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AQA A Level Chemistry Your notes

1.6 Energetics
Contents
1.6.1 Bond Energy
1.6.2 Energy Level Diagrams
1.6.3 Enthalpy Changes
1.6.4 Calorimetry
1.6.5 Hess' Law
1.6.6 Applications of Hess’s Law
1.6.7 Bond Enthalpies

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1.6.1 Bond Energy

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Bond Energy
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
The sum of the energy in and energy out determines whether the reaction is overall exothermic or
endothermic

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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 Your notes
reaction is exothermic
In reality, only some bonds in the reactants are broken and then new ones are formed

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1.6.2 Energy Level Diagrams

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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 as the reaction proceeds ( called 'extent of the reaction' below)
The transition state is a stage during the reaction at which chemical bonds are partially broken and
formed
The transition state is very unstable – a molecule in the transition state 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’

The energy level diagram for the reaction of hydrogen with chlorine to form hydrogen chloride gas
Exothermic reaction
In an exothermic reaction, the reactants are higher in energy than the products

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The reactants are therefore closer in energy to the transition state

This means that exothermic reactions have a lower activation energy compared to endothermic
reactions Your notes

The energy level diagram for exothermic reactions. ∆H is negative because the system (reactants) loses
energy to the surroundings.
Endothermic 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 have a higher activation energy compared to exothermic
reactions

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Your notes

The energy level diagram for endothermic reactions. The system (reactant substances) have gained
energy so ∆H is positive.

Worked example
Drawing energy level diagrams of the combustion of methane
The Ea and ΔH for the complete combustion of methane are +2653 kJ mol-1 and -890 kJ mol-1
respectively.
Draw the energy level diagram for this reaction.

Answer
Step 1: The chemical equation for the complete combustion of methane is:
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
Step 2: Combustion reactions are always exothermic (ΔH is negative) so the reactants should be
drawn higher in energy than the products

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Step 3: Draw the curve in the energy level diagram clearly showing the transition state

Step 4: Draw arrows to show the Ea and ΔH including their values

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Your notes

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Worked example
Your notes
Determining the activation energy
ΔH for a reaction is +70 kJ mol-1 and Ea for the reverse reaction is +20 kJ mol-1.

Use the reaction pathway diagram below to determine the Ea for the forward reaction.

The reaction pathway diagram for a reversible reaction

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

Exam Tip
The activation energy is the energy difference from reactants to the transition state.
The enthalpy change of the reaction is the energy difference from reactants to products.
Remember: Label the axis of the energy level diagrams!

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1.6.3 Enthalpy Changes

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Enthalpy Changes
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 with a thermometer
The energy 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

The enthalpy change during an exothermic reaction

Endothermic reactions

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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 Your notes
The energy of the system increases
There is an enthalpy increase during the reaction so ΔH is positive

The enthalpy change during an endothermic reaction

Exam Tip
It is important to specify the physical states of each species in an equation when dealing with enthalpy
changes as any changes in state can cause very large changes of enthalpy. For example:
NaCl (s) → Na+ (aq) + Cl- (aq) ΔH = +4 kJ mol-1
NaCl (g) → Na+ (g) + Cl- (g) ΔH = +500 kJ mol-1
Also, remember that the system is the substances that are reacting (i.e. the reaction itself) and the
surroundings is everything else (e.g. the flask the reaction is taking place in).

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Standard Enthalpy Changes

To be able to compare the changes in enthalpy between reactions, all thermodynamic measurements Your notes
are carried out under standard conditions
These standard conditions are:
A pressure of 100 kPa (you may see some older exam questions that use a figure of 101 kPa; the
exact figure is 101 325 Pa, but it has been simplified in the current syllabus for problem-solving
purposes)
A temperature of 298 K (25 oC)
Each substance involved in the reaction is in its standard physical state (solid, liquid or gas)
To show that a reaction has been carried out under standard conditions, the symbol Ꝋ is used
ΔHꝊ = the standard enthalpy change

There are a number of key definitions relating to enthalpy changes that you need to know
Enthalpy Definitions Table

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Worked example
Calculating the enthalpy change of reaction
One mole water is formed from hydrogen and oxygen, releasing 286 kJ of energy
H2 (g) + ½O2 (g) → H2O (I) ΔHrꝊ = -286 kJ mol-1

Calculate ΔHrꝊ for the reaction below:

2H2 (g) + O2 (g) → 2H2O (I)

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Answer
Since two moles of water molecules are formed in the question above, the energy released is Your notes
simply:
ΔHrꝊ = 2 mol x (-286 kJ mol-1) = -572 kJ mol-1

Worked example
Calculating the enthalpy change

Calculate ΔHfꝋ for the reaction below, given that ΔHfꝋ [Fe2O3(s)] = -824.2 kJ mol-1

4Fe(s) + 3 O2(g) → 2 Fe2O3(s)

Answer
Since two moles of Fe2O3 (s) are formed the total change in enthalpy for the reaction above is:
ΔHfꝊ = 2 x ( -824.2 kJ mol-1) = - 1648 kJ

Worked example
Calculating enthalpy changes
Identify each of the following as ΔHrꝊ, ΔHfꝊ, ΔHcꝊ or ΔHneutꝊ
1. MgCO3 (s) → MgO (s) + CO2 (g)
2. C (graphite) + O2 (g) → CO2 (g)
3. HCl (aq) + NaOH (aq) → NaCl (aq) + H2O (I)

Answer
Answer 1: ΔHrꝊ
Answer 2: ΔHfꝊ as one mole of CO2 is formed from its elements in standard state and ΔHcꝊ as one
mole of carbon is burnt in oxygen
Answer 3: ΔHneutꝊ as one mole of water is formed from the reaction between an acid and an alkali

Exam Tip
The ΔHfꝊ of an element in its standard state is zero.
For example, ΔHfꝊ of O2(g) is 0 kJ mol-1

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1.6.4 Calorimetry
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Calorimetry
Measuring enthalpy changes
Calorimetry is the measurement enthalpy changes in chemical reactions
A simple calorimeter can be made from a polystyrene drinking cup, a vacuum flask or metal can

A polystyrene cup can act as a calorimeter to find enthalpy changes in a chemical reaction
The energy needed to increase the temperature of 1 g of a substance by 1 oC is called the specific heat
capacity (c) of the liquid
The specific heat capacity of water is 4.18 J g-1 oC-1
The energy transferred as heat can be calculated by:

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Your notes

Equation for calculating energy transferred in a calorimeter

Worked example
Specific heat capacity calculations
In a calorimetry experiment, 2.50 g of methane is burnt in excess oxygen.
30% of the energy released during the combustion is absorbed by 500 g of water, the temperature of
which rises from 25 °C to 68 °C
The specific heat capacity of water is 4.18 J g-1 °C−1
What is the total energy released per gram of methane burnt?

Answer
Step 1: q = m x c x ΔT
m (of water) = 500 g
c (of water) = 4.18 J g-1 °C-1
ΔT (of water) = 68 oC - 25 oC

= 43 oC
Step 2: q = 500 x 4.18 x 43
= 89 870 J
Step 3: This is only 30% of the total energy released by methane
Total energy x 0.3 = 89 870 J
Total energy = 299 567 J
Step 4: This is released by 2.50 g of methane

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Energy released by 1.00 g of methane = 299 567 ÷ 2.50

= 119 827 J = 120 000 J Your notes
= 120 kJ g-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
Aqueous solutions of acid, alkalis and salts are assumed to be largely water so you can just use the m
and c values of water when calculating the energy transferred.
To calculate any changes in enthalpy per mole of a reactant or product the following relationship can
be used:

When there is a rise in temperature, the value for ΔH becomes negative suggesting that the reaction is
exothermic and when the temperature falls, the value for ΔH becomes positive suggesting that the
reaction is endothermic.

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1.6.5 Hess' Law

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Using Hess' Law
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

The enthalpy change from elements to products (direct route) is equal to the enthalpy change of
elements forming reactants and then products (indirect route)

Equation
ΔH2 = ΔH1 + ΔHr

Therefore,
ΔHr = ΔH2 – ΔH1

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Worked example
Your notes
Calculating the enthalpy change of reaction
Calculate the ΔHr for the following reaction:
2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (I)
The table below shows the standard enthalpy of formations (ΔHfꝋ) relevant to this reaction:

Answer
Step 1: Write the balanced equation at the top

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

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Step 3: Draw in all arrows, making sure they go in the correct directions. Write the standard enthalpy
of formations
Your notes

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 (ΔHatꝋ ) is the enthalpy change when one mole of gaseous atoms
is formed from its elements under standard conditions.
Eg. ΔHatꝋ [H2] relates to the equation:
½ H2(g) → H(g)

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1.6.6 Applications of Hess’s Law

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Hess's Law Calculations
You must make sure that you can apply Hess' Law effectively and calculate enthalpy changes in
different situations
Remember - it is the data that is important
Check whether the data you have been given is formation data or combustion data, and then complete
the cycle or calculation according to that

Worked example
Calculating the enthalpy change of formation of ethane
Calculate ΔHf [ethane].
The relevant change in standard enthalpy of combustion (ΔHc) values are shown in the table below:

Answer
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

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Your notes

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 (ΔHatꝋ ) is the enthalpy change when one mole of gaseous atoms
is formed from its elements under standard conditions.
Eg. ΔHatꝋ [H2] relates to the equation:
½ H2(g) → H(g)

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Worked example
Your notes
Calculating average C-H bond energy
Calculate the average bond energy of the C-H bond using the relevant ΔHfꝋ and ΔHatꝋ values in the
table below:

Answer
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

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Your notes

Step 4: Apply Hess’s Law

Step 5: Since there are 4 C-H bonds in methane:

Exam Tip
Remember: 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.

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1.6.7 Bond Enthalpies

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Bond Enthalpies
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 usually just simplified to bond energy or bond enthalpy
In symbols, the type of bond broken is written 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

Bond energies are affected by other atoms in the molecule, so average bond enthalpies are listed in
data tables
Calculating enthalpy change from bond energies
Bond energies are used to find the ΔHrꝋ of a reaction when this cannot be done experimentally
The formula is:

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Your notes

The formula for calculating the standard enthalpy change of reaction using bond energies

Worked example
Calculating the enthalpy change in the Haber process
Calculate the change in enthalpy of reaction for the Haber process, producing ammonia from
hydrogen and nitrogen:
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
The relevant bond energies are given in the table below:

Answer
Step 1: Use the equation to work out the bonds broken and formed and set out the calculation as a
balance sheet as shown below:
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

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Your notes

Note! Values for bonds broken are positive (endothermic) and values for bonds formed are negative
(exothermic)
Step 2: Calculate the standard enthalpy of reaction
ΔHrꝋ = enthalpy change for bonds broken + enthalpy change for bonds formed

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

= -93 kJ mol-1

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Worked example
Your notes
Calculating the enthalpy of combustion using bond enthalpies
The complete combustion of ethyne, C2H2, is shown in the equation below:

Using the average bond enthalpies given in the table, what is the enthalpy of combustion of ethyne?

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:

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Your notes

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

= (+2912 kJ mol-1) + (- 4142 kJ mol-1)

= -1230 kJ mol-1

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