JPCB Salt Praveen - 2

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

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Article

Temperature-Dependent Solubility Transition of Na2SO4 in Water

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

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

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