KENYATTA UNIVERSITY

SCHOOL OF PURE AND APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY
BSc. and BSc. Analytical & Industrial Management
SCH 201/211 CHEMICAL THERMODYNAMICS

LEVEL : II SEMESTER: I ACADEMIC YEAR: 2022/2023

Second and Third Laws of Thermodynamics

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THE SECOND LAW OF THERMODYNAMICS
Introduction
•For a particular process or change, the first law helps us
balance the books, so to speak, on the heat released,
work done and so forth. [q=ΔE + w]

•However, it says nothing about whether the process

or change we specify can in fact occur.

•That question is encompassed in the second law of

thermodynamics.

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Introduction Con’t:
Examples of Spontaneous Processes
• If you drop a brick, it falls to the floor

• A shiny nail left outdoors eventually rusts

• Expansion of an ideal gas into an evacuated space.

Reverse not spontaneous

• If we add solid KCl to a glass of water at room

temperature, we feel the solution growing colder as the
salt dissolves. Endothermic and yet spontaneous.

• At a temperature of 0 ˚C ice spontaneously absorbs

heat from the surrounding to turn into a liquid. 3
Introduction Con’t:
Which of the following processes are spontaneous? Which ones
are non-spontaneous?
a)Diffusion of perfume molecules from one side of a room to the
other side.

b) Heat flow from a cold object to a hot object.

c) Decomposition of rust (Fe2O3.H2O) to iron, oxygen and water

d) Decomposition of solid CaCO3 to solid CaO and gaseous CO2 at

25 ˚C and 1 atm pressure.

(a) Spontaneous while (b), (c) and (d) are nonspontaneous

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Introduction Con’t):
Conclusion:

In each instance, the product of the process are

in a more random or disordered state than the
reactants

In addition to enthalpy, the change in

randomness or disorder of a chemical system is
extremely important in determining whether
equilibrium favours reactants or products.

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Introduction Cont.:
The second law of thermodynamics expresses the notion that there
is an inherent direction in which any system moves if it is not at
equilibrium.

For example

• If you drop a brick, it falls to the floor

• Water placed in a freezer compartment turns into ice

• A shiny nail left outdoors eventually rusts

• Processes that are spontaneous in one direction are not

spontaneous in the reverse direction.
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Introduction (cont.):
• SPONTANEITY is associated with an increase in randomness
or disorder of a system.

• This randomness is expressed by a thermodynamic quantity

called ENTROPY, given a symbol S expressed in units of J/K
(not kJ/K). The more disordered a system, the larger its entropy.

• ENTOPY is an absolute quantity, not a relative quantity.

Therefore the entropy of a substance is S , not ∆S

• Entropy is a state function. ∆S > 0 indicates an increase in

randomness or disorder. ∆S < 0 indicates a decrease in
randomness or disorder.

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Question
By considering the relative extents of randomness or disorder in
the reactants and products, predict whether ∆S is positive or
negative for each of the following processes.

(a) H2O(l) →H2O(g)

(b) Ag+(aq) + Cl-(aq) →AgCl(s)

(c) 4Fe(s) + 3O2(g) →2Fe2O3(s)

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Prediction for ΔS sign:
• It is possible for a system to be disfavoured by enthalpy
(endothermic, +ve ΔH), yet be spontaneous because its strongly
favoured by entropy (+ve ΔS). For example melting of ice [ΔH =
+6.01 kJ/mol and ΔS =+22 J/(K.mol)].

• Ethane, C2H6 can be prepared by the reaction of acetylene

(C2H2) with hydrogen.
C2H2(g) + H2(g) → C2H6(g)
Is ΔS˚ for the reaction positive or negative? Explain.

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Prediction for ΔS sign (cont.):

Predict whether ΔS˚ is likely to be positive or negative for each

of the following reactions.
a) C6H6(l) + 7.5 O2(g)  3H2O(l) + 6CO2(g)

b) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

c) C(s) + O2(g) → CO2(g)

d) HC≡CH(g) + H2(g) → H2C=CH2(g)

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 The Second Law of Thermodynamics:
To develop a statement, we must think of an ISOLATED system,
one that does not exchange energy or matter with the surroundings.

• When a process occurs spontaneously in an isolated system,

the system always end up in a more random state

• In the real word, we really deal with isolated systems. We are

usually concerned with systems that exchange energy with their
surroundings in the form of heat and work. If we consider the
entire universe as a giant isolated system, however, we can state
the second law as follows:

• In any spontaneous process, there is always an increase in the

entropy of the universe.

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 The Second Law of Thermodynamics:
• The second law tells us that the increase in the entropy of the
surroundings must be greater than the decrease in the entropy of
the system, so that the total entropy increases:

ΔSuniverse = ΔSsystem + ΔSsurroundings >0

• No process that produce order (a decrease in entropy) in a

system can proceed without producing an even larger disorder
(an increase in entropy) in its surroundings.

• Thus, while the energy of the Universe is conserved (the first

law), the entropy of the Universe continues to increase (the
second law)

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 The Second Law of Thermodynamics:
Other Statements of the Second Law
Clausius statement: It states that heat cannot flow itself from a
cold body to a hot body spontaneously without the intervention of
an external energy.

Kelvin statement: It is impossible to take heat from a hot body and

convert it completely into work by a cyclic process without
transferring a part of heat to a cold body.

Thus, the Second Law predicts the direction of heat flow. It

explains the reason for why complete conversion of energy into
work is not possible.
• It predicts the feasibility of a process
• It introduces two new thermodynamic functions entropy and free
energy to explain spontaneity.
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 The Second Law of Thermodynamics:
• Thus, even if the entropy of a particular system decreases in a
spontaneous process, the total change in the entropy (System +
Surroundings) must be positive.

• No process that produces order (a decrease in entropy ) in a

system can proceed without producing an even larger disorder (an
increase in entropy) in its surroundings.

• Thus, while the energy of the Universe is conserved (the first

law), the entropy of the Universe continues to increase (the
second law)

• Molecular systems therefore tend to move spontaneously toward

a state of minimum enthalpy and maximum entropy.

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To quantify entropy:
• To calculate disorder or chaotic distribution of energy among
molecules requires statistical method – DIFFICULT !!

• However, we can relate the process to the heat involved in a

process

• Whenever heat is added to the system, it increases molecular

motions causing increased randomness in the system. Thus heat
(q) has a randomising influence on the system.

• Can we then equate ΔS with q? WAIT!

• From experience, distribution of heat also depends on the
temperature at which heat is added to the system.

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 To quantify entropy:
• A system at higher temperature has greater randomness in it than
at lower temperature. Thus temperature is the measure of average
chaotic motion of particles in the system.

• Heat added to a system at a lower temperature causes greater

randomness than when the same quantity is added to it at a higher
temperature.

• Thus
• The change in entropy ΔS of a system is equal to the ratio of heat
change q to the temperature (T) of the reversible process.

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The Second Law of Thermodynamics:

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ENTROPY CHANGES FOR AN IDEAL GAS

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23
Entropy Changes for an Ideal Gas (Examples.) –cont.:

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Entropy Changes (Calculations):
Example:
Calculate the entropy change when 1 mole of a perfect gas expands
isothermally thus doubling its volume;

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Entropy Change accompanying Phase Change:

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Entropy Change accompanying Phase Change (examples):
Example:
Determine the entropy change when one mole of water at boiling
point is converted to steam given that the enthalpy of vaporization of
water is 40.85kJ/mol.
Solution:
Sv = Hv/Tb = 40850/373
= 109.5 J/K
Example:
The enthalpy of transition from rhombic to monoclinic sulphur at the
transition temperature of 95.6 oC is 0.361 kJ/mole. Determine the entropy of
transition.
Solution:
St = Ht/Tt = 361/368.6
= 0.98 J/K

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Entropy Change accompanying Phase Change (examples):
Example:
The enthalpy of fusion of monoclinic sulphur is 1.26 kJ/mole. Determine the
entropy change when two moles of monoclinic sulphur melts at 392 K.
Solution:
Sf = Hf / Tf = 2 x 1260/392
=6.43 J/K

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The Physical Significance of Entropy:
A characteristic of spontaneous processes is that they are
accompanied by an increase in the 'disorder' or 'chaos' of the
system. An expansion of a gas into a vacuum is accompanied by
an increase of entropy of the system. Since expansion of a gas is
accompanied by an increase in disorder, so is the increase in
entropy.

Further, fusion and vaporization are accompanied by increase in

entropy. This increase in entropy causes an increase in disorder
since the molecules of a liquid are less orderly than those in a
solid. Likewise the molecules of vapour are less orderly than those
of a liquid. Systems tend to a state of maximum entropy. A gas
will therefore tend to occupy all the space or volume available to
it.

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Entropy and the Third Law of Thermodynamics:

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Entropy and the Third Law of Thermodynamics:

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 Entropy and the Third Law of Thermodynamics (cont.):
The third law then makes it possible to obtain absolute entropies of
chemical substances from calorimetric measurements. The standard
reaction entropies can then be calculated. The entropy of a reaction is the
difference between the entropies of the pure separated products and the
pure separated reactants, all substances being in their states at the specified
temperature. The entropies of substances are usually reported at 1 atm.
pressure and 25oC. These are standard entropies and are indicated by a
superscript o.
ENTROPIES OF SOME SUBSTANCES AT 1 ATMOSPHERE AND 25 OC
SUBSTANCE SO(Jmol-1 K-1)
H2(g) 130.59
C(c, diamond) 2.44
C(c, graphite) 5.69
C(g) 157.99
CO(g) 197.91
CO2(g) 213.64
CH4(g) 186.19
C2H2 (g) 200.82
C2H4 (g) 219.45
C2H6 (g) 229.49
O2(g) 205.03
H2O(g) 188.72
H2O(l) 69.94 33
Entropy and the Third Law of Thermodynamics (cont.):
Examples

Determine the changes in entropy for the following reactions.

a) C2H2 (g) + H2(g) → C2H4 (g)

b) 2 C(s, graphite) + 3 H2(g) → C2H6 (g)

Solutions
a)
= 219-(200.82 + 130.59)

= -112.41J/K

b)
= 229.3 – (2x5.68 + 3 x 130.5)

= -173.56 J/K
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Summary:
The thermodynamic function, Entropy, is defined as a measure of chaos/disorder.
An increase in temperature at constant pressure is accompanied by an increase in
entropy.
The second law of thermodynamics can be stated as, “heat can not be completely
converted into an equivalent amount of work without causing other changes in
some part of the system or its surroundings". The law makes it impossible to
‘freely’ harvest energy from the warm tropical ocean water, for example. The law
is also stated as, “All natural or spontaneous processes are thermodynamically
irreversible in character”.
If the experimental values of the heat capacities at constant pressure divided by
the temperatures (CP/T) are plotted against the temperatures, then the area under
the curve between the initial and the final temperature will give the entropy
change. Alternatively, if the experimental values of the heat capacities at
constant pressure (CP) are plotted against the natural logarithm of the
temperatures, then the area under the curve between the logarithms of the initial
and final temperature gives the entropy change.
The entropy change for a process involving an ideal gas depends on the initial and
final temperature and volume.
The efficiency of the engine is the fraction of the heat taken in at the higher
temperature that is converted into work. 35
SAQs
1. 10 g of ice at 273K is added to 20g of water at 363K in an
insulated flask. The heat of fusion of ice is 6000 Joule per mole
and the specific heat capacity of water is 4.2 joule per Kelvin per
gram. Ignoring the heat capacity of the flask: (a). Determine the
final temperature of the system (b). Determine S for the system

2. Calculate the entropy change for the reaction:

2C(graphite) + 2H2(g) = 2C2H4(g)
given the following standard entropies at 25 oC in units JK-1mole-1;
C(graphite) 5.7
H2(g) 131.2
C2H4(g) 221.0

Answers:
[1] (a) 306.5 K. (b) 2.72 JK-1.
[2] –52.8 JK-1. 36
Entropy : Examples:

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Entropy : Examples:

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