Ch. 9.

10: Bond Energy & Reaction Enthalpy

• Bond Energy (Bond Dissociation Energy)

o The energy required to break a bond (endothermic, >0) in 1 mol of gaseous molecules
o The energy released when 1 mol of the bond is formed (exothermic, <0)
§ Breaking bonds is always endothermic (+) and forming bonds is always exothermic (–
)
o Potential energy vs. distance:

1. Atoms far apart, little to no attraction

2. As atoms get closer, valence electrons of one atom are attracted to nucleus of
other
3. At optimal distance (bond length), have energy minimum (bond energy)
4. As atoms get closer, internuclear repulsion destabilizes bond
§ Bond energy and bond length are inversely proportional: shorter bonds have higher
bond energy (stronger), longer bonds have lower bond energy (weaker)
§ Bonds vibrate about average length (vibrational energy, IR spectra)
o Bond Energies
§ Bond Energy (ΔHbond or Dbond) required to break bond
• Positive since breaking bond is endothermic
• Forming bond would be exothermic, negative of same value

§ Bond Order and Bond Strength

• Double bonds shorter, stronger than single bonds; Triple bonds shortest and
strongest:
Bond C-C C=C C≡C
Length 1.54Å 1.34Å 1.20Å
Energy 348 kJ/mol 614 kJ/mol 839 kJ/mol
§ Bond energy determined from average bond energies of similar bonds
• For diatomic molecules (e.g. Cl–Cl,H–F), bond energy is more precise (direct
measurement)
o See table 9.4 above
Reaction Enthalpy-Bond Energies Notes.docx p.3

• For polyatomic molecules (e.g. CH4), energy required to break each bond (in
succession) depends on its exact environment, so take average:
CH4 (g) → CH3 (g) + H (g) ∆H = 435 kJ/mol
CH3 (g) → CH2 (g) + H (g) ∆H = 453 kJ/mol
CH2 (g) → CH (g) + H (g) ∆H = 425 kJ/mol
CH (g) → C (g) + H (g) ∆H = 339 kJ/mol
CH4 (g) → C (g) + 4 H (g) ∆H = 1652 kJ/mol
• Average ∆H = DC–H = 1652 kJ/mol ÷ 4 = 413 kJ/mol (D = bond energy)
o Table value is different because it averages many more C-H bonds
• Even though there is variation in energies, the concept is still useful for estimating
reaction enthalpies

• Using Bond Energies to Estimate Reaction Enthalpy

o Due to variation in bond energies, the concept is useful only for estimating ΔHrxn:
o Reaction enthalpy is due to difference in bond energies of products and reactants:
§ Add up all bonds broken: endothermic, so ΣDbroken positive
§ Add up all bonds formed: exothermic, so ΣDformed negative
§ ∆Hrxn = ΣDbroken – ΣDformed
o Calculate ∆Hrxn for the reaction CH4 + Cl2 → CH3Cl + HCl
CH4 + Cl2 → CH3Cl + HCl
4 C-H 1 Cl-Cl 3 C-H, 1 C-Cl 1 H-Cl
Broken Formed
• Don’t always have to break and reform every bond; just look at changed bonds:
o Net Bonds broken: 1 C–H, 1 Cl–Cl:
ΣDbroken = (414 kJ/mol) + (242.7 kJ/mol) = 657 kJ/mol
o Net Bonds formed: 1 C–Cl, 1 H–Cl:
ΣDformed = (328 kJ/mol) + (431.9 kJ/mol) = 760 kJ/mol
o ∆Hrxn= ΣDbroken – ΣDformed = 657 kJ/mol – 760 kJ/mol = –103 kJ/mol
§ If you know ∆Hrxn, you can estimate D for a bond:
• Given H2 (g) + O2 (g) → H2O2 (g) ∆H = –136.3 kJ/mol, using the values in Table
9.4, for H2, O2 and O-H, estimate the bond energy for the O–O single bond:
o Bonds broken: 1 H–H, 1 O=O
ΣDbroken = (436.4 kJ/mol) + (498.7 kJ/mol) = 935.1 kJ/mol
o Bonds formed: 2 O–H, 1 O–O [Note: remember to multiply by # of bonds!]
ΣDformed = 2(460 kJ/mol) + (DO-O)
o ∆Hrxn= ΣDbroken – ΣDformed
= –136.3 kJ/mol = 935.1 kJ/mol – [920 kJ/mol + DO–O];
DO–O = 935.1 kJ/mol – 920 kJ/mol + 136.3 kJ/mol = 151 kJ/mol
*Value in Table 9.4 is an average of O–O bonds in different compounds*