Standard thermochemical characteristics of formation of triphenylantimony bis(acetophenoneoximate)

Article abstract of DOI:10.1007/s10973-012-2479-z

For the first time, the energy of combustion Δ_c U of crystalline triphenylantimony bis(acetophenoneoximate) Ph₃Sb(ONCPhMe) ₂ has been measured at T = 298.15 K using the isothermal combustion calorimeter with a stationary b

Full text of DOI:10.1007/s10973-012-2479-z

J Therm Anal Calorim (2013) 111:1499–1502
DOI 10.1007/s10973-012-2479-z
Standard thermochemical characteristics of formation
of triphenylantimony bis(acetophenoneoximate)
•
A. V. Markin I. A. Letyanina N. N. Smirnova
•
•
•
V. V. Sharutin O. V. Molokova
Received: 21 February 2012 / Accepted: 3 May 2012 / Published online: 29 May 2012
´
´
ꢀ Akademiai Kiado, Budapest, Hungary 2012
Abstract For the first time, the energy of combustion
DcU of crystalline triphenylantimony bis(acetophenoneox-
imate) Ph3Sb(ONCPhMe)2 has been measured at T =
298.15 K using the isothermal combustion calorimeter
with a stationary bomb. The standard molar enthalpy of
combustion DcH8, the standard molar enthalpy DfH8, and
free Gibbs energy DfG8 of formation of the above oximate
have been calculated.
triphenylantimony dimethacrylate Ph3Sb(O2CCMe = CH2)2
[5]. Study of the heat capacity and the fusion characteristics of
triphenylantimony bis(acetophenoneoximate) Ph3Sb(ON-
CPhMe)2 is represented in [6].
This kind of compounds attracts considerable attention
of researchers due to the striking structure possibilities
ranging from discrete monomeric structures to supramo-
lecular assemblies [7]. Although the organic compounds of
antimony (V) are being obtained and their structures are
being analyzed [8, 9], physicochemical properties of these
compounds have been studied scarcely [10].
Keywords Triphenylantimony bis(acetophenoneoximate) ꢀ
Bomb combustion calorimetry ꢀ Energy of combustion ꢀ
Standard thermodynamic functions of formation
In the present study, we report the standard molar
enthalpy of formation of triphenylantimony bis(acetophe-
noneoximate) in the crystalline state, obtained by the
experimental determination of its standard molar energy of
combustion, measured by stationary-bomb calorimetry, and
calculate the standard free Gibbs energy of formation of
this compound at T = 298.15 K.
Introduction
The present study is a continuation of the complex investi-
gation of thermodynamic properties of antimony (V) organic
compounds [1–6]: pentaphenylantimony Ph5Sb [1], tetraphe-
nylantimony benzophenoneoximate Ph4SbONCPh2 [2], tet-
raphenylantimony acetophenoneoximate Ph4SbONCPhMe
[3], triphenylantimony diacrylate Ph3Sb(O2CCH = CH2)2 [4],
Experimental
Compound and purity control
Triphenylantimony
bis(acetophenoneoximate)
Ph3Sb(ONCPhMe)2 was prepared in the Chemistry
Department in Blagoveshchensk State Pedagogical Uni-
versity according to the method described elsewhere [11].
Namely, 0.32 ml of a 30 % aqueous solution (2.82 mmol)
of H2O2 was added to a solution of 1.00 g (2.83 mmol) of
antimony triphenyl Ph3Sb and 0.76 g (5.63 mmol) of ace-
tophenone oxime HON = C(Me)Ph in 20 ml of ether. The
mixture was kept for 12 h at T = 293.15 K. Colorless
crystals were formed as a result of the oxidative addition
reaction (Eq. 1).
A. V. Markin (&) ꢀ I. A. Letyanina ꢀ N. N. Smirnova
Nizhny Novgorod State University, Prospekt Gagarina,
23/5, 603950 Nizhny Novgorod, Russian Federation
e-mail: markin@calorimetry-center.ru
V. V. Sharutin ꢀ O. V. Molokova
Blagoveshchensk State Pedagogical University, ulitsa Lenina,
104, 675000 Blagoveshchensk, Russian Federation
O. V. Molokova
Far Eastern Military Institute, ulitsa Lenina, 158,
675021 Blagoveshchensk, Russian Federation
123

1500
A. V. Markin et al.
reliability of the calorimeter operation was checked by car-
rying out the combustion of reference succinic acid. The
energy of combustion of this compound conformed to its
passport value with the error of 0.017 %.
Ph3SbþH2O2 þ 2HON ¼ CðMeÞPh
! Ph3SbðONCPhMeÞ2þ2H2O
These crystals were filtered off and dried.
X-ray diffraction analysis of crystals was carried out using
a SMART-1000 CCD (Bruker) spectrometer. The structure
was solved by the direct method and refined by the least-
squares method in the anisotropic approximation for non-
hydrogen atoms. The hydrogen atoms were placed in the
geometrically calculated positions and refined in the rider
model. The X-ray diffraction analysis showed that the Sb
atom has a distorted trigonal–bipyramidal coordination with
the O atoms of the oxime ligands in the axial positions.
As elemental analysis and infrared spectroscopy showed
the content of the main compound in the sample under
study was 0.995 mol fraction. The 0.005 mol fraction
impurity is most likely caused by ether trapped within the
solid crystalline sample, and the minute quantity remained
even after drying in vacuum.
The compound under investigation was combusted in
melted paraffin in a thin-walled quartz crucible. The energy
of combustion of paraffin was evaluated after several
experiments: DcU = -46744 8 J g-1. Paraffin was used
as adjunct, and it insured necessary temperature rising on
the one hand, and on the other hand it created favorable
conditions for total oxidation of initial products. As a fuse
the cotton thread was used; DcU = - (16736 3) J g-1
.
Results and discussion
The energy of combustion of crystalline Ph3Sb(ONCPhMe)2
was measured in 5 experiments. The sample mass was
approximately 0.5 g. The experimental data are listed in
Table 1. The combustion gases were analyzed and amount of
CO2 was determined in each experiment. According to CO2
amount, the sample mass taken for an experiment was cal-
culated. The completeness of combustion was determined by
the absence of CO in the combustion gases using special
inspection pipes. After the experiments, the combustion
products were analyzed with the methods of X-ray spec-
troscopy. According to X-ray diffraction data the solid
combustion products contained antimony tetraoxide Sb2O4
(78 wt%), antimony trioxides Sb2O3 (orthorhomb.)
Combustion calorimetry measurements
The energy of combustion of the compound under study was
measured in a modified isothermal combustion calorimeter
B-08-MA with a stationary bomb [12]. Oxygen pressure in
the bomb was 30 9 105 Pa. The energy equivalent of calo-
rimeter (W = 14805.13 4.48 J X-1) was determined by
the combustion of reference benzoic acid (mark K-1) (the
double root of mean square deviation is given). The
Table 1 Results of the combustion experiments of Ph3Sb(ONCPhMe)2
Experiment number
1
2
3
4
5
m(cpd)/g
m0(paraffin)/g
m00(fuse)/g
0.51525
0.50727
0.00238
2.66261
39420.24
23711.83
39.83
0.52385
0.53752
0.00225
2.77901
41143.62
25125.83
37.66
0.51486
0.51546
0.00206
2.68799
39796.06
24094.66
34.48
0.50837
0.52116
0.00214
2.69425
39888.66
24361.10
35.82
0.52385
0.53007
0.00223
2.75729
40822.08
24777.59
37.32
DR, X
-DU/J
DU(paraffin)/J
DU(fuse)/J
DU(HNO3)/J
-DU(Sb2O3, orthorhomb.)/J
-DU(Sb2O3, cub.)/J
-DU(Sb)/J
4.62
4.04
4.62
4.62
5.20
12.54
12.75
12.54
12.38
12.75
3.97
4.04
3.97
3.92
4.04
18.25
18.55
18.23
18.00
18.55
-DcU/J
15698.73
30468.18
18932.39
16011.43
30564.91
18992.50
15697.04
30487.97
18944.69
15521.42
30531.74
18971.88
16037.32
30614.33
19023.20
-DcU/(J g-1
-DcU (kJ mol-1
)
)
m(cpd) is the mass of compound burnt in each experiment; m0(paraffin) is the mass of the paraffin used in each experiment; m00(fuse) is the mass
of fuse (cotton) used in each experiment; DR is the corrected temperature rise; DU is the energy change for the combustion reaction under actual
bomb conditions; DU(paraffin) is the energy of combustion of the paraffin; DU(fuse) is the energy of combustion of the fuse (cotton); DU(HNO3)
is the energy correction for the nitric acid formation; DU(Sb2O3, orthorhomb.), DU(Sb2O3, cub.) and DU(Sb) are the energy corrections for the
orthorhombic and cubic modifications of crystalline Sb2O3, and metallic antimony formation; DcU is the energy of combustion of the samples
under actual bomb conditions (mean value: -18973 33 kJ mol-1
)
123

Standard thermochemical characteristics
1501
(15 wt%) and Sb2O3 (cub.) (5 wt%), and free antimony
(2 wt%). In correcting for residual Sb2O3 (orthorhomb.),
Sb2O3 (cub.), and metallic antimony the corresponding
The values obtained fit the Eq. (6):
34C ðgrÞ þ 15:5 H2 ðgÞ þ Sb ðcrÞ þ O2 ðgÞ þ N2 ðgÞ
! Ph3SbðONCPhMeÞ2 ðcrÞ;
where gr = graphite.
ð6Þ
corrections (-199.158, -189.116 and -453.755 kJ mol-1
)
were adopted [13] (Table 1). The figures were obtained from
the enthalpies of formation of Sb2O4, DfH(Sb2O4) =
-907.509 4.602 kJ mol-1 [14], Sb2O3 (orthorhomb.),
DfH(Sb2O3, orthorhomb.) = -708.351 5.857 kJ mol-1
[15], Sb2O3 (cub.) DfH(Sb2O3, cub.) = -718.393
5.857 kJ mol-1 [15] according to the equations:
Conclusions
•
•
The energy of combustion of crystalline triphenylanti-
mony bis(acetophenoneoximate) at T = 298.15 K was
determined.
1
Sb2O3 ðorthorhomb:Þ þ O2 ðgÞ ! Sb2O4
2
ð2Þ
DrHꢁ ¼ ꢂ199:158 kJ molꢂ1
The values of standard thermodynamic functions of
formation of crystalline triphenylantimony bis(aceto-
phenoneoximate) at T = 298.15 K were calculated.
1
Sb2O3 ðcub:Þ þ O2 ðgÞ ! Sb2O4
2
ð3Þ
DrHꢁ ¼ ꢂ189:116 kJ molꢂ1
1
Sb þ O2ðgÞ ! Sb2O4
2
References
DrHꢁ ¼ ꢂ453:755 kJ molꢂ1
ð4Þ
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In the DcU calculation, usual corrections were adopted.
They were for the combustion of a cotton thread used as a
fuse, for the combustion of paraffin used in the experiments
as an adjunct, for HNO3 solution formation. We used the
following equation to describe the combustion process:
Ph3SbðONCPhMeÞ2 ðcrÞ þ 41:75O2 ðgÞ
! 34CO2 ðgÞ þ 15:5H2O ðlÞ þ N2 ðgÞ þ Sb2O4 ðcrÞ;
1
2
ð5Þ
where cr = crystal, g = gas, l = liquid.
In addition, the Washburn correction (p = -0.01368 %)
[16] and the correction for the change in the number of moles
of gaseous reagents (Dn = -6.75 mol) were applied into
account. The resulting standard enthalpy of combustion of
triphenylantimony bis(acetophenoneoximate) at T = 298.15 K
was DcHꢁ(298.15, Ph3Sb(ONCPhMe)2, cr) = -18967
33 kJ mol-1
The standard
.
enthalpy
of
combustion
of
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Ph3Sb(ONCPhMe)2, cr) = 703.6 40.1 kJ mol-1
.
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.
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holtz equation. It was DfGꢁ (298.15, Ph3Sb(ONCPhMe)2,
cr) = (1281.3 40.1) kJ mol-1
.
123

1502
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123