Thermodynamics-1 MIME3110

Sultanate of Oman
University of Technology and Applied Sciences

Higher College of Technology

Department of Engineering
Mechanical and Industrial Engineering Section

S.No Content Unit Slide No Theory outcomes

I Outcomes of course 1-4 3 T&P 1-11

II Assessment of course 1-4 4 T&P 1-11

1 Basic concepts and Thermodynamic 1 5-39 T&P 1,2,3

Properties
2 Zeroth law and First law of 2 40-63 T&P 4,5
Thermodynamics
3 Non-Flow Process and Second law of 3 64-87 T&P 6,7
Thermodynamics
4 Entropy, Pure substances and Third 4 88-102 T&P 8,9,11
law of Thermodynamics
I Appendix and Problems 5 103-106 T&P 1-11

II Question bank and equations table 6 107-110 T&P 1-11

References: : http://e-learning.hct.edu.om/moodle263/login/index.php
Prepared by: Dr.S.MUTHURAMAN

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 1. Differentiate between open and closed systems.

 2. Realize the thermodynamic temperature scale as a fundamental absolute scale of
temperature.
 3. Identify the assumption of formulation of the equation of state with limitation.
 4. Relate the zero law of thermodynamics-to-thermodynamics equilibrium.
 5. Appreciate the special statement of the law of conservation of energy involved in the
first law of thermodynamics.
 6. Distinguish the various equivalent statement of the second law of Thermodynamics.
 7. Analyze and solve various thermodynamics problems involving heat engine and
refrigerator with consideration of energy conversion and consideration.
 8. Select the appropriate parameters from the table of thermodynamics properties.
 9. Interpret the principle of the increase of entropy with practical applications.
 10. Perform laboratory experiments related to bomb calorimeter and Marcet boiler
 11. Relate the concept of entropy with trend events in the universe.

Theory/ Assessment Maximum marks

Lab
Theory Continuous Test 15 30 100
70% assessment Assignment 15 (21) (70%)

Mid Examination 20 20
(14)

Final examination 50 50 (35)

Lab Continuous Class work lab Experiment 100 (30) (30%)

30% evaluation and continuous assessments

Minimum passing requirement 67-69

Passing Grade C
Internal marks: 65% Theory:70%
(Theory-Tests-30, Assignment-20 & Lab-30) Lab:30%
Final marks: 35%
(Theory- Final exam-50) Total:100%

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UNIT-1

Basic Concepts and

Thermodynamic Properties

 Thermodynamics is the science that deals with

heat and work and those properties of substance
that bear a relation to heat and work.
 Thermodynamics deals with:

Energy conversion

Direction of change

Study of the relationship between work, heat, and

energy

Conversion of energy from one form to another

Interaction of a system and it surrounding.

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 Thermodynamics laws and properties are applied

to analyze and improve the performance of the
work producing and work absorbing devices such
as in:

Refrigeration
Internal
Turbines and and air-
Power plants combustion
compressors conditioning
engines
equipment

The behaviour of matter can be

studied in two different methods.

Macroscopic – Microscopic –
Classical Way Statistical Way

Thermodynamic
studies are A certain Matter is
undertaken by the quantity of considered
following two
different
matter is as a cluster
approaches: considered of molecules
without the and the
events changes
occurring at occurring in
the the
Macroscopic Microscopic molecular molecular
approach – approach – level being level are
(Macro means (Micro means taken into taken into
big or total) small)
account. consideration
for the
analysis.

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THERMODYNMAICS PROPERTIES

INTERNAL
TEMPERATURE PRESSURE VOLUME
ENERGY

SPECIFIC SPECIFIC
ENTHALPY DENSITY
GRAVITY WEIGHT

MASS AND SPECIFIC SPECIFIC

ENERGY Entropy
WEIGHT VOLUME HEAT

• This is the degree of hotness or coldness of a body.

Its SI unit is Celsius 0C (formerly called Centigrade)
Temperature
and its English unit is the Fahrenheit 0F. The
(T) thermodynamics unit of temperature is the Kelvin k.
• T (K) = T (0C) + 273

• This is the force exerted by a fluid per unit area. The SI

unit of pressure is Newton’s per square meter (N/m 2),
Pressure which is called a Pascal (pa).
•1pa = 1 N/m2
(P) •1kpa= 1000pa
•1 bar = 10 5 pa =0.1 Mpa =100kpa
•1 atm = 101,325 pa =101.325 kpa = 1.01325 bars.

• The SI unit of volume is m3.

Volume (V)

• 1 m3 = 1000 L = 10 6 cm3

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• The mass (m) of a body is the measure of the

amount of matter present in that body.

Mass • The mass of a certain body will remain constant

even if the gravitational acceleration acting upon
(m) that body changes.

•The weight (wt) of a body is the force exerted by that

body when its mass is accelerated in a gravitational

Weight field.
•The weight of a body is a force produced when the
mass of the body is accelerated by a gravitational

(wt)
acceleration.
•According to Newton’s Second Law of Motion, force
(F) = ma, where a is acceleration.

•This is the energy associated with the internal state of a system. It

represents the kinetic and potential energies of the molecules, atoms,
and subatomic particles that constitute the system on a microscopic
scale.
Internal •dU = mcvdT, where: m - mass kg , Cv – specific heat capacity at
Energy (U) constant volume (J/kgk s), dT- temperature difference k. The unit of U is
kj

•This is commonly referred to as the heat content of a system. Mathematically:

•H = U +PV
•Enthalpy = Internal energy + pressure x volume
•h = u + pv
Enthalpy (H) •Specific enthalpy = specific internal energy + pressure x specific volume The
unit of enthalpy is kJ. Or kJ/kg (for specific enthalpy)

• It is defined as the mass per unit volume: p = m/v (kg/m3)

• The inverse of density is called specific volume:v = 1/p = v/m (m3/kg)
Density

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Specific Gravity Specific Specific Volume

• Specific gravity Weight • The specific volume
represents the density (v) of a substance is
of a substance • It is defined as the total volume (V)
relative to the density the weight of of that substance
of a well-known a unit volume divided by the total
substance (at a of a mass (m) of that
specific substance: substance (volume
temperature). For per unit mass). It has
liquids, we use water
at 4oC and H2O =1000
• ᵞs = g (N/m )3 units of cubic meter
per kg. (m 3/ kg )
kg/m3.
• SG = /H2O

Potential Energy:
Kinetic Energy: Kinetic
Potential energy (PE)
energy (KE) is the
is defined as the
energy possessed by
energy possessed by
the system by virtue of
the system by virtue of
its motion. K.E=1/2mc2
its position. (P.E=mgh)

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The specific heat at The specific heat at

constant volume is constant pressure is
defined as the amount defined as the energy
of energy transferred transferred as heat at
as heat at constant constant pressure, per
volume, per unit mass unit mass of a
of a system to raise its substance to raise its
temperature by one temperature by one
degree. That is, Cv = degree. That is Cp =
(dq/dT)v (dq/dT)P

The ratio of specific heat (γ) is given by: adiabatic index γ= C P/Cv

entropy is defined as the ratio of heat transferred to the absolute

temperature of the system dS=dQ/T

(l)Length – m (A)Area – m²
(H) Enthalpy –
J/kg

(Q) Heat-J

(T)Temperature - (S) Entropy –

(F) Force - N
°C or K J/kg K

(m)Mass – kg (c)Velocity – (a)Acceleration

(W) Power – Watt – m/s²
m/s
= J/s = Nm/s

(t)Time – sec (P) Pressure – Pa

(E) Energy –
= N/m² or bar or
Joule = Nm
kg/cm²

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Fundamental Derived Units

units

MASS Kilogram kg Force(F) Newton N

Length Meter m Pressure Pascal Pa

(P)

Time Seconds s

Temperatu Celsius/Kel oC/K Energy(E) Joule J

re vin

F = m  a
[N] = [kg] [m/s2]
1N = 1 kgm/s2

P = F / A
[Pa] = [kgm/s2] [m2]
1 Pa = 1 kg/ms2

E = F  x
[J] = [kgm/s2] [m]
1J = 1 kgm2/s2

Work – Force * displacement (Nm)

Power – Rate of work done(W/t) (J/s)

Weight = m x g ; where g = acceleration due to gravity = 9.81 m/s²

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 Consider a small area (A) passing through a point in a fluid at

rest. Fluid on one side of the area exerts a compressive force
F normal to the area, the pressure, P, at a point is defined as:

P  lim

 F 
A  A  A
Units: 1 Pa = 1 N/m2, 1 standard atmosphere = 101,325 Pa, 1
bar = 100 kPa

Gauge Pressure = Any pressure above atmospheric

pressure

Vacuum Pressure = Any pressure below atmospheric

pressure
Absolute pressure = atm pressure + gauge pressure
(P = Patm +  g h)
Absolute pressure = atm pressure − vacuum pressure

Absolute pressure (Pabs) is the pressure relative to the

absolute vacuum (absolute zero pressure).

Gauge pressure (Pgauge) is the difference between the

measured pressure (absolute pressure) and the local
atmospheric pressure. Pgauge = Pabs - Patm

Vacuum pressure (Pvac) is a pressure below atmospheric pressure.

Pvac = Patm – Pabs

P
P vacuum

Patm P

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GAUGE PRESSURE Vs Vacuum Pressure

Mercury

 In thermodynamics, it is very desirable to have a temperature

scale that is independent of the properties of the substance
or substances. Such a temperature scale is called a
thermodynamic temperature scale. (Kelvin in SI)Temperature,
T, in units of degrees Celcius, oC, is a measure of “hotness”
relative to the freezing and boiling point of water. A
thermometer is based on the thermal expansion of mercury.

 Microscopic point of view:

Temperature is a measure of the internal molecular motion,
e.g., average molecule kinetic energy, At a temperature of –
273.15oC molecular motion ceases, Temperature in units of
degrees kelvin, oK, is measured relative to this absolute zero
temperature, so 0oK = -273oC

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 The two temperature scales normally employed for

measurement purposes are the Fahrenheit (F) and Celsius (C)
scales, which are based on a specification of the number of
increments between the freezing point and boiling point of
water at standard atmospheric pressure.
°F = 32.0 + (1.8)°C
 The absolute temperature scale that corresponds to the
Celsius scale is called the Kelvin (K) scale, and the absolute
scale that corresponds to the Fahrenheit scale is called the
Rankine (R) scale.
°R = °F + 460
°K = °C + 273
Relationship between thermodynamic scales
Fahrenheit T (o F )  1.8  T ( o C )  32

Kelvin scale T ( K )  T (o C )  273.15

T ( R )  T ( o F )  459.67
Rankine scale
T ( R )  1. 8  T ( K )

System: It is defined as a quality of matter or region in space chosen for

the study.

Surrounding: The region outside the system is called: the surroundings

The surface (real or imaginary) that separates the system from its
surroundings is the boundary. A boundary of a system can be fixed or
movable.

Universe = System + Surroundings

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Closed system

Types of
thermodynamic
systems

Isolated system Open system

Closed system (control mass)

energy in the form of
no mass can cross the
the amount of mass is heat or work can
boundary of the
fixed cross the boundary of
system
the system.

Open system (control volume)

a specific region that usually
encloses a device that involves mass and energy can cross the
mass flow such as a compressor, boundary of a control volume.
turbine or nozzle.

Isolated system
In the particular case where no energy crosses the boundary of the
system, the system is considered as isolated.

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State is the condition of a system at an instant of time as described

or measured by its properties like pressure, volume, temperature
etc.

Each unique condition of a system is called a state.

Any operation in which one or more properties of a system change

is called a change of state.

A system is at steady-state if none of the system properties change

with time.

Steady state is that circumstance in which there is no accumulation

of mass or energy within the Control volume, and the properties at
any point within the system are independent of time.

• In thermodynamics a property is any

System characteristic of a system that is associated with
the energy and can be quantitatively

Properties
evaluated.
• The property of a system should have a definite
value when the system is in a particular state.

Intensive properties are the properties that are independent from the
mass of the system. Examples: temperature; pressure, density

Extensive properties are the properties that are dependent on the size
–or extent- of the system. Examples: total mass, total volume

Intensive = Independent size of the Extensive = Dependent size of the

system system

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• Whenever one or more of the properties

of a system change, a change in the
state of the system occurs. The path of
the succession of states through which
Thermodynamic the system passes is called the
Process thermodynamic process.

Cyclic

Thermodyn
amic
Process

Irreversible Reversible

Examples
Cyclic Reversible Irreversible
Process Process Process
When a system in
Reversible
a given initial state A reversible process:
goes through a process for a
number of system is Friction less
different changes defined as a motion
in and finally process that, Expansion of
returns to its initial once having spring
values, the system An irreversible
taken place, process is a
has undergone a can be
cyclic process. At process that
reversed. cannot return
the end, all the
Irreversible both the
properties have
process: system and the
the same value
they had at the Friction motion surroundings to
beginning. Steam their original
that circulates conditions.
Quasi-Static Heat transfer
through a closed
Processes.
cooling loop
undergoes a
cycle.

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• This law was formulated by Robert s Boyle

in 1662. It states that, ‘the absolute
pressure of a given mass of a perfect gas
Boyle’s varies inversely as its volume, when the
temperature remains constant.
law
• Mathematically PV=Constant

• This law was formulated by a Frenchman

Jacques A.C. Charles in about 1787. It
states that, ‘the volume of a given mass of
Charles’ a perfect gas varies directly as its absolute
law temperature, when the absolute pressure
remains constant.

• Mathematically V/T=Constant

• This law was formulated by gay lussac. It

Gay states that, ‘the absolute pressure of a
given mass of a perfect gas varies
Lussac directly at temperature, when the
law volume remains constant.
• P/T=Constant

•PV = C
•T
•PV = mRT
Ideal Gas law
•Specific volume: V/m=v

•Pv=RT

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An ideal gas is one which follows the ideal gas equation of state, namely

PV = mRT

Specific volume: V/m=v

Pv=RT

R is Gas constant in J/kg K

T is Temperature in K, P: pressure in Pa, V: volume in m3

Compressibility factor= actual volume/Ideal volume of gas

z= PV
RT
Z=1 the gas is ideal gas, Z>1 or Z<1 is a real gas

An equation of state taking account the volume

occupied by the molecules and the attractive forces
between them.
(P+a/v2 )(v-b) = RT
P:pressure, v:specific volume, T: Temperature R: gas
constant, where a and b are van der Waals constants.
a = 27R2Tc2/64 Pc and b = RTc/8Pc
The equation is cubic in volume and in general there
will be three values of v for given values of T and P.
Tc(air)= 133K
Tc(water)= 647.3K
Pc(air)= 37.7 bar
Pc(water)= 220.9 bar
R(air)=0.287KJ/KgK R(water)=0.461KJ/KgK

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 Closed system & its surroundings can

interact in two ways:

By
Heat
By Work Transfer
Transfer

 These may be called ‘energy

interactions’ and these bring about
changes in the properties of the system

The direction of heat transfer is taken from the

Heat is defined as the high temperature system to the low temperature
form of energy that is system. There are three modes of heat transfer:
transferred between
two systems (or a Conduction is the transfer of energy from the
system & its most energetic particles of a substance to the
surroundings) by virtue adjacent less energetic ones as a result of
of a temperature interaction between particles.
difference.
Convection is the transfer of energy between a
solid surface and the adjacent fluid that is in
The value of a heat motion.
transfer depends on Radiation is the transfer of energy due to the
the details and nature emission of electromagnetic waves.
of the process and not
just the end states. The symbol Q denotes an amount of energy
transferred across the boundary of a system in
terms of a heat interaction with the system’s
surroundings.
Thus, heat is not a
property, and its •Heat transfer into a system is taken to be
positive, and Q > 0
differential is written as
δQ or ∆Q. •Heat transfer from a system is taken as
negative. Q<0

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Specific Specific heat Specific heat

at constant at constant
Heat pressure Cp
volume Cv
•The specific
heat is
defined as •The energy •The energy
the energy required to required to
required to raise the raise the
raise the temperature temperature
temperature of the unit of the unit
of a unit mass of a mass of a
mass of a substance by substance by
substance by one degree one degree as
one degree as the the pressure is
volume is maintained
maintained constant.
constant.

The specific heat at constant pressure Cp is always greater than Cv because at constant
pressure the system is allowed to expand and the energy for this expansion work must also
be supplied to the system.

•Electrical work
•Magnetic work

Non
mechanical
work

Mechanical
work
• Moving Boundary
Work or
Displacement Work
• Shaft Work & Spring
Work
• Work Done on
Elastic Solid Bars

Work is said to be done when a force moves through a distance. If the part of the boundary of a system
undergoes a displacement under the action of pressure, the work done W is the product of the force
(pressure x area), and the distance it moves the direction of the force.

If the work is done by the system on the surroundings, e.g., when a fluid expands pushing a piston
upwards, the work is said to be positive,
If the work is done on the system by the surroundings, e.g., when a force is applied on a rotating handle,
or to a piston to compress a fluid, the work is said to be negative.

Work output of the system = + ve

Work input of the system = − ve

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 One form of mechanical work frequently

encountered in practice is associated with the
expansion or compression of a gas in a piston–
cylinder device. During this process, part of the
boundary (the inner face of the piston) moves
back and forth. Therefore, the expansion and
compression work is often called moving
boundary work, or simply boundary work.
 Consider the gas enclosed in the piston–
cylinder device shown in Fig. The initial pressure
of the gas is P, the total volume is V, and the
cross sectional area of the piston is A. If the
piston is allowed to move distance ds in a
quasi-equilibrium manner, the differential work
done during this process is

 That is, the boundary work in the differential

form is equal to the product of the absolute
pressure P and the differential change in the
volume dV of the system. This expression also
explains why the moving boundary work is
sometimes called the P dV work.

Work (W): Work is

Work and energy

‘something’ which
appears at the boundary
when a system changes
its state due to the
movement of a part of
the boundary under the
action of force.
It is apparent that neither δW or δQ
are inexact differentials and therefore
any integration of the elemental
Heat (Q): “Heat is quantities of work or heat which
‘something’ which appear during a change from state 1
appears at the boundary to 2 must be written as
when a system changes δW = δQ
its state due to difference
in temperature between
the system and its
surroundings”.

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Point Path
function function
When two properties There are some quantities which
locate a point on the cannot be located on a graph by a
graph (co-ordinate axes) point but are given by the area on
then those properties are that graph. In that case, the area on
called as point function. the graph, pertaining to the
particular process, is a function of the
path of the process. Such quantities
are called path functions.

Examples:
Pressure, volume, Examples: Heat,
temperature etc. work etc

Since the area under each curve is different

the amount of work done for each path is
different. V2 V2
(  PdV ) path 1  (  PdV ) path 2
V1 V1

Work done depends on the path taken and

not just the value of the end states.

 It is the total energy stored in a substance. If during heating of the gas

the temperature increases its internal energy also will increase.

 Joules law of internal energy states that internal energy of a perfect

gas is a function of temperature only. In other words, change in
internal energy of a gas dependent on the temperature change only
and is not affected by the change in pressure and volume.
U = m Cv ∆T

 Changes in internal energy for solids, liquids, and gases are evaluated
using empirical data, e.g. U = f(T)
U=mCv(T2-T1)

 The change in system energy can be accounted for in terms of

internal energy of the fluid.
 H= U+ p V=mCvT+mRT=mCpT

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Thermal equilibrium

• If a system is in thermal
equilibrium, the temperature
will be same throughout the
system. A system is in
equilibrium if when the
system is isolated from its
surroundings there are no
changes in its properties

Zeroth law of Thermodynamics

• If two bodies are in thermal

equilibrium with a third body, they
are also in thermal equilibrium with
each other.

Relationship between
Energy Relations
specific heats

Cp – Cv = R Flow energy F.E=pv

γ(Gamma) = Cp/Cv
Kinetic energyK.E=1/2mc2

Cross multiplying the above two Potential energy P.E=mgh

equations we get,

If m = 1 kg then the above

quantities are called specific Work done: W=P.dV
quantities. Total Energy= K.E+P.E+IE

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The first law of thermodynamics is the

thermodynamic expression of the conservation of
energy. This law most simply stated by saying that
“energy cannot be created or destroyed” or that
“the energy of the universe is constant”.

If a closed system undergoes a

process from state 1 to state 2, then Stated for a system undergoing a
cycle, the cyclic integral of the work
E1 2 = KE1 2  PE1 2  U1 2  Q1 2  W1 2 is proportional to the cyclic integral of
the heat.
The increase in the KE + increase in PE +
increase in internal energy = heat transferred dQfrom system= ∫dWon system
into the system – work done by the system. Quite often in many situations the KE or PE
For most situations change in KE and PE is changes are negligible.
negligible so dU = dQ – dW

‘Energycan neither be created nor destroyed, but only transferred from one
system to another and transformed from one form to another’.
The total internal energy in a system is the sum of all the kinetic energies and
potential energies of its particles.

U system = (KE) system + (PE) system

We cannot determine the value of U of a system, but we can measure the

changes in internal energy ( ΔU ).

ΔU = U final – U initial

The sum of the heat absorbed or released and the work done on or by the
system is the change in internal energy. Q-W= ΔU

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First law of Thermodynamics

If Q is the amount of work transferred to the system and W is the amount of
work transferred from the system during a process, the net energy transfer (Q-W)
will be stored in the system and the name of that stored energy is Internal
energy.

Q- W = ∆U

Perpetual Motion Machine of first kind: PMM-I There can be no machine which
would continuously supply mechanical work without some form of energy
disappearing simultaneously. Such a fictitious (imaginary) machine is called a
perpetual motion machine of first kind, or in brief, PMM-I. A PMM-I is thus
impossible: WL + WM = QL + QM
PMM1 is a hypothetical machine which
continuously produces work without getting any
heat input.

The first law states that “the net heat Also the law states that “the heat energy and work
transfer is equal to the work transfer” for are mutually convertible” Though mechanical
work can be converted fully into heat energy, but
cyclic process. The limitation of this only a part of heat energy can be converted into
statement is, the direction of flow of mechanical work. This indicates heat and work are
both heat and work is not specified. not fully mutually convertible.

• A system is defined as a quantity of matter or a region in

space chosen for study. A closed system can be attributed
to the “quantity of matter” (i.e. control mass) whereas an
open system, or a control volume, as it is often called, is a
First law For properly selected “region in space”. It usually refers to a
Open Systems device that involves mass flow such as a compressor,
(Flow Process): turbine, or nozzle.

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Non-flow energy equation Steady flow energy equation

(NFEE): A non-flow process is that in (SFEE): Steady flow process is the
which a constant mass is undergoing one in which matter enters and
change of state in a closed system leaves through openings in the
where changes in potential energy control surface at a steady rate.
and kinetic energy are negligible.
Consider a system of fixed mass of
constant kinetic and potential
energy, equation therefore reduces
as shown above.

Steady flow properties

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Some Applications of SFEE

Nozzles &
Turbines & Diffusers
Compressors

Throttling
devices

Many engineering devices operate essentially under the same conditions for
long periods of time. Therefore, these devices can be conveniently analyzed as
steady-flow devices. In this section, some common steady-flow devices are
described, and the thermodynamic aspects of the flow through them are
analyzed. The conservation of mass and the conservation of energy principles
for these devices are illustrated.

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Constant
volume
(isochoric)
P/T=C:
V=Consta
nt

First Law
Analysis to
Non-flow
Processes

Adiabatic
(isentropic)
PV=C:Q=0,
S=constant

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Reversible constant
volume process
(Isochoric process )

• In a constant volume process the working substance is

contained in a rigid vessel, hence the boundaries of the system
are immovable and no work can be done on or by the system,
other than paddle- wheel work input. It will be assumed that
‘constant volume’ implies zero work unless stated otherwise
• Considering the mass of the working substance unity and
applying first law of thermodynamics to the process
Q = ( u2 – u1 ) + W
2

 pdv = 0 as dv = 0
• The work done W = 1

• ∴ Q = ( u2 – u1 ) = Cv ( T2 – T1)
• where Cv = specific heat at constant volume.
• For mass, m, of the working substance
• Q = ( U2 – U1 ) = mCv ( T2 – T1)

Reversible Constant Pressure Processes

(Isobaric process)

• When the boundary of the system is inflexible as in a

constant volume process, the pressure rises when heat is
added.
• Hence, for a constant pressure process, the boundary
must move against external resistance as heat is supplied;
for instance a gas [Fig] in a cylinder behind a piston can
be made to undergo a constant pressure process.
• Since the piston is pushed through a certain distance by
the force exerted by the gas, then the work is done by
the gas on its surroundings.
Considering unit mass of working substance and
applying first law of thermodynamics to 2 the process

Q = ( u2 – u1 ) + W The work done W =  p d v = p ( v 2 - v 1 )

∴ Q = ( u2 – u1 ) + p(v2 –v1) = u2 – u1 +1 pv2 –pv1
= (u2 + pv2) – (u1 – pv1) = (u2 + p2v2) – (u1 – p1v1)
{Since pressure is constant, therefore p1= p2= p}
= h2 – h1 = Cp(T2 – T1) (∵ h = u + pv)
where h = enthalpy and Cp= specific heat at
constant pressurefor mass, m, of the working
substance Q =H2 − H1 = mCp( T2 – T1 )

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( pv = constant,
T = constant ) Hyperbolic process: This process is an Isothermal process but
applicable only in steam. (T1=T2)[ PV=Constant ]. In an
isothermal expansion heat must be added continuously in
order to keep the temperature at the initial value. Similarly in
isothermal compression heat must be removed from the
working substance continuously during the process. Fig shows
the system and states before and after isothermal expansion.
Considering unit mass of working substance and applying first
law to the process Q = ( u2 – u1 ) + W
Q = Cv ( T2 – T1 ) + W
Q=0+W=W (∵ T = constant )

• A process at a 2

constant temperature  pdv

The work done , W = 1
C
is called an isothermal v( where C = constant )
In this case pvV =2 constant or p =
process. When a dv v2
 C v  C lnV V2
W=  C ln
working substance in a V1
V1
v1
cylinder behind a The constant C either be written as p1v1 or as p2v2, since p1v1 = p2v2 = constant
piston expands from =C
high pressure to low i.e W = p1v1 ln = p2v2ln = Q
(∵ for isothermal process W = Q ) For mass, m, of the working substance
pressure there is a
Q = W = p1V1 ln(v2/v1) = p2V2ln(v2/v1) or
tendency for the Q = W = p1V1 ln (p1/p2) = p2V2ln (p1/p2) (∵
temperature to fall. v2 p
= 1 for isothermal process )
v1 p2

An adiabatic process is one in which no heat is

transferred to or from the fluid during the
process. Such a process can be reversible or
irreversible. The reversible adiabatic non-flow
process is considered in this section.
• Considering unit mass of working substance and applying
first law to the process
• Q = ( u2 – u 1 ) + W
• 0 = ( u 2 – u1 ) + W or
• W = – ( u2 – u1 ) =(u1 – u2)
• This equation is true for all adiabatic processes whether the
process is reversible or irreversible.
• In an adiabatic expansion, the work done W by the fluid is
at the expense of reduction in internal energy of the fluid.
Similarly in adiabatic compression process all the work
done on the fluid goes to increase the internal energy of
the fluid.

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Work done during this adiabatic process 1-2 is given by the area below
the curve 1-2 in the p-v diagram, and this area can be evaluated by
integrating. 2

i.e. The work done , W =  pdv 1

v2 v2
C dv  v  1 - v2 1 
Since pv = C, then W =  v dv v1
= C
v1
v
= C 1
   1 

The constant C – can be written as p1v or 1 p2 v2 . Hence

W = p v  v  - p v  v  = p v - p v
 
 1   1
1 1 1 2 2 2 1 1 2 2
 1  1

i.e W = p1v1 - p 2 v 2 or W = R T1 - T2 

 1  1

Isentropic process: S1=S2 (entropy constant)

Adiabatic (Isentropic process) Q=0

By using the relation pv = RT, the relationship between T&v, and

T&p, may be derived as follows:
pv = RT
RT
∴ p= v γ
Putting this value in the equation pv = C

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Polytrophic Reversible Process ( pvn = C ) It is found

that many processes in practice approximate to a
reversible law of form pvn = Constant, where n is a
constant. Both vapours and perfect gases obey this
type of law closely in many non-flow processes. Such
processes are internally reversible.
We know that for any reversible process,
Work done W =  pdv
For a process in pvn = constant, we have
C
p = v , where C is constant
n

v  n 1 
-n  1
v2
dv  v -n  1   v1
W=C v v n
 C 
- n  1
  C  2
 -n 1

1 
n  n 1 n  n 1
i.e W = C  v 1
- n 1
 v2
 n 1
 P1v1 v1  P2 v 2 v 1 2
 
 n 1  n -1

(Since the constant C, can be written as p1v1n or p2v2n )

P1 v1 - P2 v 2
W= n 1
 n 2
  n  p1v1 - p2 v2 
Also Q =  1  p dv
1 =   1  n  1 
Note :In case of reversible adiabatic process n will become γ and hence Q will be zero

Polytrophic Process: (n variables)

In a polytrophic process, the index ‘n’ depends only on the

heat and work quantities during the process. The various
processes considered earlier special cases of polytrophic
process for a perfect gas. For examples,

When n=0; pv0= C i.e. p = Constant

( Constant Pressure Process)
1
When n = ∞ ; pv∞= C or p v= C or v = C
(Constant Volume Process)

When n =1 ; pv = C i.e T = C
( Isothermal Processes)

When n = γ ; pvγ = C
( Isentropic or Reversible adiabatic process )

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Consider two vessels 1 and 2 interconnected by a short pipe with

a valve A, and perfectly thermally insulated (Fig). Initially let the
vessel 1 be filled with a fluid at a certain pressure, and let vessel 2
be completely evacuated. When the valve ‘A’ is opened the
fluid in vessel 1 will expand rapidly to fill the vessel 2. The pressure
finally will be lower than the initial pressure in vessel 1. This is known
as free or unrestricted expansion.
The process is highly irreversible; since the fluid is eddying ( a
circular movement causing a small whirlpool ) continuously during
the process. Now applying the first law of thermodynamics
between the initial and final states, Q=(U2-U1) + W
In this process, no work is done on or by the fluid, since the boundary of the system does
not move. No heat flows to or from the fluid since the system is well lagged ( insulated ).
The process is therefore, adiabatic but irreversible.
i.e. u2 – u1 = 0 or u2 = u1
Q= 0 and W=0
in a free expansion, therefore, the internal energy initially equals the internal energy finally.
For a perfect gas, u = CvT
∴ For a free expansion of a perfect gas,
CvT1 = CvT2 i.e. T1 = T2

That is for a perfect gas undergoing a free expansion, the initial temperature is
equal to the final temperature.

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Second law of Thermodynamics:

The statement made by Kelvin-Planck says, “It is impossible for a heat
engine to produce net-work in a complete cycle if it exchanges heat
only with bodies at a single fixed temperature.” Thus to produce the
work the cycle should exchange heat with two reservoirs which are a
different temperatures. The high temperature reservoir is called as
source and low temperature reservoir is called as sink.

The statement
made by Clausius Perpetual Motion Machine of
says, “It is Second kind: PMM-II: is a
impossible for a hypothetical machine which
heat flows from low continuously transforms all
temperature body the heat it receives into work
to high completely.
temperature body”

Heat engines differ considerably from one

HEAT ENGINES another, but all can be characterized by the
following points:
•They receive heat from a high-temperature
source (solar energy, oil furnace, nuclear
Work can easily be converted to other forms of reactor, etc.).
energy, but converting other forms of energy •They convert part of this heat to work (usually
to work is not that easy. Work can be in the form of a rotating shaft).
converted to heat directly and completely, •They reject the remaining waste heat to a
but converting heat to work requires the use of low-temperature sink (the atmosphere, rivers,
some special devices. These devices are etc.).
called heat engines. •They operate on a cycle.

Thermal Efficiency
The fraction of the heat input that is converted For heat engines, the desired output is the net-work
to net-work output is a measure of the output, and the required input is the amount of
performance of a heat engine and is called the heat supplied to the working fluid. Then the thermal
thermal efficiency ηth . efficiency of a heat engine can be expressed as

T1  T2
Efficiency of heat engine ŋ max=
T1

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Coefficient of Performance: The

REFRIGERATORS AND HEAT PUMPS: efficiency of a refrigerator is
Heat is transferred in the direction expressed in terms of the
of decreasing temperature, that coefficient of performance (COP),
is, from high-temperature denoted by COPR. The objective
mediums to low temperature of a refrigerator is to remove heat
ones. This heat transfer process (QL) from the refrigerated space.
occurs in nature without requiring To accomplish this objective, it
any devices. The reverse process, requires a work input of Wnet,in.
however, cannot occur by itself. Then the COP of a refrigerator can
The transfer of heat from a low- be expressed as, Notice that the
temperature medium to a high- value of COPR can be greater
temperature one requires special than unity.
devices called refrigerators. Here
QL is the magnitude of
the heat removed from the
refrigerated space at
temperature TL, QH is the
magnitude of the heat rejected
to the warm environment at
temperature TH, and Wnet,in is
the net-work input to the
refrigerator. As discussed before,
QL and QH represent magnitudes Q2 T2
and thus are positive quantities. COPR =
Q1  Q2
=
T1  T2

The objective of a refrigerator is to maintain the refrigerated space at

a low temperature by removing heat from it. Discharging this heat to
a higher-temperature medium is merely a necessary part of the
operation, not the purpose. The objective of a heat pump, however, is
to maintain a heated space at a high temperature. This is
accomplished by absorbing heat from a low-temperature source,
such as well water or cold outside air in winter, and supplying this heat
to the high-temperature medium such as a house (The measure of
performance of a heat pump is also expressed in terms of the
coefficient of performance COPHP, defined as for fixed values of QL
and QH

COP of heat pump is always greater than the COP of refrigerator by

one (unity) when working between the same temperatures limit.
Q1 T1
COPHp = Heat added to hot body / Work supplied = = T1  T2
Q1  Q2
Q2 T2
COPR = Heat absorbed from cold body / Work supplied.= =
Q1  Q2 T1  T2

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Entropy
One consequence of the second
law is the development of the .The change in entropy is
physical property of matter termed defined as the ratio of .The second law
entropy (S). heat transferred during a
reversible process to the can also be expressed as
.Entropy was introduced to help absolute temperature of for a closed cycle. In
explain the Second Law of the system ∆S other words, entropy
Thermodynamics. The change in this must increase or stay the
property is used to determine the (This is for a reversible same for a cyclic system;
direction in which a given process process.)Where it can never decrease.
will proceed. Q This is also known as
 0
T principle of entropy
.Entropy can also be explained as a ∆S = the change in
measure of the unavailability of heat increase.
entropy of a system during
to perform work in a cycle. This some process ∆Q = the .If the integral of Q/T
relates to the second law since the amount of heat added to about a cycle is equal to
second law predicts that not all heat the system during the zero,
provided to a cycle can be process T = the absolute then the process is said
transformed into an equal amount temperature at which the to be reversible.
of work, some heat rejection must heat was transferred.
take place.

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Carnot Cycle:
• The cycle was first suggested by a French
Engineer Sadi Carnot in 1824 which works
on reversible cycle and known as ‘Carnot
Cycle’.

Carnot Process

Process 2-3 Process 3-4 Process 4-1

Process 1-2 Adiabatic
Isothermal Adiabatic Isothermal
Expansion Heat Rejection Compression
Heat supplied Q4-1=0
Q1-2=(S2-S1)T1 Q2-3=0 Q3-4=(S4-S3)T3
(S4=S1)
(T2=T1=TH) (S2=S3) (T3=T4=TL)

Carnot Engine Cycle: The assumptions made for describing the working of the Carnot engine are as follows:

iii. The
i. The piston cylinder iv. The
ii. The walls v. Working
moving in a head is so transfer of vi.
of piston and medium is
cylinder arranged heat does Compression
cylinder are any perfect
does not that it can not affect and
consider as gas and has
develop any be perfect the expansion
perfect constant
friction heat temperature are
insulators for specific
during conductor or of source or reversible.
heat. heat.
motion. perfect heat sink.
insulator.

Stage 2. ( Process 2- 3 ). The cylinder

Stage 1. ( Process 1-2 ). Hot energy source
becomes a perfect insulator so that no heat
is applied. Heat Q1 is taken in whilst the fluid
flow takes place. The fluid expands
expands isothermally and reversibly at
adiabatically and reversibly whilst the the
constant high temperature T1
temperature falls from T1 to T2.(TH to TL)

Four Stages Of Carnot

Cycle

Stage 4. ( Process 4-1 ). Cylinder head

Stage 3. ( Process 3-4 ). Cold energy source
becomes a perfect insulator so that no heat
is applied. Heat Q2 flows from the fluid whilst
flow occurs. The compression is continued
it is compressed isothermally and reversibly
adiabatically and reversibly during which
at constant lower temperature T2.
temperature is raised from T2 to T1.

•The first law of thermodynamics during this cycle is the difference between the heat supplied by the
source (Q1) and heat rejected to the sink (Q2 ). work done Q  Q2 T1  T2
• ∴W = Q1 – Q2 Thermal efficiency, ƞ = = 1 = T
Heat supplied by the source 1 Q 1

•Such an engine since it consists entirely reversible processes can operate in the reversed direction so
that it will operate as a heat pump or refrigerator. Carnot efficiency is the maximum efficiency of the
Engine cycle.

•Such an engine since it consists entirely reversible processes can operate in the reversed direction so
that it will operate as a heat pump or refrigerator.
•Carnot efficiency is the maximum efficiency of the Engine cycle.

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Carnot's theorems:
i) No engine can be more
efficient than a reversible
engine working between the
same limits of temperature.
ii) All reversible engines
working between the same
two limits of temperature
have the same efficiency.
cannot be performed in
practice because of the
following reasons

•Liquids and solids can be approximated as incompressible substances since their specific
volumes remain nearly constant during a process.
Entropy Change •For liquids and solids in an isentropic process, the change temperature will be zero
of Liquids and
Solids

The Entropy
Change of
Ideal Gases

•Constant Volume Processes

•S2 - S1 = mCV loge(T2/T1)
•Constant Pressure Process
Change of •S2 - S1 = mCp loge(T2/T1)
Entropy of •Isothermal Processes
Perfect Gas •S2 - S1 = m ( CP – CV )loge (V2/ V1)
for Various •Reversible adiabatic process
•S2 = S1
Processes •Polytrophic process
•S2 - S1 =m Rloge (V2/ V1) + mCV loge (T2/T1)

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A pure substance is defined as

a substance that has a fixed
chemical composition
(example: water; Co2;
nitrogen;).
•A mixture of several gases can be
considered as a pure substance, if it
has a uniform chemical composition.
•A substance can exist under several
forms: solid; liquid or gas. Furthermore,
each phase may not be unique.

Third law of Thermodynamics: “Entropy of a pure substance

approaches zero at absolute zero temperature.” This fact can also
be corroborated by the definition of entropy which says it is a
measure of molecular dis orderness. At absolute zero temperature
substance molecules get frozen and do not have any activity,
therefore it may be assigned zero entropy value at crystalline state.

Phase-change processes of pure substances: We continue to

add some heat to water, the temperature will increase until
100°C (373.15 K). At this point, any additional addition of heat
will vaporize some water. This specific point where water starts
to vaporize is called saturated liquid. The state between
saturated liquid (only liquid) and saturated vapor (only vapor)
where two phases exist is called saturated liquid-vapor
mixture . After the saturated vapor phase, any addition of
heat will increase the temperature of the vapor, this state is
called superheated vapor.

Saturation temperature and saturation

pressure: The temperature at which water
starts boiling depends on the pressure. 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 Dryness fraction :x=mass of dry
pure substance changes phase is called the steam/Total mass of steam
saturation pressure (Psat).
X=mg/mg+mf

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The answer to one of

these questions must be Some tables may not
yes. If the answer to the always give the internal
first question is yes, the energy. When it is not
How to Choose the
state is in the listed, the internal
Right Table: The correct
compressed liquid energy is calculated
table to use to find the
region, and the from the definition of the
thermodynamic
compressed liquid tables enthalpy as
properties of a real
are used to find the u  h  Pv
substance can always
properties of the state. If u  u  u
be determined by fg g f
the answer to the
comparing the known h  h  h
second question is yes, fg g f
state properties to the
the state is in the s  s  s
properties in the fg g f
saturation region, and
saturation region. Given
either the saturation The quantity hfg is called
the temperature or
temperature table or the the enthalpy of
pressure and one other
saturation pressure table vaporization (or latent
property from the group
is used to find the heat of vaporization). It
v, u, h, and s, the
properties. Then the represents the amount
following procedure is
quality is calculated and of energy needed to
used. For example if the
is used to calculate the vaporize a unit of mass
pressure and specific
other properties, u, h, of saturated liquid at a
volume are specified,
and s. If the answer to given temperature or
three questions are
the third question is yes, pressure. It decreases as
asked: For the given
the state is in the the temperature or
pressure,
is v  v ? superheated region and pressure increases, and
becomes zero at the
f
the superheated tables
is v  v  v ?
f g
are used to find the critical point.
is v  v g ? other properties.

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Office: ME212
muthuraman.subbiah@hct.edu.om

http://e-learning.hct.edu.om/moodle263/login/index.php

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