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Energetics

The energy needed to break an O – H bond in water but not in hydrogen peroxide is called
bond energy or bond enthalpy. The energy needed to break any O – H bond in water or in
hydrogen peroxide is called bond energy term or bond enthalpy term. Each C – H bond
energy in methane (CH4) has a different value due to a difference in environment.

CH4(g) → CH3(g) + H(g), ∆H = E(C – H) = + 435 kJmol–1. (1st C – H bond energy).

CH3(g) → CH2(g) + H(g), ∆H = E(C – H) = + 444 kJmol–1. (2nd C – H bond energy).
CH2(g) → CH(g) + H(g), ∆H = E(C – H) = + 440 kJmol–1. (3rd C – H bond energy).
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CH(g) → C(g) + H(g), ∆H = E(C – H) = + 343 kJmol . (4th C – H bond energy).

Thus C – H bond energy term; E(C – H) in CH4 = = +415.5 kJmol–

1
. Therefore the energy need to break any mole of C – H bond in methane (CH4) irrespective
of the environment is + 415.5 kJmol–1. It is denoted at times as E(C – H) and read as CH
bond energy for all compounds that contain the C – H bond.

CH4(g) → CH3(g) + H(g), ∆H = E(C – H) = + 435 kJmol–1. (C – H bond energy).

¼CH4(g) → ¼C(g) + H(g), ∆H = E(C – H) = + 415.5 kJmol–1. (C – H bond energy term).

Definition: Bond energy term is average energy needed to break one mole of gaseous
covalent bonds in a range of compounds with such a bond.

The energy needed to break a mole of gaseous covalent bond irrespective of the
environment or compound the bond is found is called bond energy term or bond enthalpy
term or mean bond energy or mean bond enthalpy or average bond energy or average bond
enthalpy.
Bond energies or average bond energies are always is positive because energy absorbed to
break a bond.

The gaseous state is used in defining bond energies as a reference state for fair comparison
since substances exist in different states of matter. If energy is supplied to separate one mole
samples of chlorine and bromine under standard conditions until their free gaseous atoms
are produced, then it will be difficult to compare the bond strength in chlorine and bromine.
This is because chlorine is a gas while bromine is a liquid under standard conditions.
Cl2(g) → Cl(g) + Cl(g); ∆H = +242 kJmol-1.
Br2(g) → Br(g) + Br(g); ∆H = +194 kJmol-1.
Br2(l) → Br(g) + Br(g); ∆H = +225 kJmol-1.
Act:
(a) Explain the following:
(i) The standard enthalpy change of atomisation of carbon given as +715 kJmol–1 cannot be
used alone to deduce the C – C bond dissociation energy.
(ii) The standard enthalpy change of atomisation of iodine given as +00000 kJmol–1 cannot be
used to deduce the dissociation energy for the I – I bond in iodine molecule.
(iii) The N – H bond energy as +388 kJmol–1 can neither be used alone to deduce the
atomisation energy of nitrogen nor hydrogen.
(b) Given the compound chloromethane (CH3Cl).
(i) Write down an equation for the C – Cl bond energy.
(ii) Write down an equation for the C – Cl bond energy term.
(iii) Write down an equation for the C – H bond energy.
(iv) Write down an equation for the C – H bond energy term.
(v) Explain any similarity or differences in the two equations given in (b) (i) and (ii) above.
(vi) Explain any similarity or differences in the two equations given in (b) (iii) and (iv) above.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Energetics

Example
The enthalpy of atomisation of heptane (C7H16) is + 8628 kJmol-1 and that of octane (C8H18)
is + 9789. That is:
C7H16(l) → 7C(g) + 16H(g); H = + 8628 kJmol-1.
C8H18(l) → 8C(g) + 18H(g); H = + 9789 kJmol-1.
Calculate the C – C and the C – H bond energies.

Solution
H H H H H H H
H–C–C–C–C–C–C–C–H 7C(g) + 16H(g); H = + 8628 kJmol-1.
H H H H H H H

H H H H H H H H
H–C–C–C–C–C–C–C–C–H 8C(g) + 18H(g); H = + 9789 kJmol-1.
H H H H H H H H

Let the energy to break C – H bond be ‘x’ and that needed to break C – C bond be ‘y’.

=> 16x + 6y = +8628 kJmol-1 …………….. (i)

18x + 7y = +9789 kJmol-1 …………….. (ii)
Solving the simultaneous equation gives: x = +415.5 kJmol-1 of C – H bond and
y = +330 kJmol-1 of C – C bond
Uses of bond energies.
i) To compare strength of bonds and stability of molecules. In Oxygen, O = O bond
energy 498 kJmol-1 and in nitrogen, N ≡ N bond energy 945 kJmol-1. This shows that
nitrogen has stronger bonds making it molecules more stable than oxygen molecules.
ii) Used to understanding structure and bonding.
iii) Can be used to predict reactivity. The higher the bond energy, the less reactive the
molecule. CH3F with C – F bond energy 467 kJmol-1 is less reactive compared to
CH3Cl with C – Cl bond energy 346 kJmol-1.
Used to estimating the enthalpy change of a reaction. Bond energies can be used to
calculate the enthalpy change of reaction using the formula below.
H = - . That is:
Energy is lost in order to form a bond i.e. bond formation is on exothermic process.
Energy is absorbed (gained) in order to break a bond i.e. bond breakage is an
endothermic process.
Each type of bond in a molecule makes a fixed contribution to the total energy
change of the reaction. An exothermic change is an evidence for the formation of
stronger bonds whereas an endothermic change is an evidence for the formation of
weaker bonds or the weakening of bonds.
Calculations carry out using bond energy terms usually shows a discrepancy with
experimental values for a particular molecule. Bond energy term takes into account
all molecules with a particle bond while the experiment considers only the bonds in
the molecule under study.
A common laboratory experimental evidence bond formation is an exothermic
process is a neutralisation reaction. During a neutralisation reaction, there is no bond
breaking. There is only a dative covalent bond formation between a hydroxide ion
(OH–) ion from the base and a hydrogen ion (H+) from the acid in order to produce a
water molecule. Heat energy is always released during neutralisation.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N