5.
Chemical Energetics
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
This is done by chemical bonding (we have already seen ionic and covalent
bonding) where old bonds are broken, and new bonds are formed)
This process involves the transfer of thermal energy into and out of
reaction mixtures
The terms used to describe this are the system (what happens in the
chemical reaction) and the 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 to the surroundings
so the temperature of the surroundings increases
This energy is transferred from the chemical energy store of the chemical
system to the surroundings and so the energy of the system falls - this
means that the energy change is negative
The overall transfer is from the system to the surroundings
Combustion, oxidation, and neutralization reactions are typical exothermic
reactions
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
Diagram showing the transfer of heat energy outwards from an exothermic
reaction
Endothermic Reactions
In endothermic reactions thermal energy is taken in from the surroundings
so the temperature of the surroundings decreases
This energy is transferred to the chemical energy store of the chemical
system and so the energy of the system increases - this means the energy
change is positive
The overall transfer is from the surroundings to the system
These types of reactions are much less common than the exothermic
reactions
Electrolysis, thermal decomposition reactions and the first stages of
photosynthesis are typical endothermic reactions
Sports injury treatments often use cold packs based on endothermic
reactions to take heat away from a recently injured area to prevent swelling
Diagram showing the transfer of heat energy from the surroundings into an
endothermic reaction
Exam Tip
To help you remember whether a chemical system is exothermic or endothermic:
In EXothermic reactions heat EXits the system and in ENdothermic
reactions heat ENters the system.
Exothermic reactions always give off heat and they feel hot, whereas
endothermic reactions take heat in and they feel cold.
Enthalpy Change & Activation Energy
For atoms or particles to react with each other in a chemical system they
must first of all come into contact with each other in a collision
A number of factors come into play when analysing collisions such
as energy, orientation, and number of collisions per
second (the frequency of collisions)
There is a minimum amount of energy that the particles must collide
with for the collision to be successful, that is for the particles to react
together
o This minimum amount of energy is called the activation energy (Ea)
Different reactions have different activation energies, depending on the
chemical identities involved
Reactions which have higher activation energies require more energy to
start than those with lower activation energies
The transfer of thermal energy during a reaction is called the enthalpy
change, ΔH, of the reaction.
ΔH is a positive value for endothermic reactions and a negative value for
exothermic reactions
Reaction Pathway Diagrams
Reaction pathway diagrams (a.k.a energy level diagrams) are graphical
representations of the relative energies of the reactants and products in
chemical reactions
The energy of the reactants and products are displayed on the y-axis and
the reaction pathway (a bit like time) is shown on the x-axis
The difference in height between the energy of reactants and products
represents the overall energy change of a reaction.
o This is usually a sketch but can be drawn to scale if data is provided
Arrows on the diagrams indicate whether the reaction is exothermic
(overall reaction arrow is downwards pointing, showing that the system has
lost energy) or endothermic (overall reaction arrow is upwards pointing,
showing that the system has gained energy)
The initial increase in energy represents the activation energy (Ea), which is
the minimum energy that colliding particles must have in order to react
The greater the initial rise, the more energy that is required to get the
reaction going e.g. more heat needed
You can identify a reaction pathway diagram for an exothermic reaction as
the energy of the product is lower than the reactants (as thermal energy
has been transferred to the surroundings)
You can identify a reaction pathway diagram for an endothermic
reaction as the energy of the product is higher than the reactants (as
thermal energy has been taken in from the surroundings)
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
The reaction pathway diagram for an exothermic reaction is shown below
The reaction pathway diagram for exothermic reactions
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
Therefore an endothermic reaction has a positive ΔH value, which is shown
on the energy level diagrams and in calculations
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
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
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 (delta H) is used to show the change in heat energy. H is the
symbol for enthalpy, which is a measure of the total heat of reaction of a
chemical reaction
Therefore an endothermic reaction has a positive ΔH value, which is shown
on the reaction pathway diagrams and in calculations
Breaking chemical bonds requires energy which is taken in from the
surroundings in the form of heat
Bond Energy Calculations
Energy of reaction calculations
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
Method
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 table below shows the bond energies.
Calculate the enthalpy change, ΔH, for the reaction and deduce whether it is
exothermic or endothermic.
Answer
Worked example
Hydrogen bromide decomposes to form hydrogen and bromine:
2HBr ⟶ H2 + Br2
The table below shows the bond energies.
Calculate the enthalpy change, ΔH, for the reaction and deduce whether it is
exothermic or endothermic.
Answer
Exam Tip
When answering questions to calculate the 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. The reaction thus becomes: H-H + Cl-Cl → H-Cl + H-Cl
