Electronic Supporting Information
J. Chem. Eng. Data. 2014
Thermochemistry of Halogen-Substituted Methylbenzenes
Sergey P. Verevkin,a,b* Aleksandra Yu. Sazonova,a Vladimir N. Emel’yanenko,b Dzmitry H.
Zaitsau,b Mikhail A. Varfolomeev,b Boris N. Solomonov,b Kseniya V. Zherikovac
a
Department of Physical Chemistry and Department „Science and Technology of Life, Light
and Matter“, University of Rostock, Dr-Lorenz-Weg 1, D-18059, Rostock, Germany
b
Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18,
420008 Kazan, Russia
c
Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of
Sciences, Lavrentiev Avenue 3, 630090 Novosibirsk, Russia
Table S1. Compilation of Data on Molar Heat Capacities at 298.15 K of
Halogenbenzenes
C pl
- ∆ gl C p
Compound
Ref.
J.mol-1.K-1
bromobenzene
154.3
50.7
1
iodoobenzene
158.4
51.8
2
1-bromo-2-methylbenzene
187.3
59.3
1-bromo-3-methylbenezene
187.3
59.3
187.3a
59.3
1-bromo-4-methylbenzene
156.0b
24.2 b
1-iodo-2-methylbenzene
184.2
58.5
1-iodo-3-methylbenzene
184.2
58.5
184.2
58.5
3
1-iodo-4-methylbenzene
151.5 b
23.5b
1-bromo-2,6-dimethylbenzene
215.7
66.7
1-bromo-2,5-dimethylbenzene
215.7
66.7
1-iodo-2,6-di-methylbenzene
220.2
67.8
1-iodo-2,4-dimethylbenzene
220.2
67.8
a
Experimental value 179.9 J.mol-1.K-1 from [3].
b
C crp and ∆ gcr C p values for the crystalline state.
(1) Masi, J. F.; Scott, R. B. Some thermodynamic properties of bromobenzene from 0 to
1500K. J. Res. 1975, NBS 79A, 619-628.
(2) Shehatta, I. Heat capacity at constant pressure of some halogen compounds. Thermochim.
Acta 1993, 213, 1-10.
(3) van Miltenburg, J. C.; Alvarez-Larena, A.; Labrador, M.; Palacios, L.; Rodriguez-Romero,
J.; Tauler, E.; Estop, E. The thermal properties of three (CI-, Br-, I-) para-halotoluenes.
Formation of glassy crystals. Thermochim. Acta 1996, 273, 31-42.
Table S2. A Cavity Surface Area, Sc, and a Cavity Volume, Vc Calculated by Using the
B3LYP/3-21G and Used for Evaluation of ∆ gl H m (298.15 K) of Halogen-benzenes C6H5Hal
surface area,
cavity volume,
∆gl H m (298.15 K)
C6H5-Hal
2
3
Sc, in Å
Vc in Å
kJ·mol-1
F
149.4
141.0
35.0
Cl
164.0
157.4
41.8
Br
168.7
164.2
44.3
I
178.1
176.5
48.9
Table S3. Compilation of Kovat´s Indices of Methylbenzenes and Halogen Benzenes
Measured on a Non-polar OV-1 Column with a Temperature Program Starting from
333 K and a Heating Rate of 8 K/min a
∆gl H m
∆gl H m
compound
Jx
(298.15 K)/ kJ.mol- (298.15 K)/ kJ.mol- ∆
Exp.
eq 20
1
2
3
4
5
benezene
643.1
33.90
34.5
-0.6
methylbenzene
750.1
38.10
38.6
-0.5
1,3-di-methylbenzene
853.8
42.68
42.6
0.1
1,4-di-methylbenzene
855.5
42.44
42.6
-0.2
1,2-di-methylbenzene
876.7
43.45
43.4
0.0
1,3,5-tri-methylbenzene
955.5
47.51
46.4
1.1
1,3,5-tri-methylbenzene
979.7
47.94
47.4
0.6
fluorobenzene
654.4
35.00
35.0
0.0
chlorobenzene
826.5
41.76
41.5
0.2
bromobenzene
909.5
44.54
44.7
-0.2
iodobenzene
1010.4
48.50
48.5
0.0
1-fluoro-2-methylbenzene
763.7
39.31
39.1
0.2
1-fluoro-3-methylbenzene
761.6
38.99
39.1
-0.1
1-chloro-2-methylbenzene
933.6
46.14
45.6
0.5
1-chloro-3-methylbenzene
934.9
46.84
45.7
1.2
1-chloro-4-methylbenzene
938.5
46.42
45.8
0.6
1-bromo-2-methylbenzene
1016.9
47.71
48.8
-1.1
1-bromo-3-methylbenzene
1018.7
48.41
48.9
-0.4
1-iodo-2-methylbenzene
1121.8
52.30
52.8
-0.5
1-iodo-3-methylbenzene
1122.4
52.86
52.8
0.1
1,2-dichlorobenzene
1012.7
48.82
48.6
0.2
1,3-dichlorobenzene
985.1
47.68
47.6
0.1
1,4-dichlorobenzene
990.6
47.60
47.8
-0.2
1,3-dichloro-2-methylbenzene 1104.0
51.60
52.1
-0.5
1,2-dibromobenzene
1185.3
54.30
55.2
-0.9
1,3-dibromobenzene
1162.2
54.90
54.3
0.6
1,4-dibromobenzene
1165.0
54.90
54.4
0.5
a
Data for Jx from Gautzsch, R.; Zinn, R., Use of Incremental Models to Estimate the
Retention Indexes of Aromatic Compounds. Chromatographia 1996, 43, 163-176.
Table S4. Correlation of Experimental ∆ f H mo (g, 298.15 K) Values (All Values are in
kJ.mol-1) of Parent Series of Halogenbenzenes C6H5-Hal Derived in this Work with those
for the Aliphatic Halides R-Hal (R= CH3 and i-C3H7) Available in the Literature.
i-C3H7-Hal a
C6H5-Halb
Hal
CH3-Hal a
F
-234.4
-293.5
-115.8
Cl
-81.9
-145
52.8
Br
-35.5
-98.5
105.4
I
14.7
-40.8
166.1
a
From Pedley, J. P.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds.
2nd Ed. Chapman and Hall: London. 1986
b
This work, Table 6
Table S5. Comparison of Experimental Vaporization Enthalpies, ∆gl H m (298.15 K), and
those Estimated Using the Group Additivity (all Values are in kJ.mol-1)
compound
1
1-bromo-2-methylbenzene
1-bromo-3-methylbenezene
1-bromo-4-methylbenzene
1-iodo-2-methylbenzene
1-iodo-3-methylbenzene
1-iodo-4-methylbenzene
1-bromo-2,6-dimethylbenzene
1-bromo-2,5-dimethylbenzene
1-iodo-2,6-di-methylbenzene
1-iodo-2,4-dimethylbenzene
1,2-dibromobenzene
1,3-dibromobenzene
1,4-dibromobenzene
a
Value seems to be in error.
∆gl H m
exp
2
47.7
48.4
47.8
52.3
52.9
52.5
52.7
54.3 [18]
57.6
57.7
54.3 [45]
54.9 [45]
54.9 [45]
∆gl H m
eq 21
3
48.5
48.5
48.5
53.0
53.0
53.0
52.7
52.7
57.2
57.2
54.7
54.7
54.7
exp-calc
4
-0.8
-0.1
-0.8
-0.7
-0.1
-0.5
0.0
1.6 a
0.4
0.5
-0.4
0.2
0.2
Table S6. Results of Calculation of the Enthalpy of Formation Chloro-Containing
Compounds in the Gaseous Phase at 298 K, G4, kJ·mol-1
∆ f H m° exp
∆ f H m° calc
Compounds
from [1]
AT
∆
chloromethane
-81.9±0.5
-81.6
-0.3
1-chloroethane
-112.1±1.1
-110.5
-1.6
1-chloropropane
-131.9±1.0
-131.6
-0.3
2-chloropropane
-144.9±1.0
-145.7
0.8
1-chlorobutane
-154.4±1.3
-152.5
-1.9
2-chloro-1-propene
-21.0±9.4
-20.0
-1.0
chlorocyclohexane
-163.7±3.6
-166.1
2.4
chlorobenzene
52.0±1.3
50.2
1.8
Table S7. Results of Calculation of the Enthalpy of Formation Bromo-Containing
Compounds in the Gaseous Phase at 298 K, G4, kJ·mol-1
∆ f H m° exp
∆ f H m° calc
Compounds
from [1]
AT
∆
2-bromopropane
-99.4
-97.4
-2.0
methyl bromide
-37.5
-35.1
-2.4
hydrogen bromide
-36.4
-34.0
-2.4
ethyl bromide
-63.6
-63.1
-0.5
cyanogen bromide
186.2
176.8
9.4
propyl bromide
-87.0
-84.8
-2.2
propenyl bromide
45.2
40.8
4.4
benzyl bromide [2,3]
75.3
72.3
3.0
butyl bromide
-107.1
-106.0
-1.1
pentyl bromide
-129.0
-127.5
-1.5
tert-butyl bromide
-132.4
-135.4
3.0
vinyl bromide
79.2
73.3
5.9
(1) Pedley, J. P.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds.
2nd Ed. Chapman and Hall: London. 1986.
(2) Krasnykh, E. L.; Vasiltsova, T. V.; Verevkin, S. P.; Heintz, A. Vapor Pressures and
Enthalpies of Vaporization of Benzyl Halides and Benzyl Ethers. J. Chem. Eng. Data 2002,
47, 1372-1378.
(3) Holm, T. Thermochemistry of Grignard reagents. Enthalpies of formation of
alkylmagnesium bromides and of alkyl bromides. J. Organomet. Chem. 1973, 56, 87-93.
TABLE S8. The G4 Total Energies at 0 K, Enthalpies at 298.15 K and Standard
Enthalpy of Formation ∆ f H m° (g) at 298.15 K of the Halogen-Substituted Benzenes
H298
Hartree
1-fluoro-2-methylbenzene
-370.604257
-370.596379
1-fluoro-3-methylbenzene
-370.603728
-370.595697
1-fluoro-4-methylbenzene
-370.603058
-370.595002
1-chloro-2-methylbenzene
-730.869301
-730.861148
1-chloro-3-methylbenzene
-730.868331
-730.859927
1-chloro-4-methylbenzene
-730.868060
-730.859622
1-bromo-2-methylbenzene
-2844.417299 -2844.408921
1-bromo-3-methylbenezene
-2844.416303 -2844.407664
1-bromo-4-methylbenzene
-2844.416030 -2844.407392
benzene
-232.093987
-232.088586
toluene
-271.377414
-271.370151
fluoro-benzene
-331.320103
-331.313960
chloro-benzene
-691.584572
-691.578063
bromo-benzene
-2805.132486 -2805.125753
TABLE S9. Mutual Interactions of Substituents, ∆rHo, on the Benzene Ring for Halogensubstituted Methylbenzenes as Calculated by G4 and b3lyp/6-311G(d,p) at 298.15 K in
the gas phase
∆rHo(G4)
∆rHo(b3lyp/6-311G(d,p))
methylbenzene
kJ.mol-1
kJ.mol-1
Compounds
E0
1-fluoro-2-methylbenzene
1-fluoro-3-methylbenzene
1-fluoro-4-methylbenzene
1-chloro-2-methylbenzene
1-chloro-3-methylbenzene
1-chloro-4-methylbenzene
1-bromo-2-methylbenzene
1-bromo-3-methylbenezene
1-bromo-4-methylbenzene
1-iodo-2-methylbenzene
1-iodo-3-methylbenzene
1-iodo-4-methylbenzene
a
-2.24
-0.45
1.37
-3.99
-0.79
0.02
-4.21
-0.91
-0.19
-5.03a
1.04 a
-0.56 a
-3.19
-0.84
1.03
-0.75
-0.79
-0.13
0.14
-0.79
-0.25
1.18
-1.03
-0.58
Calculated using correlations between ∆rHo(G4) and between ∆rHo(b3lyp/6-311G(d,p))
for ortho-substituted benzenes
∆rHo (g) (G4)/ kJ.mol-1 = 0.62 × ∆rHo(g) (b3lyp/6-311G(d,p)) - 4.3
for meta-substituted benzenes
∆rHo (g) (G4)/ kJ.mol-1 = -8.0 × ∆rHo(g) (b3lyp/6-311G(d,p)) - 7.2
for para-substituted benzenes
∆rHo (g) (G4)/ kJ.mol-1 = 1.20 × ∆rHo(g) (b3lyp/6-311G(d,p)) + 0.14
with (r = 0.975)
with (r = 0.937)
with (r = 0.999)
Table S10. Sum of Electronic and Thermal Enthalpies of Halogen-Substituted
Benzenes Calculated by b3lyp/6-311G(d,p) in the Gas Phase at 298.15 K
Compounds
1-fluoro-2-methylbenzene
1-fluoro-3-methylbenzene
1-fluoro-4-methylbenzene
1-chloro-2-methylbenzene
1-chloro-3-methylbenzene
1-chloro-4-methylbenzene
1-bromo-2-methylbenzene
1-bromo-3-methylbenezene
1-bromo-4-methylbenzene
1-iodo-2-methylbenzene
1-iodo-3-methylbenzene
1-iodo-4-methylbenzene
benzene
toluene
bromo-benzene
chloro-benzene
fluoro-benzene
iodo-benzene
Sum of electronic and
thermal Enthalpies, Hartree
-370.774652
-370.773757
-370.773045
-2845.052717
-2845.053073
-2845.052866
-731.132218
-731.132232
-731.131981
-7190.432497
-7190.433169
-7190.433169
-232.203030
-271.501528
-2805.754273
-691.833434
-331.474940
-7151.134449
Enthalpies of Fusion of 4-Bromo-1-Methylbenzene and 4-Iodo-1-Methylbenzene. The
melting temperatures and enthalpies of fusion of 4-bromo-1-methylbenzene and 4-iodo-1methylbenzene measured in the present work and those available from the literature are
compiled in Table 3. No phase transitions other than melting of samples under study have
been detected. Experimental enthalpies of fusion measured by DSC (see Table 4) are obtained
at the melting temperature Tfus. Because of the differences in the reference temperatures, the
experimental enthalpies of fusion have to be adjusted to T = 298 K. The adjustment was
calculated by the equation:
{ ∆lcr H m (Tfus/K) - ∆lcr H m (298 K) }/(J·mol-1) =
{(0.75 +0.15 C crp )[(Tfus/K) – 298 K]} - {(10.58 +0.26 C lp ) [(Tfus/K) – 298 K]}
where C pcr and C lp are the isobaric molar heat capacities of the solid and the liquid 4-bromo-1methylbenzene and 4-iodo-1-methylbenzene (given in Table S1 and calculated according to
procedure developed by Chickos and Acree [1]). With this adjustment (the uncertainty of the
correlation was not taken into account), the molar enthalpies of fusion, ∆lcr H m (298 K), were
calculated (see Table 4).
[1] Chickos, J. S.; Acree Jr., W.E. Enthalpies of vaporization of organic and organometallic
compounds, 1880-2002. J. Phys. Chem. Ref. Data 2003, 32, 519-878.
200
150
R=CH3
R=iC3H7
100
C6H5Hal
y = 1,120x + 213,954
R 2 = 1,000
50
0
-50
y = 1,126x + 147,013
R 2 = 1,000
-100
-150
-350
-300
-250
-200
-150
-100
-50
0
50
R-Hal
Figure S1. Comparison of ∆ f H mo (g, 298.15 K) in kJ.mol-1 of halogenbenzenes C6H5-Hal
derived in this work with those for the aliphatic halides R-Hal (R= CH3 and i-C3H7) available
in the literature (see text).
Figure S2. Correlation between G4-calculated and experimental enthalpy of formation (in
kJ·mol-1) of Cl-containing compounds in the gaseous phase at 298.15 K.
Figure S3. Correlation between G4-calculated and experimental enthalpy of formation (in
kJ·mol-1) of Br-containing compounds in the gaseous phase at 298.15 K.