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, 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

 Activation Energy- the minimum amount of energy required for a chemical reaction
to occur and enthalpy change is defined as the heat that passes into or out of a system
during a chemical reaction.
 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.
 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
 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)
 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, therefore an endothermic reaction has a positive ΔH value, which is shown
on the energy level diagrams and in calculations
 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 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.
Bond Energy 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
 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 by subtracting total energy from reactants minus total
energy from products.

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

= Reactants- Products

Example 1
Example 2
To calculate enthalpy change we first need to know the energy change, depicted by q, which
is the energy change in a reaction

q = mc▲T

Calorimetry – measurement of enthalpy

changes When the temperature of a
substance is changed, the amount of
energy needed to cause this can be
calculated: Heat energy required is given
by the equation

q = m c ΔT

Where q = energy required (J)

m = mass of stuff getting heated (g)

c = specific heat capacity (Jg-1 K-1

4.18

ΔT = change in temperature (K) = final

temp – initial temp remember to show the
sign too!

The source of this heat may be a chemical

reaction, in which case the heat energy was
produced by a change in chemical energy – an enthalpy change. The enthalpy change is given
by: ΔH = -q / (moles of reactant) Where ΔH is in Jmol-1 - you need to ÷ 1000 to get it in
kJmol-1 moles = moles of whichever reactant in NOT in excess We must also check that the
sign of ΔH is correct! If the temperature increased, the reaction was exothermic and ΔH must
have a – sign. If the temperature decreased, the reaction was endothermic and ΔH has a +
sign.

For liquids/solutions which get heated, we may know the volume rather than the mass. We
need to convert volume to mass. This is done using density: mass (g) = volume (cm3) x
density (g cm-3) The density of pure water is 1.00 g cm-1, so essentially the mass of the
liquid will be the same as the volume. You will be given the actual density to use if a
calculation is needed.

Example to calculate q