Exothermic & endothermic reactions

Heat exchange in reactions

 Chemical reactions occur so that elements can achieve a more stable energy state by
gaining a full outer shell of electrons
o This is done by chemical bonding
 This process involves the transfer of thermal energy into and out of reaction mixtures
 The terms used to describe this are:
o System: the reacting chemicals
o Surroundings: anything other than the chemicals reacting
 The energy within the system comes from the chemical bonds themselves which could
be considered as tiny stores of chemical energy

Exothermic reactions

 In exothermic reactions, thermal energy is transferred from the chemical energy store of
the chemical system to the surroundings
o The energy of the system decreases, which means that the energy change
is negative
o The temperature of the surroundings increases because thermal energy is given
out / released
 The overall transfer is from the system to the surroundings
 Diagram showing the transfer of heat energy outwards from an exothermic reaction

 Typical examples of exothermic reactions include:

o Combustion
o Oxidation
o Neutralisation
 Hand warmers used in the wintertime are based on the release of heat from an
exothermic reaction
 Self-heating cans of food and drinks such as coffee and hot chocolate also use
exothermic reactions in the bases of the containers

Endothermic reactions

 In endothermic reactions, thermal energy is transferred from the surroundings system to

the system surroundings
o The energy of the system increases, which means that the energy change
is positive
 o The temperature of the surroundings decreases because thermal energy is taken
in / absorbed
 The overall transfer is from the surroundings to the system

Diagram showing the transfer of heat energy from the surroundings into an endothermic
reaction

 Endothermic reactions are less common than exothermic reactions

 Typical examples of endothermic reactions include:
o Electrolysis
o Thermal decomposition
o The first stages of photosynthesis
 Cold packs for sports injuries are based on endothermic reactions, designed to take heat
away from a recently injured area to prevent swelling

Worked example

A student was investigating the temperature change for four different chemical reactions. The
table shows the chemicals that the student combined for each reaction along with the initial and
final temperatures of the reaction.
 Initial temperature Final temper
Experiment Chemicals
(oC) (oC)

1 10 cm3 NaOH 10 cm3 HCl 19 21

2 10 cm3 NaHCO3 2 g citric acid 20 16

3 10 cm3 CuSO4 0.5 g Mg powder 20 26

4 10 cm3 H2SO4 3 cm Mg ribbon 19 31

Explain whether each reaction is endothermic or exothermic.

Answers:

 Reactions 1, 3 and 4 are exothermic reactions because they show a temperature increase
 Reaction 2 is an endothermic reactions because it shows a temperature decrease

Reaction pathway diagrams

 Reaction pathway diagrams are graphical representations of the relative energies of the
reactants and products in chemical reactions
 On a reaction pathway diagram:
o Progress of the reaction is shown on the x-axis
o Energy is shown on the y-axis
o The difference in height between the energy of reactants and products is
the overall energy change of a reaction
 Reaction pathway diagram of an exothermic reaction and an endothermic reaction

 In exothermic reactions:
o Energy is given out to the surroundings
o The energy of the products will therefore be lower than the energy of the
reactants
o The overall energy change is negative
o This is represented on the reaction profile with a downwards-arrow as the energy
of the products is lower than the reactants
 In endothermic reactions:
o Energy is taken in from the surroundings
o The energy of the products will be higher than the energy of the reactants
o The overall energy change is positive
o This is represented on the reaction profile with an upwards-arrow as the energy of
the products is higher than the reactants
 Enthalpy change & activation energy
Extended tier only

 For atoms or particles to react with each other in a chemical system they
must collide together
 A number of factors affect the success of a collision:
o Energy
o Orientation
o Number of collisions per second - the frequency of collisions

What is activation energy?

 In terms of the energy of collisions, there is a minimum amount of energy required for a
successful collision
o A successful collision is where the particles in the reactant(s) are rearranged to
form the products
 This minimum amount of energy is called the activation energy, Ea
 Different reactions have different activation energies, depending on the chemical
identities involved
 Reactions with higher activation energies require more energy to start than those with
lower activation energies

What is enthalpy change?

 The transfer of thermal energy during a reaction is called the enthalpy change, ΔH, of
the reaction.
 ΔH is:
o Positive for en endothermic reaction
o Negative for an exothermic reaction

Reaction pathway diagrams

Extended tier only

Exothermic reactions

 A reaction is exothermic when more energy is released forming new bonds for the
products than absorbed breaking the bonds in the reactants
 So, the products have less energy than the reactants
o This means that the change in energy is negative
 Therefore, an exothermic reaction has a negative value for enthalpy, ΔH
 The reaction pathway diagram for an exothermic reaction is:
 The reaction pathway diagram for exothermic reactions

Endothermic reactions

 A reaction is endothermic when more energy is absorbed breaking the bonds in the
reactants than released forming new bonds for the products
 So, the products have more energy than the reactants
o This means that the change in energy is positive
 Therefore, an endothermic reaction has a positive value for enthalpy, ΔH
 The reaction pathway diagram for an endothermic reaction is:
 The reaction pathway diagram for endothermic reactions.

Exam Tip

You must be able to draw these pathway diagrams and label the following parts:

 Reactants
 Products
 Enthalpy change of the reaction, ΔH
 Activation energy, Ea

Bond breaking & bond forming

Extended tier only

 Whether a reaction is endothermic or exothermic depends on the difference between the

energy needed to break existing bonds and the energy released when the new bonds
are formed
 Bond breaking is always an endothermic process as energy needs to be taken in from
the surroundings to break the chemical bonds
 Bond making is always an exothermic process as energy is transferred to the
surroundings as the new bond is formed
Exothermic reactions

 If more energy is released than is absorbed, then the reaction is exothermic

 More energy is released when new bonds are formed than energy required to break the
bonds in the reactants
 The change in energy is negative since the products have less energy than the reactants
 Therefore, an exothermic reaction has a negative ΔH value
o This can be shown in reaction pathway diagrams and calculations

Making new chemical bonds releases energy which radiates outwards from the reaction to the
surroundings in the form of heat

Endothermic reactions
  If more energy is absorbed to break bonds than is released to form new bonds, this
reaction is endothermic overall
 The change in energy is positive since the products have more energy than the reactants
 The symbol ΔH is used to show the change in heat energy
o H is the symbol for enthaply, which is a measure of the total heat of reaction of a
chemical reaction
 Therefore, an endothermic reaction has a positive ΔH value
o This can be shown in reaction pathway diagrams and calculations

Breaking chemical bonds requires energy which is taken in from the surroundings in the form
of heat

Bond energy calculations

Extended tier only

 Each chemical bond has specific bond energy associated with it

  This is the amount of energy required to break the bond or the amount of energy given
out when the bond is formed
 This energy can be used to calculate how much heat would be released or absorbed in a
reaction
 To do this it is necessary to know the bonds present in both the reactants and products

How to complete bond energy calculations

 Write a balanced equation if none is present already

 Optional - draw the displayed formula in order to identify the type and number of bonds
more easily
 Add together all the bond energies for all the bonds in the reactants – this is the ‘energy
in’
 Add together the bond energies for all the bonds in the products – this is the ‘energy out’
 Calculate the enthalpy change:

Enthalpy change (ΔH) = Energy taken in - Energy given out

Worked example

Hydrogen and chlorine react to form hydrogen chloride gas:

H2 + Cl2 ⟶ 2HCl

The bond energies are given in the table below.

Bond Energy (kJ)

H–H 436

Cl–Cl 242

H–Cl 431

Calculate the overall energy change for this reaction and use this value to explain whether the
reaction is exothermic or endothermic.

Answer:

 Calculate the energy in

o 436 + 242 = 678 (kJ)
 Calculate the energy out
 o2 x 431 = 862 (kJ)
 Calculate the energy change
o 678 - 862 = –184 (kJ)
 Since the energy change is a negative number, energy is being released (to the
surroundings)
o Therefore, the reaction is exothermic

Exam Tip

When calculating enthalpy change using bond energies, it is helpful to write down a displayed
formula equation for the reaction before identifying the type and number of bonds, to avoid
making mistakes.

So, the reaction for the above worked example is:

H-H + Cl-Cl → H-Cl + H-Cl

Worked example

Hydrogen reacts with iodine to form hydrogen iodide.

H2 + I2 ⟶ 2HI

The relevant bond energies are shown in the table below.

Bond Energy (kJ)

H–I 295

H–H 436

I–I 151

Calculate the overall energy change for this reaction and use this value to explain why the
reaction is exothermic.

Answer:

 Calculate the energy in

o 436 + 151 = 587 (kJ)
 Calculate the energy out
o 2 x 295 = 590 (kJ)
 Calculate the energy change
 o 587 - 590 = -3 (kJ)
 The reaction is exothermic because:
o More energy is released than taken in

Worked example

Hydrogen bromide decomposes to form hydrogen and bromine:

2HBr ⟶ H2 + Br2

The overall energy change for this reaction is +103 kJ.

The relevant bond energies are shown in the table below.

Bond Energy (kJ)

H–Br 366

Br–Br

H–H 436

Calculate the bond energy of the Br–Br bond.

Answer:

 Calculate the energy in

o 2 x 366 = 732 (kJ)
 State the energy out
o 436 + Br–Br
 Overall energy change = energy in - energy out
o +103 = 732 - (436 + Br–Br)
o +103 = 732 - 436 - Br–Br
 Calculate the bond energy of the Br–Br bond
o Br–Br = 732 - 436 - 103
o Br–Br = +193 (kJ)