CHAPTER 6

CHEMICAL
ENERGETICS
 Learning outcomes
5.1 Enthalpy change, ΔH
1. understand that chemical reactions are accompanied by
enthalpy changes and these changes can be exothermic (ΔH
is negative) or endothermic (ΔH is positive)
2. construct and interpret a reaction pathway diagram, in
terms of the enthalpy change of the reaction and of the
activation energy 5.2 Hess’s Law
3. define and use the terms:
(a) standard conditions (this syllabus assumes 1. apply Hess’s Law to construct simple
that these are 298 K and 101 kPa) shown by ⦵. energy cycles
(b) enthalpy change with particular reference to: 2. carry out calculations using cycles
reaction, ΔHr , formation, ΔHf , combustion, ΔHc , and relevant energy terms, including:
neutralisation, ΔHneut (a) determining enthalpy changes that
4. understand that energy transfers occur during chemical cannot be found by direct experiment
reactions because of the breaking and making of chemical (b) use of bond energy data
bonds
5. use bond energies (ΔH positive, i.e. bond breaking) to
calculate enthalpy change of reaction, ΔHr
6. understand that some bond energies are exact and some
bond energies are averages
7. calculate enthalpy changes from appropriate experimental
results, including the use of the relationships q = mcΔT and
ΔH = –mcΔT/n
 5.1 Enthalpy Change, ΔH

• The total chemical energy inside a substance is called the enthalpy (or
heat content)

• When chemical reactions take place, changes in chemical energy take

place and therefore the enthalpy changes

• An enthalpy change is represented by the symbol ΔH (Δ= change; H =

enthalpy)

• An enthalpy change can be positive or negative

 Exothermic
reactions
• A reaction is exothermic when the products have less energy than the reactants
• Heat energy is given off by the reaction to the surroundings
• The temperature of the environment increases – this can be measured on a
thermometer
• The temperature of the system decreases
• There is an enthalpy decrease during the reaction so ΔH is negative
• Exothermic reactions are thermodynamically possible (because the enthalpy of
the reactants is higher than that of the products)
• However, if the rate is too slow, the reaction may not occur
• In this case the reaction is kinetically controlled
 Endothermic reactions
• A reaction is endothermic when the products have more
energy than the reactants

• Heat energy is absorbed by the

reaction from the surroundings

• The temperature of the environment decreases – this

can be measured with a thermometer

• The temperature of the system increases

• There is an enthalpy increase during the reaction so ΔH is

positive
 question

a exothermic
b exothermic
c endothermic
d exothermic
e endothermic
 Energy Level
Diagrams
• An energy level diagram is a diagram that shows the energies of the
reactants, the transition state(s) and the products of the reaction with time

• The transition state is a stage during the reaction at which chemical

bonds are partially broken and formed

• The transition state is very unstable – it cannot be isolated and is higher in

energy than the reactants and products

• The activation energy (Ea) is the energy needed to reach the transition
state

• We can define the activation energy as ‘the minimum amount of energy

needed for reactant molecules to have a successful collision and start the
reaction’
 • In an endothermic
reaction, the reactants
are lower in energy
than the products

• The reactants are

therefore further away
in energy to the
transition state

• This means that

endothermic reactions
The enthalpy change during an endothermic reaction have a higher
activation energy
compared to
exothermic reactions
 • In an exothermic
reaction, the
reactants are higher
in energy than the
products

• The reactants are

therefore closer in
energy to the
transition state

The enthalpy change during an exothermic reaction • This means that

exothermic reactions
have a lower
activation energy
compared to
endothermic
reactions
 Enthalpy Changes at
Standard Conditions
• To fairly compare the changes in enthalpy between reactions, all reactions
should be carried out under standard conditions

• These standard conditions are:

• A pressure of 101 kPa
• A temperature of 298 K (25 oC)
• Each substance involved in the reaction is in its normal physical state
(solid, gas or liquid)

• To show that a reaction has been carried out under standard conditions,
the symbol θꝊ is used
• ΔHθꝊ = the standard enthalpy change

• These are a number of key definitions for common language relating to

enthalpy change that all chemists need to know
 A variety of enthalpy change

We can describe enthalpy change according to the type of

chemical reaction taking place

• Enthalpy change of formation

• Enthalpy change of combustion
• Enthalpy change of neutralisation

• In more general cases we can use the term:

• Enthalpy change of reaction

https://
www.chemguide.co.uk/physical/energetics/definitions.h
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 Standard enthalpy change of
reaction ΔHrθ
• ΔHrθ is the enthalpy change when the amount of reactants
shown in the stoichiometric equation react to give products
under standard condition.

• The reactant and products must be in their standard states

 Standard enthalpy change of
formation ΔHfθ
• ΔHfθ is the enthalpy change when one mole of the compound is
formed from its elements under standard conditions

• It can be exothermic or endothermic

• The formula of the compound is write in ‘[ ]’ after ΔHfθ

 Standard enthalpy change of
HAPPY TURKEY
combustion ΔHc θ DAY

• ΔHcθ is the enthalpy change when one mole of a substance

is burnt in excess oxygen under standard conditions

• It is always exothermic

• The substances combusted can be either elements or

compounds
 Standard enthalpy change of
neutralisation ΔHθneut

Δhθneut is the enthalpy change when one mole of water is

formed by the reaction of an acid with an alkali under standard
condition
 s t i o n
que
 question

Answer

The Ea is the energy difference from the

energy level of the reactants to the top of the
‘hump’

Ea (forward reaction) = (+70 kJ mol-1) + (+ 20

kJ mol-1 ) = +90 kJ mol-1

As the question is asking for the reverse

reaction the Ea is the energy difference from
the energy level of the products to the ‘hump’
The reaction pathway diagram for a
reversible reaction Ea (reverse reaction) = +20 kJ mol-1
 Measuring enthalpy change
• We can measure the enthalpy change of some reactions by
different techniques for eg; calorimetry
• The apparatus used is called a calorimeter

• Suppose the reaction to be measured is between

two solutions.
• One of these solutions is introduced into the
coffee cup, and the temperature of both solutions
is measured.
• The second solution is now introduced, the
mixture stirred, and the rise in temperature
recorded.
• Since the cup is made of polystyrene foam, a
very good insulator, very little heat energy
escapes. It may be measurable, however, and
may be represented by the calorimeter constant.
 Specific heat capacity:
The energy needed to raise
the temperature of 1 g of a
substance by 1 (by 1 K)
Note:
A rise in temperature is given a positive sign. So the value of ΔH
negative for an exothermic reaction. A fall in temperature is given a
negative sign. So the value of ΔH is positive for an endothermic
reaction.
Answer

Since two moles of water molecules are formed in

the question above, the energy released is simply:

ΔHrθ = 2 mol x (-286 kJ mol-1)

= -572 kJ mol-1
Answer

Since two moles of Fe2O3 (s) are formed the total

change in enthalpy for the reaction above is:
ΔHfθ = 2 x ( -824.2 kJ mol-1)
= – 1648 kJ
question
One mole of sulfuric acid reacts with two
moles of sodium hydroxide to form two
moles of water. The definition of standard
enthalpy change of neutralisation relates
only to one mole of water formed. So the
enthalpy change for sulfuric acid is twice this.
Time taken for sodium to dissolve /
energy loss to thermometer or air or
calorimeter;
assumption that the specific thermal
capacity of the solution is the same as
that of water.
In the experiment there may be:

heat losses to the surroundings from the

flame and
into the calorimeter, thermometer and air;
incomplete combustion of the ethanol;
evaporation of ethanol so that not all the
weight loss is due to burning.
 Enthalpy & Bond Energies
• During a reaction, enthalpy changes take place because bonds are being
broken and formed

• Energy (in the form of heat) is needed to overcome attractive forces

between atoms

• Bond breaking is therefore endothermic

• Energy is released from the reaction to the surroundings (in the form of
heat) when new bonds are formed

• Bond forming is therefore exothermic

To break bonds energy is required from the surroundings and to make new
bonds energy is released from the reaction to the surroundings
• If more energy is required to break bonds than energy is released when new
bonds are formed, the reaction is endothermic

If more energy is released when new bonds are formed than energy is
required to break bonds, the reaction is exothermic

In reality, only some bonds in the reactants are broken and then new ones are
formed
 Enthalpy Calculations

Exact bond energy

• The amount of energy required to break one mole of a

specific covalent bond in the gas phase is called the
bond dissociation energy

• Bond dissociation energy (E) is also known as exact

bond energy or bond enthalpy

• The type of bond broken is put in brackets after E

• Eg. E(H-H) is the bond energy of a mole of single bonds

between two hydrogen atoms
Average bond energy

• Bond energies are affected by other atoms in the

molecule (the environment)

• Therefore, an average of a number of the same type of

bond but in different environments is calculated

• This bond energy is known as the average bond

energy

• Since bond energies cannot be determined directly,

enthalpy cycles are used to calculate the average
bond energy
• For these reason we use average bond energies taken from a number of
bonds of the same type but in different environment

• We use enthalpy cycle

• The average bond energy of the C-H bond in methane can be found using
the enthalpy change of atomisation of carbon & hydrogen and the
enthalpy change of combustion or formation of methane
An enthalpy cycle to find the average bond energy of the C-H bond.
The dashed line shows the two-step route

Using this enthalpy cycle, the average C-H bond energy can be found
by dividing the value of ΔH on the diagram by 4 (because there are 4
C-H bonds in methane)
question
Calculating enthalpy change from bond
energies
Bond energies are used to find the ΔHrθ of a reaction
when this cannot be done experimentally

Eg. the Haber Process

Formula of calculating the standard enthalpy change

of reaction using bond energies
Answer
Note! Values for bonds broken are positive
(endothermic) and values for bonds formed
Step 1: The chemical equation for the Haber
are negative (exothermic)
process is:
Step 3: Calculate the standard enthalpy of
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
reaction
Step 2: Set out the calculation as a balance
sheet as shown below: ΔHrθ = enthalpy change for bonds broken
+ enthalpy change for bonds formed

= (+2253 kJ mol-1) + (-2346 kJ mol-1)

= -93 kJ mol-1
Worked example: Calculating the average bond enthalpy
Answer

Step 1: The enthalpy of combustion is the enthalpy change when

one mole of a substance reacts in excess oxygen to produce water
and carbon dioxide

The chemical reaction should be therefore simplified such that only

one mole of ethyne reacts in excess oxygen:

H-C=C-H + 2 ½ O=O → H-O-H + 2O=C=O

Step 2: Set out the calculation as a balance sheet as shown below:

ΔHrθ = enthalpy change for bonds broken + enthalpy change for
bonds formed

= (+258 kJ mol-1) + (-418 kJ mol-1)

= -133 kJ mol-1

Exam Tip

When new bonds are formed the amount of energy

released is equal to the amount of energy absorbed
when the same bonds are broken.

For example:
O2 (g) → 2O (g) E (O=O) = +498 kJ mol-1
2O (g) → O2 (g) E (O=O) + -498 kJ mol-1
 HESS’S LAW

Hess’s Law states that:

“The total enthalpy change in a chemical

reaction is independent of the route by
which the chemical reaction takes place as
long as the initial and final conditions are
the same.”

This means that whether the reaction takes

place in one or two steps, the total enthalpy
change of the reaction will still be the same
• Hess’ Law is used to calculate enthalpy changes
which can’t be found experimentally using
calorimetry, eg:

3C (s) + 4H2 (g) → C3H8(g)

ΔHf (propane) can’t be found experimentally as

hydrogen and carbon don’t react under standard
conditions
The diagram above illustrates Hess’ Law: the
enthalpy change of the direct route, going
from reactants (A+B) to product (C) is equal
to the enthalpy change of the indirect routes
Calculating ΔHr from ΔHf using Hess’s
Law energy cycles
The products can be directly formed from the elements = ΔH2
OR
The products can be indirectly formed from the elements = ΔH1 +
ΔHr

Equation
ΔH2 = ΔH1 + ΔHr
Therefore,
ΔHr = ΔH2 – ΔH1

The enthalpy change from elements to products (direct route) is equal to

the enthalpy change of elements forming reactants and then products
(indirect route)
example
Step 1: Write the balanced equation at the top

Step 2: Draw the cycle with the elements at the bottom

Step 3: Draw in all arrows, making sure they go in the correct directions. Write
the standard enthalpy of formations
Step 4: Apply Hess’s Law
Exam Tip

Remember to take into account the number of moles

of each reactant and product.

For example, there are two moles of NaHCO3(s) so

the ΔHf value is multiplied by 2.
 Calculating ΔHf from ΔHc using Hess’s Law
energy cycles
• The combustion products can be formed directly from
elements to combustion products = ΔH1
OR
• The combustion products can be formed indirectly from
elements to compound to combustion products = ΔHr+ ΔH2

Equation
ΔH1 = ΔHr + ΔH2
Therefore,
ΔHr = ΔH1 – ΔH2

The enthalpy change going from elements to products (direct

route) is equal to the enthalpy change of elements forming
reactants and then products (indirect route)
 Worked example:
Calculating the enthalpy change of
formation of ethane
Step 1: Write the equation for enthalpy change of formation at the top and add oxygen
on both sides

Step 2: Draw the cycle with the combustion products at the bottom

Step 3: Draw all arrows in the correct direction

Step 4: Apply Hess’s Law

 Calculating average bond energies
using Hess’s cycles
• Bond energies cannot be found directly so enthalpy cycles are used
to find the average bond energy

• This can be done using enthalpy changes of atomisation and

combustion or formation

• The enthalpy change of atomisation (ΔHatθ ) is the enthalpy

change when one mole of gaseous atoms is formed from its
elements under standard conditions.

• Eg. ΔHatθ [H2] relates to the equation:

½ H2(g) → H(g)
Worked example: Calculating average C-H bond
energy
Step 1: Write down the equation for the dissociation of methane at the top

Step 2: Write down the elements at the bottom

Step 3: Draw all arrows in the correct direction

Step 4: Apply Hess’s Law Step 5: Since there are 4 C-H bonds in methane:
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