ARTICLE IN PRESS

Journal of Crystal Growth 311 (2009) 47144719

Contents lists available at ScienceDirect

Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Unseeded Supersolubility of Lithium Carbonate: Experimental Measurement

and Simulation with Mathematical Models
Yuzhu Sun, Xingfu Song , Jin Wang, Yan Luo, Jianguo Yu
National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Technology, Shanghai 200237, China

a r t i c l e in f o

a b s t r a c t

Article history:
Received 10 October 2008
Received in revised form
6 July 2009
Accepted 13 September 2009
Communicated by J. de Yoreo
Available online 22 September 2009

A laser aparatus was employed to investigate the unseeded supersolubility values of Li2CO3 in aqueous
solution. It shows the supersolubility of Li2CO3 decreases with the raise of temperature and stirring
speed, and with a reduction of feeding rate of Na2CO3. The introduce of ultrasound eld leads to obvious
reduction on supersolubility, whereas magnetic eld causes little effect. The involving factors of
impurities and additives on the supersolubility were also studied. It is found that the supersolubility
value decreases with the addition of NaCl, KCl, NaNO3 and NaBr, while increases at the presence of
Na2SO4, CH4N2O, NH4Cl, (NH4)2SO4 and EDTA disodium. Meanwhile, two mathematical models,
empirical correlation and BP neural network, were used to simulate the supersolubility value as a
function of temperature and feeding rate of Na2CO3. Compared with empirical correlation method, BP
neural network simulation has better consistence with the experimental data.
& 2009 Elsevier B.V. All rights reserved.

PACS:
81.10.Dn
82.60.Nh
Keywords:
A1. Supersaturated solutions
A2. Growth from solutions
B1. Lithium compounds
B3. Laser method

1. Introduction
Li2CO3 has wide applications in ceramic, glass, metallurgy,
pharmaceuticals and atomic energy industry. Ore and salt lakes
are two main lithium resources, and the latter one contains 69% of
the total reserve [1]. Reactive crystallization of Li2CO3 is the
key method to harvest solid lithium product, whether from ore
or salt lake resource, sodium carbonate is introduced to
concentrated lithium solution to precipitate Li2CO3, from which
many derivatives of lithium compound can be produced.
So reactive crystallization of Li2CO3 has attracted increasing
reseach interest.
Solubility and supersolubility are two key parameters in
crystallization processes, since they set the limits of metastable
state and crystallization operation has to be controlled within the
metastable state. Until now, the solubility of Li2CO3 has been well
studied [2], but its supersolubility remains limited explored.
Various techniques have been applied on supersolubility
measurement, such as naked eye [3], particle counter [4],
turbidity meter [5], ultrasound sensor [6], electrical conductivity
[7], etc. The laser method [8,9] has recently become popular

 Corresponding author. Tel.: + 86 021 64252170; fax: + 86 021 64252826.

E-mail addresses: yzsun@mail.ecust.edu.cn (Y. Sun), xfsong@ecust.edu.cn

(X. Song).
0022-0248/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2009.09.013

because of its high efciency and accuracy, while process

analytical technologies (PAT) like ATRFTIR spectroscopy [10,11],
Raman spectroscopy [12] and FBRM [13,14] are considered to
present promising future. Herein we will present a novel laser
method to determine Li2CO3 supersolubility.
In addition to this, compared with the simple solubility
having only a specic value in a certain system, the supersolubility parameter is quite complicated and may be inuenced
by many factors, such as stirring speed, seed presence or cooling
rate [15]. Although many researchers have tried to calculate the
supersolubility value [1619], no perfect model can be used to
predict accurate supersolubility so far. Another goal of this article
is to establish proper models to simulate the Li2CO3 supersolubility under various conditions.

2. Experimental
2.1. Materials
LiCl  H2O (AR) was obtained from Sinopharm Chemical
Reagent Co., Ltd., Na2CO3 (AR) was purchased from Shanghai
Hongguang Chemicals Factory, Li2CO3 (high purity Z99.99%,) was
provided by Shanghai Zhongli Co., Ltd. All the impurities and
additives (AR), including NaCl, KCl, Na2SO4, NaNO3, NaBr, CH4N2O,

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Y. Sun et al. / Journal of Crystal Growth 311 (2009) 47144719

Nomenclature
a
C
Csp
Cn

activity (mol/L)
Concentration (mol/L)
supersolubility (mol/L)
solubility, (mol/L)

NH4Cl, (NH4)2SO4 and EDTA disodium, were obtained from

Shanghai Lingfeng Chemical Reagent Co., Ltd.
The solutions were prepared with deionized water and ltered
through 3 mm membrane to eliminate impurities nuclei, which
may inuence the crystallization process. The concentrations
of LiCl and Na2CO3 were determined by ion chromatogram
(Metrohm, Switzerland), while the concentration of Li2CO3 was
determined by titration.
2.2. Set up
The experimental set up for measuring supersolubility is
shown in Fig. 1a. The crystallizer is a 150 mL jacketed glass
vessel with an internal diameter 45 mm, and its temperature was
controlled by a water-bath (DC2006, Shanghai Hengping
Apparatus Factory) with an accuracy of 0.1 1C. A magnetic stirrer
was adopted to ensure rapid mixing. Na2CO3 solution was added
by a peristaltic pump (DDB-320, Shanghai Zhingxin Apparatus Co.,
Ltd.). The laser apparatus (Shanghai Institute of Laser Technology)
composes of a laser generator, a photoelectric transformer, and a
computer to display and record the light intensity. The laser
generator can emit monochromatic spectrum with a wave length
632.8 nm, which transmits through the reactants in the
crystallizer.
The schematic diagram for solubility measurement is shown
in Fig. 1b. There were 9 tubes (diameter:15 mm) with a capacity
of 15 mL in the equilibrium cell (diameter: 90 mm). The solutions
temperature was controlled by a water-bath (THGD2015, Ningbo
Tianheng apparatus factory, China), which equipped with a
digital temperature controller and a circulation unit to keep
the temperature constant at 293.15 K with a stability of 0.02 K.
To speed up the equilibrium process, a magnetic stirrer rod was
used in each tube.
2.3. Procedures
Supersolubility measurement of Li2CO3 by the laser method
was as follows. Firstly, 40 mL LiCl solution (3.215 mol/L, except
those experiments to investigate the impact of LiCl concentration
on Li2CO3 supersolubility) was introduced into the crystallizer,
and then initiated water-bath and agitation at 500 rpm (except

4715

activity product constant

solubility product constant
relative supersaturation
relative supersaturation at Csp
temperature (1C)
feeding rate of Na2CO3

Kap
Ksp
S
Ssp
T
u

those experiments to investigate the impact of stirring speed).

When the solution temperature stabilized, turned on the laser
apparatus and peristaltic pump to feed Na2CO3 solution
(1.037 mol/L), this time was recorded as the start time. In the
initial period, the solution was clear and light intensity kept
constant, whereas when the primary nucleation occurred, for
diffraction and dispersion effect, the light intensity decreased
sharply. The amount of Na2CO3 volume added can be calculated
according to the interval between start time and the sudden drop
of light intensity. Each measurement was repeated 35 times
to obtain the average, and the deviations were less than 3%.
During the experiment, the crystallizer was sealed to avoid any
evaporation.
The experimental procedures of Li2CO3 solubility measurement in the presence of impurities or additives are described
briey below. Excessive Li2CO3 powders were added into the
tubes, which followed with the introduction of impure aqueous
solutions and magnetic stirrer rods. Next sealed the tubes, and
then initiated the water bath and agitation. The equilibrium time
lasted for 48 h. The concentrations of dissolved Li2CO3 were
titrated by dilute HCl solution.

3. Results and Discussion

3.1. Calculation of supersolubility
The rigorous denition of relative supersaturation is expressed
as Eq. (1), but due to the absence of activity coefcients of Li + and
CO23  in the multi-components system of Li + Na + Cl  CO23 
over a relatively wide temperature range (1080 1C) and at a high
ion strength level (more than 3 mol/L), for the convenience of
practical application in production, it is reasonable to simplify the
relative supersaturation denition as Eq. (2) as Li2CO3 is a
sparingly soluble salt. Then the supersolubility can be obtained
by the relationship between relative supersaturation and solubility by Eqs. (3) and (4).
!1=3
aLi 2 aCO2
3
1
S
Kap

!1=3
CLi 2 CCO2
3

Ksp

Csp
C

Csp Ssp  C

Ssp

3.2. Unseeded supersolubility in pure aqueous solution

Fig. 1. Experimental set up. (a) Experimental set up for supersolubility measurement. 1crystallizer; 2magnetic stirrer; 3thermometer; 4,5,6laser apparatus system; 7water bath; 8peristaltic pump; 9Na2CO3 solution. (b)
Experimental set up for solubility measurement. 1equilibrium cell; 2magnetic
stirrer; 3water bath.

3.2.1. Impact of feeding rate of Na2CO3

As can be seen in Fig. 2, with the increase of feeding rate of
Na2CO3 solution, supersolubility of Li2CO3 also rises up. This is
because when the solution creates supersaturation, it does not
undergo nucleation at once, but still needs a period, namely

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Y. Sun et al. / Journal of Crystal Growth 311 (2009) 47144719

Fig. 2. Effect of feeding rate of Na2CO3 on supersolubility (20 1C, 500 rpm).

Fig. 4. Effect of stirring speed on supersolubility (20 1C, u= 0.8 mL/min).

must lead to a much rapid reaction and nucleation rate, as a

result, reduces the supersolubility obviously. Generally, wider
metastable zone width is preferred in the crystallization process,
so LiCl concentration more than 5.25 mol/L should be avoided,
which is not only unsuitable for the operation control but also
consume much energy and time to concentrate dilute raw
materials to such a level.
Of course, metastable zone width is just one factor that should
be taken into consideration in the determination of reactants
concentrations. The concentrations should vary according to
different operation methods (batch, semi-batch or continuous
crystallization) and balance the process control, product yield,
crystals properties, production cost, etc., to obtain the optimum
values.

Fig. 3. Effect of LiCl concentration on supersolubility (20 1C, 500 rpm, u= 0.8
mL/min).

induction period, while in the time lag, the feed of reactant

is going on. This means that compared with the lower feeding
rate, the higher feeding rate would introduce more Na2CO3
reactant to the LiCl solution and result in the enhancement of
supersolubility. There are similar phenomenon in cooling
crystallization [2022], showing supersolubility goes up with
the increase of cooling rate. In essence, whether reactant feeding
rate or cooling rate, decides the increasing rate of supersaturation,
so such a conclusion may be achieved: for a given substance,
the higher increasing rate of supersaturation, the higher
supersolubility.

3.2.2. Impact of reactant concentration

Semi-batch reactive crystallization of Li2CO3 (LiCl+ Na2CO3) is
an important operation in production, so it is signicant to
determine a proper concentration range for LiCl. Fig. 3 illustrates
the effect of LiCl concentration on the supersolubility of Li2CO3. It
is clear that when LiCl concentration is beyond 5.25 mol/L, the
supersolubility level drops down steeply. This is because
concentration is a decisive kinetic factor, high concentration

3.2.3. Impact of stirring speed

The stirring speed varied from 100 to 900 rpm. Fig. 4 shows the
rise of stirring speed leads to a slight decrease on supersolubility.
On the one hand, stir can accelerate mass transportation and
facilitate nucleation; on the other hand, stir may crack the crystal
embryos and impede the formation of nuclei, thus, the eventual
result is the synergystic effect. This reason may accounts for the
slight increase of supersolubility at 500 rpm.

3.2.4. Impact of eld effect

The solutions were magnetized in a home-made device
(magnetic intensity: 0.3 T) for 4 h. Fig. 5 shows that magnetic
eld only causes slight reduction on supersolubility of Li2CO3.
The probe of ultrasonic equipment (JYD-900L, Shanghai Zhixin
Co., Ltd.) was inserted in the solution when exerting ultrasound
eld. The period of the ultrasound burst was set to 1 s with a
pause of 2 s between two ultrasound bursts. From Fig. 5 we can
see ultrasound reduces supersolubility obviously. This is because
the alternation vibration of the cavitation bubbles and the
pressure caused by the collapse of bubbles can increase diffusion
coefcient, moreover, the hot point caused by ultrasound
enhances the supersaturation in some micro-local region (Li2CO3
is a special salt, its solubility decreases with the increase
of temperature, see Fig. 6). Consequently, ultrasound accelerates
the primary nucleation process and leads to a lower
supersolubility.

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Y. Sun et al. / Journal of Crystal Growth 311 (2009) 47144719

4717

cantly. These impurities may be components present in the

reactants or reaction byproducts, additives are some compounds
purposely added in order to widen metastable zone width
(MSZW), restrain nucleation, control growth rate or improve the
crystal morphology. There are mainly two ways for impurities
or additives to inuence the crystallization process: the rst one is
the thermal mechanism, they can change the properties
of solution (structural or otherwise) and then inuence the
supersaturation [23]; the second is kinetic mechanism, they
can be adsorbed on some certain crystal face and alter the step
advancement velocity [2426], they may be built into the crystal,
especially if there is some degree of lattice similarity.
In this research, the dissolution quantity of Li2CO3 crystals in
the binary system of LiCl (3.215 mol/L)H2O and in the ternary
system of LiCl (3.215 mol/L)impurities/additives (0.250 mol/L or
0.050 mol/L)H2O were studied qualitatively to test whether or
not the thermal mechanism plays a role in inuencing supersolubility values.
Fig. 5. Effect of magnetic eld and ultrosonic eld on supersolubility
(u= 0.8 mL/min).

3.3.1. Impact of impurities

KCl, NaCl and Na2SO4 are the main components accompanying
Li2CO3 in salt lakes [27], so this research rstly chose them as the
impurities. The proportion of these impurities to LiCl varied from
1% to 5% (molar proportion). From Fig. 7a we can see that Na2SO4
enhances supersolubility, while KCl and NaCl cause very slight
decrease. Fig. 7b shows the presence of Na2SO4 results in an
enhancement on Li2CO3 solubility, while KCl and NaCl lead to a
decrease, indicating these impurities can change the solubility
product constant and inuence the supersolubility of Li2CO3 by a
thermal mechanism.

3.3.2. Impact of additives

Effect of several additives on supersolubility values of Li2CO3
were investigated (see Fig. 7c and see Fig. 7e). It is found that NaBr
and NaNO3 decrease supersolubility, whereas carbamide
(CH4N2O), NH4Cl, (NH4)2SO4 and EDTA disodium increase supersolubility, especially (NH4)2SO4 and EDTA disodium have the most
obvious impact. From Fig. 7d and Fig. 7f we can see the thermal
mechanism can also explain the results, for these additives which
have the same effect on solubility and supersolubility.
Fig. 6. Metastable zone of Li2CO3 in aqueous solution (500 rpm, u= 0.8 mL/min).

3.4. Simulation
3.2.5. Metastable zone
Fig. 6 shows the metastable zone of Li2CO3. Solubility data of
Li2CO3 were quoted from the literature [2], in which the solubility
values at 50 and 70 1C are lacking, because the other achieved
values present very good linear relation, so these two values
were supplemented through interpolation. As can be seen,
supersolubility curves of Li2CO3 have the same trend as its
solubility line, going down with the rise of temperature.
The supersolubility curves are basically paralell, and supersolubility curve with higher feeding rate of Na2CO3 is above to
that with lower feeding rate. With the increase of temperature,
metastable zone width narrows, because the higher temperature
can accelerate ion movement, intensify both the ion collision
frequency and mass transportation, thus, facilitates the earlier
appearance of nuclei.

3.3. Supersolubility in impure aqueous solution

In the industrial crystallization process, low concentration of
impurities or additives may alter crystallization process signi-

Experimental results show temperature and feeding rate of

Na2CO3 which are the main factors inuencing supersolubility, so
supersolubility values were simulated as a function of these two
variables in this research. The experimental scope were as
follows: LiCl concentration was 3.215 mol/L, temperature range
was 1080 1C, the feeding rate of Na2CO3 varied 0.2, 0.3, 0.4, 0.6,
0.8, 1.2 and 1.6 mL/min, totalling 56 data (for the limitation of
papers length, the overall experimental values are not listed, part
of which are shown in Fig. 6).

3.4.1. Empirical correlation

It is interesting to point out that supersolubility values and the
feeding rate of Na2CO3 present very obvious logarithm relation
(see Fig. 2), so the supersolubility values were tted with the
following pure empirical equation, with which the supersolubility
values can be predicted.
Csp 0:04011 ln u  0:0052T 0:7051

Where Csp is the supersolubility value, u the feeding rate of

Na2CO3, T the temperature.

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Y. Sun et al. / Journal of Crystal Growth 311 (2009) 47144719

Fig. 7. Effect of impurities/additives on supersolubility ((a)(c)(e), (20 1C, 500 rpm, u= 0.8 mL/min)) and on solubility ((b)(d)(f), (20 1C)).

3.4.2. BP neural network simulation

Neural network was ofen used as a black box to simulate
the complicated process that is difcult to be described by
a mechanism mode, but to the best of the authors knowledge, it
has not been adopted to calculate supersolubility. The structure of
neural network has important effect on its training and simulation, the number of neurons in input and output layers are
decided by the practical problem, while the number of hidden
layers and its neurons has no theoretical basis, mainly depend on
researchers experience.

Using neural network tool box of Matlab 6.5, such a topological

structure was set up (see Fig. 8). The two input variables are
temperature and feeding rate of Na2CO3, the output is
supersolubility. Through optimization, 8 neurons are set in the
one and only hidden layer. Other main parameters were set as
follows, network type: feed-forward backprop; training function:
trainlm; adaption learning function: learngdm; performance
function: mse; the two transfer functions are tansig and purelin.
A total of 56 samples were used as inputs to train the BP neural
network.

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Y. Sun et al. / Journal of Crystal Growth 311 (2009) 47144719

4719

temperature and stirring speed, and with a reduction of feeding

rate of Na2CO3. The introduction of ultrasound eld leads to
obvious reduction on supersolubility, whereas magnetic eld
causes the little effect. The impacts of several impurities and
additives on supersolubility were also investigated, NaCl, KCl,
NaNO3 and NaBr decrease supersolubility values, while Na2SO4,
CH4N2O, NH4Cl, (NH4)2SO4 and EDTA disodium enhance supersolubility degree.
Two methods, empirical tting and BP neural network, were
used to simulate supersolubility values as a function of temperature and feeding rate of Na2CO3. Results show BP neural network
has a better prediction, indicating neural network is a good
method to simulate supersolubility values, which may be
inuenced by many operating factors and lack perfect mechanism
model.

Fig. 8. Structure of BP neural network.

Acknowledgement
Table 1
Comparison of supersolubility between experimental values and simulation
results.
T/1C

u/ml min  1

Cexp/mol L  1

10
25
30
30
40
45
50
50
55
60
65
70
Mean

1
0.674
0.8
0.564
0.7
0.537
1.4
0.545
1
0.496
0.8
0.456
0.5
0.413
1.4
0.457
0.8
0.416
0.5
0.375
0.6
0.375
0.7
0.334
of relative error/%

Empirical tting
Csim/mol L  1 e/%

BP simulation
Csim/mol L  1 e/%

0.652
0.565
0.534
0.561
0.496
0.461
0.416
0.457
0.409
0.364
0.345
0.326

0.671
0.561
0.527
0.551
0.482
0.453
0.421
0.460
0.416
0.383
0.360
0.336

3.25
0.08
0.63
3.07
0.06
1.13
0.63
0.10
1.67
2.85
8.01
2.43
1.99

0.48
0.70
1.86
1.07
2.92
0.55
1.70
0.56
0.12
2.14
4.18
0.69
1.41

Another 12 experiments within the experimental scope

were conducted to test the simulation results. The mean
relative error of pure empirical tting and BP neural network
are 1.99 and 1.41 respectively (see Table 1), suggesting BP
neural network has a better agreement with the experimental
data.

4. Conclusions
The unseeded supersolubility values of Li2CO3 in aqueous
solution were measured by the laser method. Results show the
supersolubility values of Li2CO3 decreases with the raise of

This work was nancially supported by the Shanghai Leading

Academic Discipline Project (No. B506) and Program for New
Century Excellent Talents in University (NCET-08-0776).
References
[1] Y.Y. Zhao, Miner. Deposits 22 (2003) 99.
[2] J.W. Mullin, Crystallization, third ed., Butterworth-Heinemann, Oxford, 1992,
p. 437.
[3] O. Sohnel, J.W. Mullin, Chem. Eng. Res. Des. 66 (1988) 537.
[4] J.W. Mullin, Trans. Inst. Chem. Eng. 57 (1979) 188.
[5] B. Marciniak, J. Cryst. Growth 236 (2002) 347.
[6] H. Gurbuz, B. Ozdemir, J. Cryst. Growth 252 (2003) 343.
[7] O. Sohnel, J.W. Mullin, J. Cryst. Growth 44 (1978) 377.
[8] M. Kind, A. Mersmann, Chem. Eng. Technol. 13 (1990) 50.
[9] J.B. Gong, J.K. Wang, Chem. Ind. Eng. 21 (2004) 33.
[10] D. Dilum, Dunuwila, A. Kris, Berglund, J. Cryst. Growth 179 (1997) 185.
[11] F. Lewiner, J.P. Klein, F. Puel, G. Fevotte, Chem. Eng. Sci. 56 (6) (2001) 2069.
[12] H. Qu, M.L. Kultanen, J. Rantanen, J. Kallas, Cryst. Growth Des. 6 (9) (2006)
2053.
[13] P. Barrett, B. Glennon, Chem. Eng. Res. Des. 80 (7) (2002) 799.
[14] C. Lindenberg, M. Mazzotti, J. Cryst. Growth 311 (2009) 1178.
[15] X.H. Ding, Q. Tan, Industrial Crystallization, Chemical Industry Press, Beijing,
1985, p. 13.
[16] J. Nyvlt, J. Cryst. Growth 3/4 (1968) 377.
[17] N. Kubota, J. Cryst. Growth 310 (2008) 629.
[18] A. Mersmann, K. Bartosch, J. Cryst. Growth 183 (1998) 240.
[19] K.J. Kim, A. Mersmann, Chem. Eng. Sci. 56 (2001) 2315.
[20] J.W. Mullin, M. Chakraberty, K. Mehta, J. Appl. Chem. 20 (1970) 367.
[21] N. Lyczko, F. Espitalier, O. Louisnard, J. Schwartzentruber, Chem. Eng. J. 86
(2002) 233.
[22] Z.K. Nagy, M. Fujiwara, X.Y. Woo, R.D. Braatz, Ind. Eng.Chem. Res. 47 (2008)
1245.
[23] J.W. Mullin, Crystallization, third ed., Butterworth-Heinemann, Oxford, 1992,
p. 238.
[24] N. Kubotaa, M. Yokota, J.W. Mullin, J. Cryst. Growth 182 (1997) 86.
[25] K. Sangwal, J. Cryst. Growth 242 (2002) 215.
[26] P. Dold, E. Ono, K. Tsukamoto, G. Sazaki, J. Cryst. Growth 293 (2000) 102.
[27] Y.Y. Zhao, M.P. Zheng, L.Z. Bu, Acta Geoscientia Sin. 24 (5) (2003) 459.