CHEMICAL ENERGETICS 2

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CIE A Level Chemistry Your notes
1.5 Chemical Energetics

Contents
1.5.1 Enthalpy Change, ΔH
1.5.2 Energy Level Diagrams
1.5.3 Standard Enthalpy Change
1.5.4 Enthalpy & Bond Energies
1.5.5 Hess’s Law
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1.5.1 Enthalpy Change, ΔH

Your notes
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 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, the rate may be too slow to observe any appreciable reaction
In this case the reaction is kinetically controlled
This means the reaction could have a high activation energy which is preventing the reaction from
taking place.
The enthalpy change during an exothermic reaction
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Endothermic reactions
A reaction is endothermic when the products have more energy than the reactants Your notes
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
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:Na+Cl- (s) →
Na+ (aq) + Cl- (aq) ΔH = +4 kJ mol-1Na+Cl- (g) → Na+ (g) + Cl- (g) ΔH = + 500 kJ mol-1Also, remember
that the system is the molecules that are reacting (ie. the reaction itself) and the surroundings is
everything else (eg. the flask the reaction is taking place in).
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1.5.2 Energy Level Diagrams

Your notes
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’
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
The reactants are therefore closer in energy to the transition state
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This means that exothermic reactions have a lower activation energy compared to endothermic
reactions
Your notes
The energy level diagram for exothermic reactions

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

Worked example: Drawing energy level diagrams of the combustion of methane
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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Your notes
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
Worked example: Determining the activation energy
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Your notes
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
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’
Ea (reverse reaction) = +20 kJ mol-1
Exam Tip
The activation energy is the energy difference from reactants to transition state.The enthalpy change
of the reaction is the energy difference from reactants to products.Remember to label the axis of the
energy level diagrams!
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1.5.3 Standard Enthalpy Change

Your notes
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 Ꝋ is used
ΔHꝊ = the standard enthalpy change
These are a number of key definitions for common language relating to enthalpy change that all
chemists need to know
Enthalpy definitions table
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Your notes
Worked example: Calculating the enthalpy change of reaction of water
Page 11 of 31
Your notes
Answer
Since two moles of water molecules are formed in the question above, the energy released is
simply:
ΔHrꝊ = 2 mol x (-286 kJ mol-1)
= -572 kJ mol-1
Worked example: Calculating the enthalpy change of formation
Answer
Since two moles of Fe2O3 (s) are formed the total change in enthalpy for the reaction above is:
ΔH f Ꝋ = 2 x ( -824.2 kJ mol-1)
= - 1648 kJ
Worked example: Calculating enthalpy changes
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Your notes
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 of an acid and 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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1.5.4 Enthalpy & Bond Energies

Your notes
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
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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 Your notes
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Enthalpy Calculations
Exact bond energy Your notes
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. EE(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

Calculating enthalpy change from bond energies
Bond energies are used to find the ΔHrꝋ of a reaction when this cannot be done experimentally
Eg. the Haber Process
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Your notes
Formula of calculating the standard enthalpy change of reaction using bond energies
Worked example: Calculating the enthalpy change in the Haber process
Answer
Step 1: The chemical equation for the Haber process is:
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Step 2: Set out the calculation as a balance sheet as shown below:
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Your notes
Note! Values for bonds broken are positive (endothermic) and values for bonds formed are negative
(exothermic)
Step 3: 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
Worked example: Calculating the average bond enthalpy
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Your notes
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:
Page 19 of 31
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
Measuring enthalpy changes
Calorimetry is a technique used to measure changes in enthalpy of chemical reactions
A calorimeter can be made up of a polystyrene drinking cup, a vacuum flask or metal can
Page 20 of 31
Your notes
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:
Equation for calculating energy transferred in a calorimeter

Worked example: Specific heat capacity calculations
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Your notes
Step 1: q = m x c x ΔT
m (of water) = 500 g
c (of water) = 4.18 J g-1 K-1
ΔT (of water) = 68 oC - 25 oC
= 43 oC
= 43 K
The change in temperature in oC is equal to the change in temperature in K
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
= 119 827 J
= 120 kJ
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Exam Tip
Your notes
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-
12O (g) → O (g)
2 E (O=O) + -498 kJ mol Aqueous solutions of acid, alkalis and salts are
-1
assumed to be largely water so you can just use the m and c values of water when calculating the
energy transferred. To then 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.Also, remember that the ΔT is the same in oC and K!
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1.5.5 Hess’s Law

Your notes
Hess Cycles
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
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
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
Calculating ΔHr from ΔHf using Hess’s Law energy cycles
The products can be directly formed from the elements = ΔH2
OR
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The products can be indirectly formed from the elements = ΔH1 + ΔHr
Your notes
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
Worked example: Calculating the enthalpy change of reaction
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Your notes
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 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 = ΔHf + ΔH2
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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)
Your notes
Equation
ΔH1 = ΔHf + ΔH2
Therefore,
ΔHf = ΔH1 – ΔH2
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
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Your notes
Step 3: Draw all arrows in the correct direction
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)
Worked example: Calculating average C-H bond energy
Page 29 of 31
Your notes
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 5: Since there are 4 C-H bonds in methane:
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.
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CIE A Level Chemistry Your notes

1.5 Chemical Energetics

1.5.1 Enthalpy Change, ΔH

The enthalpy change during an exothermic reaction

The enthalpy change during an endothermic reaction

1.5.2 Energy Level Diagrams

The energy level diagram for exothermic reactions

The energy level diagram for endothermic reactions

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

Worked example: Determining the activation energy

The reaction pathway diagram for a reversible reaction

1.5.3 Standard Enthalpy Change

Worked example: Calculating the enthalpy change of reaction of water

1.5.4 Enthalpy & Bond Energies

Bond energies are affected by other atoms in the molecule

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

H-C ≡ C-H + 2 ½ O=O → H-O-H + 2O=C=O

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

Equation for calculating energy transferred in a calorimeter

1.5.5 Hess’s Law

Worked example: Calculating the enthalpy change of reaction

Step 1: Write the balanced equation at the top

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

Step 4: Apply Hess’s Law

Calculating ΔHf from ΔHc using Hess’s Law energy cycles

Worked example: Calculating the enthalpy change of formation of ethane

Step 3: Draw all arrows in the correct direction

Step 4: Apply Hess’s Law

Calculating average bond energies using Hess's cycles

Worked example: Calculating average C-H bond energy

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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