Thermodynamics

Course Outcome

1. Identify the different properties of pure substance, Ideal gas and

real gas
2. Apply thermodynamic concepts and principles in analyzing and
solving problems.
3. Apply the laws of thermodynamics in analyzing problems.
4. Evaluate the performance of thermodynamic cycles.
INTRODUCTION AND BASIC CONCEPTS

OBJECTIVES
The objectives of Chapter 1 are to:
• Identify the unique vocabulary associated with thermodynamics through the precise definition of
basic concepts to form a sound foundation for the development of the principles of
thermodynamics.
• Review the metric SI and the English unit systems that will be used throughout the text.
• Explain the basic concepts of thermodynamics such as system, state, state postulate, equilibrium,
process, and cycle.
• Discuss properties of a system and define density, specific gravity, and specific weight.
• Review concepts of temperature, temperature scales, pressure, and absolute and gage pressure.
• Introduce an intuitive systematic problem-solving technique.
What is Thermodynamics?

Thermodynamics can be defined as

the science of energy.
From: THERMODYNAMICS
AN ENGINEERING APPROACH
EIGHTH EDITION
Yunus A. Çengel & Michael A. Boles
Thermodynamics is a science in which the storage, the transformation,
and the transfer of energy are studied. Energy is stored as internal energy
(associated with temperature), kinetic energy (due to motion), potential
energy (due to elevation) and chemical energy (due to chemical
composition); it is transformed from one of these forms to another; and it
is transferred across a boundary as either heat or work.
Thermodynamics :

The study of energy transformations and

the relationships among the physical
properties of substances which are
affected by these transformations.
conservation of energy principle:

States that during an interaction, energy can

change from one form to another but the
total amount of energy remains constant.
That is, energy cannot be created or
destroyed.

The first law of thermodynamics is simply an expression of the conservation of energy

principle, and it asserts that energy is a thermodynamic property.
A rock falling off a cliff, for example, picks up speed as a result of its potential energy being converted to kinetic
energy (Fig. 1–1).
The conservation of energy principle also forms the backbone of the diet industry: A person who has a greater energy input
(food)than energy output (exercise) will gain weight (store energy in the form of fat), and a person who has a smaller energy
input than output will lose weight (Fig. 1–2). The change in the energy content of a body or any other system is equal to the
difference between the energy input and the energy output, and the energy balance is expressed as E in – E out = ΔE.
The second law of thermodynamics asserts that energy has quality as well as
quantity, and actual processes occur in the direction of decreasing quality of energy.
For example, a cup of hot coffee left on a table eventually cools, but a cup of cool
coffee in the same room never gets hot by itself (Fig. 1–3). The high-temperature
energy of the coffee is degraded (transformed into a less useful form at a lower
temperature) once it is transferred to the surrounding air.
In thermodynamics we will develop mathematical equations that relate
the transformations and transfers of energy to material properties such
as temperature, pressure, or enthalpy. Substances and their properties
thus become an important secondary theme. Much of our work will be
based on experimental observations that have been organized into
mathematical statements, or laws; the if first and second laws of
thermodynamics are the most widely used.
The engineer’s objective in studying thermodynamics is most often
the analysis or design of a largescale system—anything from an air-
conditioner to a nuclear power plant. Such a system may be regarded
as a continuum in which the activity of the constituent molecules is
averaged into measurable quantities such as pressure, temperature,
and velocity. This outline, then, will be restricted to macroscopic or
engineering thermodynamics. If the behavior of individual molecules
is important, a text in statistical thermodynamics must be consulted
Application Areas
of Thermodynamics
(as Mechanical Engineers )
Thermodynamics is applied to diverse area:

• Stationary and mobile power producing units

• Refrigeration and air conditioning processes (HVAC)
• Fluid Expanders (Turbines) and Compressors (pump for liquids)
• Jet engines and rockets
• Chemical Processing and in oil Refineries
• Industrial Manufacturing Processes
• Food & Beverages
• Combustion and hydrocarbon fuels
• Solar Energy (Thermal)
• Geothermal Energy Utilizations
• Wind Energy
• Tidal Power
IMPORTANCE OF DIMENSIONS AND UNITS

Any physical quantity can be characterized by dimensions. The

magnitudes assigned to the dimensions are called units. Some basic
dimensions such as mass m, length L, time t, and temperature T are
selected as primary or fundamental dimensions, while others such as
velocity V, energy E, and volume V are expressed in terms of the
primary dimensions and are called secondary dimensions, or derived
dimensions.
While the student is undoubtedly most at home with SI
(Systems International) units, much of the data
gathered in the United States is in English units.
Therefore, a certain number of examples and problems
will be presented in English units. Table 1-1 lists units
of the principal thermodynamic quantities. Observe
the dual use of W for weight and work; the context and
the units will make clear which quantity is intended.
When expressing a quantity in SI units certain letter prefifixes may be used to
represent multiplication by a power of 10; see Table 1-2.
The units of various quantities are interrelated via the physical laws obeyed by
the quantities. It follows that, in either system, all units may be expressed as
algebraic combinations of a selected set of base units. There are seven base units
in the SI system: m, kg, s, K, mol (mole), A (ampere), cd (candela). The last two are
rarely encountered in engineering thermodynamics.
EXAMPLE 1.2
Newton’s second law, F = ma, relates a net force acting on a body to its mass and
acceleration. If a force of one newton accelerates a mass of one kilogram at one
m/s² ; or, a force of one lbf accelerates 32.2 lbm (1 slug) at a rate of one ft/sec² ,
how are the units related?
Solution: The units are related as
1 N = 1 kg.m/s²
or
1 lbf = 32.2 lbm-ft/sec²
EXAMPLE 1.3

Weight is the force of gravity; by Newton’s second law, W = mg. How does weight
change with elevation?

Solution:
Since mass remains constant, the variation of W with elevation is due to changes in
the acceleration of gravity g (from about 9.77 m/s² on the highest mountain to 9.83
m/s² in the deepest ocean trench).
We will use the standard value 9.81 m/s² (32.2 ft/sec² ), unless otherwise stated.
EXAMPLE 1.4
Express the energy unit J (joule) in terms of SI base units: mass, length, and time.
Solution:
Recall that energy or work is force times distance. Hence, by Example 1.2, the
energy unit J (joule) is:
1 J = (1 N) · (1 m) = (1 kgm/ s²) · (1 m) = 1 kgm²/ s²
In the English system both the lbf and the lbm are base units. As indicated in Table
1-1, the primary energy unit is the ft-lbf. By Example 1.2,
1 ft-lbf = 32.2 lbm-ft²/sec² = 1 slug-ft²/sec²
THERMODYNAMIC SYSTEMS AND CONTROL VOLUME

A thermodynamic system is a definite quantity of matter contained

within some closed surface. The surface is usually an obvious one like
that enclosing the gas in the cylinder of Fig. 1-1; however, it may be an
imagined boundary like the deforming boundary of a certain amount of
mass as it flows through a pump. In Fig. 1-1 the system is the
compressed gas, the working fluid, and the system boundary is shown
by the dotted line.
All matter and space external to a system is collectively called its surroundings.
Thermodynamics is concerned with the interactions of a system and its surroundings,
or one system interacting with another. A system interacts with its surroundings by
transferring energy across its boundary. No material crosses the boundary of a given
system. If the system does not exchange energy with the surroundings, it is an
isolated system.
In many cases, an analysis is simplified if attention is focused on a volume in space into
which, or from which, a substance flows. Such a volume is a control volume. A pump, a
turbine, an inflating balloon, are examples of control volumes. The surface that
completely surrounds the control volume is called a control surface. An example is
sketched in Fig. 1-2.
We thus must choose, in a particular problem,
whether a system is to be considered or whether a
control volume is more useful. If there is mass flux
across a boundary of the region, then a control
volume is required; otherwise, a system is identified.
We will present the analysis of a system first and
follow that with a study using the control volume.
1.3 MACROSCOPIC DESCRIPTION
In engineering thermodynamics we postulate that the
material in our system or control volume is a
continuum; that is, it is continuously distributed
throughout the region of interest. Such a postulate
allows us to describe a system or control volume using
only a few measurable properties.
Consider the definition of density given by:

where ∆m is the mass contained in the volume ∆V, shown in Fig. 1-3. Physically, ∆V
cannot be allowed to shrink to zero since, if ∆V became extremely small, ∆m would vary
discontinuously, depending on the number of molecules in ∆V. So, the zero in the
definition of 𝜌 should be replaced by some quantity Ɛ, small, but large enough to
eliminate molecular effects. Noting that there are about 3 X 10ᶦ⁶ Type equation here.
molecules in a cubic millimeter of air at standard conditions Ɛ, need not be very large to
contain billions and billions of molecules. For most engineering applications Ɛ is
sufficiently small that we can let it be zero, as in (1.1)
There are, however, situations where the continuum assumption is not valid, for
example, the reentry of satellites. At an elevation of 100 km the mean free path,
the average distance a molecule travels before it collides with another molecule, is
about 30 mm; the macroscopic approach is already questionable. At 150 km the
mean free path exceeds 3 m, which is comparable to the dimensions of the
satellite! Under these conditions statistical methods based on molecular activity
must be used.
1.4 PROPERTIES AND STATE OF A SYSTEM

The matter in a system may exist in several phases: as a solid, a liquid, or a gas. A
phase is a quantity of matter that has the same chemical composition throughout;
that is, it is homogeneous. Phase boundaries separate the phases, in what, when
taken as a whole, is called a mixture.
A property is any quantity which serves to describe a system. The state of a system
is its condition as described by giving values to its properties at a particular instant.
The common properties are pressure, temperature, volume, velocity, and position;
but others must occasionally be considered. Shape is important when surface
effects are significant; color is important when radiation heat transfer is being
investigated.
The essential feature of a property is that it has a unique value when a system is
in a particular state, and this value does not depend on the previous states that
the system passed through; that is, it is not a path function. Since a property is
not dependent on the path, any change depends only on the initial and fifinal
states of the system. Using the symbol to represent a property, the mathematical
equation is

This requires that dΦ be an exact differential Φ2 − Φ1 represents the change in the

property as the system changes from state 1 to state 2. There are quantities which
we will encounter, such as work, that are path functions for which an exact
differential does not exist.
A relatively small number of independent properties suffice to fix all other
properties and thus the state of the system. If the system is composed of a single
phase, free from magnetic, electrical, and surface effects, the state is fixed when
any two properties are fixed; this simple system receives most attention in
engineering thermodynamics.
Thermodynamic properties are divided into two general types, intensive and
extensive. An intensive property is one which does not depend on the mass of
the system; temperature, pressure, density, and velocity are examples since they
are the same for the entire system, or for parts of the system. If we bring two
systems together, intensive properties are not summed.
An extensive property is one which depends on the mass of the system; volume,
momentum, and kinetic energy are examples. If two systems are brought
together the extensive property of the new system is the sum of the extensive
properties of the original two systems.
If we divide an extensive property by the mass a specifific property results. The
specific volume is thus defined to be:

We will generally use an uppercase letter to represent an extensive

property [exception: m for mass] and a lowercase letter to denote the
associated intensive property.
THERMODYNAMIC EQUILIBRIUM; PROCESSES
When the temperature or the pressure of a system is referred to, it is assumed
that all points of the system have the same, or essentially the same, temperature
or pressure. When the properties are assumed constant from point to point and
when there is no tendency for change with time, a condition of thermodynamic
equilibrium exists. If the temperature, say, is suddenly increased at some part of
the system boundary, spontaneous redistribution is assumed to occur until all
parts of the system are at the same temperature.
If a system would undergo a large change in its properties when subjected to
some small disturbance, it is said to be in metastable equilibrium. A mixture of
gasoline and air, or a large bowl on a small table, is such a system.
When a system changes from one equilibrium state to another, the path of
successive states through which the system passes is called a process. If, in the
passing from one state to the next, the deviation from equilibrium is
infinitesimal, a quasi equilibrium process occurs and each state in the process
may be idealized as an equilibrium state. Many processes, such as the
compression and expansion of gases in an internal combustion engine, can be
approximated by quasi equilibrium processes with no significant loss of
accuracy.
If a system undergoes a quasi equilibrium process (such as the thermodynamically slow
compression of air in a cylinder) it may be sketched on appropriate coordinates by using a
solid line, as shown in Fig. 1-4a.
If the system, however, goes from one equilibrium state to another through a
series of non equilibrium states (as in combustion) a non equilibrium process
occurs. In Fig. 1-4b the dashed curve represents such a process; between (V1; P1)
and (V2; P2) properties are not uniform throughout the system and thus the state
of the system cannot be well defined.
EXAMPLE
Whether a particular process may
be considered quasi equilibrium or
nonequilibrium depends on how
the process is carried out. Let us
add the weight W to the piston of
Fig. 1-5. Explain how W can be
added in a non equilibrium manner
and in an equilibrium manner.

Solution: If it is added suddenly as one large

weight, as in part (a), a nonequilibrium
process will occur in the gas, the system. If we
Note that the surroundings play no part in the notion divide the weight into a large number of small
of equilibrium. It is possible that the surroundings do weights and a dd them one at a time, in part
work on the system via friction; for quasi equilibrium
it is only required that the properties of the system (b), a quasi equilibrium process will occur.
be uniform at any instant during a process.
When a system in a given initial state
experiences a series of quasi equilibrium
processes and returns to the initial state,
the system undergoes a cycle. At the end
of the cycle the properties of the system
have the same values they had at the
beginning; see Fig. 1-6.
The prefix iso- is attached to the name of
any property that remains unchanged in a
process. An isothermal process is one in
which the temperature is held constant;
in an isobaric process the pressure
remains constant; an isometric process is
a constant-volume process. Note the
isobaric and the isometric legs in Fig. 1-6.