Classification: Internal

Unit 4 Entropy and Energetics

Specification 12A and 12B

Rules/Expectations
Camera on & Face Visible.
Blur background.
Online on time.
Muted - unless called on.
Ready to Learn.
SLANT.
Questions – hand up.
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Entropy

S:
S = start of lesson S:

E = end of lesson Carry out complex E: Learn about

E:
calculations and how Gibbs free
Grading= 1-5
justify the signs in energy can be
S:
the expression used to
E: determine the
Learning Interpret the natural
Outcomes feasibility of a
direction of change. Explain
progress why entropy changes occur
reaction
arrow: during certain types of
S: reactions

E:
What determines
whether a reaction is
spontaneous and
feasible?
What is entropy?
Describe how entropy
changes with
temperature Mrs Choudhury
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Enthalpy Recap: DO NOW Task

Endothermic or

Q2. What are standard conditions?

exothermic?
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End

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Answers

14 - B

19 - D

21 - D

Temperature: 298K (25oC)

Pressure: 1atm (101 kPa)
Concentration: 1 mol dm-3

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KEY DEFINITIONS

Entropy:
Is a measure of disorder of a system in terms of random dispersal of molecules
and of energy quanta between molecules- it gives the number of ways that
particles can be arranged and the number of ways the energy can be shared out
between the particles

System: refers to the reaction taking place

First law of Thermodynamics:

The law of conservation of energy states that the total energy of an isolated system is
constant; energy can be transformed from one form to another, but can be neither created
nor destroyed.

Second law of Thermodynamics:

Entropy will always tend to increase in any isolated system that is not in
equilibrium

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What affects the feasibility of a reaction?

feasiblility
• If a reaction can happen we use the term ­____________

• Name some reactions that happen easily – they are called

spontaneous
________________:

• The change in energy – going down an energy gradient.

• The activation energy

Generally
EXOTHERMIC
reactions!

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Feasibility of reactions

Name some reactions that happen easily – they are called

SPONTANEOUS
Acid & alkali/metal/carbonate

Name some reactions that happen but need help:

Combustion (need to light it)

Name some that don’t happen at all – not feasible:

Water with gold

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HOWEVER: there are some spontaneous

ENDOTHERMIC reactions
• Sodium hydrogencarbonate and hydrochloric acid react in the cold
• Ionic substances dissolving in water at room temperature

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Diamond burning in oxygen

is very exothermic….

….so why does it not occur spontaneously?

Activation energy needed to

break the EXTREMELY strong C-
C covalent bonds is very high.

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Entropy

Although the enthalpy change does matter in determining whether a

reaction is feasible we need another factor – entropy.

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Describe the movement and arrangement of the

particles and say who has the least and most entropy.

________________________ ________________________ ________________________

________________________ ________________________ ________________________
________________________ ________________________ ________________________
________________________ ________________________ ________________________

Which one shows it is:

a) Chaotic?
b) Ordered?

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Temperature: 298K (25oC)

STANDARD ENTROPY, SPressure:

1atm (101 kPa)
Concentration: 1 mol dm-3
Entropy (S) is a quantitative measurement of the freedom of
molecules. Units are JK-1mol-1.
• What sort of substance will have the lowest value of S?

Solid at low temperature, regularly

arranged lattice
• What sort of substance will have a high entropy?

Gas at high temperature

• Put ice, water, steam in order of increasing entropy

ice < water < steam

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Can you explain these entropies?

• Carbon (as diamond) 2.4 JK-1mol-1

• Water (as liquid) 69.9 JK-1mol-1
• Carbon monoxide 197.6 JK-1mol-1
• Carbon dioxide 213.6 JK-1mol-1
These last 2 show that as
molecules get more complicated
their entropy tend to increase

S(solid) < S(liquid)< S (gas)

generally be higher if there are more moles or more complicated molecules

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Physical State and Entropy

Changes of Entropy with Changes of State

• If you raise the temperature of a substance, you increase the
energy of the particles. So the higher the temperature, the more
_______
energy quanta a substance has, and the more ways these quanta can
be distributed- which means ______________.
higher entropy

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Entropy and temperature

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The graph shows how the entropy of a substance

typically changes with temperature:

• Within the phases the entropy increases slowly

• Change in physical state there also a rapid change in entropy at

points Tm and Tb

• There is a larger increase in entropy when a substances changes from

liquid to gas than solid to liquid

• Curve starts a 0,0 origin. When temp is zero kelvin, a substance

theoretically have zero entropy. This could happen you had a
perfectly ordered crystal.

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ENTROPY CHANGES

Using standard entropy (S) for each substance we can work out the
entropy change for the reaction:

Change = entropy of - entropy of

in all of the all of the
entropy products
reactants

S = S (products) - S (reactants)

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TASK: For the following reactions….

a) Write the balanced symbol equations (including state symbols)
b) Predict and explain whether the entropy will increase or decrease
1. Hydrogen and oxygen gases react to make water entropy decreases –
H2 (g) + O2 (g)  H2 O (l) 3 moles & 2 gases
to 2 mole of liquid

2. Calcium carbonate reacting with hydrochloric acid

CaCO3 (s) + HCl(aq)  CaCl2 (aq) + H2 O (l) + CO2 (g)

entropy increases –
solid & solution form
solution, liquid & gas
3. Sodium and chlorine react to make solid sodium chloride
entropy decreases –
Na (s) + Cl2 (g)  NaCl (s) solid & gas form solid

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Entropy change - Worked Example:

• Calculate entropy change for the thermal decomposition of calcium

carbonate to calcium oxide and carbon dioxide:
• S(CaCO3(s)) = 92.9 JK-1mol-1,
• S(CaO(s)) = 39.7 JK-1mol-1,
• S(CO2(g)) = 213.6 JK-1mol-1

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1. Write a balanced equation to check number of moles

CaCO3 (s)  CaO (s) + CO2 (g)

2. Work out entropy of products and reactants
S(products) = S(CaO(s)) + S(CO2(g)) = (39.7 + 213.6) = 253.3 JK-1mol-1

S (reactants) = S(CaCO3(s)) = 92.9 JK-1mol-1

3. Use equation
S = S(products) - S (reactants)

4. CHECK: =
253.3 - 92.9 JK-1mol-1 = + 160.4 JK-1mol-1

Entropy has increased – we would expect this

as a single solid has produced two substances,
a solid and a gas.
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1. Work out the entropy change during the reaction:

2NaHCO3  Na2CO3 + CO2 + H2O

Substance Physical state Standard

entropy/ JK-1mol-1
NaHCO3 solid 101.7
Na2CO3 solid 135.0
CO2 gas 213.6
H2O liquid 69.9

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1. Check number of moles from balanced equation

2NaHCO3 (s)  Na2CO3 (s) + CO2 (g) + H2O (l)

2. Work out entropy of products and reactants

S(products) = S(Na2CO3(s)) + S(CO2(g)) + S(H2O(g)

= (135 + 213.6 + 69.9) = 418.5 JK-1mol-1
3. Use equation
S (reactants) = S (2NaHCO

S = S(products) 3(s)) = 2 x 101.7 = 203.4 JK mol
- S (reactants)
-1 -1

4. CHECK:

=
418.5 - 203.4 JK-1mol-1 = + 215.1 JK-1mol-1

Entropy has increased – we would expect this as a as

2 moles of a single solid has produced three
substances (& 3 moles), a solid, a liquid and a gas.
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2. Work out the entropy change during the reaction:

N2 + 3H2  2 NH3

Substance Physical state Standard

entropy/ JK-1mol-1

N2 gas 191.6
NH3 gas 192.3
H2 gas 130.6

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1. Check number of moles from balanced equation

N2 (g) 3H2 (g)  2 NH3 (g)

2. Work out entropy of products and reactants

S(products) =2 x S(NH3 (g)) = 2 x 192.3 = 384.6 JK-1mol-1

S (reactants) = S(N2 (g)) + 3 x S(H2 (g)) = 191.6 + 3 x 130.6

3. Use equation
=583.4 JKS
-1
mol-1
= S(products) - S (reactants)

4. CHECK:
=
384.6 – 583.4 JK-1mol-1 = - 198.8 JK-1mol-1

Entropy has decreased – 4 moles of 2 gases has

produced 2 moles of only 1 gaseous substance
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SECOND LAW OF
THERMODYNAMICS
• For a reaction to be feasible the total entropy of the system has to
increase so S must be positive.

Entropy will always tend to increase in any

isolated system that is not in equilibrium

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This is the overall entropy - in different parts of the system the

entropy may decrease but this is because it has increased in other
parts of the system.

This includes the entropy change of the surroundings.

For a reaction to be feasible the total entropy of

the system has to increase so S must be
positive.

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Entropy change in the surroundings

• When considering entropy in changes, it is necessary to consider what happens to

the surroundings as well as the system (chemical reaction) itself.
• Any entropy increase in the surroundings comes from the energy which the system
gives out. The increase in entropy depends upon the proportional increase in
energy of particles in the surroundings. If for example the surroundings gain 20kJ
of energy, the proportional increase is greater if the surroundings originally have
low energy. Temperature is a measure of the energy of molecules, so the change
in entropy in the surroundings is;

-ΔH
ΔSSURROUNDINGS = T

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No opt out –using the description to formulate

the expression for ∆STotal
• Entropy for the reaction- change in entropy between reactants and
products- entropy change of the system.
• Entropy of the surroundings changes because energy is transferred
to or from the surroundings.
• The total entropy change is the sum of the system and surroundings.

ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS

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Now lets use

the 2
expressions to
work out total
Total Entropy change - Worked Example: entropy change

For the example of burning magnesium ΔH = -1204kJmol-1 at 298K.

ΔSSYSTEM = -221.1 JK-1mol-1

So ΔSSURROUNDINGS = -(-1204)/298 = +4.0403kJK-1mol-1

Notice that the units
of S are in JK-1mol-1. In
2. Using ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS particular J not kJ

3. Converting +4.0403kJK-1mol-1 to +4,040.3 JK-1mol-1

4. ΔSTOTAL = (-221.1) + (+4,040.3) = 3,818.8 JK-1mol-1

• It can now be seen that the overall entropy change is positive, showing that
the reaction is feasible.

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Is this reaction
Practicefeasible?
II Is this reaction feasible?
ΔSSYSTEM +165 JK-1mol-1
Decomposition of calcium carbonate
ΔH +178 kJmol-1
1.CaCO3(s)  CaO(s) + CO2(g)

2.ΔSSURROUNDINGS = -(+178)/298 = -0.597 kJK-1mol-1 (or -597 JK-1mol-1)

The negative value

3.Using ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS
shows that this
reaction is not feasible
4.ΔSTOTAL = (+165) + (-597) = -432 JK-1mol-1 at room temperature

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Summary of entropy

• If ∆S is +ve then a reaction is likely.

• If ∆S is –ve then a reaction is unlikely.
• Chemical reactions are favoured if they are accompanied by an
increase in entropy.

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The table below shows the various possibilities.

Feasibility of
ΔSSYSTEM ΔSSURROUNDINGS Comparative values ΔSTOTAL
reaction

+ + + Yes

- + ΔSSYSTEM > ΔSSURROUNDINGS

- No

- + ΔSSYSTEM < ΔSSURROUNDINGS

+ Yes

+ - ΔSSYSTEM > ΔSSURROUNDINGS

+ Yes

+ - ΔSSYSTEM < ΔSSURROUNDINGS

- No
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GIBBS FREE ENERGY, G

To work out if a reaction is feasible at a certain temperature, we need

to consider the enthalpy change of the reaction and the change in
entropy.

G = H - TSSystem
In order for a reaction to be feasible G must be NEGATIVE
G = Gibbs free energy in J mol-1
H = enthalpy change in J mol-1
S = entropy change in J K-1 mol-1
T = temperature in K
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Is a reaction feasible?

What is the connections between Gibbs free energy change and

thermodynamic feasibility?

• When ∆G is 0, a reaction is thermodynamically feasible.

• This means the reaction can happen (it cannot happen if the
activation is too high)
• The term spontaneous is taken to mean the same thing as feasible,
but it still means that a reaction can happen rather than that it
actually does.

Often we are asked if reaction is feasible at a given temperature or at

which temperature a reaction becomes feasible.

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Worked example:

a) Show that the thermal decomposition of sodium carbonate is not

feasible at 1200K.
b) At what temperature does it become feasible?
Na2CO3 (s)  Na2O(s) + CO2 (g)
H = +323 kJmol-1
S = +153.7 J K-1mol-1

Be careful with the units:

G = +13856 J mol-1 = 13.856 kJ mol-1

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For the reaction to be feasible Gibbs free

energy must be negative i.e. G is < 0
G = H - TS
= 323 – (1200 x 0.1537)
= + 139 kJ mol-1

As G is positive the reaction is not

feasible.

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To discover the temperature the reaction is

feasible at G is < 0
G = H - TS
323 – (T x 0.1537) < 0
323 < (T x 0.1537)
T > 323/0.1537 = 2100 K

For the reaction to be feasible the

temperature must be greater than 2100 K
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In the blast furnace there are 2 reactions

involved in the extraction of iron:
A: Fe2CO3 (s) + 3CO(g)  3Fe(s) + 3CO2(g)
H = -25.0 kJmol-1
S = +15.2 J K-1 mol-1
B: Fe2CO3 (s) + 3C(s)  3Fe(s) + 3CO (g)
H = + 491 kJmol-1
S = +542.9 J K-1 mol-1

Which reaction is more feasible at (a)

800K, (b) 1800K?
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You will need to calculate G at both

temperatures – the one with the most negative
value will be the most feasible.

Using G = H - TS Only A is

negative so it
is the only
At 800K feasible
A: G = -25.0 – 800 x 0.0152 = -37.16 kJ mol-1 reaction

B: G = 491- 800 x 542.9 = + 56.7 kJ mol-1

At 1800K Both are

negative but B
A: G = -25.0 – 1800 x 0.0152 = -52.4 kJ mol-1 much more
B: G = 491- 1800 x 542.9 = - 486 kJ mol-1 negative and
so it is the
MORE feasible
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Key learning points

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Plenary
• Answer question q1, 4, 5 and 6 a) & b) from exam questions
booklet.

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Plenary answers
1. B

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Entropy: Thermodynamic Stability and Kinetic Inertness

S:
S = start of lesson S:
E:
E = end of lesson E:
Grading= 1-5 Calculate ΔSsystem and ΔSsurroundings to show
S:
that endothermic reactions can occur
spontaneously at room temperature
E:
Learning Demonstrate an
Outcomes understanding of and
progress
distinguish between
arrow:
S:
the concepts of
thermodynamic
E:
stability and kinetic
inertness
Demonstrate an understanding
that the feasibility of a reaction
depends on the balance between
ΔSsystem and ΔSsurroundings.

Mrs Choudhury
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Thermodynamics vs. kinetics

Just because a reaction is spontaneous does not mean that it appears to happen. It
may be that the reaction is so slow or has such a high activation energy that it is not
generally observed.

Consider the reaction involving the combustion of carbon:

C(s) + O2(g) CO2(g)

DH = –394 kJ mol–1 DS = +3 J K–1 mol–1

This reaction has a negative value for DG, so is feasible, but a piece of carbon does not
spontaneously burn if left on the table. Energy would need to be put in for the reaction to
begin.

A reaction that is thermodynamically feasible is not necessarily kinetically feasible.

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What is the difference between thermodynamic

stability and kinetic inertness?

Effect of Temperature on ΔSTOTAL

At higher temperatures, ∆Ssurroundings gets smaller. As a result, it makes a

smaller contribution to the total entropy change than it does at lower
temperatures.

Thermodynamic Stability
A spontaneous reaction or change happens without you having to input energy
– it is thermodynamically favourable.

Kinetic Inertness
A spontaneous reaction may happen but it doesn’t mean that it will happen
quickly. The thermodynamics of a reaction do not tell you anything about how
fast02/12/2023
it will go- that’s the job of reaction kinetics. 49
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Entropy practicals- Predict if they are

thermodynamically feasible?
A. adding ammonium nitrate crystals to water
B. reacting ethanoic acid with ammonium carbonate
C. burning magnesium ribbon in air

Student plan: For each reaction

1. What equipment will you need?
2. How will you carry out the experiment? Deduce a safe method,
think about safe quantities to use. Use the hazcard booklet for
further information
3. How will you measure a change in the reaction? Think about how
this will impact your equipment list.

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Results

A. dissolving a solid, eg adding ammonium nitrate crystals to water

B. gas evolution, eg reacting ethanoic acid with ammonium
carbonate
C. exothermic reaction producing a solid, eg burning magnesium
ribbon in air

• What is you conclusion for each experiment?

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Entropy:Predicting solubility from the enthalpy and

entropy of solution

S = start of lesson S:

E = end of lesson E: Use entropy and enthalpy changes of solution

Grading= 1-5 values to predict the solubility of ionic
S: compounds
E:
Learning
Outcomes
progress Demonstrate an understanding of
arrow: the factors that affect the values of
S: enthalpy of hydration and the
E: lattice energy of an ionic compound

Define the term enthalpy of

hydration of an ion and use it and
lattice energy to calculate the
enthalpy of solution of an ionic
compound
Mrs Choudhury
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Predicting solubility from the enthalpy and

entropy of solution
• Define the terms below:
• Enthalpy of solution

• Enthalpy of hydration

• Lattice enthalpy

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Predicting solubility from the enthalpy and

entropy of solution
• Enthalpy of solution
The solution enthalpy is a measure of the amount of heat energy change when one
mole of substance is dissolved in excess water.
For one mole: M+(g) + X-(g) + aq M+(aq) + X-(aq)

• Enthalpy of hydration
The heat energy given out when one mole of gaseous ions dissolve in an excess of
water to form an infinitely dilute solution under standard conditions.
For one mole: M+(g) + aq M+(aq)

X-(g) + aq X-(aq)

• Lattice enthalpy
The heat energy given out (exothermic enthalpy change), when one mole of a crystal
lattice02/12/2023
is formed from separate, gaseous ions
M+(g) at
+ Xan
- infiniteMX
distance apart under54
(g) (s)
standard conditions.
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Solutions
• When an ionic substance is placed in water, the water molecules,
being highly polar, are attracted to the ions. The oxygen in the water
molecule carries a partial negative charge and is attracted to cations.
The hydrogen in the water molecule carries a partial positive charge
and is attracted to anions.

• The process of water molecules linking to ions is called hydration of

ions. The water molecules are vibrating, so as they bond to the ions
they shake the ions free from the lattice.

• The process of dissolving is shown below.

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• Some ionic compounds do not dissolve in water because the

electrostatic attraction between the ions is too great for the water
molecules to overcome.
• There are two key energy processes taking place as an ionic
substance dissolves.
• The lattice has to be broken apart. This is an endothermic process.
• As new bonds form between the water molecules and the ions an
exothermic process takes place.
• The energy change that takes place when a solution dissolves is a
balance of these two energy changes. This is illustrated in the
diagram below.

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Lattice Enthalpy
The lattice enthalpy is a measure of the strength of an ionic lattice. Some
values of lattice enthalpy are given below.
Compound Lattice energy/ kJmol-1
It can be seen that as the NaF -923
size of the anion increases,
NaCl -776
the value of the lattice energy
drops. This is because the NaBr -742
sum of the radii increases NaI -699
(distance between the centers KCl -701
of charge increases), and so RbCl -675
electrostatic attraction CsCl -645
decreases and the lattice MgCl2 -2493
enthalpy decreases as a
consequence. Increasing size CaCl2 -2237
of cation also causes a MgO -3933
decrease in the lattice CaO -3513
enthalpy.
Charge on the ion
The higher the charge on either or both of the ions, the greater the lattice
enthalpy. As the charge on the ion increases the electrostatic attraction also
increases, so the lattice energy becomes greater.
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Hydration Enthalpy
The hydration enthalpy is a measure of the attraction between an ion and water
molecules. Some values of hydration enthalpy are given below.

Ion Hydration enthalpy/ Ion Hydration enthalpy/

kJmol-1 kJmol-1
Li+ -499 F- -457
Na+ -390 Cl- -381
K+ -305 Br- -351
Mg2+ -1891 I- -307
Ca2+ -1562
Al3+ -4613

It can be seen that as the size of the cation increases, the value of the hydration
enthalpy drops. This is because the distance between the centre of ionic charge
and the water molecule increases, and so electrostatic attraction decreases as and
the hydration enthalpy decreases as a consequence. Increasing size of anion also
causes a decrease in the hydration enthalpy for similar reasons.

Charge on the ion

The higher the charge on the ion, the greater the hydration enthalpy. As the
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on the ion increases the electrostatic attraction also increases, so the59
hydration enthalpy becomes greater.
Classification: Internal

Do now Task QuestionQ2 (c) and (d) from the hw

booklet. 7 mins
(c) The lattice energies of magnesium chloride, MgCl 2, calcium chloride, CaCl2, and strontium
chloride, SrCl2 are shown in the table below.

Chloride Lattice energy/kJ mol–1

MgCl2 –2526
CaCl2 –2258
SrCl2 –2156

(i) Use data on ionic radii, from your data booklet, to explain the trend in these values. Estimate
a value for the lattice energy of cobalt(II) chloride, giving ONE piece of data to justify your
estimate.
4

(ii) Explain how lattice energy values, together with other data, can be used to predict the
solubility of ionic compounds. 3

(d) Cobalt forms another chloride, CoCl 3, but scientists predict that MgCl 3 cannot be made. Suggest a
reason for this.

You should consider the enthalpy changes in the Born-Haber cycle, which provide evidence about
why cobalt(III) chloride is known but magnesium(III) chloride is not. 2

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(c) (i) QWC

Radius (of cation) increases (down group)
OR any two values of radius:
Mg 2+ = 0.072, Ca 2+ = 0.100 / Sr 2+ = 0.113 (nm) data may be
shown beside the table (1)
Radius Co2+ = 0.065 nm
OR Co2+ radius smaller than other ions (1)
Data on EITHER Co2+ OR data showing increase in radius down (d) QWC
Group II required for BOTH of first two marks
First mark
Force of attraction between ions decreases (as radius of ions increases)
/ charge density of ions decreases / negative ion can come closer to Third ionization energy high(er) for Mg / Mg = 7733 kJ mol–1, (third
nucleus of positive ion (1) ionization energy for Co = 3232 kJ mol–1) (1)
ALLOW “weaker ionic bonds”
Predict lattice energy –2550 to -2900 (kJ mol–1) (1) Second mark
IGNORE sign 4 (Third ionization energy for Mg is high) because the electron is being
Atomic radii unless ionic radii also given
removed from an inner shell / full shell / 2p level / 2p orbital (1)
Radius of cobalt chloride OR
Polarising power decreases
Not compensated by higher lattice energy for Mg3+ (and so ΔHformation
of MgCl3 would be highly endothermic) (1) 2
(ii) First mark
Reference to enthalpy of hydration (may be in equation ΔHsolution
= -LE + ΔHhydration) (1)
Second mark
Solubility depends on relative size of lattice energy and enthalpy
of hydration (1)
Third mark
EITHER
Solubility more likely if ΔHsolution is negative
OR
(If ΔHsolution is positive,) may / will dissolve if ΔStotal is positive
ACCEPT solvation instead of hydration 3

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ΔHsoln = - ΔHlatt + ΔHhyd

ΔHsoln(NaCl) = - (-776) + (-390 + -381) = +5kJmol -1

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It can be seen that the enthalpy of solution for sodium

chloride is endothermic.
To understand why the process of dissolving occurs
spontaneously it is necessary to look at the entropy
changes involved in the process.
ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS

Although this is an endothermic reaction making

ΔSSURROUNDINGS negative, the ΔSSYSTEM has a high positive
value because the process of dissolving means that a highly
ordered ionic lattice becomes a much less ordered solution
of ions.

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The dissolving of ammonium chloride is even more endothermic with a ΔH soln

of +16 kJmol-1.
The values of system entropy
and enthalpy of solution are
shown below.

ΔSSYSTEM +278.5 JK-

1
mol-1
ΔHsoln +16 kJmol-1

So ΔSSURROUNDINGS = -(+16)/298 = -0.0537 kJK-1mol-1 (or -53.7 JK-1mol-1)

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Calculating ΔSTOTAL. ΔSSYSTEM +278.5 JK-

1
mol-1
ΔHsoln +16 kJmol-1
ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS

ΔSTOTAL = (+278.5) + (-53.7) = +224.8 JK-1mol-1

The positive value of ΔSTOTAL allows us to predict that

ammonium chloride will be soluble.

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Conclusion

• It can be seen that the enthalpy of solution for sodium chloride is

endothermic. To understand why the process of dissolving occurs
spontaneously it is necessary to look at the entropy changes involved
in the process.

ΔSTOTAL = ΔSSYSTEM + ΔSSURROUNDINGS

• Although this is an endothermic reaction making ΔSSURROUNDINGS

negative, the ΔSSYSTEM has a high positive value because the process of
dissolving means that a highly ordered ionic lattice becomes a much
less ordered solution of ions.

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What is Hess's Law?

• Hess’s Law states that the enthalpy change for a chemical reaction is
independent of the route taken. This means that the enthalpy change
for the overall process will be identical regardless of how many steps
are taken.
• Consider the following reaction:
A+B → C+D ΔHx
• The enthalpy change for the reaction that forms products C+D
directly (ΔHx) will be the same as the sum of the enthalpy changes
for the production of C+D via an indirect route where intermediate
products are formed and subsequently react to produce C+D.

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Enthalpy of Solution
The enthalpy of solution is related to the lattice and
hydration enthalpies as follows:

ΔHsoln = - ΔHlatt + ΔHhyd

Na+(g) + Cl-(g)
Considering sodium chloride

ΔHHyd
Enthalpy ΔHLat
Na+(aq) + Cl-(aq)

ΔHSoln
NaCl(s)
Classification: Internal

Hess’s Law = ∆H1 = ∆H2 + ∆H3

= ∆Hsol = -∆Hlatt + ∆Hhyd

02/12/2023 = ΔHsoln(NaCl) = - (-776) + (-390 + -381) = +5kJmol-1 69

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Enthalpy cycles to find enthalpy

change of solution and constructing
Born Haber cycles

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Hess’s law

Once you have worked out the Enthalpy of solution you can then use the entropy
calculation to work out if the salt is likely to dissolve spontaneously.

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Write the equations for the standard

enthalpies of formation in 5 minutes:
1. Making Ammonia (NH3) from Hydrogen and Nitrogen

2. Making Sodium Chloride from Sodium and Chlorine

3. Making Magnesium Chloride from Magnesium and Chlorine

4. Making Aluminium Oxide from Aluminium and Oxygen

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Write the equations for the standard

enthalpies of formation-answers:
1. Making Ammonia (NH3) from Hydrogen and Nitrogen

0.5 N2 + 1.5 H2  1 NH3

(g) (g) (g)

2. Making Sodium Chloride from Sodium and Chlorine

1 Na + 0.5 Cl2  1 NaCl
(s) (g) (s)

3. Making Magnesium Chloride from Magnesium and Chlorine

1 Mg + 1 Cl2  1 MgCl2
(s) (g) (s)

4. Making Aluminium Oxide from Aluminium and Oxygen

2 Al + 1.5 O2  1 Al2O3
(s) (g) (s)
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Enthalpy of formation tips

 1. Make sure that the elements are in their standard states
 2. Remember the following non-metals are di-atomic gases:
Oxygen (O2), Fluorine (F2), Chlorine (Cl2), Nitrogen (N2)
 3. Remember that Bromine is a diatomic liquid: Br2 (L)
 4. Remember that Iodine is a diatomic solid: I2 (s)
 5. Remember that the noble gases are just single atoms: Ne
 6. Remember that metals are written as single atoms: Fe, Na
 7. Remember that the equation is balanced for one mole of
substance being formed

Example: H2(g) + 0.5 O2(g)  H2O (L)

 8. All ionic compounds are solids at room temperature

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Name 3 ways that the enthalpy of

formation of an ionic compound
such as Sodium Chloride is an
oversimplification of what
happens

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r e a ct i on
The
r oc e e d s in
p ne
t ha n o
more
step
The io
energ nisati
y of a on
metal
alway is
endot s
hermi
c

el e c t ron
The f a
n i t y o
affi l is
m e t a
non
always
h e r m i c
exot
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There are at least 5 stages to forming an ionic

compound. The energy change when gaseous
anions (-) and cations (+) react is called the
lattice formation enthalpy.

Can you state the individual stages to go from a

metal and non metal in their standard states to
the lattice?

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Born-Haber cycles

Lattice energies.
Decide whether the following statements are true or false:

Lattice energies, as usually defined, are negative. This

means that the description ‘larger’ and ‘smaller’ can be
ambiguous in comparing lattice energies. For this
reason, it is better to describe one lattice energy as
more or less exothermic than another.
Remember enthalpy change of formation will have an
arrow pointing downwards as it is exothermic.
Atomisation and ionisation have upward arrows as they
are endothermic.
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4.6 Born Haber cycle

Lattice energy
The lattice energy gives you some idea of the size of the attractive forces
between the ions. You will notice that it is of a similar magnitude as the bond
enthalpies. However, in ionic lattices each ion is held by attractive forces to
a number of other ions within the lattice. As a result the overall energy
needed to separate them is much higher than that needed to break an
individual covalent bond. This explains the high melting and boiling points of
ionic substances.
You must also look at the equation to see how many moles of each
atom/ion/element you have so that you can alter the calculations accordingly.
Non-metals that have a -2 ion have 2 electron affinities. It will be
endothermic as it is the energy absorbed when one mole of negative
electrons is gained by a -1 ion.

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Na+(g) + Cl(g) Draw this

D out for
practise!
E
Na + 0.5 Cl2(g)
+
(g)
C
Na(g) + 0.5 Cl2(g) Na+(g) + Cl-(g)
B
Na(s) + 0.5 Cl2(g)
F
A
NaCl(s)
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TASK 1
Letter What is being shown?
A

1. First ionisation energy for Sodium 4. Enthalpy of atomisation for Chlorine

2. Enthalpy of formation of Sodium Chloride 5. Lattice enthalpy of Sodium Chloride

3. Enthalpy of atomisation for Sodium 6. Electron affinity of Chlorine

Extension 1: In what direction – clockwise or

anticlockwise are ENDOTHERIC REACTIONS?
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Match up the letters with the stages

Extension 2: What do we do with the electron affinity
and enthalpy of atomisation of bromine?

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Task 2
Letter What is being shown?

1. First ionisation energy for Zinc 4. Second ionisation energy for Zinc

2. Enthalpy of formation of Zinc Bromide 5. Enthalpy of atomisation for Bromine

3. Enthalpy of atomisation for Zinc 6. Electron affinity of Bromine

7. Lattice enthalpy of Zinc Bromide

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Letter What is being shown?

A 7
B 6
C 5
D 4
E 1
F 3
G 2

1. First ionisation energy for Zinc 4. Second ionisation energy for Zinc

2. Enthalpy of formation of Zinc Bromide 5. Enthalpy of atomisation for Bromine

3. Enthalpy of atomisation for Zinc 6. Electron affinity of Bromine

7. Lattice enthalpy of Zinc Bromide

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Using ideas from Hess Law, have a go at constructing an equation to show what the lattice enthalpy of Zinc Bromide is in terms of the other enthalpy changes

a =

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If you prefer…

In general for a Born Haber cycle the enthalpy of formation (‘g’ in this example) equals the sum of all of the other enthalpy changes

You would need to re-arrange this to get the lattice enthalpy on its own

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Using ideas from Hess Law, have a go at constructing an equation to show what the lattice enthalpy of Zinc Chloride is in terms of the other enthalpy changes

a = g f e d c b

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Using ideas from Hess Law, have a go at constructing an equation to show what the lattice enthalpy of Zinc Chloride is in terms of the other enthalpy changes

a = g f e d c b

- + + + + +

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Bonding 3
Constructing Born Haber cycles
B4 Mid End
C Can I describe the stages of a Born-Haber
cycle?
Can I construct a Born-Haber cycle equation?
B

A Can I evaluate the importance of different

factors in determining the strength of an
ionic lattice?

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The factors that determine the strength of an ionic

lattice:

• Lattice enthalpy is a measure of the strength of the forces

between the ions in an ionic solid. The greater the lattice
enthalpy, the stronger the forces.
• Those forces are only completely broken when the ions are
present as gaseous ions, scattered so far apart that there is
negligible attraction between them.
• The lattice dissociation enthalpy is the enthalpy change needed to
convert 1 mole of solid crystal into its scattered gaseous ions. Lattice
dissociation enthalpies are always positive (endothermic)
• The lattice formation enthalpy is the enthalpy change when 1 mole of
solid crystal is formed from its scattered gaseous ions. Lattice formation
enthalpies are always negative (exothermic)

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The two main factors affecting lattice enthalpy are the charges on the ions and the ionic radii (which affects the distance between
the ions).

The charges on the ions

Sodium chloride and magnesium oxide have exactly the same arrangements of ions in the crystal
lattice, but the lattice enthalpies are very different.
The lattice enthalpy of magnesium oxide is much greater than that of sodium chloride. That's
because in magnesium oxide, 2+ ions are attracting 2- ions; in sodium chloride, the attraction is
only between 1+ and 1- ions.

The radius of the ions

The lattice enthalpy of magnesium oxide is also increased relative to sodium chloride because
magnesium ions are smaller than sodium ions, and oxide ions are smaller than chloride ions.
That means that the ions are closer together in the lattice, and that increases the strength of the
attractions.
You can also see this effect of ion size on lattice enthalpy as you go down a Group in the Periodic
Table.
For example, as you go down Group 7 of the Periodic Table from fluorine to iodine, the lattice
enthalpies of their sodium salts fall as the negative ions get bigger . Attractions are governed by
the distances between the centres of the oppositely charged ions, and that distance is obviously
greater as the negative ion gets bigger. And you can see exactly the same effect if as you go down
Group 1.
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Calculating lattice enthalpy

• It is impossible to measure the enthalpy change starting from

a solid crystal and converting it into its scattered gaseous
ions. It is even more difficult to imagine how you could do the
reverse - start with scattered gaseous ions and measure the
enthalpy change when these convert to a solid crystal.
• Instead, lattice enthalpies always have to be calculated, and
there are two entirely different ways in which this can be done.
• You can can use a Hess's Law cycle (in this case called a Born-
Haber cycle) involving enthalpy changes which can be
measured. Lattice enthalpies calculated in this way are
described as experimental values.
• Or you can do physics-style calculations working out how
much energy would be released, for example, when ions
considered as point charges come together to make a lattice.
These are described as theoretical values. In fact, in this case,
what you are actually calculating are properly described as
lattice energies.

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Why do theoretical and experimental values sometimes differ ?????

There are two possibilities:

1.There is reasonable agreement between the experimental value (calculated

from a Born-Haber cycle) and the theoretical value.
Sodium chloride is a case like this - the theoretical and experimental values
agree to within a few percent. That means that for sodium chloride, the
assumptions about the solid being ionic are fairly good!

2.The experimental and theoretical values don't agree: Oh dear!

A commonly quoted example of this is silver chloride, AgCl. Depending on
where you get your data from, the theoretical value for lattice enthalpy for
AgCl is anywhere from about 50 to 150 kJ mol-1 less than the value that
comes from a Born-Haber cycle.
In other words, treating the AgCl as 100% ionic underestimates its lattice
enthalpy by quite a lot.
What is the reason for this?

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Answer
• The explanation is that silver chloride actually has a significant
amount of covalent bonding between the silver and the chlorine,
because there isn't enough electronegativity difference between the
two to allow for complete transfer of an electron from the silver to
the chlorine.
• Comparing experimental (Born-Haber cycle) and theoretical values
for lattice enthalpy is a good way of judging how purely ionic a crystal
is.

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Factors affecting polarising ability

• Positive ions can have the effect of polarising (electrically distorting) nearby
negative ions. The polarising ability depends on the charge density in the
positive ion.
• Polarising ability increases as the positive ion gets smaller and the number of
charges gets larger.
• As a negative ion gets bigger, it becomes easier to polarise. For example, in an
iodide ion, I-, the outer electrons are in the 5-level - relatively distant from the
nucleus.
• A positive ion would be more effective in attracting a pair of electrons from an
iodide ion than the corresponding electrons in, say, a fluoride ion where they
are much closer to the nucleus.
• Aluminium iodide is covalent because the electron pair is easily dragged away
from the iodide ion. On the other hand, aluminium fluoride is ionic because
the aluminium ion can't polarise the small fluoride ion sufficiently to form a
covalent bond.

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question
1a

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question
1a

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Exam
question 1a

MS

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 Exam
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question
1b

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Exam question 1B MS

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Exam question 2

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Exam question 2 MS

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Exam question 3

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Exam question 3 MS

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