Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 1705−1713 pubs.acs.org/IECR

Mechanism of Influence of Organic Impurity on Crystallization of

Sodium Sulfate
Nannan Su,† Yongli Wang,†,‡ Yan Xiao,† Haijiao Lu,† Yajing Lou,† Jingjing Huang,† Meng He,† Yang Li,†
and Hongxun Hao*,†,‡
†
National Engineering Research Center of Industrial Crystallization Technology, School of Chemical Engineering and Technology,
Tianjin University, Tianjin 300072, China
‡
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China
*
S Supporting Information
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ABSTRACT: To promote the development of crystallization technology for

recovering salt from high salinity wastewater, the effect of organic impurity on
crystallization of sodium sulfate was investigated by using phenol as a represen-
Downloaded via GAZI UNIV on February 12, 2024 at 07:11:01 (UTC).

tative organic impurity. The effect of phenol on crystallization thermodynamics

of sodium sulfate was evaluated by measuring solubility data of sodium sulfate in
water in the presence of phenol. It was found that the existence of phenol could
suppress the solubility of sodium sulfate in water. The effect of organic impurity
on crystal nucleation was performed by measuring the metastable zone width
(MSZW) and induction time of sodium sulfate. Two models (self-consistent
Nývlt-like equation and Classical 3D nucleation theory) were used to analyze the
experimental data. It was found that Classical 3D nucleation theory (3D CNT)
can better explain the effect of phenol on nucleation. From both MSZW data
and induction time data, it was found that the existence of phenol will apparently
increase the interfacial energy γ, which will result in higher nucleation Gibbs energy barrier and thus lower nucleation rate.
Furthermore, the existence of phenol will increase the critical nucleus radius r* and the critical Gibbs energy ΔG*, which means
that the formation of the nuclei will be more difficult in the presence of phenol. According to the above analysis, the possible
mechanism of influence of organic impurity on crystallization of sodium sulfate was proposed.

1. INTRODUCTION
As is well known, for natural resources, China is rich in coal
while poor in oil and gas. Therefore, coal is widely used in China
to produce necessary energy and raw materials for different indus-
tries. However, with the fast development of the coal industry, a
huge amount of wastewater is generated every year. With the
the concept of “zero emissions” put forward and stricter laws
and regulations on environmental protection in China, waste-
water from the coal industry is forbidden to be directly dis-
charged. As a result, many technologies, such as advanced oxi-
dization, membrane separation, and nanotechnology, have been
developed to treat wastewater. Generally, after membrane treat-
ment, high salinity wastewater with a high concentration of
sodium sulfate and sodium chloride will be obtained. To solve
the pollution issue of high salinity wastewater and to recover salt
from it, crystallization technology can be used to reclaim sodium
sulfate and sodium chloride from high salinity wastewater.
Generally, the existence of an organic impurity in wastewater,
which is inevitable, will affect the crystallization process and the
quality of the final product. Some studies have been conducted
to investigate the influence of impurities on the crystallization
of organic compounds. Lu et al.1 studied the effect of organic
additives (peptone, phenol, and heptanediacid) on the solubility,
supersolubility, and MSZW of sodium chloride in wastewater.
They found that organic additives will decrease the solubility
and increase the MSZW of sodium chloride. Peng et al.2 inves-
tigated the influence of anions on the nucleation of borax deca-
hydrate and found out that the addition of an impurity will
result in higher solubility, wider MSZW, and longer induction
time. Rajesh et al.3 and Dhanaraj et al.4 demonstrated that the
MSZW and the induction time of ammonium dihydrogen ortho-
phosphate (ADP) will be enhanced by urea and amino acid.
Becheleni et al.5 investigated the influence of phenol (0.2 wt %)
on CSD, purity, and morphology of sodium sulfate decahydrate
and found out that the crystal will be larger but the morphology
will not change in the presence of phenol.
However, no comprehensive research on the effect of typical
organic compounds on nucleation of sodium sulfate could be
found, although it is very important for the development and
optimization of crystallization technology for extracting sodium
sulfate from high salinity wastewater. Under this background, in
this work, the effect of an organic impurity on the crystallization
of sodium sulfate was investigated in detail by using phenol,
which is one of the typical organic impurities in high salinity
wastewater, as the representative impurity. The effect of phenol
Received: November 7, 2017
Revised: January 11, 2018
Accepted: January 13, 2018
Published: January 13, 2018

© 2018 American Chemical Society 1705 DOI: 10.1021/acs.iecr.7b04625

Ind. Eng. Chem. Res. 2018, 57, 1705−1713
Industrial & Engineering Chemistry Research Article

on crystallization thermodynamics was investigated by mea- ΔTmax 1‐m ⎛ ΔHS ⎞ 1 ⎛ f ⎞ 1

suring the solubility of sodium sulfate in water in the presence ln = ln⎜ ⎟ + ln⎜ ⎟ + ln R
T0 m ⎝ R GTlim ⎠ m ⎝ KT0 ⎠ m
of phenol. The effect of phenol on crystallization kinetics (mainly
nucleation) was evaluated by measuring the MSZW and induc- (5)
tion time of sodium sulfate in the presence of phenol. To inves- Therefore, the nucleation order, m, and ln ( f/KT0), can be got-
tigate the possible mechanism of influence of organic impurity ten from the slope and intercept of linear line of ln (ΔTmax/T0)
on crystallization of sodium sulfate, two different theoretical models versus ln R because ΔHS/RG can be calculated from the solu-
were used to analyze the experimental MSZW data and induc- bility data.
tion time data. 2.2. Classical 3D Nucleation Theory Model. According
The MSZW refers to the maximum supercooling ΔTmax to the classical nucleation theory, the nucleation rate can be
the difference between the saturation temperature T0 and the written as following:
temperature Tlim when visible crystals appear in the solution.6
The induction time is defined as the time interval between the ⎛ −16πγ 3V 2 1 ⎞
J = A exp⎜ 3
S
3 2
⎟
formation of a given supersaturation and the detection of the ⎝ 3kB Tlim ln S ⎠ (6)
crystals under the given supersaturation. Many techniques, such
as turbidity,7−9 conductivity,10 focused beam reflectance mea- where J is the rate of nucleation, A is the pre-exponential factor,
surements (FBRM), and attenuated total reflectance Fourier γ is the solid−liquid interfacial energy, VS is the molecular
transformed infrared (ATR-FTIR) spectroscopy,11,12 can be used volume, Tlim is the nucleation temperature, and S is the super-
to measure the MSZW and induction time. In this work, FBRM saturation.
was used to measure the MSZW and induction time. Combining eqs 4 and 6 allows the following equation to be
derived:
2. THEORETICAL MODELS
⎛ 16πγ 3V 2 ⎞⎛ R T ⎞2 ⎛ T ⎞2 ΔHS R
2.1. Self-Consistent Nývlt-like Model.13,14 The MSZW exp⎜ 3
S
⎟ G lim ⎟ ⎜ 0 ⎟ = f
3 ⎜
of a substance relies on various factors such as saturation temper- ⎝ 3kB Tlim ⎠⎝ ΔHS ⎠ ⎝ ΔTmax ⎠ R GTlim AT0 (7)
ature, impurities, seeds, stirring speed and cooling rate. Nývlt’s 15
equation which can be expressed by eq 1 has been widely used Taking the logarithm on both sides of eq 7 gives
because of its simplicity. ⎛ T0 ⎞2
⎜ ⎟ = F1(Χ + ln T0 − ln R ) = F − F1 ln R
1 − m ⎛⎜ dc ⎞⎟ 1 1 ⎝ ΔTmax ⎠ (8)
ln ΔTmax = ln ln k + ln R
m ⎝ dT ⎠ m m (1)
with F = F1(X + ln T0),
where ΔTmax is the MSZW. T and c refer to temperature and
3 kB Tlim ⎛ ΔHS ⎞
3 3 2
the mass fraction solubility, and R, m, and k denote the cooling
F1 = ⎜ ⎟
rate, apparent nucleation order, and nucleation constant, respec- 16π γ 3VS2 ⎝ R GTlim ⎠ (9)
tively.13 Generally, eq 1 can be used to correlate the measured
MSZW. However, the units of the calculated nucleation order ⎛ A R GTlim ⎞
and nucleation constant by eq 1 are complex13 and have no Χ = ln⎜ ⎟
physical significance. To overcome this disadvantage, Sangwal ⎝ f ΔHS ⎠ (10)
recently put forward the self-consistent Nývlt-like equation. where the constant A is related to the kinetics of nuclei for-
In this approach, the nucleation rate J was redefined as13 mation in the growth medium, kB is the Boltzmann constant
J = K (ln Smax )m (2) equal to RG/NA (NA is the Avogadro number).14 We can obtain
A and γ from the intercept and slope of the linear line of
According to regular solution theory, the correlation between (T0/ΔTmax)2 versus ln R.
the supersaturation ratio and the maximum temperature differ- Similar to the Arrhenius reaction rate equation, according to
ence can be written as13 the classical nucleation theory, the nucleation rate J can be
written as follows:
⎛ c ⎞ ⎛ ΔHS ΔTmax ⎞
ln Smax = ln⎜ 0 ⎟ = ⎜ ⎟ ⎛ ΔG ⎞
⎝ c lim ⎠ ⎝ R GT0 Tlim ⎠ (3) J = A exp⎜ ⎟
⎝ kBTlim ⎠ (11)
where c0 and clim are the solution concentrations corresponding
to saturation temperature, T0, and the nucleation temperature, where Gibb’s energy, ΔG, relies on nucleus radius r and can be
Tlim, respectively. Smax denotes the supersaturation ratio when given as following:
primary nucleation occurs.13 RG and ΔHS refer to the universal 4 3
gas constant and the dissolution enthalpy, respectively. ΔG = 4πr 2γ + πr ΔGv
3 (12)
In addition, the nucleation rate J is proportional to the rate of
change of solution supersaturation Δc/c0 with time t, where ΔGv is the Gibbs energy change of the transformation
per unit volume; and γ is the effective interfacial energy. When
Δc Δc ΔT ⎛ ΔHS ⎞⎛ R ⎞ d(ΔG)/dr = 0, the nucleus reaches the critical size, r* and
J=f =f = f⎜ ⎟⎜ ⎟
c limΔt c limΔT Δt ⎝ R GTlim ⎠⎝ T0 ⎠ (4) Gibbs energy ΔG reaches maximum, the critical radius can be
obtained as following equation:
where f is a constant and its unit is number of entities per unit 2γ
volume.13 Then, the following equations can be deduced from r* =
eqs 2, 3, and 4. ΔGV (13)

1706 DOI: 10.1021/acs.iecr.7b04625

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Industrial & Engineering Chemistry Research Article

According to Gibb’s−Thompson equation, fulfilled by a thermostat water bath (XOYS-2006, Nanjing Xianou
2γVS Technology Co. Ltd., China).7 A thermocouple thermometer
ln S = was used to record the temperature of the solution with a preci-
kBTlimr (14) sion of ±0.1 °C. The nucleation was monitored by using FBRM
Combining eqs 12, 13, and 14 allows the following equation to (G400, Mettler Toledo Instruments Co. Ltd., Switzerland). All
be obtained measurements were repeated at least three times to ensure the
reliability of the experimental data.16 Measurements of MSZW
16πγ 3VS2 and induction time were confirmed to be reliable with no large
ΔG* = deviations.
3(kBTlim ln S)2 (15)
3.2. Solubility Measurements. The solubilities of sodium
Theoretically, the induction time has an inverse ratio to the sulfate in water in the presence of phenol were measured by
nucleation rate: using the isothermal method.6 The concentrations of phenol in
water are 0.05%, 0.1%, 0.5%, 1%, 2%, 3% (mass fraction),
1
t ind∞ respectively. A known amount of water with phenol and excess
J (16) sodium sulfate decahydrate were added into the conical flask.
Taking the logarithm on both sides of eq 16 can give 15 First, the flask was maintained at a certain temperature and was
shaken for 12 h to make the solution reach solid−liquid equilib-
16πγ 3VS2 rium. It was confirmed by our pre-experiments that 8 h is long
ln t ind = Υ + enough for the system to reach equilibrium. Then, the oscillation
3kB3Tlim 3 ln 2 S (17)
was stopped and the solution was kept still for 1 h to ensure
2 settlement of the undissolved particles. Later, samples were
From the slope of the straight line of ln tind versus ln S, the
following value can be obtained: taken with a 2 mL syringe and filtered through nylon membranes
into 50 mL preweighed volumetric flasks, weighed, and diluted.
16πγ 3VS2 Finally, the concentration of sodium sulfate in solutions was
α=
3kB3Tlim 3 (18) obtained by automatic potentiometric titration (KH-100J, Taizhou
Datang Analytical Instrument Co. Ltd., China). Consequently,
Therefore, the interfacial energy can be obtained by the solubility data of sodium sulfate in the presence of phenol at
different temperatures were obtained.
⎛ 3αk 3T 3 ⎞1/3
γ=⎜ B lim
⎟ 3.3. MSZW and Induction Time Measurements. The
2
⎝ 16πVS ⎠ (19) MSZW experiments were conducted by using the conventional
polythermal method.6,17 Before measurements, to ensure the com-
plete dissolution of the solute, saturated solutions were maintained
3. EXPERIMENTAL SECTION at temperatures which are 5 °C higher than the saturation tem-
3.1. Materials and Instruments. Sodium sulfate decahy- peratures for 30 min under agitation of 300 rpm.16 Then, solu-
drate (analytical grade, ≥ 99.5% mass fraction purity) was tions were cooled down to saturation temperature and then fur-
purchased from Wind Boat Chemical Reagent Co. Ltd. Sodium ther cooled down at constant rates until nucleation was detected
sulfate anhydrous (guaranteed grade, ≥ 99.8% mass fraction by FBRM whose detecting frequency was set at 10 s. The dif-
purity) was purchased from Commie Chemical Reagent Co. ference between saturation temperature and the temperature
Ltd. Phenol (analytical grade, ≥ 99.5% mass fraction purity) corresponding to the onset of nucleation is defined as MSZW.16
was purchased from Yuanli Chemical Reagent Co. Ltd. Water The cooling rates are set at 12, 30, and 60 K/h, respectively.
(resistivity = 18.25 MΩ·cm) was deionized from a water puri- The induction time experiments were carried out with dif-
fication system. The prepared solutions were filtered through ferent supersaturation ratios from 1.2 to 1.36 at two different
nylon membranes (pore size = 0.45 μm).16 temperatures (293.15 K and 298.15 K). Induction time was
The solubility measurement experiments were carried out in measured by the isothermal method.17 First, saturated solutions
an immersion oscillator (WE-1, Tianjin Honor Instrument Co. were prepared according to solubility data. Then, they were
Ltd., China). The experiments of MSZW and induction time maintained at temperatures which are 5 °C higher than the sat-
were carried out in a 100 mL jacketed glass crystallizer with an uration temperature for 30 min under agitation of 300 rpm,16 to
agitation speed of 300 rpm by a magnetic stirrer (EMS-9A, Tianjin ensure the complete dissolution of the solute. Then, the solu-
Honor Instrument Co. Ltd., China) to ensure ideal mixing of tions were rapidly cooled down to a preset temperature and were
solution. Programmed heating and cooling of the solution was kept at constant temperature until nucleation was detected.

Table 1. Solubility Data of Na2SO4 in Water with Different Concentrations of Phenol at Different Temperatures from 278.15 to
303.15 K
C(g/100g)
w(phenol) (%) 278.15 K 283.15 K 288.15 K 293.15 K 298.15 K 303.15 K
0 6.383 9.111 13.12 19.50 27.88 40.80
0.05 6.268 8.774 12.71 18.30 26.50 38.69
0.1 6.149 8.670 12.55 18.21 26.48 38.56
0.5 5.998 8.563 12.41 17.96 26.29 38.20
1 5.871 8.528 12.32 17.67 25.91 37.91
2 5.542 8.039 11.71 17.11 25.16 37.69
3 5.175 7.676 11.00 16.58 24.93 36.98

1707 DOI: 10.1021/acs.iecr.7b04625

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Industrial & Engineering Chemistry Research Article

The induction time tind was the elapsing time from the reach
of target supersaturation to the detectio of the nucleation
phenomenon.
4. RESULTS AND DISCUSSION
4.1. Effect of Impurity on Solubility. To investigate the
effect of impurity on the thermodynamics of sodium sulfate, solu-
bilities of sodium sulfate in water with different concentrations of
phenol at different temperatures from 278.15 to 303.15 K were
measured. The results are shown in Table 1. It can be seen that
the solubility data decrease with the increasing concentration of
phenol and increase with the increase of temperature. The exper-
imental solubility data were correlated using empirical equations.

Figure 1. Experimental and correlated solubility data of sodium sulfate

in pure water and water with 3% phenol. Solid lines are correlated
values by the exponential function.

Figure 2. Experimental and correlated mole fraction solubility (ln x) of

sodium sulfate in water with 3% phenol versus 1/T. Solid line is
correlated values by the Van’t Hoff model.

Figure 4. Plots of ln (ΔTmax/T0) versus ln R at saturation temper-

Figure 3. MSZW of sodium sulfate in water with different concen- atures (a) 278.15 K, (b) 283.15 K, (c) 293.15 K, (d) 303.15 K. Lines
trations of phenol at saturation temperature (283.15 K). are fitted according to self-consistent Nývlt-like model.

1708 DOI: 10.1021/acs.iecr.7b04625

Ind. Eng. Chem. Res. 2018, 57, 1705−1713
Industrial & Engineering Chemistry Research Article

The results are shown in Table S1. The experimental and cor-
related solubility data of sodium sulfate in pure water and water
with 3% phenol are shown in Figure 1. As shown in Table S1 in
the Supporting Information and Figure 1, the experimental
results are well correlated as a function of temperature with the
exponential function.15 The solubility can also be described in
mole fraction x, which can be calculated by using eq 20
m1/M1
x=
m1/M1 + m2 /M 2 + m3 /M3 (20)
where m1, m2, and m3 refer to the mass of sodium sulfate, water,
and phenol, respectively. Similarly, M1, M2, M3 represent the
molar mass of sodium sulfate, water, and phenol, respectively.
From the literature,15 the data of ΔHS can be obtained from
the Van’t Hoff equation as follows
ΔHS ΔS
ln x = + like model, the plots of ln (ΔTmax/T0) versus ln R are shown in
R GT RG (21)
where x is mole fraction, T is the temperature in Kelvin, ΔHs is
the dissolution enthalpy, ΔS is the dissolution entropy and RG
is the gas constant (8.314 J K−1 mol−1). According to the eq 21,
the dissolution enthalpy can be obtained from the slope of the
straight line of ln x versus 1/T. As an example, the plot of ln x
versus 1/T in water with 3% phenol is shown in Figure 2. The
obtained ΔHs/RG are shown in Table S2.
4.2. Effect of Impurity on MSZW. To investigate the
effect of impurity on nucleation behavior of sodium sulfate, the
MSZW of sodium sulfate in the presence of phenol were measured
under different saturation temperatures and different cooling rates.
The MSZW of sodium sulfate in water with different concentra-
tions of phenol at saturation temperature 283.15 K are shown
in Figure 3 and all the MSZW data are listed in Table S3. And
the mean standard deviations of MSZW are given in Table S5.
It can be found that the MSZW increases with the increase of
saturation temperature and cooling rate. This result is different
from some other nucleation investigations. Generally, at higher
temperature, the concentration of salt will be higher, which will
increase the frequency of ions collision frequency and hence
promote the crystal nucleation rate. But on the other hand, with
the increasing of the concentration, the viscosity of solution will
also increase significantly, which will suppress the ion diffusion
process and hence delay the crystal nucleation process. Meanwhile,
at higher temperatures, the ions will possess higher energy,
meaning that more work is needed to fix them into the crystal
lattice, which will also delay the nucleation process. Therefore, the
nucleation process is controlled by many factors. As for sodium
sulfate, the restraining effect of higher viscosity and higher energy
of ions at higher temperature might be dominant and thus will
result in a wider MSZW. More importantly, it can be seen from
Figure 3 and Table S3 that the MSZW increases apparently
with the increasing of phenol concentration. This phenomenon
is in accordance with the result that the MSZW of ammonium
dihydrogen orthophosphate (ADP) was enhanced by the addi-
tion of the organic compounds (urea, L-arginine monohydro-
chloride, and L-alanine).3,4
To investigate the affecting mechanism of impurity on nucle-
ation of sodium sulfate, Self-consistent Nývlt-like model and
Classical 3D nucleation theory model were used to analyze the
experimental MSZW data. According to Self-consistent Nývlt-
Figure 4. It can be clearly seen that all the plots are straight
lines. The model parameters (listed in Table 2 and Table 3) can
be obtained by using these plots. According to Classical 3D
nucleation theory, plots of (T0/ΔTmax)2 versus ln R are plotted.
The results are shown in Figure 5. Again, it can be clearly seen
that all the plots are also straight lines. The model parameters
(listed in Table 4 and Table 5) for Classical 3D nucleation theory
were also obtained by using these plots.
From Tables 2 and 3 and Tables 4 and 5, it can be seen that
there is no regular relationship between the concentration of
phenol with the nucleation order m, the constant K and A of
sodium sulfate. From Table 4, it can be seen that, for all tested
temperatures and concentrations of impurity, the interfacial
energy γ increases with the increase of concentrations of phenol.
Although both of the two models can well correlate the MSZW
data with no significant deviations, the model parameters of the
Nývlt-like model had no apparent physical significance and hence
it is difficult to use the Nývlt-like model to interpret the influence
of impurity. However, the model parameters in the CNT model
are associated with the kinetic and thermodynamic of formation
of nuclei and γ shows a good correlation with the impurity
concentrations. Therefore, in this work, the CNT model was
used to explain the influence of impurity. According to the CNT
model, the increasing value of interfacial energy γ will increase
the nucleation Gibbs energy barrier and thus make the nucleation

Table 2. Calculated m for Sodium Sulfate in Both Pure and Impure Systems
m
w(phenol) (%)
T0 (K) 0 0.05 0.1 0.5 1 2 3
278.15 8.347 7.347 7.163 7.849 8.258 9.132 11.27
283.15 4.361 4.868 9.033 7.199 8.482 9.950 10.49
293.15 5.000 4.854 9.302 8.826 8.203 7.949 7.806
303.15 5.562 8.052 5.203 7.513 6.188 6.631 7.037

Table 3. Calculated K for Sodium Sulfate in Both Pure and Impure Systems
K(×1031 m−3·h−1)
w(phenol) (%)
T0 (K) 0 0.05 0.1 0.5 1 2 3
278.15 4218 365.6 39.31 57.91 44.78 67.84 458.9
283.15 0.9991 1.638 373.7 15.22 51.94 153.4 166.0
293.15 2.213 1.026 545.4 59.36 38.62 11.57 5.433
303.15 1.123 6.781 0.5001 8.714 1.080 1.157 1.149

1709 DOI: 10.1021/acs.iecr.7b04625

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2 respectively. f 0 and fc are the corresponding activity coefficients,
Figure 5. Plots of (T0/ΔTmax) versus ln R at saturation temperatures
(a) 278.15 K, (b) 283.15 K, (c) 293.15 K, (d) 303.15 K. Lines are
fitted according to 3D CNT model.
more difficult. That means higher concentration of phenol will
make the nucleation of sodium sulfate more difficult, which will
result in wider MSZW.
4.3. Effect of Impurity on Induction Time. The induc-
tion time tind measured at different supersaturations and different
concentrations of phenol are graphically shown in Figure 6 and
listed in Table S4. The mean standard deviations of induction
1710
Article
time are also given in Table S6. It can be seen that the induction
time decreases dramatically with the increasing of supersaturation
ratio S while it increases obviously with the increase of temper-
ature. The effect of temperature on induction time could be
explained by the fact that the increase of solubility of sodium
sulfate with temperature will cause apparent viscosity increase
in the system, which will delay the crystal nucleation process.
It can also be seen that the induction time increases with the
increasing concentrations of phenol. That means the existence
of phenol will delay the nucleation of sodium sulfate. This result
is in accordance with the effect of amino acid materials (L-arginine
monohydrochloride and L-alanine) on the induction time of ADP:
the induction time increases with the increasing concentrations
of impurity.
To further investigate the effect of impurity on nucleation of
sodium sulfate, the relationships between ln tind versus 1/(ln2S)
in pure and impure systems are displayed in Figure 7. It can be
seen that all lines are linear, which is consistent with classical
nucleation theory. From Figure 7, the interfacial energy γ can
be obtained from the slopes of the straight lines according to
eq 19. The results are listed in Table 6, it can be seen that the
interfacial energy γ increases with the increasing temperature
and the increasing concentration of phenol. The higher inter-
facial energy at higher temperature could also be explained by
the higher viscosity of the system at higher temperature since
higher viscosity will generally result in higher interfacial energy.
These results are not unique in the nucleation studies. For exam-
ple, Maheswata and Debasis18 also reported an increase of the
interfacial energy of L-asparagine monohydrate with increasing
temperature. Meanwhile, Zhou et al.19 also reported the same
results with analgin. The effect of impurity on interfacial energy
confirms again that the existence of impurity will make the
nucleation more difficult. The critical nucleus radius r* and the
critical Gibbs energy ΔG* were also obtained according to eq 13
and eq 15, and listed in Table 7 and Table 8. It can be seen that
the critical nucleus radius r* and the critical Gibbs free energy
ΔG* all increase with the addition of phenol. According to clas-
sical nucleation theory, the increasing critical nucleus radius and
the increasing critical Gibbs free energy will increase the nucle-
ation Gibbs energy barrier, which will make the formation of
new nuclei more difficult. Therefore, all these data confirm that the
existence of phenol will restrain the nucleation of sodium sulfate.
It is worth noting that the interfacial energy γ calculated by
isothermal method is slightly lower than the interfacial energy γ
obtained by the polythermal method. This might be caused by
the underestimated value of ln S. The chemical potential differ-
ence Δμ for crystallization is given by20,21
Δμ = R GTC ln(α0/αC) = R GTC ln S = R G
TC[ln(c0/cC) + ln(f0 /fC ) (22)
where α0 and αc are the activities of the solution at T0 and Tc,
and
Δμ = (ΔHS/T0)ΔT (23)
In our calculations of ln S, we used the values of the concen-
trations c0 and cc alone. Since the ratio f 0/fc > 1 for aqueous
solutions of fairly soluble electrolytes, this will make the value
of ln S lower than the real values obtained from the activities of
the solution. Therefore, the interfacial energy γ calculated using
ln S in the isothermal method will be lower than the values
obtained from ΔTmax (MSZW) by the polythermal method.2
DOI: 10.1021/acs.iecr.7b04625
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Industrial & Engineering Chemistry Research Article

Table 4. Calculated γ for Sodium Sulfate in Both Pure and Impure Systems
γ (mJ·m−2)
w(phenol) (%)
T0 (K) 0 0.05 0.1 0.5 1 2 3
278.15 7.844 8.131 8.352 10.04 10.05 10.98 11.84
283.15 7.021 7.698 10.89 11.11 11.40 12.03 12.49
293.15 7.929 8.427 11.13 11.48 11.78 13.39 14.34
303.15 10.21 10.82 11.64 12.34 13.00 14.15 16.04

Table 5. Calculated A for Sodium Sulfate in Both Pure and Impure Systems
A(×1028m−3·h−1)
w(phenol) (%)
T0 (K) 0 0.05 0.1 0.5 1 2 3
278.15 27.76 24.37 5.985 18.98 9.582 12.72 15.95
283.15 3.780 4.762 19.43 17.03 31.60 26.03 22.98
293.15 4.910 4.605 21.55 14.24 29.37 59.83 80.30
303.15 5.892 8.059 14.70 18.97 23.30 35.95 113.9

Figure 6. Plots of induction time tind versus supersaturation ratio S at Figure 7. Plots of ln tind versus 1/(ln2S) at saturation temperatures
saturation temperatures (a) 293.15 K and (b) 298.15 K. The lines are (a) 293.15 K and (b) 298.15 K in water with different concentrations
guides to the eye. of phenol. Lines are fitted according to CNT model.

4.4. Possible Mechanism of the Effect of Impurities on
Crystallization. Crystallization in multicomponent systems will
be influenced by various factors, such as solutes, foreign mole-
cules, additives, and other components. Generally, impurities will
affect both thermodynamics and kinetics of the crystallization.
In this work, obviously, the solubility is significantly affected by
the existence of phenol. According to the data of MSZW and
tind, the interfacial energy γ which is a key parameter for the
nucleation of crystals was also affected by the existence of
phenol. Therefore, the existence of phenol will affect both the
thermodynamics and kinetics of sodium sulfate. The effect of
the phenol may be explained by the interaction between phenol
1711
and sodium sulfate. There is a double bond of sulfur−oxygen in
sodium sulfate while there is π bond in phenol molecules.
Therefore, hydrogen bond could be formed between phenol
and sodium sulfate and it will affect the formation of sodium
sulfate decahydrate. To investigate the effect of the hydrogen
bond, molecular dynamic simulation was carried out. The results
showed that the energy of crystallization system changed from
−61390.7 kcal/mol to −61672.1 kcal/mol with the addition of
phenol, which reveals that the system is more stable in the pres-
ence of phenol. Meanwhile, the bond distance between phenol
and sodium sulfate is 1.386 Å while the average bond distance
between water and sodium sulfate is 1.7395 Å. These data
DOI: 10.1021/acs.iecr.7b04625
Ind. Eng. Chem. Res. 2018, 57, 1705−1713
Industrial & Engineering Chemistry Research Article

Table 6. Calculated γ for Sodium Sulfate in Both Pure and Furthermore, the effect of the existence of phenol on nucle-
Impure Systems by tind ation of sodium sulfate was also investigated by measuring the
induction time. It was found that the induction time became
γ (mJ·m−2)
longer with the increasing concentration of phenol. According
S 0 0.05% 0.1% 0.5% 1% 2% 3% to classical nucleation theory, it was confirmed again by the
T0 (K) = 293.15 induction time that the existence of phenol will increase the
1.356 7.117 7.455 7.889 8.281 8.304 8.320 8.468 interfacial energy γ, the critical nucleus radius r* and the critical
1.305 7.129 7.468 7.902 8.295 8.318 8.335 8.483 Gibbs energy ΔG*, which means that the formation of the
1.257 7.141 7.480 7.916 8.309 8.333 8.349 8.497 nuclei will be more difficult with the addition of phenol. This
1.211 7.154 7.493 7.930 8.324 8.347 8.364 8.512 phenomenon could be explained by the strong interaction between
T0 (K) = 298.15 phenol and sodium sulfate molecules.
1.356 8.192 8.700 8.734 8.775 8.784 8.795 8.808 The results presented in this work could help us to develop
1.305 8.206 8.715 8.749 8.790 8.800 8.810 8.823 and optimize the crystallization technology for extracting sodium
1.256 8.220 8.730 8.764 8.805 8.814 8.825 8.838 sulfate with ideal properties from high salinity wastewater.
1.210 8.234 8.744 8.779 8.820 8.829

Table 7. Calculated r* for Sodium Sulfate in Both Pure and

Impure Systems
8.840 8.853
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
r* (×10−10m) ACS Publications website at DOI: 10.1021/acs.iecr.7b04625.
S 0 0.05% 0.1% 0.5% 1% 2% 3% Detailed information on solubility equations, correlated
T0 (K) = 293.15 dissolution enthalpy, the data of MSZW and induction
1.356 2.863 2.999 3.174 3.331 3.341 3.347 3.407 time, the mean standard deviations in MSZW and induc-
1.305 3.266 3.421 3.620 3.800 3.811 3.818 3.886 tion time for sodium sulfate in pure and impure systems
1.257 3.802 3.983 4.214 4.424 4.436 4.445 4.524 (PDF)

■
1.211 4.550 4.766 5.043 5.294 5.309 5.319 5.414
T0 (K) = 298.15
1.356 3.238 3.439 3.452 3.469 3.472 3.476 3.482
AUTHOR INFORMATION
1.305 3.700 3.930 3.945 3.964 3.968 3.972 3.978 Corresponding Author
1.256 4.317 4.584 4.603 4.624 4.629 4.634 4.641 *E-mail: hongxunhao@tju.edu.cn. Tel.: 86-22-27405754. Fax:
1.210 5.181 5.502 5.524 5.550 5.555 5.562 5.571 +86-22-27374971.
ORCID
indicate that the nucleation of sodium sulfate will become more
difficult in the presence of phenol. Hongxun Hao: 0000-0001-6445-7737
Notes
5. CONCLUSIONS The authors declare no competing financial interest.
The effect of phenol on crystallization thermodynamics of sodium
sulfate was performed by measuring solubility data of sodium
sulfate in water in the presence of phenol. It was found that the
■ ACKNOWLEDGMENTS
This work is financially supported by the National Key Research
existence of phenol will decrease the solubility of sodium sulfate and Development (No. 2016YFB0600504)

in water. Higher concentration of phenol will result in lower solu-
bility of sodium sulfate. The effect of an organic impurity on crys-
tal nucleation was investigated by measuring the MSZW of
sodium sulfate. Two models (Nývlt-like equation and 3D CNT)
were used to analyze the experimental data. It was found that 3D
CNT theory can better explain the effect of phenol on nucle-
ation. The addition of phenol will apparently increase the inter-
facial energy γ, which will result in higher nucleation Gibbs
energy barrier and thus lower nucleation rate.
■
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1712 DOI: 10.1021/acs.iecr.7b04625

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1713 DOI: 10.1021/acs.iecr.7b04625

Ind. Eng. Chem. Res. 2018, 57, 1705−1713