, as follows: heat transfer to a system is positive, while heat transfer from a system is negative.
Reversible Heat Transfer
Reversible heat transfer is a heat transfer process in which the reservoir temperature is never more
than infinitesimally different in temperature from that of the system at any point during the process
in order that temperature gradient will not be produced in the fluid, and, thus, ensuring that the
process through a series of equilibrium states. Otherwise, the properties will be non-uniform
throughout the system and the whole process would be rendered irreversible. The implication is
that the process has to be carried out infinitesimally slowly in order to achieve a reversible heat
transfer process, which renders the complete process impracticable.
Heat Reservoir
This is the part of the surroundings, with which a system exchanges energy because it is at a
temperature different from that of the system, which has such a capacity that any quantity of heat
which crosses its boundary during a process is insignificant or insufficient to change its
temperature. The reservoir is either a heat source or heat sink.
Heat Source
A heat source is a reservoir which has such a large capacity to supply a quantity of heat without
undergoing a temperature change. Examples include furnace gases, combustion gases, condensing
vapour, and boiling liquid.
Heat Sink
A heat sink is a reservoir with such a large capacity to receive any quantity of heat without any
change in its temperature. Practical examples include lake, river, the earth`s atmosphere, and
melting solid.
1.7.2 Concept of Work
Work is an energy interaction across the boundary of a system due to the movement of a part of
the boundary under the action of force. Mechanical work is quatified as the product of
displacement and the component of force in the direction of the displacement.
For a general thermodynamic system consisting of a fluid under the action of a force, shown in
Figure 15, the elemental work dw due to the movement causing a change in volume dv of the
boundary under the action of pressure P is expressed as
𝑑𝑤 = 𝑃𝑑𝑣

dV
P

Figure 15. General thermodynamic system

The total work W for a finite deformation V of the system between any two states 1 and 2 is
expressed by
2 2
𝑊1−2 = ∫1 𝑑𝑤 = ∫1 𝑃𝑑v

where 1 and 2 represent systematic states 1 and 2. The evaluation of the integral in the equation
depends on the definition of the pressure function P.
Work, like heat, is a path function, i.e. the magnitude depends on the path followed during the
process, as well as the end states. The work transfer between any two states is, thus, expressed as
2
∫1 𝛿𝑤 = 𝑊1−2

As a form of energy transfer, work has energy units such as kJ. Like heat, work is a directional
quantity. In thermodynamics, while the production of work is viewed as desirable, positive effect,
while the consumption of work is considered undesirable. Consequently, the sign convention
adopted for work is that work done by a system is positive; while that done on a system is negative.
The similarities between heat and work can therefore be stated as follows:
(i). Both are recognized at the boundaries of a system as they cross the boundaries. That is,
both heat and work are boundary phenomena.
(ii). Systems possess energy, but not heat or work.
(iii). Both are associated with a process, not a state. Unlike properties, heat or work has no
meaning at a state.
(iv). Both are path functions (i.e., their magnitudes depend on the path followed during a
process as well as the end states).
Reversible Work
Reversible work transfer is a work transfer process in which the action force due to system pressure
is only infinitesimally different from the restraining force due to the pressure exerted by the
surroundings on the system boundary, so that no pressure gradients or eddies are set up in the fluid
and, thus, ensuring that the process passes through a series of equilibrium states. Otherwise, the
properties will be non-uniform throughout the system and the whole process would be rendered
irreversible. The process is also an infinitesimally slow process and, thus, impracticable.
Forms of work
Work can generally be classified into mechanical work and non-mechanical work.
Common mechanical forms of work are as follows:
(i). Moving boundary work Wb,
(ii). Shaft work Ws,
(iii). Gravitational work Wg,
(iv). Acceleration work Wa,
(v). Spring work Wsp, or work done on elastic solid bars Wes,
(vi). Surface tension work Wst.
(vii). Flow work Wfl
The non-mechanical forms of work include
(i). Electrical work 𝑊𝑒 ,
(ii). Magnetic force,
 (iii). Electric polarization work.
Shaft work
Mechanical work W is defined as the product of displacement s and the component of force F in
the direction of the displacement. This can be expressed mathematically as
𝑊 = 𝐹𝑠. For a non-constant force, the total work is obtained by adding or integrating the
differential amounts of work as
2
𝑊 = ∫1 𝐹𝑑𝑠

For a constant torque T applied to a shaft which generates force F at a moment arm r,
𝑇 = 𝐹𝑟,
𝑇
⇨ 𝐹=𝑟

The distance s acted through by the force in n revolutions can be expressed as

𝑠 = 2𝜋𝑟𝑛
And the shaft work
𝑇
𝑊𝑠 = 𝐹𝑠 = (𝑟 ) (2𝜋𝑟𝑛) = 2𝜋𝑛𝑇

Gravitational work
Work done in a gravitational field results in raising the height of a body above an initial position,
which thus increases the potential energy. Gravitational work is, thus, equal to the change in the
potential energy of the body, and can be expressed as follows:
𝑊𝑝 = 𝑚𝑔𝛥𝑍

where ΔZ is the change in the vertical position of the body.

Moving Boundary Work
In the cylinder-piston system, shown in Figure 16a, the pressure of the fluid at any instant is ‘P’
and the force is ‘PA’, where A is the x-sectional area of the piston. The restraining force is only
infinitesimally smaller than ‘PA’. During an infinitesimal movement of the piston over a distance
’dl’, P is assumed constant. In moving the external force PA through the distance dl, the work
done.
𝛿𝑊𝑏 = 𝐹𝑑𝑠 = 𝑃𝐴𝑑𝑠
But 𝐴𝑑𝑠 = 𝑑𝑉, which is the infinitesimal change in volume. Therefore
𝛿𝑊𝑏 = 𝑃𝑑𝑉
For an expansion process from pressure P1 to pressure P2 in which the opposing forces are
infinitesimally different in magnitude throughout the process, the total work done is the integration
of the incremental work from state 1 to state 2, i.e.
2 2
∫1 𝛿𝑊𝑏 = 𝑊1−2 = ∫1 𝑃𝑑𝑉
The specific work,
2
𝑤1−2 = ∫1 𝑃𝑑𝑣

where v is the specific volume.

The process can be represented on a P-v chart as follows (Figure 16b):

Figure 16. Work done by a piston-cylinder system

This indicates that the area under the curve in the P-v diagram represents the specific work done.
It should be noted that work is only done when there is a restraining force at the moving boundary.
In the case in which there is no restraining force at the moving boundary e.g. during free expansion,
there is no work done even through the boundary of the system has undergone some movement.
It is also to be noted that work done by a system in a reversible process is always greater than that
when the process is irreversible. The condition of reversibility of a work transfer process means
that the process is an infinitesimally slow one, which renders it an ideal process that can only be
approached but not completed achievable in practice.
Flow Work or Flow Energy
In stationary systems such as most closed systems, the two means of energy exchange are by heat
transfer and by work transfer. For non-stationary systems, such as control volumes, mass flow
provides an additional means of energy exchange. Control volumes involve mass flow across their
boundaries which requires some work to push the mass into or out of the control volume. This
work necessary for maintaining a continuous flow through the control volume is known as flow
work or flow energy.
Consider the control volume shown in Figure 17, into and out of which a fluid is flowing. The
fluid immediately upstream of the fluid element of volume V, pressure P, and mass m forces the
element to enter the control volume. The upstream fluid can, thus, be regarded as an imaginary
piston. The force F applied on the fluid element of cross-sectional area A can be written as
𝐹 = 𝑃𝐴
To push the entire fluid element into the control volume, the force must act through a distance L,
so that the work done called flow work for the process
 𝑊𝑓𝑙 = 𝐹𝐿

= 𝑃𝐴𝐿 = 𝑃𝑉
The flow work per unit mass can, thus, be expressed as
𝑤𝑓𝑙 = 𝑃𝑣

Figure 17. Control volume with a piston-cylinder system

The flow work is the energy needed to push a fluid into and out of a control volume. The work is
also referred to as convected energy, flow energy or transport energy. It is usually considered as
part of the energy of a flowing fluid as it greatly simplifies the energy analysis.

CHAPTER 2. LAWS OF THERMODYNAMICS, CONSEQUENCES & APPLICATIONS

2.1 Introduction
There are four fundamental laws upon which analysis of thermodynamic systems and process are
based. These are the zeroth law, the 1st, 2nd, and 3rd laws of thermodynamics. The laws are based
on experimental observations. The 3rd law has applications particular in chemical thermodynamics
and low-temperature physics. We would focus attention mainly on the 1st three laws.

2.2 Zeroth Law of Thermodynamics

The zeroth law states that if two bodies isolated from other environment are each in thermal
equilibrium with a third body, then the two bodies are in thermal equilibrium with each other. The
condition for thermal equilibrium is equality of temperature. If two bodies with different
temperatures are brought into contract, heat would be transferred from the body at higher
temperature to the one at lower temperature until both attain the same temperature. At this point,
heat transfer stops and the two bodies are said to have reached thermal equilibrium. However, it
must be ensured that the third body is able to reach thermal equilibrium with each of the other two
bodies as rapidly as possible. To achieve this, then the other two systems must act as heat reservoirs
or heat sink in comparison to the third body. This is the basis of thermometry.
The zeroth law forms the basis for the development of thermometry for temperature measurement.
The third body mentioned in the law is devised to possess an easily observable thermometric
property, such as the pressure of a gas in a closed vessel, the length of a column of mercury in a
capacity tube, or the resistance of a platinum wire.
The device can then be graduated with a scale of temperature. To compare the degree of hotness
or coldness of any two systems would then not require the contact interactions of the systems, but
would only need measuring the temperature of each of the systems with the thematic or
thermometer and compare the magnitude of the temperature readings of the systems.
Temperature Scales
The common temperature scale used in S. I and English system of units are the Celsius scale
(named after the Swedish astronomer Anders Celsius 1701 - 1744 who devised the scale) formerly
called the centigrade scale and the Fahrenheit scale (named after the German instrument maker
Gabriel Fahrenheit 1686 - 1736). The Celsius scale has the ice and steam points assigned the values
0oC and 100o C, respectively, while the corresponding values on the Fahrenheit scale are 32oF and
212oF.
A more useful temperature scale in thermodynamics is the absolute scale. On the scale, there is no
negative temperature values, and the lowest temperature attainable is zero. The absolute
temperature scale in the S. I system I the Kelvin scale (named after W. Thompson 1824 – 1907,
also known as Lord Kelvin). The temperature unit on the scale is the Kelvin, designated K without
a degree symbol. The Kelvin scale is related to the Celsius scale by
T(K) = T(oC) + 273.15
In the English system, the absolute temperature scale is the Rankine scale (named after W. J. M.
Rankive, 1802 – 1872). The scale is related to the Fahrenheit scale as
T(R) = T(oF) + 459.67
In practice, the constant in the equation relating the Kelvin scale and the Celsius scale and that
relating the Rankine scale and the Fahrenheit scale are normally rounded.

2.3 First Law of Thermodynamics

The first law of thermodynamics is a statement of the conservation of energy principle that energy
can be neither created nor destroyed, but that energy can only change forms. The law is stated as
follows: “when a closed system is taken through a cycle, the network delivered to the surroundings
is proportional to the net heat taken from the surroundings.” Mathematically, it is expressed as
⨊ 𝛿𝑄 𝛼 ⨊ 𝛿𝑊 (2.1)
The gas enclosed by a cylinder and piston, shown in Figure 18, is an example of a system which
may undergo the cyclic process described by the 1st law.

δQ δW

Figure 18. Gas enclosed in a piston-cylinder system undergoing a cyclic process

A source of heat supplied from the surroundings to the gas causes it to expand, pushing the piston
onward and doing work on the surroundings. To return the gas to the original state, some quantity
of heat has to be transferred from the gas to a heat sink in the surroundings and some work has to
be done by the surroundings in pushing the piston back to the original position.
In equation (2.1), denoting the constant of proportionality by 𝒯, the equation may be re-written as
𝒯. ⨊ 𝛿𝑄 = ⨊ 𝛿𝑊 (2.2)
The constant 𝒯 is called the mechanical equivalent of heat. When the units of work and heat are
defined on the same basis, 𝒯 takes a value equal to unity and the equation (2.2) reduces to
⨊ 𝛿𝑄 = ⨊ 𝛿𝑊 (2.3)
In other words, the 1st law states that the net heat is equal to the network during a cycle undergone
by a closed system. For appropriately defined elemental heat and work functions, equation (2.3)
may also be written as

∮ 𝑑𝑄 = ∮ 𝑑𝑊 (2.4)
The first law does not have a formal proof as it could not be shown to result from a more general
proposition about nature. The proof, instead, lies in showing that certain propositions, referred to
as corollaries, of the law violate the law when the contrary of the corollaries takes place.
2.3.1 Corollaries of the First Law
Corollary 1
“There exists a property of a closed system such that a change in its value is equal to the difference
between the heat supplied and the work done during any change of state.”
The Non-Flow Energy Equation (NFEE)
The non-flow energy equation emerges as a result of the proof of corollary 1 using the 1 st law of
thermodynamics. Let us consider any two processes A and B by which a system can change from
state 1 to state 2, and a third process C by which the system can return to its original state in each
case, as shown in Figure 19.

Figure 19. Process between two states in a thermodynamic cycle

By the 1st law of thermodynamics, for the complete cycle AC,
⨊(𝛿𝑄 − 𝛿𝑊)𝐴𝐶 = ∑21(𝛿𝑄 − 𝛿𝑊)𝐴 + ∑12(𝛿𝑄 − 𝛿𝑊)𝐶 = 0 (2.5)

And for the complete cycle BC,

⨊(𝛿𝑄 − 𝛿𝑊)𝐵𝐶 = ∑21(𝛿𝑄 − 𝛿𝑊)𝐵 + ∑12(𝛿𝑄 − 𝛿𝑊)𝐶 = 0 (2.6)

This indicates that ∑21(𝛿𝑄 − 𝛿𝑊) is independent of the path (process), and must therefore be a
property of the system. The resulting property is called internal energy, denoted U, of the system.
The corollary can, thus, be expressed as
∑21(𝛿𝑄 − 𝛿𝑊) = 𝑈2 − 𝑈1 (2.7)
Writing Q and W for the net quantities of heat and work, respectively, during the change of state,
equation (2.7) becomes
𝑄1−2 − 𝑊1−2 = 𝑈2 − 𝑈1 (2.8a)
Equation (2.8) is often written without the subscripts associated to the heat and work quantities as
𝑄 − 𝑊 = 𝑈2 − 𝑈1 (2.8b)
Equation (2.8) is called the non-flow energy equation (NFEE). The non-flow energy equation is
usually written on per unit mass basis as
𝑞1−2 − 𝑤1−2 = 𝑢2 − 𝑢1 (2.9a)
Dropping the subscripts attached to the heat and work quantities, the equation is expressed as
𝑞 − 𝑤 = 𝑢2 − 𝑢1 (2.9b)
For a reversible process, the form of the equation applicable to any infinitesimal part of the process
between the initial and final states is the differential form expressed as
𝑑𝑞 − 𝑑𝑤 = 𝑑𝑢 (2.10)
When compared with the expression of the total energy of a system, equations (1.2) and (1.3), it
would be observed that the non-flow energy equations (2.7) – (2.10) indicate that the total change
in the energy of a closed system arising from the exchange of energy in the form of heat transfer
and work transfer between the system and the surroundings is equal to the change in internal energy
of the system.
Corollary 2
“The internal energy of a closed system remains unchanged if the system is isolated from its
surroundings.”
Often called the law of conservation of energy, the corollary follows from the non-flow energy
equation that results from corollary 1 and the definition of an isolated system as one for which net
heat input Q and network output W are both zero. When Q and W are equated to zero in equation
(2.8), then it could be seen that 𝑈2 = 𝑈1 , or ∆𝑈, which is change in internal energy, remains