Making and breaking bonds

A chemical reaction involves the breaking of existing chemical bonds and the making of new chemical bonds.
You will recall from Topic 4 that chemical bonds are the result of electrostatic attractions between atoms or
ions. To overcome these attractions (to break the bond), energy must be absorbed. In other words, bond
breaking is endothermic. Conversely, when new chemical bonds are formed, energy is released; therefore, bond
making is exothermic (Figure 1).

Figure 1. Changes in enthalpy for bond breaking (left) and bond making (right).  

In a chemical reaction, if the energy absorbed while breaking bonds is less than the energy released when
forming new bonds, the reaction is exothermic (Figure 2a). If the energy absorbed while breaking bonds is
greater than the energy released when forming new bonds, the reaction is endothermic (Figure 2b). The
difference between the energy absorbed and the energy released can be used to calculate the overall enthalpy
change for the reaction.
 

Fi
gure 2. Energy profiles for (a) an exothermic reaction and (b) an endothermic reaction

Bond enthalpy
The energy required to break a chemical bond is called the bond enthalpy, H or bond dissociation energy,
E (note that these two terms are often used interchangeably). It is defined as the energy required to break one
mole of chemical bonds in the gaseous state. Bond enthalpy values are always positive because they refer to
bonds being broken (bond breaking is endothermic). It is also important to note that these values refer to
molecules in the gaseous state. Two examples are given below; the bond enthalpy for breaking one mole of
bonds between the bromine atoms in molecular bromine and for breaking one mole of double bonds in
molecular oxygen. Note the positive sign for the enthalpy change.

Br2 (g) → 2Br (g)   E (Br–Br) = +193 kJ mol−1

O2 (g) → 2O (g)    E (O=O) = +498 kJ mol−1

When new bonds are formed, the energy released is equal to the energy that was absorbed to break the bond.
For example, the bond enthalpy value for the formation of an oxygen molecule from oxygen atoms is:

2O (g) → O2 (g)  E (O=O) = −498 kJ mol−1

Note that the sign has changed, but the numerical value remains the same.

 Average bond enthalpy

The average bond enthalpy is the enthalpy change when one mole of bonds are broken in the gaseous state
averaged for the same bond in similar compounds. The same type of chemical bond in different compounds has
different bond enthalpy values. For example, the O-H bond in water has a slightly different bond enthalpy value
to the O-H bond in ethanol. Identical bonds in molecules with two (or more) types of bond also have different
bond enthalpy values. In water, for example, it takes more energy to break the first O-H bond than to break the
second:

H2O (g) → H (g) + OH (g)  ΔH = +502 kJ mol-1

OH (g) → H (g) + O (g)   ΔH = +427 kJ mol-1

To calculate the average bond enthalpy for the two OH bonds in water, we take the average:

Total energy to break both bonds =  + 502 + 427 = + 929  (kJ mol-1)

         Average bond enthalpy  =  + 929 / 2 = + 464.5 kJ mol-1

Compare this with the value in section 11 of the IB data booklet, which is +463 kJ mol-1. It differs slightly
because the values in the data booklet are calculated from a range of different compounds, in which the same
type of bond has different bond enthalpy values.

Calculating enthalpy changes using bond enthalpy values

The enthalpy change for a reaction can be calculated using average bond enthalpy values. The enthalpy change
is equal to the sum of the bond enthalpy values of the bonds broken minus the sum of the bond enthalpy values
of the bonds formed. This is shown in equation form as either:

ΔH = ΣE(bonds broken) − ΣE(bonds formed)

or

ΔH = Σ(bond enthalpies of reactants) – Σ(bond enthalpies of products)

Important
Enthalpy changes for reactions calculated from average bond enthalpy data may differ slightly from
experimental values. This is because they are average values taken from the same bonds in a range of similar
compounds.

Worked example 1

In the Haber process, hydrogen reacts with nitrogen to form ammonia according to the following equation:

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

The reaction involves the breaking of one triple bond between the nitrogen atoms and three single bonds
between the hydrogen atoms. The bonds formed in the products are six nitrogen to hydrogen bonds (Figure 3). 

Figure 3. Bonds broken and bonds formed in the formation of ammonia.

The relevant bond enthalpy values are:

E (N≡N) =  +945 kJ mol−1       E (H–H) = +436 kJ mol−1           E (N–H) = +391 kJ mol−1

Using the bond enthalpy values given above, calculate the enthalpy change for the formation of ammonia.

» Show solution

Bonds broken: 1 × N≡N + 3 × H–H

Bonds formed: 6 × N–H

ΔH = ΣE(bonds broken) − ΣE(bonds formed)

ΔH = (945 + 3 × 436) − (6 × 391)

ΔH = −93 kJ mol-1

Worked example 2

Ethene undergoes addition in excess chlorine according to the following equation:

C2H4 (g) + Cl2 (g) → CH2ClCH2Cl (s)

Using the bond enthalpy values given below, calculate the enthalpy change for the reaction.

E (C–C) = +346 kJ mol−1
E (C–H) = +414 kJ mol−1
E (C–Cl) = +324 kJ mol−1
E (Cl–Cl) = +242 kJ mol−1
E (C=C) = +614 kJ mol−1

» Show solution
Bonds broken: 1 × C=C + 1 × Cl–Cl

Bonds formed: 1 × C–C + 2 × C–Cl

ΔH = ΣE (bonds broken) − ΣE (bonds formed)

ΔH = (1 × 614 + 1 × 242) − (1 × 346 + 2 × 324)

ΔH = −138 kJ mol−1

Note that the four carbon−hydrogen bonds undergo no change, so they can be included or omitted in the
calculation, as they do not affect the answer.

Exam tip

Draw out the structures of compounds to check that you have accounted for all the bonds in a compound,
especially if they contain double or triple bonds.