Determination and correlation of solubility of tris(3-hydroxypropyl) phosphine oxide in selected solvents

Article abstract of DOI:10.1021/je301029j

The solubility of tris(3-hydroxypropyl)phosphine oxide (THPPO) in selected solvents was measured by a static analytic method over the temperature range from (293 to 328) K in methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, acetone, and a binary solvent mixture of ethanol + acetone. Several widely used thermodynamic models, such as the empirical equation and the Buchowski-Ksiazaczak (λh), Scatchard-Hildebrand, Wilson, nonrandom two-liquid (NRTL), and universal quasichemical (UNIQUAC) equations were applied to represent the measurement results. The binary interaction parameters of the above models were found to have a linear dependency on temperature, and the coefficients were regressed. The results show that all of these models can satisfactorily reproduce the experimental data and the NRTL equation can provide the best correlation with an overall relative standard deviation of 0.46 %.

Full text of DOI:10.1021/je301029j

Article
pubs.acs.org/jced
Determination and Correlation of Solubility of Tris(3-
hydroxypropyl)phosphine Oxide in Selected Solvents
†
,†
†,‡
†
Xian-Zhao Shao, Li-Sheng Wang,* Guo-Qing Yan, and Guo-Min Yu
†School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, People’s Republic of China
‡China Aviation Lithium Battery Co., Ltd., Luoyang 471009, People’s Republic of China
*
S Supporting Information
ABSTRACT: The solubility of tris(3-hydroxypropyl)phosphine oxide (THPPO) in selected solvents was measured by a static
analytic method over the temperature range from (293 to 328) K in methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-
butyl alcohol, isobutyl alcohol, acetone, and a binary solvent mixture of ethanol + acetone. Several widely used thermodynamic
models, such as the empirical equation and the Buchowski−Ksiazaczak (λh), Scatchard−Hildebrand, Wilson, nonrandom two-
liquid (NRTL), and universal quasichemical (UNIQUAC) equations were applied to represent the measurement results. The
binary interaction parameters of the above models were found to have a linear dependency on temperature, and the coefficients
were regressed. The results show that all of these models can satisfactorily reproduce the experimental data and the NRTL
equation can provide the best correlation with an overall relative standard deviation of 0.46 %.
INTRODUCTION
■
Engineering plastics are an important class of polymeric
materials which are widely used in both industry and daily
life, such as construction, automobiles, electrical/electronic, and
biomaterials. Generally, those compositions are organic and,
thus, easily ignitable in a fire situation. Their great uses have
been limited by the flammability. Thus, their manufacturers are
majorly concerned with rendering their products flame
retardant. Many kinds of commercial flame retardants (FRs)
are widely used to produce high-performance flame retardancy
Figure 1. Structures of the tris(3-hydroxypropyl)phosphine oxide
(THPPO).
1
polyester. The designed component centers on organo-
compositions with high thermal stability and excellent fire
5
phosphorus compounds, containing PO bonds, which have
retardancy. The merits that may be attributed to the THPPO
flame retardant include no corrosion, high ultraviolet stability,
nontoxicity, and minimal adverse change in the overall
properties of the polymer. It becomes a widely used reactive
been shown to be excellent flame retardants in the polymer
2
industry. Furthermore, phosphorus compounds have been
proved to be more environmentally benign compared to their
4
,6
7
3
flame retardant for polyurethanes,
poly(phenylene ether)-styrene.
epoxy resins, and
halogenated analogues.
8
Among these phosphorus flame retardants, tris(3-
hydroxypropyl)phosphine oxide (THPPO, chemical structure
as shown in Figure 1, CAS No. 51805-42-6) has been
Received: September 19, 2012
Accepted: February 12, 2013
Published: February 20, 2013
4
commercially applied in polymerization. It has been found
that THPPO is more compatible in polyphenylene oxide
©
2013 American Chemical Society
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Journal of Chemical & Engineering Data
Article
Table 1. Description of the Solute and Solvents Used in This Paper
chemical name
source
synthesized
initial mass fraction purity
water content (%)
purification method
analysis method
a
THPPO
0.986
0.995
0.995
0.995
0.995
0.994
0.995
0.995
0
recrystallization
none
HPLC
b
methanol
Beijing Chemical Factory
Beijing Chemical Factory
Beijing Chemical Factory
Beijing Chemical Factory
Beijing Chemical Factory
Beijing Chemical Factory
0.1
0.3
0.2
0.2
0.1
0.1
0.3
GC
b
ethanol
none
GC
b
n-propyl alcohol
isopropyl alcohol
n-butyl alcohol
isobutyl alcohol
acetone
none
GC
b
none
GC
b
none
GC
b
none
GC
b
Beijing Chemical Factory
none
GC
a
b
High-performance liquid chromatography. Gas−liquid chromatography.
The solubilities of THPPO in the single and mixed solvents
not only are helpful for the fundamental data for the products’
which is capable of maintaining the temperature within ± 0.05
K. The temperature of the inner chamber of the vessel was
measured by a calibrated mercury-in-glass thermometer
(uncertainty of ± 0.05 K). The mass of the sample was
weighed using an analytical balance with a precision of ± 0.1
mg (type FA2104B, Shanghai Yueping Scientific Instrument
Co.).
characteristics such as crystal size distribution, crystal habits,
9
purity, and yields, but also supply the fundamental data for the
modeling of solubility and understanding of interactions
between THPPO and various solvents. In the industrial
purification process, THPPO is usually crystallized with
10
isopropyl alcohol. In this study, we reported a new and
efficient method to purify the THPPO. To obtain more
systematic and useful thermodynamic information on the
crystallization of THPPO from some organic solvents, the
solubility of THPPO in the seven selected organic solvents was
measured in this study cover the temperature range from (293
to 328) K. Moreover, the solubility of THPPO in mixed
solvents ethanol + acetone were investigated with different
For each measurement, an excess mass of THPPO was added
to a known mass of the solvent. Then the equilibrium cell was
heated to a constant temperature with continuous stirring. After
at least 2 h, the stirring was stopped, and the solution was kept
still until it was clear. A preheated on−off injector with a cotton
filter withdrew 2 mL of the clear upper portion of the solution
to another previously weighed measuring vial. The vial was
quickly and tightly closed and weighed to determine the mass
of the sample. Then the vial was uncovered with a piece of filter
paper to prevent dust contamination. After the solvent in the
vial had completely evaporated, the vial was dried and
reweighed to determine the mass of the constant residue solid.
Each experimental data point was repeated three times, and
the mean value of them was chosen as solubility. The mole
fraction solubility of the THPPO in solvents was calculated as
follows:
1
1
solvent compositions. The Buchowski−Ksiazaczak (λh),
1
2
13
Scatchard−Hildebrand, Wilson, nonrandom two-liquid
1
4
15
(
NRTL), and UNIQUAC model were applied to represent
the solubility data. Comparison and discussion of the solubility
and the capability of the models were carried out.
EXPERIMENTAL SECTION
■
Materials. Tris(3-hydroxypropyl)phosphine (THPP, CAS
No. 4706-17-6, a 30 % aqueous solution) was kindly provided
by TianJin LianKuan Fine Chemicals Co., China. Hydrogen
peroxide solution (30 %) was purchased from the Weisi
Chemical Reagents Co., Beijing, China. Table 1 shows the
description of solute and solvents used in this paper, including
THPPO, methanol, ethanol, n-propyl alcohol, isopropyl
alcohol, n-butyl alcohol, isobutyl alcohol, and acetone.
m /M
1
1
x =
m /M + m /M
(1)
1
1
1
2
where m and m represent the mass of the solute and solvent,
1
2
and M and M are the molecular weights of the solute and
1
2
solvent, correspondingly.
Synthesis and Characterization of THPPO. The THPP
solution is oxidized by stirring with the dropwise solution of a
30 % hydrogen peroxide. When the temperature decreases,
adding 1 mL of carbon disulfide into the solution of phosphine
oxide until no red coloration can be detected visually in the
carbon disulfide layer. Following oxidation with hydrogen
peroxide, the solvents are removed by heating to 80 °C under
vacuum. The crude product was stored at room temperature for
a few days, and the hard solid crystal product was formed.
Recrystallization of 200 g of this product mixture from acetone
+ ethanol (300 mL 2:1 v/v) gave 96 g of THPPO, which is a
Apparatus and Procedure. Several instruments were used
to characterize the properties of THPPO. A differential
scanning calorimeter (DSC) Q100 (TA Instruments) was
used to determinate the melting point and enthalpy of fusion
−1
with a constant heating rate of 10 °C·min in the range from
(
298.15 to 415.15) K, under a high pure nitrogen dynamic
−1
atmosphere at 25 mL·min . The uncertainty and calibration of
DSC instrument is similar to the literature. An Elementar
Vario EL element analyzer was used to perform the elemental
16
1
analysis. A Bruker ARX-400 was used to obtain H nuclear
magnetic resonance (NMR) spectra with DMSO-d as a
solvent. P NMR spectra were obtained by using a JEOL ECA-
white solid.
6
31
1
H NMR (DMSO-d ): δ (ppm): 1.521.69 (m, 12H,
6
6
00 with D O as a solvent. Thermogravimetric analysis (TGA)
PCH CH ), 3.47 (t, 6H, CH OH), 4.69 (s, 3H, OH). The
2
2
2
2
1
was performed using a TA Instrument SDT Q600 thermal
result matches well with the H NMR spectra reported by
Moiseev et al.
agrees with the literature data.
calcd): C, 48.29 % (48.21 %); H, 9.36 % (9.44 %). It shows a
high purity of the THPPO sample. The DSC and TGA results
are given in Figures 2 and 3. The melting point of THPPO was
characterized at 387.76 K (ref 10, 382.15 K), and the
−1
18 31
analyzer at a heating rate of 10 °C·min in the range from
P NMR (D O-d ): δ = 60.91 ppm, which
2 6
10,18
−
1
(
300 to 850) K, under high pure N flow at 100 mL·min .
Elemental analysis (%,
2
The procedure of the measurement was described specifically
in ref 17. A jacketed equilibrium cell was used for the solubility
measurement with a working volume of 120 mL and a magnetic
stirrer, and a circulating water bath was used with a thermostat,
5
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Table 2. Mole Fraction Solubilities (x) and Activity
Coefficients (γ) of THPPO in the Selected Solvents (0.1
a
MPa)
solvent
methanol
T/K
x
γ
(x − xcalcd, eq 2)/x
298.11
0.05267
0.07018
0.09102
0.11501
0.14427
0.17565
0.20979
0.02262
0.02858
0.03605
0.04556
0.05687
0.07185
0.09188
0.03690
0.04383
0.05171
0.06198
0.07312
0.08659
0.10249
0.01552
0.01870
0.02243
0.02704
0.03210
0.03865
0.04653
0.01099
0.01377
0.01632
0.02003
0.02524
0.03025
0.03695
0.01224
0.01535
0.01895
0.02337
0.02908
0.03571
0.04364
0.00070
0.00101
0.00151
0.00217
0.00303
0.00425
0.00593
0.7804
0.7368
0.7090
0.6921
0.6817
0.6818
0.6923
1.8180
1.8150
1.7894
1.7472
1.7195
1.6647
1.5837
1.1165
1.1777
1.2453
1.2854
1.3418
1.3868
1.4208
2.6510
2.7727
2.8734
2.9525
3.0601
3.0947
3.1296
3.7437
3.7653
3.9424
3.9859
3.8855
3.9525
3.9485
2.6537
2.6903
2.7263
2.7579
2.7454
2.7452
2.7538
46.490
40.755
34.260
29.778
26.349
23.047
20.202
−0.0327
0.0029
3
3
3
3
3
3
03.15
08.18
13.10
18.22
23.14
28.11
0.0201
0.0241
0.0191
0.0001
−0.0336
0.0201
ethanol
298.12
303.22
308.17
313.10
318.08
−0.0027
−0.0116
−0.0010
−0.0158
−0.0046
0.0246
Figure 2. Experimental heat Q flow from DSC measurement of
THPPO.
323.11
328.16
298.16
n-propyl alcohol
isopropyl alcohol
n-butyl alcohol
isobutyl alcohol
acetone
0.0112
3
3
3
3
3
3
03.11
08.13
13.12
18.16
23.21
28.18
0.0010
−0.0126
−0.0036
−0.0067
−0.0010
0.0116
298.13
0.0131
3
3
3
3
3
3
03.21
08.15
13.17
18.19
23.11
28.18
−0.0010
−0.0077
−0.0063
−0.0144
0.0006
0.0156
298.13
0.0108
3
3
3
03.21
08.11
13.17
0.0147
−0.0223
−0.0243
0.0098
Figure 3. TGA thermograms of THPPO under N2.
318.15
3
3
23.1
0.0010
28.23
0.0103
293.11
0.0086
uncertainty of the melting point measurement is 0.26 K. The
2
3
3
3
3
3
98.21
03.13
08.15
13.17
18.14
23.23
0.0012
−1
enthalpy of fusion of THPPO was 34.21 kJ·mol , and the
relative uncertainty of the enthalpy of fusion is 0.25 %. From
Figure 3, the THPPO has good thermal stability before the
initial decomposition temperature (480.2 K).
−0.0062
−0.0119
−0.0017
0.0039
0.0061
RESULTS AND DISCUSSION
■
293.15
0.0036
Results and Analysis. The mole fraction solubilities of
THPPO in seven organic solvents, methanol, ethanol, n-propyl
alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and
acetone against temperatures are listed in Table 2, which are
also plotted as ln x versus 1/T in Figure 4, and THPPO in
ethanol + acetone binary mixed solvents in Table 3. It can be
found from Figure 4 that the solubility data increase with the
temperature in all selected solvents. The solubility of THPPO
in the seven selected solvents decrease in the order at constant
temperature: methanol > n-propyl alcohol > ethanol > isobutyl
alcohol > isopropyl alcohol > n-butyl alcohol > acetone. The
solubility of THPPO are different in different solvents, which
was probably contribution to the theory of “like dissolves
2
3
3
3
3
3
98.14
03.16
08.21
13.17
18.12
23.15
−0.0157
0.0111
0.0085
−0.0050
−0.0025
−5.50·10
−5
a
The standard uncertainty u is u(T) = 0.01 K; the relative standard
uncertainty u is u (x) = 0.02.
r
ln x = A + B/(T/K)
(2)
where A and B are model parameters. The values of A and B for
each solvent together with the relative standard deviations
1
9−21
like”
and the certain polarity of THPPO.
(
RSD) are presented in Table 4. The RSD was calculated as
The solubility data were fitted with a temperature depend-
ency expression:
follows:
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Journal of Chemical & Engineering Data
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Table 4. Parameters of eq 2 and Relative Standard Deviation
(
RSD) of THPPO in the Selected Solvents
solvent
methanol
A
B
RSD/%
12.215
11.454
7.8530
7.7849
8.7061
9.2576
15.787
−4509.2
−4550.3
−3328.6
−3566.7
−3943.6
−4006.6
−6758.6
2.25
1.47
0.83
1.02
1.52
0.66
0.83
ethanol
n-propyl alcohol
isopropyl alcohol
n-butyl alcohol
isobutyl alcohol
acetone
Table 5. Regressed Parameters and the Relative Standard
Deviation (RSD) of the λh Equation for THPPO in Ethanol
(
x ) + Acetone (x ) Mixed Solvents
2 3
mixed solvents
λ
h
RSD/%
x2 = 0.7998
x2 = 0.5979
x2 = 0.3986
x2 = 0.2075
0.6994
0.2392
0.2157
0.0530
7118.91
16855.36
24325.64
80551.33
2.02
3.22
4.42
3.81
Figure 4. Mole fraction solubilities of THPPO in selected solvents.
Experimental data: ●, methanol; ■, ethanol; ▲, n-propyl alcohol; ☆,
isobutyl alcohol; ◆, n-butyl alcohol; △, isopropyl alcohol; ▼, acetone;
, solubility curve calculated from eq 2.
Table 3. Mole Fraction Solubilities (x) of THPPO in
a
Ethanol (x ) + Acetone (x ) (0.1 MPa)
2
3
x /(x + x )
T/K
x
(x − xcalcd,eq5)/x
2
2
3
0
0
0
0
.7998
298.15
0.01518
0.01888
0.02565
0.03407
0.04289
0.05465
0.0112
0.0223
−0.0374
0.0006
303.15
308.15
313.15
318.15
323.15
0.0230
−0.0004
−0.0054
0.0292
.5979
.3986
.2075
298.15
303.15
308.15
313.15
318.15
323.15
0.01388
0.01655
0.02073
0.02642
0.03476
0.00400
0.00475
0.00640
0.00914
0.01202
0.01508
0.00212
0.00254
0.00312
0.00402
0.00517
0.00692
0.0124
−0.0387
−0.0351
−0.0097
0.0488
298.15
0.0638
Figure 5. Mole fraction solubilities of THPPO in binary ethanol (x ) +
2
303.15
308.15
313.15
318.15
323.15
−0.0587
−0.0468
0.0306
acetone (x ) solvent mixtures: Experimental data: ■, x = 0.7998; ●,
3
2
x = 0.5979; ▲, x = 0.3986; ▼, x = 0.2075. , solubility curve
2
2
2
calculated by the λh equation.
0.0314
−0.0089
0.0535
Table 6. Solubility Parameter (δ), Molar Volume (V),
UNIQUAC Volume Parameter (r), and Surface Parameter
298.15
303.15
308.15
313.15
318.15
323.15
−0.0101
−0.0457
−0.0274
−0.0075
0.0533
(
q) of the Selected Solvents and THPPO
6
δ
i
10 V
i
(J·cm−3)1/2
3
−1
solvent
methanol
m ·mol
r
q
29.52
26.42
24.56
23.58
23.29
23.75
19.77
27.48
40.70
58.52
74.94
76.78
91.94
93.03
73.93
193.7
1.4311
2.5755
3.2499
3.2491
3.9243
3.9235
2.5735
10.351
1.432
2.588
3.128
3.124
3.668
3.664
2.336
9.693
a
The standard uncertainty u is u(T) = 0.01 K; the relative standard
uncertainty u is u (x) = 0.02.
ethanol
r
n-propyl alcohol
isopropyl alcohol
n-butyl alcohol
isobutyl alcohol
acetone
1
/2
2
⎡
⎢
N
⎤
⎛
⎝
exp
calc
− xi
exp
xi
⎞
⎠
1
N
xi
⎥
RSD =
∑
⎜
⎜
⎟
⎟
⎢
⎣
⎥
i=1
⎦
(3)
THPPO
where N is the number of experimental data points and xexp and
i
x ci alc stand for the experimental data and calculated values,
respectively. It can be seen from Table 4, eq 2 can be used to
regress the experimental date of THPPO in seven pure
solvents.
The equilibrium solubility for nonelectrolyte solute is often
described by the following rigorous thermodynamics equa-
22
tion:
6
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Journal of Chemical & Engineering Data
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Figure 6. Residual function Y for THPPO versus solvent solubility
parameters δsolvent. ■, acetone; □, n-butyl alcohol; ●, isobutyl alcohol;
○

, isopropyl alcohol; ▲, n-propyl alcohol; △, ethanol; ◆, methanol;
, regression line.
−3 1/2
Table 7. Solubility Parameter δ (J·cm ) of the THPPO
T/K
δ from intercept
δ from slope
R2
a
2
98.15
03.15
08.15
13.15
18.15
23.15
27.25
27.29
27.34
27.43
27.57
27.79
27.29
27.32
27.39
27.49
27.65
27.90
0.9980
0.9976
0.9970
0.9962
0.9950
0.9932
3
3
3
3
3
aR2 = correlation coefficient.
1
Δ H ⎛T
⎞
⎟
fus
m
ln
=
⎜
⎝
− 1
⎠
x γ
RT
T
1
1
m
(4)
With the experimental x , T, Δ H, and T values, the activity
1
fus
m
coefficients of THPPO in solid−liquid equilibrium are obtained
and presented in Table 2.
The measured solubilities of THPPO in ethanol + acetone
binary mixed solvents were presented in Table 3. The
Buchowski−Ksiazaczak λh equation is a well-known two-
11
parameter model, as first proposed by Buchowski et al. For
most solid−liquid equilibrium systems, it can be used to
23−26
describe the SLE relations very well.
In our study, the λh
equation was used to correlate the experimental data of
THPPO in ethanol + acetone:
⎡
⎤
⎛
⎞
⎟
λ(1 − x1)
1
⎝T
1
ln⎢1 +
⎣
⎥ = λh⎜
−
x1
⎦
T ⎠
m
(5)
where Tm is the melting point of the THPPO. λ and h are
model parameters which could be obtained from the
experimental data by nonlinear regression.
The optimized parameters λ and h for THPPO in ethanol +
acetone binary solvent mixtures are summarized in Table 5
together with the RSD values. The experimental data can be
regressed by the λh equation with an average RSD of 3.34 %
and in each case no less than 5 % (Table 5). From Figure 5, it
can be seen that the λh equation can be well reproduced the
solubility data. The solubility of THPPO in ethanol + acetone
binary mixed solvents decreases with the raise of acetone
composition at constant temperature.
6
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Journal of Chemical & Engineering Data
Article
From Tables 2 and 3, for x = 0.7998, the binary mixed
The experimental activity coefficient obtained from Table 2.
The eq 9 was minimized by Levenberg−Marquardt method.
Table 8 lists the optimized parameter values for each model and
the comparison of the correlation results in terms of overall
relative standard deviation. It can be seen that all of the models
can reproduce the experimental results well with the optimized
parameters. The Scatchard−Hildebrand equation also gives
comparable correlation results (RSD % = 1.35) with the local
composition models. The smaller b values for the UNIQUAC
equation imply that its binary interaction parameters are less
sensitive to temperature than other two local composition
models. The comparison of the correlated results by different
models in terms of overall relative standard deviation is
Scatchard−Hildebrand 1.35 %, Wilson 0.53 %, NRTL 0.46 %,
and UNIQUAC 0.48 %, respectively. The NRTL model gives
the best correlation results in terms of overall relative standard
deviation.
2
solvents have higher solubilities than isopropyl alcohol when
the temperature is more than 308 K, but have nearly the same
when the temperature decreases to 303 K. This result indicates
the new method mentioned above of purified THPPO is more
efficient than previously.
Correlation with Scatchard−Hildebrand Model. Ac-
12
cording to Scatchard−Hildebrand theory, the regular-solution
equation can be expressed as follows:
2
2
2
RT ln γ = Vϕ (δ − δ )
1
1
2
(6)
1
Transforming eq 6 for a residual function Y yields:
RT ln γ
1
2
2
2
1
Y =
− δ = −2δ δ + δ
2
2
2 1
V1ϕ
(7)
With the activity coefficients listed in Table 1, the solubility
27
parameter of the solvents obtained from the literature, and
the molar volume of the subcooled liquid for THPPO (using
ACD/Laboratories Software V11.02; the value is 193.7
CONCLUSIONS
■
In this work, we have synthesized and purified THPPO by a
new and efficient method. The solubility data of THPPO in
seven organic solvents and ethanol + acetone binary mixed
solvents were determinated by a static analytic method, and the
results were compared. The experimental results show that
THPPO has the higher solubility in methanol and lower value
in acetone. The solubility data of THPPO in all solvents
increases with the temperature, and the solubilities in acetone
show the strongest dependency on temperature. The measured
solubility data were correlated by the λh, Scatchard−
Hildebrand, Wilson, NRTL, and UNIQUAC equations. All of
the models are capable of giving satisfactory correlations with
optimized parameters. The solubility parameter of THPPO was
calculated by the Scatchard−Hildebrand model. The NRTL
model gives the best overall correlation results with an overall
relative standard deviation of 0.46 %.
3
−1
cm ·mol ), the value of the solute solubility parameter δ
1
can be determined by the slope of this line (see Table 6). The
linear dependence between Y and δ at 303.15 K is displayed in
2
Figure 6. Values of solubility parameter of THPPO from
298.15 to 323.15) K given in Table 7 indicate that δ1
approaches to a constant in the considered temperature
(
range. The average value of THPPO solubility parameter δ
1
−3 1/2
is 27.48 (J·cm ) .
Correlation with Wilson, NRTL, and UNIQUAC Models.
1
3
14
15
The Wilson, NRTL, and UNIQUAC activity coefficient
models are employed in this study to correlate the experimental
data through eq 4. These models have been successfully used to
correlate the solid−liquid equilibrium properties for many
28−30
nonideal solutions over wide temperature ranges.
Physical
properties of pure components that are required in the
modeling work are obtained from the literature.
The parameters r and q are the UNIQUAC volume
parameter and surface parameter of pure component, which
can be calculated from the procedure described earlier. A new
group, PO, was introduced, and its structure parameters were
calculated from bond distance and the van der Waals radii taken
ASSOCIATED CONTENT
■
31
*
S
Supporting Information
H NMR and 31P NMR spectra of TPPPO information. This
material is available free of charge via the Internet at http://
pubs.acs.org.
1
3
2,33
from literature,
by means of the purely geometric method
34
discussed by Bondi. The van der Waals group volume (r) and
surface area (q) parameters for PO are 1.2817 and 1.233,
AUTHOR INFORMATION
35
■
which is a little different from our previous work, because the
PO band length is presumably elongated which each
phosphine oxide unit is hydrogen bonded to three hydroxyl
Corresponding Author
*Tel.: +86-10-68912660; fax: +86-10-68911040. E-mail ad-
dress: lishengwang@bit.edu.cn.
3
3
groups from three different adjacent molecules. The
calculated r and q values for each compound are given in
Table 5.
Notes
The authors declare no competing financial interest.
The binary cross-interaction parameters in the Wilson
equation (Δλ12 and Δλ ), the NRTL equation (Δg and
21
12
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Δg ), and the UNIQUAC equation (Δu and Δu ) are
■
21
12
21
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