Unit 5 – Enthalpy Changes

By: Achini Shehara

What are enthalpy changes?

Exothermic or endothermic?
Chemical reactions that release 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.
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)
Chemical reactions that absorb energy from the surroundings
are described as endothermic. In an endothermic reaction the
temperature of the surroundings decreases

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.

The citric acid and sodium hydrogencarbonate are absorbing

the heat energy from the solvent, the test tube and the air.
Enthalpy changes and enthalpy profile diagrams

We call the energy exchange between a chemical reaction

and its surroundings at constant pressure the enthalpy
change
We cannot measure enthalpy, but we can measure an enthalpy
change when heat energy is exchanged with the surroundings.

We can write this as:

ΔH = Hproducts – Hreactants
This is called Hess’s law

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’.
We can draw enthalpy profile diagrams (also known as reaction
pathway diagrams) to show enthalpy changes.

A reaction is exothermic when it releases energy, and ΔH =

negative. On the other hand, a reaction is defined endothermic
when it absorb energy, therefore the ΔH = positive.
VARIOUS ENTHALPY CHANGE DEFINITIONS

Standard enthalpy change of reaction, ΔH°r

The standard enthalpy change of a reaction is the
enthalpy change which occurs when quantities of
materials react under standard conditions, and with
everything in its standard state.

Standard enthalpy change of formation, ΔH°f

The standard enthalpy change of formation of a compound

is the enthalpy change which occurs when one mole of the
compound is formed from its elements under standard
conditions, and with everything in its standard state.
Standard enthalpy change of combustion, ΔH°c
The standard enthalpy change of combustion of a compound is
the enthalpy change which occurs when one mole of the
compound is burned completely in oxygen under standard
conditions, and with everything in its standard state.
Standard enthalpy change of neutralisation, ΔH˚n
The standard enthalpy change of neutralisation (ΔH˚n ) is
the enthalpy change when one mole of water is formed by
the reaction of an acid with an alkali under standard
conditions.
Standard enthalpy change of solution, ΔH˚sol
The standard enthalpy change of solution (ΔH˚sol) is the
enthalpy change when one mole of solute is dissolved in a
solvent to form an infinitely dilute solution under standard
conditions.
Standard enthalpy change of atomisation, ΔH˚at
The standard enthalpy change of atomisation, ΔH˚at, is
the enthalpy change when one mole of gaseous atoms is
formed from its element under standard conditions.

Standard enthalpy change of hydration of an anhydrous

salt
The standard enthalpy change of hydration of an
anhydrous salt is the enthalpy change when one
mole of a hydrated salt is formed from one mole of
the anhydrous salt under standard conditions.
Enthalpy cycles
We can illustrate Hess’s law by drawing enthalpy cycles
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.
Enthalpy change of reaction from enthalpy changes of
formation
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.
Calculating the enthalpy change of hydration of an
anhydrous salt

Hydrated salts such as hydrated copper(II) sulfate, CuSO4.5H2O,

contain water molecules surrounding their ions. It is very difficult
to measure the enthalpy change when an anhydrous salt such as
anhydrous sodium thiosulfate becomes hydrated.
We can, however, use an enthalpy cycle to calculate this. We
use the standard enthalpy changes of solution to complete the
enthalpy cycle
Bond energies and enthalpy changes

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

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:
The values of bond energies are always positive 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:

Calculating enthalpy changes using bond energies

We can use bond enthalpies to calculate the enthalpy change of

a reaction that we cannot measure directly.
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.