Basic Thermodynamics

Contents
Unit 1. Basic Thermodynamics 1.1-1.44
1. Basic concepts 1.1

2. Energy Interaction 1.6

3. First Law of Thermodynamics 1.12

4. First Law applied to Flow Process 1.17

5. Second Law of Thermodynamics 1.22

6. Entropy 1.27

7. Available Energy, Availability and Irreversibility 1.34

8. Properties of Pure Substance 1.37

Basic Thermodynamics 1
1. Basic Concepts
• System: A fixed mass or region in space on which our analysis is
focused.
• Surrounding: Everything apart from system forms surrounding.
The part of the surrounding which is effected by the system is called
immediate surrounding.
• Boundary: A real or imaginary surface which separates the system
from the surroundings.
A boundary can be fixed or movable as well as real or imaginary.

Type of System

Types of Mass Energy Example

System transfer transfer
Closed   Piston cylinder arrangement
without valves
Open   Turbine, pump, Compressor,
Piston cylinder arrangement
with valves
Isolated   Universe, hot coffee in a
perfectly insulated thermos
• Pressure: The average normal force per unit area is termed as
pressure.
 1.2 Mechanical Engineering

Pabs = Pgauge + Patm Pgauge = Patm − Pvac

5
= =
1 bar 10 Pa 100 kPa = 0.1 MPa

= =
1 atm 101 .325 kPa 1.01325 bar = 760 mm of Hg

• Properties of System: Any characteristic of the system is called

property of the system.
Properties are ‘point’ function and are ‘exact’ or ‘perfect’ differentials
Ex. internal energy, enthalpy, entropy...
• Intensive Property (Intrinsic): These properties are ‘independent’
of size or mass. These are the properties which remains constant
(same) at all points of a system.
Ex. pressure, temperature, density, all specific extensive properties.
• Extensive Property (Extrinsic): These properties are dependent
on size or mass of the system. These are the properties which varies
within the system.
Ex. mass, volume, all forms of energy, entropy.
Note: Ratio of two extensive properties is an intensive property.

Gibbs Phase Rule

P + F = C + 2
Here, P = mumber of phases (Solid, liquid, gas)
F = minimum number of ‘independent’ intensive
variables required to find the state of the
system (degree of freedom)
C = number of chemical components
 Basic Thermodynamics 1.3
Ex.

Thrmodynamic Equilibrium
A body is said to be in thermodynamic equilibrium if it is in
• Thermal equilibrium: equality of ‘temperature’
• Mechanical equilibrium: equality of ‘forces’ and ‘couples’
• Chemical equilibrium: equality of chemical potentials.
Point functions Does not depend on path history (T, P, V)
Path functions Depend on path history (Work, heat)
• State: Any condition of the system is called state of the system. State
of the system is specified by properties, if any one of the property
changes the state of the system changes.
• Process: The change of the state of the system is called process. The
infinite states through which the system passes is called process path.
The process can be classified as:
1. Quassi-static (or Quassi-equilibrium) and Non Quassi-
static Process:
‘Quassi = almost’
A process is said to be a quassi-static process if it is carried out in
a ‘very slow’ manner so that the system can be considered to be in
‘equilibrium’ at any point between initial and final states of the
process. It is represented by a joint line on property diagram.
The process which is not quassi-static is called non quassi-static
process. It is represented with a dashed line on property diagram.

Non quassi-static process when Quassi-static process when

piston is moving very fast piston is moving very slow
 1.4 Mechanical Engineering

2. Reversible and Irreversible Process: A process is said to be a

reversible process when reversed in direction follows the same path as
that of the forward path without leaving any change on the system and
the surrounding.
A process which is not reversible is called irreversible process. All
‘actual’ process are irreversible process.
Note: If a process has to be reversible then it must be quassi-static,
but all quassi-static processes need not be reversible.
3. Cyclic Process: A process is said to be a cyclic in which initial
state and final state are exactly same.
• For a cycle change in property is zero.
Note: Minimum number of process required to make a cyclic process
are two.

4 5

Zeroth Law of Thermodynamics

When a body A is in thermal equilibrium with a body B and also
separately with a body C then body B and C will be in thermal
equilibrium with each other.
 Basic Thermodynamics 1.5
thermal thermal thermal

If A   
 B 
  
 C then A  
 C
equilibrium equilibrium equilibrium

Note: Zeroth law of thermodynamics the basis of ‘temperature’

measurement.
Types of Thermometer

Type of thermometer Principle Thermometric Property

Resistance Wheat stone bridge Resistance
Thermocouple Seeback effect E.M.F. (voltage)
Constant volume gas Ideal gas equation Pressure
thermometer
Constant pressure gas Ideal gas equation Volume
thermometer

Note: • Ideal gas thermometer is ‘independent’ of material of

construction.
• Thermocouple uses copper-constantan, platinum-rhodium
combinations.
• Conversion of temperature unit:
°C °F-32 T-273.15
= =
5 9 5
Here, °C = temperature in degree celsius
°F = temperature in degree fahrenheit
T = temperature in kelvin
• Triple Point of Water:
It is point where all the phases coexist.
“Degree of freedom at triple point is zero.”
Triple point of Water = 0.01ϒC =273.16 K = Ttp
Ptp = 0.611 kPa = 4.6 mm of Hg

Method of Temperature Measurement:

• Used before 1954:
100 ( P − Pi )
T =
( Ps − Pi )
Here, T = temperature
 1.6 Mechanical Engineering

P = pressure corresponding to temperature ‘T’

Pi = pressure corresponding to ice point (0°C)
Ps = pressure corresponding to steam point (100°C)
• Used after 1954:
 P 
T = 273.16  
 Ptp 
Here, T = temperature
P = property corresponding to temperature ‘T’
Ptp = property corresponding to triple point of water (273.16 K)

2. Energy Interaction
Energy = Microscopic + Macroscopic
Microscopic energy = Sensible + latent + Chemical + Nuclear
(Internal energy ) energy energy energy energy

Macroscopic energy : Kinetic Energy, Potential Energy

Methods of Energy Transfer:
• Heat interaction,
• Work interaction
• Mass interaction
• Work: Work is said to be done by the system if the sole effect on the
things external to the system can be reduced in raising of weight
(weight may not actually be raised)
Type of Work
(i) Closed system work or Non flow work (ii) Open system work or Steady work.

I
I

F
F

F
F

Wclosed = ∫ pdv Wopen = ∫ vdp

I I

For closed system work is obtain Open system work is obtain by

by plotting it on volume axis. plotting it on 'pressure axis'.
Conditions for using Conditions for using:
[Link] system, [Link] system,
[Link]-static process. [Link]-static process.

 Basic Thermodynamics 1.7
Notes:
1. Area enclosed by cycle on P-V diagram is net work done.
Clockwise cycle = Work done by system (positive)
anticlockwise cycle = Work done on system (negitive)
2. Work is a path function i.e. inexact differential and not a property
of system
3. It is a boundary / transient phenomenon.
Representation of various process on P-V and T-s diagram:

k=∞

k
k=0

k
k=∞
k

k
s

Work done

Process Work done in closed system Work done in open

system
Constant Wv = c = 0
volume/
Isochoric/ Wopen = V(PI – PF)
Isometric(k
= ∞)
Constant Wp = c = P(VF – VI)
pressure/
Wopen = 0
Isobaric/
Isopiestic(k = 0)
Constant  VF   PI  Wopen = Wclosed
W = C ln  or  C ln 
temperature/  V 
I  PF   VF  P 
Isothermal = C ln  = C ln  I 
 VI   PF 
(k = 1) Here, C = PIVI = PFVF = mRTI = mRTF
where,
C= VI = PFVF = mRTI
= mRTF
 1.8 Mechanical Engineering

Adiabatic PI VI − PF VF mR(TI − TF ) Wopen = g Wclosed

process (k = g) W= =
γ −1 γ −1

Polytropic PI VI − PF VF mR(TI − TF ) Wopen = n Wclosed

process (k = n) W= =
n −1 n −1

n
P1  V2  P  V 
Note: P1V1n = P2 V2n , =   , ln  1  = n ln  2 
P2  V1   P2   V1 

P 
ln  1 
 P2 
n=
V 
ln  2 
 V1 
• Heat: It is a form of energy transfer due to the temperature
difference.
Heat flow ‘out’ of a system is taken as ‘negative’ while heat flow
‘into’ a system is taken as ‘positive’.
• Heat like work is also a ‘path’ function so is ‘inexact’ or imperfect
differential.
It is of two types:
(a) Sensible heat, (b) Latent heat.
Sensible Heat (SH): It is the heat transfer by the virtue of tem-
perature difference.
Latent Heat (LH): The heat required to cause the phase change
is known as latent heat.
SH = mCDT
LH = m(LH)

Where, C is known as specific heat.

It is the amount of heat which is required to rise the temperature
of a unit mass by a unit temperature difference.
Q Q J
Q = mCDT → C = =
m∆T 1 × 1 kg
 Basic Thermodynamics 1.9
 ∂u 
• Specific heat at constant volume, Cv =  ∂T 
V

The heat supplied to a system at constant volume increases its

internal energy.
 ∂h 
• Specific heat at constant pressure, C p =  
∂T  p
The heat supplied to a system at constant pressure increases its
enthalpy.

• for solid and liquid i.e. r = Constant C p = Cv 

i. e.
→γ =1
• For gasses i.e. r ≠ Constant

γR R
Cp = Cv = C p − Cv = R
γ −1 γ –1
• Ideal gas: As temperature changes the volume of Cp and Cv do not
change for ideal gas.

• Real gas: For real gas Cp and Cv value increases with temperature
whereas value of g decreases.

R
 1.10 Mechanical Engineering

• Air: Value of Cp and Cv changes with temperature linearly upto

1500 k. Above 1500 k it varies quadratically.

Note :
• The value of isothermal specific heat is infinite(Cisothermal= ∞)
whereas the value of adiabatic heat is zero.( Cadiabatic= 0)
• Heat supplied at constant pressure is more than specific heat
supplied at constant volume because Cp includes both internal
energy as well as boundary work, Cv includes only internal
energy.
PV = nR 0 T
where, P = pressure (absolute pressure) in kPa
V = volume of tank only in m3
n = number of moles in kilomoles of gas
R0 = Universal gas constant in kJ/kmol-K
T = Temperature (absolute) in kelvin (K)
(R0)oxygen = (R0)air = (R0)nitrogen = (R0)any gas = 8.314 kJ/kmol-K

PV = mRT
Here, P = absolute pressure in kPa
V = volume of container in m3
m = mass in kg
R = Characteristic gas contant in (kJ/kg-K)
T = absolute temperature in Kelvin
N R0
PV = nR0 T = = RT =
N T NkT
A 0 A
where, k is Boltzmann’s constant
8.314 kJ
R = R0 /M , R0 = MR, R02 =
32 kg − K

(CP ) air = 1.008 kJ/kg-K Rair = 0.287 kJ/kg-K

(CV ) air = 0.721 kJ/kg-K γ air = 1.4 = 7 / 5
Mair = 29

Cp
•  g = : adiabatic index → depends on nature of gases
Cv
 ↑ Cp  C p > Cv
  T ↑ Cp ↑ ↓γ =  ↑C  ↓
 v always
Cv ↑
 Basic Thermodynamics 1.11
2
•  γ =1+
n
where, n = degree of freedom

Monoatomic gas g = 1.67

Diatomic gas g = 1.4 gwater = 1

Polyatomic gas g = 1.33

 dP  − P
•  Slope of isothermal curve on P-V diagram =  =
 dV  V
dP P
•  Slope of adiabatic curve on P-V diagram = = −γ
dV V
I F F

I
F F

adiabatic slope = g (isothermal slope)

adiabatic slope > isothermal slope
Ideal Gas Equation For Various Processes

Process Ideal gas equation

Constant volume (isochoric) P2 T2
P ∝ T, =
P1 T1

Constant pressure (isobaric) V2 T2

V ∝ T, =
V1 T1

Polytropic process P1V1n = P2 V2n , T1V1n −1 = T2 V2n −1

n −1
n −1
T2  P2  n V 
= =  1
T1  P1   V2 

adiabatic replace n by γ of polyhtropic

constant temperature (isothermal) 1 P1 V2
P∝ , =
V P2 V1
n−1 n
for air = 0.2857 and = 3. 5
n n−1
 1.12 Mechanical Engineering

3. First Law of Thermodynamics

According to this law, energy can neither be created nor be destroyed
rather it converted from one form of energy to another form.
• For a cycle
Closed system ΣQ = ΣW

Note : (i) For isolated system energy (E) always constant.

(ii) Energy is a point function and property of the system. Energy
is an extensive property while specific energy is an intensive
property.
(iii) The internal energy depends only on temperature, for an ideal gas.

Formula Conditions
dW = PdV • Closed system, • Quassi-static (Reversible)

PV γ = constant • Adiabatic,
γ −1 • Reversible,
T2  P2  γ
• Ideal gas.
=
T1  P1 
γ −1
T2  V1 
=
T1  V2 

dQ = dE + dW Closed system
 Basic Thermodynamics 1.13
dQ = du + dW Closed system and DK.E. = DP.E. = 0
dQ = du + PdV • Closed system,
• DKE = 0 = DPE,
• Quassi-static (reversible)

Heat Transfer In Closed System

Process Heat transfer

Constant volume (Isochoric) dQ = du = u2 – u1 = change in
internal energy
Constant pressure (Isobaric) dQ = dh = h2 – h1 = change in
enthalpy
Constant temperature (Isothermal) dQ = dW
Adiabatic process dQ = 0
Polytropic γ − n   P1V1 − P2 V2 
dQ = 
 γ − 1   n−1 

 γ − n
dQ =  (δW )polytropic
 γ − 1 
Note: • Heat transfer at constant ‘Volume’ increases the ‘internal’ energy
of the system.
• Heat transfer at constant ‘pressure’ increases the ‘enthalpy’ of
the system
• In polytropic process, heat transfer is not zero.
Enthalpy and Specific Enthalpy : It is total heat content of the
system.
H = U + PV
Specific enthalpy is the summation of specific internal energy and
flow work.

H U V
Specific enthalpy = + P 
m m  m
h = u + Pv
Unit of Enthalpy (H) is J or N-m.
 1.14 Mechanical Engineering

Flow Work or Displacement Work: It is the amount of work which

is required to displace a small fluid element into or out of the control
volume is known as flow work.
The mathematical expression of flow work is the product of pressure
and specific volume.

• Control volume is also known as open system and control mass is

known as closed system.
• The boundary of the control volume is known as control surface.

Mass Energy
interaction interaction
Control volume   Open System
Control mass   Closed System

Expansion process Compression process

dW (+ve) dW (–ve)
dT (–ve) dT (+ve)
Tf – Ti < 0 Tf – Ti > 0
Tf < Ti Tf >
Produces cooling effect produces heating effect

Polytropic Specific Heat

γ −n
Cpoly = ⋅ CV
1−n
Cp
where, n = Polytropic index  and  γ =
Cv
 Basic Thermodynamics 1.15
• Polytropic specific heat is always negative for, 1 < n < g, because
even though heat is added to the gas temperature of gas decreases, since
the work done by gas is more than the heat supplied.
Qpoly  γ − n
= − CV 
m(T2 − T1 )  n − 1 
Perpetual Motion Machine of first Kind (PMM1)
There can be no machine which would continuously supply mechanical
work without some other form of energy disappearing simultaneously.
Such a fictitious machine is called perpetual motion machine of first kind.
Only for Ideal Gas

du

dh
Pv mRT
dh γ

P P

Free Expansion: Expansion against ‘vaccum’ is called free

expension.
It is an irreversible process. So we cannot apply ∫PdV.
Free expansion work = 0
Insulated system, Q = 0

W = 0, Q = 0, DU = 0

Uf = Ui Tf = Ti Hf = Hi Ideal gas undergoing free expansion

 1.16 Mechanical Engineering
Incompressible Substance: A substance whose specific volume
(or density) is constant is called an incompressible substance.
The specific volumes of solids and liquids essentially remain constant
during a process. Therefore, liquids and solids can be approximated as
incompressible substances without scarifying much in accuracy.
Note:

rve
Cu

ρ4°c

The density of water is maximum at 4°C and due to this on

decreasing its temperature it expands.
• The slope of fusion curve for the water is negative but for all other
substances it has positive slope.
T
Note: 1. Slope of an adiabatic curve on T-V plane = (1 − γ )
V
 
γ − 1 T
2. Slope of an adiabatic curve on T-P plane = 
 γ  P

3. Slope of adiabatic curve on lnP - lnV plane = – g
4. Slope of adiabatic curve on lnT - lnV plane = 1 – g
γ −1
5. Slope of adiabatic curve on lnT - lnP plane =
γ

6. Slope of isothermal curve on lnP - lnV plane = –1
 Basic Thermodynamics 1.17
4. First Law Applied To Flow Process
• Steady flow process/Steady flow energy equation (SFEE)

Steady flow means when the properties does not vary with respect
to time. Therefore, the mass flow rate at the entry and exit of control
volume are exactly same.

Energy Balance:
EEntering = ELeaving
1 2 1
H1 + mC1 + mgz1 + QCV = H2 + mC22 + mgz2 + WCV
2 2
for per unit mass,
1 1
h1 + C12 + gz1 + qCV = h2 + C22 + gz2 + WCV
2 2
where, H = Enthalpy C = Velocity Z = Height
QCV = Heat given WCV = Work done m = Mass flow rate

  C2 gZ1    C22 gz2 

m  h1 + 1 +  + Q = m  h + +  + WCV
 2000 1000 
CV  2
2000 1000 
• SFEE can also be written as:
C12 C2
(u1 + P1 v1 ) + gz1 + qCV + = (u2 + P2 v 2 ) + gz2 + WCV + 2
2 2

C2 C2
u1 + 1 + gz1 + qCV = u2 + 2 + gz2 + Wtotal
2 2
where,
Wtotal = (displacement work done on system + displacement work
done by system + WCV)
Wtotal = –P1v1 + P2v2 + WCV
 1.18 Mechanical Engineering
Mass Balance:
1 = m
m 2 ρ1 A1V1 = ρ2 A2 V2
or
A1C1 AC ρ1 A1C1 = ρ2 A2C2
= 2 2
v1 v2

where, V and C denotes velocity.

f or incompressible fluid flow:

r = AC = constant
A1 C
= 2 = constant
A2 C1
1
A∝
A1C1 = A2C2
C
Application of SFEE in Steady Flow Process:
1. Nozzle: It is a mechanical device which is used to increase the
kinetic energy at the expense of pressure energy.

C2 = 2000 (h1 − h2 ) = 44.72 (h1 − h2 ) = 44.72 CP (T1 − T2 )

where, T = Temperature h = Enthalpy C2 = Velocity at outlet

Condition:
(i) Nozzle is perfectly insulated,
(ii) Neglect Potential energy changes.
(iii) No work is done by Nozzle,
(iv) Neglecting inlet kinetic energy or inlet velocity
C1 <<<< C2
A1 > A2 → converging nozzle
A2 < A2 → diverging nozzle (converging diverging)
depends upon Mach number
 Basic Thermodynamics 1.19
2. Diffuser: It is of diverging shape and used to decrease the velocity.

C1 = 44.72 (h2 − h1 ) = 44.72 CP (T2 − T1 )

3. Turbine: It is a work producing device. In this the energy is
transferred from the working fluid to the rotor.
In the case of turbine pressure reduces i.e. expansion of the steam
working fluid takes place.

WT = m(h1 – h2)
h1 > h2. So, Work is positive always
Conditions:
(i) Turbine is perfectly insulated.
(ii) Neglecting potential and kinetic energy changes.
(iii) C1 ≈ C2
4. Pump and Compressor: Both are work absorbing devices. In
these devices the energy is transferred from rotor to working fluid.
Compressor: used to increase both pressure as well as temperature.
Pump: used to increase pressure

WC/P = m(h2 – h1)

h1 > h2, So Work is negative

Compressor: deals with compressible fluid, generally vapours
Pump: deals with incompressible fluid, generally liquids.
 1.20 Mechanical Engineering
5. Boiler or Evaporator: Used to convert liquid into vapour. It is a
type of heat exchanger in which external heat is supplied due to which
enthalpy of the fluid increases.

QB/E = m(h2 – h1) W1–2 = 0 and Q1–2 = positive always

P1 = P2   h2 > h1
6. Condenser: Used to condense vapour into liquid. It is a type of
heat exchanger in which heat is rejected at constant pressure.

QC = m(h2 – h1) h2 < h1  i.e.  Q = negative, rejected by

fluid
W1–2 = 0  (always)
7. Throttling: Flow through a restricted passage, a very small
orifice, partially open valve, venturi, porous plug is known as throttling.
Characteristics: 1. No work transfer,
2. No heat transfer,
3. It is an irreversible adiabatic process,
4. It is an isenthalpic process [h1 = h2],
5. Throttling always results a decrease in pressure (expansion).

–VdP work
Reversible work in a steady flow process (–VdP)
(1) steady state, (2) K.E. = P.E. = 0
h1 + q = h2 + WCV
q = (h2 – h1) + WCV
dq = dh + dWCV

 Basic Thermodynamics 1.21
Type of Wsuction Wcompression Wdischarge Wnet
compression (Closed system compressor
process work) work (open
system
work)
Isothermal same maximum minimum minimum
Polytropic same in between in between in between
Adiabatic same minimum maximum maximum

Unsteady State Flow or Transient Flow:

• Charging or discharging of a tank,
• Bottle filling process.
1. Conservation of Mass:

 dm  dMi dMe
  = −
 dt C.V . dt dt

 dm 
  i − m
=m e
 dt C.V .

2. Conservation of Energy:
 dE  dEi dEe
  = −
dt C.V . dt dt
1
Ei = mihi + mi ci2 + mi gzi + Q
2
1
Ee = mehe + me ce2 + me gze + WC.V .
2
 1.22 Mechanical Engineering
 dE  d  1 2 
  =  mi hi + mi ci + mi gzi + Q 
 dt C.V . dt  2 
d  1 2 
−
 me he + me ce + me gze + WC.V . 
dt  2 
Neglecting K.E. and P.E. changes,
 du  d d
  = (mi hi + Q) − (me he + WCV )
dt C.V . dt dt

If hi and he do not vary with respect to time,

 du  dmi  dme
  = hi + Q − he − WC.V .
dt C.V . dt dt

 du     
  = mi hi + Q − mhe − WC.V .
dt C.V .

Note: If the fluid flow is an ideal gas.

U = mCVT U/m = CVT u = CVT
H = mCPT H/m = CPT h = C PT
u2 = hi CVT2 = CPTi

T2 = gTi

5. Second Law of Thermodynamics

It is also known as law of degradation of energy or directional law or
qualitative law:
(i) First law of thermodynamics defines the concept of energy on
quantity basis whereas second law of thermodynamics defines the
concept of energy on quality basis.
(ii) It is the second law of thermodynamics which defines the feasibility
of the process or the direction of possible energy conversion through
the concept of entropy.
Note: Work is said to be high grade energy and heat is a low grade

energy. the complete conversion of ‘Low grade energy’ into ‘high
grade energy’ in a cycle is impossible while the complete conversion
of high grade energy into low grade energy is possible.
 Basic Thermodynamics 1.23
Thermal Energy Reservoir (TER): Reservoir of infinite heat capacity.
It is of two types:
Source: It is the supplier of heat energy without any change in its
temperature.
Sink: It is the absorber of heat energy without affecting its
temperature.
1. Kelvin Planck’s Statement: It is impossible to construct a device
which operates in a cycle producing work continuously while interacting
with the single thermal reservoir.

Output Wnet W Q − QL
h = = = = H
Input QS QH QH

QL Q
= 1 − =1− R
QH QS

QH = Wnet + QL
Wnet = QH – QL
Thermodynamic Temperature Scale or Kelvin Temperature Scale:
Q T
Q ∝ T h = 1 − L = 1 − L
QH TH

TL
ηcarnot = 1 −
TH
Note: Kelvin Planck statement provides the concept of work produce
device.
2. Clausius Statement: It is impossible to construct a device which
operates in a cycle transfers heat from low temperature reservoir to high
temperature reservoir without consuming any other form of energy.
(Winput = 0)
 1.24 Mechanical Engineering

Coefficient of performance(COP) or Energy performance ratio(EPR)

desired effect QH
COP or EPR = =
Winput Winput
QL + Win = QH
Win = QH – QL

QH TH
(COP) HP = =
QH − QL TH − TL
desired effect QL QL
= =
(COP)R = Winput Qinput QH − QL 

QL TL
(COP) R = =
QH − QL TH − TL

(COP)HP = (COP)R + 1

1
(COP)HP = 1 + (COP)R =
ηE

Conditions:
1. The above expression applicable between the same temperature
limt.
2. Clausius statement provides the concept of work absorbing device
i.e. Heat pump and refrigerator.
3. Both Heat pump and Refrigerator are known as reversed heat
engine.
 Basic Thermodynamics 1.25
Carnot Cycle:
1–2 : Reversible adiabatic compression
2–3 : Reversible isothermal heat addition
3–4 : Reversible adiabatic expansion
4–1 : Reversible isothermal heat rejection.

The carnot cycle is not a practical cycle because for the process to be
reversible the cycle process must be quassi-static and it is not feasible
to run a device on quassi-static process.
Carnot Principles:
• The efficiency of an irreversible heat engine cannot exceed the
efficiency of a reversible engine opperating between the same reservoirs.
hirrev  hrev
• The efficiency of all reversible heat engines operating between the
same two reservoirs are same.
(hrev)1 = (hrev)2
Note:
1. The carnot efficiency is afunction of temperature limits only.
2. If there are ‘n’ number of reversible engine operating between same
temperature limits with different working fluids (Petrol, diesel,
H2O, Air) then the value of maximum possible efficiency or carnot
efficiency or ideal efficiency is having same value.
3. Carnot efficiency is independent of working fluids.
η > ηrev  ⇒ impossible

η = ηrev  ⇒ Reversible
η < ηrev  ⇒ Irreversible

4. If two reversible engine operating between thermal reservoir at
T1, T2 and T3 (T1 > T2 > T3) as shown in figure:
 1.26 Mechanical Engineering

Case 1: If the efficiency is same for engine

T2 = T1T3
Case 2. It work output of both engine same.
T + T3
T2 = 1
2
overall efficiency of arrangement = h = h1 + h2 – h1 × h2
Effect of Temperature On The Performance of Reversible
Devices
Engine
TL ↓ T − TL
h = 1 − = H
TH ↑ TH
(a) ↓ TL by DT
hL =
(
TH − TL − ∆T ) = (T
H )
− TL + ∆T
TH TH

(b) ↑ TH by DT
(TH + ∆T ) − TL
hH =
TH + ∆T
(TH + TL ) − ∆T
hH =
TH + ∆T

ηL > ηH > η
• Efficiency of engine increases by increasing TH or by or by
decreasing TL but decreasing TL is more beneficial for increasing engine
efficiency.
• The COP of Refrigerator and Heat pump both increases by
decreasing TH and increasing TL but increasing TL is a better option.
 Basic Thermodynamics 1.27
Note: Two ‘reversible adiabatic’ paths cannot intersect each other
which violates the Kelvin-Planck’s statement. The machine which violate
Kelvin-Plank statement is called PMM2.
Perpetual Motion Machine of Third Kind (PMM-3)
Continual motion of a movable device in complete absence of friction is
known as PMM-3.
Third Law of Thermodynamics:
It is impossible by any procedure, no matter how iealized, to reduce any
system to absolute zero of temperature in a finite number of operations.

6. Entropy
Second law of thermodynamics leads to entropy
Clausius Theorem
dQ
• The cyclic integral of for a reversible cycle is equal to zero.
T
dQ
∫T
=0
R
dQ
• The cyclic integral of for a irreversible cycle is less than zero.
T
dQ
∫T
<0
R
• Entropy Principle
δQ  δQ 
dS ≥ dS =  
T  T rev
(dS)universe  0 [(dS)system + (dS)surrounding]  0
(dS)universe > 0 → Irreversible process
(dS)univers = 0 → Reversible process
(dS)universe < 0 → Impossible process
Note:
1. Entropy change in reversible process is a point function and exact
differential.
2. It is an extensive property.
3. Reversible adiabatic process is an isentropic process but reverse
in not always true.
4. When the system is at equilibrium, any conceivable change in
entropy would be zero.
 1.28 Mechanical Engineering
Clausius Inequality: It provides the criterion of reversibility or
irreversibility of cycle.
dQ
ò T
 0

dQ
∫T
= 0, the cycle is reversible

dQ
∫ T < 0, the cycle is irreversible and possible
dQ
∫ T > 0, the cycle is impossible
Change in entropy of System
Entropy can change by 3 methods
1. Heat interaction
2. Mass interaction [external interaction]
3. Entropy generation [internal interaction]
2
δQ
S2 − S1 = dS = ∫ T
+ δgeneration
1

due to heat due to internal

transfer irreversibility
• Entropy generation is a path function.
• Entropy generation is always a positive value.
Note: When a device is shown exchanging energy with more than two
reservoirs use of Clausius Inequality should be done and any expression
developed from heat ratio, temperature ratio should be avoided.

Case 1: Reversible process [(dS)gen = 0]

⊕ve
δQ
(a)
Heat addition dS = = ⊕ ve
T
– ve
δQ
(b)
Heat rejection dS = =  – ve
T
0
δQ
(c)
Adiabatic dS = = 0 [isentropic]
T
 Basic Thermodynamics 1.29
Case 2: Irreversible process [(dS)gen ≠ 0]
⊕ ⊕
δQ
Heat added
(a) dS = + (δS)gen = ⊕ve
T
–
⊕
δQ
Heat rejected dS =
(b) + (δS)gen = ⊕ve, – ve, 0
T
0 ⊕
δQ
(c)
Adiabatic dS = + (δS)gen = ⊕ve
T
Important Points:
1. If we talk about same amount of energy then entropy associated
is higher at lower temperature and lower at higher temperature.
2. If mass is same then entropy is higher at higher temperature
and lower at lower temperature because total energy is also different.
3. Area under curve on T-s diagram represents heat interaction for
a reversible process.
4. Area enclosed by reversible cycle on T-s diagram represents net
heat transfer which is equal to net work transfer.
5. All clockwise cycle  ⇒  power producing device
All anticlockwise cycle  ⇒  power consuming device
• Combined 1st and 2nd law equations or [Link] equation or join
equation of entropy:
1. [Link] = du + [Link] 2. Tds = dh – [Link]
⇒ These equations are valid for all processes and all the systems.
Representation of Constant Volume and Constant Pressure Lines
on T-s Diagram:
 1.30 Mechanical Engineering

• Constant volume process is more steeper.

Slope of constant volume line = g . slope of constant pressure line
1 1
CP > CV <
CP CV

T T  dT   dT 
<
  = 
CP CV  dS  P = C  dS V = C


O/P Wnet Wnet

h =
= or
I/P Qs QH
The maximum possible efficiency or hcarnot

or T
ηideal = 1 − L
TH

W Q
ηactual = =
QS QH

the above engine is,
δQ
(a) Reversible → ∫ = 0, (dS)universe = 0, hcarnot = hactual
T
δQ
(b) Possible Irreversible → ∫ < 0, (dS)universe > 0; hcarnot > hactual
T
δQ
(c) Impossible → ∫ > 0, (dS)universe < 0; hcarnot < hactual
T
For a cyclic device
∫ dS = 0,  [for both reversible and irreversible]

Q Q

Positive
 Basic Thermodynamics 1.31

Note: In an adiabatic process the system entropy can never decrease.

Entropy Change in Diffusion:

P  P 
DS = –m1R1 ln  1  − m 2 R 2 ln  2 
 P  P

O2 N2
P1 P2
T1 T2
where,
P1, P2 = partial pressure of O2 and N2
P = final pressure of mixture
R1, R2 = Characteristic gas constant for O2 and N2
m1, m2 = mass of O2 and N2
Entropy Calculation

Gas
Ideal gas Pv
 1.32 Mechanical Engineering

  TF  P 
 1. ∆S = S2 − S1 = CP ln   − R ln  F 
 T
 I  PI 
  TF  V 
kJ 
 2. ∆S = S2 − S1 = CV ln   + R ln  F 
kg-k   TI   VI 
    
3. ∆S = S2 − S1 = CV ln PF + CP ln VF
  
 PI  
 VI 

Control Volume Entropy Analysis:

(DE)C.V = 0
(Dm)C.V. = 0
(DS)C.V. = 0
(DS) = Sinlet – Sexit + dSgen
0 = Sinlet – Sexit + dSgen

dSgen = Sexit – Sinlet

Mixing of two incompressible fluids (liquid) or two solids:

m C T + m 2C2 T2
Tf = 1 1 1
m1C1 + m 2C2

 Tf  T 
(DS)universe = m1C1 ln + m2C2ln f
 T   T 
1 2

If m1 = m2 = m and C1 = C2 = C
T + T2  AM 
Tf = 1 and (DS)universe = 2mC ln 
2  GM 
AM = Arithematic Mean, GM = Geometric Mean
for n bodies,
AM 
(DS)universe = n × mC ln 
 GM 
 Basic Thermodynamics 1.33
Maximum obtainable Work When Two finite body are allowed
to exchange heat through Reversible Engine:
cyclic
(DS)1 + (DS)E  + (DS)2 = 0, [for max. work]
T  T 
m1C1 ln f + 0 + m2C2 ln  f  = 0
 T   T2 
1
If m1 = m2 = m and C1 = C2 = C

Tf = T1T2
Wmax = 2m (AM – GM)
for n bodies, Wmax = n×mC (AM – GM)

If W = Wmax → h = hmax → Reversible → Sgen = 0 → (DS)universe = 0

Note : For the best performance of the device l.e. if it is engine
maximum work (or) if it is work consuming device minimum work,
(∆S)universe = 0
Stirring Process :
∆Suniverse > 0 (since stirring process is an irreversible process.)
du = 0 but W1.2 = (–)ve
Since it is irreversible process, so W1–1 ≠ pdv (or) change of volume
will not decide work transfer.
Here dv = 0
But |W1-2|>0 Insulated, Q1-2 = 0 (adiabatic)

Since irreversible Stirring : adiabatic but
process
Process irreversible
Q1-2 = mCv (Tf Ti ) ⇒ only for reversible constant volume process by
ideal gas when work done will be zero

Note : If both the components are the same gas, then the entropy
change in mixing iz zero.
Second Law Efficiency: It is ratio of the actual thermal efficiency to
the maximum possible (reversible) thermal efficiency under the same
conditions.
For engine,
ηactual W
hII = = actual
ηreversible Wmax
For Refrigerator/Heat pump,
(COP)actual W
hII = = min
(COP) rev Wactual
 1.34 Mechanical Engineering

7. Available Energy, Availability

and Irreversibility
The part of low grade energy which is available for conversion to high
grade energy is referred to as available energy, which is also known as
‘exergy’ while the part of low grade energy which, according to second
law, must be rejected is called unavailable energy. Unavailable energy
is known as ‘anergy’.

1 H

H H
H

0 L
s s

Q1 = T1DS
TL T W
h= 1− = 1 − 0 = max
TH T1 Q1
   T 
Wmax = Q1 – Q1 T0 = Q1  1 − 0 
 T   T1 
1

Wmax = Q1 – T0 DS Wmax = Q1 – Q2
A.E. = QS – U.A.E
U.A.E = T0DS
• The maximum work can be obtain when the lower temperature
would be ambient temperature.
Important Points:
1. Decrease in available energy take place due to irreversible process
when heat is transferred through a finite temperature difference.
2. Same amount of heat has more available energy when it is
transferred from higher temperature body than when it is transferred
from lower temperature body.
3. The degradation is more for energy loss at a higher temperature
than that at a lower temperature.
 Basic Thermodynamics 1.35
4. The first law states that the energy is always conserved ‘quantity
wise’ while the second law emphasizes that energy always degrades
‘quality wise’.
Dead State: A system is said to be in dead state if it is in
thermodynamic equilibrium with its surrounding.
Available energy of the system is a function of:
1. Energy of the system,
2. State of the system,
3. State of the surroundings.
Availability: It is the maximum work obtained in which system
comes into equilibrium with the surrounding state.

Availability for a closed System:

(AV)C.S. = (uI – uF) – T0(SI – SF)

useful work
Maximum useful work for closed system:
(MUW)C.S. = (UI – UF) – T0(SI – SF) + P0 (VI – VF)

Availability for open System:

(AV)O.S. = (hI – hF) – T0(SI – SF)

useful work
Maximum useful work for open system:
(MUW)O.S. = (hI – hF) – T0(SI – SF)

Availability Function or Flow Availability (f):

Case 1: Closed system
fC.S. = u + P0V – T0S
Case 2: Open system
fO.S. = h – T0S
 1.36 Mechanical Engineering
Gibb’s funciton:
G = H – TS
Application for open system
Change in Gibb’s function: dG = VdP – SdT
Gibb’s Helmholtz function: F = U – TS
Applicable for closed system.
Change in GHF: dF = −PdV − SdT
Irreversibility (I): It is defined as the difference between maximum
work and actual work.
I = Wmax – Wactual

Gouy Stodula Theorem: According to this theorem the rate of

irreversibility is directly proportional to the rate of entropy generation.
I ∝ (dS)gen I = T0 (dS)universe

Note: 1. The change in availability of a open system is eqaal to

change in Gibb’s function of system at constant temperature.
2. Gibb’s function is useful in evaluating the availability of systems
in which chemical reaction occurs.
3. The change in availability of closed system is NOT equal to change
in Helmholtz function at given temperature.
Compressibility Factor
It is the factor which represents the deviation of actual gas behaviour
from the ideal gas.
PV
Z=
RT
The value of Z is 1 for ideal gas. and for real gas it can be > 1 or < 1.
Causes of Irreversibility:
• Conversion of high grade energy into low grade energy,
• Friction,
• Viscous force,
• Electric resistance,
• Inelastic collision,
• Heat transfer through finite temperature differences,
• Free expansion,
• Mixing of fluids.
 Basic Thermodynamics 1.37
8. Properties of Pure Substance
A pure substance is a substance of constant chemical composition
throughout its mass. It is one component system. It may exist in one
or more phases.

Critical pressure (H2O)

Critical temperature (H2O)

• Saturation State: A saturation state is a state where a change

of phase may occur without a change of pressure or temperature.
• Critical Temperature: At critical temperature a liquid completely
changes to vapour and vice-versa. Also above critical temperature a
vapour cannot be liquefied by any amount of pressure.
• Critical Pressure: At critical temperature the corresponding
minimum pressure required to transform a vapour to liquid is called
critical pressure.
• Critical Point: It is a point above which liquid will directly flash
off into vaopurs.
• Triple Point: Triple point is a fixed point (fixed temperature
and pressure) at which solid, liquid and vapour phases co-exist in
equilibrium.
Superheating: It is a process of increasing the temperature at constant
pressure above saturated vapour.
Subcooling or Undercooling: It is a process of decreasing the
temperature at constant pressure below saturated liquid.
Wet Region: It is mixture of liquid and vapour.
Note: Trans formation of solid to vapour directly is called sublimation
• Transformation of vapour to solid directly is called ablimation.
• Enthalpy of vapourization at critical point is zero.
 1.38 Mechanical Engineering

Degree of Subcooling: Degree of subcoolng = Tsaturation – Tactual

Where, Tsat. = Tsaturated
Tsub. = Tsubcooled

Degree of superheating:
Degree of superheating = Tactual – Tsaturation vapour

Dryness Fraction (x)

0≤x≤1
mv
x=
mv + ml

Critical point

s
 Basic Thermodynamics 1.39
where, mv → mass of vapour,
ml → mass of liquid
20% V
x = 0.20
80% L
xB (saturated liquid)  ⇒ mv = 0, xB = 0
mv
xD (Saturated vapour) ⇒ ml = 0, xD = =1
mv + 0
Note : Do not
apply f  Saturated liquid
pv = mRT in g  Saturated vapour
Wet region
The reference state taken for the steam table are
u = 0
at triple point of H2O = 0.01°C
S = 0 
Enthalpy at various points:
(Liquid), hB = hf
(Vapour), hD = hg

• Wet Region = hB + xhfg

= hf + x(hg – hf) s
• Superheated Region = hD + (CP)vap. (TE – TD) = hg + (CP)vap.(TE – TD)
• Subcooled Region = hB – (CP)liq (TB – TA) = hf – (CP)liq (TB – TA)
Entropy at Various Points :
• Wet region = Sf + x (Sg – Sf)
L.H.
• On saturated vapour line = Sf +
T

 hg − h f 
 Sg − S f = T 


 T1 
• In super heated region = Sg + ∆S = Sg + (Cp)vapln 
 Tsaturation 

T 
• In sub cooled region = Sg – ∆S = Sf – ∆S = Sf – (Cp)liqln  saturation 
 T1 
 1.40 Mechanical Engineering
Important Points :
• A gas or a pure substance require two known properties (P, V, T, H
etc.) to describe it completely i.e. it has two degrees of freedom.
• A liquid and vapour in equilibrium state (saturated state) has one
degree of freedom.
• A liquid, vapour and solid in equilibrium (triple point) has zero
degree of freedom.
• Throttling calorimeter is used to measure dryness fraction of pure
substance.
• On P-T diagram, triple point and critical point both are point.
• On P-V diagram, triple point is a line and critical point is a point.
 ∂P 
• CP = CV at 4°C as   = 0
 ∂T  P

2
  ∂P    ∂P 
• CP – CV = − T     
  ∂T    ∂V  T