Bond-dissociation energy

1.2 Homolytic versus heterolytic dissociation

In chemistry, bond-dissociation energy (BDE) or D0 ,

is one measure of the strength in a chemical bond. It is
dened as the standard enthalpy change when a bond is
cleaved by homolysis,[1] with reactants and products of
the homolysis reaction at 0 K (absolute zero). For instance, the bond-dissociation energy for one of the CH
bonds in ethane (C2 H6 ) is dened by the process:

Bonds can be broken symmetrically or asymmetrically.

The former is called homolysis and is the basis of the
usual BDEs. Asymmetrical scission of a bond is called
heterolysis. For molecular hydrogen, the alternatives are:

CH3 CH2 H CH3 CH2 + H

H2 2 H G = 102 kcal/mol (see table below)

D0 = H = 101.1 kcal/mol = 423.0 kJ/mol = 4.40 eV

(per bond)

H2 H+ + H G = 66 kcal/mol (in water)

|69r>bromocarbons are often labile and are useful re retardants

Denitions of BDE and related

parameters

The data tabulated above shows how bond strengths vary

over the periodic table. There is great interest, especially
The bond-dissociation energy is sometime also called the in organic chemistry, concerning bond strengths of bonds
bond-dissociation enthalpy (or bond enthalpy), but these within a given group of compounds.[2]
terms are not strictly equivalent, as they refer to the above
reaction enthalpy at standard conditions, and dier from
D0 by about 1.5 kcal/mol (6 kJ/mol) in the case of a bond
2 See also
to hydrogen in a large organic molecule.[2]
Bond strength

1.1

BDE versus bond energy

Bond energy

Except in the case of diatomic molecules, the bonddissociation energy is dierent from the bond energy,
which is an average calculated from the sum of the bonddissociation energies of all bonds in a molecule.[3]

Binding energy

For example, an HOH bond of a water molecule (H

OH) has 493.4 kJ/mol of bond-dissociation energy, and
424.4 kJ/mol is needed to cleave the remaining OH
bond. The bond energy of the covalent OH bonds in
water is 458.9 kJ/mol, which is the average of the values.
Hydrogen bond-dissociation energy in water is about 23
kJ/mol.[4]

3 References

Chemical bond

[1] IUPAC, Compendium of Chemical Terminology, 2nd ed.

(the Gold Book) (1997). Online corrected version:
(1994) "Bond dissociation energy".
[2] Blanksby, S. J.; Ellison, G. B.; (2003). Bond Dissociation Energies of Organic Molecules. Acc. Chem.
Res. 36 (4): 255263. doi:10.1021/ar020230d. PMID
12693923.

In the same way for removing successive hydrogen atoms

from methane the bond-dissociating energies are 104
kcal/mol (435 kJ/mol) for D(CH3 H), 106 kcal/mol (444
kJ/mol) for D(CH2 H), 106 kcal/mol (444 kJ/mol) for
D(CHH) and nally 81 kcal/mol (339 kJ/mol) for D(C
H). The bond energy is, thus, 99 kcal/mol or 414 kJ/mol
(the average of the bond-dissociation energies). Notice
that none of the C-H BDEs is 99 kcal/mol.

[3] Morrison & Boyd Organic Chemistry 4th Ed. ISBN 0205-05838-8
[4] Principles of biochemistry by Albert L. Lehninger, David
Lee Nelson, Michael M. Cox; edition 4, page 48

Following dissociation if new bonds are formed at lower

enthalpy there is a net loss of energy, and thus an overall
exothermic process.
1

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