GATE Syllabus

Thermodynamic systems and processes; Properties of pure substances; Behaviour of ideal and real gases; Zeroth and
first laws of thermodynamics; Calculation of work and heat in various processes; Second law of thermodynamics;
Thermodynamic property charts and tables; Availability and irreversibility; Thermodynamic relations.
Cha ter Outline 12.1 KEY CONCEPTS AND FORMULAS
12.1 Key Concepts and Formulas Thermodynamic Systems
Thermodynamic Systems Surroundings
System: A system is a finite quantity of
Zeroth Law of Thermodynamics matter, or a prescribed region of space,
which is under the thermodynamic
Heat and Work Transfer
study.
First Law of Thermodynamics
Boundary: The actual or hypothetical Boundary
Steady Flow Process envelope enclosing a system is the
Second Law of Thermodynamics boundary of the system. The boundary may be real or
hypothetical.
Heat Engine
Surroundings: Everything outside a system boundary is termed
Heat Pump as surroundings.
Refrigerator System + Surroundings = Universe
Statement of the Second Law Closed, Isolated and Open System
Carnot Cycle
Closed system can exchange energy (as heat or work) but not
Entropy matter, with its surroundings. An isolated system cannot
Availability exchange any heat, work, or matter with the surroundings, while
an open system can exchange all heat, work and matter.
Pure Substances
Control Volume
Properties of Steam
If the volume of a system under study remains constant, then this
Ideal Gas and Real Gas
is called the control volume (CV). The control volume is bounded
Thermodynamics Relations by the control surface (CS).
12.2 Solved Examples System Properties
12.3 Practice Paper Intensive properties: These are the properties that do not depend
12.4 Solution to Practice Paper on the mass of system, e.g., temperature, pressure, and density.
Extensive properties: These properties essentially depend on
the mass of a system, e.g., volume, entropy, and enthalpy.
Extensive properties per unit mass are intensive properties, e.g.
specific volume, specific enthalpy, specific entropy and density.
State: The condition or state of a system is specified by the values
of its properties.
12.2 GATE Mechanical Engineering

A system is in an equilibrium state (or in equilibrium) if no Internal energy U: The sum of all the microscopic forms
changes can occur in the state of the system without the aid of energy is called internal energy.
of an external stimulus. U =K + P, where K = internal energy of molecules and
Process and path: A change of a system from one state to P = internal potential energy of molecules.
another is called a process. The path of the process is the Mechanical energy: It can be defined as a form of energy
series of states through which the system passes during the that can be converted directly and completely into
process. mechanical work by an ideal mechanical device such as an
If the path is completely specified, it is called a process. It ideal turbine or pump. Thermal (heat) energy is not a form
may be a of mechanical energy.
1. Constant pressure (isobaric) process, 2. Constant Mechanical energy of a flowing fluid:
volume (isochoric) process, 3. Consant temperature V2
(isothermal) process, 4. Constant entropy (isentropic) Emech = /11
. pv + — gz
process, 5. Adiabatic process. 2
Cyclic process: If a system undergoes a series of processes Enthalpy
and is returned to its original state, it is said to have
undergone a cycle or cyclic process. The sum of the internal energy U and the product of
pressure P and volume V.
Non-flow process: A process may be a non-flow process
in which no mass transfer occurs across the system Enthalpy, H =U + PV (kJ)
boundary while the system is undergoing a change of state. Specific enthalpy, h = u + P v (kJ/kg)
Flow process: A process may be a flow process if mass
enters or leaves the system boundary. This is feasible in Heat
open system only. It is a transfer form of energy that flows between two
Reversible Process: A reversible process is defined as a system (or a system and its surroundings) by virtue of the
process that once having taken place in a direction, can be temperature difference between them, q = (kJ/kg).
reversed without leaving any trace on either system or
surroundings. Heat capacity: The product of mass and specific heat is
Quasi-equilibrium: If during a process, a system passes defined as heat capacity of the system.
through series of only equilibrium states, so that the system
at any instant is in equilibrium close to being equilibrium, Work
the process is called a quasi-equilibrium process.
Work like heat is also a form of energy in transit. Energy
Point function: Thermodynamic properties are the point can cross the boundary of the system as heat or work.
function for a given state where there is one and only one
value for each property. Sign convention for work transfer: Work done by system
is considered as positive. Work done on system is
Path function: There are certain quantities which cannot considered as negative.
be located on a graph by a point but are given by the area
under the graph. Such quantities are called path functions. Forms of Work Transfer
Heat and work are path functions.
Zeroth Law of Thermodynamics 1. Electric work, WE = VI At,

It states that if two bodies are in thermal equilibrium with a 2. Mechanical work, W = f PdV
third body, they are also in thermal equilibrium with each
other. 3. Flow work, W = pv
Temperature scales, T (K) = T (° C) + 273.15 4. Gravitational work, APE = mg(z2 — z,)
Heat and Work Transfer 2
5. Acceleration work, AKE = 1m(V2 — 17, 2 )
Forms of Energy 2
6. Shaft work, We = 27cnT
Potential energy, PE = mgz
1
Kinetic energy, KE = 1my
2 7. Spring work, Wspring = — k (x 2 — x ,)
2 2
 Thermodynamics 12.3

First Law of Thermodynamics a steady-state flow, there is neither any accumulation of

First law of thermodynamics states that energy can be mass nor energy.
neither created nor destroyed. However, energy can (E Energy). = (E Energy )out
change forms, and energy can flow from one place to Steady flow energy equation (SFEE)
another. The total energy of an isolated system remains the
same. 4i2 ,P2,1)2
V2 , T2, Z2
Q= AU +W m

where Q is the energy entering a system causing an

increase in the system's internal energy by AU and
producing some external work W.
In differential form 6Q = dU + PdV, and in the internal •
Q w• rh zu
( 2 ) (p2 v 2 - p,v,)+ (V22 - V, 2) + (Z2 - z,),g (J/s)
form, Q=AU +IPdV 2

Application of the First Law of

Or 4- - h,)+ —21 (v22 v-12 )+ (z2 — z 1 )g (J/kg)
Thermodynamics
Steady flow energy equation is applied to 1. Steam turbine,
Isolated system: AU = 0, W = 0, Q = 0 2. Pump, 3. Nozzle, 4. Boiler, 5. Compressor, 6. Throttling,
7. Adiabatic mixing, etc.
Isobaric process: A U = mcv (T,—T,)
2 Second Law of Thermodynamics
W = f PdV = P (V2 —V,) The second law of thermodynamics states that the total
entropy of an isolated system always increases over time,
or remains constant in ideal cases where the system is in a
Q=m 7.1 (T2 — T,)= mcp(T2 —T,) steady-state or undergoing a reversible process.
7 —1
Heat Reservoir
Isochoric process: AU = mc, (T2 — T,)
A thermal reservoir is a heat source or heat sink that
2
remains at a constant temperature, regardless of energy
W = PdV = 0
interaction.
Heat Engine
Q=mcv (T2 —T,)
Isothermal process: AU = 0 High temperature
2
reservoir
Source THA
W=f PdV = P,V, log e
\V
/ Q1
17 \
Q = P,V, loge 2
V
\ I
Q2
Adiabatic process: Q =0
Sink TL
P, V, — P2V2 Low temperature
AU + W = 0, W = — AU =
7 —1 reservoir

Polytropic process: Q= AU +W A heat engine is a device that converts heat into work.
P V, — P2V2 Heat input = Q,
Q=inc,(T2—T,)+,
n-1 Heat rejected to the sink = Q2
Net heat converted to work, 0
A., net = Wnet = Q I — Q2
Q=mcv(T2—T,) n-7\
\ n-1 i
Efficiency of the heat engine, =r/Vletor ri = 1 — Qz
Steady Flow Process Qi Qi
In a steady flow process, the mass flow rate and energy Or 1=1— T,
flow rate across the system boundary are constant. During
12.4 GATE Mechanical Engineering

Steam power plant: It is a typical heat engine in which Q2

(COP) Ref = w
low grade energy (heat) is converted to high grade energy
(mechanical work).
Q2 Q2
Heat Pump Or (COP) =
W Q —Q2
A heat pump is a reversed heat engine. It receives heat from Statement of the Second Law
a low temperature reservoir (source) and rejects it to a high
temperature reservoir (sink). There are two classical statements of the second law of
High temperature thermodynamics:
p Sink T; Clausius Statement

Q1 It is impossible to construct a device that will produce no

effect other than the transfer of heat from a low
temperature body to a high temperature body while
operating in a cycle.
Kelvin-Plank Statement
Low temperature No heat engine, operating in cycle, can convert entire heat
into work. It is impossible to build a heat engine that can
A heat pump extract, Q2 amount of heat from the low
register 100% efficiency.
temperature (T2) source and delivers Q, amount of heat to
the high temperature (T,) sink by consuming W amount of Perpetual motion machine of second kind (PMM II):
external work. PMM II is a hypothetical machine that will continuously
Desired effect transfer heat from a low temperature reservoir to a high
Coefficient of performance (COP) — temperature without taking up any input work energy from
Work input
its surrounding.
Q, Carnot Cycle
(COP) HP
P T
1 T, TH
or Q, Q,
(COP) HP
W Q,
Refrigerator
High temperature
QR TL 3 TL
Sink T, QR 3
V —S
P-V diagram T-S diagram
It is theoretically a heat engine that converts the maximum
amount of energy into mechanical work. The Carnot cycle,
also called reversible cycle, comprises of four reversible
Source T2 processes as given:
Low temperature 1. Reversible isothermal expansion

A refrigerator is a device, operating in a cycle, that 2. Reversible adiabatic (isentropic) expansion

maintains a body at lower temperature than its 3. Reversible isothermal compression
surroundings. A refrigerator extracts heat continuously
4. Reversible adiabatic (isentropicc) compression
from a controlled space, and thus it is maintained at a lower
temperature than its surroundings. (v2
Heat supplied, Q5. =RT, ln
The desired effect of a refrigerator is to remove Q2 heat \ V1
from refrigerated space at temperature T2. The work input
V3
to the compressor is W and heat rejected at the condenser Heat rejected, QR =RT, ln
is Q,. \V4

Desired effect (v2

Coefficient of performance (COP) — Net work done, Wnet = Qs —QR =(T, — TL )R ln
Work input
\V
 Thermodynamics 12.5

Thermal efficiency of Carnot heat engine,

Wet Qs — QR _ 1 11
11 — — Critical int
Qs Qs TH
Clasusis Inequiality T Saturate
liqu'd d
dQ
= 0 ; for a reversible process
rheated
dQ vapo
< 0 ; for a irreversible process region

dQ
>0 ; fora process that is impossible

Entropy
Thermodynamic properties chart
Entropy is an abstract property. It is the quantitative
measure of molecular disorder within a system. The M
g
Dryness fraction, x—
entropy change dS is defined as: + mt

s,-s,= Ids = f dQ mg = Mass of dry steam

T
mi = Mass of wet steam
{
Thermodynamic relations:
Tds= du + pdv Specific volume of wet steam, v = It / + x vig
For closed system
Tds = dh — vdp where v/g = vg —vi
Enthalpy of wet steam, h = hi + xhig
Entropy change in ideal gas:
Internal energy of wet steam, u = ut + x u1g
(T (V\
As= cv ln —2 + R ln Entropy of wet steam, s = st + x sig
\ \V
Tsup
T \ Specific volume of superheated steam, v, = v
As = c ln 2. — R ln gT
\
Specific enthalpy of superheated steam,
IT2\
For solids and incompressible liquids, As = c ln hsup =hg + cp (Tsup —Tg)
\ ( Tsup
Entropy of superheated steam, ssup = sg + cp ln
Availability T
g
The available energy is that portion of heat energy applied Internal energy of superheated steam,
to a reversible engine, which could be converted into usup =hg + cg (Tsui, — Tg ) — Pv sup
useful work.
Ideal Gas and Real Gas
The maximum useful work potetial of a system at the
specified state is called availability. Equation of state: Any equation that relates the pressure,
Pure Substances temperature and specific volume of a substance is called an
equation of state.
A substance that has fixed chemical composition
throughout is called a pure substance. Ideal gas relation: PV = mRT
Phases of a pure substance: (a) Solid, (b) Liquid, (c) Gas R =8.3144
PV = m —T. R — kJ/kmolK
Properties of Steam <— Molecular weight
Relation between specific heats: cp — cv = R
Dryness fraction: It is a parameter that defines the quality
of wet steam. It is the ratio of the mass of dry steam (mg) to D R
the mass of wet steam (mg +
where c = cu —
P 7 —1 7 —1
12.6 GATE Mechanical Engineering

Real gas relation: 12.2 SOLVED EXAMPLES

a\ Previous Years GATE Questions
P+ —2 (v - b)= RT (van der Waals equation)
v )
a Example 12.1
P+ (v — b) = RT [Berthelot]
Tv 2 The van der Waals equation of state is
Pv a \
Compressibility factor, Z =— P+ (v - b) = RT, where P is pressure, v is specific
RT
Dalton's law of partial pressures, volume, T is temperature and R is characteristic gas
constant. The SI unit of a is
P = PA + PB + Pc •••
Density of gas mixture, p=p A +p, + Pc + (A) J/kgK (B) m 3 /kg
(C) m 5/kg s 2 (D) Pa/kg
Thermodynamics Relations
GATE 2015
Maxwell Relations
Solution
aT = -( ap` First relation
av)s. ,as ,v The unit of term ± is N/m 2 (unit of pressure)
v
ray' = (av` Second relation
aP ,as „ N i m 3 \2
Thus, the unit of a,
m x
\—kg
ap ( as `
= — Third relation \2
aT)v ,av „ kgm/s 2 1 m
3

Or x
ray =- as` 111
2 \ kg )
Fourth relation
aT), ,ap „ m5
Unit of a is
Thermodynamic Relation kgs 2

as` ( as` Example 12.2

c, =(— ,cv =
aT „ ,aT The COP of a Carnot heat pump operating between 6°C
( ap `
TdS = cvdT +T — dV
and 37°C is
\aT iv GATE 2015
av Solution
TdS = cpdT — dP
273+37
\aT„
cp - cV = -T
( ap` ( av` 2 Qi
a V T\aT
HP W
( ay
dh=TdS +VdP = cp dT + V -T idP Q2
,aT
T2 =273+6

du =TdS - PdV = cv dT +
ap` -play
\ aT jv
COP of Carnot heat pump is given by COP —
T,
T, -T2
Joule-Thomson Coefficient
273 +37
aT` 1 ,„(av` -v 1 COP —
Il i =( — =— i (273 + 37) — (273 + 6)
aP j h Cp _ „aT „
COP =10
Clausius-Clapeyron Equation Example 12.3
dP L Work is done on a adiabatic system due to which its
(where L is latent heat)
dT T velocity changes from 10 m/s to 20 m/s, elevation
increases by 20 m and temperature increases by 1K. The