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Densities, Viscosities, and Conductivities of Phosphonic Acid Solutions in N ,

N -Dimethylformamide and Water

Article  in  Journal of Chemical & Engineering Data · November 2016

DOI: 10.1021/acs.jced.6b00430

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Densities, Viscosities, and Conductivities of Phosphonic Acid
Solutions in N,N‑Dimethylformamide and Water
Yuliya A. Fadeeva,* Liudmila E. Shmukler, and Lyubov P. Safonova
G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaja St, 1, Ivanovo, 153045,
Russia RU
ABSTRACT: The viscosities, specific conductivities, and
densities of phosphonic acid solutions in N,N-dimethylforma-
mide and water have been measured at temperatures from
298.15 to 338.15 K over the whole possible concentration
range. Dependences of these properties on the mixture com-
position have been discussed and compared with the data for
phosphoric acid solutions in the same solvents.
1. INTRODUCTION
The information on physicochemical properties of solutions of
the simplest oxyacids of phosphorus in different solvents is of
special interest because the systems are widely used in various
branches of science and technology. The temperature and con-
centration dependences of such properties as conductivity,
viscosity, or density are, from the one side, important process
parameters, but, from the other side, they can be analyzed from
the standpoint of possible interactions in solutions. These
systems can also be considered as model ones in order to study
the properties and interaction mechanism in the systems with
more complex phosphorus-containing acids.
The aqueous solutions of phosphoric acid (H3PO4) are
studied more deeply than solutions of other phosphorus
oxyacids, though the data are not too numerous, as could be
expected. The conductivity of aqueous solutions of phosphoric
acid has been studied in some works, but frequently the
data are limited either by a certain range of H3PO4 con-
centrations1−4 or by the temperature range studied;5,6 however,
the only work, in which the conductivity of the acid aqueous
solutions was studied over a wide concentration and temper-
ature range, was published by Chin and Chang.7 The same
situation is observed for the data on density4,8 and vis-
cosity6,7,9,10 of aqueous H3PO4 solutions. The H3PO4−DMF
system was investigated by us earlier with various phys-
icochemical methods11−16 in order to study its physicochemical
properties and the dissociative and intermolecular interac-
tions possible in the system. It was established that the acid
dissociation in DMF was low, and only interactions of neutral
species needed to be taken into consideration.13 Strong inter-
molecular interactions through hydrogen bonding, both between
acid molecules and between the acid and DMF, over the entire
composition range investigated was demonstrated.11,14−16 The
dissociation of phosphoric acid dimers was assumed only at low
H3PO4 concentrations (<0.1 mole fraction),14,15 while above this
© XXXX American Chemical Society
Article
pubs.acs.org/jced
concentration dimeric phosphoric acid units (or even its
polymerized species) predominated and formed strong hydro-
gen bonds with DMF molecules. When the acid concentration
was x(H3PO4) > 0.9 the conductivity of solutions went up
mainly due to autoprotolysis of phosphoric acid: 2H3PO4 =
H2PO4− + H4PO4+, pKs = 0.8.17 The dissociation constants of
phosphoric acid (pK1 and pK2) in water−dimethylformamide
mixtures were determine by the potentiometric titration
method.18 The data obtained, as well as literate data on the
dissociation constants of a number of protic acids in water and
DMF, were processed to estimate the acid dissociation constant
in DMF (pK1 varied from 7.97 to 8.84 depending on the way
how they were determined).18 Thus, it was supposed that DMF
was not a sufficiently strong Bronsted base for a total proton
transfer from phosphoric acid as it was in water.
The aim of this work was to study the properties of
[H3PO3(1) + DMF(2)] and [H3PO3(1) + H2O(2)] systems by
physicochemical methods. This work is the continuation of our
systematic investigation of interactions in solutions of phos-
phorus oxyacids in various solvents.
2. EXPERIMENTAL SECTION
All chemicals used in this work were of the highest purity
commercially available and used as received without additional
purification. The suppliers and purity of these chemicals are
given in Table 1. The key properties of pure solvents, both
experimental and literature data, are shown in Table 2.
The crystalline phosphonic acid was considered as pure
substance (1 weight fraction (wt.f.)) as it was not possible to
state the content of impurities more exactly. The water content
Received: May 28, 2016
Accepted: October 31, 2016
A DOI: 10.1021/acs.jced.6b00430
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 1. Characteristics of the Chemicals Used
initial weight fraction purity
chemical name source (as stated by the suppliers)
phosphonic acid −99% Sigma- 0.985−1.015
(H3PO3) Aldrich
N,N-dimethylformamide dry Panreac 0.998, max. 0.0001 wt.f. of
(DS-ACS-ISO), DMF water
in pure DMF was controlled with Karl Fischer’s method and
did not exceed 0.0001 wt.f. Double-distilled water with specific
conductance of 1.5 × 10−6 S·cm−1 was used for the solutions
preparation.
Pure crystalline phosphonic acid and its solutions in
DMF were handled in a dry glovebox, wherever it was possible,
because of the reagents hygroscopicity. The solutions of phos-
phonic acid in DMF and water were prepared by gravimetric
method. The weights were measured with an accuracy of
±0.00025 g. The highest H3PO3 concentration both in DMF
and water was limited by the acid solubility in the solvents at
ambient temperature and was equal to 80 wt.f. that corre-
sponded to 0.8 and 0.3 mol fraction of the acid in DMF and
water, respectively.
The viscosity (η) of [H3PO3(1)+DMF(2)] system was
measured with a Brookfield DV-II+Pro rotational viscometer.
The small sample adapter was use for all measurements. The
spindle SC4-18 was immersed into the sample and share rate
(RPM) was set in order to obtain a suitable torque (>10%).
Autozeroing of the viscometer was performed each time the
power switch was turned on. The accuracy of the temperature
control was 0.05 K. The relative standard uncertainty of the
viscosity measurement was 0.03. The kinematic viscosity of
phosphonic acid solutions in water was determined with an
Ubbelohde viscometer with hanging meniscus and automated
measurement of the liquid efflux time. The viscometer was
calibrated with water, 1-propanol, and water−glycerol solutions.
The kinematic viscosity was recalculated into a dynamic one
using the experimental data on the system density.
The solutions specific conductivity (κ) was determined by
the electrochemical impedance method with the impedance/
gain-phase analyzer Solartron 1260A (UK) over the frequency
range of 0.1 Hz−1 MHz with signal amplitude of 10 mV.
The resistance value was determined from high-frequency
cutoff corresponding to the bulk solution resistance. The
measurements were carried out in the cell (V ≈ 7 cm3) with flat
platinum electrodes (S ≈ 1 cm2) fixed at the opposite cell sides;
platinum wire was used to supply current.
The temperature was kept with thermostat HAAKE
DC50-K35 within ±0.01 K. The cell was calibrated by
the conductometric standard potassium chloride solution
(RADELKIS) at 298.15 K. The cell constants at other temper-
atures were determined as described in ref 34. The spectra
corresponded to the equivalent circuit consisting of bulk
resistance of the electrolyte connected in series with double
layer capacity.
The density (ρ) measurements were conducted with the
vibrating tube densimeter Anton Paar DMA-4500 with an
accuracy of 5 × 10−2 kg·m−3. The densimeter was equipped
with internal thermostat with two platinum thermometers
(Pt 100). The temperature reproducibility (standard deviation)
was 0.01 K. Before every experiment the densimeter was
calibrated with dry air and bidistilled deionized water.
Experimental data on the specific conductivity, dynamic vis-
cosity, and density of H3PO3 solutions in N,N-dimethylformamide
and water over the entire possible concentration range at
temperatures from (298.15 to 338.15) K are listed in
Tables 3, 4, and 5. Hereinafter the concentration dependences
of all properties studied are compared at 298 K only as no
temperature anomaly or peculiarity is observed.
3. RESULTS AND DISCUSSION
In Figure 1 the concentration dependences of the specific
conductivity of phosphonic acid solutions in DMF (Figure 1a)
and water (Figure 1b), along with the literature data5,13 for
phosphoric acid solutions in the same solvents, are shown for
T = 298.15 K. The behaviors of σ = f(x1) functions for solutions
of the acids in DMF or water are similar.
The specific conductivity values of solutions of both acids in
DMF are considerably lower than in water; they are rather close
and vary weakly with the acid concentration change within
the concentration range studied (Figure 1a, left axis, filled
symbols). In the case of the aqueous solutions (Figure 1b, left
axis, filled symbols) the behavior of the σ = f(x1) functions is

Table 2. Dynamic Viscosities (η), Densities (ρ), Dielectric Permittivities (ε), Donor (DN) and Acceptor (AN) Numbers of
pure DMF and Water at Various Temperatures at Atmospheric Pressure (0.1 MPa)

η/(mPa·s) ρ·10−3/(kg·m−3)
solvent T/K exp. lit. exp. lit. ε DN AN
DMF 298.15 0.783 0.796;19 0.805;20 0.8130;21 0.94392 0.9445;19 0.94406;20 0.9446;21 37.06;27 36.728 26.629 16.029
0.809;22 0.858623 0.944163;22 0.94386;24
0.94460;25 0.942915;26 0.946023
308.15 0.699 0.7194;21 0.710;22 0.93435 0.9357;21 0.934606;12 0.93408;24 33.7327
0.776323 0.93505;25 0.933964;26 0.939923
318.15 0.623 0.6446;21 0.7125;23 0.6430 0.92472 0.9266;21 0.92406;24 0.92549;25 30.21;27 34.7330
0.924674;26 0.931623
328.15 0.555 0.91506 0.9159225
338.15 0.495 0.90535 0.9063225
water 298.15 0.8900831 0.9970531 78.5432 78.43;33 78.3581 ≈3329 54.829
31 31 32 1
308.15 0.71932 0.99403 75.00; 74.846
318.15 0.5960731 0.9902131 71.5932
328.15 0.5039831 0.9856931
31
338.15 0.43326 0.9805531
348.15 0.3777431 0.9748431

B DOI: 10.1021/acs.jced.6b00430
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 3. Specific Conductivity of Phosphonic Acid Solutions Table 4. Dynamic Viscosity of Phosphonic Acid Solutions at
at Various Temperatures and Compositions at Atmospheric Various Temperatures and Compositions at Atmospheric
Pressure (p = 0.1 MPa)a Pressure (p = 0.1 MPa)a
σ/(Ohm−1·m−1) η/(mPa·s)
T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K =
x1 298.15 308.15 318.15 328.15 338.15 x1 298.15 308.15 318.15 328.15 338.15
[H3PO3(1) + DMF(2)] [H3PO3(1) + DMF(2)]
0.1181 0.0572 0.0647 0.0725 0.0815 0.120 0.0000 0.783 0.699 0.623 0.555 0.495
0.2984 0.0925 0.116 0.142 0.173 0.212 0.1973 2.92 2.49 2.16 1.92 1.67
0.3298 0.0934 0.119 0.148 0.183 0.226 0.2507 4.75 3.92 3.35 2.88 2.45
0.3968 0.129 0.169 0.217 0.275 0.351 0.2984 7.07 5.72 4.77 4.07 3.49
0.4479 0.141 0.190 0.250 0.316 0.356 0.3115 7.88 6.30 5.21 4.29 3.66
0.5761 0.216 0.301 0.397 0.512 0.642 0.3491 11.5 9.06 7.26 6.02 5.02
0.6316 0.294 0.410 0.548 0.710 0.891 0.3968 17.6 13.3 10.5 8.65 7.00
0.6554 0.333 0.476 0.626 0.802 1.06 0.3988 17.8 14.0 10.6 8.50 6.98
0.6820 0.411 0.589 0.810 1.07 1.39 0.4107 20.7 15.4 12.0 9.62 7.75
0.7694 0.663 0.959 1.33 1.77 2.29 0.4479 28.7 20.9 15.8 12.3 9.91
0.7832 0.702 1.02 1.41 1.91 2.42 0.4968 41.6 29.2 21.2 16.2 12.7
[H3PO3(1) + H2O(2)] 0.5074 43.9 30.3 22.2 16.0 11.6
0.0122 7.43 7.89 8.18 8.38 8.40 0.5503 62.4 42.4 30.0 22.0 17.2
0.0215 10.4 11.3 11.8 12.1 12.2 0.5761 73.5 48.6 34.1 24.9 18.7
0.0299 13.4 14.3 15.0 15.3 15.6 0.5993 80.5 51.0 35.2 25.5 19.2
0.0403 16.9 18.4 19.2 19.6 20.3 0.6261 90.0 59.4 41.2 29.5 22.6
0.0484 18.5 20.0 20.9 21.9 22.9 0.6316 95.2 61.2 42.0 30.1 22.3
0.0541 20.0 21.3 22.4 23.5 24.2 0.6478 102.8 64.5 43.6 32.2 23.8
0.0682 22.1 23.9 25.4 26.5 27.7 0.6554 103.3 66.1 45.0 32.0 23.6
0.0704 22.4 24.2 25.8 26.9 28.2 0.6820 113.5 72.4 49.0 34.4 25.2
0.0799 23.9 25.5 27.3 28.6 30.0 0.7142 122.7 78.3 51.4 37.1 27.0
0.1011 25.9 27.4 29.7 31.0 32.9 0.7694 139.8 87.4 57.3 39.8 28.6
0.1335 26.0 28.6 31.3 33.3 35.3 0.7832 142.5 88.2 58.4 40.5 29.1
0.1689 25.7 28.5 31.5 33.8 35.5 [H3PO3(1) + H2O(2)]
0.1909 25.2 28.5 31.2 33.3 35.0 0.0000 0.890 0.719 0.596 0.504 0.434
0.1970 25.0 28.0 30.8 33.2 34.9 0.0122 0.962 0.782 0.636 0.529 0.464
0.2154 24.5 28.0 30.0 32.5 34.1 0.0215 1.05 0.852 0.689 0.567 0.490
0.2524 23.1 25.8 28.8 31.3 33.5 0.0299 1.17 0.940 0.754 0.617 0.531
0.2920 20.7 23.9 27.2 30.2 32.4 0.0704 1.64 1.31 1.06 0.866 0.749
0.3959 15.4 18.5 21.1 24.1 25.9 0.1011 2.06 1.65 1.32 1.07 0.922
a
Standard uncertainties u are u(x) = 1 × 10−4 mole fraction, u(T) = 0.1335 2.60 2.08 1.66 1.35 1.16
0.01 K, and u(p) = 0.01 MPa; the relative standard uncertainty ur is 0.2154 4.24 3.32 2.68 2.20 1.88
ur(σ) = 0.05. 0.2524 5.19 4.12 3.27 2.65 2.25
0.2920 6.26 4.94 3.90 3.14 2.66
typical for electrolyte solutions for which the dependences pass a
Standard uncertainties u are u(x) = 1 × 10−4 mole fraction, u(T) =
through maxima. The decrease of specific conductivity above a 0.01 K, and u(p) = 0.01 MPa; the relative standard uncertainty ur is
certain electrolyte concentration is commonly explained by the ur(η) = 0.03.
increase of viscosity and ion association processes in the
solution. The conductivity of phosphonic acid solutions in
both solvents is somewhat higher with respect to solutions of on concentration for H3PO4(1) + DMF(2)] and H3PO3(1) +
phosphoric acid. It is known that in aqueous solutions both DMF(2)] systems differ dramatically (Figure 1a).
acids are of medium strength, but H3PO3 is slightly stronger Such unlike effects of viscosity on the conductivity values are
as compared with H3PO4 (with the first-step dissociation probably caused by different conductivity mechanisms in DMF
constants pK1(H3PO3) = (1.3;35,36 pK1(H3PO4) = 2.14837,38), and water. In general there are two key mechanisms of electrical
probably therefore its conductivity values are some larger. conductivity in solutions: the proton transport (ion-migration
The dynamic viscosity concentration dependences, η = f(x1), or vehicle mechanism) and the Grotthus (proton-hopping) mec-
for the systems under investigation, as well as those for phos- hanism. In the case of the first mechanism the solution viscosity
phoric acid solutions in DMF11 and water,9 are also shown in will significantly influence the conductivity values, whereas the
Figure 1 (right axes, empty symbols) for 298.15 K. The com- Grotthus mechanism is affected weakly by viscosity variation. To
parison of the conductance and dynamic viscosity dependences obtain some additional evidence of the proton transfer mechanism
on concentration allows supposing that the higher conductance in the system under investigation the activation energies of
of phosphonic acid aqueous solutions can be also determined the transport properties (viscosity and conductivity), Eη/σ
a , were
by their lower viscosity (Figure 1b). In the case of solutions of the evaluated from the well-known Arrhenius equation:
acids in DMF their viscosity does not influence considerably the ⎡E η⎤ ⎡ E σ⎤
conductance values, which are very close and rise for both acids η = A η exp⎢ a ⎥ or σ = Aσ exp⎢ − a ⎥
(Figure 1a) with x2 increasing, whereas the viscosity dependences ⎣ RT ⎦ ⎣ RT ⎦ (1)

C DOI: 10.1021/acs.jced.6b00430
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 5. Density of Phosphonic Acid Solutions at Various Temperatures and Compositions at Atmospheric Pressure
(p = 0.1 MPa)
ρ·10−3/(kg·m−3) ρ·10−3/(kg·m−3)
T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K = T/K =
x1 298.15 308.15 318.15 328.15 338.15 348.15 x1 298.15 308.15 318.15 328.15 338.15 348.15
[H3PO3(1) + DMF(2)] [H3PO3(1) + DMF(2)]
0 0.944 0.934 0.925 0.915 0.905 0.896 0.7250 1.402 1.393 1.385 1.384 1.369 1.373
0.0911 0.993 0.983 0.974 0.963 0.955 0.945 0.7592 1.433 1.425 1.417 1.411 1.400 1.395
0.1365 1.016 1.007 0.998 0.9873 0.979 0.970 0.7694 1.444 1.436 1.428 1.420 1.412 1.401
0.1798 1.041 1.031 1.022 1.012 1.004 0.994 0.7845 1.451 1.443 1.435 1.431 1.423 1.411
0.1829 1.042 1.033 1.023 1.014 1.005 0.996 1 1.629a 1.621a 1.613a 1.602a 1.600a 1.594a
0.2293 1.069 1.060 1.051 1.041 1.033 1.024 [H3PO3(1) + H2O(2)]
0.2910 1.105 1.096 1.087 1.078 1.069 1.060 0 0.997 0.994 0.990 0.986 0.981
0.3298 1.130 1.121 1.112 1.103 1.094 1.084 0.0122 1.022 1.019 1.014 1.009 1.001
0.3442 1.138 1.129 1.120 1.112 1.102 1.093 0.0215 1.040 1.036 1.031 1.026 1.019
0.3712 1.155 1.146 1.137 1.129 1.120 1.111 0.0299 1.055 1.051 1.046 1.041 1.034
0.3937 1.169 1.160 1.152 1.144 1.134 1.125 0.0403 1.073 1.069 1.064 1.059 1.051
0.4107 1.182 1.173 1.165 1.155 1.156 1.147 0.0451 1.082 1.077 1.072 1.067 1.060
0.4210 1.188 1.179 1.171 1.162 1.160 1.151 0.0484 1.087 1.082 1.077 1.072 1.065
0.4479 1.207 1.198 1.190 1.181 1.172 1.158 0.0541 1.097 1.092 1.087 1.081 1.074
0.4707 1.222 1.213 1.204 1.196 1.187 1.178 0.0682 1.119 1.114 1.109 1.103 1.096
0.4930 1.236 1.227 1.216 1.211 1.201 1.193 0.0704 1.123 1.118 1.112 1.106 1.099
0.5074 1.245 1.236 1.228 1.221 1.210 1.202 0.0799 1.137 1.132 1.126 1.120 1.114
0.5196 1.255 1.246 1.238 1.230 1.221 1.211 0.0832 1.142 1.137 1.131 1.125 1.118
0.5429 1.271 1.262 1.253 1.246 1.236 1.228 0.1011 1.168 1.162 1.156 1.150 1.143
0.5724 1.292 1.284 1.275 1.268 1.258 1.254 0.1335 1.211 1.204 1.198 1.191 1.184
0.5925 1.306 1.298 1.289 1.283 1.272 1.264 0.1689 1.252 1.245 1.239 1.232 1.225
0.6245 1.329 1.320 1.312 1.306 1.295 1.287 0.1909 1.275 1.269 1.262 1.254 1.247
0.6554 1.356 1.347 1.339 1.331 1.322 1.310 0.1970 1.281 1.274 1.267 1.260 1.253
0.6753 1.365 1.356 1.348 1.345 1.331 1.325 0.2154 1.300 1.293 1.285 1.278 1.270
0.6923 1.379 1.371 1.362 1.358 1.346 1.338 0.2524 1.332 1.325 1.317 1.310 1.301
0.7142 1.399 1.391 1.383 1.375 1.374 1.366 0.2920 1.363 1.356 1.348 1.340 1.332
0.3959 1.434 1.426 1.418 1.410 1.402
a
The density values obtained by extrapolation of the concentration dependences of the densities of solutions, ρ = f(x1), to x1 = 1. The appropriate
equations and their adjustable coefficients are presented in Table 6 (see below). Standard uncertainties u are u(x) = 1 × 10−4 mole fraction, u(T) =
0.01 K, u(p) = 0.01 MPa, and u(p) = 5 kg·m−3.

The first approximation of the equation was applied, that is,
the independence of Aη/σ on temperature was assumed.
The estimated values of the activation energies of con-
ductivity and dynamic viscosity of [H3PO3(1) + DMF(2)]
and [H3PO3(1) + H2O(2)] systems are presented in Figure 2.
For solutions in DMF (Figure 2a) the activation energies
both of viscosity and conductivity are comparable at acid
concentrations up to 0.4−0.5 mol fraction, but their differ-
ence increases at higher concentrations and Eηa > Eσa at that;
that is, probably the significant contribution from the Grot-
thuss (proton-hopping) mechanism to the conductance of
[H3PO3(1)+DMF(2)] system appears with the acid concen-
tration increasing. As one can see for aqueous solutions of the
acids, Eηa and Eσa values differ significantly; Eηa values are two
or even three times as large as Eσa ones, over the whole
concentration range studied (Figure 2b). Such phenomenon
is probably evidence of the greater contribution coming from
the Grotthus mechanism to the total conduction. It is quite
possible that such a difference for the acid solutions in water
and DMF is the result of the solvents’ different nature, so the
former is an aprotic solvent with spatial H-bond network
and the latter is a protic one. The experimental values of
the density of [H3PO3(1) + DMF(2)] and [H3PO3(1) +
H2O(2)] systems are tabulated in Table 5. All obtained
density values decrease with the temperature rising, as expec-
ted. The concentration dependences of density were fitted by
D DOI: 10.1021/acs.jced.6b00430
the second and third order polynomials for [H3PO3(1) +
DMF(2)] and [H3PO3(1) + H2O(2)] systems, respectively.
These equations and their adjustable coefficients are shown in
Table 6. Here we should note that the absolute terms in all
expressions were equal to the density of pure solvents (DMF or
water), ρ0, therefore they were fixed as the appropriate constant
values.
The fitted concentration dependences of the density of
[H3PO3(1) + DMF(2)] system were used for the excess molar
volumes, VE, calculation:
M mix ⎛x M xM ⎞
V E = Vmix − (x1V10 + x 2V 20) = − ⎜⎜ 1 1 + 2 2 ⎟⎟
ρ ⎝ ρ1* ρ2 ⎠
(2)
where Mmix, M1, and M2 were molar masses of solution, acid,
and solvent, respectively; x1 and x2 were mole fractions of the
system components; ρ, ρ1*, and ρ2 were densities of solution,
pure acid, and pure solvent, respectively. The density of pure
H3PO3 was not measured because of the rather high melting
point of the acid (Tmelting = 346 K); it was determined by
extrapolation of the fitted ρ = f(x1) dependences (the
adjustable coefficients of appropriate equations are listed in
Table 6) to x1 = 1 at every temperature studied. For the
[H3PO3(1) + H2O(2)] system the extrapolation from the
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 1. Concentration dependences of the specific conductivity,
σ, (left axes, filled symbols) and dynamic viscosity, η, (right axes,
empty symbols) of phosphoric (-▲-,-Δ-) and phosphonic (-●-, -○-)
acid solutions in DMF (a) and water (b) at 298.15 K. The conductivity
values for [H3PO4(1) + DMF(2)] and [H3PO4(1) + H2O(2)] systems
were taken from refs 13 and 5, respectively. The data on the dynamic
viscosity of [H3PO4(1) + DMF(2)] and [H3PO4(1) + H2O(2)]
systems were taken from refs 11 and 9, respectively.
narrow concentration range studied (on the mole fraction
scale) was not reasonable.
The excess molar volumes for [H3PO4(1) + DMF(2)] and
[H3PO4(1) + H2O(2)] systems were determined on the basis
of literature data on densities of those systems taken from refs
13 and 8, respectively. VE = f(x1) dependences for [H3PO3(1) +
DMF(2)], [H3PO4(1) + DMF(2)] and [H3PO4(1) + H2O(2)]
systems at 298.15 K are shown in Figure 3.
As one can see the negative values of the excess molar
volumes are observed for all systems under consideration and
this fact is indicative of the intermolecular interactions between
the systems components. However, VE values of phosphonic
acid solutions in DMF are less negative against H3PO4−DMF
solutions and are more exothermic as compared with aqueous
solutions of phosphoric acid.
The calculated values of the excess molar volumes were fitted
using the Redlich−Kister equation:
n
V E = x1x 2 ∑ Ai (2x1 − 1)i
i=0 (3)
The values and number of the adjustable parameters Ai
were calculated by using the method of least-squares. These
E DOI: 10.1021/acs.jced.6b00430
Article
Figure 2. Dependences of the activation energies of viscosity, Eηa (-○-),
and conductivity, Eσa(-●-), of [H3PO3(1) + DMF(2)] (a) and
[H3PO3(1) + H2O(2)] (b) systems.
coefficients are given in Table 7 together with the standard
deviations of the fitting.
4. CONCLUSIONS
The comparison of various physicochemical properties of
H3PO4 and H3PO3 solutions in DMF or water gives the basis
for some conclusions on interactions in the systems.
• The difference in the acids behavior in every solvent is
observed, first of all, for the concentration dependences
of dynamic viscosity, whereas the conductivity and the
excess molar volumes change similarly. The difference of
η = f(x1) functions for the acids under investigation can
be caused by the different spatial structure of their
hydrogen bond networks; that is, in H3PO4 molecules
there are “free” protons able to form additional hydrogen
bonds with the solvent molecules.
• The different behavior of the acids in the solvents
examined is the most pronounced for the specific con-
ductivity of the acids solutions in DMF and water as
well as for the concentration dependences of dynamic
viscosity of phosphoric acid solutions in DMF and water.
It is quite possible that such difference is the result of the
solvents different nature, so the former is an aprotic
solvent and the latter is a protic one with spatial H-bond
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 6. Adjustable Parameters and the Coefficients of Determination of the Polynomial Equations for Description of the
Experimental Concentration Dependences of the Density of [H3PO3(1) + DMF(2)] and [H3PO3(1) + H2O(2)] Systems at
Various Temperatures
ρ·10−3/(kg·m−3)
T/K
x1 T/K = 298.15 T/K = 308.15 T/K = 318.15 T/K = 328.15 T/K = 338.15 T/K = 348.15
[H3PO3(1) + DMF(2)]
ρ·10−3/(kg·m−3) = a + bx1 + cx21
a = ρ0·10−3/(kg·m−3) 0.94392 0.93435 0.92472 0.91506 0.90535 0.89557
B 0.5053 0.5074 0.5094 0.5127 0.5159 0.5178
C 0.1794 0.1788 0.1788 0.1747 0.179 0.1802
R2 0.9903 0.9895 0.9902 0.999 0.9652 0.9642
[H3PO3(1) + H2O(2)]
ρ·10−3/(kg·m−3) = a + bx1 + cx21 + dx31
a = ρ0·10−3/(kg·m−3) 0.99704 0.99403 0.99021 0.98569 0.98055
B 2.0516 2.0127 1.9623 1.9532 1.8746
C −3.8855 −3.7475 −3.433 −3.535 −2.8848
D 3.8598 3.6671 3.0735 3.3705 2.0637
R2 0.9968 0.9972 0.9996 0.9975 0.9975

■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +7 4932 351679. Fax: +7 4932 336237. E-mail:
jaf@isc-ras.ru.
Funding
This work was carried out under partial financial support of the
Russian Foundation for Basic Research (Grant No. 14-03-
00481).
Notes
The authors declare no competing financial interest.

Figure 3. Concentration dependences of the excess molar volumes of
phosphoric acid solutions in DMF (-○-) and water (-■-), calculated
from the density values from refs 13 and 8, respectively, and
phosphonic acid solutions in DMF (-□-) at 298.15 K.
network. Thus, it is supposed that in the case of aqueous
solutions the Grotthus conductivity mechanism can be
realized over the whole concentration range studied,
whereas in DMF solutions the considerable contribution
coming from the Grotthus mechanism appears at large
concentrations of the acids, which can form the intrinsic
H-bond networks.
■ ACKNOWLEDGMENTS
The density and conductivity measurements were made with the
vibrating tube densimeter Anton Paar DMA-4500 and the
impedance/gain-phase analyzer Solartron 1260A (UK), respec-
tively, at the center for joint use of scientific equipment (the
upper Volga regional center for physico−chemical research).
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