Entropy and Free Energy

What is this resource and who is it for?

This is an Open Educational Resource designed to
summarise key concepts in thermodynamics that are
required for entry to an undergraduate course. The
resource is designed for 1st year undergraduates and
revisits ideas from A-level. It also begins to show how
they are applied early in a University course.
It is therefore anticipated that you will have some
knowledge of A-level chemistry before undertaking the
activity but even with good subject knowledge, there
should also be some material here you are unfamiliar
with.
This resource is not designed to support any specific
A-level specification but may also be used in schools
alongside other resources where appropriate.

Who made it?

Declan Fleming worked at the University of Bath as a Teacher
Fellow 2010-2011 as part of The Royal Society of Chemistrys work
under the National HE STEM Programme. Part of his remit was
looking into ways that e-learning can be used to support students at
the KS5/HE interface.

Learning Objectives
On completion of this activity you
should be able to
Relate entropy to the temperature
and state of a substance
Calculate S for the system and
surroundings
Calculate G
Use S or G to predict whether a
process will be spontaneous
Describe the limitations of S or
G for predicting whether a
reaction will occur
Appreciate
the
connection
between
entropy
and
the
distribution of energy between
quantised energy levels in the
system.

Related Resources
This resource builds on some of the
ideas presented in the activities on
dynamic equilibria.

Declans work is copyright The Royal Society of Chemistry.

The Royal Society of Chemistry 2010-11

Introduction to Entropy

People and animals can pass out

for many reasons. You can be
reasonably certain though that if
you were to see it happen, it
wouldnt just be because all of the
oxygen suddenly found itself on
one side of the room!
Image by: Kitby

The reason that some things

seem to happen and others
just dont, is down to entropy.

Image by: B Rosen

The Royal Society of Chemistry 2010-11

Introduction to Entropy (contd.)

O O
Nitrogen and other atmospheric gases
A

Probability: 0.5

The Royal Society of Chemistry 2010-11

Introduction to Entropy (contd.)

O O
Nitrogen and other atmospheric gases
O O

B
O

Probability = 0.52 = 0.25

O

B
The Royal Society of Chemistry 2010-11

Introduction to Entropy (contd.)

O

O
O
O

A
O

Probability: 0.53 = 0.13

B

O
O

Probability: 0.54 = 0.06

O
O

What about 1000

particles?

O O

O O

O O

O O

O O

O O

O O
O O

O O
O O

Probability: 0.56 = 0.02

O O

O O

O O
O O

Probability: 0.510 = 0.001

O O
O O

or a mole of
particles?
The Royal Society of Chemistry 2010-11

So what is Entropy?
Boltzmann
constant

Weight of the
configuration

Simplistic
definition alert!

Entropy is a measure of disorder or

randomness. The more ways you have
of arranging something, the higher its
entropy.
The units of entropy (S) are J K-1 mol-1
Entropy is deeply connected to energy.
Ludwig Boltzmann

Entropy is not the reason your bedroom

gets messy!

Image by: martinroell

The Royal Society of Chemistry 2010-11

The connection between entropy and energy

E

N!

O
O

1
O

1
O

Energy

Low T

W =

2!

2!

O O OO
O OO O

W =

O O
O O

2!

O O O
O O O

O O
O O

O
O

W =
n0! n1!

O O
O O

High T

2
1! x 1!

If we set a constant energy and number of

particles for our system, we need to look for
the arrangement which has the greatest
weight. This distribution follows an
exponential pattern and underpins the work
that Boltzmann did connecting energies of
particles to their temperature.
The Royal Society of Chemistry 2010-11

 The Royal Society of Chemistry 2010-11

Spontaneous Processes

A spontaneous process, once

started will continue towards
equilibrium without intervention.

Ink mixing with water

happens spontaneously

When ice is removed

from a freezer, it melts
spontaneously
Image by: Mike_tn

In
spontaneous
processes,
entropy increases but how do
we account for water freezing
spontaneously?
Image by: gagstreet

The Royal Society of Chemistry 2010-11

Image by: takkk

Image by:
Eugen Nosko
Image by: Alex Anlicker

Image by: Theresa Knott

Image by:
Andreas Ti
lle

The Royal Society of Chemistry 2010-11

We must consider the entropy not only

of
the
system,
but
of
the
surroundings..
Liquid
becomes
solid

Heat energy
released to
surroundings

Overall
increase
in
entropy

Energy

The Second Law of Thermodynamics

Ea

Reactants
H Heat
released to
surroundings

Products

Reaction
As the energy of the system decreases,
that energy is released to the
surroundings

The Second Law of

Thermodynamics:
In a spontaneous process,
the entropy of the Universe
increases.
Image by: stevendepolo
The Royal Society of Chemistry 2010-11

An example: Will ice melt at 5 C?

The entropy of the
Universe must increase
for a spontaneous
reaction

Change in heat
(Hfus)

S = Ssys + Ssurr

From data book

Will this value
be-1
-1
+22.0
J
K
mol
?
+ve or ve?

S = 22.0 + (-21.6)
= + 0.4 J K-1 mol-1

Ssurr =

qrev
T

Absolute Temperature
(Kelvin)

Image by: Mike_tn

Will this value be

? -(6010
+ve or ve?
J)

Ssurr =

278 K

= -21.6 J K-1 mol-1

The Royal Society of Chemistry 2010-11

Image by: Today is a Good Day

The Royal Society of Chemistry 2010-11

Entropy Questions Walkthrough

What is the change in entropy when steam condenses at

50.0 C?
Hvap = +44.1 kJ mol-1, Svap = +118 J K-1 mol-1

+ Hvap = -118 + 44100

S = -Ssys +
(273+50)
T

= +18.5 JK-1mol-1

Given the following information, calculate the boiling point of

ethanol.
Hvap = +38.56 kJ mol-1, Svap = +109.67 J K-1 mol-1.

0 = Ssys +

- Hvap
T

TSsys = Hvap

T=

Hvap
Ssys

-273

T=

38560
109.67

T = 351.6 K

T = 78.60 C
The Royal Society of Chemistry 2010-11

What can entropy not tell us about?

Lets look at an example of a
change we try to expect the
outcome of.

Sreaction = 5.7 3.4 = + 3.3 J K-1mol-1

Cdiamond Cgraphite

Entropy predicts that diamond should

spontaneously change into graphite .
But how fast?

Sdiamond = 2.4 JK-1mol-1

Sgraphite = 5.7 JK-1mol-1

Energy

Sreaction = Sproducts - Sreactants

Ea

Reactants
H Heat
released to
surroundings

Reaction
Image by: swamibu

Products

Image by: Hypocentre

The Royal Society of Chemistry 2010-11

Minimising Energy or Maximising Entropy?

Historically, chemists used to think

that reactions were driven by a
need to move to a lower, more
stable energy state. We now know
that this is only half the story
because we see endothermic
changes happening all the time.
Out of copyright

Weve seen that entropy is the driving

factor behind changes that occur around
us and we have seen how that can be
connected to enthalpy changes.
As chemists, it would be useful to us to
express the chances of a reaction
happening spontaneously in terms of the
entropy and enthalpy changes occurring
in the system.

S = Ssys + Ssurr
Ssurr =

Hsurr
T

The Royal Society of Chemistry 2010-11

Gibbs Free Energy

S = Ssys + Ssurr > 0 (1)

For spontaneous reaction, the entropy
of the universe must increase

Substitute (2) into (1)

Ssurr =

Hsurr
T

(2)

The entropy of the surroundings is

increased by the release of heat energy

Ssys + Hsurr > 0

Multiply by T

T
T Ssys + Hsurr > 0

Surroundings is negative of system

T Ssys - Hsys > 0

Rearranging

0 > H - T S = G

(kJ mol1)

The Royal Society of Chemistry 2010-11

Gibbs Free Energy

G = H T S

If G < 0 : reaction spontaneous

If G > 0 : reverse reaction spontaneous
If G = 0 : reaction is at equilibrium

100% Reactants
0% Products

50/50 mix

0% Reactants
100% Products

Progress of Reaction

100% Reactants
0% Products

50/50 mix

0% Reactants
100% Products

Progress of Reaction

The Royal Society of Chemistry 2010-11

Summary

Entropy increases with increasing temperature and as the state of a substance moves from solid to
liquid to gas.
S / G show only whether a reaction is feasible they cannot say how fast that reaction is likely to
proceed
The Second Law of Thermodynamics: In a spontaneous process, the entropy of the Universe
increases. S = Ssys + Ssurr > 0 for spontaneous change
The Gibbs Free Energy (the useful energy available to do work) will be less than zero for
spontaneous change (0 > H - T S = G)

Further Reading
Engorge yourself in entropy at http://entropysite.oxy.edu/
and
http://secondlaw.oxy.edu/
- this page is a good place to start:
http://entropysite.oxy.edu/students_approach.html
Chemistry3 : introducing inorganic, organic and physical chemistry,
Burrows, Price et al Oxford University Press 2009
The Royal Society of Chemistry 2010-11

Image Credits

By Abbey
Hendrickson

By Mike_tn

By
Phillip Howell

By B Rosen

By
stevendepolo

By delphwynd

By Kitby

By swamibu

By takkk

By martinroell

By
Hypocentre

By
Andreas Tille

By gagstreet

Out of copyri
ght

By
Alex Anlicker

The Royal Society of Chemistry 2010-11

Image Credits
This resource was created
by Declan Fleming.
By Eugen
Nosko

By Theresa
Knott

The content of this resource,

together with The Royal Society of
Chemistrys name, is subject to a
Creative Commons licence on an
Attribution, Non-Commercial,
Share-Alike basis.

By Today is a
Good Day

By
georgeogoodman

Other images public domain or

by Declan Fleming.

Thanks to David Read and

Ian
Williams
for
their
feedback on and input into
this resource.

The HE STEM Programme name

and logo are the name and
registered marks of the University
of Birmingham. To the fullest extent
permitted by law the University of
Birmingham reserves its rights I its
name and marks which may not be
used except with its prior written
permission.

The Royal Society of Chemistry 2010-11