Group Additivity Values for Estimating the Enthalpy of Formation of Organic
Compounds; an Update and Reappraisal. Part 2: C, H, N, O, S and Halogen
Professor John L. Holmes and Dr. Christiane Aubry*
Chemistry Department, University of Ottawa, Ottawa, Ontario, K1N 6N5 Canada
Email addresses: [email protected] and [email protected]
1
Supporting information
Table 1: Group Additivity Values for molecules containing C,H,N and O
Terms
C-(H)3(N)
C-(H)2(C)(N)
C-(H)(C)2(N)
C-(C)3(N)
C-(H)2(CB)(N)
C-(H)(C)(CB)(N)
C-(C)2(CB)(N)
Cd-(H)(N)
Cd-(C)(N)
CB-(N)
CB-(NI)(H)
CB-(NI)(CB)
CB-(NI)(C)
CB-(NI)(O)
CB-(NI)(N)
CB-(NI)(CO)
CdN-(H)2
CdN-(C)2
CdN-(H)(C)
CdN-(H)(Cd)
Benson’s
GAV
GAV
(kJ/mol)
(kJ/mol)
-42
-42
-23 ± 1 -27.6
-18 ± 2 -21.7
-13 ± 2 -13.4
-26 ± 2
-15 ± 2
-6 ± 2
36
41 ± 4
25
10 ± 2
15
12
-18
1
7
28
22
23 ± 2
20 ± 4
C-(H)2(N)(CO)
-21 ± 2
C-(H)(C)(N)(CO) -12 ± 2
C-(H)2(O)(CN)
105 ± 1
C-(H)2(C)(CN)
-21
C-(H)2(Cd)(CN)
-23
CB-(CN)
35 ± 4
Ct-(CN)
123 ± 4
CN-(C)
115 ± 2
CN-(Cd)
115 ± 2
CN-(CB)
115 ± 4
CN-(Ct)
115 ± 4
Cd-(Cd)(CN)c
166 ± 5
-25 ± 3
C-(C)(H)2(NO2)
C-(C)2(H)(NO2)
-25 ± 5
d
CB-NO2
20 ± 2
-2.1
Terms
GAV
Benson’s
(kJ/mol)
GAV
(kJ/mol)
N-(H)2(C)
18 ± 1
20.08
N-(H)(C)2
65 ± 2
64.4
N-(C)3
102 ± 2
102
N-(H)2(CB)
-11 ± 4
20.08
N-(H)2(Cd)
0±5
20.08
N-(H)(Cd)2
19 ± 4
N-(H)(Cd)(C)
41
64.4
N-(CO)(H)2
-60
-62.3
-20
18
N-(CO)(C)(H)
N-(CO)(C)2
17
NI-(H)
64 ± 2
16.3
NI-(CB)2
79 ± 2
NI-(C)
96 ± 2
89.1
NI-(Cd)
98 ± 2
O-(NI)
CO-(H)(N)
CO-(C)(N)
CO-(CB)(N)
NC-(C)
ONO-(C)
NO2-(C)
NO2-(CB)
-12 ± 2
-128
-136
-128
-124
-137
210 ± 10
-25 ± 4
-35 ± 3
-25 ± 2
94.4
150
267
2
Table 2: Group Additivity Values for molecules containing C,H and S
Terms
C-(H)3(S)
C-(C)(H)2(S)
C-(C)2(H)(S)
C-(C)3(S)
C-(Cd)(H)2(S)
C-(CB)(H)2(S)
Cd(H)(S)
Cd(S)(C)
Cd(CO)(S)
CB-(S)
GAV
Benson’s
(kJ/mol)
GAV
(kJ/mol)
-42
-42
-23
-23.6
-12
11.0
-2
-2.3
-21
-27.0
-20
-19.8
36
42 ± 6
37 ± 6
24
C-(CS)(H)3
C-(H)2(C)(CS)
C-(H)(C)2(CS)
35.8
45.7
Terms
S-(H)(C)
S-(C)2
GAV
Benson’s
(kJ/mol)
GAV
(kJ/mol)
19
19.3
46
48.16
S(H)(Cd)
S(C)(Cd)
S(Cd)2
17 ± 6
43 ± 6
44 ± 6
25.5
54.4
56.5
S-(H)(CB)
S-(CB)(C)
S-(CB)2
19
46
48
80.17
108.4
CS-(H)2
CS-(C)(H)
CS-(C)2
113
111
110
-7.5
-42
-20
-3
Table 3. Ring strain (RS) in saturated cyclic sulfides and N-compounds.
Molecule
Number of
RS
atoms in ring
(kJ/mol)
thiirane
3
82
methyl-thiirane
3
77
thietane
4
81
thiolane
5
8
2-methyl-thiolane
5
9
5
5
3-methyl-thiolane
penthiophane
6
0
Note that for the N-analogs with 3-, 4-, 5- and 6- membered rings, (aziridine, azetidine,
pyrollidine and piperidine) the ring strains are the same as for their hydrocarbon analogs, namely
118, 111, 28 and 2 kJ/mol respectively.
Table 4. GAV terms for the thiocarbonyl group.
Term
GAV
(kJ/mol)
CS-(H)2
113d
CS-(C)(H)
111f
CS-(C)2
110g
C-(H)2(C)(CS)
-20h
Table 5: GAV terms for aliphatic and aromatic halogen containing compounds
3
Group
C-(H)2(C)(F)
C-(H)(C)2(F)
C-(C)3(F)
C-(H)(C)(F)2
C-(C)2(F)2
C-(C)(F)3
GAV
Benson Group
(kJ/mol) (kJ/mol)
-223 ± 10
-215
C-(H)2(C)(Cl)
-224 ± 5
-205
C-(H)(C)2(Cl)
-222 ± 9
-203
C-(C)3(Cl)
-456 ± 6
-427
C-(H)(C)(Cl)2
-449 ± 10
-414
C-(C)2(Cl)2
-675 ± 6
-674
C-(C)(Cl)3
C-(H)2(Cd)(Cl)
C-(H)2(C)(Br)
C-(H)(C)2(Br)
C-(C)3(Br)
C-(H)(C)(Br)2
C-(C)2(Br)2
C-(C)(Br)3
-22 ± 3
-16 ± 3
-10 ± 4
0±2
16 ± 2
39 ± 2
Cd-(C)(F)
Cd-(H)(F)
Cd-(F)2
Cd-(H)(Cl)
Cd-(C)(Cl)
Cd-(Cl)2
-160 ±5
-165 ± 4
-368 ± 5
-4 ± 4
-10 ± 2
-25 ± 2
Ct-(F)
Ct-(Cl)
CB-(F)b
CB-(Cl)b
C-(CB)(F)3
CO-(CF3)(O)
C-H)2(CO)(Cl)
C-Cl)2(H)(CO)
C-(Cl)3(CO)
C-Br)(H)2(CO)
C-(I)(H)2(CO)
-38
-46
-46
5
63
Benson
(kJ/mol)
-69
-62
-54
-79
-92
-87
-23
-14
-2
C-(H)2(C)(I)
C-(H)(C)2(I)
C-(C)3(I)
C-(H)(C)(I)2
33 ± 2
42 ± 3
54 ± 4
109 ± 4
33
44
54
-157
-324
-5
-9
-8
Cd-(H)(Br)
Cd-(Br)2
Cd-(C)(Br)
Cd-(H)(I)
Cd-(C)(I)
46 ± 2
46
59 ± 4
93
105(est)
103
+7
116
-182 ± 3
-16 ± 2
-675 ± 7
-110 ± 6
GAV
(kJ/mol)
-70 ± 4
-62 ± 4
-58 ± 4
-91 ± 4
-90 ± 4
-96 ± 11
-68 ± 4
-179
-16
-681
Ct-(Br)
Ct-(I)
156 ± 4
210 ± 10 (est)
CB-(Br)
CB-(I)
35 ± 4
96 ± 6
CO-(CF3)(C)
-98 ± 4
CO-(C)(Cl)
CO-(CB)(Cl)
-201
-195
36
94
4