Department of Chemistry

Thermodynamics II

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Test Yourself
1) If Ssurr = Ssys , the process is at equilibrium. True/False
2) For any process, Ssurr and Ssys have opposite signs.
True/False
3) As long as the disorder of the surroundings is increasing, a
process will be spontaneous. True/False

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Why Are Some Changes

Spontaneous & Some Are Not?
What is the driving force for spontaneity?
Examples of spontaneous processes:
a gas expands to fill the vessel, a hot object cools to
the temp of its surroundings, iron + water + O2 rust

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Spontaneous Processes
A process that is spontaneous occurs without outside
intervention/without work done
A non-spontaneous change can be brought about
only by doing work
Driving force for a spontaneous change: tendency of
energy & matter to disperse in disorder
40 oC

25 oC
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Entropy S
Measure of the disorderly dispersal of energy or matter
Entropy increases as disorder increases
(order disorder)
(fewer microstates more microstates)
(lower entropy higher entropy)
Entropy (S) is related to the number of ways that a
system can distribute its energy, which in turn is closely
related to the freedom of motion of the particles and the
number of ways they can be arranged
S is a state function

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Lower entropy

Higher entropy

How many ways (microstates) can each arrangement

(state) be achieved?

the number of microstates, the probability of

occurrence of the arrangement
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Ludwig Boltzmann:
S = k In W
k = Boltzmann constant = R/NA = 1.38 x 10-23 J K-1
W = number of microstates
S has units of J K-1

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What is the sign of S?

N2 (g) + 3H2 (g) 2NH3 (g)
S __ 0

A phase change
S __ 0 in going from solid
to liquid to gas

Unfolding of a protein from a compact conformation to a more

flexible comformation
S __ 0

Association of 2 reactants to form a more compact structure

S __ 0

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Second Law of Thermodynamics

In any spontaneous process, there is always an increase
in the entropy of the universe
Suniv = Ssys + Ssurr
We need to consider the entropy of both the system &
surroundings when deciding whether or not a process is
spontaneous.
Suniv > 0: spontaneous
Suniv < 0: non-spontaneous
Suniv = 0: system is at equilibrium
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Entropy Change
q rev
S
T

For an isothermal process (constant temperature process)

T is in Kelvin

Entropy change of a system is equal to the energy transferred as

heat to it reversibly divided by the temp at which the transfer
takes place.
Reversible transfer of heat (qrev) is smooth, careful, restrained
transfer between 2 bodies at the same temp.
What does temp appearing in the denominator signify?
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q rev
S
T
dqrev = nCp,mdT

qrev = Htransition

T2
S nC p,m ln( )
T1

Stransition = Htransition/T

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S & Temperature Change

What if T changes from T1 to T2 at constant pressure?

T2
S nC p,m ln( )
T1

If T2 > T1, S > 0

If T2 < T1, S < 0

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Calculate S for the process where 5.4 moles of liquid water at 18 C

is heated to 70 C. The entire process takes place at 1 atm. Given: Cp,m
of water = 75.3 J K-1 mol-1
Constant pressure process

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S & Phase Transition

Melting, freezing, vaporization, condensation are reversible
processes taking place at a constant pressure & temp
In general,
Stransition = Htransition/T

H vap
T

H fus
S
T

Fusion and vaporization are endothermic processes, hence S

are +ve values. Entropy increases when a substance vaporizes
or melts.

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The protein lysozyme, an enzyme that breaks down bacterial

cell walls, unfolds at a transition temp of 75.5 oC, and the
standard enthalpy of transition is 509 kJ mol-1. Find the Sotrs.
Stransition = Htransition/T

Entropy increases as the lysozyme unravels into a long, flexible

chain that can adopt many different conformations, hence
dispersal of matter & energy.
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If you are asked to calculate the change in entropy when 2.00

moles of water is heated from 50 oC to 150 oC, what information
do you need?

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Entropy Change of Surrounding

At constant temp & pressure:
Ssurr

Hsys
T

Suniv = Ssys + Ssurr

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Consider the binding of oxidized nicotinamide adenine

dinucleotide (NAD+) to enzyme lactate dehydrogenase. It is given
that rSo = -16.8 J K-1 mol-1. Does this mean that the process of
NAD+-enzyme complex formation is non-spontaneous?

Suniv = Ssys + Ssurr

Given that rHo = -24.2 kJ mol-1, hence at 25 oC,

Hence reaction is spontaneous. The spontaneity is a result of the

dispersal of energy that the reaction generates in the
surroundings.
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We cannot determine the absolute values of H & G, we

can only determine H and G.
But we can determine absolute entropy S.

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Third Law of Thermodynamics

The entropy of a perfect crystal at 0 K is zero.

A perfect crystal has absolute regular arrangement.

Molecular motion virtually ceases. Only 1 way to
achieve this perfect order. S = k In W

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Starting from S = 0 at T = 0 K, and

T2
S C p ln( )
T1
S

H phase change
T

we can easily calculate the standard entropy value at a

particular temp.

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Calculate So of a substance at 393 K.

x

So393K = S0K +S
So393K = S =
Cp,solid In(T2/T1) + Hfus/Tfus +
Cp,liq In(T3/T2) + Hvap/Tvap +
Cp,gas In(T4/T3)

T1

T2

T3

T4

Equation assumes that the T interval is small enough that the T

dependence of Cp can be neglected.
T1 has to be ~0 K, e.g. 0.0001 K
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rSo = vSoproducts vSoreactants

rHo = vfHo (products) vfHo (reactants)

So : standard entropy; entropy of a substance in its standard state

at the temp of interest
v are the stoichiometric coefficients in the chemical equation

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The enzyme carbonic anhydrase catalyses the hydration of CO2

gas in red blood cells:
CO2 (g) + H2O (l) H2CO3 (aq)
Find rSo at 25oC.
So of CO2 (g) = 213.74 J K-1 mol-1
So of H2O (l) = 69.91 J K-1 mol-1
So of H2CO3 (aq) = 187.4 J K-1 mol-1

rSo = vSoproducts vSoreactants

rSo =
=
Entropy is ve because a gas is consumed.

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Summary

Spontaneous and Non-spontaneous Processes

Entropy
Molecular Interpretation of Entropy
The Second Law of Thermodynamics
Entropy Changes
The Third Law of Thermodynamics
Standard Entropy

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