CH-1 Introduction and First Law of Thermodynamics

 Thermodynamics is a branch of physics and an engineering science

 The word thermodynamics stems from the Greek words therme (heat) and dynamis (force).
 Definition: Thermodynamics is the science of energy transfer and its effect on the physical properties
of substances
 Basic Law’s of thermodynamics:
 Zeroth law: deals with thermal equilibrium and establishes a concept of temperature
 First law: deals with relation between work and heat and establishes concept of internal energy
 Second law: deal with limit of converting heat into work and introduces the concept of entropy
 Third law: defines the absolute zero of entropy
 Application Areas of thermodynamics:
 Energy converting devices: Steam Engine, IC Engine, Steam and Gas Turbines, Refrigeration and A-C
 Electrical power generation: Thermal, Nuclear, Solar, Chemical
 Heat transfer devices : Heat Exchanger, cooling
 Macroscopic and Microscopic point of View:
 Macroscopic Approach (Classical thermodynamics): concerned with gross or overall behavior
 Microscopic Approach (Statistical thermodynamics): deals with molecular level behavior
 Thermodynamic System and Control Volume:
 System: a quantity of matter or a region in space chosen for study
 Surroundings/environment: The mass or region outside the system
 Boundary: Real or imaginary surface that separates the system
from its surroundings
Thermodynamic System
 Universe: A system and its surroundings together comprise a universe
 Classification of Thermodynamic systems:
 Closed system (fixed mass)
 Open system (fixed volume)
 Isolated system (fixed mass and energy)

 Homogeneous, Heterogeneous, Adiabatic System Closed system Open system Isolated system
 Control Volumes:
 Control volume : Selected region(arbitrary of space within a prescribed boundary through which
mass, energy can cross the system boundary.
 The boundaries of a control volume are called a control surface, and they can be real or imaginary
 A control volume can involve fixed, moving, real, and imaginary boundaries
 A control volume can involve mass interaction in addition to heat and work interactions

Control Volume and Control Surface Control Volume with real and Control Volume with fixed and
imaginary boundaries moving boundaries
 Thermodynamic Properties:
 Property: Any characteristic of a system by which its physical condition may described of a system.
 e.g. volume, temperature, pressure, viscosity, thermal conductivity, electric resistivity, etc.
 Properties are considered to be either intensive or extensive
 Intensive properties : Independent of the mass of a system, e.g. temperature, pressure, density
 Extensive properties: values depend on the size or extent of the system, mass, volume, momentum
 Uppercase letters are used to denote extensive properties (exception mass ‘m’)
 Lowercase letters are used for intensive properties (exception Pressure ‘P’, and Temperature ‘T’)
 Specific properties: Extensive properties per unit mass e.g. specific volume, specific total energy
 Continuum: Matter is made up of atoms that are widely spaced in the gas phase. Yet it is very
convenient to disregard the atomic nature of a substance and view it as a continuous,
homogeneous matter with no holes, that is, a continuum.
 The continuum idealization, the properties considered as point functions without discontinuities
 This idealization is valid for the system which has large size than the space between the molecules
 Thermodynamic State and Equilibrium:
 State: When all the properties of a system have definite values. In other word, At a given state, all
the properties of a system have fixed values
 Change of state: One or more of the properties of a system changes
 Equilibrium: there are no unbalanced potentials (or driving forces) within the system
 Thermodynamic Equilibrium: If the system is isolated from its surroundings then There is no
spontaneous change in any macroscopic property of system
 Thermal equilibrium: The temperature of the system does not change with time and has same
value at all points of the system.
 Mechanical equilibrium : There are no unbalanced forces within the system or between the
surroundings. The pressure in the system is same at all points and does not change within system
 Chemical equilibrium: No chemical reaction takes place in the system and the chemical
composition which is same throughout the system does not vary
 Phase equilibrium: The mass of each phase remains same
 When the conditions for any one of types of equilibrium are not satisfied, a system is said to be in a
nonequilibrium state.
 Thermodynamic Processes and Cycles:
 Process: Any change that a system undergoes from one
equilibrium state to another
State 2
 Path: The series of states through which a system passes during
a process
 Quasi-static Process: When a process proceeds in such a manner
that the system remains infinitesimally close to an equilibrium
State 1 Process path
state at all times. The prefix iso- is often used to designate a
process for which a particular property remains constant e.g.
isothermal process, isobaric process, isochoric process
 Reversible Process: if the initial state together with all energies
transferred or transformed during the process can be completely
restored in both system and environment.
 A quasi-static process is also called a reversible process.
 Cycle: A system returns to its initial state at the end of the series
of processes.
 Pure substance:
 Phase: A quantity of matter homogeneous in chemical composition and physical structure.
 e.g. Atmospheric air, steam-water mixture and combustion products of a fuel
 Homogeneous system: A system consisting of a single phase
 Heterogeneous system: A system consisting of more than one phase
 Units and Dimensions:
 Fundamental Units : Length (L) :meter (m); Mass (M): Kilogram (kg) ; Time (t): Second (s) ; Amount of
substance: Mole (mol) Temperature (T): Kelvin (K)
 Derived Units : Force (F): Newton (N) ; Energy (E): Joule (J)

Assignment No. 1
Q1 : Write the definition and SI units of following quantities:
Force, Pressure, Specific volume, Density, Specific Weight, Energy and Power
Q2 . Write a short note on measurement of pressure and Relationship between absolute, gauge, vacuum
and atmospheric pressure
 Temperature and The Zeroth Law of Thermodynamics:
 Temperature : The temperature is a thermal state of a body which distinguishes a hot body from
a cold body. It is measure of “hotness” or “coldness”
 The temperature of a body is proportional to the stored molecular energy i.e., the average
molecular kinetic energy of the molecules in a system.
 Zeroth Law of Thermodynamics:
“When a body A is in thermal equilibrium with a body B, and also separately with a body C, then
B and C will be in thermal equilibrium with each other”
or
“If two bodies are in thermal equilibrium with a third body, they are also in thermal equilibrium
with each other”

B A C
 Temperature Measuring Instruments:
 Thermometric property: property that changes as its temperature changes. The substance that
exhibits changes in the thermometric property is known as a thermometric substance.
 One measurable property that changes as its temperature changes can be used
 Triple point of water: the state at which ice, liquid water and water vapour coexist in equilibrium

Thermometer Thermometric Property

Alcohol or mercury-in-glass Length (L)
Constant pressure Volume (V)
Constant volume Pressure (p)
Electric resistance Resistance (R)
Radiation (pyrometer) Intensity of radiation (I or J)
Thermocouple Electromotive force (E)
 Temperature Scales:
 Temperature scales enable us to use a common basis for temperature measurements.
 All temperature scales are based on some easily reproducible states e.g. ice and steam point
 Celsius scale: the ice and steam points were assigned the values of 0 and 100°C, respectively
 Fahrenheit scale: The corresponding values on the Fahrenheit scale are 32 and 212°F.
 Thermodynamic temperature scale: a temperature scale that is independent of the properties of
any substance or substances.
 The thermodynamic temperature scale in the SI is the Kelvin scale, named after Lord
Kelvin(1824–1907). The temperature unit on this scale is the kelvin, which is designated by K
 The thermodynamic temperature scale in the English system is the Rankine scale, named after
William Rankine (1820–1872). The temperature unit on this scale is the Rankine, which is
designated by R.
 Relation between Kelvin and Celsius scale : T  K   T  o C   273.15
 Relation between Rankine and Fahrenheit scale : T  R   T  o F   459.67
 Relation between two unit systems: T  R   1.8T  K 
T  F   1.8T  C   32
o o
 ENERGY, WORK AND HEAT :
 Energy is defined as the capacity to exert a force through a distance i.e. capacity to do work.
 Energy is a scalar quantity.
 Dimension: [E]=[MLT-2]; Unit=Joule (J)
 Energy may be broadly classified as Stored energy and Energy in Transition
 Stored energy: contained within the system boundaries
i. Potential energy (PE):energy due to position and the elevation of mass  PE  mgz
2
mV
ii. Kinetic energy (KE): the energy created from the motion of a mass  KE 
2
iii. Internal energy (U): energy associated with the configuration and motion of its molecules,
atoms and subatomic particles relative to its centre of mass.
• Internal energy is a consisting the combined molecular kinetic and potential energy.
• Combined effect of translational, rotational, vibrational, spin, molecular binding, dipole
energy.
Total Energy  E   U  KE  PE
mV 2
U   mgz
2
 Energy in Transition (energy interactions): which crosses the system boundaries
 Heat transfer (Q): The form of energy that is transferred between two systems (or a system and
its surroundings) by virtue of a temperature difference.
 The transfer of heat into a system is often referred to as heat addition and the transfer of heat
out of a system as heat rejection.
 The direction of heat transfer is taken from the high temperature system to the low temperature
system
 Heat is transferred by three mechanisms: Conduction, Convection, and Radiation
 Heat flow into a system is taken to be positive, and heat flow out of a system is taken as negative
 Process during which there is no heat transfer is called an adiabatic process
t2

 Rate of heat transfer: heat transferred over some time interval Q   Qdt  Q  Q t
t1
 The specific heat of a substance is defined as the amount of heat required to raise a unit mass of
the substance through a unit rise in temperature
 The latent heat is the amount of heat transfer required to cause a phase change in unit mass of
a substance at a constant pressure and temperature
 Energy in Transition (energy interactions): which crosses the system boundaries
 Work (W): the energy transfer associated with a force acting through a distance.
 Work is one of the basic modes of energy transfer.
 Power: The work done per unit time
 Work done by the system is positive, and Work done on the system is taken as negative
 pdV-work or Displacement work:
The system is in thermodynamic equilibrium, the state of which is P1 , V1 .
Let the piston move out to a new final position 2. which is also a thermodynamic equilibrium
state specified by P2 and V2 .
At any intermediate point in the travel of the piston, let the pressure be P and the volume V.
P
dW  F  dl
P2
 PA  dl L1
P
 PdV
V2
P1 P2
A V1
 PdV
P1
W1  2  V2
V1
V1 dV V2 V
L2
 Path Function and Point Function: which crosses the system boundaries
 Point Function: Any quantity whose change is independent of the path is a point function.
• Two quantities can locate a point on the graph (co-ordinate axes)
• depend on the state only, and not on how a system reaches that state, it is a property
• Point functions have exact differentials.
V2

e .g .   dV
V1
 V2  V1  V

 Path Function: Any quantity whose change (magnitude) is depend on the path followed during a
change of state (process).
• It cannot be located on a graph by a point but are given by the area on that graph
• Path functions have inexact differentials. e.g. Heat and work are inexact differentials.
2
e .g .   δQ  Q
1
1 2  Q and

 δW  W
1
1 2  W

 Heat is a low grade energy while work is a high grade energy

 Work and Heat are path functions and not the property of the system
2
p
Q1A 2   δQ along path A  Q2  Q1  Q and 1
1 p2 pC
2

 δW along path A  W2  W1  W
pB
W1A 2 =
1 pC

 PdV-Work in Various Quasi-Static Processes

p1
Constant pressure process  Isobaric isopiestic process  2
2 2
V1
 δW =  pdV
dV V2 V
W1  2 =
1 1
2
 p  dV  p V2  V1   pV
1

Constant volume process  Isochoric 

2
W1  2 =  pdV
1
0
 Work and Heat are path functions and not the property of the system
2
P
Q1A 2   δQ along path A  Q2  Q1  Q and 1
1 P2 PC
2

 δW along path A  W2  W1  W
PB
W1A 2 =
1 PC

 PdV-Work in Various Quasi-Static Processes

P1
Constant pressure process  Isobaric isopiestic process  2
2 2
W1  2 =  δW =  pdV
1 1
V1 dV V2 V

2 P 1 P 2 P 2
 p  dV  p V2  V1   pV P2
1

Constant volume process  Isochoric 

2
W1  2 =  pdV
1
0 P1 1

V1 V2 V V
Constant Pressure Process Constant Volume Process
 PdV-Work in Various Quasi-Static Processes p
Constant Tempearure process  pV  C  p2
1

2 2 2
C
W1  2 =  δW =
1
 pdV  
1 1
V
dV

V2 p1 p1 p1
 C ln  C ln  P1V1 ln 2
V1 p2 p2

Polytropic process pV n  C 
2 2 2 V1 dV V2 V
C
W1 2 =  δW =  pdV   n dV p
1 1 1
V
1
V2 p
 V  n1  p1V1n 1 n
C
 
 

V2  V1
1 n
 2

 n 1 V1 1 n
p2V2nV21 n  p1V1nV11 n p V  p1V1
  2 2
1n 1n p1
2
 n

p1V1  p2V2  p1V1   p2  n-1 
 1  1 
n1 p1V1  n  1   p1  
 V1 dV V2 V
 
 Indicator Diagram: An indicator diagram is a trace made by a recording pressure gauge attached to
the cylinder of a reciprocating engine
 The area of the indicator diagram represents the magnitude of the net work done by the system in
one engine cycle
mean effective pressure(m.e.p.) Pm
ad
pm = K
ad
 Work done in one engine cycle   pm A  L

Indicated power:
power developed inside the cylinder of the engine
pm AL  N or N 2 
IP  kW
60
Brake power (BP) or shaft power (SP ) :  Other Types of Work Transfer
The power available at the crankshaft Electrical Work: WE = EI
2 TN Shaft Work: W S = Tω
BP  Tω= kW
60 Paddle-Wheel Work or Stirring Work : W p = 0
BP
ηmech  Flow Work: WF = pv
IP
 First Law of Thermodynamics:
 Heat and work are different forms of the same entity, called energy which is conserved
 Energy which enters a system as heat may leave the system as work, or energy which enters the
system as work may leave as heat.
 For a closed system undergoing a cycle, heat and work interaction given as:

 dW   dQ
 W     Q 
cycle cycle

 Closed system undergoing a change of state:

Q  ΔU  W
Q  ΔE  W
Q  ΔU   pdV  Q  ΔE  W
 Energy- A Property of the System:
 Consider a system which changes its state from state 1 to state 2 by following the path A
 Returns from state 2 to state 1 by following the path B
 Writing the first law for path A and path B: P
1
Q A  ΔE A  W A C
QB  ΔE B  WB
 The processes A and B together constitute a cycle B
 Q cycle
   W cycle
A
 Q A  QB  W A  W B 2
 Q A  W A  W B  QB
 ΔE A   ΔE B
 Similarly, If the system returned from state 2 to state 1 by following the path C
 Q cycle
   W cycle  Q A  QC  W A  WC  ΔE A   ΔEC
 The change in energy between two states of a system is the same, i.e. independent on the path
follow in undergoing that change of state. Hence, energy is a point function and a property
 Specific Heat at Constant Volume (cv):
 The specific heat of a substance at constant volume (cv) is defined as the rate of change of specific
internal energy with respect to temperature when the volume is held constant.
 dU 
cv   
 dT v
 The first law may be written for a closed stationary system:
Q  ΔE  W
Total Energy  E   U  KE  PE  ΔE  ΔU  ΔKE  ΔPE
Q  ΔU  W
For a process in the absence of work other than pdV work
δQ  dU  δW
δQ  dU  pdV
When the volum e is held constant : dV  0
 δQ  dU   Q v   U v
2
  Q  v   c v dT
1
 Specific Enthalpy (h):
 The enthalpy of a substance, h, is defined as:
h  u  pv
 The first law may be written for a closed stationary system:

Q  ΔU  W
For a process in the absence of work other than pdV work
δQ  dU  δW
δQ  dU  pdV
When the pressure is held constant : p  constant
 δQ  dU+pdV
  Q  p   U  p  p  V  p
  Q  p   h 
  δQ  p  dh
 Energy of an isolated System
 An isolated system is one in which there is no interaction of the system with the surroundings.
δQ  0 ; and δW  0
dE  0  E  constant
 Perpetual Motion Machine of the 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 a perpetual motion machine of the first kind
 A PMM1 is thus impossible.
 There can be no machine which would continuously consume work without some other form of
energy appearing simultaneously
Q Q

W W

A PPM-1 The Converse of PPM-1

 First Law Applied to Flow Processes
 When there is mass transfer across the system boundary, the system is called an open system
 Control Volume: attention is focused upon a certain fixed region in space through which the
moving substance flows.
 In the system (closed) boundary usually changes shape, position and orientation relative to the
observer, the control volume boundary remains fixed and unaltered.
 The surface of the control volume which is known as the control surface
 Steady Flow Process: At the steady state of a system, any thermodynamic property will have a
fixed value at a particular location, and will not alter with time. Mass IN
Control
For any system and in any process, the first law can be written as : Surface
Q  ΔE  W
W
For a pure substance :
E  U  KE  PE
 Q  ΔU  ΔKE  ΔPE  W Q

Mass OUT
 Mass Balance and Energy Balance in a Simple Steady Flow Process:
 There is no accumulation of mass or energy within the control volume,
 The properties at any location within the control volume are steady with tim e
A1 , A2  cross-sectional area m 2   dQ
m1 , m 2  mass flow rate  kg s  dt C.S.
p1 , p2  absolute pressure N m 2   m2


v1 , v 2  Specific Volume m 3 kg 
u1 , u2  specific internal energy  J kg 
V1 , V2  velocity m s m1
Z2 dW
Z1 , Z 2  elevation  m  dt
δQ Z1
  net rate of heat transfer through C.S. J s
δt
δW
  net rate of work transfer through C.S. J s
δt
 Mass Balance in a Simple Steady Flow Process:
Mass balance:
m1  m 2  mass flow rate  kg s 
 v1  v 2  volume flow rate  kg s 
dQ
 ρ1 A1V1  ρ2 A2V2  mass flow rate  kg s  dt C.S.
A1V1 AV m2
  2 2  mass flow rate  kg s 
v1 v2
 Mass Energy in a Simple Steady Flow Process:
Enegy balance:
m1
Q  E+W Z2 dW
W  Winternal  Wexternal dt
Z1
δWinternal  p2 v 2 dm 2  p1v1dm1
δW  δWinternal  δWexternal
δW  δW x  p2 v 2 dm 2  p1v1dm1
E  ΔU  ΔKE+ ΔPE
e  Δu  Δke+ Δpe
 Energy Balance in a Simple Steady Flow Process:
 V12   V22 
e1  u1    + gZ 1 ; e2  u2    + gZ 2
 2   2 
  V12     V22  
E1  m1  u1    + gZ 1  ; E 2  m 2  u2    + gZ 2 
  2     2  
  V22     V12  
Q  m  u2    + gZ 2    u1    + gZ 1   +W x  p2 v 2 m  p1v1 m
  2     2   
  V22     V12  
Q  m  h2    + gZ 2    h1    + gZ 1   +W x
  2     2   
δQ δm   V22     V12    δWx
  h2    + gZ 2    h1    + gZ 1   +
δt δt   2     2    δt
  V22     V12  
q   h2    + gZ 2    h1    + gZ 1    w x
  2     2   
 V22 V12 
q  w x   h2  h1      + g  Z 2  Z1 
 2 2 