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Chemistry · Thermochemistry

Bond Energy

Estimate a reaction’s enthalpy from the bonds broken and the bonds formed.

Bonds broken

Every bond in the reactants. Breaking them costs energy.

Bond
Bond
2642 kJ

Bonds formed

Every bond in the products. Forming them releases energy.

Bond
Bond
3450 kJ
Estimated ΔH
-808kJExothermic

2642 kJ put in to break bonds − 3450 kJ released as bonds form.

These are average bond enthalpies, so the answer is an estimate — typically within about 10 kJ/mol of the measured value, and only for gas-phase species.

Worked reactions — tap to load

Breaking a bond costs energy and forming one releases it, so a reaction’s enthalpy is the difference: ΔH ≈ Σ(bonds broken) − Σ(bonds formed). Burning methane gives −808 kJ this way, against a measured −802 kJ.

Why breaking always costs and forming always pays

A chemical bond exists because the bonded arrangement is lower in energy than the separated atoms. Pulling those atoms apart therefore requires energy in, always — there is no such thing as an exothermic bond break. Forming a bond is the same event run backwards and releases exactly the same amount.

That makes the sign convention automatic. Bonds broken enter the sum positive and bonds formed negative, and a reaction is exothermic when the products’ bonds are collectively stronger than the reactants’. Combustion is exothermic because the C=O and O–H bonds it creates are unusually strong, not because oxygen is somehow energetic on its own.

Where the number comes from

A tabulated bond energy is an average across many molecules. A C–H bond is not identical in methane, ethanol and benzene, so 413 kJ/mol is a compromise that fits them all approximately and none exactly. That averaging is the source of nearly all the error in this method, and why the answer should be quoted as an estimate.

ΔH ≈ Σbonds broken − Σbonds formed

positive ΔH is endothermic; negative is exothermic

  1. 1
    Draw both sides and count every bond. For CH₄ + 2O₂ → CO₂ + 2H₂O the reactants hold 4 C–H and 2 O=O.
  2. 2
    Total the energy needed to break the reactant bonds. 4 × 413 + 2 × 495 = 1652 + 990 = 2642 kJ.
  3. 3
    Total the energy released forming the product bonds. CO₂ has 2 C=O and two waters have 4 O–H: 2 × 799 + 4 × 463 = 1598 + 1852 = 3450 kJ.
  4. 4
    Subtract. 2642 − 3450 = −808 kJ. Negative, so the reaction is exothermic.
  5. 5
    Read it as an estimate. The measured value is −802.3 kJ. Six kJ out of 800 is typical for this method.

Common bond energies

Average bond enthalpies in kJ/mol. The tool holds all 52; these are the ones that recur.

BondkJ/molBondkJ/mol
H–H436C=C614
C–H413C≡C839
N–H391C=O799
O–H463C≡N891
C–C348N=N418
C–O358N≡N941
O–O146O=O495
Cl–Cl242H–Cl431

Three limits worth knowing before you trust the answer

The first is the averaging already described, which puts the typical error around 10 kJ/mol. That is fine for deciding whether a reaction is exothermic and roughly how strongly, and useless for anything needing better than about 1% accuracy.

The second is phase. Bond energies describe gas-phase species, so the method silently ignores the energy of vaporising a liquid or dissolving a solid. Burning methane to liquid water rather than steam releases about 890 kJ, not 802 — the extra 88 kJ is condensation, which involves no bonds breaking at all. If your equation has an (l) or (aq) in it, this method is answering a different question.

The third is that it only sees covalent bonds. Ionic lattices, metallic bonding and intermolecular forces are all invisible to it, so a precipitation or neutralisation reaction cannot be estimated this way. When accuracy matters, standard enthalpies of formation give the exact value instead, and Hess’s law assembles it from known steps.

What is the bond energy formula for ΔH?
ΔH ≈ total energy of bonds broken minus total energy of bonds formed. Breaking always costs energy and forming always releases it, so the difference gives the reaction enthalpy.
Why is breaking a bond always endothermic?
Because a bond exists only when the bonded state is lower in energy than the separated atoms. Pulling them apart must supply that difference, so there is no such thing as an exothermic bond break.
How accurate is this method?
Typically within about 10 kJ/mol. Burning methane estimates at −808 kJ against a measured −802.3 kJ. The error comes from bond energies being averages across many different molecules.
Why do different textbooks give different bond energies?
Because each averages over a slightly different set of compounds. Values for C–H range from about 410 to 416 kJ/mol depending on the source. Using one consistent set matters more than which set you pick.
Does this work for reactions in solution?
No. Bond energies describe gas-phase species, so anything involving dissolution, ionic lattices or a change of phase is outside the method. Use standard enthalpies of formation instead.
Why does burning methane give −890 kJ in my textbook?
That figure is for liquid water as the product. The bond-energy method gives gaseous water, at about −802 kJ; the extra 88 kJ is the enthalpy of condensation, which breaks no bonds.
When should I use enthalpies of formation instead?
Whenever you need an exact value, or the reaction involves liquids, solutions or ionic compounds. Formation enthalpies are measured for specific substances rather than averaged across many.