Struct Chem (2013) 24:2083–2088
DOI 10.1007/s11224-013-0340-z
ORIGINAL RESEARCH
The standard molar enthalpies of combustion and formation
of 2-methylbenzothiazole, 2-methylbenzoxazole,
and 2-methyl-2-thiazoline
Henoc Flores • Juan Mentado • E. Adriana Camarillo
Arturo Ximello • M. Patricia Amador
Received: 25 July 2013 / Accepted: 21 August 2013 / Published online: 5 September 2013
Ó Springer Science+Business Media New York 2013
Abstract A static-bomb combustion calorimeter and a
rotating-bomb combustion calorimeter were used to deter-
mine the energies of combustion of 2-methylbenzothiazole,
2-methylbenzoxazole, and 2-methyl-2-thiazoline. The static-
and rotating-bomb calorimeters were recently calibrated by
the standard benzoic acid combustion runs and they were
tested with adequate secondary combustion standards. The
rotating-bomb calorimeter was tested using thianthrene and,
in the present work, 1,2,4-triazole was used to test the static-
bomb calorimeter. From the energies of combustion of the
compounds under study, the liquid-phase standard molar
enthalpies of formation were derived, at T = 298.15 K, as:
(72.5 ± 1.5), (-50.7 ± 2.1), and (-88.5 ± 2.8) kJ mol-1,
respectively.
Keywords Energy of combustion  Enthalpy of
formation  Rotating-bomb calorimeter  Static-bomb
calorimeter  2-Methylbenzothiazole 
2-Methylbenzoxazole  2-Methyl-2-thiazoline
This paper is a contribution to the special collection of articles
dedicated to Professor Marı́a Victoria Roux of CSIC-IQFR, on
occasion of her retirement.
H. Flores (&)  E. A. Camarillo  A. Ximello  M. P. Amador
Facultad de Ciencias Quı́micas de la Benemérita Universidad
Autónoma de Puebla, 14 Sur y Av. San Claudio,
C.P. 72570 Puebla, Puebla, Mexico
e-mail: henoc.flores@correo.buap.mx
J. Mentado
Instituto de Industrias, Universidad del Mar, Distrito de San
Pedro Pochutla, C.P. 70902 Puerto Ángel, Oaxaca, México
•
Introduction
2-CH3-(azoles and benzazoles) are cyclic chemical com-
pounds with five-member rings for azoles and (6 ? 5)
bicycles for benzazoles. 2-CH3-(azoles and benzazoles)
play an important role in the organic chemistry field. They
have wide applications as fungicides and pharmaceuticals.
For instance, 2-CH3-(azoles and benzazoles) take part in
the synthesis of Ruthenium(III) complexes, which have
recently been applied in some cancer therapies with mod-
erately good results [1, 2]. On the other hand, some ben-
zazole derivatives are used in the anionic polymerization of
heterocyclic compounds in the synthesis of new polymeric
materials [3]. 2-Methylbenzoxazole (2CBO) derivatives
are medicinally effective anti-cancer and anti-inflammatory
agents [4, 5].
Roux et al. [6] carried out two experimental and theo-
retical studies of compounds related to the present work. A
study covering the tautomerism of the species 3H-1,3-
benzoxazole-2-thione and 3H-1,3-benzothiazole-2-thione
and the second one is a very complete study of 1,3-thia-
zolidine-2-thione and 1,3-oxazolidine-2-thione [7].
We have not found, in the literature, reports on the
thermochemical properties of the 2-CH3-(azoles and ben-
zazoles) studied here.
The aim of this work is to determine, by using a rotating-
bomb and a static-bomb calorimeters, the condensate phase
energies of combustion of three 2-CH3-(azoles and ben-
zazoles) and the derivation of the corresponding enthalpies
of formation in the standard state at T = 298.15 K. The
molecular structures of the compounds studied here are
shown in Fig. 1. According to Fig. 1, the compounds 2CBS
and 2CBO are derivatives of benzothiazole (BS) and benz-
oxazole (BO), respectively, for which their enthalpies of
formation in condensate state are (144.03 ± 0.70) and
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2084
(-24.20 ± 1.1) kJ mol-1, respectively. Steele et al. [8]
also report the enthalpies of formation of BS and BO in gas
phase as (204.17 ± 0.37) and (45.14 ± 0.52) kJ mol-1,
respectively.
Experimental section
Compounds 2-methylbenzothiazole (2CBS) (CAS number:
120-75-2), 2CBO (CAS Number: 95-21-6), and 2-methyl-
2-thiazoline (2CS) (CAS Number: 2346-00-1) are com-
mercial products and were supplied by Aldrich and by
Fluka. The chemical supplier reports mass fractions of
better than 0.99 for all of them (all in the liquid state). The
samples were used without further additional purification.
Their purities were determined by differential scanning
calorimetry (DSC). The secondary standard, 1,2,4-triazole,
is a Fluka product with a mass fraction of 0.99 and it was
purified by repeated crystallization from ethanol.
The mass fraction (x), heat capacity (Cp), fusion tem-
perature, and fusion enthalpy of 2CBS (l), 2CBO (l), and
2CS (l) were carefully determined with a DSC 2010 TA
Instruments.
For the purity and heat capacity determinations, the
compound samples of *3 and 6 mg of mass were used.
Mass was measured with a UMX2 Mettler Toledo balance
(inaccuracy: ±0.1 lg).
The calibration constant and the thermal resistance for
the temperature correction of the DSC were obtained by the
fusion of high-purity metallic indium [9]. The purities,
temperatures, and enthalpies of fusion were obtained from
fusion peak analysis by using the fractional fusion tech-
nique with a non-hermetic aluminum cell under a constant
flow of dry nitrogen [10]. To determine the purity of 2CBS
and 2CBO it was necessary to lower the temperature of the
DSC cell down to T = 258.15 K, using a Haake K 20 re-
circulator, in order to have solid samples, and to analyze
their fusion peaks. For the fusion analysis of 2CS, the
temperature in the DSC chamber was lowered to
T = 205.15 K with a mixture of solid CO2 and acetone.
The mass fractions obtained from fusion analysis for
2CBS, 2CBO, and 2CS were: (0.9985 ± 0.0004), (0.9980 ±
0.0003), and (0.9981 ± 0.0004), respectively.
The molar heat capacities were obtained by comparison to
results for a synthetic sapphire sample over a 263.15–333.15 K
temperature range [11, 12].
N N N
S O S
Fig. 1 Molecular structure of 2-methylbenzothiazole (2CBS), 2CBO,
and 2-methyl-2-thiazoline (2CS)
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Struct Chem (2013) 24:2083–2088
Table 1 shows the auxiliary quantities used in the cal-
culation of the energies of combustion of 2-CH3-(azoles
and benzazoles), the quantities obtained from the DSC
analysis, and the physical properties of 1,2,4-triazole and of
all the materials which take part in the combustion process.
The energy of combustion of 2CBO was determined
using an isoperibolic static-bomb calorimeter with a Parr
1108 combustion bomb with an internal volume of
0.346 dm3. The static-bomb calorimeter was calibrated, in
a former work, by combustion experiments of the standard
benzoic acid (RSM 39j, NIST) which led to a value of
e(calor) = (10.1583 ± 0.0042) kJ K-1 [18]. In the present
work, the static-bomb calorimeter was also tested with a
secondary calorimetric standard, namely, 1,2,4-triazole.
The combustion experiments for 2CBS and 2CS were
carried out in an isoperibolic rotating-bomb calorimeter which
has a platinum-lining Parr 1004 C combustion bomb with an
internal volume of 0.348 dm3. This rotating-bomb calorime-
ter was calibrated, as the static-bomb calorimeter, by the
standard benzoic acid combustion experiments (RSM 39j,
NIST) leading to a value of e(calor) = (14.3212 ± 0.0024)
kJ K-1, described in a former paper. Also, the rotating-bomb
calorimeter was tested with thianthrene as the secondary
calorimetric standard [19].
All the combustion experiments for the compounds
under study were carried out in the presence of deminer-
alized water inside the corresponding bombs: 0.001 dm3
for the static bomb and 0.01 dm3 for the rotating one, and
under 3.04 MPa of high-purity gaseous oxygen (Airgas
Co., x = 0.99999). To eliminate the air from the inside of
the static bomb, this was flushed out for 5 min after having
been filled with oxygen. In the case of the rotating-bomb,
the air was not flushed out from the bomb as an usual
practice in combustion experiments for compounds con-
taining sulfur.
The combustion bombs were put into their respective
metallic vessels, which contained a given amount of dis-
tilled water: 2000.0 g, for the static bomb, and 2700.0 g,
for the rotating-bomb. The quantity of water was measured
with a BP 12000 Sartorius balance (inaccuracy ±0.1 g).
The evolution of the temperature during each combus-
tion experiment was followed by a 5610 Hart Scientific
thermistor, calibrated over a range of 273.15–373.15 K.
Resistances were measured with an HP 34420A digital
multimeter (sensitivity 10-6 kX) plugged to a PC to record
data automatically. Resistance values were converted to
temperature values using a calibration equation. The cor-
rected temperature rise was calculated by the Regnault–
Pfaundler method [20].
The electrical energy for ignition was supplied by a Parr
2901 ignition unity and the circuit was closed by a plati-
num wire (55 mm long and 0.05 mm diameter) connected
to the sample. The sample was placed into the platinum
Struct Chem (2013) 24:2083–2088 2085

Table 1 Physical properties of the compounds under study and of all the materials which took part in the combustion processes at T = 298.15 K
M (g mol-1)a q (g cm-3) ðou=opÞT (J g-1 MPa-1) Cp (J g-1 K-1)c Tfus (K)c DfusH (kJ mol-1)c

Polyethene 14.100 0.938 [14] 0.228 [14] 2.0 [14]

Cotton 28.502 1.500 [15] 0.289 [15] 1.65 [15]
1,2,4-Triazole 69.065 1.394 [16] 0.094 [16] 1.15 [16] 393.1 ± 0.1 [16] 15.5 ± 0.1 [16]
b
2CS 101.170 1.077 0.2 [17] 2.1 ± 0.1 209.1 ± 0.1 6.6 ± 0.8
2CBO 133.147 1.119b 0.2 [17] 1.3 ± 0.1 280.1 ± 0.1 11.5 ± 0.1
2CBS 149.213 1.173b 0.2 [17] 1.4 ± 0.1 287.1 ± 0.1 13.1 ± 0.3
The parameters obtained from the DSC analysis are also given
a
Molar masses are based on the 2007 IUPAC recommendations [13]
b
Supplier values
c
Experimental values

crucible with a cotton thread (empirical formula:
C1H1.742O0.921). The massic energy of combustion of the
cotton thread fuse was taken as Dcuo = -(16945.2 ± 4.2)
J g-1 [15, 21].
In all the combustion experiments it was necessary to
use polyethene bags (empirical formula: C1H2.073) as an
auxiliary material to promote the complete combustion of
the sample and to protect it against dampness inside the
bomb. The combustion energy of polyethene was deter-
mined previously as Dcuo = -(46.3726 ± 0.0022) kJ g-1
[15].
The masses of all the substances participating in the
combustion processes were measured with a ME235S
Sartorius balance (in accuracy ±0.01 mg).
The quantity of nitric acid after the combustion of
2CBO was determined as follows: the final solution in the
bomb was quantitatively transferred to a volumetric flask
together with the rinsing water and diluted to a volume of
100.0 cm3. Aliquots of the diluted bomb solution were
titrated with the standard alkali (0.1 mol dm-3) to deter-
mine the total acidity. Additionally, the quantity of nitric
acid was determined using Devarda’s alloy method [21, 22]
and no differences, energetically significant, were found
between both methods.
For 2CS and 2CBS (sulfur-containing compounds) the
quantity of nitric acid was taken as the difference between
total acid, determined by titration with the standard alkali,
and the theoretical quantity of sulfuric acid, calculated
from the compound mass [14, 23, 24].
Results and discussion
To test the performance of the static-bomb calorimeter,
combustion experiments with 1,2,4-triazole were made.
This test compound has been recommended for the verifi-
cation of the chemistry of the combustion process and of
the accuracy of the energy corrections involved in the
analysis of results for compounds containing C, H, O, and
N in their structure [25]. Table 2 shows results of the
combustion of 1,2,4-triazole. They correspond to the
combustion reaction represented by Eq. (1).
C2 H3 N3 ðcrÞ þ 2:75 O2 ðgÞ ¼ 2 CO2 ðgÞ þ 1:5 H2 O ðlÞ
þ 1:5 N2 ðgÞ
ð1Þ
From eight combustion experiments, the energy of com-
bustion of 1,2,4-triazole was found as Dcu° (298.15 K) =
-(19.2037 ± 0.0004) kJ g-1, which agrees with the litera-
ture values, -(19.2042 ± 0.0041) kJ g-1 [24], -(19.2003 ±
0.0034) kJ g-1 [16].
Tables 3, 4, and 5 show results for the combustion of
2CBS, 2CBO, and 2CS, and correspond to idealized
combustion reactions represented by Eqs. (2)–(4).
C8 H7 NS ðlÞ þ 11:25 O2 ðgÞ þ 112:5 H2 O ðlÞ
¼ 8 CO2 ðgÞ þ H2 SO4  115 H2 O ðaqÞ þ 0:5 N2 ðgÞ ð2Þ
C8 H7 NO ðlÞ þ 9:25 O2 ðgÞ ¼ 8 CO2 ðgÞ þ 3:5 H2 O ðlÞ
þ 0:5 N2 ðgÞ ð3Þ
C4 H7 NS ðlÞ þ 7:25 O2 ðgÞ þ 112:5 H2 O ðlÞ
¼ 4 CO2 ðgÞ þ H2 SO4  115 H2 O ðaqÞ þ 0:5 N2 ðgÞ ð4Þ
The molar energies of combustion, obtained from at
least six combustion experiments for each compound, are
(-3081.2 ± 2.7) kJ mol-1 for 2CS (l), (-4095.9 ± 1.8)
kJ mol-1 for 2CBO (l), and (-4816.1 ± 1.1) kJ mol-1 for
2CBS (l). The corrections for nitric acid were based on the
value of -59.7 kJ mol-1 for the molar energy of formation
of 0.1 mol dm-3 of HNO3 (aq) solution from O2 (g), N2
(g), and H2O (l) [26].
The energies of combustion under the standard condi-
tions were obtained by applying the Washburn correction
[27, 28].

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Table 2 Results of the combustion experiments for 1,2,4-triazole at T = 298.15 K and p° = 0.1 MPa
m (cpd) (g) 1.00396 0.99774 1.00132 1.00451 1.00434 0.99777 1.00011 1.01491
m (cotton) (g) 0.00184 0.00161 0.00204 0.00184 0.00176 0.00183 0.00175 0.00198
m (platinum) (g) 11.51549 11.51507 11.51528 11.51132 11.51104 11.51689 11.51759 11.51635
Ti (K) 296.0651 296.0352 296.0237 296.0523 296.0451 296.0596 296.0778 296.0631
Tf (K) 298.0128 297.9503 297.951 297.9986 297.9861 297.9953 298.0286 298.0314
DTc = (Tf - Ti ? DTcorr) (K) 1.9089 1.8987 1.9094 1.9137 1.9116 1.8997 1.9022 1.9293-
eicont (kJ K-1) 0.0171 0.0171 0.0171 0.0171 0.0171 0.0171 0.0171 0.0171
efcont (kJ K-1) 0.0176 0.0176 0.0177 0.0177 0.0177 0.0177 0.0176 0.0176
ecalor (DT) 19.3912 19.2876 19.3963 19.4399 19.4186 19.2977 19.3231 19.5984
-DUIBP (kJ) 19.4209 19.3163 19.4252 19.4695 19.4480 19.3272 19.3531 19.6285
DUdec (HNO3) (kJ) 0.0944 0.1161 0.1477 0.1358 0.1164 0.1225 0.1038 0.0907
DUign (kJ) 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042
DUR (kJ) 0.0138 0.0136 0.0135 0.0136 0.0137 0.0136 0.0137 0.0140
(mDcu°) (cotton) (kJ) 0.0312 0.0273 0.0346 0.0312 0.0298 0.0310 0.0297 0.0336
(-mDcu°) (cpd) (kJ) 19.2815 19.1593 19.2294 19.2889 19.2881 19.1601 19.2059 19.4902
(-Dcu°) (cpd) (kJ g-1) 19.2054 19.2027 19.2041 19.2023 19.2048 19.2029 19.2038 19.2039
h-Dcu°(298.15 K) (kJ g-1)i = 19.2037 ± 0.0004
m (cpd) mass of compound, m (cotton) mass of the cotton thread, m (platinum) mass of platinum which includes crucible and wire for ignition,
DTc corrected temperature rise, e (cont.) energy equivalent of the bomb contents, calculated as: econt (-DT) = ei cont(Ti - 298.15 K) ? ef
cont(298.15 - Tf ? DTcorr), DUign ignition energy, DUIBP energy of the isothermal bomb process, calculated as: DUIBP = econt (DT) ? eca-
lor(DT) - DUign, DUdec (HNO3) energy of decomposition of nitric acid, DUR correction to the standard state, which includes the energy of
dilution of nitric acid, Dcu°(cpd) massic energy of combustion, calculated as: Dcu°(cpd) = [-DUIBP - DUdec (HNO3) - DUR - (mDcu°)
(cotton)]/m (cpd)

Table 3 Results of the combustion experiments for 2CBS at T = 298.15 K and p° = 0.1 MPa
m (cpd) (g) 0.80117 0.80195 0.80801 0.80265 0.80550 0.80524 0.80845
m (polyethene) (g) 0.08005 0.09068 0.09431 0.07631 0.07878 0.10683 0.07056
m (cotton) 0.00210 0.00212 0.00189 0.00266 0.00216 0.00181 0.00166
m (platinum) (g) 6.25468 6.25486 6.25958 6.25909 6.26062 6.26811 6.258419
Ti (K) 295.9138 295.9121 295.964 295.9125 295.9241 295.9135 295.8744
Tf (K) 297.99647 298.02935 298.1046 297.98858 298.0119 298.09182 297.94067
DTc(Tf - Ti ? DTcorr) (K) 2.0677 2.1042 2.1285 2.0593 2.07384 2.16262 2.05204
ei(cont.) (kJ K-1) 0.0538 0.0539 0.0539 0.0538 0.0539 0.0539 0.0538
ef(cont.) (kJ K-1) 0.0542 0.0542 0.0543 0.0542 0.0542 0.0543 0.0542
ecalor (-DT) 29.6119 30.1347 30.4827 29.4916 29.6999 30.9713 29.3877
-DUIBP (kJ) 29.7205 30.2453 30.5945 29.6000 29.8089 31.0854 29.4953
DUdec (HNO3) (kJ) 0.0873 0.0877 0.0840 0.0861 0.0847 0.0870 0.0818
(DUign) (kJ) 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042
DUR (J) 0.0259 0.0263 0.0259 0.0259 0.0260 0.0270 0.0258
(mDcu°) (polyethene) (kJ) 3.7122 4.2052 4.3735 3.5388 3.6533 4.9541 3.2721
(mDcu°) (cotton) (kJ) 0.0356 0.0359 0.0320 0.0451 0.0366 0.0307 0.0281
(-mDcu°) (cpd) (kJ) 25.8595 25.8902 26.0791 25.9041 26.0083 25.9866 26.0875
(-Dcu°) (cpd) (kJ g-1) 32.2772 32.2840 32.2757 32.2732 32.2884 32.2719 32.2685
h-Dcu°(298.15 K) kJ g-1i = 32.2770 ± 0.0026i
m (cpd) mass of compound, m (polyethene) mass of polyethene, m (cotton) mass of the cotton thread, m (platinum) mass of platinum which
includes crucible and wire for ignition, DTc corrected temperature rise, e (cont.) energy equivalent of the bomb contents, calculated as: econt
(-DT) = eicont(Ti - 298.15 K) ? efcont(298.15 - Tf ? DTcorr), DUign ignition energy, DUIBP energy of the isothermal bomb process, cal-
culated as: DUIBP = econt (DT) ? ecalor(DT) - DUign, DUdec (HNO3) energy of decomposition of nitric acid, DUR correction to the standard
state, which includes the energy of dilution of sulfuric acid and nitric acid, Dcu°(cpd) massic energy of combustion, calculated as:
Dcu°(cpd) = [-DUIBP - DUdec (HNO3) - DUR - (mDcu°) (polyethene) - (mDcu°) (cotton)]/m (cpd)

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Table 4 Results of the combustion experiments for 2CBO at T = 298.15 K and p° = 0.1 MPa
m (cpd) (g) 0.80157 0.80136 0.79986 0.80100 0.80016 0.80490 0.80124
m (polyethene) (g) 0.12691 0.12676 0.10970 0.10163 0.10109 0.09420 0.09810
m (cotton) (g) 0.00203 0.00155 0.00218 0.00181 0.00167 0.00196 0.00185
m (platinum) (g) 11.51517 11.51738 11.51519 11.51788 11.51549 11.51511 11.51535
Ti (K) 294.9856 294.9852 294.9785 294.7853 294.9827 294.9825 294.9822
Tf (K) 298.03393 298.0296 297.94429 297.71456 297.91094 297.9 297.8977
DTc = (Tf - Ti ? DTcorr)(K) 3.0165 3.0138 2.9335 2.8985 2.8941 2.8765 2.8836
-1
e i(cont.) (kJ K ) 0.0173 0.0173 0.0172 0.0172 0.0172 0.0172 0.0172
ef(cont.) (kJ K-1) 0.0185 0.0185 0.0184 0.0183 0.0183 0.0183 0.0183
ecalor (-DT) 30.6425 30.6151 29.7994 29.4438 29.3991 29.2203 29.2925
-DUIBP (kJ) 30.6915 30.6640 29.8465 29.4901 29.4457 29.2668 29.3387
DUdec (HNO3) (kJ) 0.0943 0.0943 0.1003 0.0943 0.0967 0.0835 0.0943
(DUign) (kJ) 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042
DUR (kJ) 0.0169 0.0169 0.0166 0.0166 0.0165 0.0166 0.0165
(mDcu°) (polyethene) (kJ) 5.8853 5.8783 5.0872 4.7129 4.6879 4.3684 4.5492
(mDcu°) (cotton) (kJ) 0.0344 0.0263 0.0369 0.0307 0.0283 0.0332 0.0313
(-mDcu°) (cpd) (kJ) 24.6606 24.6482 24.6055 24.6356 24.6163 24.7651 24.6474
(-Dcu°) (cpd) (kJ g-1) 30.7654 30.7580 30.7623 30.7561 30.7642 30.7679 30.7616
h-Dcu°(298.15 K) (kJ g-1)i = 30.7622 ± 0.0016
The symbols have the same meanings as in Table 3, except that no sulfuric acid exists in the combustion processes considered in this table

Table 5 Results of the combustion experiments for 2CS at T = 298.15 K and p° = 0.1 MPa
m (cpd) (g) 0.85456 0.84690 0.85572 0.84486 0.85770 0.83461
m (polyethene) (g) 0.07692 0.07466 0.0858 0.0837 0.07559 0.08772
m (cotton) (g) 0.00276 0.00238 0.00189 0.00205 0.0019 0.0017
m (platinum) (g) 6.2127 6.21175 6.2104 6.20282 6.21249 6.21183
Ti (K) 295.9149 296.0391 295.9153 295.9257 295.913 295.9608
Tf (K) 297.99999 298.07773 298.02332 298.00736 298.0011 298.03143
DTc = (Tf - Ti ? DTcorr)(K) 2.0670 2.0440 2.0916 2.0651 2.0709 2.0547
ei(cont.) (kJ K-1) 0.0546 0.0545 0.0546 0.0546 0.0546 0.0545
ef(cont.) (kJ K-1) 0.0549 0.0550 0.0550 0.0551 0.0549 0.0550
ecalor (-DT) 29.6019 29.2725 29.9542 29.5747 29.6578 29.4258
-DUIBP (kJ) 29.7125 29.3791 30.0660 29.6850 29.7685 29.5352
DUdec (HNO3) (kJ) 0.0158 0.0440 0.0353 0.0593 0.0138 0.0417
DUign (kJ) 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042
DUR (kJ) 0.0178 0.0178 0.0183 0.0180 0.0178 0.0179
(mDcu°) (polyethene) (kJ) 3.5671 3.4623 3.9789 3.8815 3.5054 4.0679
(mDcu°) (cotton) (kJ) 0.0468 0.0403 0.0320 0.0347 0.0322 0.0288
(-mDcu°) (cpd) (kJ) 26.0650 25.8147 26.0015 25.6915 26.1993 25.3789
(-Dcu°) (cpd) (kJ g-1) 30.5011 30.4814 30.3855 30.4092 30.5460 30.4081
h-Dcu°(298.15 K) (kJ g-1)i = 30.4552 ± 0.0260
The symbols have the same meanings as in Table 3

From the results for the specific energy of combustion,
the standard molar energy, the enthalpy of combustion, and
the standard molar enthalpy of formation were derived.
They are given in Table 6.
To derive the enthalpies of formation of the compounds
under study, the standard enthalpies of formation of the
chemical compounds participating in the combustion
reactions were taken into account as: -(285.830 ± 0.042)
kJ mol-1 for H2O (l) [29], -(393.51 ± 0.13) kJ mol-1 for
CO2 (g) [26], and -(887.811 ± 0.042) kJ mol-1 for
H2SO4115 H2O (aq) [29].
The uncertainties assigned to the enthalpies of formation
are the final overall standard deviations of the mean, which
include random errors in the energies of combustion of

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2088
Table 6 The standard molar energy, enthalpy of combustion, and the
standard molar enthalpy of formation of the compounds under study
at T = 298.15 K and p8 = 0.1 MPa
-DcUm° -DcUm° DfUm°
(kJ mol-1) (kJ mol-1) (kJ mol-1)
2CS (l) 3081.2 ± 2.7 3088.0 ± 2.7 -88.4 ± 2.8
2CBO (l) 4095.9 ± 1.8 4097.8 ± 1.8 -50.7 ± 2.1
2CBS (l) 4816.1 ± 1.1 4823.0 ± 1.1 72.5 ± 1.5
benzoic acid, the auxiliary material, the compound under
study, and in the calorimetric equivalent. They were cal-
culated using the method described by Olofosson [30].
The enthalpies of formation of 2CBS and 2CBO in the
condensate state have the same order relationship as BS
and BO, although the 2-methyl benzazoles have formation
enthalpies smaller than those of the benzazoles.
Merely for comparative purposes, the enthalpies of
vaporization of 2CBS and 2CBO were estimated by using
the Chickos’s method [31] leading to values of 57.31 and
62.72 kJ mol-1, respectively. From these values, the
enthalpies of formation in gaseous phase were also esti-
mated as 135.21 and 3.59 kJ mol-1.
The last behavior is the same as that of 3H-1,3-benz-
oxazole-2-thione and 3H-1,3-benzothiazole-2-thione (or
their tautomeric forms, 2-mercaptobenzothiazole and
2-mercaptobenzoxazole) present [6]; as the heteroatom
electronegativity increases (from sulfur to oxygen), the
formation enthalpies of compounds decrease.
Acknowledgments This research has received financial support
from VIEP-BUAP through Project NAT 2011. J. M., E. A. C., and A.
X. thank CONACYT and VIEP-BUAP for their scholarships. We
thank Prof. Joel Liebman for useful comments on the present work.
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