Topic 5

Energetics/Thermochemistry
Topic 5.1: Measuring energy
changes
ESSENTIAL IDEA: THE ENTHALPY CHANGES
FROM CHEMICAL REACTIONS CAN BE
CALCULATED FROM THEIR EFFECT ON THE
SURROUNDINGS.
Chemistry Guide Statements T5.1 SL SL
Topic 5.1 —Measuring energy changes

Nature of science
Fundamental principle—conservation of energy is a fundamental principle of science. (2.6)
Making careful observations—measurable energy transfers between systems and surroundings. (3.1)

Understandings: International-mindedness:
• Heat is a form of energy. • The SI unit of temperature is the Kelvin (K), but the Celsius scale (°C), which has
• Temperature is a measure of the average kinetic energy of the particles. the same incremental scaling, is commonly used in most countries. The
• Total energy is conserved in chemical reactions. exception is the USA which continues to use the Fahrenheit scale (°F) for all
• Chemical reactions that involve transfer of heat between the system and the non-scientific communication.
surroundings are described as endothermic or exothermic. Theory of knowledge:
• The enthalpy change (ΔH) for chemical reactions is indicated in kJ mol-1. • What criteria do we use in judging discrepancies between experimental and
• ΔH values are usually expressed under standard conditions, given by ΔH°, theoretical values? Which ways of knowing do we use when assessing
including standard states. experimental limitations and theoretical assumptions?
Applications and skills: Utilization:
• Calculation of the heat change when the temperature of a pure substance is • Determining energy content of important substances in food and fuels.
changed using 𝑞 = mcΔ𝑇. • Syllabus and cross-curricular links:
• A calorimetry experiment for an enthalpy of reaction should be covered and Topic 1.1—conservation of mass, changes of state
the results evaluated. Topic 1.2—the mole concept
Guidance:
• Enthalpy changes of combustion (ΔHc ° ) and formation (ΔHf°)should be Aims:
covered. • Aim 6: Experiments could include calculating enthalpy changes from given
• Consider reactions in aqueous solution and combustion reactions. experimental data (energy content of food, enthalpy of melting of ice or the
• Standard state refers to the normal, most pure stable state of a substance enthalpy change of simple reactions in aqueous solution).
measured at 100 kPa. Temperature is not a part of the definition of standard • Aim 7: Use of databases to analyse the energy content of food.
state, but 298 K is commonly given as the temperature of interest. • Aim 7: Use of data loggers to record temperature changes.
• The specific heat capacity of water is provided in the data booklet in section 2.
• Students can assume the density and specific heat capacities of aqueous
solutions are equal to those of water, but should be aware of this limitation.
• Heat losses to the environment and the heat capacity of the calorimeter in
experiments should be considered, but the use of a bomb calorimeter is not
required.
Heat and Temperature
Heat is a form of energy that flows from something at a higher temperature to something
with a lower temperature.
So it is the amount of energy (J) exchanged due to a temperature difference between two
substances.

Temperature is a measure of the average kinetic energy of particles.

Internal energy is the name given to the total amount of energy (kinetic + potential) in a
sample of a substance.

In thermochemistry, the system is our chemical reaction and the surroundings is everything
else in the universe.
Exothermic and endothermic reactions and enthalpy changes

The enthalpy change is the amount of heat energy taken in/out in a reaction. Enthalpy is given the
symbol H and therefore enthalpy change is ΔH.
Remember: the higher the enthalpy the less stable the substance!

In an exothermic reaction heat energy is transferred from a system (chemical reaction) to the
surroundings – the surroundings get hotter. For an exothermic reaction energy is given out and ΔH is
negative. ΔH= enthalpy of products – enthalpy of reactants < 0
ΔH = HP –
HR

Example: https://www.youtube.com/watch?v=YRPuDQtB_5Y
Exothermic and endothermic reactions and enthalpy changes

In an endothermic reaction a system (chemical reaction) takes in heat energy from the surroundings – the
surroundings get cooler. For an endothermic reaction energy is absorbed and ΔH is positive.

ΔH= enthalpy of products – enthalpy of reactants > 0

ΔH = HP –
HR

Example: https://www.youtube.com/watch?v=IZaGmUGBdC0
Exothermic and endothermic reactions and enthalpy changes

Enthalpy changes are all quoted for the same set of conditions, which is called standard conditions.

Standard enthalpy change has the symbol ΔH°, which means that it is measured at T=298K and
P=100kPa (1.00x105Pa).

Standard enthalpy change of reaction (ΔH°r) is the enthalpy change when one mole of a substance
reacts under standard conditions to give products  ΔH°=Q/n

Example: 1/2N2(g) + 3/2H2(g) → NH3(g) ΔHr = −46 kJ mol−1

This value (-46 kJ/mol) refers to the reactions if molar amounts were involved [N2(g) + 3H2(g) →
2NH3(g)]
But actually this reaction involves half the molar amounts, therefore enthalpy change for this reaction is to
be recalculated for 0.5 mol of N2 ΔHr = kJ mol -1= 23 kJ mol -1

Standard enthalpy change of combustion (ΔH°c) is the enthalpy change when one mole of a substance
is completely burnt in oxygen under standard conditions.
Remember: ΔH°c is always negative, because combustion is always an exothermic process (think about
how we produce energy!!)

Example: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔHc = −890 kJ mol−1

Measuring enthalpy changes
Specific heat capacity (c) is the energy required to raise the
temperature of 1g of substance by 1K (1°C). Unit measure is J g-1 K-1
or J g-1 °C -1; other units can be kJ Kg-1 K-1 or J Kg-1 °K -1.

The amount of heat required is proportional to the mass and the

temperature change. An important equation can be derived for how
much heat energy (q) must be supplied to raise the temperature of
mass m by ΔT °C

q= m c ΔT

Measuring an enthalpy change of combustion

The technique is called calorimetry, where The idea is that the heat
given out in a combustion reaction is used to heat another substance
of known specific heat capacity, such as water. The equation q =
mcΔT can be therefore used to calculate the amount of heat given
out.
This experimental set-up shown could be used to determine the
enthalpy change when one mole of a liquid substance is burnt (the
enthalpy change of combustion). The mass and temperature change of
the water must be measured, as well as the mass change of the
alcohol.
Note: more accurate values of the enthalpy change of combustion need a bomb calorimeter!
C2H5OH + 3O2 → 2CO2 + 3H2O
Knowledge check: measuring enthalpgy change of combustion

Exercise on colorimetry

A calorimetry experiment was used to determine the enthalpy change of combustion of 1.20 g of hexane
(C6H14) given that the specific heat capacity of water is 4.18 J g–1 °C –1.

Write the reaction equation.

Mass of water = 250.00 g
ΔT of water = 56 °C
The amount of heat energy supplied to the water is given by: q = mcΔT

q = 250 × 4.18 x 56 = 58520 J

Number of moles of hexane burnt is given by:
Therefore = 0.0139 mol
When 0.0139 mol of hexane are burnt, 58520 J of heat energy are released. Therefore the amount of
energy released when one mole is burnt is given by

• What happens if hexane is burnt with an insufficient supply of oxygen??

 incomplete combustion!!
• How can we improve the calorimetry experiment?
Measuring enthalpgy changes in solution
A general method for measuring enthalpy changes involving solutions in the laboratory is to
measure out known amounts of reagents, record their initial temperatures, mix together the
reagents in a polystyrene cup and record the maximum/minimum temperature observed. The
specific heat capacity of the final solution is assumed to be the same as for water.

Enthalpy change of neutralisation (ΔHn) is the enthalpy change when one mole of water
molecules are formed when an acid (H+) reacts with an alkali (OH−) under standard
conditions:
H+(aq) + OH−(aq) → H2O(l)

Remember: ΔH°n is always negative, because neutralisation is always an exothermic process

Enthalpy change of solution (ΔHsol) is the enthalpy change when one mole of solute is
dissolved in excess solvent to form a solution of ‘infinite dilution’ (meaning that any further
dilution of the solution produces no further enthalpy change) under standard conditions.

Remember: ΔH°sol can be positive or negative since the process may be endothermic or
exothermic.
Knowledge check: measuring enthalpy change of neutralisation
Exercise

200.0 cm3 of 0.150 mol dm−3 hydrochloric acid is mixed with 100.0 cm 3 of 0.300 mol dm−3 sodium
hydroxide solution. The temperature rose by 1.36 °C. If both solutions were originally at the same
temperature, calculate the enthalpy change of neutralisation.
First write the reaction equation.

HCl + NaOH  NaCl + H2O

Total volume: 300 cm3

We assume that density of the mixture is the same as water (1 g/cm 3 or 1g/mL meaning 1 cm3
has a mass of 1 g), and therefore 300 cm3 of this solution has a mass of 300 g.
We can work out how much heat (q) has been released in this reaction by using the temperature change of
the mixture:
q = mcΔT = 300 x 4.18 x 1.36 = 1705 J

Now to work out ΔHn we need to know the number of moles of water that have formed (remember n=CV
page 40 book).
n HCl= C x V (in dm3) = 0.15 x 200/1000= 0.03 mol
n NaOH = 0.3 x 100/1000 = 0.03 mol
Therefore the number of moles of water produced is 0.03 mol. Therefore 1705 J is released when 0.03 mol
of water are formed. ΔHn always refers to 1 mol, so heat released= 1/0.03 x 1705 = 56833 J  ΔHn = 56.8 kJ
mol-1
Knowledge check: measuring enthalpy change of combustion

Exercise: 1200 kJ of heat is evolved when 2 moles of magnesium react completely with 1
mole of oxygen. How much energy is released if 0.600g of Mg is burnt?

2Mg(s) + O2(g)  2MgO(s)

So Hc(Mg) = -1200kJmol-1/2 = -600 kJmol-1

n(Mg) = m/M = 0.600g/24.3g/mol = 0.0247mol

H = Q/n
so Q = H x n = -600 kJmol-1 x 0.0247mol = 14.8 kJ
Knowledge check: measuring enthalpy change of solution

Exercise:

A. When 1.00 g of magnesium chloride is dissolved in 50.0 cm 3 of water, the temperature goes up from 21.5
°C to 29.1 °C. Calculate the enthalpy change of solution of magnesium chloride.

Mass of water = 50.0 g

ΔT of water = 29.1 – 21.5 = 7.6°C

The amount of heat energy supplied to the water is given by:

q = mcΔT
q = 50 × 4.18 x 7.6 = 1588 J

Number of moles of magnesium chloride dissolved is given by:

Therefore = 0.0105 mol
When 0.0105 mol of MgCl2 are dissolved in water, 1588 J of heat energy are released. Therefore the amount
of energy released when one mole is dissolved is given by

B. Calculate the temperature change when 2g of MgCl 2 are dissolved in 100 cm3 of water.
C. Calculate the temperature change when 2g of MgCl 2 are dissolved in 50 cm3 of water.
Knowledge check: measuring enthalpy change of reaction
Exercise:
The following experiment may be used to determine the enthalpy change of reaction for:
Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s) [this type of reactions is a displacement reaction or single replacement
reaction]

50.0 cm3 of 0.200 mol dm−3 copper(II) sulfate solution are placed in a polystyrene cup. The temperature was recorded
every 30s for 2 min. At 2 min 30s, 1.20 g of powdered zinc are added. The mixture was stirred vigorously and the
temperature recorded every half minute for several minutes. The results obtained were then plotted to give the following
graph:

Figure: temperature against time for the reaction of zinc with copper sulfate solution
Knowledge check: measuring enthalpy change of reaction

Solution:

From the graph we estimate the temperature change as ΔT = 10.3 °C.

The heat given out in the reaction is given by: q = mcΔT = 50.0 × 4.18 × 10.3 = 2150 J

To work out the enthalpy change of reaction, we need to know how many moles of copper
sulfate reacted (the zinc was in excess).
number of moles of CuSO4 = concentration × volume in dm3
number of moles of CuSO4 =
Therefore 2150 J of energy are released when 0.0100 mol copper sulfate reacts.
For the ΔH value, we need to make a proportion considering the reaction of one mole of
copper sulfate:
heat energy released =
Therefore the enthalpy change of reaction = −215 kJ mol−1.
Topic 5.2: Hess’s law
E S SE NT I AL I DE A: I N CHE M I C AL T R ANSFORM AT I ONS
E NE RGY CAN NE I T HE R BE C RE AT E D NOR
DE ST R OYE D ( T HE FI RS T L AW OF
T HE RM ODYNAM I C S) .
Chemistry Guide Statements T5.2 SL SL
Topic 5.2 —Hess’s law

Nature of science
Hypotheses—based on the conservation of energy and atomic theory, scientists can test the hypothesis that if the same products are
formed from the same initial reactants then the energy change should be the same regardless of the number of steps. (2.4)

Understandings: International-mindedness:
• The enthalpy change for a reaction that is carried out in a series • Recycling of materials is often an effective means of reducing the
of steps is equal to the sum of the enthalpy changes for the environmental impact of production, but varies in its efficiency in
individual steps. energy terms in different countries.
Applications and skills: Theory of knowledge:
• Application of Hess’s Law to calculate enthalpy changes. • Hess’s Law is an example of the application of the Conservation
• Calculation of Δ𝐻𝐻 reactions using Δ𝐻𝐻𝑓𝑓 ° data. of Energy. What are the challenges and limitations of applying
• Determination of the enthalpy change of a reaction that is the general principles to specific instances?
sum of multiple reactions with known enthalpy changes. Utilization:
Guidance: • Hess’s Law has significance in the study of nutrition, drugs, and
• Enthalpy of formation data can be found in the data booklet in Gibbs free energy where direct synthesis from constituent
section 12. elements is not possible. Syllabus and cross-curricular links:
• An application of Hess's Law is Δ𝐻𝐻 reaction = Σ(Δ𝐻𝐻𝑓𝑓 ° Physics topic 2.3—conservation of mass-energy
products) − Σ(Δ𝐻𝐻𝑓𝑓 ° reactants). Aims: :
• Aim 4: Discuss the source of accepted values and use this idea to
critique experiments.
• Aim 6: Experiments could include Hess's Law labs.
• Aim 7: Use of data loggers to record temperature changes.
Hess’s law
It is not always possible to design experiments to measure certain enthalpy changes and so
we often have to use data from other reactions in which the enthalpy change can be
measured to work out the enthalpy change for a particular reaction in which it cannot be
measured directly.
In order to do this, we use Hess’s law, which states that the enthalpy change
accompanying a chemical reaction is independent of the pathway between the initial
and final states.

So if we consider the conversion between A into product B in the following figure, the
enthalpy change of the reaction is the same if we go directly from A to B or indirectly via
other reactions and intermediates (C).
Hess’s law states that the enthalpy change for
the direct conversion of A to B is exactly the
same as the enthalpy change for the indirect
route between A and B. Therefore, in this case:
ΔHr = ΔH1 + ΔH2

Be very careful with the direction of the

indirect reactions and therefore the sign of ΔH
Why Hess’s law works
Knowledge check: working out enthalpy changes
Exercise

Given these enthalpy changes:

2C(s) + O2(g) → 2CO(g) ΔH = −222 kJ mol−1 ΔH1

Reaction 1
C(s) + O2(g) → CO2(g) ΔH = −394 kJ mol−1 ΔH2
Reaction 2

calculate the enthalpy change for the reaction:

2CO(g) + O2(g) → 2CO2(g)
Knowledge check: working out enthalpy changes
Solution

Method A (constructing a cycle)

The enthalpy changes given are used to construct a
cycle. The enthalpy change that we have to find is put
at the top of the cycle.
Only the first reaction has been added here.
Reaction 1 is highlighted in yellow (there is 1 O2
which is on both sides of the equation and therefore
does not affect the overall enthalpy change.
Reaction 2 is highlighted in green, but it must be
multiplied by two, because we need to form 2 mol CO 2.
The enthalpy change must also be multiplied by two,
hence 2ΔH2.
The values can now be put into the cycle:
The overall enthalpy change is given by
ΔH = −ΔH1 + 2ΔH2
ΔH = −(−222) + (2 × −394) = −566 kJ mol−1
Knowledge check: working out enthalpy changes
Solution

Method B (equations)
Equations are rearranged for the data given to produce the equation for the reaction
corresponding to the enthalpy change we have to find.

So, Reaction 1 is reversed to give 2CO on the left-hand side, as in the overall equation:
2CO(g) → 2C(s) + O2(g) ΔH = +222 kJ mol−1 (sign changed)

Then Reaction 2 is multiplied by 2 to give 2CO2 on the right-hand side, as in the overall
equation:
2C(s) + 2O2(g) → 2CO2(g) ΔH = −788 kJ mol−1 (enthalpy change multiplied by two)

We now have the equation written in the correct directions. The two equations and their
enthalpy changes are now added together, and common terms cancelled to produce the
overall equation and its enthalpy change:

2CO(g) → 2C(s) + O2(g) ΔH = +222 kJ mol−1

2C(s) + 2O2 (g) → 2CO2 (g) ΔH = −788 kJ mol−1
2CO(g) + O2(g) → 2CO2(g) ΔH = −566 kJ mol−1
Knowledge check: working out enthalpy changes
Exercise

Use the information given below to calculate the enthalpy change for the reaction:

C2H4(g) + H2O(g) → C2H5OH(l)

H2O(l) → H2O(g) ΔH = +44 kJ mol−1 ΔH1 Reaction 1

ΔHc [C2H5OH(l)] = −1371 kJ mol −1 ΔH2 Reaction 2
ΔHc [C2H4(g)] = −1409 kJ mol −1 ΔH3 Reaction 3

Solution

We are given standard enthalpy change of combustion data and so, knowing the definition,
we can write out the full chemical equations for the enthalpy changes:
Reaction 2: C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) ΔH2 = −1371 kJ mol−1
Reaction 3: C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l) ΔH3 = −1409 kJ mol−1
Knowledge check: working out enthalpy changes
Solution

Method A (constructing a cycle)

The enthalpy change for the

direct route is the same as that
for the indirect route:
ΔH = −1409 − (+44) − (−1371)
= −82 kJ mol−1
Knowledge check: working out enthalpy changes
Solution

Method B (equations)
Equations 1 and 2 are reversed to produce the equation for the reaction corresponding to the
enthalpy change we have to find.

So, Reaction 1 is reversed to give H2O(l) on the right-hand side and Reaction 2 is reversed to
give C2H5OH on the right-hand side:

H2O(g) → H2O(l) ΔH1 = −44 kJ

mol−1 (sign changed)
2CO2(g) + 3H2O(l) → C2H5OH(l) + 3O2(g) ΔH2 = +1371 kJ mol−1 (sign changed)

We now have the equation written in the correct directions. The three equations and their
enthalpy changes are now added together, and common terms cancelled to produce the overall
equation and its enthalpy change:

H2O(g) → H2O(l) ΔH1 = −44 kJ

mol−1
2CO2 (g) + 3H2O(l) → C2H5OH(l) + 3O2 (g) ΔH2 = +1371 kJ mol−1
C2H4(g) + 3O2(g) → 2CO2 (g) + 2H2O(l) ΔH3 = −1409 kJ mol−1
Knowledge check: working out enthalpy changes
Exercise

Calculate the enthalpy change for the following reaction, given the data in the table:
C4H8(g) + H2(g) → C4H10(g)
Substance ΔH°c (kJ mol−1)
C4H8(g) -2717
C4H10(g) -2877
H2(g) -286

C4H8(g) + 6O2  4H2O + 4CO2

ΔH°c= -2717 kJ/mol +

C4H10(g) + 13/2 O2  5H2O + 4CO2

5H2O + 4CO2  C4H10(g) + 13/2 O2 ΔH°c= +2877
kJ/mol +

H2 (g) + ½ O2  H2O
ΔH°c= -286 kJ/mol =
Standard enthalpy change of formation
Standard enthalpy change of formation (ΔHf ) is the enthalpy change when one mole of a
substance is formed from its elements in their standard states under standard conditions.
A standard enthalpy change of formation may be exothermic or endothermic, depending on the
substance. ΔHr = ΣΔHf (products) − ΣΔHf (reactants)

Example: the equation representing the enthalpy change of formation of methane is:
C(s) + 2H2(g) → CH4(g)
The carbon here is graphite, which is the most stable form of carbon.

Example: For ammonia, the enthalpy change of formation is for the reaction:
12N2(g) + 32H2(g) → NH3(g)

Both examples show the formation of one mole of product, methane and ammonia respectively.

The standard enthalpy change of formation of any element in its standard state is zero because,
by definition, no heat energy is taken in or given out when one mole of an element in its standard
state is formed from one mole of the element in its standard state.
ΔHf for any element in its standard state is zero. Ex. I2(s) → I2(s) ΔHf =
0
Knowledge check: Using standard enthalpy changes of formation to work
out enthalpy changes
Exercise:
Given the enthalpy changes:
calculate the standard enthalpy change for the
ΔHf [Fe2O3(s)] = −822 kJ mol−1;
reaction:
ΔHf [CO(g)] = −111 kJ mol−1; Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
ΔHf [CO2(g)] = −394 kJ mol−1

2Fe(s) + 3/2 O2(g) → Fe2O3(s) ΔHf = −822 kJ mol−1

C(s) + ½ O2(g) → CO(g) ΔHf = −111 kJ mol−1
C(s) + O2(g) → CO2(g) ΔHf = −394 kJ mol−1

The total enthalpy change for the formation of the reactants, Fe2O3(s) and 3CO(g), from their elements is:
ΔHf [Fe2O3(s)] + 3 ΔHf [CO(g)] = −822 + (3 × −111) = −1155 kJ mol−1
The total enthalpy change for the formation of the products, 2Fe(s) and 3CO2(g), from their elements is:
2 ΔHf [Fe(s)] + 3 ΔHf [CO2(g)] = 0 + (3 × −394) = −1182 kJ mol−1
Note that the standard enthalpy change of formation of Fe(s) is 0 because it is an element in its standard state.

The enthalpy change for the direct route is the same as the enthalpy change for the indirect route. The indirect
route goes in the opposite direction to the blue arrow and therefore the sign of this enthalpy change is reversed:
ΔH r = −(−1155) + (−1182) = −27 kJ mol−1
Therefore the enthalpy change of reaction is −27 kJ mol
Using standard enthalpy changes of formation to work out enthalpy changes

The easiest way to calculate the enthalpy change of reaction knowing the enthalpy change of
formaton is to subtract the total enthalpy change of the reactants from the total enthalpy change
of the products to give the overall enthalpy change. This can be shown as:

ΔHr = ΣΔHf (products) − ΣΔHf (reactants)

ΔHf [NH3(g)] = −46 kJ mol−1
ΔHf [NO (g)] = 90 kJ mol−1
ΔHf [H2O (g)] = −242 kJ mol−1

Calculate the enthalpy change for the reaction:

4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

Using ΔHr = ΣΔHf (products) − ΣΔHf (reactants)

ΣΔHf (products)= (4 × 90) + (6 × −242) = −1092 kJ mol −1
ΣΔHf (reactants)= (4 x -46) + 0 = -184 kJ mol-1
Note that ΔHf for O2 is zero because it is an element in its standard state.

ΔHr= -1092 – (-184) = -908 kJ mol-1

So this is enthalpy change for this reaction.

Determining an enthalpy change of formqation from an enthalpy change of
reaction
If you are given an enthalpy change of reaction and some enthalpy changes of formation, it
may be possible to work out a missing enthalpy change of formation.

Exercise:
Given that the standard enthalpy change of formation of ethane (C 2H6 (g)) is -85 kJ mol-1 and
this reaction:
C2H2 (g) + 2H2 (g)  C2H6 (g) H=-311 kJ mol-1

Work out the enthalpy change of formation of ethyne, C 2H2(g).

Using ΔHr = ΣΔHf (products) − ΣΔHf (reactants)

-311 = - 85 – (ΔHf [C2H2(g)] + [2x0])

ΔHf [C2H2(g)]= -85 +311 = +226 kJ mol -1
Topic 5.3: Bond enthalpies
ESSENTIAL IDEA: ENERGY IS ABSORBED
WHEN BONDS ARE BROKEN AND IS
RELEASED WHEN BONDS ARE FORMED
Chemistry Guide Statements T5.3 SL SL
Topic 5.3 — Bond enthalpies
Nature of science:
Models and theories—measured energy changes can be explained based on the model of bonds broken and bonds formed. Since these
explanations are based on a model, agreement with empirical data depends on the sophistication of the model and data obtained can be
used to modify theories where appropriate. (2.2)

Understandings: International-mindedness:
• Bond-forming releases energy and bond-breaking requires • Stratospheric ozone depletion is a particular concern in the
energy. polar regions of the planet, although the pollution that causes
• Average bond enthalpy is the energy needed to break one mol it comes from a variety of regions and sources. International
of a bond in a gaseous molecule averaged over similar action and cooperation have helped to ameliorate the ozone
compounds. depletion problem.
Applications and skills: Utilization:
• Calculation of the enthalpy changes from known bond enthalpy • Energy sources, such as combustion of fossil fuels, require high
values and comparison of these to experimentally measured ΔH values. Syllabus and cross-curricular links: Topic 4.3—
values. covalent structures
• Sketching and evaluation of potential energy profiles in Aims:
determining whether reactants or products are more stable • Aim 6: Experiments could be enthalpy of combustion of
and if the reaction is exothermic or endothermic. propane or butane.
• Discussion of the bond strength in ozone relative to oxygen in • Aim 7: Data loggers can be used to record temperature
its importance to the atmosphere. changes.
Guidance: • Aim 8: Moral, ethical, social, economic and environmental
• Bond enthalpy values are given in the data booklet in section consequences of ozone depletion and its causes.
11.
• Average bond enthalpies are only valid for gases and
calculations involving bond enthalpies may be inaccurate
because they do not take into account intermolecular forces.
Bond enthalpies
Enthalpy changes for reactions in the gas phase can be worked out if we know the amount of energy
required/released when bonds are broken/made. To be able to do this we must first consider the definition of
bond enthalpy/bond energy:

Bond enthalpy is the enthalpy change when one mole of covalent bonds, in a gaseous molecule, is broken
under standard conditions. Bond enthalpies are used for reactions occurring in the gaseous state.

Example: the H-H bond enthalpy is 436 kJ mol -1 which means that one mole of H2 molecules is broken down
to give 2 moles of gaseous hydrogen atoms.

H2(g)  2H(g) ΔH°= +436 kJ mol-1

Example: the H-Cl bond enthalpy is 431 kJ mol -1 which means that one mole of HCl molecules is broken
down to give 1 mole of gaseous hydrogen atoms and 1 mole of gaseous chlorine atoms .

HCl(g)  H(g) + Cl (g) ΔH°= +431 kJ mol-1

Note: Br2(l) → 2Br(g) does not represent the bond enthalpy Br-Br, because this reaction refers to the
enthalpy change of atomisation ΔHat (referred to 1 mole of gaseous atoms, so in this case the enthalpy
change would be twice the ΔHat) and energy must be supplied to overcome the London forces in Br 2 and to
break the Br-Br bonds.
Bond breaking requires energy (endothermic): ΔH
positive.
Chemistry data booklet: average bond enthalpiesBond making releases energy (exothermic): ΔH
values
Average bond enthalpies

The bond energies given the booklet are average values.

Example: the C–H bond energy in ethane (C2H6) is slightly different from that in benzene
(C6H6) so the value quoted in the table (412 kJ mol -1) is an average value, averaged over the
values for C–H bonds in many compounds.
This can introduce some inaccuracies into calculations involving bond energies. Bond energy
calculations are therefore most accurate when they involve breaking/making only a few bonds.

Average bond enthalpy is the average amount of energy required to break one mole of
covalent bonds, in gaseous molecules under standard conditions.
‘Average’ refers to the fact that the bond enthalpy is different in different molecules and
therefore the value quoted is the average amount of energy to break a particular bond in a
range of molecules.
Using bond enthalpies to work out enthalpy changes for reactions

Exercise: Consider the reaction between ethene and bromine to produce

1,2-dibromoethane and calculate the enthalpy chengae for the reaction:
C2H4(g) + Br2(g) → C2H4Br2(g)
ΔHr = Σ(bonds broken) − Σ(bonds made
From the booklet we know that:
Bond broken Bond energy (kJ Number of Total energy (kJ
mol-1) bonds broken mol-1)
C–H 412 4 1648
ΔH = 2453 − 2548 = −95 kJ mol−1
C=C 612 1 612

Br-Br 193 1 193

The total enthalpy change when all bonds are broken is: + 2453
A shortcut for doing this
Bond made Bond energy (kJ Number of Total energy
mol-1) bonds broken (kJ mol-1)
question would be to realise
that there are 4 C–H bonds in
C-H 412 4 1648
ethene and 4 C–H bonds in
C-C 348 1 348 1,2-dibromoethane, and
C-Br 276 2 552 therefore there is no need to
make or break these bonds
The total enthalpy change when all bonds are formed is –2548
Knowledge check
Question:

If the enthalpy change for: C2H4(g) + Br2(g) → C2H4Br2(g)

is calculated using enthalpy changes of formation the value obtained is −121 kJ mol−1, which is
different from the value of −95 kJ mol−1 obtained using bond enthalpy calculations.

Why?

The value obtained using enthalpy changes of formation is expected to be more reliable,
because enthalpy changes of formation are specific to the particular substances, whereas bond
enthalpies are average values. The C–H bond energies in C 2H4 and C2H4Br2 would not be
expected to be the same, and the values used for the C=C and C–C bonds are not necessarily the
actual bond energies in these compounds (they are an average!).

Values for enthalpy changes of reaction obtained using bond enthalpies are less reliable
than those calculated using experimental data such as the enthalpy change of combustion
or formation.
Using a cycle in calculations involving bond enthalpies

Exercise:
Knowing the bond enthalpies of H-H, O=O and O-H, calculate the enthalpy change for the
reaction:
H2(g) + ½ O2(g)  H2O(g) Note: in order to use bond enthalpies, the
substances must be in the gas phase. This
is because intermolecular forces must
also be taken into account in the case of
liquid and solid states. So, in order to use
bond enthalpies with solids and liquids
we must first generate gaseous species.
If we wanted to find the enthalpy change
for the formation of liquid water from its
elements – i.e. for the process:
H2(g) + ½ O2(g) → H2O(l)
we would also have to know the enthalpy
change of vaporisation of water!

ΔHr = (436 + ½ × 496) − (2 × 463) = −242 kJ mol −1

Important concepts
A reaction in the gas phase will be endothermic if
less energy is released when bonds are formed
(exothermic) than is required to break bonds
(endothermic). This could be the case if stronger/
more bonds are broken than are formed.

A reaction in the gas phase will be exothermic if

more energy is released when bonds are formed
(exothermic) than is required to break bonds
(endothermic). This could be the case if stronger/
more bonds are made than are broken.

It is important to note that bond energies can only be

used to decide whether a reaction in the gas phase is
exothermic or endothermic. For reactions involving
solids and liquids, other interactions, such as
intermolecular forces, must also be taken into account.
Knowledge check: using a cycle in calculations involving bond enthalpies

Exercise:
Calculate the enthalpy change for the process:
3C(s) + 4H2(g) → C3H8(g)
using the following bond energies: C–H = 412 kJ mol−1
H–H = 436 kJ
mol−1
C–C = 348 kJ
mol−1
and the enthalpy change: C(s) → C(g) ΔH° = +715 kJ mol−1
Knowledge check
Exercise:

Calculate the enthalpy change for the reaction N2 + 3H2  2NH3

By using bond enthalpy values.

Bonds broken
1 N≡N: = 945
3 H-H: 3(435) = 1305
Total = 2250 kJ/mol
Bonds formed
2x3 = 6 N-H: 6 (390) = - 2340 kJ/mol

Net enthalpy change

ΔH = bond broken – bonds made
= + 2250 - 2340 = - 90 kJ/mol
Working out a bond enthalpy from an enthalpy change of reaction

Exercise

Using the bond enthalpies for the F-F and Br-Br bonds and the enthalpy change of reaction
given, calculate the mean Br-F bond energy in BrF 3.

Br2(g) + 3F2(g) 2BrF3(g) ΔH°= -545 kJ/mol

ΔHr = Σ(bonds broken) − Σ(bonds made)

-545 = [193 + (3x158)] – [6x Br-F]

6x Br-F = 193 + (3x158) + 545

6x Br-F = 1212

Br-F = 1212/6 = 202 kJ/mol

Potential energy profiles and stability
A potential energy diagram (profile) can be used to show the energy changes occurring during
a chemical reaction. The reaction coordinate (X axis) represents the progress of a reaction
from reactants to products. As reactant particles approach each other, repulsion between the
particles and the partial breaking of bonds causes the potential energy of the system to
increase. The activation energy is the minimum energy that colliding particles must have for
a collision to result in a chemical reaction (more AHL).

In an exothermic reaction, the products are at For an endothermic reaction, the products
lower energy than the reactants and are are at higher energy and are less stable
therefore said to be more stable than the than the reactants.
reactants.
Absorption of UV ligth in the atmosphere
Ozone (O3) and oxygen (O2) in the atmosphere are important in protecting the surface of the
Earth from the damaging effects of UV radiation.
O2 molecules absorb higher energy UV radiation than O 3 because the bond between the
oxygen atoms in O2 is stronger than that between the oxygen atoms in O 3. As a result, ozone
is decomposed more easily than oxygen!

ƛ<242 nm
O2(g) O•(g) O2 requires 498kJ/mol to break
UV-C
+ O•(g)
ƛ<330 nm
O3 requires 364kJ/mol to break
UV-B Remember
O3(g) O2(g) E = hν = hc/λ
+ O•(g)
Knowledge check
Exercise Remember ΔHr = Σ(bonds broken) − Σ(bonds made)

Use the bond enthalpies to work out the enthalpy changes for the following reactions:

A. CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g)

B. C2H2(g) + 2H2(g) → C2H6(g)

A. -115 kJ/mol
B. -287 kJ/mol
Knowledge check
Exercise Remember ΔHr = Σ(bonds broken) − Σ(bonds made)

Calculate the mean Cl–F bond enthalpy and the Cl–Cl and F–F bond enthalpies, given the
following data:

Cl2(g) + 3F2(g) → 2ClF3(g) ΔH = −164 kJ mol−1

ClF3 just contain single
bonds between Cl and
Solution: 147 kJ/mol F

Exercise
Work out the enthalpy change for the reaction:
S(s) + F2(g) → SF2(g)

given the bond energies: S–F = 327 kJ mol−1 and F–F = 158 kJ mol −1
and this enthalpy change: S(s) → S(g) ΔH = +223 kJ mol−1

Solution:
223 + 158 – (327x2) = 381-654= -273 kJ/mol