Bond-dissociation energy

The bond-dissociation energy (BDE, D₀, or DH°) is one measure of the strength of a chemical bond A−B. It can be defined as the standard enthalpy change when A−B is cleaved by homolysis to give fragments A and B, which are usually radical species.^[1]^[2] The enthalpy change is temperature-dependent, and the bond-dissociation energy is often defined to be the enthalpy change of the homolysis at 0 K (absolute zero), although the enthalpy change at 298 K (standard conditions) is also a frequently encountered parameter.^[3]

As a typical example, the bond-dissociation energy for one of the C−H bonds in ethane (C₂H₆) is defined as the standard enthalpy change of the process

CH₃CH₂−H → CH₃CH₂• + H•,

DH°₂₉₈(CH₃CH₂−H) = ΔH° = 101.1(4) kcal/mol = 423.0 ± 1.7 kJ/mol = 4.40(2) eV (per bond).^[4]

To convert a molar BDE to the energy needed to dissociate the bond per molecule, the conversion factor 23.060 kcal/mol (96.485 kJ/mol) for each eV can be used.

A variety of experimental techniques, including spectrometric determination of energy levels, generation of radicals by pyrolysis or photolysis, measurements of chemical kinetics and equilibrium, and various calorimetric and electrochemical methods have been used to measure bond dissociation energy values. Nevertheless, bond dissociation energy measurements are challenging and are subject to considerable error. The majority of currently known values are accurate to within ±1 or 2 kcal/mol (4–10 kJ/mol).^[5] Moreover, values measured in the past, especially before the 1970s, can be especially unreliable and have been subject to revisions on the order of 10 kcal/mol (e.g., benzene C–H bonds, from 103 kcal/mol in 1965 to the modern accepted value of 112.9(5) kcal/mol). Even in modern times (between 1990 and 2004), the O−H bond of phenol has been reported to be anywhere from 85.8 to 91.0 kcal/mol.^[6] On the other hand, the bond dissociation energy of H₂ at 298 K has been measured to high precision and accuracy: DH°₂₉₈(H−H) = 104.1539(1) kcal/mol or 435.780 kJ/mol.^[5]

^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Bond-dissociation energy". doi:10.1351/goldbook.B00699
^ The value reported as the bond-dissociation energy (BDE) is generally the enthalpy of the homolytic dissociation of a gas-phase species. For instance, the BDE of diiodine is calculated as twice the heat of formation of iodine radical (25.5 kcal/mol) minus the heat of formation of diiodine gas (14.9 kcal/mol). This gives the accepted BDE of diiodine of 36.1 kcal/mol. (By definition, diiodine in the solid state has a heat of formation of 0.)
^ The IUPAC Gold Book does not stipulate a temperature for its definition of bond-dissociation energy (ref. 1).
^ The corresponding BDE at 0 K (D₀) is 99.5(5) kcal/mol.
^ ^a ^b Luo, Y. R. (2007). Comprehensive handbook of chemical bond energies. Boca Raton: CRC Press. ISBN 978-0-8493-7366-4. OCLC 76961295.
^ Mulder P, Korth HG, Pratt DA, DiLabio GA, Valgimigli L, Pedulli GF, Ingold KU (March 2005). "Critical re-evaluation of the O−H bond dissociation enthalpy in phenol". The Journal of Physical Chemistry A. 109 (11): 2647–55. Bibcode:2005JPCA..109.2647M. doi:10.1021/jp047148f. PMID 16833571.

[:0-1] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "Bond-dissociation energy". doi:10.1351/goldbook.B00699

[2] The value reported as the bond-dissociation energy (BDE) is generally the enthalpy of the homolytic dissociation of a gas-phase species. For instance, the BDE of diiodine is calculated as twice the heat of formation of iodine radical (25.5 kcal/mol) minus the heat of formation of diiodine gas (14.9 kcal/mol). This gives the accepted BDE of diiodine of 36.1 kcal/mol. (By definition, diiodine in the solid state has a heat of formation of 0.)

[3] The IUPAC Gold Book does not stipulate a temperature for its definition of bond-dissociation energy (ref. 1).

[4] The corresponding BDE at 0 K (D₀) is 99.5(5) kcal/mol.

[:1-5] Luo, Y. R. (2007). Comprehensive handbook of chemical bond energies. Boca Raton: CRC Press. ISBN 978-0-8493-7366-4. OCLC 76961295.

[6] Mulder P, Korth HG, Pratt DA, DiLabio GA, Valgimigli L, Pedulli GF, Ingold KU (March 2005). "Critical re-evaluation of the O−H bond dissociation enthalpy in phenol". The Journal of Physical Chemistry A. 109 (11): 2647–55. Bibcode:2005JPCA..109.2647M. doi:10.1021/jp047148f. PMID 16833571.

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