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The Journal of Physical Chemistry B Article

pairs.612 The derived properties from the primary thermody- limit of error of 1 104. The temperature of the apparatus
namic data of solutions, such as isentropic compressibility, are was controlled to within 0.1 K by a built-in Peltier device. The
particularly helpful for interpreting the structural changes of viscosity and refractive index values were entered into
water as a consequence of addition of electrolytes.5,1316 CONTIN algorithm software before measurement as viscosity
Herein, we have found that the compressibility changes of does aect the size of concentrated solutions via the Stokes
saturated Na2SO4water solutions closely follow the Na2SO4 Einstein equation (Rh = kT/6Df) and refractive index values
water cluster behavior detected from DLS, and the results are are important for accurate measurement of the scattering vector
complementary to each other. [q = (4nr/) sin(/2)]. Measurement time was varied from 10
Salt water dynamics, particularly in concentrated solutions, to 30 s, and the number of measurements was varied from 25 to
are highly complex because of the existence of many species 30. Prior to measurements, the cell was rinsed several times
ranging from small hydrated ions/ion pairs to large salt water with ltered water and then lled with ltered sample solutions.
clusters and bulk water. Ionic charge densities govern water The temperature of the measurements was controlled with an
ion interactions and dene the relative importance of ion accuracy of 0.1 K.
water dipole interactions and the extent of hydrogen bonding 2.3. Densimetry. The density () of the saturated salt
between water molecules. Due to enhanced electrostatic solutions at dierent temperatures was measured with an Anton
ordering, ions with higher charge density perturb the bulk Paar (Model DMA 4500) vibrating-tube densimeter with a
hydrogen bonding to a greater extent than larger ions with resolution of 5 102 kgm3. The temperature of the
lo wer charge d ensity . Through FT-IR 1 7 3 0 and apparatus was controlled to within 0.03 K by a built-in Peltier
NMR,1721,3138 which are sensitive and noninvasive techni- device that corresponds to uncertainty in density of 0.0002%.
ques, it is possible to detect the changes in the hydrogen To prevent the uncertainty in the density readings from being
bonding environment of water and also the shifts in ion nuclei. aected by the sample viscosity, a number of corrections are
The water structural changes and shifts in ion nuclei are more needed. Such corrections rely on both the availability of
pronounced with larger and more polarizable anions and experimental viscosity data over the pressure and temperature
smaller and high charge density cations such as sulfate and ranges considered and the use of properly dened and
sodium in the present case. Because water is a highly structured evaluated damping equations. The deviations between the
liquid with distinct local structures,39,40 the variation in viscosity corrected and noncorrected density data can climb up
temperature also has a signicant eect on local structures, from 0.5 to 1% for lower temperatures. In light of the full
which can be explicitly involved in solubility limits of dierent accuracies of all factors involved in the density readings, an
salts. We have, therefore, recorded temperature-dependent FT- accuracy of 1 105 gcm3 for the raw density data is
IR and 2D diusion-ordered spectroscopy (DOSY) 1H NMR assumed. Reproducibility of the results was conrmed by
spectra precisely to complement the DLS and compressibility performing at least three measurements for each sample.
information in elucidating the water structure, cluster stability, 2.4. Ultrasonics. The speed of sound (u) in the salt
and ion pairwater interactions in the saturated Na2SO4 solutions at varying temperatures was measured at 51600 Hz
solutions. The combination of DLS and compressibility data, using a concentration analyzer (Model 87, SCM Laboratory
together with temperature-dependent FT-IR and NMR results, Sonic Composition Monitor) based on the sing-around
have enabled us to account for the solubility transition of technique with a single transducer cell, immersed in a water
Na2SO4 at 32.38 C, unlike other alkali metal sulfates. bath with temperature controlled to 0.01 K. The analyzer was
calibrated by measurements of speeds of sound in water as a
2. EXPERIMENTAL SECTION reference, and the error was estimated to be less than 0.1 m
2.1. Materials and Methods. NaCl and Na2SO4 (>99.5% s1. Measurements were carried out in a specially designed
by mol) were obtained from S.D. Fine Chemicals (Mumbai). sample jar of low volume capacity. Sample jars were provided
Salts were used after drying in an oven at 70 C without further with an airtight Teon covering to avoid the sample
purication. Aqueous Na2SO4 solutions were prepared by evaporation during measurements. Not less than three
weight, using an analytical balance with a precision of 0.0001 experiments were performed at each temperature to check
g (Denver Instrument APX-200) in Millipore grade water. The the reproducibility of the results.
solubility of Na2SO4 in water and in aqueous NaCl solutions (5, 2.5. FT-IR Measurements. FT-IR measurements of
10, and 15 wt % NaCl) in the temperature range of 1070 C saturated aqueous salt solutions were carried out at room
was determined by gravimetric and volumetric methods. temperature using a NICOLET 6700 FT-IR spectrometer. For
Detailed procedures are provided in Annexure 1 (Supporting recording spectra, a cell with BaF2 windows and a Teon spacer
Information). was used; the optical path length was 0.02 mm. For each
2.2. DLS. Cluster size measurements were performed from spectrum, 132 scans were made with a selected resolution of 4
10 to 70 C using a Zetasizer Nano ZS light scattering cm1.
apparatus (Malvern Instruments, U.K.) with a HeNe laser 2.6. NMR Measurements. 1D 1H NMR and 2D DOSY 1H
(633 nm, 4 Mw) at a scattering angle of 90. Salt solutions were NMR experiments were performed on Bruker Avance 500
ltered directly into quartz cell using a membrane lter of 0.45 MHz NMR spectrometer. Variable-temperature DOSY experi-
m pore size. The measurements were done by considering the ments were acquired using a stimulated echo gradient pulse
viscosity and refractive index values (Table S1 and S3, sequence with a 500 ms diusion delay, 1200 s gradient
Supporting Information) of the saturated solutions at the length, 816 gradient levels, and 8 scans. Processing DOSY
concerned temperature. The viscosity of solutions was experiments were performed through DOSY software. All
measured by using Brookeld DV-II+ Pro viscometer. chemical shifts were referenced through the water peak of a 0.1
Refractive index measurements were done on a Mettler-Toledo M Na2SO4 aqueous solution capillary at 30 C to 4.8 ppm, and
(Model RE-40 D) refractrometer having a high-resolution the reference capillary was used externally with respect to
optical sensor. Measurements were made with a resolution and saturated aqueous Na2SO4 samples. The temperature of the
12735 dx.doi.org/10.1021/jp507949h | J. Phys. Chem. B 2014, 118, 1273412742
The Journal of Physical Chemistry B Article

solutions in a resonance cavity during measurements of minimum in S increased from 194 to 235 TPa1 with a
concentration dependences of DOSY 2D NMR spectra was transition temperature shift from 32.38 to 25 C, following
xed with the precision of 0.1 C. exactly the solubility trend, albeit in an opposite manner. The
DLS measurements of saturated solutions at all of the
3. RESULTS temperatures showed a bimodal size distribution, that is, a
The solubility of Na2SO4 in pure water and in NaCl solutions small component corresponding to solvated ions (1.53 nm)
(515 wt %) as a function of temperature is shown in Figure 1. 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
Figure 1. Temperature dependence of Na2SO4 solubility in aqueous solutions at 15 and 32.38 C, respectively, as a function of
NaCl solutions. temperature. The separate plots of the 15 C saturated sample
at dierent temperatures showing a smaller solvated ion pair
As established in the literature,3 the solubility of Na2SO4 and large cluster are also shown in Figures S2 (Supporting
increases sharply until 32.38 C and becomes almost constant Information). Plots of the apparent hydrodynamic diameter
thereafter. Addition of NaCl decreases both the solubility and (Dh) versus the intensity of scattered light and S as a function
solubility transition temperature of Na2SO4 while maintaining of temperature are compared in Figure 4C,D. For the solution
the basic solubility pattern. It has been observed that the saturated at 15 C, both the Dh and S decreased from 132 to
solubility of Na2SO4 decreased from 3.5 to 1.72 molkg1, and 107 nm and 347 to 336 TPa1, respectively, with the increase
the solubility transition temperature decreased from 32.38 to 25 in temperature from 15 to 30 C, whereas for the solution
C as the concentration of NaCl in the solution increased to 15 saturated at 32.38 C, the Dh and S increased from 300 to 530
wt %. The temperature dependence (2070 C) of Na2SO4 nm and 195 to 205 TPa1, respectively, with an increase in
solubility in water was probed by examining the saturated temperature from 32.38 to 60 C, thus showing a similar trend.
solutions through compressibility changes and DLS. Precise The investigated aqueous solutions contain a very high
measurements of the density and speed of sound (Table S1S3 amount of SO42 ions having oxygen atoms with a capability of
in the Supporting Information) allow the determination of forming hydrogen bonds with the protons of water. Therefore,
solution compressibility (S) by using the NewtonLaplace SO42H2O hydrogen bonding interactions in the saturated
equation (S = 1/2),1316 where is the speed of sound and solutions at dierent temperatures have been studied by
is the solution density. Figure 2 shows the variation in S for analyzing the vibrational shifts in the characteristic frequency of
saturated solutions with or without NaCl. The pattern of S is the OH band of water (OH) using FT-IR spectroscopy. The
exactly opposite to that of solubility wherein it decreased with OH of water in the saturated Na2SO4 aqueous solutions at
an increase in concentration of Na2SO4 until 32.38 C and dierent temperatures is shown in Figure S3 (Supporting
increased slightly afterward. With the addition of NaCl (515 Information). A red shift from 3406 to 3415 cm1 in OH
wt %), although the basic pattern remained the same, the 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
Figure 2. Temperature dependence of S of saturated solutions of OH asymmetric stretching vibrational modes24 and the
Na2SO4 containing varying amounts of NaCl. dangling OH stretching modes from three- and two-coordinate
12736 dx.doi.org/10.1021/jp507949h | J. Phys. Chem. B 2014, 118, 1273412742