Bond energies and enthalpy changes

Recap of previous knowledge

-

State Hesss law.

Why is Hesss law used to determined the standard enthalpy change of formation of
methane (CH4)?

Bond energies (bond Enthalpies)

Enthalpy changes (H) are due to bond breaking (BB) and bond formation (BF). Each type of
bond in a molecule makes a fixed contribution to the total energy of the reaction.
Bond breaking is endothermic (BOBEN) and bond formation is exothermic (BOFEX)
- For an exothermic reaction, the sum of bond breaking (BB) is less than the sum of bond
formation (BF) i.e. BB < BF. Thus Hrxn = BB - BF = -ve.
- For an endothermic reaction, the sum of bond breaking (BB) is greater than the sum of
bond formation (BF) i.e. BB > BF. Thus Hrxn = BB - BF = +ve.
In some reactions, all the bonds in reactants are broken e.g. H2(g) + Cl2(g) 2HCl(g).
In some reactions, all the bonds in reactants are completely broken e.g.
H2C=CH2 + Cl2 ClCH2CH2Cl.
The minimum amount of energy needed to break bonds in reactants so that a reaction can start
is called activation energy.
Definition: Bond energy is defined as the energy needed to break one mole of a particular
covalent bond in one mole of a gaseous molecule.
Bond energies are also called bond enthalpies or bond dissociation energies. Bond energies are
measured in kiloJoules per mol (kJmol-1). The bond energy for a CH bond is written as E(C
H), where E represents energy. The values of bond energies are always positive because
they refer to bonds being broken.
Note: The amount of energy needed to break a bond is equal to the energy released when the
bond is formed. The energies simply differ in sign. For example, the energy needed to break a
mole of NN bond in a N2 is +945Kjmol-1 and the energy released when a mole of NN bond
in a N2 is formed is -945Kjmol-1.
Average bond energy.
Bond energy is affected by the environment of the bond (other atoms in the molecule) and also
by the bond length. Water and ethanol all have O H bonds but the E(O H) in water and
ethanol are different. Even in the same molecule, the energy needed to break a particular bond
is not the same. Thus average bond energy breaks a particular bond in a molecule taking into
consideration all the different environments to that bond.
Energy cycles are used to find bond energies because they cannot be determined directly.
The following are required to find the average C H bond energy in methane:
- The enthalpy change of formation or combustion of methane
- The enthalpy of atomisation of carbon and hydrogen
Definition: Average bond energy is defined as the average energy needed to break one mole
of covalent bonds in a range of compounds with such a bond in the gaseous state.
Calculating enthalpy changes using bond energies

Bond energies are used to calculate enthalpy changes that cannot be measured directly.
Example 1:
Calculate the enthalpy change for the reaction H2(g) + Cl2(g) 2HCl(g), given the following
bond energies. E(H H) = 436, E(Cl Cl) = 242, E(H Cl) = 431,
Solution:
H

=
=
=
=
=

+ energy to break bonds energy when new bonds made

+ ( HH + ClCl )
( 2 HCl)
+ ( 436 + 242 )
( 2
+
678

862
184 kJ/mol of H2 and Cl2 reacting.

(negative sign means 184 kJ given out when 2 mol of HCl are formed)
We can show this on an energy diagram which represents the heat energy content of the
molecules. 678kJ/mol is put in to split the HH and the ClCl up into atoms, and then
862 kJ/mol is given out when the two new HCl bonds are formed:
2H + 2Cl
atoms
heat energy
content

+678
862
HH +
ClCl
before

184 kJ/mol
net change
progress of reaction

Final level is below level on

left, since reaction gives out
heat i.e. the reaction is
exothermic

2 HCl
after

Example 2:
Use the bond energies given to find the energy released when one mole of methane is burnt:
CH4 + 2O2 CO2 + 2H2O. Data: CH 413; O=O 497; C=O 803; HO 463 kJ/mol
Solution:
Rewrite the equation showing all the bonds:
H
O=O
HCH +
O=C=O +
O=O
H
H

HOH
HOH

= + energy to break bonds energy when new bonds made

= + ( 4 CH + 2 O=O)
( 2C=O + 4 HO )
= + (4 413 + 2 497)
( 2 803 + 4 463)
= 812 kJ/mol
(i.e. 812 kJ released for each mole of methane)

Example 3.
Given the following bond enthalpies.
Bond
FF
NN
Energy
158
163

NH
390

NN
945

HF
563

Calculate the energy change for the reaction: N2H4(g) + 2F2(g) N2(g) + 4HF(g).
Solution.

H
H
NN
+ 2F F N N + 4H F.
H
H
{Sum of bonds broken in reactants} {sum of bonds formed in products}
{4E(N H) + E(N N) + 2E(F F)} {E(N N) + 4E(F F)}
{4(390) + (163) + 2(158)} {(945) + 4(563)}
=> (1560 +163 + 316) (945 + 2252) => 2039 3197 = -1158 kJ.
=> H rxn = -1158kJ.
Example 4.
Calculate the enthalpy of formation of ethane using the following information:
E(C C) = 348 kJmol-1,
E(C H) = 410 kJmol-1.
-1
C(s) C(g);
H = +718 kJmol .
H2(g) H(g); H = +218 kJmol-1.
Solution.
H1 + H2 = H f + H3.
3C(s) + 3H2(g)
=> H f = H1 + H2 H3.

H1
H1 = 2H at [C(s)] = 2(+718) = +1436
H3

H2 = 6H at H2(g) = 6(+218) = +1308

2C(g) + 6H(g)

H3 = H at CH3CH3(g) = 6E(CH) + E(CC).

=> H3 = H at CH3CH3(g) = 6(+410) + 348 = +2808.

H f = H1 + H2 H3. => H f = +1436 + 1308 2808 = - 64.
=> H f CH3CH3(g) = - 64 kJmol-1.
H
CH3CH3(g)
H2

Enthalpy changes calculated using bond energies are always different from the correct
enthalpy change because bond energies are not usually exact values for the molecules in any
particular reaction. OR The bond energies used are average and not the exact values of the
molecules in question. Besides, bond energies apply to molecules in the gaseous state while
the compound in question could be in the solid or liquid state.
Uses of bond energies.
i)
Used in comparing bond strength, hence stability of a molecules. The more energy that
is required to break a bond, the more stable the molecule. Oxygen; O = O bond energy
498 kJmol-1 is less stable compared to nitrogen; N N bond energy 945 kJmol-1.
ii)
Used to understanding structure and bonding
iii)
Can be used to predict reactivity. The smaller the bond energy the more reactive the
compound. For elements (non-metal), this only applies across the period not down the
group. Oxygen; O = O bond energy 498 kJmol-1 is more reactive than nitrogen; N N
bond energy 945 kJmol-1.
iv)
Used to estimating the enthalpy change of a reaction.
v)
Used to compared the effectiveness of different molecules as fuels