Entropy & Free Energy: A Guide For A Level Students

ENTROPY &
FREE ENERGY
A guide for A level students
KNOCKHARDY PUBLISHING
2015
SPECIFICATIONS
ENTHALPY CHANGES
INTRODUCTION
This Powerpoint show is one of several produced to help students understand
selected topics at AS and A2 level Chemistry. It is based on the requirements of
the AQA and OCR specifications but is suitable for other examination boards.
Individual students may use the material at home for revision purposes or it may
be used for classroom teaching if an interactive white board is available.
Accompanying notes on this, and the full range of AS and A2 topics, are available
from the KNOCKHARDY SCIENCE WEBSITE at...
www.knockhardy.org.uk/sci.htm
Navigation is achieved by...

either clicking on the grey arrows at the foot of each page
or using the left and right arrow keys on the keyboard
ENTROPY
CONTENTS
• Spontaneous changes
• Free enthalpy and entropy
• Second Law of Thermodynamics
• Change of state
• Is a reaction spontaneous? - worked examples
FREE ENERGY & ENTROPY
SPONTANEOUS CHANGES
- occur in one particular direction and not the other
- take place without the need for work
Exothermic reactions are usually spontaneous

- this is because they go from higher to lower enthalpy
SPONTANEOUS CHANGES

However ...
Why should reactions with a positive DH value take place spontaneously ?
(some salts dissolve readily in water and the solution gets colder, not hotter)
ENDOTHERMIC
Energy is put in to
overcome the
electrostatic
attraction between
ions
SPONTANEOUS CHANGES

However ...
ENDOTHERMIC EXOTHERMIC
Energy is put in to Energy is released

overcome the as the ions are
electrostatic attracted to polar
attraction between water molecules
ions
SPONTANEOUS CHANGES

However ...
ENDOTHERMIC EXOTHERMIC
If the energy released when the ions dissolve is less than that put in to break up the lattice, the
overall process will be ENDOTHERMIC and the temperature of the solution will drop.
SPONTANEOUS CHANGES

However ...
This must mean that energy has to be put in for the reaction to take place
SPONTANEOUS CHANGES

However ...
This must mean that energy has to be put in for the reaction to take place
The answer is that enthalpy change DH does not give the full story.
Free energy changes, DG, give a better picture.
FREE ENERGY (G)
A reaction is only spontaneous if it can do work - it must generate free energy
A negative DG indicates a reaction capable of proceeding of its own accord

FREE ENERGY (G)
DG < 0 (- ive) Spontaneous reaction

DG > 0 (+ ive) Non-spontaneous reaction
(will be spontaneous in reverse direction)
DG = 0 The system is in equilibrium
FREE ENERGY (G)
DG < 0 (- ive) Spontaneous reaction

DG > 0 (+ ive) Non-spontaneous reaction
(will be spontaneous in reverse direction)
DG = 0 The system is in equilibrium
ENTROPY (S)
• Entropy (symbol S) is a measure of the disorder of a system
• The more the disorder, the greater the entropy
• If a system becomes more disordered, the value of DS is positive
• Values tend to be in JOULES - not kJ
DS = Sfinal - Sinitial
THE SECOND LAW
The Second Law of Thermodynamics is based on entropy and states that…
‘Entropy tends to a maximum’
This infers that... ‘all chemical and physical changes

involve an overall increase in entropy’
THE SECOND LAW

Entropy increases when • solids melt

• liquids boil
• ionic solids dissolve in water
• the number of gas molecules increases
• the temperature increases
THE SECOND LAW

Entropy increases when SOLIDS MELT
Regular arrangement Less regular arrangement;

of particles in solids more disorder in liquids
THE SECOND LAW

Entropy increases when LIQUIDS BOIL
Irregular arrangement; Random nature and disorder

some disorder in liquids of particles in a gas
THE SECOND LAW

Entropy increases when IONIC SOLIDS DISSOLVE IN WATER
Regular arrangement in Ions dissociate in water;

an ionic crystal lattice there is less order
THE SECOND LAW

Entropy increases when THE MOLES OF GAS INCREASE
Particles in gases move in a

random way. The more gas
molecules there are, the greater
the degree of randomness.
THE SECOND LAW

Entropy increases when THE TEMPERATURE INCREASES
Lower temperature; less Higher temperature; more

energy energy and more disorder
Free energy, enthalpy and entropy are related ... DG = DH - TDS
Special
case For a reversible reaction at equilibrium the value of DG is zero
If DG = ZERO then DH = T DS
and DS = DH
T
This occurs during changes of state (melting, boiling etc)
Free energy, enthalpy and entropy are related ... DG = DH - TDS
Special
case For a reversible reaction at equilibrium the value of DG is zero
If DG = ZERO then DH = T DS
and DS = DH
T
Worked Example
Calculate the entropy change when water turns to steam at 100°C (373K).
The enthalpy of vaporisation of water is +44 kJ mol-1
DS = DH = + 44 kJ mol -1 = + 118 J K -1 mol -1

T 373 K (+ive as gases have more disorder)
Entropy change values are much smaller than enthalpy

change values; they tend to be in Joules rather than kJ
IS A REACTION SPONTANEOUS?
A reaction should be spontaneous if DG is negative, so ...
• Work out if it is exothermic (DH -ive) or endothermic (DH +ive)
• Is there an increase in disorder ? If YES then DS will be positive.
• Is the temperature high or low ? This can affect the value of TDS°
A reaction should be spontaneous if DG is negative, so ...
• Work out if it is exothermic (DH -ive) or endothermic (DH +ive)
• Is there an increase in disorder ? If YES then DS will be positive.
• Is the temperature high or low ? This can affect the value of TDS°
General examples
• If DH is –ive and DS is +ive then DG must be negative
• If DH is +ive and DS is -ive then DG must be positive

Specific examples
DG = DH - TDS
(1) H2(g) + F2(g) —> 2HF(g)
DH - ive
DS 0
Specific examples
DG = DH - TDS
(2) Na+(g) + Cl¯(g) —> NaCl(s)
DH - ive highly exothermic (Lattice Enthalpy)

DS - ive more order in a solid
DG - ive mostly due to the high value of lattice enthalpy
Specific examples
DG = DH - TDS
(3) NH4NO3(s) —> NH4+(aq) + NO3¯(aq)
DH +ive endothermic (the solution goes colder)

DS +ive more disorder as lattice breaks up
DG - ive if T is high or the value of DS is big enough
Specific examples - summary
(1) H2(g) + F2(g) —> 2HF(g)
DH - ive highly exothermic process

DS 0 same number of gas molecules
DG - ive must be negative (taking 0 away from a negative number)
(2) Na+(g) + Cl¯(g) —> NaCl(s)
DH - ive highly exothermic (Lattice Enthalpy)

DS - ive more order in a solid
DG - ive mostly due to the high value of lattice enthalpy
(3) NH4NO3(s) —> NH4+(aq) + NO3¯(aq)
DH +ive endothermic (the solution goes colder)

DS +ive more disorder as lattice breaks up
DG - ive if T is high or the value of DS is big enough
What is the sign of the entropy change in the following reaction ?
Give reasons for your decision.
What is the sign of DG?
a) CaCO3(s) —> CaO(s) + CO2(g)
DG = DH - T DS
Temperature
DG = DH - T DS is ALWAYS
positive
+ + +
Endothermic increase in the
number of gas
molecules
Because DS is positive; TDS must be positive

DH is positive (very endothermic reaction)
For DG to be NEGATIVE, TDS must be bigger than DH
This is more likely with a higher temperature
The reaction is more likely to be spontaneous if heated
b) NH3(g) + HCl(g) —> NH4Cl(s)
DG = DH - T DS
Temperature
positive
+
Exothermic decrease in
the number of
gas molecules
Because DS is negative; TDS must be negative

DH is negative
For DG to be negative TDS must be less negative than DH
This is more likely if the value of T is lower
The higher the temperature the less likely that the reaction will proceed
What is the sign of the entropy change in the following reactions ?
c) Na(s) —> Na(g) (Equivalent to Enthalpy of Atomisation)
DG = DH - T DS
c) Na(s) —> Na(g) (Equivalent to Enthalpy of Atomisation)
Temperature
positive
+ + +
Endothermic increase in the
number of gas
molecules

DH is positive
For DG to be NEGATIVE, TDS must be bigger than DH
This is more likely with a higher temperature so the reaction
Solids are more likely to become gases if heated
d) C6H12(l) + 9O2(g) —> 6CO2(g) + 6H2O(g)
DG = DH - T DS
d) C6H12(l) + 9O2(g) —> 6CO2(g) + 6H2O(g)
Temperature
positive
+ +
COMBUSTION increase in the
is exothermic number of gas
molecules

DH is negative
Taking a +ive value away from a –ive value must give a –ive value
DG must be NEGATIVE so the reaction is SPONTANEOUS
e) C(s) + O2(g) —> CO2(g)
DG = DH - T DS
e) C(s) + O2(g) —> CO2(g)
Temperature
positive
+ very small
COMBUSTION no change in
is exothermic the number of
gas molecules
DS is very small (could be –ive or +ive)

TDS will therefore not be a large number
DH will be have a relatively large negative value
Taking a small +ive value away from a –ive value must give a –ive value
DG must be NEGATIVE so the reaction is SPONTANEOUS
Examples of spontaneous change in our daily life:
 Wine glass breaks into smaller pieces as it drops onto the floor
(small piece of glass beads do not form back the wine glass
spontaneously)
 A cube of sugar spontaneously dissolves in a cup of tea (the
dissolved sugar does not spontaneously combine to its original
solid state).
 A bottle of perfume is opened, the fragrance diffuses into the
atmosphere and fill up the room.
ANSWERS
What is the sign of the entropy change (DS) in the following reactions ?
c) Na(s) —> Na(g)
d) C6H12(l) + 9O2(g) —> 6CO2(g) + 6H2O(g)
e) C(s) + O2(g) —> CO2(g)

ANSWERS
What is the sign of the entropy change (DS) in the following reactions ?
a) CaCO3(s) —> CaO(s) + CO2(g) + more gas molecules
b) NH3(g) + HCl(g) —> NH4Cl(s) - fewer gas molecules
c) Na(s) —> Na(g) + goes from solid to gas
d) C6H12(l) + 9O2(g) —> 6CO2(g) + 6H2O(g) + more gas molecules
e) C(s) + O2(g) —> CO2(g) ‘0’ ‘similar’ moles of gas

Practice
ENTROPY &
FREE ENERGY
The End
© 2015 JONATHAN HOPTON & KNOCKHARDY PUBLISHING

Entropy & Free Energy: A Guide For A Level Students

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ENTROPY &

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Exothermic reactions are usually spontaneous

Exothermic reactions are usually spontaneous

Exothermic reactions are usually spontaneous

Energy is put in to Energy is released

Exothermic reactions are usually spontaneous

Exothermic reactions are usually spontaneous

Exothermic reactions are usually spontaneous

A negative DG indicates a reaction capable of proceeding of its own accord

A negative DG indicates a reaction capable of proceeding of its own accord

DG < 0 (- ive) Spontaneous reaction

A negative DG indicates a reaction capable of proceeding of its own accord

DG < 0 (- ive) Spontaneous reaction

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when • solids melt

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when SOLIDS MELT

Regular arrangement Less regular arrangement;

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when LIQUIDS BOIL

Irregular arrangement; Random nature and disorder

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when IONIC SOLIDS DISSOLVE IN WATER

Regular arrangement in Ions dissociate in water;

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when THE MOLES OF GAS INCREASE

Particles in gases move in a

‘Entropy tends to a maximum’

This infers that... ‘all chemical and physical changes

Entropy increases when THE TEMPERATURE INCREASES

Lower temperature; less Higher temperature; more

DS = DH = + 44 kJ mol -1 = + 118 J K -1 mol -1

Entropy change values are much smaller than enthalpy

• Work out if it is exothermic (DH -ive) or endothermic (DH +ive)

• Is there an increase in disorder ? If YES then DS will be positive.

• Work out if it is exothermic (DH -ive) or endothermic (DH +ive)

• Is there an increase in disorder ? If YES then DS will be positive.

• If DH is –ive and DS is +ive then DG must be negative

• If DH is +ive and DS is -ive then DG must be positive

(1) H2(g) + F2(g) —> 2HF(g)

(2) Na+(g) + Cl¯(g) —> NaCl(s)

DH - ive highly exothermic (Lattice Enthalpy)

(3) NH4NO3(s) —> NH4+(aq) + NO3¯(aq)

DH +ive endothermic (the solution goes colder)

DH - ive highly exothermic process

(2) Na+(g) + Cl¯(g) —> NaCl(s)

DH - ive highly exothermic (Lattice Enthalpy)

(3) NH4NO3(s) —> NH4+(aq) + NO3¯(aq)

DH +ive endothermic (the solution goes colder)

a) CaCO3(s) —> CaO(s) + CO2(g)

a) CaCO3(s) —> CaO(s) + CO2(g)

Because DS is positive; TDS must be positive

b) NH3(g) + HCl(g) —> NH4Cl(s)

b) NH3(g) + HCl(g) —> NH4Cl(s)

Because DS is negative; TDS must be negative