Thermochemical Properties of Triphenylantimony Dibenzoate Ph3Sb(OC(O)Ph)2

Article abstract of DOI:10.1134/S0036024420090162

Abstract: The energy of combustion of crystalline triphenylantimony dibenzoate is measured using an isoperibolic combustion calorimeter with a static bomb at T = 298.15 K. The experimental data show that the standard enthalpy of combustion of this substance in the crystalline state is calculated for T = 298.15 K. Standard functions ?_fH° and ?_fG° of the formation of the compound in the crystalline state are calculated for T = 298.15 K.

Full text of DOI:10.1134/S0036024420090162

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2020, Vol. 94, No. 9, pp. 1776–1779. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Fizicheskoi Khimii, 2020, Vol. 94, No. 9, pp. 1333–1336.
CHEMICAL THERMODYNAMICS
AND THERMOCHEMISTRY
Thermochemical Properties of Triphenylantimony Dibenzoate
Ph3Sb(OC(O)Ph)2
D. V. Lyakaeva, A. V. Markina,*, N. N. Smirnovaa, A. V. Knyazeva, V. V. Sharutinb, and O. K. Sharutinab
aLobachevsky State University, Nizhny Novgorod, 603950 Russia
bSouth Ural State University, Chelyabinsk, 454080 Russia
*е-mail: markin@calorimetry-center.ru
Received December 9, 2019; revised December 9, 2019; accepted December 10, 2019
Abstract—The energy of combustion of crystalline triphenylantimony dibenzoate is measured using an iso-
peribolic combustion calorimeter with a static bomb at T = 298.15 K. The experimental data show that the
standard enthalpy of combustion of this substance in the crystalline state is calculated for T = 298.15 K. Stan-
dard functions ∆fH° and ∆fG° of the formation of the compound in the crystalline state are calculated for
T = 298.15 K.
Keywords: calorimetry, enthalpy of combustion, enthalpy of formation, triphenylantimony dibenzoate
DOI: 10.1134/S0036024420090162
INTRODUCTION
∆fH° of formation was calculated, and standard Gibbs
function ∆fG° of formation in the crystalline state of
triphenylantimony dibenzoate was calculated for T =
298.15 K.
Organic antimony derivatives have the potential to
be used in the treatment of oncological diseases [1–6];
in the fight against pathogenic organisms as biocides
and fungicides [7–9]; in fine organic synthesis as
reagents and catalysts components [10–12]; and for
preparing metal-containing polymers [13–15].
Organic antimony complexes are used in the develop-
ment of new photocatalytic and thermo-radioresistant
materials [16–19]. In addition, various organic anti-
mony compounds exhibit the ability to absorb carbon
dioxide [20, 21].
Due to the wide range of applications of organic
pentavalent antimony derivatives, studying the phys-
ical and chemical properties of new members of this
class of compounds remains a key task in many stud-
ies [22–25]. Information about the thermodynamic
and thermochemical properties of promising anti-
mony compounds is needed for calculating and opti-
mizing technological processes that involve them.
The thermodynamic properties of Ph5Sb and
Ph3Sb(OC(O)Ph)2 and several other pentavalent anti-
mony derivatives of the Ph3SbX2 type, where X
denotes organic substituents, were determined via adi-
abatic vacuum and differential scanning calorimetry in
[26–30]. Thermochemical characteristics (ΔcU°,
∆cH°, ∆fH°) of Ph3Sb(OC(O)Ph)2 are missing from
the literature.
EXPERIMENTAL
Samples
The studied compound was synthesized and iden-
tified according to the procedure in [31]. A sample of
triphenylantimony dibenzoate was obtained by the
authors of [31] via the oxidative addition reaction from
triphenylantimony, hydrogen peroxide, and benzoic
acid (molar ratio 1 : 1 : 2) in ether:
Ph3Sb + 2PhCOOH + H2O2
(1)
→ Ph3Sb(OC(O)Ph)2 + 2H2O.
The reaction time was 12 h at T = 293 K. The obtained
light gray crystalline compound is stable in air under
normal conditions. The compound was identified via
elemental analysis (found, %: C 64.63; H 4.34; calcu-
lated for C32H25O4Sb, %: C 64.56; H 4.23). IR spec-
trum (ν, cm−1): 1610, 1565 (С=О). The errors in
determining carbon and hydrogen were 0.1 and 2%,
respectively.
The structure of the compound was determined via
X-ray diffraction analysis. Figure 1 shows the molecu-
lar structure of the compound. Our study showed that
the crystals were monoclinic a = 19.862 (2) Å, b =
15.848 (2) Å, c = 16.854 (2) Å, with α = 90°, β = 90°,
In this work, we continued our calorimetric studies
of the thermodynamic properties of a number of
organic antimony(V) derivatives, enthalpy ΔсН° of γ = 90°, V = 5305 (1) Å3, sp. gr. Pccn, Z = 8, ρ(calc.) =
combustion was determined, the standard enthalpy 1.491 g/cm3.
1776

THERMOCHEMICAL PROPERTIES
1777
racy of CO2 determination, established using the
results from analyzing the combustion of the standard
benzoic acid, was 5 × 10−4 g. The completeness of
combustion was determined from the concentration of
carbon monoxide in the combustion products by pass-
ing the gas through special indicator tubes. CO was not
detected within the error of analysis (6 × 10−6 g). A
visual inspection of the surface of the bomb revealed
no evidence of incomplete combustion of the sub-
stance. An X-ray phase analysis of the solid products
of combustion was performed after each experiment.
C(14)
C(13)
C(15)
C(16)
C(12)
C(11)
C(1)
O(1)
O(2)
C(53)
C(35)
C(34)
C(33)
C(52)
C(36)
Sb
C(54)
An approximate Washburn formula was used to
reduce measured value ∆cU to standard conditions
(∆cU°) [34, 35]:
C(32)
C(51)
C(31)
C(46)
C(42)
C(55)
C(56)
C(43)
C(44)
C(45)
O(4)


0.30P
b − 2c
4a
2
p
C(41)
(2)
π =
−1 + 1.1
−
,
(
)




−Δ U /a
c
O(3)
C(2)
C(21)
where p is the initial oxygen pressure in the bomb, atm
(usually 30 atm); ∆cU/a is the energy of combustion of
carbon contained in the burned substance, kcal/mol;
and a, b, c are the indices in the chemical formula of
the substance that was burned. Using Washburn cor-
rection (π) and the correction resulting from the
change in the number of moles of gases (Δn), standard
values ΔсU° and ΔсН° were calculated for the combus-
tion reaction of the studied substance. Enthalpy of for-
mation ΔfH° of the compound in the crystalline state
at T = 298.15 K was calculated from the obtained val-
ues of ΔсН°.
C(22)
C(26)
C(23)
C(25)
C(24)
Fig. 1. Structure of triphenylantimony dibenzoate
Ph Sb(OC(O)Ph) .
3
2
RESULTS AND DISCUSSION
According to the results in [31], the content of the
main substance in the Ph3Sb(OC(O)Ph)2 sample was
99.0 mol %. Impurities were not identified; given their
quantity, however, we may assume they did not affect
the values of thermodynamic quantities within the
limits of their errors of determination.
The energy of combustion of crystalline triphe-
nylantimony dibenzoate Ph3Sb(OC(O)Ph)2 was
determined in six experiments. The weight of the test
substance was ∼0.2 g. The experimental data are pre-
sented in Table 1. An X-ray phase analysis of the solid
products of combustion was performed after each
experiment. According to the results, the solid prod-
ucts of the combustion of triphenylantimony dibenzo-
ate contained antimony tetraoxide Sb2O4 (85 wt %),
antimony trioxide Sb2O3 (15 wt %). Free antimony was
not found in the products of combustion.
The error of our X-ray phase analysis did not
exceed 3%, which did not appreciably distort the
experimental value of the enthalpies of combustion.
Since the products of combustion contained antimony
trioxide along with antimony tetraoxide, we intro-
duced the appropriate corrections for incomplete
metal oxidation:
Instrumentation and Measuring Technique
The enthalpy of combustion of the investigated
compound was determined in an improved B-08MA
calorimeter equipped with a static calorimeter bomb
[32]. The calorimetric system was calibrated with stan-
dard benzoic acid of K-2 grade (ΔcU = −(26454.4
2.2) J/g) weighed in air. The energy equivalent of the
system was W = 14805 3 J/K with a doubled stan-
dard deviation from the average result of 0.02%.
The sample was burnt at an oxygen pressure of 3 ×
106 Pa in molten paraffin. This provided a standard
temperature rise in the experiments, and created the
conditions for complete oxidation of the initial sam-
ple. The gaseous products of combustion were ana-
lyzed for CO2 content, the amount of which was used
to calculate the mass of the substance used in the
(3)
Sb2O3(cr.) + 0.5O2(g) → Sb2O4(cr.).
In light of the molar content of oxides and the value
of the enthalpy of reaction (3), calculated from enthal-
pies of formation ∆fH°(Sb2O3(cr.)) = −715.46 3.422
[36], ∆fH°(Sb2O4(cr.)) = −907.509
4.602 [36], it
experiment. The procedure for analyzing gaseous was found that the value of the correction for incom-
products of combustion was given in [33]. The accu- plete metal oxidation (3–6 J) does not appreciably
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 94 No. 9 2020

1778
LYAKAEV et al.
Table 1. Results from experiments 1–6 to determine the energy of combustion of triphenylantimony dibenzoate
Ph3Sb(OC(O)Ph)2
Value
No. 1
No. 2
No. 3
No. 4
No. 5
No. 6
m, g
m(par), g
m(c.th.), g
W, J/g
ΔT, K
0.15068
0.70670
0.00202
0.13572
0.72230
0.00245
0.20269
0.70518
0.00185
0.18579
0.70988
0.00192
0.11086
0.71058
0.00196
0.35823
0.71337
0.00256
14805
2.51096
37174.8
14805
2.53252
37494.0
14805
2.60151
38 515.4
14805
2.58479
38 267.8
14805
2.44995
36 271.5
14805
2.91304
43127.6
−ΔcU, J
−ΔcU(par), J
−ΔcU(c.th.), J
ΔcU(soot), J
−ΔfU(HNO3), J
ΔcU(Sb2O3), J
−∆cUcorr, J
−ΔcU°, J/g
−ΔсU°, kJ/mol
33033.7
33.8
33762.9
41.0
32962.7
31.0
33182.4
32.1
33215.1
32.8
33345.5
42.8
5.18
5.86
3.98
1.94
4.67
6.97
6.39
3.81
12.3
9.37
9.47
4.61
27208.9
2.93
3.59
1.75
5.86
5.36
2.61
2.93
4.91
2.39
5.44
2.93
1.43
27267.2
27215.1
16201.1
27260.9
16228.3
27231.3
16210.7
27273.0
16235.5
(−∆Uс = 16217.5 13.7 kJ/mol)
m is the mass of the burned substance; ∆Т is the change in temperature in the experiment, corrected for heat transfer; Δ U(par),
16232.1
16197.4
c
Δ U(c.th.), Δ U(soot), Δ U(HNO ), and Δ U(Sb O ) care the corrections for the energies of combustion of paraffin and cotton thread,
c
c
f
3
c
2 3
the incompleteness of carbon combustion, the energy of formation of an aqueous solution of HNO and crystalline Sb O , respectively;
3
2 3
and Δ U° is the energy of combustion of the considered substance, reduced to standard conditions. The average values are given in
с
parentheses.
affect the final value of ∆cU (≈30000 J). In addition, formation of products of combustion ∆fH°(CO2(g)) =
the usual thermochemical corrections were made in –393.513
0.046 kJ/mol [36], ∆fH°(H2O(l)) =
‒285.829 0.040 kJ/mol) [36], ∆fH°(Sb2O4(cr.)) =
‒907.509 4.602 [36], the standard enthalpy of for-
mation of the investigated compound in the crystalline
calculating ΔUc: for the combustion of the cotton
thread used to fire a sample of the substance
(CH1.686O0.843 [37], ∆cU(c.th.) = −(16736.0 11.1) J/g);
for the combustion of the applied paraffin (n-hexade- state was calculated for T = 298.15 K:
cane, mass fraction >99.9%, ΔсU(par) = −(46744
Δf H°(298.15, Ph3Sb(OC(O)Ph)2(cr.))
8) J/g); and for the formation of HNO3 solution
= –388.6 14.5 kJ/mol.
(∆rH° = ‒59.7 kJ/mol for 0.1 mol/L HNO3 (s) from
simple substances N2(g), O2(g), and H2O(l) [38]).
According to the calculated ∆fH° value of the studied
compound and the standard entropy of formation
ΔfS°(298.15, Ph3Sb(OC(O)Ph)2(cr.)) = −1597
7 J/(K mol) obtained in [27], the standard Gibbs
function of formation (∆fG°, kJ/mol) was determined
using the Gibbs–Helmholtz equation
The process that occurs in a bomb is described by
the equation
Ph3Sb(OC(O)Ph)2(cr.) + 37.25O2(g)
(4)
→ 32СО2(g) + 12.5Н2О(l) + 0.5Sb2O4(cr.).
ΔfG°(298.15,Ph3Sb(OC(O)Ph)2(cr.))
= 87.55 14.5 kJ/mol.
The obtained values of the standard thermochemi-
cal formation functions correspond to the equation
In calculating the standard enthalpy of combustion
of crystalline triphenylantimony dibenzoate, the
Washburn correction (π = −0.04723%) and the cor-
rection for changing the number of moles of gaseous
combustion reagents (Δn = −5.25 mol) were also
introduced in accordance with [34, 35]. As a result,
the standard enthalpy of combustion of crystalline
Ph3Sb(OC(O)Ph)2 at T = 298.15 K was
31С(gr.) + 12.5H2(g) + 2O2(g) + Sb(cr.)
→ Ph3Sb(OC(O)Ph)2(cr.),
where gr. is graphite.
(5)
ΔсH°(298.15, Ph3Sb(OC(O)Ph)2(cr.))
= –16 230.5 13.7 kJ/mol.
FUNDING
Using the values of the standard enthalpy of com-
bustion of a substance and the standard enthalpy of
This work was supported by the Russian Foundation for
Basic Research, project no. 19-33-90070.
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No. 9
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THERMOCHEMICAL PROPERTIES
1779
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