Calorimetry

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 Calorimetry is a technique used to measure changes in enthalpy of chemical reactions

 There are two types of calorimetry experiments you need to know:
o Enthalpy changes of reactions in solution
o Enthalpy changes of combustion

Reactions in solution

 The principle of these calorimetry experiments is to carry out the reaction with an excess of one reagent and
measure the temperature change over the course of a few minutes
 This technique is suitable for reaction such as dissolving, displacement and neutralisation
 For the purposes of the calculations, some assumptions are made about the experiment:
o That the specific heat capacity of the solution is the same as pure water, i.e. 4.18 J g-1 K-1
o That the density of the solution is the same as pure water, i.e. 1 g cm-3
o The specific heat capacity of the container is ignored
o The reaction is complete
o There are negligible heat losses
 A calorimeter can be made up of a polystyrene drinking cup, a vacuum flask or metal can

A polystyrene cup can act as a calorimeter to find enthalpy changes in a chemical reaction

 A fixed volume of one reagent is added to the calorimeter and the initial temperature taken with a
thermometer
 An excess amount of the second reagent is added and the solution is stirred continuously
 The maximum temperature is recorded and the temperature rise calculated
Enthalpy of combustion experiments

 The principle here is to use the heat released by a combustion reaction to increase the heat content of water
 A typical simple calorimeter is used to measure the temperature changes to the water

A simple combustion calorimeter

 A fixed volume of water is measured and transferred to the copper can

 The spirit burner containing, for example, an alcohol, is weighed on a 2 d.p. balance
 The initial temperature of the water is measured and recorded
 The alcohol is ignited and the water is stirred continuously
 When the temperature has risen by about 20 degrees the flame is extinguished and the spirit burner is re-
weighed
 The final temperature of the water is recorded

Sources of error

 Not all the heat produced by the combustion reaction is transferred to the water
o Some heat is lost to the surroundings
o Some heat is absorbed by the calorimeter
 To minimise the heat losses the copper calorimeter should not be placed too far above the flame and a lid
placed over the calorimeter
 Shielding can be used to reduce draughts
 In this experiment the main sources of error are
o Heat losses
o Incomplete combustion
Calculate Heat Energy Change

 In order the calculate heat energy changes you need to know the mass of the substance being heated, the
temperature change and the specific heat capacity of the substance
 The specific heat capacity (c) is the energy needed to raise the temperature of 1 g of a substance by 1 K
 The specific heat capacity of water is 4.18 J g-1 K-1
 The energy transferred as heat can be calculated by:

Equation for calculating energy transferred in a calorimeter

 The temperature change in Kelvin is the same as the temperature change in degrees Celsius
Calculate Molar Enthalpy Change

 Molar enthalpy change is the heat energy change per mole of substance
 The symbol is ΔH and it has the unit kJ per mole
 If is found by first determining the heat energy change for the reaction, q, and then dividing by the number of
moles, n, of the substance

molar enthalpy change = heat change for the reaction ÷ number of moles

ΔH = q ÷ n
Energy Level Diagrams

 Energy level diagrams (sometimes called reaction profiles) 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 is shown on
the x-axis
 Arrows on the diagrams indicate whether the reaction is exothermic (downwards pointing) or endothermic
(upwards pointing)
 The difference in height between the energy of reactants and products represents the overall energy
change of a reaction
 The initial increase in energy represents the activation energy required to start the reaction
 The greater the initial rise then the more energy that is required to get the reaction going e.g., more heat
needed

Reaction profile of an exothermic reaction and an endothermic reaction

 Energy is given out in exothermic reactions

 The energy of the products will be lower than the energy of the reactants, so the change in energy
is negative
 This is represented on the reaction profile with a downwards-arrow as the energy of the products is lower
than the reactants
 Energy is taken in endothermic reactions
 The energy of the products will be higher than the energy of the reactants, so the change in energy
is positive
 This is represented on the reaction profile with an upwards-arrow as the energy of the products is higher
than the reactants
Bond Energy

 Energy is needed to break bonds which is absorbed from the reaction surroundings, so bond breaking is
an endothermic process
 The opposite occurs for forming bonds as it releases energy back to the surroundings in
an exothermic process
 Both processes occur in the same chemical reaction, for example, in the production of ammonia:

N2 + 3H2 ⟶ 2NH3

 The bonds in the N-N and H-H molecules must be broken which requires energy while the bonds in the
NH3 molecule are formed which releases energy
 Most reactions occur in a number of steps including steps that are exothermic and steps that are
endothermic
 Whether a reaction is overall endothermic or exothermic depends on the difference between the sum of
the exothermic steps and the sum of the endothermic steps

Endothermic

 If more energy is absorbed than is released, this reaction is endothermic

 More energy is required to break the bonds than that gained from making the new bonds
 The change in energy is positive since the reactants have more energy than the products
 Therefore an endothermic reaction has a positive change in energy

Energy must be absorbed from the surroundings for bonds to be broken

Exothermic

 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 reactants have less energy than the products
 Therefore an exothermic reaction has a negative change in energy

Making new bonds gives off heat from the reaction to the surroundings

Bond Energy Calculations

 Each chemical bond has a 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
 We can calculate the total change in energy for a reaction if we know the bond energies of all the species
involved
 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 energy change using the equation:

Energy change = Energy taken in – Energy given out

Worked Example
Example 1

Hydrogen and chlorine react to form hydrogen chloride gas:

H2 + Cl2 ⟶ 2HCl

The table below shows the bond energies. Calculate the energy change for the reaction and deduce whether it is
exothermic or endothermic

Answer

Worked Example

Example 2

Hydrogen bromide decomposes to form hydrogen and bromine:

2HBr ⟶ H2 + Br2

The table below shows the bond energies. Calculate the energy change for the reaction and deduce whether it is
exothermic or endothermic.
Answer

Exam Tip

For bond energy questions, 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.