Lecture 2

THERMODYNAMICS

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Zeroth Law of Thermodynamics
• When two bodies have equality of temperature
with a third body, they in turn have equality of
temperature with each other.
• Consider two blocks of copper. Let one block be
brought into contact with the thermometer until
equality of temperature is established and then
remove it. Then let 2nd block be brought into
contact with thermometer. Suppose that no
change in the level of thermometer occurs.
• We can say that both blocks are in thermal
equilibrium with the given thermometer.
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 Thermodynamics Equilibrium
– Thermal Equilibrium (Temperature)
– Mechanical Equilibrium (P dV)
– Chemical Equilibrium
– Phase Equilibrium
• Quasi-static / Quasi Equilibrium

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 Thermodynamics Concept of Energy

• Energy as Point function

– State
– Properties
• Energy as Path Function
– Work Transfer
– Heat Transfer

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 Types of Work Transfer
• Displacement or PdV Work
• Paddle wheel work
• Shaft work
• Flow work

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 First Law of Thermodynamics
• Joules Experiment
– Stirred liquid in adiabatic closed container,
containing a thermometer and calculated
change in temperature.
– Added heat from other body and noted the
same raise in temperature
– Placed the container in (another) big
container, containing cold liquid and found
that heat has transferred from hot liquid

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Sign Convention of Work and Heat
• Heat added to the system is taken to be
Positive
• Work done by the system is Positive

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 First Law of Thermodynamics
(For Cyclic Process)
Cyclic Process. A cyclic process is one which returns the
system to the state it was in before the process began.
• First Law Definition.
1. Whenever a closed system executes a cycle, the net amount
of work done by the system is equal to the net amount of heat
added to the system during the cycle.

ƩQ - Ʃ W = 0

∮ᵟQ- ᵟW = 0
• The internal energy of the system is the same at the
beginning and end of the cycle.

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 First Law of Thermodynamics
(For Cyclic Process)
2. Whenever a system undergoes a cyclic change, the algebraic
sum of the work (or net work output) is proportional to the
algebraic sum of the heat transfer (the net heat input).

First law is also called law of conservation of energy.

3. “Energy can be neither created nor destroyed, although it can
be stored in various forms and can be transferred from one
system to another as heat or work.”

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 First Law of Thermodynamics
• Consider a closed system which is comprised of a gas in a
rigid vessel fitted with a paddle wheel. If work is done on the
gas by means of the paddle wheel (process A), the
temperature of the gas will rise. Then heat must be removed
from the gas (process B) in order to restore the gas to its
initial state.
• During process A, there is work done but no heat transfer.
• During process B, there is heat transferred but no work done.
• During the complete cycle, there is a net work input and a net
heat transfer from the system.
• As the amount of work input is increased, the amount of heat
that must be removed to restore the system to its initial state
increases proportionally.

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 Practice Problem 1

• A closed system passes from state 1 to state 2

while 40kJ of heat is added and 60kJ of work is
done. As the system is returned to state 1, 35kJ
of work is done on it. What is the heat transfer
during process 2-1. (Ans: -15kJ)

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 First Law of Thermodynamics
(For Non-Cyclic Process)
Non Cyclic Process

• Consider a process in which the intrinsic energy of the system

is finally greater than the initial intrinsic energy. The sum of
the net heat supplied and the net work input has increased
the intrinsic energy of the system i.e.
∮ᵟQ- ᵟW = 0 as ∮dx=0
So ᵟQ- ᵟW = dX
• dX = dU + d(KE) + d(PE)
• Gain in intrinsic energy = Net heat supplied - net work input

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 First Law of Thermodynamics
(For Non-Cyclic Process)
• Gain in intrinsic energy = Net heat supplied - net work input
• Gain in internal energy in changing from state 1 to 2 can be
written as
• U2 – U1

• Or for unit mass, specific internal energy

q - w = u2 - u 1

ᵟQ = dU + PdV - - - (Closed System-quasi static)

𝛿𝑄 𝛿𝑊 𝑣22 𝑣12
− = ℎ2 −+ 𝑔𝑧2 − ℎ1 − + 𝑔𝑧1 - - - (Open System)
𝛿𝑚 𝛿𝑚 2 2
𝛿𝑄 𝛿𝑊
− = ℎ2 − ℎ1
𝛿𝑚 𝛿𝑚
where, “h” is Enthalpy of system = u + Pv 13
 Practice Problem 1

• The internal energy of a closed system changes

from 300 to 260 KJ/Kg while the system
performs 20 KJ/Kg of work. Compute the heat
transfer. (Ans : - 20 KJ/Kg)

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 Practice Problem 2,3
• In the compression stroke of an internal combustion engine
the heat rejected to the cooling water is 45 kJ/kg and the
work input is 90 kJ/kg. Calculate the change in specific
internal energy of the working fluid stating whether it is a gain
or a loss. (Ans : 45kJ/kg)

• In the cylinder of an air motor the compressed air has a

specific internal energy of 420kJ/kg at the beginning of the
expansion and a specific internal energy of 200 kJ/kg after
expansion. Calculate the heat flow to or from the cylinder
when the work done by the air during the expansion is
100kJ/kg. (Ans : 120 kJ/kg)

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 Limitations of First Law
• Direction of Heat Transfer
• Mutual transformation of Work and Heat
• The rate of Heat transfer

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 Heat Engine
• A heat engine is a system that receives heat and produces
work by executing a cycle. Heat engine may be as simple
as a gas confined within a cylinder fitted with a piston or as
complex as an entire power plant.

• Thermal Efficiency of Heat Engine.

• Net Work out put :

Wnet = W out – W in

• for a closed system and cycle

Wnet = Q in – Q out

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 Heat Engine
• thermal efficiency, ɳth = net work out put
heat input

Q in – Q out
ɳth = _________
Q in

ɳth = 1 - Q out
Q in

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 Heat Engine
Heat engines have the following characteristics:

• Receive heat from a high temperature source

• Convert part of this heat to work
• Reject remaining heat to a low temperature sink
•Operate in a cycle

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• The second law of thermodynamics states that
processes occur in a certain direction, not in just
any direction.
• Physical processes in nature can proceed
towards equilibrium spontaneously. For
example:

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 Heat always flows from high
temperature to low temperature

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Water always flows downhill

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Can We Take Advantage of These
Naturally Occurring Processes?

• Yes!! We can use them to produce

work
• Or… we can just let them happen
and lose the opportunity

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Can we reverse these processes?
• It requires the expenditure of work.
• The first law:
– Gives us no information about the direction
in which a process occurs!
– It only tells us that energy must balance.
• The second law tells us what direction
processes occur.

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 The Second Law
• Can be defined in many ways!
• But most widely used definitions are those
stated by:
– Clausius
– Kelvin-Planck

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 2ND Law Of Thermodynamics
• Two well known statements of 2nd law of
thermodynamics are:

• Clausius Statement. It is impossible for any device

to operate in such a manner that it produces no
effect other than the transfer of heat from one body
to another at a high temperature.

Impossible

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 Clausius Statement

In order to accomplish heat

transfer from cold to hot body:
you need a device that
consumes work, e.g.
refrigerator

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 Refrigerators
The transfer of heat from a low temperature medium to high
temperature requires special device called Refrigerator.

Refrigerators like Heat Engine are cyclic devices. The

working fluid used in the refrigeration cycle is called
Refrigerant.

A system which absorbs heat from some low temperature

parts of its surroundings (food compartment) and
discharges heat to some other parts of surroundings at a
higher temperature while executing a cycle is called
Refrigerator.

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2ND Law Of Thermodynamics
• Kelvin Plank Statement. It is impossible for any
device that operates in a cycle to receive heat from a
single reservoir and produce a net amount of work.

Impossible

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Thus the Kelvin-Planck statement of the
second law of thermodynamics may be
presented as:
“No heat engine can produce a net amount
of work while exchanging heat with a single
reservoir only”
i.e. it needs both, a source and a sink, to
produce work!

In other words:
“The maximum possible efficiency of a heat
engine is always less than 100%”
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Enthalpy. It is defined as the heat content per
unit mass.

It is also defined as the sum of internal energy

and the system’s volume multiplied by pressure
exerted by the system on the surroundings.

H = U + PV
H = u + Pv

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Experiments show that it takes different amount
of energy to raise the temperature of identical
mass of different substances by one degree.

Specific Heat. It is defined as the energy

required to raise the temperature of a unit mass
of a substance by one degree.

In thermodynamics, we analyze two kinds of

specific heats :
• Specific heat at constant volume cv
• Specific heat at constant presssure cp
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Experiments show that :
Cn = dQ
dT
Where Cn = an experimental factor called
Specific Heat.

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Specific heat at constant volume cv. It is defined as
the change in internal energy of a substance per unit
change in temperature at constant volume.
cV = du
dT
Specific heat at constant pressure cp. It is defined as
the change in enthalpy of a substance per unit change
in temperature at constant pressure.
cp = dh
dT

Where h is a property called enthalpy

h = u + Pv (specific enthalpy)
H = U + PV (Total Enthalpy) 34
Reversible and Irreversible Process
A process of a system is reversible if the system
and all parts of its surroundings can be exactly
restored to their respective initial state after the
process has taken place.

• Once a cup of hot coffee cools, it will not heat

up by retreaving the heat it lost by the
surroundings itself. If it could, the surroundings
as well as the system (coffee) would be
restored to their original condition and this
would be a reversible process. Processes that
are not reversible are called irreversible.
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QUESTIONS ?

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