Engg Thermodynamics

21AE44 : IV Sem AE

UNIT I: FUNDAMENTAL CONCEPTS AND

DEFINITIONS

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Thermodynamics can be defined as the science of energy.

Although everybody has a feeling of what energy is, it is difficult to

give a precise definition for it.

Energy can be viewed as the ability to cause changes.

The name thermodynamics stems from the Greek words therme

(heat) and dynamics (power), which is most descriptive of the early
efforts to convert heat into power.

Today the same name is broadly interpreted to include all aspects of

energy and energy transformations including power generation,
refrigeration, and relationships among the properties of matter.

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One of the most fundamental laws of nature is the
conservation of energy principle. It simply 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.
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The first law of thermodynamics is simply an expression of the conservation of
energy principle, and it asserts that energy is a thermodynamic property.

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.

The first and second laws of thermodynamics

emerged simultaneously in the 1850s,
primarily out of the works of William Rankine,
Rudolph Clausius, and Lord Kelvin (formerly
William Thomson).

The term thermodynamics was first used in a

publication by Lord Kelvin in 1849.

The first thermodynamics textbook was

written in 1859 by William Rankine, a
professor at the University of Glasgow.
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Thermodynamics:

Therme - Heat/ Power, Dynamics - Transit

“ Heat Power” “ Energy in transit”

It is the science of “ Energy & Entropy”

Alternative Definition: Thermodynamics is the

science that deals with Heat and Work and
those properties that bear a relation with heat
and work.

Temperature, Pressure, Volume

Thermodynamic System:
It is a quantity of matter or region in space upon which attention is
focused for study.
Or
A thermodynamic system is a device or combination of devices
containing a quantity of matter that is being studied.
Examples of TD Systems
CONTROL MASS AND CONTROL VOLUME

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 1-2

Classification of systems:
1) Closed Systems 2) Open Systems 3)Isolated Systems

1. Closed System:

Energy, not mass, crosses closed-system boundaries

Ex: INTERNAL COMBUSTION
ENGINE CYLINDER
 1-4

2. Open System (Control Volume)

Mass and Energy Cross

Control Volume Boundaries
Ex: Centrifugal Pump
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3. ISOLATED SYSTEM
Neither energy nor
mass can cross
system boundary

Ex: Thermos
Flask
Systems may be considered to be closed or open, depending on
whether a fixed mass or a fixed volume in space is chosen for study.

A closed system (also known as a control mass or just system when

the context makes it clear) consists of a fixed amount of mass, and no
mass can cross its boundary.

That is, no mass can enter or leave a closed system. But energy, in the
form of heat or work, can cross the boundary; and the volume of a
closed system does not have to be fixed.

If, as a special case, even energy is not allowed to cross the boundary,
that system is called an isolated system.

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A large number of engineering problems involve mass flow in and
out of a system and, therefore, are modeled as control volumes.

A water heater, a car radiator, a turbine, and a compressor all involve

mass flow and should be analyzed as control volumes (open
systems) instead of as control masses (closed systems).

In general, any arbitrary region in space can be selected as a control

volume. There are no concrete rules for the selection of control
volumes, but the proper choice certainly makes the analysis much
easier.

If we were to analyze the flow of air through a nozzle, for example, a

good choice for the control volume would be the region within the
nozzle
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The macroscopic approach of the study of thermodynamics that
does not require a knowledge of the behavior of individual particles
is called classical thermodynamics. It provides a direct and easy way
to the solution of engineering problems.

A more elaborate approach, based on the average behavior of large

groups of individual particles, is called statistical thermodynamics.
This microscopic approach is rather involved and is used in this text
only in the supporting role.
Terms used in THERMODYNAMICS:

Phase, State, Properties, Equilibrium, Process, Cycle

Phase of a substance:
A quantity of matter that is homogeneous throughout.

Water can exist as liquid, vapour (steam) or solid (ice)

Liquid phase, Vapour phase, Solid phase

When more than one phase is present, the phases are separated
from each other by the phase boundaries. In each phase the
substance may exist at various pressures and temperatures or, to
use the thermodynamic term, in various states
State of a substance
1) Water at 1 atm pressure and 20oC

2) Water at 1 atm pressure and 90oC

What is the difference in above two phases of substance?

Conclusion: Within a given phase, a substance can exist in different

states.
Properties of a substance
Within a given phase, a substance can exist in different states. The state may be
identified or described by certain observable, macroscopic properties; some
familiar ones are temperature, pressure, and density…

In this statement “Water at 1 atm pressure and 20oC” the state is identified by 1
atm pressure and temperature of 20oC

Each of the properties of a substance in a given state has only one definite value,
and these properties always have the same value for a given state, regardless of
how the substance arrived at the state.

A property can be defined as any quantity that depends on the state of the
system and is independent of the path (that is, the prior history) by which the
system arrived at the given state
Classification of properties:
1. Intensive properties:
One which does not depend on mass of system

2. Extensive properties:
One which depends on mass of system

Intensive properties are those that are independent of the mass of a

system, such as temperature, pressure, and density.

Extensive properties are those whose values depend on the size—or

extent—of the system.
Total mass, total volume, and total momentum are some examples of
extensive properties
Classification of properties: How to distinguish?

Divide the system into 2 equal parts and check what happens
to the property.
Classification of properties:
Intensive properties remain the same as original values whereas
extensive properties reduce to half the original value.

Ex: Pressure, Temperature, density, specific volume

are intensive properties

Ex: Total volume, Total mass, Kinetic energy, Potential energy

are extensive properties

Note: Extensive property per unit mass is again intensive property…

called as specific properties… ex: specific volume

Generally, uppercase letters are used to denote extensive

properties (with mass m being a major exception), and lowercase
letters are used for intensive properties (with pressure P and
temperature T being the obvious exceptions)
Thermodynamics deals with equilibrium states. The word
equilibrium implies a state of balance. In an equilibrium state there
are no unbalanced potentials (or driving forces) within the system.
A system in equilibrium experiences no changes when it is isolated
from its surroundings.
Thermodynamic equilibrium: If the system is in
equilibrium with regard to all possible changes of
state, then it is said to be in thermodynamic
equilibrium
Important note:
 The concept of equilibrium is an outcome of “Macroscopic
approach”.
 If the system is not in equilibrium, properties cannot be
measured.
 If properties cannot be measured, then thermodynamic state
cannot be defined..
 Obviously, we cannot talk about thermodynamic processes and
cycles

The State Postulate

The state of a system is described by its properties. But we know from experience
that we do not need to specify all the properties in order to fix a state. Once a
sufficient number of properties are specified, the rest of the properties assume
certain values automatically.
That is, specifying a certain number of properties is sufficient to fix a state.

The number of properties required to fix the state of a system is given by the
state postulate:
Graphical representation of thermodynamic states:
Process: The path of succession of states through which
the system passes through is called a process
Example of a
Compression
Process
 Isothermal Process…… Constant temperature process

 Isobaric Process….. Constant pressure process

 Isochoric Process….. Constant volume process

 Isenthalpic Process…… Constant enthalpy process

 Isentropic Process….. Constant entropy process

Quasi-equilibrium Process: (Quasi-static Process)

From macroscopic point of view, systems must be in

equilibrium in order to measure properties.

For process to take place, the equilibrium must be

disturbed, then only the system moves from one state
to another state.

Then the obvious question is:

Since properties describe the state of a system only
when it is in equilibrium, how can we describe the
states of a system during a process if the actual process
occurs only when equilibrium does not exist?
The first step in answering this question is to define an ideal process
called “ Quasi-equilibrium” or “Quasi-static” process.

A quasi-equilibrium process is the one in which deviation from one

equilibrium state to the next equilibrium state is “ infinitesimal”.

Quasi-Equilibrium Process:
Quasi-Equilibrium Process:

Fine
Sand
grains
 The Steady-Flow Process
A large number of engineering devices operate
for long periods of time under the same
conditions, and they are classified as steady-
flow devices.

Processes involving such devices can be

represented reasonably well by a somewhat
idealized process, called the steady-flow
process, which can be defined as a process
during which a fluid flows through a control
volume steadily.

The fluid properties can change from point to

point within the control volume, but at any
fixed point they remain the same during the
entire process.

Therefore, the volume V, the mass m, and the

total energy content E of the control volume
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remain constant during a steady flow process
 A system is said to have undergone a cycle if it returns to its initial
state at the end of the process. That is, for a cycle the initial and
final states are identical.

Therefore, at the conclusion of a

cycle, all the properties have the
same value they had at the
beginning. Steam (water) that
circulates through a steam power
plant undergoes a cycle
Internal Combustion Engine – otto cycle
Classification of cycles:

1. Mechanical Cycle:
A cycle in which the working substance is not
recycled at the conclusion of cycle.
Ex: IC Engine, Open Gas turbine Cycle
A four-stroke-cycle internal-
combustion engine goes through a
mechanical cycle once every two
revolutions.
However, the working fluid does not
go through a thermodynamic cycle in
the engine, since air and fuel are
burned and changed to products of
combustion that are exhausted to the
atmosphere.
2. Thermodynamic Cycle:
A cycle in which working substance is recycled at the
conclusion of cycle. Ex. Steam power plant
1. Why units?
Kelvin in his own words”

“If you cannot measure it, you cannot improve it.” “When you
can measure what you are speaking about, and express it in
numbers, you know something about it; but when you
cannot measure it, when you cannot express it in numbers, your
knowledge is of a meagre and unsatisfactory kind.”

Since we are considering thermodynamic properties from a macroscopic

perspective, we are dealing with quantities that can, either directly or indirectly,
be measured and counted. Therefore, the matter of units becomes an important
consideration.

In The following sections Certain Thermodynamic Properties And The Basic Units
have been defined…
1. Why units?
Units give us an idea
of which property we
are referring to.
1. 15
2. 5
3. 0.25
4. 25
Some SI and English Units

In SI, the units of mass, length, and time are the kilogram (kg), meter
(m), and second (s), respectively. The respective units in the English
system are the pound-mass (lbm), foot (ft), and second (s).

The mass and length units in the two

systems are related to each other by

1 lbm = 0.45359 kg
1 ft = 0.3048 m

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Rules in use of SI Units:

N n Ns ns
m mtr M ms
s sec S secs
Pa P psc
Nm N-m N.m Nms
kW KW kWs KW
kg Kg kG kgs
Conversion of Units:

Convert 1 kgf/cm2 in to kPa

W.K.T 9.81N/kgf and 100 cm/m Or 0.01m/cm

1kgf = 9.81 N and 1 cm2 = (10-2 )2m2 = 10-4 m2

1 kgf/cm2 = 9.81 N / 10-4 m2 = 98100 N/m2 = 98100 Pa =98.1 kPa
 Pressure (P):

Mathematically,

P = lim δFn / δA
δA δA’

Where, δA’ is the smallest area

over which the system can be
considered continuum.
What is pressure?
 Units of pressure:
N/m2 or Pa, kPa, MPa
1 bar = 105 Pa =100 kPa = 0.1 MPa
1 atm = 101325 Pa = 101.325 Pa = 1.01325 bar
Pressure as height of fluid:

P=ρg h
where ρ is density of fluid,
g is acceleration due to gravity and
h is the height of fluid column (manometer height diff)

ex: 100 kPa of pressure is equivalent to 10.2 m of

water or 0.75 m of mercury.
(1 atm = 101.325 kPa = 10.33 m water or 760 mm Hg)

Or Pressure at base of a tank of height 1.0 m

containing water is 9810 pa
Application of Hydrostatic principle

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PRESSURE MESURING DEVICES
Differential manometer
EXAMPLE : 1
The hydraulic piston/cylinder system shown in Fig has a cylinder
diameter of D= 0.1 m with a piston and rod mass of 25 kg. The rod
has a diameter of 0.01 m with an outside atmospheric pressure of
101 kPa. The inside hydraulic fluid pressure is 250 kPa. How large a
force can the rod push with in the upward direction?

We will assume a static

balance of forces on the
piston (positive upward),

Fnet = Fupwards - F downwards

Fnet = ma = 0 = Pcyl Acyl −1 P0(Acyl − Arod) − F − mp

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Specific Volume (v):

Specific Volume = Volume / mass

Mathematically,

P = lim δV / δm
δV δV’

Where, δV’ is the smallest volume

over which the system can be
considered continuum.

Specific volume is defined as the number of cubic meters

occupied by one kilogram of matter. Units (m3/kg)
Units of Volume: m3, litre
1 L = 10-3 m3 Or 1000 L = 1m3
Values at 1 atm and 0oC
EXAMPLE : 2. A 1 m3 container, shown in
Fig, is filled with 0.12 m3 of granite, 0.15
m3 of sand, and 0.2 m3 of liquid 25◦C
water; the rest of the volume, 0.53 m3, is
air with a density of 1.15 kg/m3. Find the
overall (average) specific volume and
density.

By definition

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 Temperature
Temperature is a physical quantity that expresses hot and cold.

It is the manifestation of thermal energy, present in all matter,

which is the source of the occurrence of heat, a flow of energy,
when a body is in contact with another that is colder.

Temperature at microscopic level:

Although we are familiar with temperature as a measure of “hotness”

or “coldness,” it is not easy to give an exact definition for it.

Based on our physiological sensations, we express the level of

temperature qualitatively with words like freezing cold, cold, warm,
hot, and red-hot.
However, we cannot assign numerical values to temperatures based
on our sensations alone.

Furthermore, our senses may be misleading. A metal chair, for

example, will feel much colder than a wooden one even when both
are at the same temperature.

To avoid this difficulty, we define “ equality of temperature”.

The equality of temperature

is the only requirement for
thermal equilibrium
Properties that change with temperature:
• Volume
• Length of a side (if constrained in other direction)
• Electrical resistance
 Equality of temperature

Two bodies have equality of temperature, if when they are in thermal

contact, there will be no change in any measurable property.

If

TA = TB & TA = TC

Then TB = TC
 ZEROTH LAW OF THERMODYNAMICS
The zeroth law of thermodynamics states that if
two thermodynamic systems are each in thermal
equilibrium with a third one, then they are in thermal
equilibrium with each other.

If TA = TB & TA = TC , Then TB = TC

It may seem silly that such an obvious fact is called one of the basic
laws of thermodynamics. However, it cannot be concluded from
the other laws of thermodynamics, and it serves as a basis for the
validity of temperature measurement.

By replacing the third body with a thermometer, the zeroth law

can be restated as two bodies are in thermal equilibrium if both
have the same temperature reading even if they are not in
contact.
Zeroth Law is the basis of temperature measurement

The zeroth law was

first formulated and
labeled by R. H.
Fowler in 1931

Std Object with

Substance unknown
temperature
 Temperature Scales

Temperature scales enable us to use a common basis for

temperature measurements, and several have been introduced
throughout history.

All temperature scales are based on some easily reproducible states

such as the freezing and boiling points of water, which are also
called the ice point and the steam point, respectively.

A mixture of ice and water that is in equilibrium with air saturated

with vapor at 1 atm pressure is said to be at the ice point, and a
mixture of liquid water and water vapor (with no air) in equilibrium
at 1 atm pressure is said to be at the steam point

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Two scales are commonly used for measuring temperature, namely,
the Fahrenheit (after Gabriel Fahrenheit, 1686–1736) and the
Celsius.
The Celsius scale was formerly called the centigrade scale but is
now designated the Celsius scale after Anders Celsius(1701–1744),
the Swedish astronomer who devised this scale

The thermodynamic temperature scale in the SI is the Kelvin scale,

named after Lord Kelvin (1824–1907). The temperature unit on this
scale is the kelvin, which is designated by K (not °K; the degree
symbol was officially dropped from kelvin in 1967). The lowest
temperature on the Kelvin scale is absolute zero, or 0 K.

The thermodynamic temperature scale in the English system is the

Rankine scale, named after William Rankine (1820–1872).
The temperature unit on this scale is the rankine, which is
designated by R. 1
 Temperature Scales

On the Celsius scale, the ice

and steam points were
originally assigned the
values of 0 and 100°C,
respectively.

The corresponding values

on the Fahrenheit scale are
32 and 212°F.

These are often referred to

as two-point scales since
temperature values are
assigned at two different
points.
Temperature Scales
Review Questions on UNIT 1:

1. Explain open. Closed and isolated systems with examples. Draw

suitable sketches.
2. Distinguish between Macroscopic and microscopic view points of
thermodynamics.
3. Distinguish between intensive and extensive properties with
examples.
4. Define the following: i) Phase ii) State iii)Properties
iv)Equilibrium v) Process vi)cycle
5. Explain the concept of quasi-equilibrium process.
6. State and explain zeroth law of thermodynamics. Explain how it is
the basis of temperature measurement.
 PROBLEM-SOLVING TECHNIQUE

The first step in learning any science is

to grasp the fundamentals and to gain a
sound knowledge of it.

The next step is to master the

fundamentals by testing this
knowledge. This is done by solving
significant real-world problems. Solving
such problems, especially complicated
ones, requires a systematic approach.

By using a step-by-step approach, an

engineer can reduce the solution of a
complicated problem into the solution
of a series of simple problems

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EXAMPLE : 3
Suppose that in an orbiting space station, an artificial gravity of 2
m/s2 is introduced by rotating the station. How much would a 75
kg man weigh inside?

Solution:
As per Newton’s 2nd law, F = m.a

Weight = Mass X acceleration due

to gravity

Weight = 75 kg X 2 m/s2

= 150 kgm/s2

W = 150 N
EXAMPLE : 4
A tank is filled with oil whose density is 850 kg/m3. if the volume of
the tank is 2 m3, determine the amount of oil (mass) in the tank.

Sol:
Given: ρ = 850 kg/m3 V = 2 m3

Analysis: relation between mass, volume and density

ρ = m/V
Therefore,
m=ρV

= (850) kg/m3 (2) m3

= 1700 kg.
EXAMPLE : 5

A school is paying Rs.8/kWh for

electric power.
To reduce its power bill, the school
installs a wind turbine with a rated
power of 30 kW.
If the turbine operates for 2200
hours per year at the rated power,
determine the amount of electric
power generated by the wind
turbine and the money saved by
the school per year.
 Given:

Cost of energy = Rs. 8/ kWh

Rated power of turbine = 30 kW
Duration of turbine operation = 2200 h

Solution:

Total power produced = 30 kW X 2200 h/year

= 66,000 kWh/year

Money saved = 66,000 kWh/year X Rs. 8/ kWh

Money saved = 5,28,000 Rs. per year

 EXAMPLE : 6
Ex on a Barometer
Determine the atmospheric
pressure at a location where the
barometric reading is 740 mm of Hg
and the gravitational acceleration is
g = 9.805 m/s2. Assume the
temperature of mercury to be 10°C,
at which its density is 13,570 kg/m3.

W.K.T.
EXAMPLE : 7

A pressure gauge reads 2.10 MPa and the barometer

reads 98 kPa. Calculate absolute pressure.

Solution:
(Absolute Pressure = Gauge + Atmospheric pressure)
Pabs = Patm + Pg

= 98 kPa + 2.10 Mpa

= 98 kPa + 2100 kPa or 0.098 Mpa + 2.10 MPa

= 2198 kPa or 2.198 Mpa.

EXAMPLE : 8
The height of a mercury manometer column which is used to
measure vacuum is 700 mm, and the barometer reads 97 kPa.
Determine the (absolute) pressure.

Solution:
Absolute Pressure = Atmospheric pressure + Gauge
Absolute Pressure = Atmospheric pressure + (- Vacuum Pr)
Pabs = Patm - Pvacuum

= 97 kPa - 700 mm of Hg
Answer ?
= 97 kPa - (ρ g h)Hg

= 97 kPa - (13600 kg/m3 X 9.81 m/s2 X 0.7 m) X ( 1 kPa / (1000) Pa )

Pabs = 3.6088 kPa

EXAMPLE : 9
A manometer contains a fluid having a density of 800 kg/m3. The
difference in height of two columns is 300 mm. What pressure
difference is indicated?
What would the height difference be if this same pressure difference
had been measured by a manometer containing mercury of density
13600 kg/m3?
Solution:
Case 1: P = ρ g h
= (800) kg/m3 (9.81)m/s2 (0.3)m
= 2354.4 N/m2 or Pa
= 2.354 kPa
Case 2: Now,
h=P/ρg
= (2354.4) N/m2 / (13600) kg/m3 (9.81) m/s2
= 0.0176 m or 17.6 mm

Conclusion: Denser fluid causes lesser height difference

 EXAMPLE : 10
The level of water in an enclosed water tank is
40 m above the ground. The pressure in the air
space above the water is 120 kPa. The average
density of water is 1000 kg/m3. What is the
pressure of water at the ground level?
Air space
120 kPa

Solution: 40 m

Pground = Pair + Pwater = Pair + ρ g h

= [120 kPa] + [1000kg/m3 * 9.81 m/s2 *40m] X (1) kPa/(1000)Pa

P ground = 512.4 kPa
OR = 120000 + 1000*9.81* 40 = 512400 Pa = 512.4 kPa
EXAMPLE : 11
A piston has an area of 500 mm2. What mass must the piston have
if it exerts a pressure of 50 kPa above atmospheric pressure on the
gas enclosed in the cylinder? Assume standard gravitational
acceleration.
Solution:
Free body diagram of piston for equilibrium:

Patm

Pgas
W=m g
 For equilibrium of piston :

Patm ∑ Fdownward = ∑ Fupward

Patm A + m g = Pgas A
Pgas
m = (Pgas – Patm) A / g
W=m g

m = (Patm + 50 kPa – Patm) A / g

= (50) kPa * A / g

= [ 50,000 Pa * 500 mm2 X (1 m)2/ (1000 mm)2 ] / (9.81) m/s2

= 2.55 kg
Also m = 50000 * 500 * 10-6 / 9.81 = 2.55kg
EXAMPLE : 12
A vertical cylinder containing Argon gas is fitted with a piston of 40
kg mass and cross-sectional area of 0.025 m2. The atmospheric
pressure outside is 95 kPa and the local gravitational acceleration is
9.79 m/s2. What is the argon pressure inside the cylinder?
Solution:
Free body diagram of piston for Patm=95 kPa
equilibrium
Patm

Piston area = 0.025 m2

Pgas
Argon
W=m g Gas
 For equilibrium of piston :
Pat ∑ Fdownward = ∑ Fupward
m

Patm A + m * g = Pgas A
Pg
as
W=m Pgas = Patm + (m*g / A)
g

Pgas = 95 kPa + [( 40 kg * 9.79 m/s2 ) /(0.025)m2]

X (1 kPa / 1000 Pa)

Pgas = 110.7 kPa

Pgas = 95000 + 40*9.81 / 0.025 = 110700 Pa = 110.7 kPa
EXAMPLE : 13
Estimate the mass of a piston that can be supported by a gas
entrapped under the piston in a 200 mm diameter vertical cylinder
when a manometer indicates a difference of 117 mm of Hg column
for the gas pressure. (Poona University, May 1996)

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EXAMPLE : 14

A gas is contained in two cylinders A and B connected by

a piston of two different diameters as shown in figure.
The mass of the piston is 10 kg and the gas pressure
inside cylinder A is 200 kPa. Calculate the pressure in
cylinder B.
Free body diagram of piston:
FA = PA AA

F = P0 (AA – AB)

FB = PB AB

W=mg
 FA = PA AA

F = P0 (AA – AB)

FB = PB AB

1 W=mg
 Free body diagram of piston:
FA = PA AA
PA AA + mg = P0 {AA – AB} + PB AB

LHS = PA (0.00785) m2 + {(10) kg (9.81)

m/s2 X 1kN/1000N}

RHS = (100)kPa {(0.00785) m2 – (0.00049 m2) }

+ (200) kPa (0.00049) m2

F = P0 (AA – AB)
Solving we get PA = 1.9 MPa

FB = PB AB

W=mg
EXAMPLE : 15 Temperature Scales:

The temperature t on a thermometric scale is defined in terms of a

property K by the relation t = a ln K + b Where a and b are
constants. The values of K are found to be 1.83 and 6.78 at the ice
point and the steam point, the temperatures of which are assigned
the numbers 0 and 100 respectively. Determine the temperature
corresponding to a reading of K equal to 2.42 on the thermometer.

Solution: GIVEN t = a ln K + b
At ice point: 0 = a ln 1.83 + b …… (1)
At steam point: 100 = a ln 6.78 + b ……. (2)
Solving Equation (1) – (2) gives 0 -100 = a ln (1.83/6.78)
Hence a = 76.35
Substituting a=76.35 in (1) and solving for b:
0 = 76.35 ln 1.83 + b
b = - 46.143
Therefore, t = 76.35 ln x – 46.143 ……. (3)
Substituting x = 2.42 in (3),
t = 76.35 ln (2.42) – 46.143
t = 21.33

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EXAMPLE : 16

The readings tA and tB of two Celsius thermometers A and B agree at

the ice point (0oC) and steam point (100oC) but elsewhere are
related by the equation tA = L + M tB + N tB2 Where L,M,N are
constants. When both thermometers are immersed in a well stirred
oil bath, A registers 26oC, B registers 25oC. Determine the reading on
B when A registers 37.4oC.

Sol: tA = L + M tB + N tB2
At ice point: 0 = L + 0 +0 therefore L=0

Hence tA = M tB + N tB2

At Steam point: 100 = M 100 + N 1002 OR 1 = M + 100 N …. (1)

When tA=26oC, tB=25oC

We get 26 = M 25 + N 252 OR 1.04 = M + 25 N …. (2)

From equation (2) – equation (1) we get

0.04 = 25 N – 100 N = -75 N OR N = -5.33x10-4

Substituting in (1)

1 = M + (-5.33x10-4) 100 M = 1.0533

Therefore, tA = 1.0533 tB + (-5.33x10-4) tB2

Substituting tB = 37.4oC,

tA = 1.0533 (37.4) + (-5.33x10-4) (37.4)2

tA = 38.65oC.
EXAMPLE : 17
A thermocouple with test junction at t°C on gas thermometer scale and reference
junction at ice point gives the e.m.f. as

The milli-voltmeter is calibrated at ice and steam points. What will be the reading
on this thermometer where the gas thermometer reads 70°C ?

1
 EXAMPLE : 18
The temperature t on a thermometric scale is defined in terms of a property K by
the relation t = a ln K + b Where a and b are constants. The values of K are found
to be 1.83 and 6.78 at the ice point and the steam point, the temperatures of which
are assigned the numbers 0 and 100 respectively. Determine the temperature
corresponding to a reading of K equal to 2.42 on the thermometer.

Solution:

solving:
Hence:
 EXAMPLE : 19
A new scale N of temperature is divided in such a way that the
freezing point of ice is 100°N and the boiling point is 400°N. What is
the temperature reading on this new scale when the temperature is
150°C? At what temperature both the Celsius and the new
temperature scale reading would be the same?
Solution:

C N
1
Unit of mass: kg
Unit of Length: m
Unit of time: s
 PURE SUBSTANCE
Pure Substance behaviour:
Pure substance – Definition. Vapour – Liquid – Solid phase
equilibrium of a pure substance. T-v and P-T diagram. Independent
properties of a pure substance. Tables of thermodynamic
properties. Problems on use of tables of thermodynamic
properties. Advanced problems on pure substances.

Ideal Gas Equation of state: P-V-T behaviour of low and moderate

density gases. Equations of state for the vapour phase of a simple
compressible substance. Ideal gas equation of state.
Compressibility factor. Compressibility chart of Nitrogen.

1
 Pure Substance:
A pure substance is one that has a homogeneous and invariable
chemical composition.
OR
A substance that has a fixed chemical composition throughout is
called a pure substance.

Homogeneous: Identical Invariable: Unchanging

Ex: Water, nitrogen, helium, and carbon dioxide etc
– Liquid water, steam and Ice all have same composition and uniformity.
Characteristics:
A pure substance does not have to be of a single chemical
element/compound..
A mixture of various chemical elements or compounds also
qualifies as a pure substance as long as the mixture is
homogeneous
A mixture of two or more phases of a pure substance is still a
pure substance as long as the chemical composition of all phases
is the same

??
PHASES OF A PURE SUBSTANCE
 PHASE-CHANGE PROCESSES OF PURE SUBSTANCES
There are many practical situations where two phases of a pure substance
coexist in equilibrium. Water exists as a mixture of liquid and vapor in the
boiler and the condenser of a steam power plant. The refrigerant turns from
liquid to vapor in the freezer of a refrigerator.

water is used to demonstrate the

As a familiar substance,
basic principles involved.

Compressed Liquid and Saturated Liquid

Saturated Vapor and Superheated Vapor

Saturation Temperature and Saturation Pressure

Temperature

Pressure = Constant

volume
Compressed Liquid (1)

Consider a piston–cylinder device containing liquid water at 20OC and 1 atm

pressure . Under these conditions, water exists in the liquid phase, and it is
called a compressed liquid, or a sub-cooled liquid, meaning
that it is
not about to vaporize..
Hence State 1 is compressed liquid
Saturated Liquid (2)

As more heat is transferred, the temperature

keeps rising until it reaches 1000C (state 2).

At this point water is still a liquid, but any heat

addition will cause some of the liquid to
vaporize.
That is, a phase-change process from liquid to
vapor is about to take place. A liquid that is
about to vaporize
is called a saturated liquid.

Therefore, state 2 is a saturated liquid state.

Saturated liquid + vapor mixture (3)

Once boiling starts, the temperature stops rising

until the liquid is completely vaporized. That is,
the temperature will remain constant during the
entire phase-change process if the pressure is
held constant.
Midway about the vaporization line (state 3), the
cylinder contains equal amounts of liquid and vapor.
As we continue transferring heat, the vaporization
process continues until the last drop of liquid is
vaporized..

A substance at states between 2 and 4 (Saturated vapor) is referred to as a

saturated liquid–vapor mixture (State 3)
since the liquid and vapor phases coexist in equilibrium at these states

Therefore, state 3 is a saturated (liquid + vapor) state

Saturated Vapor (4)

At 1 atm and 1000C , when phase change is over,

the entire cylinder is filled with vapor that is on
the borderline of the liquid phase. Any heat loss
from this vapor will cause some of the vapor to
condense (phase change from vapor to liquid).
about to condense
A vapor that is is

called a saturated vapor.

Therefore, state 4 is a saturated vapor state.

 Superheated Vapor (5)
One the phase-change process is completed, again
it’s a single phase region again (this time vapor),
and further transfer of heat results in an increase in
both the temperature and the specific volume

At state 5, the temperature of the vapor is 3000C (for ex)

and if some heat is removed from the vapor, the
temperature may drop somewhat but no condensation
will take place as long as the temperature remains above
1000C (for P =1 atm).
A vapor that is
not about to condense
(i.e., not a saturated vapor) is called a
superheated vapor.
Therefore, water at state 5 is a superheated vapor.

These 5 states are represented on a T-v diagram

 T-v diagram of a pure substance (water)

If the entire process described here is reversed by cooling the water while
maintaining the pressure at the same value, the water will go back to state 1,
retracing the same path, and in so doing, the amount of heat released will exactly
match the amount of heat added during the heating process
Tsat = f(Psat)
Saturation Temperature and Saturation Pressure

Strictly speaking, the statement “water boils at 1000C” is incorrect.

The correct statement is “water boils at 1000C at 1 atm pressure.”

The temperature at which water starts boiling depends on the

pressure; therefore, if the pressure is fixed, so is the boiling
temperature

At a given pressure, the temperature at which a pure substance

changes phase is called the saturation temperature Tsat.

Likewise, at a given temperature, the pressure at which a pure

substance changes phase is called the saturation pressure Psat.

At a pressure of 101.325 kPa, Tsat is 99.970C. Conversely, at a

temperature of 99.970C, Psat is 101.325 kPa.
This table indicates that the
pressure of water changing phase
(boiling or condensing) at 258C must
be 3.17 kPa, and the pressure of
water must be maintained at 3976
kPa (about 40 atm) to have it boil at
2508C. Also, water can be frozen by
dropping its pressure below 0.61
kPa.
 Heat of Superheat

Superheated
vapour
T 0.1 MPa
Compressed B Saturated Mixture C
liquid
Latent Heat
A
Sensible heat

v
T-v diagram
 Latent heat.
It takes a large amount of energy to melt a solid or vaporize a
liquid. The amount of energy absorbed or released during a
phase-change process is called the latent heat.

The amount of energy absorbed during melting is called the

latent heat of fusion and is equivalent to the amount of energy
released during freezing. Similarly, the amount of energy
absorbed during vaporization is called the latent heat of
vaporization and is equivalent to the energy released during
condensation.

The magnitudes of the latent heats depend on the temperature

or pressure at which the phase change occurs. At 1 atm pressure,
the latent heat of fusion of water is 333.7 kJ/kg and the latent
heat of vaporization is 2256.5 kJ/kg.
During a phase-change process, pressure and temperature are
obviously dependent properties, and there is a definite relation
between them, that is, Tsat = f(Psat).
A plot of Tsat versus Psat, such as the one given f or water is called
a liquid–vapor saturation curve. A curve of this kind is
characteristic of all pure substances.
1. Saturation Temperature:
For a pressure of 100 kPa, saturation temperature is 99.6oC
2. Saturation Pressure:
For a temperature of 99.6oC , saturation pressure is 100 kPa
3. Saturated Liquid: 100 kPa, 99.6oC

4. Saturated Vapour: 100 kPa, 99.6oC

5. Sub-cooled Liquid (Compressed Liquid): 100 kPa, 50oC

6. Superheated Vapour: 100 kPa, 120oC

7. Quality or Dryness Fraction: x = mass of vapour / Total mass

Ex: If mass of vapour is 0.2 kg and mass of liquid is 0.8 kg, then
X= 0.2/(0.2+0.8) = 0.2 or 20%
PROPERTY DIAGRAMS FOR PHASE-CHANGE PROCESSES
The variations of properties during phase-change processes are best
studied and understood with the help of property diagrams.
T-v, P-v, and P-T diagrams for pure substances, and PVT surfaces

1) T-v diagram

1 kg of water at 0.1 MPa (100

kPa), 200C & Constant Pressure
heating of water
 T-v diagram
Q O
CRITICAL
POINT (374.4oC) L
40 MPa N 22.09 MPa
H
(311.1oC)
10 MPa
K D
J o
1 MPa (179.9 C)
F G
T 0.1 MPa (99.6oC)
B C

M
20oC
P A
I E

v
T-v Diagram
Liquid
Superheated
Vapour

Liquid + Vapour
As the pressure is increased further, this saturation line continues to
shrink, as shown in Fig. 3–15, and it becomes a point when the
pressure reaches 22.06 MPa for the case of water. This point is
called the critical point, and it is defined as the point at which the
saturated liquid and saturated vapor states are identical.
The temperature, pressure, and specific volume of a
substance at the critical point are called,
the critical temperature Tcr,
respectively,
critical pressure Pcr, and critical
specific volume vcr.

The critical-point properties of water are Pcr = 22.06

MPa, Tcr = 373.958C, and vcr = 0.003106 m3/kg.

For helium, they are 0.23 MPa, 2267.858C, and

0.01444 m3/kg.
 Superheated
Vapour

Liquid

Liquid + Vapour
2) P-v diagram
Psat Tsat
1000 kPa 100 0C 180 0C Sub cooled
500 kPa 100 0C 150 0C Sub cooled
100 kPa 100 0C 100 0C Saturated
80 kPa 100 0C 85 0C Superheated
50 kPa 100 0C 680 0C superheated
Extending the Diagrams to Include the Solid Phase
The two equilibrium diagrams (T-v and P-v ) developed so far represent the
equilibrium states involving the liquid and the vapor phases only. However, these
diagrams can easily be extended to include the solid phase as well as the solid–
liquid and the solid–vapor saturation regions. The basic principles discussed in
conjunction with the liquid–vapor phase-change process apply equally to the
solid– liquid and solid–vapor phase-change processes.

Most substances contract during a solidification (i.e., freezing)

process. Others, like water, expand as they freeze. The P-v
diagrams for both groups of substances are given in following fig.

These two diagrams differ only in the solid–liquid saturation

region. The T-v diagrams look very much like the P-v diagrams,
especially for substances that contract on freezing.
ICE

a b c d

Constant Pressure heating of ice

We are all familiar with two phases being in equilibrium, but under some
conditions all three phases of a pure substance coexist in equilibrium . On P-v or T-
v diagrams, these triple-phase states form a line called the triple line.

The states on the triple line of a substance have the same pressure and
temperature but different specific volumes. The triple line appears as a point on
the P-T diagrams and, therefore, is often called the triple point.

For water, the triple-point temperature and pressure are 0.018C and 0.6117 kPa,
respectively. That is, all three phases of water coexist in equilibrium only if the
temperature and pressure have precisely these values.
There are two ways a substance
can pass from the solid to vapor
phase: either it melts first into a
liquid and subsequently
evaporates, or it evaporates
directly without melting first. The
latter occurs at pressures below
the triple-point value, since a
pure substance cannot exist in the
liquid phase at those pressures.

Passing from the solid phase

directly into the vapor phase is
called sublimation.
 P-T diagram
Fusion LINE
CRITICAL
POINT,
374.4oC
100 kPa, -20oC
0oC LIQUID 99.60
PHASE o
A B C DC E F
P Vapourisation
LINE
SOLID
0.6113 kPa, -20oC 0.01o
TRIPPLE
PHASE
K LC MNO POINT P
VAPOUR
o
-10 C Sublimation PHASE
0.26 kPa, -20oC
LINE J
G H I

T
P-T diagram
The P-T diagram is often called the phase diagram since all three
phases are separated from each other by three lines.

The sublimation line separates the solid and vapor regions, the
vaporization line separates the liquid and vapor regions, and the
melting (or fusion) line separates the solid and liquid regions.

These three lines meet at the triple point, where all three phases
coexist in equilibrium.

The vaporization line ends at the critical point because no

distinction can be made between liquid and vapor phases above
the critical point.

Substances that expand and contract on freezing differ only in the

melting line on the P-T diagram.
THERMODYNAMIC
SURFACES
Use of Tables of Thermodynamic
Properties
 PROPERTY TABLES
Saturated Liquid and Saturated Vapor States
The subscript f is used to denote properties of a saturated liquid,
and the subscript g to denote the properties of saturated vapor.
These symbols are commonly used in thermodynamics and
originated from German. Another subscript commonly used is fg,
which denotes the difference between the saturated vapor and
saturated liquid values of the same property.
 Pressure of Saturated Liquid in a Tank

Solution:
Volume Change during Evaporation

Solution:

The process described is

illustrated on a P-v
diagram.
The volume change per
unit mass during a
vaporization process is vfg
, which is the difference
between vg and vf.
PROPERTY TABLES Cotd
Saturated Liquid–Vapor Mixture
During a vaporization process, a substance exists as part liquid and part vapor.
That is, it is a mixture of saturated liquid and saturated vapor. To analyze this
mixture properly, we need to know the proportions of the liquid and vapor
phases in the mixture. This is done by defining a new property called the quality
x as the ratio of the mass of vapor to the total mass of the mixture:
Consider a tank that contains a
saturated liquid–vapor mixture.
The volume occupied by saturated
liquid is Vf , and the volume
occupied by saturated vapor is Vg.
The total volume V is the sum of
the two:
Pressure and Volume of a Saturated Mixture

Solution:
Another way is to first determine the quality x, then the average
specific volume v, and finally the total volume:
 Saturated Mixture….

• Solution:
Values of the saturation properties for R-134a are found from
Table.

Vg = 0.02667 m3/kg
Vf =1/1187 = 0.0008429 m3/kg
The mass–volume relations then gives:
At this point we do not know
whether the refrigerant is in the
compressed liquid, superheated
vapor, or saturated mixture region.
This can be determined by
comparing a suitable property to
the saturated liquid and saturated
vapor values. From the
information given, we can
determine the specific volume
Vg = interpolate between 0.1256 and 0.1161 = 0.12355m3/kg

Vf = interpolate between 1/1344 and 1/1338 = 0.0007435 m3/kg

= interpolate between 0.000744 and 0.000747 = 0.0007435 m3/kg

Superheated Vapor PROPERTY TABLES Cotd

In these tables, the properties are listed against temperature for

selected pressures starting with the saturated vapor data. The
saturation temperature is given in parentheses following the
pressure value.
Temperature of Superheated Vapor

Determine the temperature of

water at a state of P=0.5 MPa &
v= 0.45 m3/kg.

• Solution:
At 0.5 MPa, the sp. volume of saturated
water vapor is vg = 0.3749 m3/kg.

Since v > vg, we have superheated

vapor.
Under 0.5 MPa in Table we
read: given value lies
between 200 C & 250 C.

We need to go for linear

interpolation technique.

Y2

Y1

X1 X X2
Linear Interpolation
Technique:
 Phase Identification of Superheated Vapor

Determine the phase for each of the following states using the
tables and indicate the relative position in the P–v, T–v phase
diagrams.
a. Ammonia: 30◦C, 1000 kPa b. R-134a: 200 kPa, 0.125 m3/kg

Solution:
a) Ammonia: 30◦C, 1000 kPa

The saturation pressure is 1167 kPa. As we have a

lower P (1000 kPa), it is a superheated vapor state.
• b. R-134a: 200 kPa, 0.125 m3/kg
At 200 kPa, v=0.099663 m3/kg, and notice that,
Hence, the state is superheated vapor.
PROPERTY TABLES Cotd

Compressed Liquid

In general, a compressed liquid is characterized by

Higher pressures (P > Psat at a given T)
Lower temperatures (T , Tsat at a given P)
Lower specific volumes (v , vf at a given P or T)
Lower internal energies (u , uf at a given P or T)
Lower enthalpies (h , hf at a given P or T)
Approximating Compressed Liquid as Saturated Liquid

• Solution:
(a) From the compressed liquid table:

(b) From the saturation table:

The error involved is:

Problems on use of
tables of properties
 1. Determine whether water at each of the following states is a
compressed liquid, a superheated vapour or a mixture of
saturated liquid and vapour:
a) 120oC , 150 kPa.

Liquid
Vap Refer
1200C p-11
111.370C
150
T kPa

Liq + Vap
Since actual temperature of
120oC is > saturation
v temperature of 111.37oC, the
phase is superheated vapour.
 Problems on use of tables of properties
b) 0.35 MPa , 0.4 m3/kg

Vapour Refer
Liquid
p-11
138.880C
350
T kPa

Liquid + Vapour Since actual specific volume of

0.4 m3/kg 0.4m3/kg is in between vf and
v vg, the phase is mixture of
vf = 0.001079 m3/kg
vg = 0.5243m3/kg liquid and vapour.
Problems on use of tables of properties
c) 160oC , 0.4 m3/kg

Vapour Refer
Liquid
p-8
1600C

T
0.4 m3/kg
Liquid +
Vapour Since actual specific volume of
v
0.4m3/kg is > vg, the phase is
vf = 0.001102 m3/kg vg = 0.3071 m3/kg
Superheated vapour.
 Problems on use of tables of properties
d) 110oC , 200 kPa.

Refer
p-11
Vap
Liquid

120.230C
200 kPa
T
1100C
Liq + Vap Since actual temperature of
110oC is < saturation
temperature of 120.23oC, the
v
phase is Subcooled Liquid.
e) Water at 300oC, 0.01 m3/kg

Vapour
Liquid

300oC

T 0.01 Since vf < v < vg,

substance is in liquid +
Liquid + vapour state
Vapour

vf = 0.001404 v vg = 0.02167
 f) Water at 5 kPa, 10oC

Vapour
Liquid

Tsat = 5
32.88oC kPa
T
10oC
Liquid +
Vapour
Subcooled liquid state
v (Compressed liquid state)
COMPUTERIZED TABLES
Specific volume calculation in mixture region:

v = x vg + (1-x) vf

= x vg + vf - x vf

v = vf + x (vg - vf ) OR

V = vf + x vfg
This form of equation can be extended for other
properties also in mixture region.
 2. Calculate the specific volume:
a) Water at 8MPa , 98% quality

Refer
p-12

Vapour
Liquid
98% quality
295.060
C 8 MPa
v = vf + x (vg - vf )
T
= 0.001384 + 0.98 (0.02352 –
Liquid + 0.001384)
Vapour

vf = 0.001384 m3/kg vg = 0.02352m3/kg = 0.023 m3/kg

v
 Calculate the specific volume:
b) Freon -12 at 50oC , 15% quality

Refer
p-35

Vapour
Liquid
15%
500C
quality
T v = vf + x (vg - vf )

Liquid + = 0.82573 X10-3 + 0.15

Vapour (0.0141701 – 0.82573X10-3)
v
0.82573X10-
vf = vg =
3m3/kg
0.0141701m3/kg
= 2.83 X 10-3 m3/kg
 Calculate the specific volume:
c) NH3 at 30oC , 80% quality

Refer
p-57

Vapour
Liquid

300C

T v = vf + x (vg - vf )
80%
quality
Liquid + = 1.68X10-3 + 0.80 (0.11043 –
Vapour 1.68X10-3)
v
1.68X10-
vf = vg = 0.11043
3m3/kg
m3/kg
= 0.08868 m3/kg
 3. Determine the quality (if saturated) or temperature (if
superheated) of the following:
a) Water at 8MPa , 0.01 m3/kg

Refer
p-12

Vapour
Liquid

295.06
0C
8 MPa
T
Since actual specific volume of
0.01m3/kg is in between vf and
Liquid +
Vapour
vg, the phase is mixture of
0.01
m3/kg liquid and vapour.
v
vf = 0.001384 vg =
3 3
 Therefore, Quality
x = (v – vf) / ( vg – vf)

(0.01 – 0.001384)
x= ____________________________

( 0.02352 – 0.001384)
Vapour
Liquid X = 0.389 or 38.9%
295.06
0C
8 MPa
T

Liquid +
Vapour
0.01
m3/kg
vf = 0.001384 v vg =
m3/kg 0.02352m3/kg
 Determine the quality (if saturated) or temperature (if
superheated) of the following:
c) Freon12, 744.9 kPa, 0.0255 m3/kg

Refer
p-35

Vapour
Liquid

30oC
T 744.9 kPa

Since actual specific volume of

Liquid + 0.0255 m3/kg
0.0255 m3/kg is greater than Vg
Vapour v , (0.0235083) the phase is
SUPERHEATED vapour.
vf = 0.0.77386X10-3
vg = 0.0235082 m3/kg
 Superheated R-12 Tables
Refer P-38

Vapour
Liquid
45oC
30oC
T 744.9
kPa

0.0255 m3/kg
Liquid +
Vapour
Temperature is 450C
v
vf = 0.0.77386X10-3 vg = 0.0235082 m3/kg
 4. Linear Interpolation:

Determine the temperature of water at a state of P=0.5 MPa &

v= 0.45 m3/kg.
Sol:

At 0.5 MPa,

vf = 0.001093 m3/kg

vg = 0.3749 m3/kg

v > vg

Therefore state is “Superheated Vapour”

Since 0.45 m3/kg lies in between 0.4249
and 0.4744 m3/kg, linear interpolation
is necessary. Page -14 of tables

250

200 x

0.4249 0.450 0.4744

 250

200 x

0.4249 0.45 0.4744

( x -200 ) / (0.45 - 0.4249 ) = (250 – 200 ) / (0.4744 – 0.4229 )

SOLVING x = 24.36

There fore,
Temperature = 200 + 24.36 = 224.36oC
 5. A closed tank contains vapour and liquid water in
equilibrium at 250oC. The distance from the bottom
of the tank to the liquid level is 10 m. What is the
pressure reading at the bottom of the tank?

10 m

Pressure at bottom of tank =

Vapour pressure of water vapour above free
Liquid
surface of water +
250oC pressure due to liquid water column
T
P = Psat + ρ g h

Liquid + = (3.973) MPa + (1/0.001251) kg/m3 (9.81) m/s2

Vapour (10) m (10-6)MPa/Pa
v
= 4.05 Mpa.
6

600 Sol:
kPa

Specific vol v = V/m = 0.4/2 =

0.2 m3/kg
Vapour
Liquid Refer p-11

600
kPa
T

Liquid +
Vapour
0.2
vf = v vg = 0.3157
0.001101
 Quality
x = (v – vf) / ( vg – vf)
600
kPa
(0.2 – 0.001101)
x= ____________________________

( 0.3157 – 0.001101)

= 0.632 or 63.2%
Vapour
Liquid
Mass of vapour = x m
600
= 0.632 X 2
kPa = 1.2644 kg
T
Mass of liquid = (1-x) m = ( 1 – 0.632 )
Liquid + X 2 = 0.7356 kg
Vapour
0.2 OR
vf = 0.001101 v vg = 0.3157 Mass of liquid = 2 – 1.2644 = 0.7356 kg
600
kPa Volume of liquid = mf X vf
= 0.7356 X 0.001101
= 0.0008 m3

Volume of vapour= mg X vg
Vapour = 1.2644 X 0.3157
Liquid = 0.3992 m3
600
kPa
T OR

Liquid + Volume of vapour = 0.4 – 0.0008 = 0.3992

Vapour
0.2 m3
vf = 0.001101 v vg = 0.3157
 Analysis:
P-34
For process 1-2,
Vapour
Liquid v1 = v2
30oC State
1 v2 = vg at 10oC =0.0409 m3/kg
T
Hence state 1 is defined by
10oC State
2
T1 = 30oC & v1=0.0409
Liquid +
Vapour m3/kg
v
 P-38
30oC
T1 = & v1=0.0409
m3/kg

Hence P1 = 0.4645 MPa

…(after interpolation)
Engg Thermodynamics
21AE44 : IV Sem AE

UNIT I: WORK AND HEAT

1
Can you define WORK?
Definition of Work:
The classical definition of work means mechanical work.

In mechanics, work is defined as a force (F) acting through a displacement (x).

Incrementally, δW = F dx

and the finite work becomes,

In thermodynamics, work transfer is considered as occurring between the
system and the surroundings, and is defined as:

Work is said to be done by a system if the sole effect on things external to

the system can be reduced to the raising of a weight.
Sign Convention:

The symbol W is used for work transfer.

When work is done by a system,

it is arbitrarily taken to be positive

When work is done on a system,

it is taken to be negative
Units of Work:
Definition of work involves the product of a unit force (one newton) acting
through a unit distance (one meter).

This unit for work in SI units is called the joule (J). 1 J = 1Nm

Power is the time rate of doing work and is designated by the symbol Ẇ or P
The unit for power is a rate of work (one joule per second), which is a watt (W):
1W = 1 J/s

Note: It is often convenient to speak of the work per unit mass of the system,
often termed specific work. This quantity is designated w and is defined as
w ≡ W/m…. (work done/mass)
WORK DONE AT THE MOVING BOUNDARY OF A SIMPLE COMPRESSIBLE SYSTEM

Consider as a system the gas contained in a cylinder

and piston. Remove one of the small weights from the
piston, which will cause the piston to move upward a
distance dL. We can consider this quasi-equilibrium
process and calculate the amount of work W done by
the system during this process.

The total force on the piston is PA, where P is the

pressure of the gas and A is the area of the piston.

Therefore, the work δW is : δW = F dL = PA dL

But A dL = dV, the change in volume of the gas. Therefore,

δW = P dV
WORK DONE AT THE MOVING BOUNDARY OF A SIMPLE COMPRESSIBLE SYSTEM

At the beginning of the process the piston is

at position 1, and the pressure is relatively
low. This state is represented on a pressure–
volume diagram (usually referred to as a P–V
diagram).

At the conclusion of the process the piston is

in position 2, and the corresponding state of
the gas is shown at point 2 on the P–V
diagram.
Let us assume that this compression was a
quasi-equilibrium process and that during the
process the system passed through the states
shown by the line connecting states 1 and 2
on the P–V diagram.
The assumption of a quasi-equilibrium process is essential here because each point on
line 1–2 represents a definite state, and these states correspond to the actual state of
the system only if the deviation from equilibrium is infinitesimal. The work done on the
air during this compression process can be found by integrating Eq

The symbol 1W2 is to be interpreted as the work done during

the process from state 1 to state 2. It is clear from the P–V
diagram that the work done during this process,

is represented by the area under curve 1–2, area a–1–2–b–a. In this

example the volume decreased, and area a–1–2–b–a represents work
done on the system. If the process had proceeded from state 2 to state 1
along the same path, the same area would represent work done by the
system.
It is possible to go from state 1 to state 2
along many different quasi-equilibrium
paths, such as A, B, or C. Since the area
under each curve represents the work for
each process, the amount of work done
during each process not only is a function
of the end states of the process but also
depends on the path followed in going from
one state to another.

For this reason, work is called a path

function or in mathematical parlance,
δW is an inexact differential and the
integration is simply:
Path Function & Point Function:
Thermodynamic properties are point functions, a name
that comes from the fact that for a given point on a
diagram the state is fixed, and thus there is a definite
value for each property corresponding to this point. The
differentials of point functions are exact differentials, and
the integration is simply

Thermodynamic properties are point functions or in mathematical parlance, dV is an

exact differential & and the integration is simply:

Note: For a cyclic process, the initial and final states of the system are the same,
and hence, the change in any property is zero.
Work, however, is a path function, for, as has been indicated, the work
done in a quasi-equilibrium process between two given states
depends on the path followed. The differentials of path functions are
inexact differentials, and the symbol δ will be used in this book to
designate inexact differentials (in contrast to d for exact differentials).
Thus, for work, we write

It would be more precise to use the notation 1W2A, which would

indicate the work done during the change from state 1 to state 2
along path A. However, the notation 1W2 implies that the process
between states 1 and 2 has been specified.
Note that we never speak about the work in the system in state 1 or
state 2, and thus we never write W2 − W1.
• pdV-Work or Displacement Work:

The integration pdV can be performed

only on a quasi-static path.
• Path Function and Point Function…..:
PdV-Work in Various Quasi-Static Processes:
c) Constant Temperature Process (Process in which PV = C):
Summery of All Processes on PV diagram:
 Isothermal Compression of an Ideal Gas- ANALYSIS
A piston–cylinder device initially contains 0.4 m3 of air at 100 kPa and
800C. The air is now compressed to 0.1 m3 in such a way that the
temperature inside the cylinder remains constant. Determine the work
done during this process.
SOLUTION:
Air in a piston–cylinder device is compressed isothermally. The
boundary work done is to be determined.
Problem 1A:
Consider a system the gas in the cylinder shown in Figure. The cylinder is
fitted with a piston on which a number of small weights are placed. The
initial pressure is 200 kPa, and the initial volume of the gas is 0.04 m3.
Calculate work transfer for the following cases and draw the processes on
P-v diagram.
Case 1: After heating the system, let the volume of the gas increase
to 0.1 m3 while the pressure remains constant.

Solution:

Since pressure
remains constant,
Problem 1B:
Consider as a system the gas in the cylinder shown in Fig. The cylinder is
fitted with a piston on which a number of small weights are placed. The
initial pressure is 200 kPa, and the initial volume of the gas is 0.04 m3.
Calculate work transfer for the following cases and draw the processes on
P-v diagram.
Case 2: Heating is under process, and the piston is rising. Let the weights be
removed from the piston at such a rate that, during the process, the
temperature of the gas remains constant.

Solution:

Since temperature
remains constant,
Problem 1C:
Consider as a system the gas in the cylinder shown in Fig. The cylinder is
fitted with a piston on which a number of small weights are placed. The
initial pressure is 200 kPa, and the initial volume of the gas is 0.04 m3.
Calculate work transfer for the following cases and draw the processes on
P-v diagram.

Case 3: During the heat transfer Let the weights be

removed from the piston at such a rate that the
expression PV1.3 = constant describes the relation
between pressure and volume during the process.
Again, the final volume is 0.1 m3.
 Solution:

Since the process is polytropic process, with n=1.3, the equation is

Problem 1D:
Consider as a system the gas in the cylinder shown in Fig. The cylinder is
fitted with a piston on which a number of small weights are placed. The
initial pressure is 200 kPa, and the initial volume of the gas is 0.04 m3.
Calculate work transfer for the following cases and draw the processes on
P-v diagram.

Case 4: Consider the system and the initial state

given in the first three examples, but let the piston
be held by a pin so that the volume remains
constant. In addition, let heat be transferred from
the system until the pressure drops to 100 kPa.
Solution:
Since volume remains constant,
work transfer is Zero.
Problem 2:
A mass of 1.5 kg of air is compressed in a quasi-static process from 0.1 MPa
to 0.7 MPa for which PV = constant. The initial density of air is 1.16 kg/m3.
Find the work done by the piston to compress the air.

Solution:
Problem 3:
Determine the total work done by a gas system following an expansion
process as shown in Figure.
Solution:
Problem 4:
If a gas of volume 6000 cm3 and at pressure of 100 kPa is compressed quasi-
statically according to PV2 = constant until the volume becomes 2000 cm3.
Determine the final pressure and the work transfer.
Solution:

Final
Pressure,
Problem 5:
The piston/cylinder setup shown in Figure contains 0.1 kg of water vapour at
1000 kPa, 500̊ C. The water is now cooled with a constant force on the piston
until it reaches half the initial volume. After this, it cools to 25̊ C while the
piston is against the stops. Find the final water pressure and the work in the
overall process, and show the process in a P–v diagram.

Solution:

This is a two-step process, one of constant P

and one of constant V.
At 1000 kPa (1MPa), the saturation temperature is
179.91◦C.
Since 500◦C > 179.91◦C, the phase is Superheated.
State 1: (P, T) From Table; v1 = 0.3541 m3/kg

State 2: (T, v2 = v1 / 2 = 0.17706 m3/kg)

At state 2, T2 = 25◦C, v2 = 0.17706 m3/kg.

From Table vf < v2 < vg,

Phase is two phase (mixed phase)

(i) P2 = Psat = 3.169 kPa.

 (ii) Work
expression:
Problem 6:
Expansion of a Gas against a Spring
A piston–cylinder device contains 0.05 m3 of a gas initially at
200 kPa. At this state, a linear spring that has a spring
constant of 150 kN/m is touching the piston but exerting no
force on it. Now heat is transferred to the gas, causing the
piston to rise and to compress the spring until the volume
inside the cylinder doubles. If the cross-sectional area of the
piston is 0.25 m2,
determine
(a) the final pressure inside the cylinder,
(b) the total work done by the gas, and
(c) the fraction of this work done against the spring to
compress it.

SOLUTION A gas in a piston–cylinder device equipped

with a linear spring expands as a result of heating. The
final gas pressure, the total work done, and the fraction
of the work done to compress the spring are to be
determined.
Assumptions 1 The expansion process is quasi-equilibrium. 2 The spring is linear in the range of interest.
(c) The work represented by the
rectangular area (region I) is done
against the piston and the
atmosphere, and the work
represented by the triangular area
(region II) is done against the spring.

Therefore
Problem 7: A spherical balloon has a diameter of 25 cm and contains air at a
pressure of 1.5 bar. The diameter of the balloon increases to 30 cm in a
certain process and during this process the pressure is proportional to the
diameter. Calculate the work done by the air inside the balloon during this
process.
Solution:
 ALTERNATE METHOD
OR D α V 1/3

We have Or P α V1/3 OR P/V1/3 = C or PV-1/3 = C

Polytropic process with n = -1/3

Now V1 = 3.142 * 0.253 / 6 = 0.0081823 m3

V2 = 3.142 * 0.303 / 6 = 0.014139 m3

P1V 1-1/3 = P2V2 -1/3

Substituting P2 = 1.8 bar

Work done = 1.8 *105* 0.014139 - 1.5*105 * 0.0081823 / (1 –(-1/3))

= 988300 J or 988.3 kJ
 HEAT TRANSFER
The thermodynamic definition of heat is somewhat different from the
everyday understanding of the word. It is essential to understand clearly
the definition of heat given here, because it plays a part in many
thermodynamic problems.

If a block of hot copper is placed in a beaker of cold water, we know from

experience that the block of copper cools down and the water warms up
until the copper and water reach the same temperature.

What causes this decrease in the temperature of the copper and the
increase in the temperature of the water?

We say that it is the result of the transfer of energy from the copper block
to the water. It is from such a transfer of energy that we arrive at a
definition of heat.
Definition of Heat:
Heat is defined as the form of energy that is transferred across the
boundary of a system at a given temperature to another system (or the
surroundings) at a lower temperature by virtue of the temperature
difference between the two systems.

• The symbol Q is used for heat transfer.

• When heat is transferred to the system, it is arbitrarily taken to be
positive

• When heat is transferred from the system, it is arbitrarily taken to

be negative
If we consider the hot block of copper as one system and the cold water in
the beaker as another system, we recognize that originally neither system
contains any heat (they do contain energy, of course).

When the copper block is placed in the water and the two are in thermal
communication, heat is transferred from the copper to the water until
equilibrium of temperature is established.
At this point we no longer have heat transfer, because there is no
temperature difference. Neither system contains heat at the conclusion of
the process.

It also follows that heat is identified at the boundary of the system, for
heat is defined as energy transferred across the system boundary.
Heat, like work, is a form of energy transfer to or from a system.
The units for heat, and for any other form of energy as well, are the
same as the units for work, or at least are directly proportional to them
Points to Remember Regarding Heat Transfer:

• From a mathematical perspective, heat, like work, is a path function and

is recognized as an inexact differential.

• In the integral form, it can be expressed as:

• It is also convenient to speak of the heat transfer per unit mass of the
system, q, often termed specific heat transfer, which is defined as:

• A process in which there is no heat transfer (Q = 0) is called an adiabatic

process.
COMPARISON OF HEAT AND WORK:
1. Similarities:
• Heat and work are both transient phenomena. (Systems never possess heat or
work, but either or both cross the system boundary when a system undergoes a
change of state)
• Both heat and work are boundary phenomena. (Both are observed only at the
boundary of the system, and both represent energy crossing the boundary)
• Both heat and work are path functions and inexact differentials.
• Heat, like work, cannot be stored by the system.

2. Differences:
• +Q represents heat transferred to the system and
thus is energy added to the system, and +W represents work done by the
system and thus is energy leaving the system.
• Heat transfer is the energy interaction due to temperature difference
only. All other energy interactions may be termed as work transfer.
Free Expansion with Zero Work Transfer:
• Points to Remember Regarding Heat Transfer and Work
Transfer:

(a) Heat transfer and work transfer are the energy interactions. A
closed system and its surroundings can interact in two ways: by
heat transfer and by work transfer. Thermodynamics studies how
these interactions bring about property changes in a system.

(b) The same effect in a closed system can be brought about either by
heat transfer or by work transfer. Whether heat transfer or work
transfer has taken place depends on what constitutes the system.

(a) Both heat transfer and work transfer are boundary phenomena.
Both are observed at the boundaries of the system, and both
represent energy crossing the boundaries of the system.
• Points to Remember Regarding Heat Transfer and Work
Transfer:

d) It is wrong to say 'total heat' or 'heat content' of a closed system,

because heat or work is not a property of the system. Heat, like
work, cannot be stored by the system. Both heat and work are the
energy in transit.

e) Heat transfer is the energy interaction due to temperature

difference only. All other energy interactions may be termed as
work transfer.

f) Both heat and work are path functions and inexact differentials.
The magnitude of heat transfer or work transfer depends upon the
path the system follows during the change of state.
• Review Questions:

1. Explain thermodynamic definition of work.

2. Differentiate between Path function & Point function.

3. Derive Pdv work expressions for various quasi-static processes.

4. Write a note on free expansion of work.

5. Comparison between work & heat.

6. Numerical on work (Simple & advance).

 ADDITIONAL
PROBLEMS ON
WORK
Problem 8:
Problem 9:
Problem 10:

Dr. SHK KLSGIT

CHECK (alternate method)

= (300 *.47833) – (125 *0.7462)

(1-1.969)

= 51.84 kJ
Problem 11:

Dr. SHK KLSGIT

SOLVE THE PROBLEM by INTEGRATING PdV method
Problem 12:

P1V1/T1 =
P2V2/T2

P2V2/T2 =
P3V3/T3
Further away from the saturated vapor curve at a given temperature
the pressure is lower and the specific volume is higher, so the forces
between the molecules are weaker, resulting in a simple correlation
among the properties.

UNIT I: self study

Ideal gas equation of
state.
If we plot the constant P, T, or v
curves in the two-dimensional
projections of the three-
dimensional surfaces, we get
curves as shown.
Further away from the saturated vapor curve at a given temperature the pressure
is lower and the specific volume is higher, so the forces between the molecules
are weaker, resulting in a simple correlation among the properties.

The constant-pressure curve in the T–v diagram and the constant–specific volume
curve in the P–T diagram move toward straight lines further out in the
superheated vapor region.

A second observation is that the lines extend back through the origin, which gives
not just a linear relation but one without an offset.
This can be expressed mathematically as

T = Av for P = constant
P = BT for v = constant

The final observation is that the multiplier A increases with P and the multiplier B
decreases with v following simple mathematical functions:

A = AoP and B = Bo/v

Both of these relations are satisfied by the ideal gas equation of
state
Pv = RT
where the constant R is the ideal gas constant and T is the absolute
temperature in kelvins or rankines called the ideal gas scale.

Comparing different gases gives a further simplification such that R

scales with the molecular mass: R = R0/M

In this relation, R0 is the universal gas constant with the value

R0 = 8.3145 kJ/ kmolK

An ideal gas has a specific volume that is very sensitive to both P and T, varying
linearly with temperature and inversely with pressure, and the sensitivity to
pressure is characteristic of a highly compressible substance. If the temperature
is doubled for a given pressure the volume doubles, and if the pressure is
doubled for a given temperature the volume is reduced to half the value.
 CENGEL

Property tables provide very accurate information about the

properties, but they are bulky and vulnerable to typographical
errors. A more practical and desirable approach would be to have
some simple relations among the properties that are sufficiently
general and accurate.
Any equation that relates the pressure, temperature, and specific
volume of a substance is called an equation of state. Property
relations that involve other properties of a substance at
equilibrium states are also referred to as equations of state. There
are several equations of state, some simple and others very
complex.
The simplest and best-known equation of state for substances in
the gas phase is the ideal-gas equation of state.

This equation predicts the P-v-T behavior of a gas quite

accurately within some properly selected region.
In 1662, Robert Boyle, an Englishman, observed during his experiments with a
vacuum chamber that the pressure of gases is inversely proportional to their
volume. In 1802, J. Charles and J. Gay-Lussac, Frenchmen, experimentally
determined that at low pressures the volume of a gas is proportional to its
temperature. That is,
P = R(T / v)

Pv = RT
where the constant of proportionality R is called the gas constant.

Above Equation is called the ideal-gas equation of state, or simply

the ideal-gas relation, and a gas that obeys this relation is called an
ideal gas. In this equation, P is the absolute pressure, T is the
absolute temperature, and v is the specific volume.

The gas constant R is different for each gas and is determined from
R = Ru / M (kJ/kg·K or kPa·m3/kg·K)
THE IDEAL-GAS EQUATION OF STATE
The molar mass M can simply be defined as the mass of one mole
(also called a gram-mole, abbreviated gmol) of a substance in
grams, or the mass of one kmol (also called a kilogram-mole,
abbreviated kgmol) in kilograms.

Notice that the molar mass of a substance has the same numerical
value in both unit systems because of the way it is defined. When
we say the molar mass of nitrogen is 28, it simply means the mass of
1 kmol of nitrogen is 28 kg, That is, M = 28 kg/kmol

By writing Eq. Pv = mRT twice for a fixed mass and simplifying,

the properties of an ideal gas at two different states are related
to each other by
 Problems on Ideal Gas

Solution:
Assume air to be an ideal gas
Problems on Ideal Gas

Solution:
An ideal gas is an imaginary substance that obeys the relation Pv =
RT. It has been experimentally observed that the ideal-gas relation
given closely approximates the P-v-T behavior of real gases at low
densities. At low pressures and high temperatures, the density of a
gas decreases, and the gas behaves as an ideal gas under these
conditions.

In the range of practical interest, many familiar gases such as air,

nitrogen, oxygen, hydrogen, helium, argon, neon, krypton, and
even heavier gases such as carbon dioxide can be treated as ideal
gases with negligible error (often less than 1 percent). Dense gases
such as water vapor in steam power plants and refrigerant vapor in
refrigerators, however, should not be treated as ideal gases.
Instead, the property tables should be used for these substances.
T–v diagram for water that indicates the error in assuming ideal gas for saturated vapor and
for superheated vapor. As would be expected, at very low pressure or high temperature the
error is small, but it becomes severe as the density increases.
Is Water Vapor an Ideal Gas?
This question cannot be answered with a simple yes or no. The error
involved in treating water vapor as an ideal gas is calculated and
plotted in Fig. 3– 45. It is clear from this figure that at pressures
below 10 kPa, water vapor can be treated as an ideal gas, regardless
of its temperature, with negligible error (less than 0.1 percent).

At higher pressures, however, the idealgas assumption yields

unacceptable errors, particularly in the vicinity of the critical point
and the saturated vapor line (over 100 percent). Therefore, in air-
conditioning applications, the water vapor in the air can be treated
as an ideal gas with essentially no error since the pressure of the
water vapor is very low. In steam power plant applications, however,
the pressures involved are usually very high; therefore, ideal-gas
relations should not be used.
COMPRESSIBILITY FACTOR—A MEASURE OF DEVIATION FROM IDEAL-
GAS BEHAVIOR

Definition: This deviation from ideal-gas behavior at a given

temperature and pressure can accurately be accounted for by the
introduction of a correction factor called the compressibility factor Z
defined as:

The farther away Z is from unity, the more the gas deviates from ideal-gas behavior.
Compressibility of Nitrogen
 Principle of Corresponding States
Gases behave differently at a given temperature and pressure, but
they behave very much the same at temperatures and pressures
normalized with respect to their critical temperatures and
pressures. The normalization is done as:

The Z factor for all gases is approximately the same at the

same reduced pressure and temperature.

This is called the principle of corresponding states.

Comparison of Z factors for various gases
 Generalized Compressibility Chart
By curve-fitting all the data, we obtain the generalized
compressibility chart that can be used for all gases, and
the following observations can be made from the
generalized compressibility chart:
1. At very low pressures (PR << 1), gases behave as an ideal gas
regardless of temperature
2. At high temperatures (TR >> 2), ideal-gas behavior can be assumed
with good accuracy regardless of pressure (except when PR .. 1).
3. The deviation of a gas from ideal-gas behavior is greatest in the
vicinity of the critical point
OTHER EQUATIONS OF STATE