Thermodynamics

• Thermodynamics may be defined as the science

of energy
• Energy can be viewed as the ability to cause changes
• therme + dynamis
• First law is simply an expression of energy
principle
• The second law asserts that energy has quality
as well as quantity and actual processes occur
in the direction of decreasing quality.
A substance consists of a large number of
particles called molecules. The properties
of the substance naturally depend on the
behavior of the particles.
The macroscopic approach to study of thermodynamics
provides a direct and easy way to the solution of
engineering problems. This does not require a
knowledge of behavior of individual particles. This
approach is also named CLASSICAL
THERMODYNAMICS.
A more elaborate approach, based on average behavior of large
groups of
individual particles is called
STATISTICAL THERMODYNAMICS or Microscopic approach
and is rather involved
Application areas
 Systems and control volumes
• A system is defined as a quantity of matter
or region in space chosen for study.
• The mass or region outside the system is
called the surroundings.
• The real or imaginary surface that
separates the system from surrounding is
called the boundary.
 SURROUNDINGS

SYSTEM

BOUNDARY
 Characteristics of a boundary
• The boundary of a system can be fixed or
movable.
• The boundary is a contact surface shared
by both the system and surroundings.
• Mathematically, the boundary has a zero
thickness and thus it can neither contain
any mass nor occupy any volume in
space.
 Closed system
• A closed system consists of fixed mass
and no mass can cross its boundary. But
energy, in form of heat or work, can cross
the boundary and the volume of a closed
system does not have to be fixed.
• If , in a special case, even energy is not
allowed to cross the boundary that system
is called an isolated system.
 Open system
• An open system usually encloses a device
that involves mass flow such as a
compressor, turbine or nozzle.
• Flow through these devices is studied by
selecting the region within the device as
the control volume.
• The boundaries of a control volume are
called a ‘control surface’ and they can be
real or imaginary.
 PROPERTIES OF A SYSTEM
• Any Characteristic of a system is called a
property.
• Intensive properties are independent of
the mass of system.
• Extensive properties are those properties
whose value depend on the size- or extent
of the system.
• Extensive properties per unit mass are
called specific properties.
 Thermodynamic property
• It refers to the characteristic describing the
condition or state of a system
– It is a measurable characteristic describing the
system.
– It has a definite unique value when the system is in a
particular state.
– It is dependent only on the state of the system; it does
not depend on the path or route, the system follows to
attain that particular state.
– Its differential is exact.
 Properties
• Temperature
• Pressure
• Volume
• Colour
• Composition etc
• dP
• dZ
 Properties
• A given expression is a property if its
differential is exact

• dP = M dx + N dy is exact if
Partial derivative of M wrt y =
Partial derivative of N wrt x
 Properties
Which of the below listed terms are
properties?

p dv + v dp;
p dv;
v dp;
(v/T) dp + (p/T) dv subject to pv=RT
dT/T + p/T dv subject to pv = RT
 Continuum
• It is 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 allows us to treat
properties as point functions and to assume the
properties vary continually in space with no jump
discontinuities.
• This idealization is valid as long as the size of
the system we deal with is large relative to the
space between the molecules.
 Continuum
Oxygen
1 atm, 20 degree C

Void
 Rarefied gas flow theory
• Application limited to very high vacuums or
very high elevations
• For atmospheric air at elevation of 100km
the mean free path is 0.16m!
 Equilibrium
• Equilibrium implies State of balance.
• Thermal equilibrium
20 23
• Mechanical equilibrium 30

• Chemical equilibrium 35 40

30 30
30
30 30
 State postulate
• The state of a simple compressible system
is completely specified by two
independent, intensive properties

T=300 K
v=0.9cum/kg
 PROCESSES AND CYCLES
• Any change that a
system undergoes from State 2
one equilibrium state to
another is called a
process, and the series
of states through which State 1
a system passes during
a process is called the
path of the process.
 Quasistatic process
• When a process proceeds in such a
manner that the system remains
infinitisimally close to equilibrium state at
all times, it is called a quasistatic or quasi-
equilibrium process. This can be viewed
as a sufficiently slow process.

QUASI-EQUILIBRIUM NON-QUASI-EQUILIBRIUM
 PROCESSES AND CYCLES
• Quasi-equilibrium process is an idealized
process and is not a true representation of
an actual process.
• A non-quasi-equilibrium process is
denoted by dashed line between initial
and final states
 Processes and cycles
• The prefix iso- designates process for
which a particular property remains
constant
– Iso thermal process
– Iso baric process
– iso choric/iso metric process
• A system is said to have undergone a
cycle if it returns to its initial state at the
end of the process. For a cyclic process
the initial and final states are identical.
 The steady flow process
• Steady: No change with time
• Uniform: No change with location
 Temperature and
the zeroth law of thermodynamics

Iron Iron
150 C 60 C

Copper Copper
20 C 60 C

Two bodies reaching thermal equilibrium after being brought into contact in
an isolated enclosure
 Temperature and
the zeroth law of thermodynamics
• If two bodies are in thermal equilibrium
with a third body, they are also in thermal
equilibrium with each other.
• Two bodies are in thermal equilibrium if
both have the same temperature reading
even if they are not in contact.
• R H Fowler (1931)
 TEMPERATURE
• IS ASSOCIATED WITH THE
ABILITY TO DISTINGUISH HOT
FROM COLD
• ZEROTH LAW IS THE BASIS OF
TEMEPRATURE MEASUREMENT
• The working fluid • Thermometric
substance
• Characteristic • Thermometric
varying property
• Reference body • Temperature

THERMOMETER
 MEASUREMENT OF TEMPERATURE
METHODS

Note

X – Thermometric property
θ (X): Temperature at X
 Temperature on linear scale

• θ (X)= aX, where a is an arbitrary

constant
• θ (X2)= [θ (X1)/X1].X2
 Temperature measurement methods

• θ (X1)/ θ (X) = X1/X

• θ (X2)/ θ (X) = X2/X

[θ (X1)- θ (X2)] / [θ (X)] = [X1-X2] / X

 Temperature measurement methods

θ (X)=[{θ (X1)- θ (X2)} / (X1-X2)]X

 Temperature scales
Scale Ice point Steam point

Degree Celsius 0 100

Degree Farhrenheit 32 212
Kelvin 273.15 373.15
Rankine 491.67 671.67
Try this
• Same numeric value is obtained
in degree Centigrade and degree
Fahrenheit scale for a particular
bath. In Kelvin scale and degree
Rankine scale what would be the
value of this temperature.
 Try this
• A new temperature scale in degree N
is designed with ice point 100 degree
N and steam point 400 degree N.
What shall be the reading
corresponding to 150 degree C? At
what temperature both the Celsius
and the new temperature scale
reading would be same?
 Temperature Scales
• Temperature scales enable us to
use a common basis for
temperature measurements.
• These are based on easily
reproducible states called fixed
point.
 Measurement of Temperature
• Before 1954 two fixed points were used

–Ice point :Ice-Air saturated water

equilibrium at 1 atm.

–Steam point: Pure water-Pure

steam at 1 atm.
 Temperature measurement
• Limitations with 2 fixed point method

1. Difficulty of achieving equilibrium

between ice and air-saturated water
2. Extreme sensitiveness of the steam point
to the change in pressure

Only one fixed point then!

 Temperature measurement
methods (after 1954)
• θt = a Xt
• a = θt / Xt = 273.16/ Xt
• θ = (273.16/Xt) X
• θ = (273.16) (X / Xt)

θt = Triple point of water = 273.16 K

 Types of thermometers

• Constant • θ = (273.16) (p/pt)

volume gas
thermometer
 Types of thermometers

• Constant • θ = (273.16) (V/Vt)

pressure gas
thermometer
 Types of thermometers

• Electrical • θ = (273.16) (R/Rt)

resistance
thermometer
 Types of thermometers

• Thermocouple • θ = (273.16) (e/et)

 Types of thermometers

• Liquid-in- • θ = (273.16) (L/Lt)

glass
thermometer
Fact: Gas is chosen as
the standard
thermometric
substance
 Pressure is defined as a normal
force exerted by a fluid per unit area
 Do U compute the number of
molecules or count the collision
with wall or use software program
to find the net rate of change of
momentum to get the pressure?
I use a
barometer or
manometer
to determine
it.
• SI unit of pressure, i.e , Pascal is too
small. The pressure exerted by 102 gm
object on 1sqm table.
• In practice we use kPa and MPa
• Other units are
• 1 bar = 0.1 Mpa
• 1 atm = 1.01325 bar
• 1 atm =14.696 psi
• 1 kgf/cm2=9.807X104 Pa
 Pressure effects
• Snow shoes are large
• Sharp knives need lower effort
• Discomfort for a man with excessive
weight while standing
• Standing on one foot only!
Absolute, gage and vacuum pressure

P
gage
P
atm
P
vac P
abs
P P
atm atm
P
abs
 Facts
• Pressure is not a vector!
 Density

Compute the density of a substance, 2 kg of which occupies 0.4 cubic metre.

Density = Mass/Volume

Just a minute!
Will the density be different if we
consider 1 kg of mass
Equation of state of an ideal gas

• pv = RT
• pV=mRT
• pV0=MoRT
 Gas constants
• Air (28.97) • 0.287
• H2(2) • 4.124
• N2 (28) • 0.297
• O2 (32) • 0.260
• He (4) • 2.077
• CO2 (44) • 0.189
M0 R = 8.314 kJ/kg mol K
 Try this!
• A pressure bottle stores 5 cubic
metre of an inert gas at a
pressure of 10 MPa and
temperature 300K. Make
calculations for the mass, density
and specific volume of the gas.
Molecular mass is 28.
Ans: m= 561.3 kg
Density = 112.26 kg/cubic m
Specific volume = 0.0089 cubic
m/kg
 Try this!
• Two spheres each of capacity 2 cum, are
connected by a pipe with a valve inserted
in between. Sphere 1 contains Oxygen at
50 kPa and 320K. Sphere 2 contains
Oxygen at 45 kPa and 290K. The valve is
opened and the entire system is allowed to
come to equilibrium. If temperature at this
equilibrium is 300 K, determine final
pressure neglecting volume of the pipe.
• Ans 45.94kPa