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J. Chem. Thermodynamics 127 (2018) 117–125

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Experimental and computational thermochemistry of 3- and

4-nitrophthalic acids
c b
Miguel A. Garcia-Castro a , Patricia Amador b,ÿ , Aaron Rojas, Julio M. Hernandez-Perez ,
b b b
JM Solano-Altamirano , Enoch Flores , Karina Salas-Lopez
to
Faculty of Chemical Engineering of the Meritorious Autonomous University of Puebla, 18 South and Av. San Claudio, CP 72570 Puebla, Pue, Mexico
b
Faculty of Chemical Sciences of the Meritorious Autonomous University of Puebla, 14 South and Av. San Claudio, CP 72570 Puebla, Pue, Mexico
cDepartment of Chemistry, Center for Research and Advanced Studies of the IPN, Av. Instituto Politécnico Nacional 2508, CP 072360 Mexico, Mexico

article info abstract

Article history: In this work, we present experimental and theoretical thermochemistry of the 3- and 4-nitrophtalic acids.
Received January 31, 2018 We report their standard molar enthalpies of formation in crystalline phase, at T = 298.15 K, which were
Received in revised form July 26, 2018 obtained from their energies of combustion. The latter were determined through an isoperibolic bomb
Accepted 28 July 2018
calorimeter. We measured the change-phase enthalpies, as well as the fusion and sublimation enthalpies,
Available online 1 August 2018
by differential scanning calorimetry (DSC) and thermogravimetry (TG). Also via DSC, we found the heat
capacity equations (in crystalline phase) for both isomers as functions of temperature. We determined
Keywords:
the enthalpies of formation in both crystal- and gas-phase from the previous measurements. In addition,
3- and 4-Nitrophthalic acids
Combustion we computed the enthalpies of formation in gas-phase of both isomers using the composite Gaussian-G4
Formation enthalpy method and atomization reactions. The final theoretical enthalpies were computed using a weighted
theoretical study Boltzmann averaging procedure, and the weights were estimated using the Gibbs free energy at
T = 298.15 K. The absolute differences between theoretical and experimental enthalpies are below
1
3.3 kJmol. Finally, we apply our results for obtaining the isomerization enthalpy of 3- to
4-nitrophthalic acid, and difference enthalpies between the nitrophthalic acids and their anhydrides.
2018 Elsevier Ltd.

1. Introduction type, between different combinations of the oxygens and hydro

3- and 4- Nitrophthalic acids are commonly used in the
production chains of a wide variety of commercial products such as
pigments, dyes, plasticizers, etc. [1]. They are also used as precursors group) [11,12]. This provides building blocks for designing
of 4- and 5-nitro-2-benzofuran-1,3-dione, which in turn are used
as intermediate reactants in polypeptide synthesis [2]. the
nitrophthalic acids constitute some of the basic synthetic blocks
for producing polyamides and coordination polymers [3,4]. Fur
thermore, they present catalytic properties [5], and act as ligands
in metallic coordination complexes [6]. 4-nitrophthalic acid forms
proton-transfer compounds [7]. More generally, the acids show
potential applications in the synthesis of compounds with interest
ing magnetic [8], optoelectronic [9], and photoluminescence
properties [10]. Coordination and nano-chemistry are other fields
wherein these nitrophthalic acid isomers present promising
applications [11,12]. This stems from the acids' tendency to form strong anhydride-acid interconversion reactions.
and flexible hydrogen bonds, both of intra- and inter-molecular
ÿ Corresponding author.
E-mail address: maria.amador@correo.buap.mx (P. Amador).
gens of the two carboxylic groups, and in conjunction with the
electronic effects induced by the nitrobenzene group (which may
also participate in hydrogen bonding through the –NO2 functional
supramolecular structures and molecular architectures with special
properties [13–15]. The relative position of the nitro group
allows an even bigger number of structural variants [13–15].
Closer to our group interests, the 3- and 4-nitrophthalic acids
can be obtained from 3- and 4-nitrophthalic anhydrides [16],
respectively, whereof we have reported their thermochemical
properties [17]. In this work, we report our experimental and the
oretical procedures to determine the enthalpies of formation of the
3- and 4-nitrophthalic acids (denoted hereafter as 3NFAc and
4NFAc, respectively, and as NFAcs to refer to both isomers taken
as a set, Fig. 1), in order to obtain the enthalpies for the
The NFAcs standard molar energies of combustion and standard
molar enthalpies of sublimation, at T = 298.15 K, were measured
with a static bomb combustion calorimeter, and a thermogravime
try analyser, respectively. Subsequently, from these quantities we

https://doi.org/10.1016/j.jct.2018.07.026
0021-9614/ 2018 Elsevier Ltd.
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118 MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125

the sapphire of 78.58 J mol1 K1 at 300 K, 88.71 J mol1 K1

at 350 K, and 95.54 J mol1 K1 at 400 K, which shows an agree ment
above 99.39% with the values reported in the literature
(79.43 J mol1 K1 at 300 K, 88.87 J mol1 K1 at 350 K and
96.10 J mol1 K1 at 400 K) [23].

2.2. Combustion calorimetry

The energies of combustion that we report here were obtained

using a static-bomb isoperibolic calorimeter. Flores and co workers
Fig. 1. Structural formulae of 3- and 4-nitrophthalic acids.
have described the apparatus as well as the procedure in
a previous work, thus we refer the interested reader to Ref. [24]
calculated the NFAcs standard molar enthalpies of formation in for further details. We found the energy equivalent of calorimeter
gas-phase, at T = 298.15 K. from the combustion of benzoic acid, which, under the conditions
Complementary to the experimental determinations, we also specified by the NIST certificate, has a mass energy of combustion
report the NFAcs standard molar enthalpies of formation in Dcu = (26434.0 ± 3.0) J g1 (here the uncertainty is the standard
gas-phase, calculated with the Gaussian G4 composite method deviation of the mean). For this we performed seven experimental
combined with atomization reactions and a Boltzmann averaging runs using high-purity oxygen (Airgas Co, x = 0.99999) at 3.04 MPa
procedure. We found nine and ten stable conformers, which pressure and using 1.00 cm3 of water added into the bomb. ace to
exclude specular images, for 3NFAc and 4NFAc, respectively. result we found an energy equivalent ecal = (10135.1 ± 2.6) J K1
Both our experimental determinations and theoretical analysis (here the uncertainty is twice the standard deviation of the mean).
improve the understanding of the NFAcs thermochemical The experiments for calibration as well as for determining the
properties. NFAcs' combustion energies were performed as follows. Solid com
pounds (ie benzoic acid, 3NFAc, and 4NFAc) were oxidized with
oxygen excess and 1 cm3 of water. We flushed the bomb and filled
2.Experimental
it with high-purity oxygen (Airgas Co, x = 0.99999) at 3.04 MPa
pressure, and used a cotton thread fuse, whose empirical formula
2.1. Materials and purity control
and specific energy of combustion are C1.000H1.742O0.921 and
Dcu = (16945.2 ± 4.2) J g1 (here the uncertainty is the standard
In our experiments we used commercial 3NFAc and 4NFAc, as
deviation of the mean) [25,26]. To ensure the complete samples'
provided by Sigma-Aldrich Chemical, and whose mole fraction
oxidation we used paraffin oil as auxiliary material, which has a
purities are 0.99 and 0.92, respectively, according to the vendor.
specific combustion energy Dcu = (46238.5 ± 6.6) J g1 (here
All samples were purified twice by recrystallization from water
the uncertainty is the combined standard uncertainty) [24]. Energy
for 3NFAc and from ether for 4NFAc, respectively, and dried under
corrections related to formation of HNO3(aq), due to the presence
reduced pressure for two hours before use. After this procedure, we
of nitrogen in the NFAcs, were made using 59.7 kJ mol1 for the
measured molar fractions through differential scanning calorime try
enthalpy of formation of HNO3(aq) (0.1 mol dm3 ) [27]. To determine
(DSC), with a Perkin-Elmer DSC7 device, and found purities
the apparent masses of all samples involved in our combustion
above 0.99. Subsequently, we placed the samples into hermetically
experiments, we used an ME215S Sartorius balance, which has
sealed gold cells, and heated them under a dry constant-flow nitrogen
at ±0.01 mg accuracy. Energies and enthalpies in standard conditions,
atmosphere [18]. No phase transitions were observed between
at 298.15 K, were evaluated using Washburn corrections following the
298.15 K and the corresponding melting temperature of each
procedure proposed by Hubbard et al. [28]. For these
compound.
corrections, we used the physical parameters shown in Table 1,
Before performing our experiments, we calibrated the DSC
and we considered NFAcs' (du/dp)T to be 0.2 J g1 MPa1 , at T =
device for energy and temperature with high-purity indium. desde
298.15 K, as this value is representative for most organic com pounds
this operation we obtained the calibration constant to correct peak
[29].
areas, and the thermal resistance to correct temperatures [19]. We
also determined the NFAcs fusion temperatures, fusion enthalpies,
and heat capacities. To ascertain the DSC device accuracy for 23. Thermogravimetry/TGA
determining heat capacities, we measured the heat capacity, Cp,
of high-purity synthetic sapphire, using the ''two steps” method, Enthalpies of sublimation were measured by the indirect Thermal
from 295.15K to 412.15K [20–22]. The device rendered a Cp for Gravimetric Analysis (TGA) method. This consists on applying

Table 1
Physical Properties at T = 298.15 K.
condensed formula Ma what
ðdu=dpÞT zip
compound 1 g cm 3 1
g mole Jg1 MPa1 _ Jg 1K _

c d
3NFAc C8H5O6N 211,139 1.740b 0.2 1.17 ± 0.03
c d
4NFAc C8H5O6N 211,139 1.647c 0.2 1.10 ± 0.09
and and and

benzoic acid C7H6O2 122,122 1.320 0.115 1.21 2.22

F
paraffin oil
and and and

CH2 14,027 0.857 0.257

and and

Cotton CH1.742O0.921f 28,183 1.500e 0.289 1.67

to
Molecular masses are based on 2011 IUPAC recommendations [30]. b
Taken from Ref. [31].
c
Value estimated from experimental data.
d
Experimental value, the uncertainties are expanded uncertainties with a 95% confidence level, which include the contributions from the calibration and u(T) = 0.1. the
experiments were performed at an average pressure of 78.8 kPa. Standard uncertainty for P is u(P) = 1 kPa.
and

Estimated values taken from Ref. [32].

F
Obtained by elemental analysis.
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MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125
the Langmuir equation to a heating process, wherein one assumes
that the mass loss rate of the heated compound, per unit area, is
proportional to its vapor pressure, ie
1=2 ð Þ dm=dt ð Þ¼ 1=A p cð Þ M=2pRT
In Eq. (1), dm/dt is the mass loss rate of the sample, T is the
temperature, A is the area exposed to sublimation, p and M are the
vapor pressure and the molar mass of the compound, R is the
ideal gas constant, and c is a vaporization constant. In our experiments,
A was calculated from the internal transversal section of the
cylindrical alumina cup, whose internal diameter was 5.25 mm.
Merging the Clausius-Clapeyron equation, lnp ¼ C Dg crHm=R ð
Þ 1=T , with Eq. (1) gives:
ln t ¼ B Dg crHm=R ð Þ 1=T
1=2 stants.
and B includes all other with
where t ¼ ð Þ
sublimation
1=A ð Þ dm=dt
can be
ðÞobtained
T=M through
Hence, enthalpies of
eq. (2) by linearly fitting ln t vs 1/T. However, in order for this
method to render accurate results, one requires a highly sensitive
device, for recording dm/dt, that can be well controlled over a wide
temperature range. Therefore, in our experiments we used a TGA/
DSC TA Instruments SDT Q600 device, which we calibrated for mass,
temperature, and heat flow as we described in a previous work [33].
In addition, we tested the thermogravimetric system against the
sublimation of the phenanthrene and pyrene standards. J. T. Baker
provided these materials, which we further purified by repeated
sublimation under vacuum at 20 Pa residual pressure. Our testing
experiments rendered (92.5 ± 1.6) and (100.9 ± 1.0) kJ mol1 for the
enthalpies of sublimation, at T = 298.15 K, of phenanthrene and
pyrene, respectively (the uncertainties correspond to the expanded
uncertainty of 0.95 confidence level). These enthalpies are in excellent
slow agreement with those reported in the literature, this is,
Dg crHm(298.15 K) = (91.300 ± 2.733) kJ mol1 for phenanthrene and
Dg crHm((298.15 K) = (100.2 ± 3.6) kJ mol1 for pyrene [23].
3. Computational details
To perform the structural analysis of the NFAcs, and to support
the consistency of the experimental results, we performed a series
of molecular orbital calculations. To determine the enthalpies of
formation, we used the Gaussian G4 composite method [34], which
has been thoroughly validated to render trustable results [35]. Our
theoretical enthalpies of formation were estimated through
atomization reactions, considering the correction proposed by
Nicolaides et al. [36]. Atomic enthalpies of formation in
gas-phase, at T = 0 K, as well as their thermal corrections, at
T = 298.15 K, were taken from literature, and they follow the NIST
conventions [37]. Since we found more than one stable conformer
for each compound, we calculated the final enthalpies of formation
as a Boltzmann average, for which we used the Gibbs free energy at
T = 298.15 K to compute the weights. Our procedure closely follows
Simmie and Somers [38]. The calculations were performed
Table 2
Source and purity of the compounds studied and reference substances.
Chemical Name (Abbreviation) Source Initial Mole Fraction Puritya
3-nitrophthalic acid(3NFAc) 4- Aldrich 0.99
nitrophthalic acid(4NFAc) Aldrich 0.92
Pyrene JTBaker 0.99
Phenantrene JTBaker 0.99
to
Values reported by the providers.
b
The uncertainties correspond twice the overall standard deviation of the mean, and include the contributions from the calibration and u(T) = 0.1 K. The experiments were
performed at an average pressure of 78.8 kPa. Standard uncertainty for P is u(P) = 1 kPa.
119
with Gaussian 09 [39], DensToolKit [40], and other unpublished
programs developed in our research group.
4.Results and discussion
ð1Þ
4.1. experimental results
In Table 2 we show the sources, molar fractions (both before
and after their purification), and the methods used for increasing
the purity of the NFAcs, as well as of the reference substances used
in this work.
Enthalpies and temperatures of fusion of NFAcs are shown in
Table 3. Because the two compounds melt and sublimate at the
same time, these properties were obtained through DSC using her
ð2Þ
metically sealed gold cells. The uncertainties correspond to twice
the standard deviation of the mean. They include the contributions
from the calibration, and were obtained from averaging four and
five individual experiments for the 3NFAc and 4NFAc, respectively.
If the values of the Tfus that have been obtained in this work are
compared with the reported ones in Scifinder, it can be observed
that the main objective of these publications is to perform diverse
synthesis from the NFAc compounds, and they do not focus on
obtaining their thermochemical properties. Besides, in the majority
of cases it is not specified the purity of the compound and neither
the method used to obtain the Tfus. For the 4NFAc, there is a work
performed by Howell et al [41], where they reported a value of Tfus
of 445.15 K which was obtained by DSC, however, in their thermo
gram it is possible to appreciate a broad peak that does not return
to its baseline, they attribute this fact to a decomposition, further more
they do not specify if they performed a calibration of the DSC.
For this compound, the 4NFAc, most of the values reported in Sci
finder are in the range from 440.7 to 433.2 K and our Tfus falls in
this interval. In the case of the 3NFAc, most values of Tfus are in
the range of (496.2–487.2) K (except very distant values) and
the medium value is 489.15 K. Our value is closer to the higher
limit of this interval, which was obtained previously by Pono marenko
[42], who used a sealed capillary, while in this work we
used high pressure sealed pans to avoid sublimation, as it was
previously specified. The discrepancy of our Tfus with medium value
from other publications can be explained by the purity of the com
pound, since the presence of its isomer, the 4NFAc, causes a
Table 3
NFAc fusion molar enthalpies and fusion temperatures, as determined from DSC.
Tfus
compound Dl crH
kJ mol
1 K
3NFAc 55.3 ± 0.7 496.4 ± 0.4
4NFAc 37.0 ± 0.3 440.0±0.7
The uncertainties correspond twice the overall standard deviation of the mean, and
include the contributions from the calibration and u(T) = 0.1 K. The experiments
were performed at an average pressure of 78.8 kPa. Standard uncertainty for P is u
(P) = 1 kPa.
purification method Final Mole Fraction Purityb Analysis Method
recrystallization 0.9968 ± 0.0017 DSC
recrystallization 0.9923 ± 0.0019 DSC
sublimation 0.9996 ± 0.0012 DSC
sublimation 0.9997 ± 0.0011 DSC
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120 MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125

decrease in the melting temperature of the 3NFAc. From the publications Table 6
found in Scifinder, only the one from Murthy et al. [43] Standard (P = 0.1 MPa) molar enthalpies of formation in crystalline phase, at T =
298.15K
reported the purity of the 3NFAc with a value of 99.5%, which
was obtained by HPLC. In this case, the value of the Tfus was of compound DcU mðcrÞ
1
DcH mðcrÞ
1
Df H mðcrÞ
1
kJ mol kJ mol kJ mol
489.15 K, however, they did not specify the stationary phase or
3NFAc 3075.6 ± 1.2 3070.0 ± 1.2 792.7 ± 1.6
any other condition for the HPLC analysis, which is important 4NFAc 3080.5 ± 1.1 3074.9 ± 1.1 787.8 ± 1.5
information for the successful separation of these isomers by this
technique, since it is necessary the use of a special type of stationary phase The uncertainty associated with each averaged value corresponds to the expanded
uncertainty for a 0.95 confidence level, which includes the error contributions
[44,45].
stemming from the calibration with benzoic acid, and from the uncertainties of the
In Table 4, we show the results of one typical combustion combustion energies of the auxiliary materials and cotton. For Df H mðcrÞ are include
experiment for 3NFAc, and one for 4NFAc. The complete data set the uncertainties of the standard enthalpy of formation of water and carbon
(ie data of all experiments for both NFAcs) can be found in Tables dioxide.

S1 and S2 of the Supporting information.

Energies of combustion, Dcu, at T = 298.15 K, for each experiment and NFAcs standard molar energies, DcU mð Þ cr , enthalpies of combustion,
each compound, as well as the mean energies of combustion and the , and standard
DcH mð Þ cr the crystalline molar
phase, DfH mðenthalpies
Þ cr at T =of298.15
formation in given in
K, are
corresponding uncertainties are given in Table 5. Table 6. ,
In this Table, the uncertainties are the expanded standard deviations, which
include uncertainties stemming from the calibration
procedure, as well as the uncertainties related to the combustion
energies of the auxiliary materials [46–49]. For calculating
Table 4
Typical Combustion Experiments at T = 298.15 K.
DfH mð Þ cr from DcH mð , we used (285.83 ± 0.04) and (393.51
Þ cr ± 0.13) kJ mol1 as the standard molar enthalpies of formation, at
3NFAc 4NFAc
T = 298.15 K, of H2O(l) and CO2(g) [50].
m (compound)/gm 1.34565 1.29487
In Table 7, we show representative data of Thermogravimetric
(paraffin oil)/gm 0.04681 0.08695
0.00194 0.00199
experiments for 3NFAc, and 4NFAc. Enthalpies of sublimation, at
(cotton)/gm
(platinum)/g Ti/K 11.51423 11.51328 experimental mean temperature, Dg crHmð Þ Tm , were estimated using
Tf/K DTcorr/ K 295.2831 295.2886 eq. (2) and the least squares method, and they are weighted average ages
DTc/ K ei (cont)/kJ 297.4793 297.5975
taken over several individual experiments (Tables S3 and S4
K1 ef (cont)/kJ K1 0.0433 0.0450
2.1529 2.2639
of the Supporting information) [48,49,51].
e ( cont) (DTc)/kJ
e(heat) (DTc)/kJ 0.0176 0.0175 We estimated the standard molar enthalpies of sublimation, at
DUign/kJ DUIBP/ 0.0201 0.0202 T = 298.15 K, through Kirchoff's law:
kJ DU (HNO3)/kJ 0.0360 0.0380
tm
DUcorr/kJ (mDcu) 21.8203 22.9446
Dg crH mð Þ¼ DC p;mdT ð3Þ
(paraffin oil)/kJ 0.0042 0.0042 T ¼ 298:15K Dg crH mð Þ Tm Z
298:15K
(mDcu) (cotton)/kJ 21.8521 22.9784
(mDcu ) (compound)/ 0.0328 0.0125 In Eq. (3), DC ¼ C p;mð Þ g - C p;mð Þ cr Heat capacities in gaseous
p.m
kJ Dcu(compound)/ 0.0185 0.0185
2.1643 4.0202 phase, C p;mð Þ g , as functions of temperature, for 3NFAc and 4NFAc,
kJ.g1
0.0329 0.0337 are given below in Eqs. (4) and (5). The numerical coefficients were
19.6036 18.8935 obtained from a polynomial regression applied to a set of C p;mð Þ g vs
14.5681 14.5910
You date. This set was, in turn, obtained theoretically from the partition
m(compound), m(cotton)and m(paraffin oil) are the masses of the compound, cot ton of function obtained from the vibrational frequencies of the
paraffin oil respectively, the masses were corrected for buoyancy using respective most-stable conformer. The frequencies were calculated
densities listed in Table 1; Ti and Tf are the initial and final temperature, respectively, DTcorr from optimized geometries (which were obtained as we explain in
is a correction term, DTc is the temperature increment corrected for
Section 4.3, below), at B3LYP/6-31G(2df,p) theory level.
adiabatic conditions: DTc = Tf - Ti -DTcorr; ei (cont) and ef (cont) are the initial and
final bomb content energies, respectively; e(cont)ÿ(DTc) = ei (cont)ÿ(298.15 K - Ti) +
ef (cont)ÿ(Tf - 298.15 K - DTcorr); e(heat) represents the energy equivalent of the C p;mð Þ g ½ 3NFAc = J K1 mol1 ¼

entire system; DUign is the experimental energy of ignition, DUIBP is the energy 3 two
4:192334 107 ð Þ T=K þ 6:289000
Þþ T=K
101 ðþ 5:040864 106 ð Þ T=K
change for the isothermal bomb process, DU (HNO3) is the experimental energy of
formation of nitric acid, DUcorr is the correction to standard states, and Dcu is the
2:521117 101 r2 ¼ 0:999 ð4Þ
standard mass energy of combustion.

C p;mð Þ g ½ 4NFAc = J mol1 K1 ¼ 4:931622

Table 5
3 two
107 ð Þ T=K þ 5:962142 101 ð 2:874579
Þþ T=K þ 9:075108 105 ð Þ T=K
Individual mass energies of combustion, at T = 298.15 K.
3NFAc 4NFAc 101 r2 ¼ 0:999 ð5Þ

Dcu/(kJ g1 )
14.5681 14.5910 On the other hand, we determined the heat capacities in crys talline phase,
14.5693 14.5900 C p;mð Þ cr as functions of ,temperature, from DSC
14.5680 14.5929 experimental data (see Tables S5 and S6 of the Supporting information for
14.5610 14.5884
further details). The heat capacities of the NFCs are given
14.5682 14.5906
below.
14.5633 14.5863
14.5677
(Dcu) (kJ g1 ) C p;mð Þ cr ½ 3NFAc = J K1 mol1 ¼ 1:488549
14.5665 ± 0.0024 14.5899 ± 0.0018
3 two
105 ð 1:721611 102 ð Þ T=K102
Þ T=K
r2 ¼þ 0:999
7:116819ð Þ T=K 7:392816
The uncertainties correspond to twice the standard
deviation of the mean. ð6Þ
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MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125 121

Table 7
Enthalpies of sublimation at mean experimental temperature and at T = 298.15 K.
b c
compound No.series tm to Dg crHmðTm Þ Dg crHmðT¼298:15KÞ
K 1
kJ mol kJ mol1

3NFAc 4 474.5 126.9 ± 3.0 136.7 ± 3.6

4NFAc 4 422.0 114.1 ± 2.6 118.9 ± 3.2
to
Tm is mean experimental temperatures and corresponds to the interval of temperatures shown in Tables S3 and S4, respectively, its uncertainty is u(T) = 0.1 K. b
The values of enthalpies of sublimation correspond to weighted average values.
Their uncertainties are twice the standard deviation of the weighted average. The experiments were performed at an average pressure of 78.8 kPa. Standard uncertainty for P
is u(P) = 1 kPa.
c
The uncertainty is the expanded uncertainty with a 0.95 level of confidence and includes the uncertainties of heat capacities, u(T) = 0.1 K, and those corresponding to
phenanthrene and pyrene used in the validation of the method.

C p;mð Þ cr ½ 4NFAc = J K1 mol1 ¼ 4:076764

energy surfaces yielded a set of initial geometries that we subsequently
optimized. From the latter, we varied /3 and /4 to be
3 two

105 ð 4:302508 102 ð Þ T=K1:680569

Þ T=K þ 103
1:562179
r2 ¼ 0:999
101 ð Þ T=K (180, 0, or 180) degrees, followed by optimizations of this
extended set of initial geometries. Geometry optimizations related
ð7Þ
to G4 calculations were all performed at B3LYP/6-31g(2df,p) the ory
In Table 8, we summarize the standard molar enthalpies of level, and the geometries of the most stable conformers
sublimation and formation, both in crystalline and gaseous phases, at obtained as explained were also used to compute the heat capacities
T = 298.15 K. Uncertainties are the expanded uncertainties, which (see the above text, from Eq. (3) to Eq. (5)). Our method/basis
include uncertainties stemming from the experimental determinations. choice is based on the fact that the G4 procedure internally re
To the best of our knowledge, the enthalpies of formation of optimizes the geometries using precisely this method and basis.
the NFAcs have not been reported before. From the procedure described above we found nine and ten
The uncertainties are the expanded uncertainty with a 0.95 stable non-equivalent conformers for 3NFAc and 4NFAc, respectively.
level of confidence. We considered specular images to be equivalent, and their
contributions to the Boltzmann average was accounted for through
4.2. Molecular and electronic structures degeneracy factors (see Eqs. (3) and (4) of Ref. [38]). Along with the
Supporting Information, we provide the optimized geometries of
To determine the stable molecular structures of the NFAcs, for the non-equivalent stable conformers in the form of a zipped file.
each isomer, we first performed a Potential Energy Scan, by varying
the dihedral angles /1 and /2 (see Fig. 2 for their definitions) from 4.3. Theoretical results
(180 to 180) degrees with increments of 20 degrees, using the
Gaussian 09 software [39] at the B3LYP/6-31G(d) theory level. The enthalpies of formation in gas-phase, at T = 0 K, of the
The corresponding potential energy surfaces are shown in Fig. 3 stable non-equivalent conformers were determined, as explained
Supporting information. Identifying the minimum of the potential
Table 9
Theoretical enthalpies of formation in gas-phase at T = 298.15 K.
compound Df H m ðg;theorÞ
1
Df H m ðg;theorÞDf H mðg;expÞ
1
Table 8 kJ mol kJ mol

Enthalpies of sublimation and standard (P = 0.1 MPa) molar enthalpies of formation. 3NFAc 659.3 3.3 (±3.9)
4NFAc 671.6 2.7 (±3.5)
compound Df H mðcrÞ Dg crHm
1
Df H mðgÞ
kJ mol1 kJ mol kJ mol1
The numbers enclosed in parentheses are the uncertainties reported in Table 8 of
3NFAc 792.7 ± 1.6 136.7 ± 3.6 656.0 ± 3.9
this work. The abbreviation ''theor” stands for theoretical, and ''exp” for
4NFAc 787.8 ± 1.5 118.9 ± 3.2 668.9 ± 3.5
experimental.

Fig. 2. Numbering system and dihedral angle definitions for (a) 3NFAc and (b) 4NFAc. Here /1 (/2) is the dihedral angle formed by atoms 1-2-5-6 (4-3-7-8), and /3 (/4) is
formed by atoms 6-5-9-10 (8-7-11-12), respectively.
Machine Translated by Google
122 MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125
Fig. 3. 3-dimensional representation of the most stable conformers of (a) 3NFAc and (b) 4NFAc.
Fig. 4. Experimental and computationalb enthalpy of isomerization (in kJ mol-1) of
3NFAc to 4NFAc.
above, with the Gaussian G4 composite method along with atomization
reactions, and the corrections to T = 298.15 K were obtained following
Nicolaides et. to the. approaches [36]. Detailed intermediate data, ie
weights, degeneracy factors, and individual enthalpies of formation, are
given in Tables S7 and S8 of the Supporting information. In Table 9 we
show the final Boltzmann averaged enthalpies of formation, at T =
298.15 K, and deviations from our mean experimental values. The
theoretical enthalpies of formation are in excellent agreement with our
experimental results.
For completeness purposes, in Fig. 3 we show the 3D molecular
structures of the most stable conformers of the NFAcs, which were
rendered with DensToolKit [40]. These structures correspond to the
conformers labeled as 3NFAca and 4NFAca in Tables S7 and
S8 of the Supporting information, and the geometries are given as xyz
files along with the Supporting Information. 3NFAc shows a RMSD of
5.56 10-6 Å, relative to the X-ray structure (unfortu nately we did not
find the X-ray structure of 4NFAc).
The first two most-stable conformers of 3NFAc determine its enthalpy
of formation, as the corresponding populations are 75.37% and 24.42%
(see conformers 3NFACa and 3NFACc in Tables S7 and S8 of the
Supporting information). 4NFAc presents a more varied conformational
population, and its enthalpy of formation is given by the contributions of
four conformers, whose populations are 35.44%, 35.40%, 18.28%, and
10.75%, respectively (see with formers 4NFACa, 4NFACb, 4NFACd,
and 4NFACc in Tables S7 and S8 of the Supporting information).
4.4. Isomerization enthalpy and enthalpy differences
Since in this work we have determined the formation of enthalpies
of the NFAcs, it becomes possible to analyze chemical processes (and
consequently their associated enthalpies) wherein these com pounds
are involved. For instance, the isomerization enthalpy of 3NFAc to
4NFAc is (12.9 ± 5.2) kJ mol1 from experimental values
in gaseous phase, and 12.3 from theoretical values. This means that
4NFAc is the most stable isomer (see Fig. 4).
In the same manner, we can determine the enthalpic increments
between different acids and their associated anhydrides (which are
structurally similar to the NFAcs). In Fig. 5, for comparison and
completeness purposes, we depict a series of these transformations,
which are the result of adding/removing carboxylic and presence of nitro
groups. The enthalpic increment between maleic acid and its anhydride
is (281.1 ± 5.7) kJ mol1 [52], and it coincides with that of the phthalic
acid/anhydride pair, which is (281.5 ± 5.4) kJ mol1 [53,54]. The enthalpic
increments of the pairs 3-nitrophthalic acid/anhydride (274.9 ± 5.7) kJ
mol1 [17] and 4-nitrophthalic acid/anhydride (272.9 ± 7.1) kJ mol1 [17]
coincide between them as well, within the uncertainties. In these cases,
the stability decrease is due both to the loss of a water molecule and to
the lack of hydrogen bonding in the anhydrides, relative to the acids
where hydrogen bonds are present. On the other hand, adding a
carboxylic group to the benzoic acid, and to 2- and -nitrobenzoic acids
renders enthalpic increments of and (364.9 ± 3.5) kJ mol1 respectively
[53–56]. All these enthalpic increments are of the same order of
(356.7 ± 2.1) kJ mol1 , (376.2 ± 4.0) kJ mol1 , magnitude,
compared to the Carvalho et al. reported values [57]. (In [57] Carvalho
et al. analyzed the energetic effect of adding a carboxylic group to
several indole derivatives and several heterocyclic rings). Regarding the
isomer ization enthalpy, increasing the distance between the nitro and
the carboxylic group (ie going from 2- to 3-nitrobenzoic acid [56], or from
3- to 4-nitrophthalic acid, see Fig. 5) increases the stability of the
molecule, which stems from removing the steric repulsion that exists
between the adjacent nitro and carbonyl groups.
This effect has been theoretically confirmed through a NBO analysis
for 3- and 4- nitrophthalic anhydrides [17]. Similar conclusions can be
drawn for the 2- to 3- nitrobenzoic anhydrides, and for the 3- to 4-
nitrophthalic anhydrides (see also Fig. 5).
5.Conclusions
We studied the thermochemical properties of the 3- and 4-nitrophthalic
acids, both experimentally and theoretically. From this we showed that
the 4-nitrophthalic acid is more stable than the 3-nitrophthalic acid. The
isomerization enthalpy of 3- to 4-nitrophthalic acid obtained from
experimental values is and from theoretical values is 12.3 kJ mol1 Our
12.9 kJ mol1 , theoretical analysis showed that these compounds .
present a rich conformational variety comprised by nine and ten stable
conformers, respectively, and the theoretical enthalpies of formation in
gas-phase showed an excellent agreement with our experimental
determinations.
Machine Translated by Google

MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125 123

Fig. 5. Enthalpy differences, DDfHm(g), between acids and their respective anhydrides, DDfHm(g) due to the insertion of carboxylic acid group and enthalpies of
isomerization. All values are given in kJ mol1 . to Ref. [52]; b Ref. [55]; c Ref. [53]; d Ref. [54]; Ref. [56]; Fthis work; g Ref. [17].
and
Machine Translated by Google

124 MA Garcia-Castro et al. / J. Chem. Thermodynamics 127 (2018) 117–125

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JCT 2018-425