Article

pubs.acs.org/JPCB

Temperature-Dependent Solubility Transition of Na2SO4 in Water

and the Eect of NaCl Therein: Solution Structures and Salt Water
Dynamics
Pankaj Bharmoria, Praveen Singh Gehlot, Hariom Gupta,, and Arvind Kumar*,,,

Academy of Scientic and Innovative Research (AcSIR) and Salt and Marine Chemical Discipline, Analytical Discipline &
Centralized Instrument Facility, Central Salt and Marine Chemicals Research Institute, Council of Scientic & Industrial Research
(CSIR), G. B. Marg, Bhavnagar-364002, Gujarat, India
*
S Supporting Information

ABSTRACT: Dual, aqueous solubility behavior of Na2SO4 as a function of

temperatures is still a natural enigma lying unresolved in the literature. The
solubility of Na2SO4 increases up to 32.38 C and decreases slightly thereafter at
higher temperatures. We have thrown light on this phenomenon by analyzing the
Na2SO4water clusters (growth and stability) detected from temperature-
dependent dynamic light scattering experiments, solution compressibility changes
derived from the density and speed of sound measurements, and water structural
changes/Na2SO4 (ion pair)water interactions observed from the FT-IR and 2D
DOSY 1H NMR spectroscopic investigations. It has been observed that Na2SO4
water clusters grow with an increase in Na2SO4 concentration (until the solubility
transition temperature) and then start decreasing afterward. An unusual decrease
in cluster size and solution compressibility has been observed with the rise in
temperature for the Na2SO4 saturated solutions below the solubility transition temperature, whereas an inverse pattern is
followed thereafter. DOSY experiments have indicated dierent types of water cluster species in saturated solutions at dierent
temperatures with varying self-diusion coecients. The eect of NaCl (515 wt %) on the solubility behavior of Na2SO4 at
dierent temperatures has also been examined. The studies are important from both fundamental and industrial application
points of view, for example, toward the clean separation of NaCl and Na2SO4 from the euent streams of textile and tannery
industries.

1. INTRODUCTION intention is to shed light on this intriguing phenomenon that

Sodium sulfate (Na2SO4) is a mineral of universal distribution
and is widely used in many chemical industries such as in
detergents, pulp/paper, textiles, leather tanning, or glass and is
also used as a phase change thermal energy storage material. In
Na2SO4H2O systems, it occurs in two stable phases, that is,
below 32.38 C as mirabilite (Na2SO410H2O; Glaubers salt)
and above this temperature as thenardite (Na2SO4).13 The
solubility of sodium sulfate is of geological interest in
connection with the natural occurrence of the minerals and
water that contain it and also in reference to methods of
separation and extraction from the mixtures in which it occurs.
Temperature-dependent solubility behavior of Na2SO4, how-
ever, is peculiar among all of the alkali metals sulfates. The
solubility of Li2SO4 decreases, and that of K2SO4, Rb2SO4, and
Cs2SO4 increases almost linearly with the increase in temper-
ature; a sharp increase in the solubility is observed for Na2SO4
up to 32.38 C, and thereafter, it starts decreasing slightly with
the further rise in temperature (Figure S1, Supporting
Information).3 Although, the release of crystal water above
32.38 C has been cited as the reason for this behavior in the
literature, surprisingly, no information is available on why such
a transition occurs and how Na2SO4 interacts with water-
saturated solutions at various temperatures. Herein, our
is of considerable interest both fundamentally and technically
by analyzing the Na2SO4water solution structures.
There are reports in the literature on the characteristics of
aqueous salt solutions and their structures (existence of free
ions, solvated ions, ion pairs, and higher-order clusters)
investigated by employing various techniques, namely,
scattering, thermodynamic, and spectroscopic.422 Georgalis
et al. have detected the presence of large clusters in unsaturated
aqueous salt solutions under ambient conditions from dynamic
light scattering (DLS) experiments.4 In a recent paper, we have
also observed very large size salt water clusters in the saturated
solutions of NaCl, KCl, and NH4Cl solutions and correlated
the size and stability of clusters with their temperature-
dependent solubility behavior.5 In the saturated Na2SO4water
solutions, we have observed large size clusters that behaved in a
peculiar fashion as a function of temperature. At the
macroscopic level, thermodynamic and transport properties of
aqueous salt solutions have been found useful for elucidating
eect of salts on water structure and hydration of ions/ion
Received: August 6, 2014
Revised: October 14, 2014
Published: October 14, 2014

2014 American Chemical Society 12734 dx.doi.org/10.1021/jp507949h | J. Phys. Chem. B 2014, 118, 1273412742
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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Article
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