Journal of Molecular Liquids 342 (2021) 117504

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Effect of phosphorus P-p bonding on the volumetric properties and

vapor-liquid equilibrium of phosphorus trichloride-benzene liquid
mixtures
Bingwen Long ⇑, Jiapo Song, Keke Yao, Yigang Ding
Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education, Key Laboratory for Green Chemical Process of Ministry of Education,
Hubei Key Laboratory for Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430074, China

a r t i c l e i n f o a b s t r a c t

Article history: New density and vapor–liquid equilibrium data of PCl3-benzene binary system at atmospheric pressure
Received 21 July 2021 (99.7–101.3 kPa) were carefully measured to provide crucial information for their industrial reaction and
Revised 2 September 2021 separation. The experimental mixture densities show excellent linear dependence on both solution com-
Accepted 6 September 2021
position and temperature and a generalized empirical correlation is proposed with an average relative
Available online 09 September 2021
deviation of 0.13%. The specific attractive P-p interaction between the phosphorus atom of PCl3 and
the p cloud of benzene seems to be quite strong in solution, leading to large negative excess volumes.
Keywords:
But the p-p antibonding effect from benzene dimers are predominant in PCl3 highly dilute solution,
Phosphorus trichloride
Benzene
where positive excess volume and excess partial molar volumes of PCl3 were observed. Experimental
Density bubble points of the binary mixture were corrected to those under 101.325 kPa. Two distinctive methods
Vapor–liquid equilibrium of coexistence equation and activity coefficient models of Wilson and NRTL equations were applied to
P-p interaction model the VLE data, and they yielded very consistent results. Although no azeotrope were found, this
Modeling mixture exhibited quite low relative volatility.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction
Phosphorus trichloride (PCl3) and benzene are the most impor-
tant feedstocks to manufacture phosphorus flame-retardants and
photo-initiators, such as dichlorophenyl phosphine (DCPP) and
diphenyl phosphine chloride (CDPP). While CDPP is one of the
most important intermediates for phosphorus photo-initiators,
ligands of catalyst and organophosphorous flame retardant [1],
the industrial production of CDPP uses the Friedel-Crafts reaction
of PCl3 and benzene with anhydrous aluminum chloride [2] or
Lewis acid ionic liquid such as [BuPy]Cl–xAlCl3 [3] as the catalyst.
A recent reaction modeling study [4] has shown that the vapor–liq-
uid equilibrium (VLE) has significant influence on the catalytic effi-
ciency and product selectivity as well as the hydrodynamics inside
the reactor and hence a full and accurate thermodynamic descrip-
tion of the reactants and products is a must. After the reaction,
most unreacted PCl3 and benzene must be recovered from the liq-
uid system by atmospheric distillation as mixture and then vac-
uum distillation is applied to separate residual PCl3 and benzene
from raw CDPP [2]. Due to the high volatility and close boiling
⇑ Corresponding author.
E-mail address: Bingwen_long@163.com (B. Long).
points of PCl3 and benzene, the further separation of them is quite
challenging. However, the fundamental physicochemical and
phase equilibrium properties of this binary mixture and their the-
oretical modeling, which are highly demanded for the reliable
design and optimal operation of their separation, transportation
and storage, are not available.
From a theoretical perspective, any deviation from ideal solu-
tion behavior is considered as the joint results of various intra/in-
termolecular interactions between molecules of different size,
shape and polarity [5–7]. It is well established that benzene molec-
ular contains electron rich p cloud that could accept proton to form
molecular complexes with the proton donor by hydrogen bonding.
For example, the formation of X-H


p bonding complexes have
been demonstrated in binary liquid mixtures of benzene with
HCl and with chloroform through both quantum chemistry compu-
tations [8] and nuclear magnetic resonance (NMR) [9] and Raman
spectroscopy measurements [10]. This X-H


p bonding has
resulted in the formation of eutectic mixture of benzene and chlo-
roform at 85℃ and benzene mole fraction of 0.735. On the other
hand, as chlorine is quite electronegative, the three chloride atoms
on chloroform direct away from the benzene ring, causing an pos-
itive excess volume over the entire composition upon mixing them
[11,12]. Apart from the hydrogen atom, phosphorus atom can also

https://doi.org/10.1016/j.molliq.2021.117504
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
B. Long, J. Song, K. Yao et al.
act as the p electron acceptors through the P-p bonding. The P-p
bonding is a new class of non-covalent intermolecular interaction,
which was firstly reported from an ab initio computation study by
Klinkhammer and Pyykko in 1995 [13]. The p-type bonding inter-
action of PCl3 with benzene was explored by Xu [14] using DFT cal-
culations, which showed that benzene could provide high p-
electron energy capacity and form stable complex with PCl3. More
recently, the PCl3-benzene dimer was experimentally detected by
Ramanathan using matrix isolation infrared spectroscopy and the
further ab initio computations confirmed that the experimentally
detected dimer is stabilized through the strong non-covalent phos-
phorus bonded P-p interactions [15]. Although the phosphorus
bonded P-p interaction has been recognized computationally,
experimental studies of its effect on the macroscopic thermophys-
ical properties and fluid phase equilibrium relationship are still
rare.
In summary, accurate determination of the thermodynamic
properties of binary mixtures of PCl3 and benzene would provide
not only fundamental data for their industrial reaction and separa-
tion but also useful information to extend our understanding of the
phosphorus bonded P-p interaction formed in them. In this contri-
bution, the measurements of the densities and vapor–liquid equi-
librium of PCl3-benzene binary mixtures of various compositions
and temperatures under atmospheric pressure were carefully per-
formed, as they are sensitive indicators of the behavior of mixed
liquid systems and good thermodynamic tools to explore the accu-
racy of liquid mixture theories. As expected, deviations to ideal
solution behavior have been observed and hence the obtained data
were correlated with robust thermodynamic models and further
discussions were undertaken to probe the nature of the observed
nonideality.
2. Experimental
2.1. Materials
Phosphorus trichloride (PCl3) and anhydrous benzene were pur-
chased from Zhengzhou Paini Chemicals Co. and Aladdin Co.,
respectively. The obtained anhydrous benzene was of HPLC grade
with a stated purity greater than 99.9% and was used without fur-
ther purification. The stated purity of PCl3 was greater than 98%
and it was purified by fractional distillation, in which only the frac-
tions with boiling points in between 348 and 350 K were collected
for subsequent mixture preparation. All the liquids were tightly
sealed in dark bottles and stored in dry box to prevent moisture
and air contamination.
The purity of the chemicals used in this work was further
checked by measuring their densities at different temperatures
and compared with those found in literature. The density of pure
liquid at different temperatures can serve as a good indicator of
its purity [16], because liquid density of pure component is very
sensitive to temperature and the presence of impurities. More
important, liquid density can now be measured very fast and pre-
cisely with commercial vibrating U-tube densitometer. The densi-
ties of benzene at virous temperatures have been measured
extensively and Wilhoit et al. [17] have collected and critically
evaluated the experimental density data of benzene reported in lit-
erature since 1883. The most reliable density value at 293.15 K rec-
ommended by them is 0.87899 g/cm3 while our measured one is
0.87896 g/cm3. Fig. 1 compares our measured densities for ben-
zene at various temperatures with those recommended by Wilhoit
et al. [17] and reasonably excellent agreement can be observed. For
PCl3, however, there is no such data source to refer. The density
data of PCl3 documented in CRC’ Handbook is 1.574 g/cm3 at
294.15 K [18], while our experimental value at 293.15 K is
2
Journal of Molecular Liquids 342 (2021) 117504
Fig. 1. Densities of benzene at different temperatures measured in this work
(points) and the recommended equation calculations (line) as the best fit to the
critically evaluated experimental data from literature.
1.57464 g/cm3 and those at other temperatures are listed in
Table 1.
2.2. Apparatus and procedures
2.2.1. Density measurements
The volumetric properties of the mixtures of phosphorus
trichloride (PCl3) + benzene were derived from their experimental
densities. So, a serials of binary liquid mixtures were prepared
gravimetrically based on the mole fraction of PCl3 in a mixing
chamber under N2 atmosphere to avoid their contact with air
and atmospheric moisture. The two components of desired
amounts were weighted individually on an electronic analytical
balance (AUW220D, accuracy ±0.01 mg, Shimadzu, Japan) and then
were quickly subject to adequate mixing in sealed vials. The exact
compositions of the solutions were calculated from the added mass
of each component and the uncertainty of the mole factions of the
mixtures was estimated to be better than ±0.0002. All the vials
were immediately tightly sealed after the solution sample were
syringed in so as to minimize the sample evaporation.
Density measurements were carried out right after the prepara-
tion of solutions by using an automatic vibrating U-tube densito-
meter (DMA 4500 M, Anton Paar, Austria). The detailed
experimental procedure can be referred to our previous work
[19,20]. Special care was taken to ensure that all the samples did
not contact air during the injection step and then they were kept
in a completely sealed U tube all through the subsequent density
measurement. For each measurement, the apparatus automatically
equilibrated the injected liquid sample at the pre-setting tempera-
ture with an accuracy and stability of ±0.01 K through a built-in
Peltier thermostat and then gave the density value after viscosity
correction. Each sample was measured at least three times and
the uncertainty in the density measurement was better than ±0.0
0005 g/cm3. The apparatus was periodically calibrated by ambient
dry air and ultra-pure water under atmospheric pressure according
to the protocol recommended by the producer for acquiring the
best accuracy.
2.2.2. Vapor-liquid equilibrium
The vapor–liquid equilibrium (VLE) relations of the binary mix-
ture of PCl3 and benzene were determined by measuring their
pressure, temperature and liquid composition (PTx) at equilibrium
in a flow-type ebulliometer, as PTx measurement is quicker, easier,
and more precise compared to measuring PTxy data for highly vola-
tile mixtures at low pressure [21]. The ebulliometer used in this
work is structurally the same as that used by Kato and Tanaka,
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

Table 1
Experimental densities (q) of (PCl3 (1) + benzene(2)) binary mixtures over the entire composition and temperatures (T) from 283.15 to 313.15 K at atmospheric pressure.

x1 q/(g
cm3)
283.15 K 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K
0.0000 0.88965 0.88432 0.87896 0.87361 0.86823 0.86284 0.85746
0.0499 0.92326 0.91775 0.91222 0.90667 0.90112 0.89554 0.88999
0.0999 0.95849 0.95279 0.94705 0.94131 0.93554 0.92976 0.92398
0.1499 0.99403 0.98813 0.98220 0.97625 0.97028 0.96429 0.95828
0.1999 1.03003 1.02393 1.01763 1.01164 1.00546 0.99927 0.99305
0.2498 1.06567 1.05937 1.05302 1.04665 1.04043 1.03385 1.02742
0.2997 1.10155 1.09504 1.08835 1.08191 1.07531 1.06869 1.06204
0.4000 1.17310 1.16619 1.15920 1.15220 1.14516 1.13808 1.13097
0.4994 1.24419 1.23688 1.22949 1.22204 1.21456 1.20707 1.19951
0.5999 1.31702 1.30930 1.30149 1.29364 1.28575 1.27783 1.26988
0.6997 1.38972 1.38191 1.37371 1.36548 1.35722 1.34891 1.34058
0.8004 1.46256 1.45435 1.44576 1.43718 1.42853 1.41984 1.41109
0.9000 1.53124 1.52196 1.51345 1.50449 1.49547 1.48639 1.47724
0.9494 1.56316 1.55355 1.54494 1.53577 1.52658 1.51736 1.50802
0.9696 1.57533 1.56593 1.55693 1.54766 1.53838 1.52906 1.51964
1.0000 1.59324 1.58397 1.57464 1.56520 1.55583 1.54640 1.53692


who have used such ebulliometer to successfully determine the q= g=cm3 ¼ ð0:000805x1 þ 0:001075ÞðT=K Þ þ 0:939018x1
vapor–liquid equilibrium of a number of polar systems such as
þ 1:193001
alcohols with tetrahydrofuran [22], amines [23] and alkoxides
[24] with very high accuracy. At the start of each VLE measure-
ment, around 40 cm3 liquid mixture of desired composition was 0  x1  1; 283:15  ðT=K Þ  313:15 ð1Þ
charged into the boiling flask of the ebulliometer and heated with
an electric cartridge heater. The glass heat-transfer surface was where x1 is the mole fraction of PCl3 in solution. Eq. (1) gives an
frosted to ensure a stable boiling and a drying tube containing cal- average relative deviation of only 0.13% to the 112 experimental
cium chloride was placed on the top of the condenser to prevent density data over the entire composition range and temperatures
moisture contamination. After the mixture was boiled, the current from 283.15 to 313.15 K. The deviation was found to be indepen-
of the heater was carefully adjusted to allow good and stable flash dent on temperature but randomly distributed with x1, indicating
of the vapor–liquid mixture. The boiling point was measured by a the density is more sensitive to solution composition. Fig. 2 shows
Pt-100 Type thermometer (CENTER-376, Qunte, China) with an the density data of the mixtures determined at 283.15 K
uncertainty of ±0.01 K. The exact experimental pressure were mea- covering the entire composition. The excellent q  x relationship
sured by an electronic barometer (DYM3-01, Yongzhi Instrument (linear correlation coefficient R2 = 0.9999) allows it to be an ideal
Co., China) with an uncertainty of ±0.01 kPa. Equilibrium between tool to correct the liquid compositions for the subsequent vapor–
the vapor and liquid phases was assumed to be achieved when the liquid equilibrium measurements.
flow of the condensed liquid was stabilized and the boiling point
was constant with a variation less than 0.02 K for at least
30 min. Then the composition of the liquid phase at equilibrium 3.2. Derived volumetric properties
were corrected by measuring their density at 283.15 K and the liq-
uid composition uncertainty was better than 0.001 in mole frac- The nonideality of a liquid mixture is usually characterized by
tion. As a test of the accuracy of the above apparatus and its excess thermodynamic properties [5]. Hence, the excess molar
procedure for vapor–liquid equilibrium measurement, the vapor volumes, V EM of the binary mixtures with different compositions
pressures of pure PCl3 and benzene measured by us were
100.07 kPa at 348.09 K and 99.69 kPa at 352.66 K, respectively,
while the NIST database gives very close values of 104.27 kPa at
348.5 K and 99.62 kPa at 352.32 K. Then the measurements were
performed for PCl3-benzene mixtures over the entire composition
range.

3. Results and discussion

3.1. Density of the binary mixture

The experimental densities (q) of the binary liquid mixtures of

phosphorus trichloride (PCl3) and benzene at different composi-
tions and at temperatures from 283.15 to 313.15 K under atmo-
spheric pressure are summarized in Table 1. In general, the
densities for the mixtures of certain composition always decrease
linearly with an increase of temperature, while those for the mix-
tures at certain temperature show very good linear relationship
with the mole fraction of PCl3. Hence, an attempt to generalize
the experimental density data was made by the following Fig. 2. Densities of binary mixtures of PCl3 (1) + benzene (2) at 283.15 K and the
equation, straight line is the linear regression of the experimental density data.

3
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

at certain temperature are calculated from their densities by the

following equation:

1 1 1 1
V EM ¼ x1 M 1 ð  Þ þ x2 M 2 ð  Þ ð2Þ
qM q1 qM q2
where x and M are the mole fraction and molar mass of each
component, respectively. The subscript 1, 2 and M denote PCl3,
benzene and their mixture, respectively. The calculated V EM are
summarized in Table 2 and those at 288.15 K are visually shown
in Fig. 3 against PCl3 mole fraction. Further, the dependence of VE
on solution composition is quantitatively represented by the
Redlich-Kister polynomial equation:

X
n X
n
V E ¼ x1 x 2 Ai ðx1  x2 Þi ¼ x1 ð1  x1 Þ Ai ð2x1  1Þi ð3Þ
i¼0 i¼0

where n is the degree of polynomial and Ai are the coefficients,

which were determined simultaneously by using multiple linear
regression method. Analysis of variance (ANOVA) results showed
that Eq. (3) with n = 4 could give significant enough correlations
to all the systems according to the F-test at 95% confidence level
and hence the corresponding best Ai values are summarized in
Table 3 together with the standard deviation d to characterize
the goodness of the correlations. d is defined as:
2  2 312
E E
6Xm V exp  V calc 7 force or both. The free volume and interstitial accommodation con-
d¼4 5 ð4Þ
mn
1
where m is the number of experimental points at each working
temperature, while V Eexp and V Ecalc are the experimental excess
molar volumes in Table 2 and those calculated with Eq. (3), respec-
tively. The obtained d in Table 3 are all less than 0.007 cm3
mol1
and the |d/V Emin | for all the mixtures are less than 0.01, which is con-
sistent with the precision attainable with the instrument used. The
VE curve calculated by Eq. (3) at 288.15 K is also graphically
depicted in Fig. 3, in which fairly excellent agreement has been
observed, suggesting an adequate and continuous representation
of the experimental VE data that allows the derivation of other vol-
umetric properties.
It can be seen from Fig. 3 that the V EM , with the exception at PCl3
very dilute region, is generally negative, as an indication of volume
contraction upon mixing the two components. The V EM curve is
visually asymmetric and skewed towards higher mole fraction of
PCl3. With the increase of PCl3 content in the solution,
Fig. 3. Excess molar volumes (VE) for binary mixture of PCl3 (1) + benzene (2) at
288.15 K and the curve is calculated by the Redlich-Kister polynomial equation.
more negative until PCl3 mole fraction reaches 0.8, afterwards it
increases sharply with PCl3 mole fraction though still being nega-
tive. The large and negative value of V EM in general is most likely
due to molecular packing effect, strong intermolecular attractive
tribution that tend to decrease V EM is considered to be minor as the
molar volumes of the two components are very close (87.21 and
88.87 cm3
mol1 for PCl3 and benzene respectively at 293.15 K).
On the other hand, the strong attractive P-p interaction between
the phosphorus atom of PCl3 and the electron rich p cloud of ben-
zene tends to form PCl3-benzene complex with the most stable
structure of the phosphorus atom facing towards the plane of the
benzene ring with a distance of 3.26 Å, shorter than the distance
of between the preferred T-shaped dimer of two benzene mole-
cules (4.96 Å) [25]. This P-p interaction was found to be even
stronger than the hydrogen bonding one under the same condi-
tions [15]. Besides, the three electronegative chloride atoms on
PCl3 could have Cl-p interaction with benzene ring by accepting
its p electrons. Imai [26] has shown that Cl-p interaction is attrac-
tive in nature and mainly from the dispersion force which is even
stronger than the CH-p interaction. Such Cl-p interaction would
increase the molecular deformation and tends to decrease the sys-
tem volume so that the V EM for binary mixtures of chloroform-
V EM becomes benzene [11] is much less positive than that of dichloromethane-

Table 2
Excess molar volumes (VE) of (PCl3 (1) + benzene(2)) binary mixtures over temperatures (T) from 283.15 to 313.15 K at atmospheric pressure.

x1 VE/(cm3
mol1)
283.15 K 288.15 K 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K
0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
0.0499 0.0828 0.0820 0.0805 0.0808 0.0797 0.0791 0.0759
0.0999 0.0297 0.0277 0.0256 0.0247 0.0238 0.0227 0.0217
0.1499 0.0478 0.0507 0.0538 0.0555 0.0569 0.0584 0.0579
0.1999 0.1541 0.1576 0.1471 0.1644 0.1666 0.1694 0.1704
0.2498 0.2222 0.2263 0.2297 0.2327 0.2491 0.2366 0.2377
0.2997 0.2983 0.3029 0.2952 0.3103 0.3122 0.3142 0.3152
0.4000 0.3812 0.3862 0.3880 0.3913 0.3913 0.3913 0.3893
0.4994 0.4505 0.4557 0.4574 0.4594 0.4574 0.4573 0.4533
0.5999 0.5535 0.5586 0.5615 0.5644 0.5644 0.5644 0.5634
0.6997 0.6532 0.6789 0.6834 0.6904 0.6934 0.6964 0.6994
0.8004 0.7012 0.7258 0.7317 0.7427 0.7477 0.7527 0.7567
0.9000 0.5392 0.5227 0.5533 0.5643 0.5683 0.5723 0.5743
0.9494 0.3406 0.3143 0.3475 0.3553 0.3584 0.3633 0.3639
0.9696 0.2114 0.2003 0.2144 0.2194 0.2204 0.2224 0.2214
1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

4
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

Table 3
Redlich-Kister coefficients and standard deviations for representation of the excess molar volumes of (PCl3 + benzene) binary mixtures at temperatures from 283.15 to 313.15 K.

T/K A0 (cm3
mol1) A1 (cm3
mol1) A2 (cm3
mol1) A3 (cm3
mol1) A4 (cm3
mol1) 103d (cm3
mol1)

283.15 1.8098 1.5108 3.3236 3.9031 2.7411 6.60
288.15 1.8186 1.7168 3.8793 3.4392 3.8098 5.56
293.15 1.8336 1.6832 3.6226 3.7824 3.0158 4.90
298.15 1.8405 1.6336 3.8667 3.9641 3.2397 5.92
303.15 1.8333 1.6026 4.0737 4.0477 3.4712 4.99
308.15 1.8340 1.6340 4.0514 4.0404 3.3527 6.66
313.15 1.8225 1.6553 4.1731 4.0141 3.4725 6.59

benzene [27]. Therefore, the positively cooperation of the P-p and

Cl-p interactions that are mainly originated from the electrostatic
interactions and dispersion interactions respectively, should be
responsible for the observed negative V EM . Nevertheless, we think
that the P-p interaction should be the dominant and decisive
one, as the V EM of benzene with most halogen derivatives such as
chloroform, carbon tetrachloride and chlorobenzene are all posi-
tive [28].
The positive V EM at PCl3 very dilute region should be attributed
to the break of the self-aggregation of benzene molecules that tend
to form dimers in the pure state due to the dispersion and electro-
static quadrupole–quadrupole interactions (aromatic p-p interac-
tions) [29] but the benzene dimer should bind less strongly than
the PCl3-benzene complex which is increasingly formed and lead-
ing the contraction of solution volume as the gradual addition of
PCl3. The experimental data in Table 2 also show that V EM overall
becomes more negative as the increase of temperature, however,
the impact of temperature on V EM is much less notable and the min-
Fig. 4. Excess partial molar volumes of binary mixture of PCl3 (1) + benzene (2) at
imum V EM decreases only by 7.9% from 283.15 to 313.15 K. 283.15 K.
Further, the partial molar volumes (V
i ) and the excess partial
molar volumes (V
i  V 0 ) of PCl3 and benzene in solution can

E ¼ V
i i
be estimated by applying the obtained Redlich-Kister correlations, abrupt changes of V
E at both ends suggest the occurrence of more
i
which could provide a more direct indication of composition remarkable interactions between the unlike molecules in dilute
impact on the solution volume. solutions, in which solute molecules are isolated from each other
and only surrounded by vast majority of solvent molecules and thus
E solute–solvent interactions play a central role. Therefore, by letting
V
1 E ¼ V
1  V 0 ¼ V E þ x2 dV  V 0 ¼ ð1  x1 Þ2
1
dx1 1 x1 = 0 in Eq. (5) and x1 = 1 in Eq. (6), the excess partial molar volumes
X4 X 4 at infinite dilution (V
E;1 ) of PCl3 (V
1 E;1 ¼ P4 Ai ð1Þi ) and benzene
A ð2x1  1Þi þ 2x1 ð1  x1 Þ2 i¼0 i Ai ð2x1  1Þi1
i¼0 i
ð5Þ P
i i¼0

(V
2 E;1 ¼ 4i¼0 Ai ) were estimated. The calculated V
E;1 at different

i

temperatures are plotted in Fig. 5, in which V
E;1

of PCl3 are all posi-
E i

2  V 0 ¼ V E þ x1 dV  V 0
V
2 E ¼ V tive whereas those of benzene are negative and both of them are
2 2
dx2
X4
¼ x1 2 i¼0 Ai ð2x1  1Þi  2x1 2 ð1
X4
 x1 Þ i¼0 i Ai ð2x1  1Þi1 ð6Þ

E of PCl3 and benzene in solutions of

Fig. 4 shows the calculated V i

different compositions at 283.15 K. It has been observed that the V
E

1
of PCl3 decreases very sharply from positive to negative upon its ini-
tial addition into benzene till its mole fraction reached 0.2, after-
wards it increases slowly back to zero till the end, while V
E of
2
benzene keeps almost unchanged at around zero with the increase
of PCl3 until the mole fraction of PCl3 exceeded 0.7, after which the

E of benzene decreases much more rapidly to a large negative value
V 2

around 8 cm3
mol1. The negative of V
of PCl3 at intermediate to

E
1
PCl3-rich composition region means when PCl3 was added to the
mixture, the solution’s volume increase is actually smaller than
the adding PCl3 volume, confirming the attractive P-p interaction

E , adding benzene into
with solution volume contraction. While for V 2
benzene-rich solution, this effect is much insignificant due to the Fig. 5. Excess partial molar volumes at infinite dilution of PCl3 and benzene in
antibonding p-p interactions of benzene dimers. Nevertheless, the respective binary mixtures of PCl3 + benzene at different temperatures.

5
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

independent of temperature with mean values of 3.14 and equation and excess Gibbs energy based activity coefficient equa-
7.90 cm3
mol1, respectively. The positive V
E;1 of PCl3 is likely tions are used and compared. The coexistence equation relates
1
due to the strong p-p interactions between majority benzene mole- pressure, temperature, heats of vaporization and fugacities of the
cules that tends to keep the T-shape benzene dimer structure and equilibrated two phases to satisfy the Gibbs-Duhem equation
thus counteracts the phosphorus P-p bonding interactions, which [31]. At constant pressure, the equation is given by [31]:
however is the principal interactions in solution of benzene at infi- " #
dy1 dlnðcV1 =cV2 Þ DHVap

E;1 of benzene.
nite dilution in PCl3, resulting in large negative V ¼ y1 ðy1  1Þ þ m
ð10Þ
2 dT dT ðy1  x1 ÞRT 2

3.3. Vapor-liquid equilibrium Vap

DHVap
m ¼ x1 D H 1 þ x2 DHVap
2 ð11Þ
The experimental P-T-x data of binary mixtures of PCl3 + benzene where xi and yi are the mole fractions of component i in liquid
of different compositions are summarized in Table 4. To obtain iso- and vapor phase respectively. DHVap and cVi are the molar heat of
i
baric vapor–liquid equilibrium data, the raw boiling points were
vaporization and vapor activity coefficient of component i. DHVap
corrected to those under 101.325 kPa using the following equa- i

tions [22]: at different temperatures are calculated from the empirical corre-
  lations given by Yaws [32]
dT
T cor ¼ T exp þ ð101:325  Pexp Þ ð7Þ DHVap ¼ Að1  T=T Ci Þn ð12Þ
dP P¼101:325 i

      The component-dependent constants A and n of PCl3 and ben-

dT dT dT zene are listed in Table 6 together with their critical temperatures
¼ x1 þ x2 ð8Þ
dP P¼101:325 dP 1;P¼101:325 dP 2;P¼101:325 (TCi) . Therefore, the dew point curve of y1  T can be obtained by
numerical integration of Eq. (10), provided the ratio of cVi can be
The dependence of pure components’ bubble point on pressure

 properly estimated. Further, the truncated virial equation of state
at 101.325 kPa, dT
dP i;P¼101:325
, were estimated from the well estab-
was used to estimate the vapor activity coefficient term in Eq. (10):
lished Antoine equation:
cV1 d12 Pð1  2y1 Þ
B ln ¼ ð13Þ
log10 ðP=kPaÞ ¼ A  ð9Þ cV2 RT
T=K þ C
in which A, B and C are the Antoine constants that should be fit- d12 ¼ 2B12  B11  B22 ð14Þ
ted to the experimental vapor pressure data for specific compo-
The second virial coefficients of Bij are only functions of temper-
nent. The Antoine constants for PCl3 were fit to the experimental
ature, and that of pure benzene, B22 were correlated from the
vapor pressure data stored in NIST database while those for ben-
experimental data given by Bottom and Spurli [33], while that of
zene were directly taken from the handbook edited by Dykyj
PCl3 B11 and the cross virial coefficients of B12 were calculated from
et al. [30]. These parameters are summarized in Table 5. Fig. 6
the correlations developed by Tarakad and Danner [34] who pro-
shows the experimental and calculated vapor pressures of PCl3
vided size-shape and polar corrections to the Pitzer-Tsonopoulos’
and benzene, and it suggests that relative volatility between them
general second virial coefficient correlation for non-polar com-
are rather small at around atmospheric pressure. Then, the cor-
pounds [35]. To simplify the subsequent differential calculation,
rected boiling points under 101.325 kPa can be calculated by Eqs.
the calculated d12 (cm3/mol) by Eq. (14) were correlated as a
(7) and (8) and they are listed in Table 4.
dlnðcV1 =cV2 Þ
To determine the composition of the equilibrated vapor phase three-order polynomial function of temperature so that dT
that is difficult to measure accurately, two methods of coexistence in Eq. (10) can be readily estimated.

Table 4
Experimental boiling-point data of (PCl3(1) + benzene (2)) a binary mixtures and the estimated vapor composition by the coexistence equation (Eq. (10)), Wilson and NRTL model.

x1 Texp/(K) Pexp/(kPa) Tcor/(K) ycal

1

Eq. (10) Wilson NRTL

0.000 352.66 99.69 353.18 0.000 0.000 0.000
0.085 352.13 99.70 352.65 0.094 0.102 0.102
0.129 351.82 99.71 352.34 0.149 0.151 0.152
0.153 351.76 100.02 352.18 0.176 0.177 0.178
0.160 351.66 100.01 352.08 0.194 0.184 0.185
0.192 351.56 100.51 351.82 0.239 0.218 0.219
0.233 351.38 100.51 351.64 0.270 0.261 0.263
0.277 351.16 100.52 351.42 0.308 0.308 0.309
0.325 350.80 100.51 351.06 0.372 0.356 0.356
0.397 350.60 100.74 350.79 0.422 0.431 0.430
0.475 350.27 100.85 350.42 0.493 0.511 0.510
0.551 349.93 100.91 350.06 0.568 0.588 0.586
0.591 349.77 101.31 349.77 0.633 0.625 0.623
0.647 349.49 101.05 349.58 0.677 0.683 0.681
0.673 349.45 101.31 349.45 0.709 0.708 0.706
0.706 348.97 100.12 349.35 0.735 0.741 0.739
0.790 348.71 100.17 349.08 0.807 0.824 0.823
0.889 348.36 100.19 348.72 0.911 0.919 0.919
1.000 348.09 100.07 348.49 1.000 1.000 1.000

a: x1 is the liquid mole fraction of PCl3; Texp is the experimental boiling point and Pexp is the experimental atmospheric pressure; Tcor is the boiling points corrected to
101.325 kPa. ycal
1 is the mole fraction of PCl3 in the equilibrated vapor phase as evaluated from the three models.

6
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

Table 5
The Antoine constants of PCl3 and benzene used in Eq. (9).

Chemical A B C T range (dT/dP)|p=101.325

a
PCl3 6.70537 1632.930 0.119 340–440 0.31689
b
Benzene 5.98523 1184.236 55.623 278–376 0.32051

a: The constants were obtained by fitting Eq. (9) to the experimental vapor pressure data stored in NIST database;
b: The constants were directly taken from ref. [30]

Fig.6. Vapor pressure of PCl3 and benzene at different temperatures. The points are
literature data stored in NIST database while the curves are calculated by the Fig. 7. Experimental boiling point curve of PCl3-benzene at 101.325 kPa and the
Antoine equation (Eq. (7)). calculated dew point curves with the coexistence equation (solid), Wilson model
(dashed) and NRTL model (dotted).

d12 ¼ 1:3309  104 T 3  0:1482T 2 þ 54:86T  6775:93 ð15Þ By doing this, the vapor composition yi can be determined
simultaneously because of the composition summation constraint
Hence, the vapor composition y1 at given temperature T can be P
of yi ¼ 1. This method finds wide and very successful applica-
obtained straightforward by numerical integration of Eq. (10) using
tions in correlation of VLE data but it should be undertaken in a
the fourth-order Runge-Kutta method in descending temperature
regression way because most activity coefficient models contain
sequence. As shown by Barrier and Adler [31], the accuracy of y1
system-dependent unknown model parameters [36]. The Wilson
estimated by the coexistence equation method is generally better
and NRTL(Non-Random Two Liquid) models are among the most
than 0.01 with maximum deviation of 0.02 for five binary systems
commonly used activity coefficient models due to their high accu-
of polar compounds including benzene, ammonia and acetone. The
racy, fair simplicity, and good extensibility. The Wilson Equation is
calculated vapor compositions of PCl3, y1 at each experimental
given as [36]:
point are listed in Table 4 and the entire y1  T curve is plotted !
in Fig. 7. It can be seen that, although no azeotrope has been found X X x K
lnci ¼ ln xj Kij þ1 P m mi ð17Þ
j¼1 xj Kmj
for this binary mixture computationally, the saturated vapor and
j¼1 m¼1
liquid boundaries are quite close especially at the two ends, sug-
gesting an infeasible complete separation of them by conventional 
Vj Dkij
distillation. Kij ¼ exp  ð18Þ
Vi RT
The activity coefficient equation method, on the other hand,
employs a composition dependent model to describe the liquid- in which Vi is the molar volume of pure component i and Dkij are
phase activity coefficients cLi and regulates the model parameters the two unknown binary energy parameters to be determined. The
to best fit the experimental equilibrium properties such as pres- expression of the NRTL model is [36]:
sure or temperature under the phase-equilibrium criteria of Eq. P  P 
s
j¼1 ji xj Gji
X xj Gij m¼1 xm smj Gmj
(16): lnci ¼ P þ P sij  P ð19Þ

 m¼1 xm Gmi j¼1 m¼1 xm Gmj m¼1 xm Gmj
V i P  Psi
xi cLi Psi /si exp ¼ P/Vi yi ð16Þ
RT Dg ji
sji ¼ ð20Þ
RT

Table 6
Critical constants and acentric factor of PCl3 and benzene and the constants used in Eq. (12)

Chemical TC/K PC/Mpa VC/(cm3/mol) x A n

PCl3 563.15 5.670 260 0.2344 45.9178 0.4229
Benzene 562.05 4.895 256 0.210 43.7047 0.3747

7
B. Long, J. Song, K. Yao et al.
Gji ¼ exp asji
where a is an empirical parameter relevant to the non-
randomness of system and was set as a constant of 0.3 in this work,
and Dgij are the unknown binary energy parameters. In this work,
/si , the fugacity coefficient of pure component i under its saturated
pressure Psi
and that in mixed gas phase /Vi
in Eq. (16) were also
estimated by the truncated virial equation of state
Bii
ln/si ¼
RT
PðBii þ y2j d12 Þ
ln/Vi ¼
RT
and Psi and Vi at each experimental temperature T was calcu-
lated by Eq. (9) and the modified Rackett equation [32], respec-
tively. Therefore, the calculated equilibrium pressure and vapor
composition should satisfy Eq. (16) and the constrain of
y1 + y2 = 1 at the same time. Further, the energy parameters of
the Wilson and NRTL models were optimized to best fit the calcu-
lated pressure to the experimental one at each experimental tem-
perature using the Levenberg–Marquardt method [37]. The
obtained Dk12 and Dk21 of the Wilson model are 3210.89 and
2066.71 J/mol respectively with an average relative deviation
(ARD) of the calculated equilibrium pressure from the experimen-
tal ones of 0.31%, while the best Dg12 and Dg21 of the NRTL model
are 3565.36 and 4753.75 J/mol respectively with a slightly lower
ARD of 0.27%. The relative residual distributions of the calculated
equilibrium pressure by the two models are shown in Fig. 8, which
can be a good alternative reliability test for VLE data without mea-
sured vapor composition [21]. It can be seen that most relative
residual values of the two models are less than ±0.5% without sys-
tematic errors except for the data for solutions of very high PCl3
content, where the experimental uncertainties in T and x were
higher due to the high volatility of PCl3. But they still do not exceed
1.5% even when the mole fraction of PCl3 was above 0.9. Moreover,
the calculated vapor composition y1 at each experimental temper-
ature by the Wilson and NRTL models are listed in Table 4 and the
entire y1  T curves are also plotted in Fig. 7 for comparison.
Though different procedures were taken to derive y1, the disparity
between the three models is actually quite minor, confirming their
quite good consistency. Nonetheless, due to the nature of regres-
Fig. 8. Calculated equilibrium pressure residual distribution over the entire
composition of PCl3-benzene mixture by the Wilson and NRTL activity coefficient
models.
Journal of Molecular Liquids 342 (2021) 117504
ð21Þ sion, the y1 given by the two activity coefficient models are a little
bit lower than that given by the coexistence equation at benzene-
rich region, while slightly higher at PCl3-rich region.
4. Conclusions
Experimental determinations and theoretical modeling of volu-
metric properties and vapor–liquid equilibrium at atmospheric
pressure were performed for the binary mixture of PCl3 and ben-
zene over the entire composition range. The obtained density data
ð22Þ
of the binary mixture at constant temperature showed excellent
linear relationship with the PCl3 mole fraction which allows the
mixture density as a good tool to predict solution composition.
The densities of the binary mixture at certain composition also
ð23Þ decrease with the increase of temperature in a perfect linear
way. So, a generalized empirical correlation for the mixture density
from 283.15 to 313.15 K and over the entire composition is pro-
posed which is simple and accurate enough for quick and reliable
engineering calculations with an average relative deviation of only
0.13%. Excess volumes of the binary mixture calculated from the
measured density data were negative for solutions of PCl3 mole
fraction from around 0.2 to 1 as a result of dominant strong attrac-
tive P-p interaction between the phosphorus atom of PCl3 and the
electron rich p cloud of benzene, whereas the excess volumes are
small positives for solutions of PCl3 mole fraction from 0 to around
0.2, which is considered as the strong p-p interactions of benzene
dimer to counteract the phosphorus P-p bonding interactions. The
P-p bonding and p-p antibonding effects were further confirmed
by the estimation of excess partial molar volumes of PCl3 and ben-
zene at infinite dilution, which are found to be positive and nega-
tive respectively and both are independent of temperature.
Ebulliometric measurements of PTx data for PCl3-benzene sys-
tem were carefully performed over the entire composition range.
Two methods of coexistence equation and activity coefficient are
applied to estimate the vapor composition at equilibrium. Two
activity coefficient models of Wilson and NRTL equations were
used and the respective model parameters were optimized to best
fit the experimental vapor pressure data. Pressure residual distri-
bution diagrams showed that the measurements have no signifi-
cant systematic errors. Albeit the two methods are
computationally in distinctive integration and regression modes,
they gave very close results. Although no azeotrope has been found
for this binary mixture, the two-phase area in the vapor–liquid
phase diagram is very narrow due to the strong attractive P-p
interaction, suggesting their full separation by conventional distil-
lation is practically infeasible.
CRediT authorship contribution statement
Bingwen Long: Conceptualization, Formal analysis, Writing –
original draft, Writing – review & editing, Supervision. : . Jiapo
Song: Investigation, Formal analysis, Resources, Visualization.
Keke Yao: Investigation, Formal analysis, Visualization. Yigang
Ding: Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
Financial supports from National Natural Science Foundation of
China (No. 22078250) are gratefully acknowledged.
8
B. Long, J. Song, K. Yao et al. Journal of Molecular Liquids 342 (2021) 117504

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