Chapter 2: Some Concepts

and Definitions

Thermodynamics 1
Thermodynamics system: It is
defined as „a quantity of matter or
a region in space chosen for study‟.

Surrounding: The region outside

the system is called surrounding.

Boundary: The real or imaginary

surface that separate the system
from its surroundings is called
boundary. It can be fixed or
movable.
Thermodynamics – Chapter 2 2
Closed, Open, and Isolated Systems
A closed system or Control mass consists of a fixed
amount of mass and no mass may cross the system
boundary. The closed system boundary may move.

Thermodynamics – Chapter 2 3
Examples of closed systems are sealed tanks and
piston cylinder devices (Note: The volume does not
need to be fixed).

Thermodynamics – Chapter 2 4
An open system, or control volume, has mass as
well as energy crossing the boundary, called a
control surface. Examples are pumps, compressors,
turbines, valves, and heat exchangers.

Thermodynamics – Chapter 2 5
An isolated system is a special case of a closed
system where no heat or work may cross the
boundaries. It is no interaction with the
surroundings. The universe by default is an isolated
system.
Isolated System Boundary

Heat = 0
Work
Work = 0 Surr 4
Mass = 0
Mass System
Across
Mass Surr 3
Isolated Surr 1 Heat
Boundary
Surr 2

Thermodynamics – Chapter 2 6
Macroscopic & Microscopic Approach
A substance consists of a large number of particles
called „molecules.‟ The properties of the substance
naturally depend on the behavior of these particles.
The behavior of a system may be investigated from
either a Microscopic point of view (statistical
thermodynamics) or Macroscopic point of view
(classical thermodynamics)

Thermodynamics – Chapter 2 7
Macroscopic & Microscopic Approach
 Microscopic approach (statistical thermodynamics):
In which, on the basis of statistical considerations
and probability theory, we deal with average values
for all particles under consideration.
 Macroscopic approach (classical thermodynamics):
Based on the gross or average effects of many
molecules. These effects can be perceived by our
senses and measured by instruments. However, what
we really perceive and measure is the time-averaged
influence of many molecules.
Thermodynamics – Chapter 2 8
Properties of a System
Any observable characteristic of a system is called a
property. Examples are pressure P, temperature T,
volume V, and mass m.

Not all properties are independent. Some are defined

in terms of other ones. For example,

Density is defined as the mass per unit volume,

m
  (kg / m )
3

V
Thermodynamics – Chapter 2 9
Specific gravity is the ratio of the density of a
substance to the density of some standard substance.

s 
H O (at 4 C)
o
2

Specific volume is defined as the volume per unit

mass:

V 1 3
m


m / kg 

Properties may be intensive or extensive.

Thermodynamics – Chapter 2 10
Extensive properties are those that vary directly
with size or content of the system.
Intensive properties are those that are independent
of the size of a system, such as temperature,
pressure, and density.

Thermodynamics – Chapter 2 11
If the value of any extensive property is divided by
the mass of the system, the resulting property is
intensive and is called a specific property.
Volume V  m 3

Eg. Specific volume v    
mass m  kg 

E  KJ 
Specific total energy e   
m  kg 

U  KJ 
Specific internal energy u   
m  kg 

Thermodynamics – Chapter 2 12
Examples of Properties:

Property Intensive Extensive symbol specific units

property
temperature √ T K
pressure √ p Pa (N/m²)
internal energy √ U u J/kg
volume √ V v m³/kg
mass √ m kg
dynamic viscosity √ µ Ns/m²
velocity √ V or c m/s
entropy √ S s J/kgK
enthalpy √ H h J/kg

Thermodynamics – Chapter 2 13
State and Equilibrium
The state of a system is the condition of the system
described by the values of its properties.

Thermodynamics – Chapter 2 14
A system is said to be in thermodynamic
equilibrium if it maintains thermal, mechanical,
phase and chemical equilibrium. Thermodynamics
deals with equilibrium states.

Thermal equilibrium requires that the temperature

be uniform throughout the system.

Thermodynamics – Chapter 2 15
Mechanical equilibrium implies an equality of
pressure throughout the system.

If a system involves two phases, it is in phase

equilibrium when the mass of each phase reaches
an equilibrium level and stays there.

A system is in chemical equilibrium if its chemical

composition doesn‟t change with time, that is, no
chemical reactions occur.

Thermodynamics – Chapter 2 16
Process and Path
Any change that a system undergoes from one
equilibrium state to another is called process.
The series of states through which a system passes
during a process is called the path of the process.

Thermodynamics – Chapter 2 17
When a process proceeds in a
very slow manner that the
system remains infinitesimally
close to equilibrium state at all
times, it is called a quasi-static,
or quasi-equilibrium process.

Thermodynamics – Chapter 2 18
The quasi-equilibrium process is an idealized
process. But many actual processes closely
approximate it, and they can be modeled as quasi-
equilibrium with negligible error.

Engineers are interested in quasi-equilibrium for

two reasons:
 They are easy to analyze.
 Work-producing devices deliver the most work
when they operate on quasi-equilibrium process.

Thermodynamics – Chapter 2 19
Process diagrams plotted with thermodynamics
properties as co-ordinates are very useful in
visualizing the process. The P-V diagram of a
compression process is shown below.

Thermodynamics – Chapter 2 20
The prefix iso- is often used to designate a process
for which a particular property remains constant.
Some of these processes are

Process Property held constant

isobaric Pressure
isothermal Temperature
isochoric Volume
isentropic Entropy
isenthalpic Enthalpy

Thermodynamics – Chapter 2 21
Cycle
A system is said to have undergone a cycle if it
returns to its initial state at the end of the process.

The change in any property „y’ for a cycle is

mathematically given by  dy  0
Where the symbol  denotes
P 2 Process
B
the cyclic integral for the
closed path. “The cyclic
Process
A
integral of a property is
1
always zero.”
V

Thermodynamics – Chapter 2 22
 A property change for a
process with given end
states 1 and 2 is described
mathematically
2

 dy  y
1
2  y1  y

“The change in the value of a property that occurs

when a system is altered from one equilibrium
state to another is always the same, regardless of
the process used to bring about the change.”

Thermodynamics – Chapter 2 23
The State Postulate (State Principle)
 The state of a system is described by its
properties.
 No need to specify all the properties in order to
fix a state.
 The number of properties required to fix the state
of a simple, homogeneous system is given by the
state postulate:
“The thermodynamic state of a simple
compressible system is completely specified by
two independent, intensive properties.”

Thermodynamics – Chapter 2 24
A system is called a simple compressible system in
the absence of electrical, magnetic, gravitational,
and surface tension effects. These effects are due to
external force fields and are negligible for most
engineering problems.

Otherwise, an additional property needs to be

specified for each effects that is significant. If the
gravitational effects are to be considered, the
elevation z needs to be specified in addition to the
two properties necessary to fix the state.

Thermodynamics – Chapter 2 25
Independent properties:
 One property can be varied while the other one is
held constant.
 Temperature and specific volume are independent
properties.
 p and T are independent properties in single-phase
systems.

Dependent properties:
 Function of independent property (or properties).
 p = f(T) or T = f(p) in two-phase systems.

Thermodynamics – Chapter 2 26
What is Energy?
 Viewed as the capacity to do work or the ability
to cause changes.
 It can be stored within a system and can be
transferred from one system to another.
 From the molecular view point:
 Intermolecular potential energy (forces between
molecules).
 Molecular kinetic energy (translational velocity of
individual molecules).
 Intramolecular energy (molecular and atomic
structure and related forces).

Thermodynamics – Chapter 2 27
 From the macroscopic view point:

Energy that is transferred as

heat, the change in properties,
and the total amount of
energy (relative to some base)
water contains at any instant.

How energy is stored in the

water don‟t concern.

Thermodynamics – Chapter 2 28
Specific Volume and Density
Specific volume is defined as the volume per unit
mass.
V 1
 
m 
 m /kg 
3

Density is defined as the mass per unit volume.

m
 (kg/m3 )
V
Both of them are intensive properties.

Thermodynamics – Chapter 2 29
If atmosphere is considered a system, the specific
volume increases as the elevation increases.
Therefore, the definition of specific volume
involves the specific volume at a point in a system.

V
v  lim
 V  V   m

 V   Smallest volume for which the mass

can be considered continuum

The continuum limit for the specific volume

Thermodynamics – Chapter 2 30
 Fluid as a Continuum

• Molecules are widely spaced in

the gas phase. However, we
can disregard the molecular
nature of a substance.
• View it as a continuous,
homogeneous matter with no
holes, that is, a continuum.
• This allows us to treat
About 3×1016 molecules of properties as smoothly varying
O2 in the tiny volume of
1 mm3 at 1 atm and 20oC quantities.

Thermodynamics – Chapter 2 31
 Fluid as a Continuum
• Continuum is valid as long as
size of the system is large in
comparison to mean free path
of the molecules.
• As a consequence of the
continuum, each fluid property
is assumed to have a definite
value at every point in space.
About 3×1016 molecules of
They are considered to be
O2 in the tiny volume of continuous functions of
1 mm3 at 1 atm and 20oC position and time.

Thermodynamics – Chapter 2 32
Mean Free Path
It is the average distance covered by a moving particle
(such as an atom, a molecule, a photon) between
successive impacts (collisions) which modify its
direction or energy or other particle properties.
Pressure in
Vacuum range Molecules / cm3 Molecules / m3 Mean free path
(mbar)
Ambient
1013 2.7 × 1019 2.7 × 1025 68 nm
pressure
Low vacuum 300 – 1 1019 – 1016 1025 – 1022 0.1 – 100 μm
Medium
1 – 10−3 1016 – 1013 1022 – 1019 0.1 – 100 mm
vacuum
High vacuum 10−3 – 10−7 1013 – 109 1019 – 1015 10 cm – 1 km
Ultra high
10−7 – 10−12 109 – 104 1015 – 1010 1 km – 105 km
vacuum
Extremely high
<10−12 <104 <1010 >105 km
vacuum

Thermodynamics – Chapter 2 33
Pressure
 Defined as normal force per unit area.
 If δA is a small area, δÀ the smallest area over
which we can consider the fluid a continuum, and
δFn the component of force normal to δA, we
define pressure, P, as
 Fn
P  lim
 A A  A

 The pressure P at a point in a fluid at rest is the

same in all directions (Pascal’s law).
Thermodynamics – Chapter 2 34
 SI unit for pressure is Pa (Pascal) = 1 N/m2
1 bar = 105 Pa = 0.1 MPa = 100 kPa

 Standard atmosphere is defined as the pressure

produced by a column of mercury (13595 kg/m3)
exactly 760 mm (29.92 in) in height at 273.15 K
and under standard gravitational acceleration
(9.80665 m/s2).

1 atm = 760 mm Hg = 29.92 in Hg = 1.01325 bars

= 1.01325 × 105 N/m2 = 14.696 lbf/in2 or psi
(pound-force per square inch).

Thermodynamics – Chapter 2 35
 The pressure in a fluid increases with depth as a
result of the weight of the fluid (Fig. a).
 Pressure in a liquid at rest increases linearly
with distance from the free surface (Fig. b).

Fig. a Fig. b

Thermodynamics – Chapter 2 36
 The pressure in a gas tank may be considered to
be uniform since weight of the gas is too small to
make a significant difference.

Thermodynamics – Chapter 2 37
The pressure is same at all points on a horizontal
plane in a given fluid regardless of geometry,
provided that the points are interconnected by the
same fluid.

Thermodynamics – Chapter 2 38
Absolute pressure: The actual pressure at a given
position is called the absolute pressure. It is
measured relative to absolute vacuum, that is,
absolute zero pressure.

Note: Pressure values in numerical problems must

be absolute. If atmospheric pressure is not given
use standard value.

Absolute, gauge, and vacuum pressures are all

positive quantities.

Thermodynamics – Chapter 2 39
Gauge pressure: Most pressure measuring devices
are calibrated to read zero in the atmosphere, and so
they indicate the difference between the absolute
pressure and the local atmospheric pressure. This
difference is called the gauge pressure.

Fig: Some basic pressure gages

Thermodynamics – Chapter 2 40
Vacuum pressure: Pressures below atmosphere are
called vacuum pressure and are measured by
vacuum gages that indicate the difference between
the atmospheric pressure and the absolute pressure.

Thermodynamics – Chapter 2 41
 2
2
2

vacuum gages that indicate the difference between

the atmospheric pressure and the actual (absolute)
pressure. The difference is known as vacuum
pressure.
Thermodynamics – Chapter 2 42
Pabs = Pgauge + Patm (for pressure above Patm)
Pabs = Patm – Pvacc (for pressure below Patm)
Thermodynamics – Chapter 2 43
Barometer: Apparatus used to measure atmospheric
pressure; derived from the Greek word "baros"
meaning "weight“. Created by Evangelista
Torricelli in 1646.

Patm A   gh A
Patm   gh
Thermodynamics – Chapter 2 44
Consider a fluid column of height H standing above
point B in the manometer. The force acting
downward at point B is P0 A + mg  P0 A + ρAHg
upward force = PB A
upward force = downward force
PB A = P0 A + ρgHA
PB - P0 = ρgH
Since points A and B are at
the same elevation Example of pressure
P = PA = PB  measuring using a
column of fluid.
ΔP = P – P0 = ρgH
Thermodynamics – Chapter 2 45
Equality of Temperature
Two bodies have equality of temperature if, when
they are in thermal contact, no change in any
observable property occurs.

This is the only requirement for thermal

equilibrium.
Thermodynamics – Chapter 2 46
Zeroth Law of Thermodynamics
If two bodies are in thermal equilibrium with a third
body, they are also in thermal equilibrium with each
other. This simple fact is known as the zeroth law
of thermodynamics.

Thermodynamics – Chapter 2 47
Thermometric properties
Several properties of materials change with
temperature in a repeatable and predictable way, and
this forms the basis for accurate temperature
measurement. Any such property is called a
thermometric property.
Commonly used properties of materials employed in
temperature-sensing devices include

1. Volume of gases, liquids, and solids : eg. glass

thermometer.

Thermodynamics – Chapter 2 48
2. Pressure of gases at constant volume: eg.
constant-volume thermometer.
3. Electrical resistance of solids : electrical
resistance sensors involves both normal
conductors (such as platinum) as well as
semiconductors. Eg. Resistance temperature
detectors (RTD)
4. Electromotive force of two dissimilar solids :
eg. Thermocouples.
5. Intensity of radiation (high temp): eg. Optical
pyrometers.
Thermodynamics – Chapter 2 49
Temperature Scale
• Temperature scales aim at using a common basis
for temperature measurements.
• All the temperature scales are based on some
easily reproducible states, the freezing and
boiling point of water, also called the as the ice
point and the steam point.
• The temperature of the ice point is defined as the
temperature of a mixture of ice and water that is
in equilibrium with saturated air at pressure of
1 atm .
Thermodynamics – Chapter 2 50
• The temperature of the steam point is the
temperature of water and steam, which are in
equilibrium at a pressure of 1 atm.
• The temperature scales in SI and English system
are the Celsius scale (formerly called the
centigrade scale) and the Fahrenheit scale.
• On Celsius scale, the ice and steam points are
assigned the values 0 and 100oC, respectively.
The corresponding values on the Fahrenheit scale
are 32 and 212oF. These are often referred to as
two-point scales.

Thermodynamics – Chapter 2 51
 Comparison of magnitude of
various temperature units

Comparison of temperature scales

Thermodynamics – Chapter 2 52
A more useful temperature scale in TD is the
thermodynamics temperature scale or absolute
scale. They are Kelvin scale and Rankine scale.
Independent of the properties of any substance or
substances.

Thermodynamics – Chapter 2 53