MODULE 4:

THE LAWS OF
THERMODYNAMICS

4.1 Zeroth Law of Thermodynamics

4.2 The First Law
4.3 The Second Law
4.4 The Third Law
 Laws of thermodynamics
0th
– Definition of temperature
• Systems at different temperatures exchange
energy until reaching a thermal equilibrium
1st
– Conservation of energy
• heat is a form of energy
2nd
– Entropy of an isolated system never decreases
• perpetual motions of machines is impossible
3rd
– Entropy at absolute zero temperature (0 K)
• it is impossible to cool a system until zero
Laws of thermodynamics

ZEROTH LAW
Zeroth Law of Thermodynamics
 Zeroth Law of Thermodynamics
- definition of temperature

If A anb C are at thermal equilibrium, i.e. at the same

temperature, and B and C are at thermal equilibrium, then it follows that
A and B are at thermal equilibrium, then it follows that A and B are at
thermal equilibrium, i.e. at the same temperature
 TEMPERATURE AND THE ZEROTH LAW OF
THERMODYNAMICS
• 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.
• By replacing the third body with a thermometer, the zeroth law can
be restated as two bodies are in thermal equilibrium if both have the
same temperature reading even if they are not in contact.

Two bodies reaching

thermal equilibrium
after being brought
into contact in an
isolated enclosure. 6
Laws of thermodynamics

FIRST LAW
THE FIRST LAW OF THERMODYNAMICS
 THE FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics (conservation of energy
principle) states that energy can neither be created nor destroyed
during a process; it can only change forms.
The net change (increase or
decrease) in the total energy of
the system during a process is
equal to the difference between
the total energy entering and the
total energy leaving the system
during that process.

The energy balance for any

system undergoing any process
in the rate form

9
In heat transfer problems it is convenient to
write a heat balance and to treat the
conversion of nuclear, chemical,
mechanical, and electrical energies into
thermal energy as heat generation.

10
 The First Law of Thermodynamics
• Heat and work are equivalent

• Energy is conserved in any transformation

• The change of energy of a system is independent of the path taken

Energy can be neither created nor detroyed

E = q - w or dE = dq - dw dE = dq - P dV

E = internal energy P = pressure

q = heat V = volume
w = work
 Conservation of Energy
The total amount of energy in a closed system remains constant over
time (are said to be conserved over time)
– The increase in the internal energy of a system is equal to the
amount of energy added by heating the system minus the
amount lost as a result of the work done by the system on its
surroundings.
• Energy cannot be created nor destroyed
• Energy can change form (for example chemical to thermal)
QUESTIONS:

A) Which among the following statements are correct?

(1) Energy is an extensive property
(2) Specific energy is an extensive property
(3) Energy is a point function
(4) Heat capacity is an extensive property

a. Statement (1), (2) and (3)

b. Statement (1), (3) and (4)
c. Statement (2), (3) and (4)
d. Statement (1), (2), (3) and (4)
ANSWER:
Statement (1), (3) and (4)

Explanation:

We know that, when a system changes from state 1 to state 2, the

change in internal energy (ΔE) of the state 2 is same as that of the state
1. Therefore value of internal energy of the system is independent of the
path followed by the system. It has a fixed value along the path,
therefore energy is the point function [statement (3) is correct]. But
energy changes with mass of the body, therefore it is an extensive
property [statement (1) is correct]. Specific energy is the energy of the
system per unit mass of the system, therefore it will become intensive
property [statement (2) is wrong]. Heat capacity is the product of specific
heat and mass of the body. It depends on mass of the system, therefore
heat capacity is an extensive property.
QUESTIONS:

Total amount of energy in the universe is

a. increasing
b. decreasing
c. constant
d. none of the above
ANSWER:

constant

EXPLANATION:
The first law of thermodynamics states that the energy can neither
be created nor be destroyed. It can only get transformed from one form to
another form. The universe consists of the system as well as the
surrounding together. Energy can only be transferred from system to
surrounding or surrounding to system in various forms, but it can never be
destroyed or created. Thus the total amount of energy in the universe is
constant. We cannot produce a device which can supply mechanical work
without consuming any energy.
QUESTIONS:
Consider the below diagram of heat transfer and work transfer for a
system. What will be the first law equation for the below system?

a. (Q1 – Q2) = ΔE – ( W2 + W3 – W1 )
b. (Q1 + Q2) = ΔE + ( W2 – W3 + W1 )
c. (Q1 – Q2) = ΔE + ( W2 + W3 – W1 )
d. none of the above
ANSWER:

C) (Q1 – Q2) = ΔE + ( W2 + W3 – W1 )
When a system undergoes cycle, then the algebraic sum of
all energy transfer across the boundaries is zero. But when a system
undergoes a change of state in which both heat transfer and work
transfer are involved, the net energy transfer is stored and collected
within the system. If Q is the amount of heat transferred to the system
and W is the amount of work transferred from the system during the
process, then the net energy (Q – W) is stored in the system. This
energy is neither heat nor work but it is called as internal energy(ΔE).
Q – W = ΔE
Therefore,
Q = ΔE + W
QUESTIONS:
A system changes its state from state 1 to state 2 through path A and
returns from state 2 to state 1 through path B. Path C is also an alternate
returning path from state 2 to state 1 as shown in figure. What will be the effect
on change in internal energy of the system(ΔE), if the system undergoes these
different paths A, B and C?

a. ΔE of path C will be greater then ΔE of path B and path A

b. ΔE of path A and path C are equal but ΔE of path B is different than rest
c. ΔE of all the paths are equal
d. none of the above
ANSWER:
c) ΔE of all the paths are equal

According to the description of path given, through the path A and path B system undergoes
cycle,
Writing the first law equation for path A,
QA = ΔEA + WAand for path B,
QB = ΔEB + WB

The processes A and B together constitute a cycle, for which

(∑ W)cycle = (∑ Q)cycle
WA + WB = QA + QB
QA – WA = WB – QB
ΔEA = – ΔEB

Similarly, when the system returns from state 2 to state 1 through path C,
ΔEA = – ΔEC

Therefore,
ΔEB = ΔEC

Therefore above equations show that the change in internal energy between two states of
the system is the same, no matter which path may system follow.
Laws of thermodynamics

SECOND LAW
The Second Law of Thermodynamics
 The Second Law of Thermodynamics
• It is impossible to construct a machine that is able to convey heat
by a cyclical process from one reservoir at a lower temperature to
another at a higher temperature unless outside work is done
(i.e, air conditioning is never free)

• Heat cannot be entirely extracted from a body and turned into work
(i.e., an engine can never run 100% efficiently) — a certain fraction
of the enthalpy of a system is consumed by an increase in entropy

• Every system left to itself will, on average, change toward a

condition of maximum randomness — entropy of a system
increases spontaneously and energy must be spent to reverse this
tendency
Entropy (S)
Thermodynamics
– Measure of uniformity of the distribution (quality) of energy
Information
– For a system whose exact description is unknown, its entropy is
defined as the amount of information needed to exactly specify the
state of the system
Entropy increases in nature
Temperature differences between systems in contact with each other
tend to even out and that work can be obtained from these non-
equilibrium differences, but that loss of heat occurs, in the form of
entropy, when work is done
– In a system, a process that occurs will tend to increase the
total entropy of the universe
– Heat generally cannot flow spontaneously from a material at
lower temperature to a material at higher temperature
(Clausius)
– It is impossible to convert heat completely into work in a cyclic
process (Kelvin)
Reversible and Irreversible Processes
Reversible (ideal)
– system and surroundings can be restored to the initial state from
the final state without producing any changes in the
thermodynamics properties
• it should occur infinitely slowly due to infinitesimal gradient
• all the changes in state occurred in the system are in
thermodynamic equilibrium with each other
Irreversible (natural)
– All processes in nature are irreversible
• Finite gradient between the two states of the system
– heat flow between two bodies occurs due to temperature
gradient between the two bodies;
QUESTIONS:

A) Match the following irreversibilities

(1) Mechanical irreversibility ------ (A) Refrigeration cycle

(2) Thermal irreversibility --------- (B) Forming of water by combination
of Hydrogen and Oxygen
(3) Chemical irreversibility -------- (C) Free expansion of gas in a
system
(4) External irreversibility --------- (D) Melting of ice cube under the
sunlight

a. (1)-(A), (2)-(B), (3)-(C), (4)-(D)

b. (1)-(A), (2)-(D), (3)-(B), (4)-(C)
c. (1)-(C), (2)-(D), (3)-(A), (4)-(B)
d. (1)-(C), (2)-(D), (3)-(B), (4)-(A)
ANSWER:

D. (1)-(C), (2)-(D), (3)-(B), (4)-(A)

If the irreversibility is due to a finite pressure gradient, it is called as

mechanical irreversibility. Thus, free expansion of gas in a system is the
example of mechanical irreversibility.

It the irreversibility is due to a finite temperature gradient, it is called as

thermal irreversibility. Thus, melting of ice cube under the sunlight is the
example of mechanical irreversibility.

If the irreversibility is due to a finite concentration gradient or chemical

reaction in the system, it is called as chemical irreversibility. Thus, forming
of water by combination of Hydrogen and Oxygen is the example of
mechanical irreversibility.

In refrigeration cycle, irreversibility occurs due to temperature difference

between the source and a working fluid that is refrigerant at heat supply and
the temperature difference between the sink and the refrigerant at heat
rejection.
QUESTIONS:

2) When a process becomes irreversible due to

heat interaction between system and surrounding at
the boundary due to finite temperature gradient,
then the irreversibility is______

a. internal irreversibility
b. external irreversibility
c. mechanical irreversibility
d. chemical irreversibility
ANSWER:

B. external irreversibility
All the spontaneous processes are irreversible in nature. The
irreversibility is caused by finite potential gradient like temperature
gradient etc. or by any dissipative effect like friction. There are two
types of irreversibility

i.) Internal irreversibility

ii.) External irreversibility

The external irreversibility occurs due to the temperature difference

between the source and a working fluid at heat supply and the
temperature difference between the sink and the working fluid at
heat rejection. If the hypothetical heat source and sink is
considered then the process becomes reversible.
QUESTIONS:

To achieve a definite zero point on the Kelvin

scale, we have to violate

a. first law of thermodynamics

b. second law of thermodynamics
c. both first law and second law of
thermodynamics
d. no law has to be violated
ANSWER:
B. second law of thermodynamics
To achieve a definite zero point on the Kelvin scale or absolute zero temperature scale, we have to
consider a series of reversible engines, passing from a source at T1 to lower temperatures. Consider
the following diagram,

Series of heat engines

The heat engine E1 is operating between temperatures T1 and T2.

Therefore,

( T1 / T2 ) = ( Q1 /Q2 )

( T1 – T2 ) / T2 = ( Q1 – Q2 ) / Q2

( T1 – T2 ) = ( Q1 – Q2 ) ( T2 / Q2 )

Similarly,

( T2 – T3 ) = ( Q2 – Q3 ) ( T3 / Q3 )
and so on

If we make this series of heat engines continue so that the total work output equals to heat supplied
Q1. This means there will not be any heat rejection and definite zero point on the Kelvin scale is
achieved. But as there is no any heat rejection means total heat supplied is completely converted into
work output. This condition violates the second law of thermodynamics.
Laws of thermodynamics

THIRD LAW
Entropy at absolute zero (0 K)
As a system approaches absolute zero, all processes cease and the
entropy of the system approaches a minimum value
– decreasing entropy of a system requires increasing the
entropy of surroundings
The Third Law
 For substances in internal equilibrium, undergoing an isothermal process, the
entropy change goes to zero as T (in K) goes to zero.

lim S  0
T 0

 The law is valid for pure substances and mixtures.

 Close to Zero Kelvin, the molecular motions have to be treated using quantum
mechanics → still it is found that quantum ideal gases obey the third law.

Phenomenological description of the third law.

 There does not exist any finite sequence of cyclical process, which can cool a
body to zero Kelvin (absolute zero).