The Journal of Physical Chemistry B
pairs.612 The derived properties from the primary thermody-
namic data of solutions, such as isentropic compressibility, are
particularly helpful for interpreting the structural changes of
water as a consequence of addition of electrolytes.5,1316
Herein, we have found that the compressibility changes of
saturated Na2SO4water solutions closely follow the Na2SO4
water cluster behavior detected from DLS, and the results are
complementary to each other.
Salt water dynamics, particularly in concentrated solutions,
are highly complex because of the existence of many species
ranging from small hydrated ions/ion pairs to large salt water
clusters and bulk water. Ionic charge densities govern water
ion interactions and dene the relative importance of ion
water dipole interactions and the extent of hydrogen bonding
between water molecules. Due to enhanced electrostatic
ordering, ions with higher charge density perturb the bulk
hydrogen bonding to a greater extent than larger ions with
lo wer charge d ensity . Through FT-IR 1 7 3 0 and
NMR,1721,3138 which are sensitive and noninvasive techni-
ques, it is possible to detect the changes in the hydrogen
bonding environment of water and also the shifts in ion nuclei.
The water structural changes and shifts in ion nuclei are more
pronounced with larger and more polarizable anions and
smaller and high charge density cations such as sulfate and
sodium in the present case. Because water is a highly structured
liquid with distinct local structures,39,40 the variation in
temperature also has a signicant eect on local structures,
which can be explicitly involved in solubility limits of dierent
salts. We have, therefore, recorded temperature-dependent FT-
IR and 2D diusion-ordered spectroscopy (DOSY) 1H NMR
spectra precisely to complement the DLS and compressibility
information in elucidating the water structure, cluster stability,
and ion pairwater interactions in the saturated Na2SO4
solutions. The combination of DLS and compressibility data,
together with temperature-dependent FT-IR and NMR results,
have enabled us to account for the solubility transition of
Na2SO4 at 32.38 C, unlike other alkali metal sulfates.
2. EXPERIMENTAL SECTION
2.1. Materials and Methods. NaCl and Na2SO4 (>99.5%
by mol) were obtained from S.D. Fine Chemicals (Mumbai).
Salts were used after drying in an oven at 70 C without further
purication. Aqueous Na2SO4 solutions were prepared by
weight, using an analytical balance with a precision of 0.0001
g (Denver Instrument APX-200) in Millipore grade water. The
solubility of Na2SO4 in water and in aqueous NaCl solutions (5,
10, and 15 wt % NaCl) in the temperature range of 1070 C
was determined by gravimetric and volumetric methods.
Detailed procedures are provided in Annexure 1 (Supporting
Information).
2.2. DLS. Cluster size measurements were performed from
10 to 70 C using a Zetasizer Nano ZS light scattering
apparatus (Malvern Instruments, U.K.) with a HeNe laser
(633 nm, 4 Mw) at a scattering angle of 90. Salt solutions were
ltered directly into quartz cell using a membrane lter of 0.45
m pore size. The measurements were done by considering the
viscosity and refractive index values (Table S1 and S3,
Supporting Information) of the saturated solutions at the
concerned temperature. The viscosity of solutions was
measured by using Brookeld DV-II+ Pro viscometer.
Refractive index measurements were done on a Mettler-Toledo
(Model RE-40 D) refractrometer having a high-resolution
optical sensor. Measurements were made with a resolution and
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limit of error of 1 104. The temperature of the apparatus
was controlled to within 0.1 K by a built-in Peltier device. The
viscosity and refractive index values were entered into
CONTIN algorithm software before measurement as viscosity
does aect the size of concentrated solutions via the Stokes
Einstein equation (Rh = kT/6Df) and refractive index values
are important for accurate measurement of the scattering vector
[q = (4nr/) sin(/2)]. Measurement time was varied from 10
to 30 s, and the number of measurements was varied from 25 to
30. Prior to measurements, the cell was rinsed several times
with ltered water and then lled with ltered sample solutions.
The temperature of the measurements was controlled with an
accuracy of 0.1 K.
2.3. Densimetry. The density () of the saturated salt
solutions at dierent temperatures was measured with an Anton
Paar (Model DMA 4500) vibrating-tube densimeter with a
resolution of 5 102 kgm3. The temperature of the
apparatus was controlled to within 0.03 K by a built-in Peltier
device that corresponds to uncertainty in density of 0.0002%.
To prevent the uncertainty in the density readings from being
aected by the sample viscosity, a number of corrections are
needed. Such corrections rely on both the availability of
experimental viscosity data over the pressure and temperature
ranges considered and the use of properly dened and
evaluated damping equations. The deviations between the
viscosity corrected and noncorrected density data can climb up
from 0.5 to 1% for lower temperatures. In light of the full
accuracies of all factors involved in the density readings, an
accuracy of 1 105 gcm3 for the raw density data is
assumed. Reproducibility of the results was conrmed by
performing at least three measurements for each sample.
2.4. Ultrasonics. The speed of sound (u) in the salt
solutions at varying temperatures was measured at 51600 Hz
using a concentration analyzer (Model 87, SCM Laboratory
Sonic Composition Monitor) based on the sing-around
technique with a single transducer cell, immersed in a water
bath with temperature controlled to 0.01 K. The analyzer was
calibrated by measurements of speeds of sound in water as a
reference, and the error was estimated to be less than 0.1 m
s1. Measurements were carried out in a specially designed
sample jar of low volume capacity. Sample jars were provided
with an airtight Teon covering to avoid the sample
evaporation during measurements. Not less than three
experiments were performed at each temperature to check
the reproducibility of the results.
2.5. FT-IR Measurements. FT-IR measurements of
saturated aqueous salt solutions were carried out at room
temperature using a NICOLET 6700 FT-IR spectrometer. For
recording spectra, a cell with BaF2 windows and a Teon spacer
was used; the optical path length was 0.02 mm. For each
spectrum, 132 scans were made with a selected resolution of 4
cm1.
2.6. NMR Measurements. 1D 1H NMR and 2D DOSY 1H
NMR experiments were performed on Bruker Avance 500
MHz NMR spectrometer. Variable-temperature DOSY experi-
ments were acquired using a stimulated echo gradient pulse
sequence with a 500 ms diusion delay, 1200 s gradient
length, 816 gradient levels, and 8 scans. Processing DOSY
experiments were performed through DOSY software. All
chemical shifts were referenced through the water peak of a 0.1
M Na2SO4 aqueous solution capillary at 30 C to 4.8 ppm, and
the reference capillary was used externally with respect to
saturated aqueous Na2SO4 samples. The temperature of the
dx.doi.org/10.1021/jp507949h | J. Phys. Chem. B 2014, 118, 1273412742
The Journal of Physical Chemistry B
solutions in a resonance cavity during measurements of
concentration dependences of DOSY 2D NMR spectra was
xed with the precision of 0.1 C.
3. RESULTS
The solubility of Na2SO4 in pure water and in NaCl solutions
(515 wt %) as a function of temperature is shown in Figure 1.
Figure 1. Temperature dependence of Na2SO4 solubility in aqueous
NaCl solutions.
As established in the literature,3 the solubility of Na2SO4
increases sharply until 32.38 C and becomes almost constant
thereafter. Addition of NaCl decreases both the solubility and
solubility transition temperature of Na2SO4 while maintaining
the basic solubility pattern. It has been observed that the
solubility of Na2SO4 decreased from 3.5 to 1.72 molkg1, and
the solubility transition temperature decreased from 32.38 to 25
C as the concentration of NaCl in the solution increased to 15
wt %. The temperature dependence (2070 C) of Na2SO4
solubility in water was probed by examining the saturated
solutions through compressibility changes and DLS. Precise
measurements of the density and speed of sound (Table S1S3
in the Supporting Information) allow the determination of
solution compressibility (S) by using the NewtonLaplace
equation (S = 1/2),1316 where is the speed of sound and
is the solution density. Figure 2 shows the variation in S for
saturated solutions with or without NaCl. The pattern of S is
exactly opposite to that of solubility wherein it decreased with
an increase in concentration of Na2SO4 until 32.38 C and
increased slightly afterward. With the addition of NaCl (515
wt %), although the basic pattern remained the same, the
Figure 2. Temperature dependence of S of saturated solutions of
Na2SO4 containing varying amounts of NaCl.
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minimum in S increased from 194 to 235 TPa1 with a
transition temperature shift from 32.38 to 25 C, following
exactly the solubility trend, albeit in an opposite manner. The
DLS measurements of saturated solutions at all of the
temperatures showed a bimodal size distribution, that is, a
small component corresponding to solvated ions (1.53 nm)
and a large component corresponding to bigger size clusters. A
typical plot of the apparent hydrodynamic diameter (Dh)
(calculated from the CONTIN method) versus concentration
(Figure 3A) shows the growth pattern of clusters in solutions
saturated with Na2SO4 at dierent temperatures. As shown in
Figure 3B, the cluster size increased for the solutions saturated
at increased temperatures and attained a maximum size (Dh
300 nm) for the solution saturated at 32.38 C, which
corresponds to the temperature of the highest solubility.
Thereafter, the cluster size started decreasing following the
solubility pattern. We also performed the temperature-depend-
ent DLS and S studies for the solutions saturated (i) below the
solubility transition temperature and (ii) at the solubility
transition temperature. Figure 4A,B shows the CONTIN plots
of the hydrodynamic diameter (Dh) versus the normalized
intensity of Na2SO4water clusters formed in the saturated
solutions at 15 and 32.38 C, respectively, as a function of
temperature. The separate plots of the 15 C saturated sample
at dierent temperatures showing a smaller solvated ion pair
and large cluster are also shown in Figures S2 (Supporting
Information). Plots of the apparent hydrodynamic diameter
(Dh) versus the intensity of scattered light and S as a function
of temperature are compared in Figure 4C,D. For the solution
saturated at 15 C, both the Dh and S decreased from 132 to
107 nm and 347 to 336 TPa1, respectively, with the increase
in temperature from 15 to 30 C, whereas for the solution
saturated at 32.38 C, the Dh and S increased from 300 to 530
nm and 195 to 205 TPa1, respectively, with an increase in
temperature from 32.38 to 60 C, thus showing a similar trend.
The investigated aqueous solutions contain a very high
amount of SO42 ions having oxygen atoms with a capability of
forming hydrogen bonds with the protons of water. Therefore,
SO42H2O hydrogen bonding interactions in the saturated
solutions at dierent temperatures have been studied by
analyzing the vibrational shifts in the characteristic frequency of
the OH band of water (OH) using FT-IR spectroscopy. The
OH of water in the saturated Na2SO4 aqueous solutions at
dierent temperatures is shown in Figure S3 (Supporting
Information). A red shift from 3406 to 3415 cm1 in OH
has been observed for the Na2SO4 saturated solutions in the
temperature range of 2032.38 C, that is, until the Na2SO4
solubility transition temperature, which then starts blue shifting
(though very low) for the saturated Na2SO4 prepared at still
higher temperatures. Further, the FT-IR spectroscopy has been
extensively used to study the inuence of salts on water
structure.2230 Curve tting of the water vibrational spectrum
into four deconvoluted bands developed by Walrafen22 and
others27,28 has been often used for describing the water
structure. The deconvoluted FT-IR spectra of pure water and
aqueous NaCl (515 wt %) solutions saturated with Na2SO4 at
dierent temperatures are shown in Figure 5AE. The
prominent bands at around 3250 and 3420 cm1 correspond
to the strongly H-bonded patches of water molecules with
strongly and weakly H-bonded molecules, respectively. The
component bands at 3550 and 3620 cm1 signify coupling of
OH asymmetric stretching vibrational modes24 and the
dangling OH stretching modes from three- and two-coordinate
dx.doi.org/10.1021/jp507949h | J. Phys. Chem. B 2014, 118, 1273412742