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Introduction
The making and breaking of bonds is the basis of all
chemical transformation. A sound knowledge of the
energies required to break bonds and the energies released
upon their formation is fundamental to understanding
chemical processes.1 The energy required for homolytic
bond cleavage at 298 K corresponds to the enthalpy of
reaction 1, rxnH298(1), which is by definition2 the bond
dissociation enthalpy of the molecule AB, DH298(AB):
AB f A + B
(1)
Thermochemistry
The bond dissociation energy for a species, AB, at room
temperature is the bond enthalpy, DH298(AB). By definition,
it is the reaction enthalpy of the bond homolysis reaction
1, rxnH298(1), and thus depends exclusively on the relative
enthalpies of formation of reactant and product states:
rxnH298(1) ) fH298(A) + fH298(B) - fH298(AB) ) DH298(AB)
(3)
298
Stephen Blanksby obtained his Ph.D. from the University of Adelaide in 1999
under the supervision of John Bowie. He then worked as a postdoctoral
researcher at the University of Colorado from 2000 to 2002, and has recently
taken up a faculty position in the Department of Chemistry at the University of
Wollongong.
Barney Ellison studied at Trinity College (Hartford, CT) and then earned a Ph.D.
in chemistry at Yale University under the supervision of K. B. Wiberg. Ellison
teaches organic chemistry at the University of Colorado and studies the chemical
physics of organic molecules.
(2)
blanksby@
255
Table 1. Molecular Bond Dissociation Energies for RH f R + H: Experimental Bond Enthalpies and Radical
Heats of Formation at 298 K
DH298
(kcal mol-1)
H2
HF
HCl
HBr
HI
H-CN
NH3
H2O
OH
CH4
CH3
CH2
CH
CH3CH2-H
(CH3)2CH-H
CH3CH2(CH3)CH-H
(CH3)3C-H
fH298(R)
(kcal mol-1)
104.206 ( 0.003
136.25 ( 0.01
103.15 ( 0.03
87.54 ( 0.05
71.32 ( 0.06
126.3 ( 0.2
107.6 ( 0.1
118.82 ( 0.07
101.76 ( 0.07
52.103 ( 0.003
18.83 ( 0.17
29.03 ( 0.04
28.62 ( 0.06
26.04 ( 0.08
105.0 ( 0.7
44.5 ( 0.1
8.86 ( 0.07
59.55 ( 0.02
104.99 ( 0.03
110.4 ( 0.2
101.3 ( 0.3
80.9 ( 0.2
101.1 ( 0.4
98.6 ( 0.4
98.2 ( 0.5
96.5 ( 0.4
35.05 ( 0.07
93.3 ( 0.2
142.5 ( 0.2
171.3 ( 0.1
29.0 ( 0.4
21.5 ( 0.4
16.1 ( 0.5
12.3 ( 0.4
ref
Inorganics
4
6
9
9
9
6
6
34
34
OH- f O- + H
OH+ f O + H+
H2S
SH
H-NO
H-ONO (trans)
H-ONO2
SiH4
GeH4
Hydrocarbons
31
CH2CH-H
31
HCC-H
9
C6H5-H
9
C6H5 f o-C6H4 + H
10
C6H5 f m-C6H4 + H
10
C6H5 f p-C6H4 + H
10
CH2CHCH2-H
10
C6H5CH2-H
Alcohols
16
6
39,40
39, 40
DH298
(kcal mol-1)
fH298(R)
(kcal mol-1)
ref
110.21 ( 0.07
115.2 ( 0.1
91.2 ( 0.1
84.1 ( 0.2
49.5 ( 0.7
79.1 ( 0.2
101.7 ( 0.4
91.7 ( 0.5
83 ( 2
-33.23 ( 0.07
59.55 ( 0.02
34.2 ( 0.2
66.2 ( 0.3
21.8 ( 0.1
8.2 ( 0.1
17.6 ( 0.3
47.9 ( 0.6
53 ( 2
34
34
6
6
4
4
35
9
9
110.7 ( 0.6
133.32 ( 0.07
112.9 ( 0.5
78 ( 3
94 ( 3
109 ( 3
88.8 ( 0.4
89.8 ( 0.6
71.1 ( 0.7
135.6 ( 0.2
80.5 ( 0.5
106 ( 3
122 ( 3
138 ( 3
41.4 ( 0.4
49.7 ( 0.6
6
36
6
37
37
37
38
38
104.7 ( 0.8
105.7 ( 0.7
106.3 ( 0.7
90 ( 3
-3.6 ( 0.8
-11.5 ( 0.7
-20.5 ( 0.7
-58 ( 3
6
6
6
41
H-CH2OH
CH3O-H
CH3S-H
H-CH2SH
96.1 ( 0.2
104.6 ( 0.7
87.4 ( 0.5
94 ( 2
-4.08 ( 0.2
4.3 ( 0.7
29.8 ( 0.4
36 ( 2
HOO-H
CH3OO-H
87.8 ( 0.5
88 ( 1
3.2 ( 0.5
4.8 ( 1.2
Peroxides
14
CH3CH2OO-H
42
(CH3)3COO-H
85 ( 2
84 ( 2
-6.8 ( 2.3
-25.2 ( 2.3
42
42
10.1 ( 0.1
-2.4 ( 0.3
2.5 ( 2.2
-30 ( 3
Carbonyls
6
H-COOH is g
43
CH3COO-H
9
C6H5COO-H
44
96 ( 1
112 ( 3
111 ( 4
-46.5 ( 0.7
-43 ( 3
-12 ( 4
45
44
44
H-CHO
CH3C(O)-H
H-CH2CHO
HCOO-H
88.144 ( 0.008
89.4 ( 0.3
94 ( 2
112 ( 3
CH3CH2O-H
(CH3)2CHO-H
(CH3)3CO-H
C6H5O-H
(5)
Electronic structure calculations (such as those provided by the GAUSSIAN suite of codes)7 can derive E0 by
a range of ab initio and semiempirical methods. Thus,
D0(AB) values provide a useful comparison between
experimental and theoretical thermochemistry. While this
is outside the scope of this Account, these theoretical
methods show excellent agreement with experimental
bond dissociation energies.8
(12)
RH f R- + H+
acidH298(R-H)
(13)
R- + h f R + e-
EA0(R)
(14)
H+ + e- f H + h
-IE0(H)
(15)
(7)
[CH3CH2] + e f CH3CH2 + h
CH3CH3 f CH3CH2 + H
AEthresh(CH3CH2+,CH3CH3)
(9)
-IE0(CH3CH2)
(10)
D0(CH3CH2-H)
(11)
(16)
H
F
Cl
Br
I
HO
CH3O
NH2
CN
NO2
CH3
CH3CH2
(CH3)2CH
(CH3)3C
CH2CH
CH2CHCH2
HCC
HCC-CH2
C6H5
C6H5CH2
methyl
CH3
ethyl
CH2CH3
isopropyl
CH(CH3)2
tert-butyl
C(CH3)3
vinyl
CHCH2
allyl
CH2CHCH2
phenyl
C6H5
benzyl
CH2C6H5
methoxy
CH3O
formyl
HC(O)
acetyl
CH3C(O)
104.9(0.1)
115(4)a
83.7(0.1)
72.1(0.3)
57.6(0.4)
92.1(0.1)
83.2(0.9)
85.2(0.3)
122.4(0.7)
61.0(0.2)
90.1(0.1)
R
R
R
R
R
126.5(0.3)
78(3)
R
R
101.1(0.4)
84.8(0.5)
72.4(0.6)
56.9(0.7)
94.0(0.4)
85(1)
84.8(0.4)
121.6(0.8)
61.6(0.4)
89.0(0.4)
87.9(0.6)
R
R
R
R
125.1(0.5)
77(3)a
R
R
98.6(0.4)
110.6(0.5)
85.2(0.5)
73.9(0.7)
57(1)
95.5(0.4)
85.8(0.5)
86.0(0.4)
120.9(0.5)
62.9(0.5)
88.6(0.4)
87.1(0.5)
85.6(0.5)
R
R
R
124.5(0.6)a
R
R
96.5(0.4)
84.9(0.7)
72.6(0.6)
55.6(0.9)
95.8(0.4)
84(1)
85.7(0.5)
117.8(0.8)
62.8(0.9)
87.5(0.4)
85.6(0.6)
82.7(0.6)
78.6(0.7)
R
R
122.3(0.5)a
R
-
110.7(0.7)
123.3(0.8)
91.2(0.7)
80.8(0.8)
133(1)
101.4(0.7)
100.0(0.8)
99.2(0.8)
97.8(0.8)
116(1)
R
R
-
88.8(0.4)
59(1)
45.6(0.9)
80.1(0.6)
108.7(0.9)
76.5(0.5)
75.4(0.6)
75.2(0.7)
73.2(0.7)
87.3(0.8)
62.7(0.6)
-
112.9(0.6)
127.2(0.7)
97.1(0.6)
84(1)
67(2)
112.4(0.6)
101(1)
104.2(0.6)
134(1)
72.5(0.6)
103.5(0.6)
102.2(0.7)
101.0(0.7)
98.3(0.8)
116(1)
118(1)
97(1)
89.7(0.6)
98.7(0.7)a
74(1)
63(1)
51(2)
82.6(0.7)
71.7(0.7)
50.5(0.9)
77.6(0.6)
76.7(0.7)
76.4(0.8)
R
65.2(0.9)
104.6(0.7)
38(1)
42(1)
R
R
R
R
R
-
88.1(0.2)
109.5(0.2)
99.6(0.9)
84.8(0.2)
83.3(0.5)
83.1(0.5)
99.3(0.9)
-
89.4(0.3)
122.2(0.9)
84.7(0.4)
71.7(0.3)
53.8(0.7)
109.9(0.7)
100(1)
99.1(0.4)
84.5(0.4)
83.5(0.5)
81.9(0.5)
79.4(0.6)
41(3)a
98.8(0.8)
71.4(0.9)
a Bond enthalpies of stable organic molecules are tabulated along with their uncertainties. For example, DH
298(C6H5-OH) ) 112.4 (
0.6 kcal mol-1. These bond enthalpies are calculated from the radical heats of formation from Table 1 and the parent fH298 values
tabulated by Pedley et al.19,20 There are a few entries (such as CH3F or C6H5CH2F) where fH298(parent) is not provided by Pedley et al.,
so we have adopted the value recommended by the NIST Web site46 (http://webbook.nist.gov); we have marked these parent compounds
with an a. In some cases the heat of formation of the parent species is not available (e.g., vinylmethyl ether, CH2CH-OCH3), so the
bond enthalpy cannot be computed, and this is marked with a dash. There are a number of redundant entries in this table [e.g., DH298(C6H5CH3) ) DH298(CH3-C6H5)], so the second entry is marked with an R. The uncertainties have been added in quadrature.
X + CH3OH a HX + CH2OH
(17)
measured9
(18)
with the
ionization
energy of the hydroxymethyl radical, IE0(CH2OH) )
7.553 ( 0.006 eV, gives the bond energy of methanol as
D0(H-CH2OH) ) 94.55 ( 0.14 kcal mol-1, which corrects
to room temperature as DH298(H-CH2OH) ) 96.15 ( 0.14
kcal mol-1. As in the earlier case of ethane, the kinetics
studies and the PIMS measurements on methanol arrive
at values for the C-H bond energy which are in agreement
with each other.
Acidity/electron affinity experiments are negative ion
techniques, so methanol is studied through [CH3O]-. Gasphase acidity studies6,17 reveal acidH298(CH3O-H) ) 381.9
( 0.5 kcal mol-1, and photoelectron spectroscopy has
been used13,18 to measure the electron affinity of the
methoxyl radical, EA0(CH3O) ) 1.570 ( 0.006 eV. Consequently, the acidity/electron affinity cycle in eq 16 provides the BDE of the O-H bond, DH298(CH3O-H) ) 104.6
258 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 36, NO. 4, 2003
(20)
(21)
CH2sCH2sH f CH2dCH2 + H
(22)
a Values are in kcal mol-1 and represent the energy required to break
only the single bond indicated. Thus, DH298(HCtCH f HC + CH) ) 230.7
( 0.2 kcal mol-1 but DH298(HCCsH f HCC + H) ) 133.32 ( 0.07 kcal
mol-1.
a Values are in kcal mol-1 and represent the energy required to break
only the single bond indicated. Thus, DH298(CH3OsH f CH3O + H) )
104.6 ( 0.7 kcal mol-1 but DH298(HsCH2OH f H + CH2OH) ) 96.1 ( 0.3
kcal mol-1 and DH298(CH3sOH f CH3 + OH) ) 92.1 ( 0.1 kcal mol-1.
a Values are in kcal mol-1 and represent the energy required to break
only the single bond indicated. Thus, DH298(C6H5sH f C6H5 + H) ) 112.9
( 0.5 kcal mol-1 but DH298(C6H4sH f H + o-C6H4) ) 78 ( 3 kcal mol-1,
DH298(C6H4sH f H + m-C6H4) ) 94 ( 3 kcal mol-1, and DH298(C6H4sH
f H + p-C6H4) ) 109 ( 3 kcal mol-1.
Scheme 1
(23)
(24a)
(24b)
While in reaction 24a both methanol and the hydroxymethyl radical can hydrogen bond to the surrounding
solvent, such stabilization may be less prevalent for the
methoxyl radical in reaction 24b due to the absence of
the highly polarized O-H bond. Therefore, one might
surmise that the H-CH2OH bond energy of methanol in
a protic solvent would be largely unchanged from the gas
phase, while the CH3O-H value could be slightly higher
in solution. There is clearly much work to be done in this
area.
VOL. 36, NO. 4, 2003 / ACCOUNTS OF CHEMICAL RESEARCH 261
Scheme 2
Summary
The critically evaluated bond enthalpies listed in Tables
1 and 2 should serve as an important resource for the
organic chemist. The values listed may be used to calculate rigorous experimental thermochemistry for many
common reactions, and further, with appropriate care,
instructive estimations of reaction thermochemistry can
be made for complex chemical problems.
This work was supported by grants from the Chemical Physics
Program, United States Department of Energy (DE-FG0287ER13695), and the National Science Foundation (CHE-0201848).
We are grateful for the sustained advice and criticism from our
Colorado colleagues: Carl Lineberger, Veronica Bierbaum, Shuji
Kato, Mark Nimlos, Xu Zhang, Bob Damrauer, Charles H. DePuy,
Geoff Tyndall, and Veronica Vaida. We are also continually
educated by our friends: Emily Carter, George Petersson, Larry
Harding, Kent Ervin, Richard OHair, and Branko Ruscic. Finally
G.B.E. would like to thank Joseph Berkowitz, now retired, for 25
years of friendship and physics.
References
(1) Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley-Interscience: New York, 1976.
(2) Mills, I.; Cvitas, T.; Homann, K.; Kallay, N.; Kuchitsu, K. Quantities,
Units, and Symbols in Physical Chemistry; Blackwell Scientific
Publications: Oxford, 1988. This reference lists the IUPACs
guidelines concerning thermochemical symbols, which we adopt.
Instead of the more common expressions Grxn 298(1), Hf 0(R),
or Hf 298(RH), the use of rxnG298(1), fH0(R), or fH298(RH) is
recommended. See p 46.
(3) Herzberg, G. H. Molecular Spectra and Molecular Structure:
Infrared and Raman Spectra of Polyatomic Molecules; D. Van
Nostrand: Princeton, NJ, 1945; Vol. II, see Chapter V.
(4) Gurvich, L. V.; Veyts, I. V.; Alcock, C. B.; Iorish, V. S. Thermodynamic Properties of Individual Substances, 4th ed.; Hemisphere:
New York, 1991; Vol. 2.
(5) Ervin, K. M.; Gronert, S.; Barlow, S. E.; Gilles, M. K.; Harrison, A.
G.; Bierbaum, V. M.; Charles H. DePuy; Lineberger, W. C.; Ellison,
G. B. Bond Strengths of Ethylene and Acetylene. J. Am. Chem.
Soc. 1990, 112, 5750-5759.
(6) Ervin, K. M.; DeTuri, V. F. Anchoring the Gas-Phase Acidity
Scale: Experiment and Theory. J. Phys. Chem. A 2002, 106, 99479956.
(7) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.,
Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.;
Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.;
Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.;
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
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