6.1 What are enthalpy changes?

Exothermic or endothermic?
Chemical reactions that transfer heat energy to the surroundings are described as exothermic. In an
exothermic reaction, the temperature of the surroundings increases. For example, when magnesium
reacts with sulfuric acid in a test-tube, the energy released is transferred to the surroundings and the
temperature of the reaction mixture in the tube increases.

Mg(s) + H2SO4(aq) → MgSO4(aq) + H2(g) (energy released)

The surroundings include:

the solvent (in this case water)

the air around the test-tube
the test-tube itself
anything dipping into the test-tube (e.g. a thermometer).

Other examples of exothermic reactions include:

the combustion of fuels

the oxidation of carbohydrates in the bodies of animals and plants (respiration)
the reaction of water with quicklime (calcium oxide) (see Section 11.4).

We describe chemical reactions that absorb heat energy from the surroundings as endothermic. In an
endothermic reaction, the temperature of the surroundings decreases (Figure 6.2). For example, when
sodium hydrogencarbonate reacts with an aqueous solution of citric acid in a test-tube, the temperature of
the reaction mixture in the tube decreases because the citric acid and sodium hydrogencarbonate are
absorbing the heat energy from the solvent, the test-tube and the air.

Figure 6.2: Using a cooling pack to treat a sports injury. When you rub or press the pack, water and ammonium chloride
crystals mix. As the crystals dissolve, energy is transferred from the surroundings, cooling the injury.

Other examples of endothermic reactions include:

the decomposition of limestone by heating (all thermal decomposition reactions are endothermic)
photosynthesis (in which the energy is supplied by sunlight)
dissolving certain ammonium salts in water

Question
1 Classify each process as exothermic or endothermic:

a the burning of magnesium in air

b the crystallisation of copper(II) sulfate from a saturated solution

c the thermal decomposition of magnesium nitrate

d the fermentation of glucose by yeast

e the evaporation of sea water.

Enthalpy changes and enthalpy profile diagrams

The energy exchange between a chemical reaction and its surroundings at constant pressure is called the
enthalpy change. Enthalpy is the total energy associated with the materials that react. The symbol for
enthalpy is H. We cannot measure enthalpy, but we can measure an enthalpy change when heat energy is
exchanged with the surroundings. We can write this as:

The symbol Δ is the upper case Greek letter ‘delta’. This symbol is often used to mean a change in a
quantity.

For example, ΔT means a change in temperature and ΔH means the enthalpy change.

The units of enthalpy change are kilojoules per mole (kJ mol−1).
We can draw reaction pathway diagrams (also known as enthalpy profile diagrams) to show enthalpy
changes. The enthalpy of the reactants and products is shown on the y-axis. The x-axis shows the reaction
pathway, with reactants on the left and products on the right. Reaction pathway diagrams usually also
show the activation energy, EA, as a hump (up and down curve) between the reactants and the products.
The activation energy is the minimum energy that colliding particles must possess for a reaction to
happen. Activation energy always has a positive value of ΔH because enough energy has to be absorbed to
increase the kinetic energy of the reactant molecules so that they collide with enough force to break bonds
(see Section 6.5).

For an exothermic reaction, energy is released to the surroundings. So the enthalpy of the reactants must
be greater than the enthalpy of the products. We can see from the reaction pathway diagram for the
combustion of methane (Figure 6.3) that Hproducts − Hreactants is negative.

Figure 6.3: Reaction pathway diagram for the combustion of methane.

We can include this information in the equation for the reaction:

CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890.3 kJ mol−1

The negative sign shows that the reaction is exothermic.

For an endothermic reaction, energy is absorbed from the surroundings by the substances in the reaction.
So the enthalpy of the products must be greater than the enthalpy of the reactants. We can see from the
reaction pathway diagram for the thermal decomposition of calcium carbonate (Figure 6.4) that Hproducts −
Hreactants is positive.

CaCO3(s) → CaO(s) + CO2(g) ΔH = +572 kJ mol−1

The positive sign shows that the reaction is endothermic.

Figure 6.4: Reaction pathway diagram for the decomposition of calcium carbonate

IMPORTANT

For an exothermic reaction, heat is lost from the reactants. The value of ΔH is negative.

For an endothermic reaction, heat is gained by the reactants. The value of ΔH is positive.

1 When drawing reaction pathway diagrams, remember that the activation energy arrow should start
at the level of the reactants and end at the highest point on the energy hump.

2 When drawing the arrow for ΔH make sure that the arrow points downwards for an exothermic
reaction and upwards for an endothermic reaction.

Question
2 Draw full reaction pathway diagrams including activation energy for:

a the combustion of sulfur to form sulfur dioxide

b the endothermic reaction H2O(g) + C(s) → H2(g) + CO(g)

6.2 Standard enthalpy changes

Standard conditions
To make any comparison of enthalpy changes a fair comparison, we must use the same conditions, called
standard conditions. These are:

a pressure of 101 kPa (1.01 × 105 Pa, approximately normal atmospheric pressure)
a temperature of 298 K (25 °C) (add 273 to the Celsius temperature to convert a temperature into
kelvin)
each substance involved in the reaction is in its normal physical state (solid, liquid or gas) at 101 kPa
and 298 K.

The symbol ⦵ is used to indicate that the enthalpy change refers to a reaction carried out under standard
conditions.

The information in the equation:

⦵
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) = −890.3 kJ mol−1

shows us that when one mole of methane gas reacts with two moles of oxygen gas to form one mole of
carbon dioxide gas and two moles of water in the liquid state, the standard enthalpy change is −890.3 kJ
mol−1.

A variety of enthalpy changes

We can describe enthalpy changes according to the type of chemical reaction taking place. For example:

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.

⦵
Standard enthalpy change of reaction,
⦵
The standard enthalpy change of reaction, is the enthalpy change when the amounts of
reactants shown in the stoichiometric equation react to give products under standard conditions. The
reactants and products must be in their standard states.
⦵
The symbol for standard enthalpy change of reaction is . Enthalpy changes of reaction can be
exothermic or endothermic.

The equation that describes the reaction must be given. For example, the equation:

⦵
H2(g) + O2(g) → H2O(l) = −286 kJ mol−1

shows us the enthalpy change when one mole of water is formed from hydrogen and oxygen. In this case,
286 kJ of energy is released.

However, if we write the equation as:

⦵
2H2(g) + O2(g) → 2H2O(l) = −572 kJ

two moles of water are formed from hydrogen and oxygen. In this case, 572 kJ of energy is released.

⦵
Standard enthalpy change of formation,

⦵
 ⦵
The standard enthalpy change of formation, is the enthalpy change when one mole of a
compound is formed from its elements under standard conditions. The reactants and products must be in
their standard states.
⦵
The symbol for standard enthalpy change of formation is . Enthalpy changes of formation can be
⦵
exothermic or endothermic. We write the formula of the compound in square brackets after to help us
when we do calculations involving enthalpy changes. Examples are:

⦵
2Fe(s) + 1 O2(g) → Fe2O3(s) [Fe2O3(s)] = −824.2 kJ mol−1

⦵
C(graphite) + 2S(s) → CS2(l) [CS2(l)] = +98.7 kJ mol−1

Note that the state symbol for carbon is shown as ‘graphite’. This is because there are several forms of
carbon but the most stable is graphite. We choose the most stable form when writing equations where
enthalpy changes are shown.

By definition, the standard enthalpy change of formation of any element in its standard state is zero.

⦵
Standard enthalpy change of combustion,
⦵
The standard enthalpy change of combustion, is the enthalpy change when one mole of a
substance is burnt in excess oxygen under standard conditions. The reactants and products must be in
their standard states.
⦵
The symbol for standard enthalpy change of combustion is . Enthalpy changes of combustion are
always exothermic. The substances combusted can be either elements or compounds.
⦵
S(s) + O2(g) → SO2(g) [S(s)] = −296.8 kJ mol−1

⦵
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) [CH4(g)] = −890.3 kJ mol−1

Note that the first equation can be considered as either the enthalpy change of combustion of sulfur or the
enthalpy change of formation of sulfur dioxide.

Question
3 Identify each of the following reactions as ⦵
, ⦵
or ⦵

a MgCO3(s) → MgO(s) + CO2(g)

b C(graphite) + O2(g) → CO2(g)

c HCl(g) + NH3(g) → NH4Cl(s)

d
H2(g) + O2(g) → H2O(l)

⦵
Standard enthalpy change of neutralisation,
⦵
The standard enthalpy change of neutralisation, is the enthalpy change when one mole of
water is formed by the reaction of an acid with an alkali under standard conditions.

For example:
⦵
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) = −57.1 kJ mol−1

For any acid–alkali reaction the ionic equation is:

H+(aq) + OH−(aq) → H2O(l)

The other ions in solution (Cl− and Na+) are spectator ions and take no part in the reaction (see Section
3.6).
6.3 Measuring enthalpy changes
We can measure the enthalpy change of some reactions by different techniques.

We can measure the enthalpy change of some reactions by a technique called calorimetry. The apparatus
used is called a calorimeter. A simple calorimeter can be a polystyrene drinking cup (Figure 6.5), a vacuum
flask or a metal can.

Figure 6.5: A polystyrene cup can act as a calorimeter for finding some enthalpy changes.

When carrying out experiments in calorimeters, we use known amounts of reactants and known volumes of
liquids. We also measure the temperature change of the liquid in the calorimeter as the reaction occurs.
The thermometer should be accurate to 0.1 or 0.2 °C.

Calorimetry relies on the fact that it takes 4.18 J of energy to increase the temperature of 1 g of water by 1
°C. The energy required to raise the temperature of 1 g of a substance by 1 °C (1 K) is called the specific
heat capacity, c, of the liquid. So, the specific heat capacity of water is 4.18 J g−1 °C−1.
The energy transferred as heat is given by the relationship:

q = mcΔT

where:

q is the heat transferred, in J

m is the mass of water, in g

c is the specific heat capacity, in J g−1 °C−1

ΔT is the temperature change, in °C

As 1 cm3 of water weighs 1 g, we can substitute volume of water in cm3 of water for mass of water in g in
the equation. Aqueous solutions of acids, alkalis and salts are assumed to be largely water.

With solutions we make the assumptions that:

1 cm3 of solution has a mass of 1 g

the solution has the same specific heat capacity as water.

The heat transferred for a known number of moles of reactants in the calorimeter is given by

q = mcΔT

We can scale this up to get the enthalpy change per mole of defined reactant or product. The relationship
we then use is

ΔH = −mc∆T

Note: A rise in temperature is given a positive sign. So the value of ΔH is 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.

IMPORTANT
The energy released in calorimetry experiments for a known number of moles of a specified reactant is
given by q = mcΔT.

When we multiply this up to 1 mole of a stated product or reactant, the equation we use is

ΔH = −mc∆T

The negative sign shows that the reaction is exothermic.

PRACTICAL ACTIVITY 6.1

The enthalpy change of neutralisation by experiment

SAFETY: Only carry out this activity in the presence of a teacher after safety aspects have been
explained.

We can find the enthalpy change of neutralisation of sodium hydroxide with hydrochloric acid by
mixing equal volumes of known equimolar concentrations of acid and alkali together in a polystyrene
cup.

Procedure

1 Place 50 cm3 of 1.0 mol dm−3 hydrochloric acid in the cup and record its temperature.

2 Add 50 cm3 of 1.0 mol dm−3 sodium hydroxide (at the same temperature) to the acid in the cup.

3 Stir the reaction mixture with the thermometer and record the highest temperature.

In this experiment most of the heat is transferred to the solution, as the polystyrene cup is a good
insulator. Cooling of the warm solution is not a great problem: the reaction is rapid so the maximum
temperature is reached before much cooling of the warm solution has occurred. However, there are
still heat losses to the air and to the thermometer, which make the result less exothermic than the
data book value of −57.1 kJ mol−1.

Specimen results and calculation

mass of solution = 100 g

(50 cm3 of acid plus 50 cm3 of alkali and assuming that 1.0 cm3 of solution has a mass of 1.0 g)

specific heat capacity = 4.18 J g−1 °C−1

(assuming that the heat capacity of the solution is the same as the heat capacity of water)

starting temperature = 21.3 °C reactant solutions

final temperature = 27.8 °C product solution

temperature rise = +6.5 °C

(use the relationship q = mcΔT )

heat energy released = 100 × 4.18 × 6.5 = 2717 J

At the start, the reaction mixture contained 50 cm3 of 1.0 mol dm−3 hydrochloric acid and 50 cm3 of
1.0 mol dm−3 sodium hydroxide. The number of moles of each (and of the water formed) is calculated
using

= 0.050 moles

So 2717 J of energy was released by 0.050 moles of acid.

Therefore, for one mole of acid (forming one mole of water) the energy released was
 ⦵
= = 54 340 J mol−1

⦵
= −54 kJ mol−1 (to 2 significant figures)

The negative sign shows that the reaction is exothermic.

PRACTICAL ACTIVITY 6.2

Finding the enthalpy change of combustion of propan-1-ol

SAFETY: Only carry out this activity in the presence of a teacher after safety aspects have been
explained.

We can find the enthalpy change of combustion by burning a known mass of substance and using the
heat released to raise the temperature of a known mass of water. The apparatus used for this consists
of a spirit burner and a metal calorimeter (Figure 6.6).

Figure 6.6: A simple apparatus used to find the enthalpy change of combustion of fuels.

Procedure
Weigh the spirit burner containing propan-1-ol. The cap on the burner must be kept on when the
burner is not lit to avoid evaporation of the fuel.

Pour 100 cm3 (100 g) of water into the calorimeter. For greater accuracy this should be weighed out.

Stir the water and record its temperature with a thermometer reading to at least the nearest 0.1 °C.
Place the spirit burner beneath the calorimeter, remove the cap and light the wick. The length of the
wick should have been previously adjusted so that the material of the wick does not burn and the
flame just touches the bottom of the calorimeter.

Keep stirring the water with the thermometer until there is a temperature rise of about 10 °C. Record
this temperature.

Remove the spirit burner, place the cap on it and reweigh it.

To find the standard enthalpy change of combustion we need to know:

the mass of fuel burnt

the temperature rise of the water
the mass of the water
the relative molecular mass of the fuel (propan-1-ol).

Specimen results and calculation

mass of water in calorimeter = 100 g

mass of spirit burner and propan-1-ol at start = 86.27 g
mass of spirit burner and propan-1-ol at end = 86.06 g
 mass of propan-1-ol burnt = 0.21 g
initial temperature of water = 20.2 °C
final temperature of water = 30.9 °C

temperature change of the water = +10.7 °C

Using the relationship q = mcΔT (mass of water × specific heat capacity of water × temperature
change):

energy released by burning 0.21 g propanol

= −(100 × 4.18 × 10.7) = 4472.6 J

the mass of 1 mole of propan-1-ol, C3H7OH, is 60 g

⦵
so for 60 g propan-1-ol the energy released is
− 4472.6 × = −1 277 885.7 J mol−1

⦵
= −1300 kJ mol−1 (to 2 significant figures)

This is much less than the data book value of −2021 kJ mol−1, mainly due to heat losses to the
surroundings.

Questions
4 a Calculate the energy transferred when the temperature of 75 cm3 of water rises from 23 °C to 54
°C.

b When 8 g of sodium chloride is dissolved in 40 cm3 of water, the temperature falls from 22 °C to
20.5 °C. Calculate the energy absorbed by the solution when sodium chloride dissolves.

c A student added 50 cm3 of sodium hydroxide to 50 cm3 of hydrochloric acid. Both solutions were
at 18 °C to start with. When the solutions were mixed a reaction occurred. The temperature rose
to 33 °C. How much energy is released in this reaction?

5 Explain why the enthalpy change of neutralisation of one mole of sulfuric acid, H2SO4, is not the
standard enthalpy change of neutralisation in kJ mol−1.

6 A student added 10 g (0.25 mol) of sodium hydroxide to 40 cm3 of water to make a concentrated
solution. All the sodium hydroxide dissolved. The student measured the maximum temperature rise.
The student suggested that these results would give an accurate value for the standard enthalpy
change of solution. Give two reasons why the student is incorrect.

7 A student calculated the standard enthalpy change of combustion of ethanol ⦵

[C2H5OH] by
−1 −1
calorimetry as −870 kJ mol . The data book value is −1367 kJ mol . Explain why there is a
difference between these values.
6.4 Hess’s law

Conserving energy
The law of conservation of energy states that ‘energy cannot be created or destroyed’. This is also called
the first law of thermodynamics.

The first law of thermodynamics also applies to chemical reactions: the total energy of the chemicals and
their surroundings must remain constant. In 1840, Germain Hess applied the law of conservation of energy
to enthalpy changes.

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’. The states
of the reactants and products must also be the same whichever route is followed.

Enthalpy cycles (Energy cycles)

Figure 6.7: The enthalpy change is the same no matter which route is followed.

We can illustrate Hess’s law by drawing enthalpy cycles. These are often called energy cycles or Hess
cycles. In Figure 6.7, the reactants A and B combine directly to form C. This is the direct route.

Two indirect routes are also shown. One other way of changing A + B to C is to convert A + B into different
substances F + G (intermediates), which then combine to form C.

Hess’s law tells us that the enthalpy change of reaction for the direct route is the same as for the indirect
route. It does not matter how many steps there are in the indirect route. We can still use Hess’s law.

We can use Hess’s law to calculate enthalpy changes that cannot be found by experiments using
calorimetry. For example, the enthalpy change of formation of propane cannot be found by direct
experiment because hydrogen does not react with carbon under standard conditions.

IMPORTANT

You may be asked to draw an energy cycle. This is just another way of describing an enthalpy cycle or
Hess cycle. Energy cycle is the more general term.

Figure 6.8: An enthalpy cycle (energy cycle) for calculating an enthalpy change of reaction. The dashed line shows the
indirect (two-step) route.
Enthalpy change of reaction from enthalpy changes of formation
We can calculate the enthalpy change of reaction by using the type of enthalpy cycle (energy cycle) shown
in Figure 6.8.

We use the enthalpy changes of formation of the reactants and products to calculate the enthalpy change
of the reaction. We take note of the directions of the arrows to find the one-stage (direct) and two-stage
(indirect) routes. When we use Hess’s law we see that:

So ΔHr = ΔH2 − ΔH1

To calculate the enthalpy change of reaction using this type of enthalpy cycle, we use the following
procedure:

write the balanced equation at the top

draw the cycle with elements at the bottom
draw in all arrows, making sure they go in the correct directions
apply Hess’s law, taking into account the number of moles of each reactant and product.

If there are 3 moles of a product, e.g. 3CO2(g), we must multiply the enthalpy change of formation by 3.
Also remember that the standard enthalpy change of formation of an element in its standard state is zero.

WORKED EXAMPLE

1 Calculate the standard enthalpy change for the reaction:

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

Solution
The relevant enthalpy changes of formation are:
⦵
[NaHCO3(s)] = −950.8 kJ mol−1
⦵
[Na2CO3(s)] = −1130.7 kJ mol−1
⦵
[CO2(g)] = −393.5 kJ mol−1
⦵
[H2O(l)] = −285.8 kJ mol−1
The enthalpy cycle is shown in Figure 6.9.

Figure 6.9: The enthalpy cycle for the decomposition of sodium hydrogencarbonate. The dashed line shows the two-
step route.

Step 1: Apply Hess’s law.

ΔH2 = ΔH1 + ΔHr
⦵ ⦵ ⦵
= [Na2CO3(s)] + [CO2(g)] + [H2O(l)]
⦵ ⦵
=2 [NaHCO(s)] +

Step 2: Insert the values of ΔH taking care to multiply by the correct number of moles.
⦵
(−1130.7) + (−393.5) + (−285.8) = 2(−950.8) +
 −1810.0 = −1901.6 + ΔHr

Step 3: Rearrange the figures to make ΔHr the subject.

⦵
So = (−1810.0) − (−1901.6)
⦵
= +91.6 kJ mol−1 (for the equation shown)

Note:

⦵
the value for [NaHCO(s)] is multiplied by 2 because 2 moles of NaHCO3 appear in the
equation

⦵ ⦵ ⦵
the values for [Na2CO3(s)], [CO2(g)] and [H2O(l)] are added together to give
ΔH2. Take care to account for the fact that some values may be positive and some negative.

Figure 6.10: An enthalpy cycle for calculating an enthalpy change of formation from enthalpy changes of combustion.

IMPORTANT

When doing enthalpy cycle (energy cycle) calculations remember that:

1 the enthalpy change of an element in its normal state is zero

2 you must take into account the number of moles of reactants and products in each part of the
energy cycle.

WORKED EXAMPLE

2 Calculate the standard enthalpy change of formation of ethane, C2H6.

Solution
The relevant enthalpy changes of combustion are:

C(graphite) + O2(g) → CO2(g)

⦵
[C(graphite)] = −393.5 kJ mol−1

H2(g) + O2(g) → H2O(l)

⦵
[H2(g)] = −285.8 kJ mol−1

C2H6(g) + 3 O2(g) → 2CO2(g) + 3H2O(l)

⦵
[C2H6(g)] = −1559.7 kJ mol−1

Step 1: Write the enthalpy change of formation at the top and then draw the energy cycle with
the combustion products at the bottom. Make sure the arrows are in the correct
direction.
The enthalpy cycle is shown in Figure 6.11.

Step 2: Apply Hess’s law.

 ΔH1 = ΔHf + ΔH2

Step 3: Insert the values of ΔH taking care to multiply by the correct number of moles.

ΔH1 = ΔHf + ΔH2

2(−393.5) + 3(−285.8) = ΔHf + (−1559.7)

−1644.4 = ΔHf + (−1559.7)

Step 4: Rearrange the figures to make ΔHf the subject.

ΔHf = −1644.4 − (−1559.7) = −84.7 kJ mol−1

Figure 6.11: The enthalpy cycle to find the enthalpy change of formation of ethane using enthalpy changes of
combustion. The dashed line shows the two-step route.

Question
8 a Draw an enthalpy cycle to calculate ⦵
for the reaction

2Al(s) + Fe2O3(s) → 2Fe(s) + Al2O3(s)

b Calculate ΔHr using the following information:

⦵
[Fe2O3(s)] = −824.2 kJ mol−1
⦵
[Al2O3(s)] = −1675.7 kJ mol−1

Enthalpy change of formation from enthalpy changes of combustion

We can calculate the enthalpy change of formation of many compounds by using the type of enthalpy cycle
shown in Figure 6.10.

We use the enthalpy changes of combustion of the reactants and products to calculate the enthalpy
change of formation. When we take note of the direction of the arrows to find the one-stage (direct) and
two-stage (indirect) routes and use Hess’s law we see that:

So ΔHf = ΔH1 − ΔH2

To calculate the enthalpy change of formation using this type of cycle:

write the equation for enthalpy change of formation at the top; add oxygen on both sides of the
equation to balance the combustion reactions
draw the cycle with the combustion products at the bottom
draw in all arrows, making sure they go in the correct directions
apply Hess’s law, taking into account the number of moles of each reactant and product.

IMPORTANT

Remember that in constructing enthalpy cycles (energy cycles) to calculate ΔHf, ΔHc or ΔHneut, the
 reaction required is put at the top of the energy cycle triangle.

Questions
9 a Draw an enthalpy cycle to calculate the enthalpy change of formation of ethanol, C2H5OH, using
enthalpy changes of combustion.

b Calculate a value for ΔHf [C2H5OH(l)] using the following data:

⦵
[C(graphite)] = −393.5 kJ mol−1
⦵
[H2(g)] = −285.8 kJ mol−1
⦵
[C2H5OH(l)] = −1367.3 kJ mol−1

10 Look at this equation.

3Mg(s) + Fe2O3(s) → 2Fe(s) + 3MgO(s)

Which one of the following gives the correct value for the enthalpy change of this reaction?

A ∆Hr = ∆Hf [Fe2O3(s)] − 3∆Hf [MgO(s)]

B ∆Hr = ∆Hf [MgO(s)] − ∆Hf [Fe2O3(s)]

C ∆Hr = 2∆Hf [Fe(g)] + 3∆Hf [MgO(g)]

− 3∆Hf [Mg(g)] + ∆Hf [Fe2O3(g)]

D ∆Hr = 3∆Hf [MgO(s)] − ∆Hf [Fe2O3(s)]

6.5 Bond energies and enthalpy changes

IMPORTANT

Remember that bond breaking is endothermic and bond making is exothermic.

Bond breaking and bond making

Enthalpy changes are due to the breaking and forming of bonds. Breaking bonds requires energy. The
energy is needed to overcome the attractive forces joining the atoms together. Energy is released when
new bonds are formed. Bond breaking is endothermic and bond forming is exothermic.

In a chemical reaction:

if the energy needed to break bonds is less than the energy released when new bonds are formed, the
reaction will release energy and is exothermic.
if the energy needed to break bonds is more than the energy released when new bonds are formed,
the reaction will absorb energy and is endothermic.

We can draw reaction pathway diagrams to show these changes (Figure 6.12). In reality, not all the bonds
in a compound are broken and then re-formed during a reaction. In most reactions only some of the bonds
in the reactants are broken and then new bonds are formed in a specific sequence.

Bond energy
The amount of energy needed to break a specific covalent bond is called the bond dissociation energy. We
sometimes call this the exact bond energy or bond enthalpy.

Figure 6.12: a An energy level diagram showing bond breaking and bond forming for the combustion of methane
(exothermic). b An energy level diagram showing bond breaking and bond forming for the decomposition of hydrogen
bromide (endothermic).

The symbol for bond energy is E. We put the type of bond broken in brackets after the symbol.

So E(C─H) refers to the bond energy of a mole of single bonds between carbon and hydrogen atoms.

The bond energy for double and triple bonds refers to a mole of double or triple bonds. Two examples of
equations relating to bond energies are:

Br2(g) → 2Br(g) E(Br─Br) = +193 kJ mol−1

O═O(g) → 2O(g) E(O═O) = +498 kJ mol−1

The values of bond energies are always positive (endothermic) because they refer to bonds being broken.

When new bonds are formed the amount of energy released is the same as the amount of energy absorbed
when the same type of bond is broken. So, for the formation of oxygen molecules from oxygen atoms:
 2O(g) → O2(g) E(O═O) = −498 kJ mol−1

Average bond energy

Bond energy is affected by other atoms in the molecule. The O─H bond in water has a slightly different
bond energy value to the O─H bond in ethanol. In ethanol, the oxygen is connected to a carbon atom
rather than another hydrogen atom. We call these bond energies exact bond energies. The O─H bond is in
a different environment. Identical bonds in molecules with two (or more) types of bond have different bond
energies when we measure them. It takes more energy to break the first O─H bond in water than to break
the second. For these reasons we use average bond energies taken from a number of bonds of the same
type but in different environments.

We cannot usually find the value of bond energies directly, so we have to use an enthalpy cycle. The
average bond energy of the C─H bond in methane can be found using the enthalpy changes of
atomisation of carbon and hydrogen and the enthalpy change of combustion or formation of methane.

IMPORTANT
⦵
The standard enthalpy change of atomisation, , is the enthalpy change when one mole of
⦵
gaseous atoms is formed from its element under standard conditions. So, [H2] relates to the
equation H2(g) → H(g)

Figure 6.13: An enthalpy cycle to find the average bond energy of the C─H bond. The dashed line shows the two-step
route.

The enthalpy cycle for calculating the average C─H bond energy is shown in Figure 6.13. Using the
enthalpy cycle shown in Figure 6.13, the average C─H bond energy can be found by dividing the value of
ΔH on the diagram by four (because there are four C─H bonds in a molecule of methane).

Question
11 Use the information in Figure 6.13 and the information below to demonstrate that the average bond
energy of the C─H bond is 415.9 kJ mol−1.
⦵
[CH4] = −74.8 kJ mol

⦵
[ H] = +218 kJ mol−1

⦵
[C(graphite)] = +716.7 kJ mol−1
6.6 Calculating enthalpy changes using bond
energies
We can use bond energies to calculate the enthalpy change of a reaction that we cannot measure directly.
For example, the reaction for the Haber process (see Section 8.5):

N2(g) + 3H2(g) ⇌ 2NH3(g)

The enthalpy cycle for this reaction is shown in Figure 6.14. The relevant bond energies are:

E(N≡N) = 945 kJ mol−1

E(H─H) = 436 kJ mol−1

E(N─H) = 391 kJ mol−1

Figure 6.14: The enthalpy cycle for ammonia synthesis. The dashed line shows the two-step route.

It is often easier to set out the calculation as a balance sheet, as shown below:

Bonds broken ΔH1 (kJ) Bonds formed ΔH2 (kJ)

1 × N≡N = 1 × 945 = 945 6 × N─H = 6 × 391

3 × H─H − 3 × 436 = 1308

total = +2253 total = −2346

Note in these calculations that:

one triple bond in nitrogen is broken

three single bonds in hydrogen are broken
six single N─H bonds in hydrogen are formed (because each of the two ammonia molecules has three
N─H bonds)
values for bond breaking are positive, as these are endothermic, and values for bond forming are
negative, as these are exothermic.

From the enthalpy cycle in Figure 6.14:

ΔHr = ΔH1 + ΔH2

ΔHr = enthalpy change for bonds broken

+ enthalpy change for bonds formed

ΔHr = 2253 + (−2346) = −93 kJ mol−1

Questions
12 The equation for the combustion of ethanol is:

C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

a Rewrite this equation to show all the bonds in the reactants and products.
 b Use the following bond energies (in kJ mol−1) to calculate a value for the standard enthalpy
change of this reaction:

i E(C─C) = +347

ii E(C─H) = +410

iii E(C─O) = +336

iv E(O═O) = +496

v E(C═O) = +805

vi E(O─H) = +465

c The standard enthalpy change of combustion of ethanol is −1367.3 kJ mol−1. Suggest why this
value differs from the value obtained using bond energies.

13 Look at this equation.

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Which one of the following statements is completely correct?

A four C─H bonds and two O═O bonds are broken (exothermic) reaction and two C═O bonds and four
O─H bonds are formed (endothermic)

B four C─H bonds and two O═O bonds are broken (endothermic) and two C═O bonds and four O─H
bonds are formed (exothermic)

C four C─H bonds and two O─O bonds are broken (endothermic) and two C─O bonds and four O─H
bonds are formed (exothermic)

D four C─H bonds and two O═O bonds are broken (endothermic) and two C═O bonds and two O─H
bonds are formed (exothermic)

REFLECTION

1 Work with another learner to make a list of differences between the definitions of the standard
enthalpy changes of formation, reaction, combustion and neutralisation as well as any differences
in the way that you draw the energy cycle diagrams.

2 Work with another learner to describe the sequence of operations in one of the experiments that
appear in this chapter, e.g. deducing enthalpy change of combustion or deducing the enthalpy
change of reaction. Think about what you would need to measure and the variables you would
need to control. What equations would you need to use when processing the results? What would
you change if you had to do this again?
SUMMARY

Exothermic enthalpy changes have negative ∆H values. Endothermic enthalpy changes have positive ∆H values.

Enthalpy changes can be calculated experimentally using the relationship:

enthalpy change, q = mass of liquid × specific heat capacity × temperature change.
For a mole of defined substance this is written ΔH = −mc∆T

Standard enthalpy change of formation relates to the enthalpy change when one mole of a compound is formed
from its elements under standard conditions. Similar definitions can be written for standard enthalpy changes of
combustion and reaction.

Hess’s law can be used to calculate enthalpy changes for reactions that do not occur directly or cannot be found by
experiment.

Bond breaking is endothermic; bond making is exothermic.

Average bond energies are often used because the strength of a bond between two particular types of atom is
slightly different in different compounds.
EXAM-STYLE QUESTIONS

1 Copper(II) nitrate decomposes on heating. The reaction is endothermic.

2Cu(NO3)2(s) → 2CuO(s) + 4NO2(g) + O2(g)
[3]
a Sketch a reaction pathway diagram for this reaction to include the activation energy.

b Draw an energy cycle to calculate the standard enthalpy change for this reaction, using [3]
enthalpy changes of formation.

c Calculate the enthalpy change for this reaction using the following enthalpy changes of
formation.
⦵
[Cu(NO3)2(s)] = −302.9 kJ mol−1
⦵
[CuO(s)] = −157.3 kJ mol−1
[3]
⦵
[NO2(g)] = +33.2 kJ mol−1

d Copper(II) sulfate is soluble in water. A student dissolved 25.0 g of copper(II) sulfate in

100 cm3 of water in a polystyrene beaker stirring all the time. The temperature of the
water fell by 2.9 °C.

i Calculate the enthalpy change of solution of copper(II) sulfate. (specific heat

capacity of water = 4.18 J g−1 °C−1; relative molecular mass of copper(II) sulfate = [3]
249.7 g mol−1)

ii Suggest one source of error in this experiment and explain how the error affects the [2]
results.
[Total: 14]
2 Propanone is a liquid. It has the structure

The equation for the complete combustion of propanone is:

CH3COCH3(l) + 4O2(g) → 3CO2(g) + 3H2O(l)

a Use the following bond energies (in kJ mol−1) to calculate a value for the standard
enthalpy change of this reaction:
E(C─C) = +347
E(C─H) = +413
E(O═O) = +496
E(C═O) = +805
[4]
E(O─H) = +465

b Explain why it would be more accurate to use exact bond energies rather than average [2]
bond energies in this calculation.

c The standard enthalpy change of combustion of propanone is −1816.5 kJ mol−1. Suggest [2]
why this value differs from the value obtained using bond energies.

d The standard enthalpy change of formation of propanone is −248 kJ mol−1.

[3]
i Define the term standard enthalpy change of formation.

ii Write the equation that describes the standard enthalpy change of formation of [2]
propanone.

iii Explain why the enthalpy change of formation of propanone cannot be found by a [1]
single experiment.
[Total: 14]
3 240 cm3 of ethane (C2H6) was burnt in a controlled way and found to raise the
temperature of 100 cm3 of water by 33.5 °C. (specific heat capacity of water = 4.18 J g−1 K−1; 1
mol of gas molecules occupies 24.0 dm3 at r.t.p.)
[1]
a Calculate the number of moles of ethane that were burned.
[2]
b Calculate the heat change, q, for the experiment.

c Calculate the molar enthalpy change of combustion for ethane, as measured by this [2]
experiment.

d Use the values below to calculate the standard molar enthalpy change for the complete
combustion of ethane.
⦵
[CO2] = −394 kJ mol−1
⦵
[H2O] = −286 kJ mol−1
[4]
⦵
[C2H6 ] = −85 kJ mol−1
[2]
e Give possible reasons for the difference between the two results.
[Total: 11]

[3]
4 a Define standard enthalpy change of combustion.

b i When red phosphorus burns in oxygen the enthalpy change is −2967 kJ mol−1. For
white phosphorus the enthalpy change is −2984 kJ mol−1. For both forms of
phosphorus the reaction taking place is:
P4(s) + 5O2(g) → P4O10(s)
Use this information to calculate the enthalpy change for the transformation: [5]
P4(white) → P4(red)
[3]
ii Represent these changes on an energy level diagram.
[Total: 11]

[3]
5 a Define standard enthalpy change of formation.

b Calculate the standard enthalpy change of formation of methane from the following
standard enthalpy changes of combustion:
carbon = −394 kJ mol−1
hydrogen = −286 kJ mol−1
[4]
methane = −891 kJ mol−1

c Calculate the standard enthalpy change of combustion of methane using the following
bond energies:
E(C─H) = +412 kJ mol−1
E(O═O) = +496 kJ mol−1
E(C═O) = +805 kJ mol−1
[4]
E(O─H) = +463 kJ mol−1
[Total: 11]

[2]
6 a Define average bond energy.

b Use the average bond energies that follow to calculate a value for the enthalpy change
for the reaction:
H2 + I2 → 2HI

E(H─H) = +436 kJ mol−1

E(I─I) = +151 kJ mol−1
[3]
E(H─I) = +299 kJ mol−1
 c Represent these changes on an energy level diagram. [3]
[Total: 8]

[3]
7 a Define standard enthalpy change of reaction.

b Given the enthalpy changes ΔH1 and ΔH2 below, construct a Hess’s cycle that will enable
you to find the enthalpy change, ΔHr, for the reaction:
MgCO3(s) → MgO(s) + CO2(g) ΔHr
MgCO3(s) + 2HCl(aq) → MgCl2(aq) + CO2(g) + H2O(l) ΔH1
[4]
MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l) ΔH2
[Total: 7]
8 In an experiment, a spirit burner is used to heat 250 cm3 of water by burning methanol
(CH3OH). (Ar values: C = 12.0, H = 1.0, O = 16.0; specific heat capacity of water = 4.18
J g−1 °C−1)
Results:
starting temperature of water = 20.0 °C
starting mass of burner + fuel = 248.8 g
final temperature of water = 43.0 °C
final mass of burner + fuel = 245.9 g
[2]
a Calculate the energy in joules that went into heating the water.
[2]
b Calculate the number of moles of fuel burned.

c Calculate an experimental value for the enthalpy change of combustion of methanol [2]
from these results.

d Suggest three reasons why your answer is much smaller than the accepted standard [3]
enthalpy of combustion of methanol.
[Total: 9]
SELF-EVALUATION

After studying this chapter, complete a table like this:

See Needs more Almost Ready to

I can section... work there move on

explain and use the term enthalpy change (∆H) and apply it to
exothermic chemical reactions (∆H is negative) and 6.1
endothermic chemical reactions (∆H is positive)

construct and interpret a reaction pathway diagram in terms

6.1
of enthalpy changes and activation energy

define and use the term standard conditions 6.2

define and use the term enthalpy change of formation 6.2

define and use the term enthalpy change of combustion 6.2

define and use the term enthalpy change of neutralisation 6.2

explain energy transfers during chemical reactions in terms of

6.3, 6.5
bond breaking (endothermic) and bond making (exothermic)

use bond energies to calculate enthalpy change of reaction 6.5, 6.6

understand that some bond energies are exact and some bond
6.5, 6.6
energies are averages

calculate enthalpy changes from experimental results,

including the use of the relationships: q = mc∆T and ∆H = 6.3
−mc∆T

use Hess’s law to construct simple energy cycles 6.4

carry out calculations using energy cycles to determine

6.6
enthalpy changes that cannot be found by direct experiment

carry out calculations using bond energy data. 6.6