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Bond-dissociation energy - Wikipedia, the free encyclopedia

Bond-dissociation energy
From Wikipedia, the free encyclopedia

In chemistry, bond-dissociation energy (BDE) or D0 , is one measure of the strength in a chemical bond. It is defined 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 C-H bonds in ethane (C2H6) is defined by the process: CH3CH2-H CH3CH2 + H D0 = H = 101.1 kcal/mol (423.0 kJ/mol)

Contents
1 Definitions of BDE and related parameters 1.1 BDE vs bond energy 1.2 Homolytic vs heterolytic dissociation 2 Tabulated data 3 See also 4 References

Definitions of BDE and related parameters

The bond-dissociation energy is sometimes also called the bond-dissociation enthalpy (or bond enthalpy), but these terms are not strictly equivalent, as they refer to the above reaction enthalpy at standard conditions, and differ from D0 by about 1.5 kcal/mol (6 kJ/mol) in the case of a bond to hydrogen in a large organic molecule.[2]

BDE vs bond energy

Except in the case of diatomic molecules, the bond-dissociation energy is different from the bond energy, which is an average calculated from the sum of the bond-dissociation energies of all bonds in a molecule.[3] For example, an HO-H bond of a water molecule (H-O-H) has 493.4 kJ/mol of bond-dissociation energy, and 424.4 kJ/mol is needed to cleave the remaining O-H bond. The bond energy of the covalent O-H 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] 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(CH-H) and finally 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.

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Bond-dissociation energy - Wikipedia, the free encyclopedia

Note that, following dissociation, if new bonds are formed at lower enthalpy, then there is a net loss of energy, and thus an overall exothermic process.

Homolytic vs heterolytic dissociation

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: H2 2 H G = 102 kcal/mol (see table below) H2 H+ + H- G = 66 kcal/mol (in water)

Tabulated data
Bond Bond Bond-dissociation energy (kcal/mole) (kJ/mole) 98 117 79 69 83-85 58 46 410 490 331 285 347-356 242 192 (eV) 4.25 5.08 3.43 2.95 3.603.69 2.51 1.99 Comment C-H bond strength affected by substituents (see next table) one of the strongest single bonds to carbon more labile than C-H and C-F bonds, chlorocarbons degrade photochemically weaker than C-Cl bonds bromocarbons are often labile and are useful fire retardants strong, but weaker than C-H bonds indicated by the yellowish colour of this gas indicated by the brownish colour of Br2 source of the Br. radical indicated by the purplish colour of I2 source of the I. radical strong, nonpolarizable bond cleaved only by metals and by strong oxidants comparable to strength of O=O and C-H bonds strong bond, but O-H bonds are of comparable strength one of the strongest bonds production of ammonia consumes significant energy

C-H C-H bond C-F C-F bond C-Cl C-Cl bond C-Br C-Br bond

C-C C-C bond Cl-Cl chlorine BrBr I-I bromine

iodine

36 104 110 119 226

151 436 460 497 945

1.57 4.52 4.77 5.15 9.79

H-H hydrogen O-H O=O NN hydroxyl oxygen nitrogen

The data tabulated above shows how bond strengths vary over the periodic table. There is great interest, especially in organic chemistry, concerning bond strengths of bonds within a given group of compounds.[2]
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Bond-dissociation energy - Wikipedia, the free encyclopedia

Bond H3C-H C2H5-H (CH3)3C-H CH2CH-H HC2-H C6H5-H CH2CHCH2H C6H5CH2-H H3C-CH3 H2C=CH2 HCCH

Bond Methyl C-H bond Ethyl C-H bond tertiary C-H bond vinyl C-H bond acetylenic C-H bond phenyl C-H bond allylic C-H bond benzylic C-H bond Alkane C-C bond Alkene C=C bond alkyne CC triple bond

Bond-dissociation energy (kcal/mole) 105 101 96.5 111 133 113 89 90 83-85 146-151 200 (kJ/mole) 439 423 404 464 556 473 372 377 347-356 611-632 837

Comment One of the strongest aliphatic C-H bonds slightly weaker than H3C-H tertiary radicals are stabilized vinyl radicals are rare acetylenic radicals are very rare comparable to vinyl radical, rare such bonds show enhanced reactivity akin to allylic C-H bonds such bonds show enhanced reactivity much weaker than a C-H bond about 2x stronger than a C-C single bond about 2.5x stronger than a C-C single bond

See also
Bond strength Bond energy Binding energy Chemical bond

References
1. ^ Nic, M.; Jirat, J.; Kosata, B., eds. (2006). "Bond dissociation energy" (http://goldbook.iupac.org/B00699.html). IUPAC Compendium of Chemical Terminology (Online ed.). doi:10.1351/goldbook.B00699 (http://dx.doi.org/10.1351%2Fgoldbook.B00699). ISBN 0-9678550-9-8. 2. ^ a b Blanksby, S. J.; Ellison, G. B.; (2003). "Bond Dissociation Energies of Organic Molecules". Acc. Chem. Res. 36 (4): 255263. doi:10.1021/ar020230d (http://dx.doi.org/10.1021%2Far020230d). PMID 12693923 (//www.ncbi.nlm.nih.gov/pubmed/12693923). 3. ^ Morrison & Boyd Organic Chemistry 4th Ed. ISBN 0-205-05838-8 4. ^ Principles of biochemistry by Albert L. Lehninger, David Lee Nelson, Michael M. Cox; edition 4, page 48 [1] (http://books.google.com/books? id=7chAN0UY0LYC&pg=PA48&lpg=PA48&dq=%22hydrogen+bonds%22+dissociation&source=bl&ots=MzlSaIF Uft&sig=V81po0G4OTZaNG4xiCRhba1_4s&hl=en&ei=VQ6eSrf6I9CpnAeuxfmrDA&sa=X&oi=book_result&ct=result&resnum=4#v= onepage&q=%22hydrogen%20bonds%22%20dissociation&f=false)

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