3.

0 The 2nd Law of Thermodynamics

3.1 Introduction
1st law tells us that for a system undergoing a

change of state, the consequent change in internal

energy of the system, which is dependent only on
the initial and final states, is equal to the algebraic
sum of the heat and work effects i.e.

 It states that a chemical reaction is feasible at

constant T and P if the H is negative.

The law does not explain the magnitudes that q
and w may have and the factors that govern
these magnitudes i.e. it does not explain the
efficiency of converting q into w
Many spontaneous reactions satisfy the above
criterion (i.e. ve H) , but there are also many
spontaneous reactions that have +ve values of
Hrxn !!!

 e.g. CaCO3 decomposes spontaneously at about

900oC into CaO and CO2 absorbing a lot of heat

in the process (endothermic).
In another example, the phase transformation of
tin,
According to the 1st law of the thermodynamics,

grey tin should exist at 25oC

However in reality white tin is found to exist as
the stable form at that temperature

 Therefore the law does not provide a complete

criterion of whether a reaction will occur or not

There is need to define another thermodynamic
property which can provide spontaneity of a given
reaction. This is obtained from 2nd Law

3.2 Spontaneous or Natural

Processes
For an isolated system (left on its own), either of

the following will occur

o If the system is initially in equilibrium with its
surroundings, it will remain in its equilibrium
state.
o If the initial state is not the equilibrium state,
the system will spontaneously move toward its
equilibrium state.

 A process which involves the self-

generated movement of a system from a

non-equilibrium state to an equilibrium
state is called a natural or spontaneous
process
Determination of the equilibrium state is of
prime importance in thermodynamics, as it
allows us to predict the stability and
direction in which any reaction will
proceed from its initial state

3.3 Reversible and Irreversible

processes
A process in which the system and surroundings

can be restored to the initial state from the final

state without producing any changes in the
thermodynamics properties of the universe is
called as the reversible process
suppose that the system has undergone change
from state A to state B

 If the system can be restored from state B to

state A, and there is no change in the universe,

then the process is said to be reversible process.

 A reversible process can be reversed completely

leaving no trace left to show that the system had

undergone thermodynamic change
For this to happen there are 2 important
conditions:
o the process should occur in infinitesimally small time

and
o all the initial and final state of the system should be in
equilibrium with each other

 In actual practice the reversible process never

occurs, thus it is an ideal/hypothetical process.

For example;
o Wood will burn spontaneously in air if ignited, but the

reverse process, i.e., the spontaneous recombination

of the combustion products to wood and oxygen in air,
has never been observed in nature!
o Ice at 1 atm pressure and a temperature above 0C
always melts spontaneously, but water at 1 atm
pressure and a temperature above 0C never freezes
spontaneously in nature.
o Heat always flows spontaneously from higher to lower
temperature systems, and never the reverse

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 These are typical natural processes and

they are irreversible.

Thus for an irreversible process
o The initial state of the system and surroundings

cannot be restored from the final state

o During the process the various states of the
system on the path of change from initial state
to final state are not in equilibrium with each
other

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3.4 Statement of 2nd Law

The 2nd law has been expressed in various ways.
According to Clausius: No process is possible

whose sole result is the transfer of heat from a

colder body to a hotter body
According to Kelvin and Planck: No process is
possible whose sole result is the complete
conversion of heat into work.
Simply put: spontaneous/natural processes are
not thermodynamically reversible

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3.5 Heat and work exchange in

Reversible and Irreversible
Processes
For a system undergoing a process, let the

maximum work that the system can do be

wmax.
For a reversible process, w = wmax and from
1st law

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 However for an irreversible reaction the amount

of work done w, is less than wmax because some

of the energy available to do work is converted
into heat, and the total heat of the system
increases.
i.e. Total heat entering the system (qtot) = heat
entering from surroundings (q) + heat
produced by degradation of work due to
irreversibility (wmax-w) or (qr-q)

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 The fact that less heat enters from the

surroundings in the irreversible process than in

the reversible process is due to the heat
produced by the degradation of work in the
irreversible process (e.g. pulley-paddle wheel assembly)

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 Therefore an irreversible process is one in

which the system is degraded during the

process.
extent of degradation differs from process to
process.
This suggests that there exists a quantitative
measure of the extent of degradation, or degree
of irreversibility, of a process

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3.5 Entropy
Consider a reversible process in which the

system absorbs an infinitesimal quantity of heat

q in a reversible manner at a temperature T.
The term q/T defines the degree of irreversibility
of the process and is called entropy change (S)

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 Entropy (S) is an extensive property as it depends

on the mass of the system (its values are additive

just like enthalpy)
It is a thermodynamic property: i.e. depends on the
final state of the system and not on its history!
Entropy is not directly measurable, but entropy
changes are calculated from measurable quantities
such as temperature, pressure, volume and heat
capacity
It represents the degree of disorderliness of a
system

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 The greater the dispersal of energy or matter in

a system, the higher is its entropy

Adding heat to a material increases the disorder
or entropy of the system.
Unit of S is J/K and that of molar entropy is
J/K.mol.

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 In evaluating entropy, it is important to distinguish

between the system and the surroundings.

The total entropy change associated with the process
consists of two terms:
o Entropy change of the system : Ssys
o Entropy change of the surroundings : Ssurr,

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 Recall that the total heat appearing in the system

is the sum of heat entering from the surroundings

(q) and heat produced by degradation due to
irreversibility (qr - q) [eqn 3.1]
We can deduce that the heat of the system

From which
The total heat leaving the surroundings is q . i.e.

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 Negative sign indicates that relative to the

surroundings the heat is lost

Thus
combining equations 3.4 and 3.5 into equation

3.3 gives us

i.e.

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3.6 Entropy Change for a

Reversible Process
For a reversible process the sum of entropy

change of the system and the surroundings is

always zero.
Since
It implies

And
Thus
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 Total entropy gain of the system is equal to

entropy loss by the surroundings

And for infinitesimal changes,

Simply put: there is no creation or degradation

of entropy; it is only interchanged between

system and surroundings

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3.7 Entropy Change for an

Irreversible Process
For an irreversible (or spontaneous) process, the

sum of entropy change of the system and its

surroundings is always a positive quantity
Since
It implies,
And

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 Thus;
Or,
There is a net creation of entropy and this is due

to the degradation of work due to its irreversible

nature.

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3.8 Entropy change for a chemical

reaction
entropy change accompanying a chemical

reaction is defined as the difference between

the sum of the entropies of all products and
the sum of the entropies of all reactants.
Thus for a reaction,
The entropy change;

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 Where SM, SN, are the entropies per mole of

the various substances.

If the reactants and products are in their standard
states, then the entropy change becomes
standard entropy change of reaction

Where SoM, SoN . refer to the standard molar

entropies of the various substances.

The entropy change of a reaction is generally
evaluated at constant T an P
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 Entropy values of elements and compounds are

calculated with the help of the 3rd Law of

thermodynamics and values at 298K and 1atm
are given, just like enthalpy values.
Example 3.1
Calculate the standard entropy change for the
reaction
<Cr2O3> + 3<C> = 2<Cr> + 3(CO) at 298K
Given:
So298<Cr2O3> = 81.17 J/K/mol
So298<C> = 5.69 J/K/mol
So298<Cr> = 23.76 J/K/mol
So298(CO) = 197.90 J/K/mol
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3.9 Variation of Entropy Change

with Temperature
If there is change of state of a system such that

the temperature changes, the entropy change

accompanying such a process can be calculated
by integrating between the limit of the
temperature

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 Where ST2 and ST1 are the entropies of the

system at temperatures T2 and T1, respectively

And since

It follows that

Or

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 The reference entropy is usually that at 298K,

thus
And for substances in their standard state, the

expression becomes;

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 In the case of a chemical reaction involving

reactants and products in their standard states,

the changes in standard entropies and heat
capacities must be considered
Eqn 3.11 becomes
If there is any phase transformation taking place

between T1 and T2, then the entropy changes

accompanying such transformations must be
added

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 The eqn becomes;

Example 3.2
Zinc melts at 420oC and its standard entropy at
25oC is 41.63 J/K/mol. Calculate the standard
entropy of zinc at 750oC.
Given: Hfusion<Zn> = 7.28 kJ/mol
Cp<Zn> = 22.98 + 10.04 x 10-3 T J/K/mol
Cp[Zn] = 21.38 J/K/mol

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3.10 Entropy as Criterion for

Equilibrium or Spontaneity
The entropy function is useful in metallurgical

operations in determining the direction in

which a process will proceed and the final
equilibrium state of the process.
For a chemical reaction proceeding from initial
state A to final state B, then
Stotal = SB,total - SA,total

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 In an isolated system of constant internal energy

and constant volume,

o If Stotal = 0, then the system is at equilibrium
and no spontaneous change will occur
o If Stotal > 0, the reaction will occur
spontaneously from sate A to state B
o If Stotal < 0, the reaction will occur
spontaneously in the reverse direction i.e.
from state B to state A

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 Thus for a chemical reaction within a system will

have positive affinity to take place (or

spontaneous) if it leads to an increase in entropy,
without there being any exchange of heat with the
surroundings.
Most chemical reactions may be carried out
either reversibly or irreversibly, but more heat is
absorbed from the surroundings if the reaction is
carried out in a reversible manner.

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3.11 Heat Engines

work can easily be converted to other forms of

energy, but converting heat to work requires the

use of some special devices
A heat engine is a device for converting heat into
work. (e.g., steam engine, internal combustion
engine)
They differ considerably from one another, but all
can be characterized by the following:

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 They receive heat from a high-temperature

source (solar energy, oil furnace, nuclear reactor,

etc.)
They convert part of this heat to work (usually in
the form of a rotating shaft)
They reject the remaining waste heat to a lowtemperature sink (the atmosphere, rivers, etc.)
They operate on a cycle.

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 The maximum work obtained from the operation of

a heat engine is that generated when all the

processes are reversible i.e. without degradation of
work.
The Carnot cycle (after French Engineer Sadi
Carnot) is the operation of an ideal (reversible)
engine in which heat transferred from a hot
reservoir, is partly converted into work, and partly
discarded to a cold reservoir.

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 Work done by the engine for each cycle

w = w1 + w2 - w3 -w4
(w3 and w4 have negative signs because the
system will be contracting)
From 1st law U = q-w = 0 for a cyclic process

and q = q2 q1 = w
Efficiency of the engine is defined as

=
=
=
=

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 Also, the entropy change for each cycle

Scycle = S1 + S2 + S3 + S4 = 0
In this case

=

And therefore

=
=

Thus the efficiency depends only on the

temperatures of the reservoirs, and is

independent of the nature of the engine, working
substance, or the type of work performed
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 A Carnot engine can be run in reverse and used

to transfer energy as heat from a low

temperature reservoir to a high temperature
reservoir
The device is called a heat pump, if it is used as
a heat source
If it is used to remove heat then it is a
refrigerator
In that case work has to be done on the engine.

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