Basic Thermo Concept

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BASIC THERMODYNAMICS
CONTENTS
CHAPTER TOPIC PAGE No.
1. Basic Concepts
OR 2
2. First Law of Thermodynamics 6
3. Second Law of thermodynamics 15
SF
4. Entropy 20
5. Availability and Irreversibility 29
6. Properties of Steam 34
7. Properties of Gases & Gas Mixture 37
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1
BASIC CONCEPTS
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SCOPE : Thermodynamics is study of energy transfer and its effect on physical properties of substances. Thermodynamic
laws govern the principle of energy conversion. The application of thermodynamic laws and principles are found in all fields
of energy conversion like Power Plants, I.C. Engine and Environmental Control like refrigeration air Air-conditioning.
Concept of Macroscopic Vs. Microscopic View Point : Macroscopic (Classical Thermodynamics) is only concerned with
effect of action of many molecules and their effects can be perceived by human senses.
Microscopic (statistical thermodynamics) point of view considers that matter is composed of myriad of molecules. The
behaviour of substance is described by summing up the behaviour of each molecule.
Concept of Continum :
OR δm
δv
ρ
δv
1
δv
From the macroscopic view point, we are always concerned with volumes which are very large compared to molecular
dimensions.
Even a very small volume of system is assumed to contain large number of molecules so that statistical averaging is
meaningful and property value can be assigned to it.
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m
Let us consider mass δm in a volume surrounded by volume δv. the ratio is average mass density of system within
v
volume δv.
When δv is so small so as to contain relatively few molecules, the average density fluctuates substantially with time as
m
molecules pass into and out of volume in random motion, so its 13 impossible to speak of definite value of . The smallest
v
volume which may be regarded as continuous is δv.
m
ρ = Lim
v →v ' v
Concept of Thermodynamic System : A thermodynamic system is defined as quantity of matter on a region of space upon
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which attention is concentrated in analysis of problem.

Everything external to system is called surrounding Environment. The system is separated from surrounding by the system
boundary. The boundary may be either fixed or moving.
The system and surrounding together comprise a universe.
Closed System / Open System / Isolated System : There are 3 classes of systems –
(a) Closed system (b) Open system (c) Isolated system
The closed system is a system of fixed mass. There is no mass transfer across the system boundary. There may be energy
transfer into or out of the system. A certain quantity of fluid in a cylinder bounded by piston constitutes closed system.
The open system is a system in which matter crosses the boundary of system. There may be energy transfer also. Most of
engineering devices are open system.
Isolated system is a system in which there is no mass or energy transfer across the system boundary.
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Concept of Control Volume and Control Surface : For thermodynamic analysis of an open system, such as an air
compressor, attention is focussed on certain volume in space surrounding the compressor known as control volume bounded
by a surface called control surface. Matter as well as energy cross the central surface.
Air out
Work
Heat
Motor Air Compressor
Air in
Thermodynamic Properties, State, Processes and Cycles : Every system has certain characteristics by which its
physical condition may be described e.g. Volume, Temperature, Pressure etc. Such characteristics are called properties of
OR
the system. These are all macroscopie in nature.
When all the properties of a system have definite values, No system is said to exist at a definite state.
Properties are the co-ordinates to describe the state of a system.
Any operation in which one or more of the properties of a system changes is called change of State.
The succession of states passed through during change of state is called path of the change of state.
When the path is completely specified, the change of state is called process.
A Thermodynamic cycle is defined as series of state changes such that final state is identical with initial state.
Properties : Properties may be of two types : Intensive properties and Extension Properties.
Intensive properties are independent of mass of system e.g. pressure, temperature.
Extensive properties are related to mass e.g. Volume, energy etc. specific extensive properties like specific volume, specific
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energy are intensive properties.
Concept of Thermodynamic Equilibrium : A system is said to be in Thermodynamic equilibrium if there can be no
spontaneous change in any macroscopic properties and it is in complete balance with its surrounding.
A system will be in state of thermodynamic equilibrium, if the condition of following three type of equilibrium are satisfied–
(a) Mechanical equilibrium (b) Chemical equilibrium (c) Thermal equilibrium
Mechanical Equilibrium : A system is said to be in mechanical equilibrium, if there are no unbalanced force in the system
with its surrounding.
Chemical Equilibrium : It represents the absence of any phase change no chemical reaction or transfer of matter from one
part of system to another such as diffusion or solution. The system is said to exist in Chemical equilibrium.
Thermal Equilibrium : If temperature of a system remains solve as its surrounding, then it is known as thermal equilibrium.
Hence, temperature gradient does not exist.
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1
x
x
x
Concept of Quasi Static Process : A process which occurs such that at each state of process, P x
x
Thermodynamic equilibrium exist in system. Infinite slowness is characteristic of quasi static x x x
2
process. Quasi static process is also called reversible process.
V
1
Non quasi Static Process : The process in which only initial and final states are in x
thermodynamic equilibrium (succession points of process are not in thermodynamic equilibrium)
is known as Non quasi static process. P
Practically, most of the processes are non quasi static. x2

Non quasi static process are represented by dotted lines / curve. State 1 and 2 represent only initial V
and final states.
Non quasi static processes are also irreversible process.
Concept of Reversible Process and Irreversible Process :
Reversible Process : A process is said to be reversible, if initial states of the system can be achieved from other state by
reversing the process.
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To be reversible process, some conditions are necessary :
(i) It must be quasi static process.
(ii) Friction, viscosity should be present.
Concept of Point Function and Path Function :
P1 P2 1
P C
B
V1 V2 A 2
V2 V
w1− 2 = ∫
V1
PdV
OR
It is possible to take a system from State 1 to State 2 along many qursi static points, such as A, B or C.
Snce the area under each curve represent the work for each process, the amount of work involved in each case is nut
function of end state of the process. It depends on path the system follows in going from State 1 to State 2.
For this reason, work is called path Function : dw is an inexact or imperfect differential.
2
∆W1 – 2 = ∫ dw ≠ w
1 2
– w1
Thermodynamic properties are point function, since for a given state, thou is definite value for each properties. The change
in thermodynamic property of a system in change of state is independent of the path the system follows during change of
state, and depends only on initial and final states of system.
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2
∆W = ∫ dV = V
1
2 − V1
The change in volume that depends only on the end states of the system irrespective of the path the system follows. The
differentials of point function are exact or perfect differential.
V2
∫
V1
dV = V2 − V1
To distinguish, an inexact differential (say dw ) from exact differential (say dV), the differential sign is being cut by a line at
its top.
For a cyclic process, the initial and final states of the system are the same, hence the change in any property is zero.
∫ dV = 0 ∫ dp = 0 ∫ dT = 0
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Symbol ∫ denotes the cyclic Integral for the closed path. The cyclic integral of a property is always zero.
Zeroth Laws of Thermodynamics : If two bodies A and C are individually in thermal equilibrium with a third body B, then
the two bodies A and C will also be in thermal equilibrium.
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A Thermal B
T Equilibrium T
Thermal
Equilibrium al m
m
h er ibriu
T uil
Eq
C
T
This is known as Zeroth Law of Thermodynamics. It is the basis of Temperature measurement.

Temperature and Thermal Equilibrium : Temperature is property of system which determines the flow of heat between
two system / bodies.
In order to obtain a quantitative measure of temperature, a reference body is used and a certain physical characteristics of
this body, which changes with temperature is selected. The selected characteristic is called thermodynamic property and
Constant Volume gas thermometer

Constant Pressure gas thermometer
Electrical Resistance Thermometer
Thermocouple
OR
reference body which is used in determination of temperature is called Thermometer.
Thermometer Thermometric Property
Pressure
Volume
Resistance
emf
Mercury in glass thermometer Length
•••
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FIRST LAW OF 2
THERMODYNAMICS
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(Work Transfer and Heat Transfer)
First Law of Thermodynamics is based on the Law of Conservation of Energy according to which the total amount of
energy in any Thermodynamic system remains constant.
Energy can not be produced or destroyed, it can only be converted from one form to another.
Statement of first law of thermodynamics is as follows –
“Whever, a closed system executes a cyclic process, the algebric sum of work transfer is proportional to algebric sum of
heat transfer”.
Mathematically, ∫ dQ = ∫ dw
The expression applies only to system undergoing cycles. But if a system undergoes a change of state during which both
heat transfer and work transfer are involved, the net energy transfer will be stored or accumulated within the system.
OR
If Q is amount of heat transferred to system and w is amount of work transferred from system during the process, the net
energy transfer (Q – W) will be stored in system. Energy in storage is neither heat not work and is given name internal energy
or simply energy of system.
Ek +
p E + U

Q – W = ∆E E =  Micro
Macro
Q = w + ∆E In absence of motion and gravity – E = U

Q = W + U
Work and Heat Transfer
Closed System (Non flow Process)
Convention
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W
W
System System
(a) W is positive (b) W is negative
Q Q
System System
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(a) Q is positive (b) Q is negative
Displacement Work (Flow work)
dl
P2
P1
V1
V2
Work done by gas on piston
dW = F . dl
= p . a. dl
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dW = p . dV
2
W1-2 = ∫ 1
pdv
P
2
dV
Application of First Law of Thermodynamics for Closed System
Constant Volume Process (Isochoric Process)
V
OR
PdV (displacement work 1 Flow Work) in various quasi static process
Q – W = ∆U
dQ – dW = dU
dQ = dU
here dW = pdV = 0
dQ = m CV dT
Constant Pressure Process (Isobaric Process)
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1 2 Q – w = ∆U
P MCp (T2 – T1) – p (V2 – V1) = ∆U
here dW = pdV = p (V2 – V1) = p2V2 – p1V1 = MR (T2 – T1)

dQ = MCp dT = MCp (T2 – T1)
MCp (T2 – T1) – MR (T2 – T1) = MCv (T2 – T1)

M Cp (T2 – T1) – M Cv (T2 – T1) = MR (T2 – T1)
Cp – C v = R
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This equation is known as Meyer Formula.

Constant Temperature or Isothermal Process :
PV = MRT = Constant 1
PV = C
2
∫ dv P 2
W= 1
2 C V
= ∫
1 V
dV
V
= C[lnV ]V12
V2 V V
W = P1V1 ln = P2V2 ln 2 = m RT
T ln 2
V1 V1 V1
∆U = m CV dT = 0
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Q – W = ∆U = 0
Q=W
Reversible Adiabatic Process : An adiabatic process is one in which there is no heat transfer between system and
surrounding. Q = 0.
It follows law PVr = C 1
2 2 C
W= ∫
1
pdV = ∫ 1 Vr
dV
P
2
− +1 V2
C[V ] V
= V
−  +1
1
1− 1−
W = 1 −  V2 − V1 
 1−  1−
= 1 −   P2 V2 V2 − P1 V1 V1 
OR
1
W = 1 −  [P2V2 – P1V1] Q=0
dU = Q – W = – W
Reversible Polytropic Prcess :
2 2 dv
∫ ∫
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PVn = C W= Pdv = C
1 1 Vn
P1V1 = P2V2
W=
n −1
∆U = mq (T2 – T1)
Q = W + ∆U, after solving / simplification
 n −   − n  P1V1 − P2V2 
Q=   m CV (T2 – T1)
 − 1  n − 1 
Q=
 n −1 
 −n
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Q= × Work transfer
 −1
n=0
n
PV = C
n=∞
For adiabatic process n = γ PVr = C P n=1

n == rγ
For isothermal process n = 1 PV = C
For Isochoric process n = ∞ V=C V
For Isobaric process n = 0 P=C
Concept of Enthalpy : Enthalpy is property of gas which is equal to algebric sum of internal energy and product of its
pressure and volume.
H = U + PV
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Specific enthalpy h = u + pV
Heat Transfer in Constant Pressure Process Involving no work other than PdV Work :
dQ = dV + dW at constant pressure
= dV + pdV d (PV) = PdV + VdP
= d (V) + d (PV) = PdV + O
dQ = d (V + PV) d (PV) = PdV
dQ = dH
Heat transfer at constant pressure increase the enthalpy of a system
Application of First Law of Thermodynamics to steady flow open System : If mass and energy both transfer across the
boundary of the system, the system is categorised as open system.
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Steady flow means that the rate of flow of mass and energy across the control surface are constant.
In most of engineering devices, there is constant rate of flow of mass and energy through constant surface and control
volume (in course of time, steady state is attained)
At the steady state of a system, any thermodynamic property will have fixed value at a particular location and will not alter
with time. Thermodynamic properties may vary along space co-ordinates, but do not vary with time.
Control
Surface
Q
Notations are as follows
m Mass flow rate (kg/sec)
P2 V2 T2
P Pressure (Pa)
2
u2 C2 ρ2
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Control m3
volume V Specific volume kg
1 Wsf J
P1 V1 T1 u Specific internal energy kg
u1 c1 ρ1 Z2
m
c Velocity / flow
sec
Z1
z Elevation m
ρ density kg /m3
Bottom Line
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Steady Flow Energy Equation

According to law of Conservation of energy.
Total rate of flow of energy into control volume = Total rate of flow of energy out of control volume
G2  C 22 
m (u1 + p1v1 +   u
+ g z1) + Q = m  2 + p V
2 2 + + gz 2  + W sf
2  2 
Mass Balance
m 1 = m 2
A1 C1 A2 C2
=
V1 V2
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ρ1 A1 C1 = ρ2 A2 C2
This equation is known as equation of continuity
dQ
Energy Balance: Q → → Net rate of heat transfer through Control surface
d
dw

w→ → Net rate of work transfer through
d
dQ dw
w 1e1 + w 1 p1v1 + = w 2 e2 + w 1 p2 v2 +
d d
e = ek + e p + u
e=
C2
2
C 2
+ Zg + u
OR dQ
m 1  1 + Z1 g + u1 + p1V1  +
 2  d
m
= 2
 C 22
 2
 dw
+ Z 2 g + u 2 + p2V2  +
 d
as we known —→ h1 = u1 + p1V1
 C2   C2 
so, m 1 h1 + 1 + Z1 g  + Q = m 2 h2 + 2 + Z 2 g  + W
 2   2 
as m 1 = m 2 = m
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C12 Q C2 W
h1 + + Z1 g + = h2 + 2 + Z 2 g +
2 m 2 m
C12 C2
h1 + + Z1 g + q = h2 + 2 + Z 2 g + w
2 2
 C22 − C12 
⇒ q – w = (h2 – h1) +   + g (Z – Z )

 2  2 1
small letters represent specific properties or per unit mass

q – w = ∆h + ∆KE + ∆PE
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In different form dq – dw = dh + cdc + gdz

Mechanical work in steady flow open system :
q – w = ∆h + ∆KE + ∆PE
For infinitesimal process
dq – dw = dh + dkE + dPE
dq – dw = d (u + pV) + dkE + dpE
Assume KE and PE changes are negligible, dq – dw = dh
dq – dw = d (u + pv)
dq – dw = du + pdv + Vdp .......... (1)
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From first law of thermodynamics → (For closed system)
dq – dw = du
du = dq – pdv .......... (2)
As Internal energy is function of temperature only (point function). Hence, du does not depend upon flow on non-flow
process and for same temperature difference, it will be equal for both process :
Hence from (1) dq – dw = (dq – pdv) + pdv + Vdp
dw = – Vdp
For Steady Flow open system work transfer can be calculated as W = − Vdp ∫
1
OR P
V
2
Work Transfer in Steady Flow open System :

Steady Flow Constant Volume Process :
P2
W= − ∫
P1
V dp = – V (P2 – P1)
dq – dw = dh + ∆KE + ∆PE
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If ∆KE = 0, ∆PE = 0
Then, dq – dw = dh
dq – (Vdp) = du + pdv + Vdp
dq + Vdp = du + pdv + Vdp
dq = du + pdV
dq = du as pdV = 0
∆Q = M CV (T2 – T1) = ∆U
Steady Flow Constant Pressure Process
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P2
W= − ∫P1
Vdp = 0
dq – dw = dh
dq = dh
Isothermal Process (pV = C)
P2 2 C p
W= − ∫
P1
Vdp = − ∫
1 P
dp = − C ln 2
p1
p2 p1 V2
W = – p1V1 ln
p1 = p1v1 ln p2 = p1v1 ln V
1
Adiabatic Process :
∫
W = − Vdp
C
pv = C V=
pv
UM
2
dp
W= − C ∫
1
p v
r
W =  − 1 (p1V1 – p2V2)
Q=0
Polytropic Process :
PVn = C
n
W= (P1V1 – P2V2)
n −1
1. Nozzle and Diffuser :

 n − 
∆Q = 
 n −1 
OR
 m CV (T2 – T1)
Application of First Law of Thermodynamics for Steady Flow Process :
(1) (2)
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A nozzle is a device which increase the velocity or KE of fluid at expense of pressure drop.
Whereas a diffusion increases the pressure of fluid at expense of its K.E.
G2 C2
h1 + + Z1g + q = h2 + 2 + Z2g + W
2 2
here q = 0 w=0 Z1 = Z2
C12 C2
so h1 + = h2 + 2
2 2
C22
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when q = 0 h1 – h2 =
2
C2 = 2 ( h1 − h2 )
2. Throttling Device : When a fluid flows through a constricted passage. Like a partially opened valve, an orifice, on a porous
plug, there is an appreciable drop in pressure and the flow is said to be throttled. This is an irreversible process.
q=0 w=0 z1 = z2
C12 C2
h1 + = h2 + 2 as C1 = C2 low values
2 2
h1 = h2
If fluid is ideal gas, then T1 = T2
u1 = u2
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Steady Flow Energy equation for Turbine and Compressor : Turbines and Engines gives positive power output, whereas
compressors and pumps require power input.
(1)
WT
(2)
C12 C2
For Compressor
h1 +
here
2
h1 + h2 + W
z 1 = z2
OR
+ z1 q + q = h 2 + 2 + z2 g + W
2
C1 = C2
W = (h1 – h2)
q=0
Air out
SF
Air in
C12 C2
h1 + + z1 g + q = h 2 + 2 + z2 g + W
2 2
C 1 = C2 z 1 = z2 q=0
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h1 = h2 – W
W = (h2 – h1)
The enthalpy of the fluid increases by the amount of work input.
Heat Exchanger : Heat exchanger is devices in which heat is transferred from one fluid to another. e.g. Boiler / Condenser.
mS
Steam in
(2)
(3)
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Cooling water in
Cooling water out
mC mC
(1) (3)
(4)
Condensate
C22 C2
here ms ( h2 + + z2g + q) + mc ( h1 + 1 + z1g + q)
2 2
C42 C32
ms ( h 4 + + z4g + W) + mc ( h3 + + z3g + w)
2 2
Simplifying mc h 1 + ms h 2 = mc h 3 + mc h 4
ms (h2 – h4) = mc (h3 – h1)
OR
Here KE and PE terms are considered small (flow velocities are small), there is no external work done and energy exchange
in form of heat is confined only between two fluids. There is no external heat interactions or heat loss.
Comparison of steady flow energy equation with Euler and Bernauli Equation :
C12 dQ C22 dW
h1 + + z1 g + = h2 + + z2 g +
2 dm 2 dm
dQ C 2 − C12 dw
= (h2 – h1) + 2 + (z2 – z1) g +
dm 2 dm
In differential form,
dQ = dh + C dc + g dz + dw or h = u + pv
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du + pdv = du + pdv + Vdp + cdc + gdz + dw

Vdp + Cdc + gdz + dw = 0
For an inviscid frictionless fluid flowing through pipe
Vdp + Cdc + gdz = 0
This is Euler equation
V 1
For Imcompressible Fluid : = Constant   specific volume / density in constant
m 
Integrating Euler Equation
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2 2 2
∫
1
Vdp + ∫1
Cdc + ∫
1
gdz = 0
C22 C2
V (p2 – p1) + – 1 + g (Z2 – Z1) = 0
2 2
1 p2 C 22 p C2 p C2
as V =  + + gz 2 = 1 + 1 + gz1 Or + + g 2 = Constant
 2  2  2
This is Bernauli Equation.
SECOND LAW OF 3
THERMODYNAMICS
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This law has been mentioned by two statements clausius statement and Kelvin. Plank statement.
Clausius Statement : It is impossible to construct a device (Refrigeration Plant / Heat Pump) operating on a cycle whole
sale effect is the transfer of heat for low temperature body to higher temperature body.
T1
Q1
HP W=0
Q2
T2
OR
Kelvin Plank Statement : It is impossible to construct a device (Heat engine) operating on a cycle whose sole effect is
transfer of heat energy from single heat reservoir and do equivalent amount of work.
T1
HE Wnet = Q1
Q2 = 0
(A PMM 2)
Description of Some Device :

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Heat reservoir : It is defined as source of Infinite heat energy. Finite amount of heat absorbed or heat rejected from heat
reservoir does not effect its temperature.
Heat Source : Heat reservoir which supplies heat to a system.
Heat Sink : Heat reservoir which absorbs heat from system.
Heat Engine : A device which can produce work continuously (which operates on cyclic process) at the expense of heat
input is called heat engine. (E.g. Steam engine, steam turbine, petrol engine, Diesel engine, gas turbine etc.)
As per first law
∫ dQ = ∫ dW Heat Source
T1
Q1 – Q 2 = W
Q1
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Efficiency of heat engine is defined as

ratio of work output to energy input
He
W Q1 − Q2
η= Q = Q
1 1 Q2
Heat Sink
Q2 T2
η=1– Q
1
Cyclic Heat Engine :
Vapour
Turbine
Furnace QBoiler WT
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1 Q1 WE
T1
Condenser River WC
Q2 Rivet
H2O TT22
Q2
WP Closed System
Steady Flow system
Refrigerator : A refrigerator is a device operating on a cycle which removes heat from a low temperature body and rejects
it to body at higher temperature on the expense of external work supplied.
The objective of the system is to produce cooling effect at low temperature.
Heat Reservoir at
OR T1
Q1
(WC – WE)
Q2
Heat Reservoir
T2
The efficiency of refrigerator is expressed in terms of coefficient of performance.

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Desired effect Q2 Q2
(COP)R = = =
Energy input W Q1 − Q2
T2
(COP)R =
T1 − T2
Cyclic Refrigeration Plant :
Expander
WE
Q2
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Atmosphere
WC Compressor Q1 T1
Heat Pump : Its working is same as refrigerator but objective of system is to deliver heat energy at higher temperature.
Desired effect
(COP)n = Energy input
Q1
=
W
Q1
= Q −Q
1 2
T1
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(COP)n = T − T
1 2
Q1 Q2 Q1 − Q2
(COP)H – (COP)R = Q − Q − Q − Q = Q Q = 1
1 2 1 2 1 2
(COP)H = 1 + (COP)R
Equivalence of Kelvin Plank and Clausius Statement : At first sight, Kelvin Planck and Clausius statement may appear
to be unconnected, but it can easily be shown that they are virtually two parallel statement of second law and are equivalent
in all respects.
The equivalence of two statements will be proved if it can be shown that violation of one statement implies the violation of
second and vice-versa.
(a) Let us first consider a cyclic heat pump which transfer heat from low temperature Hot Reservoir
at T1
reservoir (T 2) to high temperature reservoir (T 1) with no other effect i.e. no
Wnet in one cycle.

OR
expenditure of work violating Claussius statement.
Let us assume a Cyclic Heat Engine E operating between same reservoirs producing
The rate of working of the heat engine is such it drows an amount of heat Q1 from hot
reservoir equal to heat Q1 discharged by the heat pump.
Then the hot reservoir may be eliminated and heat Q1 discharged by heat pump is fed
to heat engine.
W=0 HP
Q1
Q1
Cold Reservoir
at T2
HE
Violation of Classius
Q1
Q2
Wnet =
Q1 – Q2
HE Wnet = Q1 – Q2
So we see that heat pump P and heat engine E working together constitute a heat engine Q1 – Q2
operating in cycle producing net work while exchanging heat only with cold reservoir.
Cold Reservoir
This is violation of Kelvin Plank. T2
Violation of Kelvin Plank
SF
Reversibility and Irreversibility (Carnot Cycle / Carnot Theorem / Carnot Heat Engine) :
The Second Law of Thermodynamics enables us to divide all processes into two classes :
(a) Reversible or Ideal process
(b) Irreversible or Natural process
A reversible process is one which is performed in such a way that at the conclusion of the process, both the system and
surrounding may be restored to initial states, without producing any change in rest of universe.
A reversible process is carried out infinitely slowly with an infinitesimal gradient so that every state passed through by the
system is an equilibrium state. So a reversible process coincides with quasi static process.
Any natural process carried out with a finite gradient is irreversible process.
A reversible process is an idealized hypothetical process approached only as limit.
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Causes of Irreversibility :
The Irreversibility of a process may be due to either one or both of the following :
(a) Lack of equilibrium during the process
(b) Involvement of dissipative effects.
Irreversibility due to lack of equilibrium :
The lock of equilibrium (mechanical, chemical or thermal) between the system and surrounding on between two system or
two parts of the system causes a spontaneous change. Which is irreversible. Following are specific examples in this regard.
(a) Heat transfer through a finite temperature difference :
A heat transfer process approaches reversibility or the temperature difference between two bodies approaches zero. We
define a reversible heat transfer process as one in which heat is transferred through infinitesimal temperature difference.
To transfer finite amount of heat through infinitesimal temperature difference would require infinite amount of time or infinite
area.
All actual heat transfer processes are therefore irreversible and greater the temperature difference, the greater is the
irreversibility.
(b) Irreversibility due to lack of Pressure equilibrium within the interior of system or between system and
surrounding :
UM
When there exist a pressure difference between system and surrounding, then both system and surrounding will undergo
change of state will cease when mechanical equilibrium is established. The reverse of this process is not possible
spontaneously.
Irreversibility due to dissipative effect :
Irreversibility of a process may be due to dissipative effects in which work is done without producing equivalent increase in
KE or PE of system. Some energy is lost into molecular internal energy of the system.
Some of dissipative phenomena are –
Friction, Viscosity, Inelasticity, Electrical resistance, Magnetic hysterisis etc.
Perpetual Motion Machine of IIIrd Kind :
Friction is always present in moving device. Friction may be reduced by suitable lubrication, but in can never be complete
eliminiated. If this were possible, a movable device could be kept in continual motion without violating either of two laws of
thermodynamics.
Condition for Reversibility :

OR
The continual motion of moving device in complete absence of friction is known as perpetual motion of the third kind.
A natural process is irreversible because the condition for mechanical, thermal and chemical equilibrium are not satisfied and
dissipative effects are present.
A process will be reversible when it is performed in such a way that system is at all times infinitesimaly near a state of
thermodynamic equilibrium and in absence of disipative effect of any form.
Carnot Cycle :
A reversible cycle is an ideal hypothetical cycle in which all processes are reversible. Carnot cycle is reversible cycle.
Carnot heat Engine Carnot heat Engine
(Closed system) (Open system)
SF
Adiabatic Heat Source

Source Diathermic Cover T1
T1 Cover
1
2
Heat Exchange
Turbine WT
WP Pump
4
Heat Exchange 3
Sink
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T2 Heat sink T2
Reversible Adiabatic heat Addition 1 (Reversible Adiabatic

Reversible Isothermal work input Q1 heat addition)
WP
η (efficiency of Carnot
2
W P
4 WT
heat engine) = Q Reversible Isothermal
1
work output
Q2 3
First Law Q1 = Q2 + W
V
W = Q1 – Q2
Q1 − Q2 Q
η= =1− 2
Q1 Q1
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Carnot Theorum :
All heat engines operating between given constant temperature source and sink, none has higher efficiency than reversible
engine.
T1 Let EA be reversible heat engine and EB be reversible
Q1A Q1B heat engine.
WA WB Let violate convert theorem

Let ηEA > ηEB
Q2A Q2B
Let Q1A = Q1B = Q1
T2
WA > WB
Violation of Carnot Theorum
T1
T1
Q1
Q2A
WA WB
T2
Q1B = Q1
Q2B
OR
Absolute Thermodynamic Temperature Scale :
≡
Q1
EA
Q2A
WA WB
T2
WA – WB
Violation of Kelvin Plank

EB
Q1
Q2B
T1
Q1
E1 W1 Q1
Q2
T2 E3 W3
SF
Q2
E2 W2
Q3
Q3
T3
We know that
Efficiency of all heat engines operating between same temperature level is same.
Q2
η1 = 1 – = f (t1, t2)
Q1
Q2
η2 = 1 – Q = f (t2, t3)
IE
Q1
η3 = 1 – = f (t1, t3)
Q3
Q1 Q1 / Q3 f (t1 , t3 )
= =
Q2 Q2 / Q3 t (t 2 , t3 )
Q1  (t1 ) T1
= =
Q2  (t 2 ) T2
Q1 T1
=
Q2 T2
ENTROPY 4
UM
dQ dQ
Clausius Inequality : It can be proved that ∫ T
= 0 for a reversible process cycle and ∫ T
≤ 0 for natural (irreversible
process)
dQ
If ∫ T
=0 Cycle is reversible
dQ
∫ T
<0 Cycle is irreversible
dQ
∫ T
>0 Cycle is not possible
The property of Entropy

As per Claussius Theorum
∫i
R1
f dQ
T
+
R2
∫
i
f
dQ
T
=0
OR P
i
R1
R2
f dQ f dQ
∫i T
= ∫i T
f
R1 R2 V
dQ
hence ∫ T
is independent of path. So it is an property of system. Let it be known as entropy (s).
f dQ
∫ = S f − Si
SF
i T
R
If system is taken from initial equilibrium state i to final equilibrium state f by irreversible path
f (dQ ) rev
(∆S)irreversible = Sf – Si = (∆S)Reversible path = ∫
i T
As entropy is point function, it does not depend on path.
Integration can be performed only on reversible path.
Temperature Entropy Plot : The infinitesimal change in entropy dS due to reversible heat transfer dQ as temperature T is
dQrev
dS =
T
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If dQrev = 0 i.e. the process is reversible and adiabatic

dS = 0
S = Constant
hence reversible adiabatic process is isentropic process
dQrev = Tds
f
Qrev = ∫
i
Tds
i
f
Area under T-s curve ∫
i
Tds is equal to T f
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heat transferred in the process
S
T – S curve for a Carnot Cycle
Rev
4
Isothermal
1
4 1
Rev WP Q1 WT Rev Q1
P Adiabatic T WP WT
Adiabatic
3 2 3 2
Q2 Q2
Rev Isothermal
S
V
T1 − T2 Q1 − Q2 T1 ( S1 − S 4 ) − T2 ( S 2 − S 3 )
ηCarnot =
ηCarnot = 1 −
T1
=
T2
T1
Q1
=
T (S − S3 )
=1− 2 2
T1 ( S1 − S 4 )
Entropy Change in Irreversible Process :
2
OR
T1 ( S 3 − S 4 )
It can be proved that

A
1 1 dQ
T B ∫ dS > ∫
2 2 T
C C
1
S For irreversible process
SF
For reversible cycle
dQ
∫T =0
For irreversible cycle For reversible process

1 1 dQ
∫
dQ
T
<0 ∫ dS = ∫
2 2 T
B B
Principle of Entropy :
For any irreversible process – For reversible process
IE
dQ dQ
dS > dS =
T T
Therefore for any isolated system For isolated system reversible process
dSiso > 0 dSiso = 0
S = constant
It is thus proved that entropy of an isolated system can never decrease. It always increases and remains constant when
process is reversible.
Universe is an isolated system. An isolated system can always be formed by including any system and its surrounding.
dSuniverse ≥ 0
dSsystem + dSsurrounding ≥ 0
Not effect of an irreversible process is an entropy increase of the whole system. The entropy increase of an isolated system
is measure of extent of irreversibility of the process undergone by the system.
Radolf Claussius summarised the First and Second law of Thermodynamics in following words :
(a) The energy of the world (universe) is constant.
(b) The entropy of the world (universe) toward maximum.
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Application of Entropy Principle : Every irreversible process is accompanied by entropy increase of the universe and this
entropy increase quantifies the extent of irreversibility of the process.
Transfer of Heat through a finite Temperature difference.
T1 T2
Reservoir A Reservoir B
Let Q be the rate of heat transfer from reservoir A at T1 to reservoir B at T2 (T1 > T2)
Q
For Reservoir A, ∆S = − T (entropy decreases for reservoir A)
1
+Q
For Reservoir B, ∆S = T (entropy increases for reservoir B)
=
−Q Q
T1
+
T2
2
(∆S)universe = (∆S)A + (∆S)B
 −1 1 
= Q  + 
 T1 T2 
OR
T −T 
(∆S)universe = Q  T T  ← Positive value
1 2
 1 2 
Entropy change in mixing of two fluids
M1 C1 M2 C2
SF
t1 t2 Adiabatic Enclosure
When two fluids are mixed together, at equilibrium let tf be the final temperature.
M1 C1 (t1 – tf) = M2 C2 (tf – t2)
M1 C1 t1 – M1 C1 tf = M2 C2 tf – M2 C2 t2
M 1C1t1 + M 2 C 2 t 2
=tf
M 1C1 + M 2 C 2
Entropy change for fluid in subsystem 1

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Tf dQ T2 M 1 C1 dt Tf
∆S1 = ∫
T1 T
rev = ∫
T1 T
= M 1C1 ln
T1
This will be negative as T1 > Tf
Entropy change for fluid in subsystem 2
Tf M 2 C2 dt Tf
∆S2 = ∫ T2 T
= M 2C2 ln
T1
This will be positive as Tf > T2
(∆S)universe = ∆S1 + ∆S2
Tf
(∆S)universe = M1 C1 ln + M2 C2 ln
T2
UM
Note : Although the mixing process is irreversible, to evaluate the entropy change, the irreversible path was replaced by
reversible path on which integration was performed.
The use of the term irreversible process is doubtful since no irreversible path or process can be plotted on thermodynamic
co-ordinates. It is more logical to state that change of state is irreversible rather than say it is an irreversible process.
A natural process which is inherently irreversible is indicated by dotted line connecting the initial and final states, both of
which are in equilibrium. The dotted line has no meaning, since it can be drawn in any way.
To determine the entropy change for a real process, a known reversible path is made to connect the two end states and
integration is performed on this path.
Therefore, the entropy change of a system between two identifiable equilibrium state is same whether the intervening
process is reversible or irreversible as entropy is point function / property of system.
Maximum work obtainable from two finite bodies at Temperature T1 and T2 :
OR Body 1
T1 Tf
He
Q1
Q2
W = Q1 – Q2
Body 2
T2 Tf
As work is delivered by heat engine, the temperature of body 1 will be decreasing on body 2 will be increasing when both the
SF
bodies attain the final temperature Tf , the heat engine will stop operating.
Q1 = CP (T1 – Tf) Assumption — Let bodies remain at constant
Q2 = CP (Tf – T2) pressure and undergo no change of phase
W = Q1 – Q2
W = CP (T1 + T2 – 2Tf)
For given values of CP, T1, T2, W depends upon Tf.
W is maximum, when Tf is minimum.
Tf dT Tf
For body 1, the entropy change ∆S1 = ∫
T2
CP
T
= CP ln
T1
IE
Tf dT Tf
For body 2, ∆S2 = ∫
T2
CP
T
= C P ln
T2
(∆S)universe = ∆S1 + ∆S2
Tf Tf
= CP ln + CP ln
T1 T2
 Tf Tf 
= C P ln T + ln T 
 1 2 
T f2
(∆S)universe = CP ln
T1 T2
T f2
(∆S)universe = Cp ln
T1 T2
UM
For work to be maximum —→ Tf to be minimum
T f2
Cp ln =0
T1 T2
T f2
ln =0
T1 T2
T f2
=1
T1 T2
T f = T1 T2
Wmax = Cp (T1 + T2 – 2 T1 T2 )
Wmax = Cp (T 1 − T2 )
2
OR
dQrev
Entropy Transfer with Heat Flow : dS =
T
When heat is added to system, dQ is positive and entropy of system increases. When heat is removed from system, dQ is
negative, the entropy of system decreases.
Heat transfer to a system increases the internal energy of system, as a result molecules of gas move with higher kinetic
energy and colloid more frequently and so the disorder in the system increases. Heat is thus regarded as disorganised or
disordered energy transfer which increases molecular chaos.
SF
If heat flows from system to surrounding reversibly at to the entropy increase of surrounding is,
Q
(∆S)surr = T
0
Q
(∆S)system = − T
0
It may be said that system has lost entropy to the surrounding. Alternatively, one may state that surrounding has gained
entropy from system. In other words, since the heat inflow increases the molecular disorder, there is flow of disorder along
with heat.
Entropy Generation in a closed system : (Difference between Adiabatic and Isentropic Process)
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The entropy of any closed system can increase in two ways –

(i) by heat interaction in which there is entropy transfer
(ii) Internal irreversibility or dissipative effects in which work (KE) is dissipated into internal energy increase
dS = (dS)e + (dS)i
dQ
dS = + (dS)i
T
The entropy increase due to internal irreversibility is called entropy production or entropy generation.
It may so happen that in a process (e.g. expansion of heat fluid in a turbine), the entropy decrease of system due to heat loss
 dQ 
to surrounding  −  is equal to entropy increase of system due to internal irreversibility such as friction etc. In such
 T 
UM
case, dS = 0
Therefore an Isentropic proceed need not be adiabatic.
But if Isentropic process is reversible, it will be adiabatic. An adiabatic process also need not be isentropic since entropy can
also increase due to friction.
But reversible adiabatic process will be isentropic.
Entropy generation (Sgen) :
2
dQ
By the second law S2 – S1 ³ ∫T1
2
dQ
The entropy change of the system (S2 – S1) exceeds the entropy transfer ∫T
1
(due to heat transfer)
OR
The difference is produced internally due to irreversibility.
(S2 – S1) –
(Entropy change)
2
∫T
1
dQ
Entropy transfer
= Sgen
Entroy production
due to heat due to interval
interaction irreversibility (dissipative effects)
2 dQ
(S2 – S1) = ∫ 1 T
= S gen
SF
2 dQ
For reversible process (S2 – S1) = ∫ 1 T
2 dQ
For irreversible process (S2 – S1) ≥ ∫ 1 T
dQ
For any process ds ≥
T
dQ
or ≤ ds
T
dQ
∫ T ≤ ∫ ds
IE
For any cycle
dQ
∫T ≤0 Claussius inequality
Entropy change for a closed system (General Cases) : Let m kg of gas at pressure P1, volume V1, Temperature T1 and
entropy S1 be heated and these state variables become P2, V2, T2, S2.
Then, dQ = dU + dW
Tds = mCvdT + PdV
By gas equation, PV = mRT
dU
Tds = mCVdT + mRT
V
S2 T2 dT V2 dV
∫ S1
ds = ∫
T1
M Cv
T
+ MR ∫ r1 V
UM
T2 V2
S2 – S1 = mCV ln T + mR ln V T1 → T2 ; V1 → V2
1 1
P1V1 P2V2  P2 V2  V
as T = T S2 – S1 = m CV ln   + m R ln 2
1 2  P1 V1  V1
T2 P2 V2 P2 V2 V2
= = m CV ln P m CV ln V + m R ln V
T1 P1 V1 1 1 1
P2 V2
= m CV ln P + m (CV + R) ln V (as CP – CV = R)
1 1
P2 V2
S2 – S1 = m CV ln P + m CP ln V
OR P1 → P2 ; V1 → V2
1 1
P1V1 P2V2 T2 P1 T2
= S2 – S1 = m CV ln T + m R ln P T
T1 T2 1 2 1
V2 P1 T2 T2 P1 T2
= = m CV ln + m R ln + m R ln
V1 P2 T1 T1 P2 T1
T2 P1
= m (CV + R) ln T + m R ln P
1 2
T2 P2
SF
S2 – S1 = m CP ln T – m R ln P P1 → P2 ; T1 → T2
1 1
Entropy charge for a closed system : Special case

Constant Volume Process :
dQ = dV + dW
dQ = dU + O
dQ = dV = mCvdT
S2 T2 dT
∫S1
ds = ∫
T1
M Cv
T
IE
T2
S2 – S1 = M CV ln T
1
Constant Pressure Process : dQ = M Cp dT

Tds = M Cp dT
dT
ds = M Cp
T
S2 T2 dT
∫S1
∆S = ∫
T1
M Cp
T
UM
T2
S2 – S1 = M Cp ln T
1
Isothermal Process : (PV = mRT = Constant)

dQ = dV + dW
dQ = CVdT + dW
V2
dQ = MRT ln V
1
dQ V2
∫ ds = ∫ T = MR ln
V1
Adiabatic Process : dQ = 0
dS = 0
Polytropic Process : OR PVn = C

n−r
∆Q = 
dQ
∫ ds = ∫ T
 M C dT
 n −1 
=
 n
V
n−r
− 1
T
 Cv ln 2

Third Law of Thermodynamics : It states that entropy of all perfect crystalline solids is zero at absolute zero temperature.
T1
It means zero entropy datum is chosen at 0°K or – 273°C.

Absolute Thermodynamic Temperature Scale : Let there be series of reversible engines, extending from a source of T1 to
lower temperature.
SF
T1
Q1
E1 W1 = Q1 – Q2
Q2
T2
Q2
E2 W2 = Q2 – Q3
Q3
T3
Q3
E3 W3 = Q3 – Q4
IE
Q4
T4
Q4
T1 − T2 Q1 − Q2
=
T2 Q2
T2
(T1 – T2) = (Q1 – Q2) Q
2
T3 T2
(T2 – T3) = (Q2 – Q3) Q = (Q2 – Q3) Q
3 2
 T2 
(T3 – T4) = (Q3 – Q4)  
 Q2 
UM
If T1 – T2 = T2 – T3 = T3 – T4
then, Q1 – Q2 = Q2 – Q3 = Q3 – Q4 = .......
W1 = W2 = W3 = .........
Conversely, by making the work performed by engines in series equal, we get,
T1 – T2 = T2 – T3 = T3 – T4
A scale having one hundred equal interval between steam point and ice point could be realised by series of one hundred
Carnot Engine.
If enough engines are placed in series to make the total work output equal to Q1, the heat rejected from last engine will be
zero. When heat rejected approaches zero, the temperature of heat rejection also approaches zero as limit.
Thus it appears that a definite zero point exists on absolute temperature scale but this point cannot be reached without
violation of second law.
Thus any attainable value of absolute temperature is always greater than zero.
OR
This is also known as Third Law of Thermodynamics which may be stated as follows :
It is impossible by any procedure, no matter how idealised, to reduce any system to absolue zero of temperature in finite
number of operations.
•••
SF
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5
UM
AVAILABILITY & IRREVERSIBILITY
Available Energy : The maximum work output obtainable from a certain heat input in cyclic heat engine is called Available
Energy or available part of the energy supplied (also known as energy). The minimum energy that has to be rejected to the
sink by second law is called unavailable energy or unavailable part of energy supplied (Also known as Energy)
T Q1 = AE + UE
1
Wmax = AE = Q1 – UE = Q1 – Q2
Q1
For given T1 and T2,
E W T2
ηrev = 1 – T
1
Q2
For a given T1 ηrev will increase with decrease of T2. The lowest
T
1
4
T2
3
2 Available
energy
Unavailable
energy
OR practicable temperature of heat rejection is temperature of surrounding to
T0
ηrev = 1 – T
1
 T0 
Wmax = 1 −  Q1
 T1 
a b
S
Availability = Q – Ta (Sb – Sa)
Unavailability = Ta (Sb – Sa)
SF
y
dQ1
x T1
T
T0
S
Let us consider a finite process x – y in which heat is supplied reversibly to a heat engine. Taking an elementary cycle, if
dQ1 is the heat received by the engine reversibly at T1, then
 T0 
dWmax = 1 −  dQ1
 T1 
IE
T0
= dQ1 – dQ1
T1
For the heat engine receiving heat for the whole process x – y and rejecting heat at T0.
y y yT
∫x
dWmax = ∫
x
dQ1 − ∫
x
0
T1
dQ1
Wmax = AE = Qxy – T0 (Sy – Sn)
UE = Qxy – Wmax = Qxy – AE
VE = T0 (Sy – Sx)
y
Qxy Available
energy
x
T
UM
T0 Unavailable
S energy
Decrease in Available Energy when heat is transferred through finite temperature difference : Whenever heat is
transferred through a finite temperature difference, there is decrease in the availability of energy so transferred. Let us
consider a reversible heat engine operating between T1 and T0.
Q1
T1
WC
WE
T T0
Q1 = T1 ∆S Q2
∆S
Q2 = T0 ∆S
W = AE = (T1 – T0) ∆S
OR S
Let us now assume that heat Q1 is transferred through a finite temperature difference from source at T1 to engine absorbing
heat at T11 . The availability of Q1 as received by the engine at T11 can be found by allowing the engine to operate reversibly
in a cycle between T11 and to receiving Q1 and rejecting Q2.
Q1 = T1 ∆S = T11 ∆S′ Q1 as T11 < T1

T1
Q2 = T0 ∆S Q1 In both cases, we want same heat
T1′
Q21 = T0 ∆S′ addition Q1
T0
W = Q1 – Q2 = (T1 – T0) ∆S
T ∆S Q2 Q2′ Q1 = T1 ∆S = T1' ∆S 1
SF
W = Q1 – Q2′ = (T1′ – T0) ∆S′ ∆S′ So ∆S′ > ∆S

W< W as T1 > T1 S So Q2′ > Q2
W – W′ = (Q1 – Q2) – (Q1 – Q2′) = Q2′ – Q2
W – W = T0 ( S – S)
The decrease in available energy (or energy) is thust the product of lowest feasible temperature of heat rejection and
additional entropy change in system while receiving heat irreversibly compared to case of reversible heat transfer from
same source.
The greater is the temperature difference (T1 – T1′) the greater is the heat rejection Q2′ and the greater will be unavailable part
of energy supplied or energy. Energy is said to be degraded each time it flows through a finite temperature difference.
Quality of Energy : Let us assume that a heat gas is flowing through a pipeline. Due to heat loss to surrounding, the
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temperature of gas decreases continuously from inlet at state a to exit at state b. Although process is irreversible, let us
assume a reversible isobaric path between inlet and exit state of gas.
a
T1′
MC p dT T1″
dS = T2′
T T2″ 1
T b 2
dT T
=
dS MC p
∆S2 ∆s1
S
dT
depends upon gas temperature T
dS
As T increases, slope increases
UM
Let us assume that Q units of heat are lost to the surrounding as the temperature of gas decreases from T1′ to T2″, then
Heat loss Q = M CP (T1′ – T1″ )
Q = T1 ∆S1 ......... (1)
Available energy lost with this heat loss at temperature T1 is
W1 = Q – T0 ∆S1 ......... (2)
When gas temperature has reached T2 (T2 < T1), let us assume that the same heat loss Q occurs as gas temperature decreases
from T2′ to T2″.
Heat loss Q = MCP (T2′ – T2″) = T2 ∆S2 ......... (3)
Available energy lost with this heat loss at temperature T2 is
W2 = Q – T0 ∆S2 ......... (4)
From equation (1) and (3)
Q = T1 ∆S1 = T2 ∆S2
⇒ ∆S1 < ∆S2
From equation (2) and (4)
decreases as the temperature decreases.

OR (as T1 > T2)
W1 > W2
Hence available energy (exergy) of a fluid at higher temperature (T1) is more than that a lesser temperature (T2) and
The second law therefore affixed a quality of energy of a system at any state. The quality of energy of a gas at say 1000°C
is superior to quality of energy of gas at 100°C since the gas at 1000°C has the capacity of doing more than the gas at 100°C
under same environmental condition.
An awareness of this energy quality as of energy quantity is essential for efficient use of our energy resources and for energy
conservation.
As available energy (exergy) of high temperature fluid is more, adequate insulation must be provided for higher temperature
fluid to prevent loss of availability. This may not be so important for low temperature fluids.
SF
Law of Degradation of Energy :
The available energy of a system decreases as its temperature (or pressure) decreases.
While the first low states that energy is always conserved quantitywise, the second law emphasizes that energy always
degreades qualitywise.
When a gas is throttled adiabatically from high pressure to low pressure, the enthalpy (energy per unit mass) remains the
same but available energy for work is reduced (i.e. there is degradation of energy).
Maximum Work in Reversible Process :
1
R First Law :
IE
T QR = (U2 – U1) + WR .............. (1)

I
QI = (U2 – U1) + WI .............. (2)
2 WR – WI = QR – QI .............. (3)
S
Surrounding Second Law :
P0T0
(∆S)system = (S2 – S1)
System Q
(∆S)surrounding = −
T0
Q W Q
(∆S)universe = (S2 – S1) −
T0
Q
From (4) and (5) For reversible ( ∆S) universe = (S 2 – S 1 ) − = 0
T0
QI < QR QR = T0 (S2 – S1) .............. (4)
Q1
From (3) —→ For irreversible (∆S)universe = (S2 – S1) − >0
UM
T0
QI < T0 (S2 – S1) .............. (5)
WR > WI
Concept of Useful Work : All of the work W of the system would not be available for delivery, a certain portion of it would
be spent in pushing out atmosphere.
The useful work is defined as actual work delivered by system less the work performed on atmosphere.
If V1 and V2 are initial and final volume of system and p0 is the atmospheric pressure then the work done on atmosphere is
p0 (V2 – V1).
W4 = Wact = p0 (V2 – V1)
Similarly maximum useful work :
Wumax = Wmax – p0 (V2 – V1)
For Closed System : OR
(Wu)max = (V1 + P0V1 – T0S1) – (V2 + P0V2 – T0S2)
(Wu)max = φ1 – φ2
where φ is called availability function for a closed system given by :
 = U + P0V –T0S
For Open System (Steady Flow) :
(Wu)max = Wmax as V1 = V2
Availability :
The Availability (A) of a given system is defined as the maximum useful work that is obtainable in a process in which system
comes to equilibrium with its surroundings.
SF
Availability in Closed System :

A = (U + p0V – T0S) – (V0 + p0 V0 – T0 S0)
A = φ – φ0
Availability for Open system (Steady flow) :
A = (U + p0V – T0S) – (V0 + p0 V0 – T0 S0)
A = φ – φ0
Availability for Open system (Steady flow)
1
A = (H1 – T0 S1 + mv2 + mgz1) – (H0 – T0 S0 + mgz0)
2
A = ψ – ψ0
IE
where ψ is called availability function for a steady flow system.

Irreversibility :
The actual work done by a system is always less than Idealized reversible work and difference between the two is called
Irreversibility of the process.
I = Wmax – W
This is also sometimes referred to as degradation and dissipation.
For Non-flow process when system exchanges heat only with environment.
I = (U1 – U2) – T0 (S1 – S2)] – [(U1 – U2) + Q]
= T0 (S2 – S1) – Q
= T0 (∆S)system + T0 (∆S)surrounding
UM
I = T0 [(∆S)system + (∆S)surrounding]
I = T0 (S)universe
Similarly for flow process :
I = Wmax – W
= T0 [(∆S)System + (∆S)Surrounding]
I = T0 (S)Universe
The quantity [T0 (∆S)Universe] represents an increase in unavailable energy (or Anergy)
Second Law Efficiency : The second law efficiency ηII of a process is defined as ratio of minimum available energy which
must be consumed to do a task divided by actual amount of available energy consumed in performing the task.
Amin
ηII =
A
OR
A Power Plant converts a fraction of available energy A or Wmax to useful work w.
ηII =
W Actual work
Wmax Maximum available energy
W
ηI = Q = W
1
W Wmax
max Q1
ηI = ηII ηCarnot
I Efficiency of actual cycle

ηI =
 Carnot Efficiency of Carnot cycle
Energy Cascading : Let source temperature be Tr and use temperature be Ta.
SF
 T 
1− 0 
 T 
It can be shown that, ηII = ηI 
a
T0  when T0 is surrounding temperature
1− 
 Tr 
1.0
0.662 Heating in furnace
ηII (700 K)
IE
0.434 Process steam generator

0.5 (480 K)
.072 Space heating (320 K)
O
300 500 1000 1500 2000
Tr = 2200 K T0 = 300 K
A fuel or any energy source is consumed efficiently when first user temperature approaches the fuel temperature. This
means that fuel should first be used for high temperature application. The heat rejected from these application can be
cascaded to low temperature application. This is called energy cascading and ensures more efficient energy utilisation.
6
PROPERTIES OF STEAM
UM
P – V diagram of a Pure substance :
Pure substance : It is substance of constant chemical composition. It may exist in one or monophases.
Saturated
Saturated liquid line
solid line Critical Saturated
state vapour line
S+L
2 4 5 V 6 1.5 atm
3
1 atm
2 3 4 5 6
P 0.5 atm
1 2 3 4 5 6
S+L L+V
rv ion
S V
Triple
Cu mat
Triple
OR e
point S+V
i
bl
point line
Su
The line passing through all saturated solid states 2 is called saturated solid line.
The line passing through all saturated liquid state 3 and 4 w.r.t. solidification and vapourisation is known as saturated liquid
line.
The line passing through all saturated vapour state 5 is known as saturated vapour line.
Triple point is a line on the p-v diagram when all the three phases solid, liquid and gas exist in equilibrium.
At a pressure is a line on the p-v diagram when all the three phases solid, liquid and gas exist in equilibrium.
At a pressure below the triple point line, the substance can not remain in liquid phase, and the substance when heated
transforms from solid to vapour (known as sublimation).
SF
For water triple point line is P = 4.587 mm Hg, T = 273.16 K (0°C)

Critical state : If we keep on increasing the pressure a state comes when liquid is directly converted into gaseous state
without coming into vapour state.
The corresponding pressure, volume and temperature are known as critical pressure (pc), critical volume (vc) and critical
temperature (tc)
For water, pc = 221.2 bar
tc = 374.15°C
vc = .00317 m3 / kg
Liquid and gas is most often the working fluid in Power / Refrigeration Cycles and intrust is often confined to liquid-vapour
region only. Hence to locate state points, the solid regions can be omitted.
IE
D L
V
L+V
P
Isotherm on
C B P-V Curve
Isotherm on P-V diagram :
UM
P
C B
A
If the vapour at State A is compressed slowly and isothermally, the pressure will rise until there is saturated vapour at point
B. If compression is continued. Condensation takes place, pressure remaining constant so long as temperature remains
constant. At any point between B and C, the liquid and vapour are in equilibrium. Since a very large increase in pressure is
needed to compress the liquid, line CD is almost vertical. ABCD is a typical isotherm of a pure substance in p-v diagram.
Phase change occurs at constant pressure and temperature. A pure liquid at a given pressure will transform into vapour at a
pressure which is function of temperature.

P – T diagram of a Pure Substance :
OR
particular temperature which is known as saturation temperature which is function of pressure.
Similarly, if temperature is fixed, the liquid will boil (or condense) only at particular pressure which is known as saturation
Fusion curve
Vapourisation curve
1 L
1 2, 3
S 1 atm
P 4, 5 6
1
SF
Triple point V
Sublimation curve
T
If the heating of ice at – 10°C to steam at 250°C at the constant pressure of 1 atm is considered, 1 – 2 is solid (ice) heating,
2 – 3 is melting of ice at 0°C, 3 – 4 is liquid heating, 4 – 5 is vavporization of water at 100°C and 5-6 is heating in vapour
phase. The process will be reversed from state 6 to state 1 upon cooling.
T – V diagram of Pure substance :
T p = 2 atm
IE
6 p = 1 atm
4
5
6
4
5
3
T – S diagram of Pure substance :
The entropy change of 1 kg of ice from – 5°C to steam at 250°C, can be calculated (the pressure being maintained constant
at 1 atm) and plotted on T – S diagram.
200 6 (1 atm)
UM
100
4
5
T
0 2 3
–5
1
Similar curves may be obtained for other pressures. The states 2, 3, 4, 5 are saturation station. If these states for different
pressure are joined, T – S diagram of the substance is obtained.
6
S+L
L 4 5
6
OR 1
S
2
2
3
S+V
4
L+V
5
V
Most of ten, liquid-vapour transformations only are of interest.

hence, liquid, vapour and transition zones are used.
SF
L
V
T p increasing
Sf L+V Sg
Saturated
Saturated vapour line
Liquid line
S
Sfg
IE
At a particular pressure, Sf is the specific entropy of saturted liquid and Sg is that of saturated vapour.
The entropy change of the system during phase change from liquid to vapour at that pressure is Sfg (Sg – Sf). The value of
Sfg decreases, as pressure increases and becomes zero at critical point.
•••
7
UM
PROPERTIES OF GASES & GAS MIXTURES
Concept of Mole (Avogadro Law)
A mole of a substance has a mass numerically equal to molecular weight of the substance.
One gram mole of oxygen has mass of 32 gram
One Kg mole of oxygen has mass of 32 Kg.
One Kg mole of Nitrogen has mass of 28 Kg and so on.
For a certain gas / substance, if m is mass in Kg and M is its molecular weight, then
m
N u m b e r o f K g m o l e o f g a s n=
M
Molar volume is defined as v =

V
n ORm3
Kg mole
Avogadro Law : Avagadro Law states that volume of 1 gram mole of all gases at pressure of 760 mm Hg. Temperature of
0°C is same and is equal to 22.4 litre.
There are 6.023 × 1023 molecules in 1 Kilo gram mole of a substance. This is known as Avagadro Number (A).
Ideal gas Equation : A hypothetical gas which obeys ideal gas equation ( p v = R T ) at all pressure and temperature is
called an ideal gas.
Real gases approaches the ideal gas behaviour at very low pressure (p → 0) and high temperature (T → ∞)
p v = RT ............ (1)
SF
kJ
R is universal gas constant. Its value is 8.314 (kJ Mole) K
pV = n R T ............ (2)
m
pV = RT
M
R 
pV = m   T
M 
IE
R kJ
is known as characteristic gas constant (R) which will have different value for different gases. Rair = 0.287
M Kg K
pV = mRT ............ (3)
In 1 kg mole of gas, Number of molecules = A
In n kg mole of gas, Number of molecules = A × n
Let N be Number of molecules in n Kg mole of gas → N = An
N
n=
A
P1V1n = P2V2n pV = n R T
n −1
T2  P2  n R NR
=  =N T K=
T1  P1 
Boltzmann constant
A A
UM
n −1
T2  V1 
= 
T1  V2 
pV = NKT ............ (4)
Properties of Mixture of Gases :

(Dalton Law of Partial Pressure )
n2 p T
n1
V n3 nk
Let us imagine a homogenous mixture of inert ideal gases at temperature T, pressure p and volume V. Let us suppose there
p=
OR
are n1 moles of gas A1, n2 moles of gas A2 ......... and upto nc moles of gas Ac.
V
pV = (n1 + n2 + ....... + nc) R T
n1 R T n2 R T
+
V
n RT
+ ....... + k
V
n RT
+ ....... + c
V
nk R T
The expression represents the pressure that Kth gas would exert if it occupied the volume V alone at temperature T.
V
This is known as Partial pressure of Kth gas.
p = p1 + p2 + ............. + pk + .............+ pc
This is known as Dalton Law of Partial pressure which states that the total pressure of mixture of ideal gases is equal to sum
SF
of the partial pressure.
RT RT
V = (n1 + n2 + ...... + nc) = ( Σn K ) +
p p
R T nk R T n
pk = nk = p= k p
V Σnk R T Σnk
nk
th
Σnk is known as mole fraction of K gas and denoted by xk.
IE
n1
x1 =
∑ nk
n2
x2 =
∑ nk
p 1 = x1 p p 2 = x2 p
Also x1 + x2 + ...... + xc = 1
p1V = M1R1T
p2V = M2R2T
UM
pcV = McRcT
Adding and using Daltons law :
pV = (M1R1 = m2R2 + ...... + mcRc) T
Let m1R1 + m2R2 + ........ + mcRc = m Rm

Rm be equivalent gas constant for mixture (pV = m Rm T)
m1 R1 + m2 R2 + ...... + mc Rc
then Rm =
m
Similarly equivalent molecular weight of mixture having n total number of moles.
Me = x1 M1 + x2 M2 + ........ + xc Mc
•••
OR
SF
IE

Basic Thermo Concept

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UM

For ‘IES FORUM’ Students Only

which attention is concentrated in analysis of problem.

Motor Air Compressor

Practically, most of the processes are non quasi static. x2

This is known as Zeroth Law of Thermodynamics. It is the basis of Temperature measurement.

Constant Volume gas thermometer

Q = w + ∆E In absence of motion and gravity – E = U

(a) W is positive (b) W is negative

(a) Q is positive (b) Q is negative

Displacement Work (Flow work)

Application of First Law of Thermodynamics for Closed System

Constant Volume Process (Isochoric Process)

here dW = pdV = p (V2 – V1) = p2V2 – p1V1 = MR (T2 – T1)

MCp (T2 – T1) – MR (T2 – T1) = MCv (T2 – T1)

This equation is known as Meyer Formula.

For adiabatic process n = γ PVr = C P n=1

Steady Flow Energy Equation

small letters represent specific properties or per unit mass

In different form dq – dw = dh + cdc + gdz

Work Transfer in Steady Flow open System :

1. Nozzle and Diffuser :

Application of First Law of Thermodynamics for Steady Flow Process :

du + pdv = du + pdv + Vdp + cdc + gdz + dw

Vdp + Cdc + gdz = 0

This is Euler equation

This is Bernauli Equation.

Description of Some Device :

Efficiency of heat engine is defined as

The efficiency of refrigerator is expressed in terms of coefficient of performance.

Wnet in one cycle.

Condition for Reversibility :

Adiabatic Heat Source

Reversible Adiabatic heat Addition 1 (Reversible Adiabatic

WA WB Let violate convert theorem

Violation of Kelvin Plank

The property of Entropy

If dQrev = 0 i.e. the process is reversible and adiabatic

It can be proved that

For irreversible cycle For reversible process

(∆S)universe = (∆S)A + (∆S)B

Entropy change for fluid in subsystem 1

The entropy of any closed system can increase in two ways –

For any cycle

Entropy charge for a closed system : Special case

Constant Pressure Process : dQ = M Cp dT

Isothermal Process : (PV = mRT = Constant)

Polytropic Process : OR PVn = C

It means zero entropy datum is chosen at 0°K or – 273°C.

Wmax = AE = Qxy – T0 (Sy – Sn)

UE = Qxy – Wmax = Qxy – AE

in a cycle between T11 and to receiving Q1 and rejecting Q2.

Q1 = T1 ∆S = T11 ∆S′ Q1 as T11 < T1

W = Q1 – Q2′ = (T1′ – T0) ∆S′ ∆S′ So ∆S′ > ∆S

decreases as the temperature decreases.

T QR = (U2 – U1) + WR .............. (1)

Availability in Closed System :

where ψ is called availability function for a steady flow system.

I Efficiency of actual cycle

0.434 Process steam generator

.072 Space heating (320 K)

For water triple point line is P = 4.587 mm Hg, T = 273.16 K (0°C)

pressure which is function of temperature.