Materials Chemistry and Physics xxx (2015) 1e9

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Materials Chemistry and Physics

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

Study of the synthesis and crystallization kinetics of magnesium

hydroxide
Qiuhua Yuan a, Zhengwu Lu b, Peixin Zhang a, **, Xiongbiao Luo a, Xiangzhong Ren a,
Teresa D. Golden c, *
a
School of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, China
b
Shenzhen Graduate School, Harbin Institute of Technology, Xili, Shenzhen 518055, China
c
Department of Chemistry, University of North Texas, 1155 Union Circle#305070, Denton, TX 76203, USA

h i g h l i g h t s

Ion conductivity method was used to study nucleation and growth of Mg(OH)2.

Induction times were determined for various concentrations and temperatures.

Kinetic parameters were determined from experimental data.

Particle size of the crystals were in the nanometer range.

a r t i c l e i n f o a b s t r a c t

Article history: The crystallization kinetics of magnesium hydroxide in low concentration solutions has been studied
Received 10 March 2015 using an electrical conductivity method. Using various experimental relationships, several kinetic factors
Received in revised form could be determined during the nucleation and growth process. From measurements of ion concen-
15 June 2015
trations at various temperatures, the induction period of nucleation could be determined. As concen-
Accepted 24 June 2015
Available online xxx
tration and temperature increase, the crystallization rate increases affecting the nucleation and crystal
growth of Mg(OH)2. The crystal-solution interfacial surface tension was also calculated and shown to be
affected by the magnesium anion source. The results show that a uniform particle size distribution of
Keywords:
Inorganic compounds
nuclei is formed during the initial homogeneous nucleation process and the nucleation and crystal
Crystal growth growth rates can be represented by a first order reaction equation. Through the study of crystallization
Precipitation kinetics, a control strategy is proposed to synthesize a uniform particle size distribution of magnesium
Chemical techniques hydroxide.
Electrical characterization (conductivity) © 2015 Published by Elsevier B.V.
Electron microscopy (SEM)

1. Introduction important [7]. Study on the crystallization kinetics of Mg(OH)2 can

Magnesium hydroxide (Mg(OH)2) is used in many industries.
For example, Mg(OH)2 can be used as a flame-retardant filler in
polymer and inorganic materials [1e4], acid neutralizer in the area
of environmental protection [5], and one of the raw materials for
the production of magnesium oxide [6]. Since the size and
morphology of Mg(OH)2 determine its properties, having a
controlled synthesis to obtain uniform particle size distribution is
* Corresponding author.
** Corresponding author.
E-mail addresses: pxzhang2000@163.com (P. Zhang),
(T.D. Golden).
provide important technological parameters for production in
industry.
When the ion product of Mg(OH)2 is greater than its solubility
product in solution, it is possible to precipitate Mg(OH)2 crystals.
However, crystal growth in a saturated solution is a delicate process
and the crystallization kinetics is determined by several complex
factors [8]. Crystallization of precipitates typically includes four
processes: formation of supersaturation, emergence of a new
phase, nucleation, and grain growth. In a solution system, various
ionic or molecular units do not exist individually but interact with
each other to form small molecular clusters. The molecular clusters
reach a dynamic equilibrium, and the whole system is thermody-
tgolden@unt.edu namically stable. When the solution system reaches

http://dx.doi.org/10.1016/j.matchemphys.2015.06.048
0254-0584/© 2015 Published by Elsevier B.V.

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supersaturation, the dynamic equilibrium between the clusters will

change and simultaneously form a large number of molecular
clusters with varying sizes. These molecular clusters are thermo-
dynamically unstable, and gradually grow to a critical size (r*) as the
energy reaches a maximum. When the cluster size is greater than r*,
excess energy will be released and a new phase will be formed; the
newly formed nuclei continue to absorb the molecular clusters and
grow to complete the irreversible grain growth process.
The research methods to study crystallization kinetics are
generally divided into two categories. The concentration moni-
toring method measures ion concentrations during the solution
reaction process [9,10]. The particle size analysis route measures
particle size of the final precipitates [11e15]. However, in the par-
ticle size analysis route, Mg(OH)2 particles readily aggregate with
each other, leading to difficultly in determining the kinetics during
particle formation. Solutions must be precipitated and filtered to
analyze. Therefore, the particle size analysis method does not
efficiently reflect the crystallization kinetics throughout the
nucleation and growth process. In this paper, we studied the
crystallization kinetics of magnesium hydroxide in a low concen-
tration solution via an electrical conductivity method, a concen-
tration monitoring method. By monitoring electrical conductivity
during the solution reaction process, changes in [Mg2þ] and [OH]
can be measured during nucleation and growth. The induction
period of nucleation (tind), the specific surface Gibbs energy func- Fig. 1. Schematic for a typical experimental apparatus. (a) stirring motor, (b) ther-
tion of nucleation, and the variation of the critical particle size r*, mometer, (c) conductivity electrode, (d) constant temperature water bath, (e) inner
container, (f) water inlet, and (g) water outlet.
can be obtained from various experimental relationships. The effect
of different anions on the specific surface Gibbs energy of nucle-
ation was investigated by changing the anion sources for
magnesium.

2. Experimental

The starting chemicals were reagent grade MgCl2$6H2O,

Mg(CH3COO)2, Mg(NO3)2, or MgSO4 (>99%) and sodium hydroxide
NaOH (>99%). The magnesium salt (i.e. MgCl2$6H2O) and NaOH
were first dissolved in distilled water, separately. Then the two
solutions were preheated in a water bath. Subsequently, the same
volume solutions were mixed together by constant mechanical
stirring (300 r/min) and monitored for an electrical conductivity
change. Fig. 1 shows the diagram for a typical experimental
apparatus.
The relationship between ion concentration and electrical con-
ductivity in the supersaturated solution can be determined by
measuring the variation of electrical conductivity (k) versus time
Fig. 2. Formation process of Mg(OH)2 crystals.
(t). Reaction order of Mg(OH)2, the nucleation rate constant K1, and
the crystal growth rate constant K2 are determined via curve fitting
at different experimental temperatures. By plotting lnK vs. 1/T, the
The limiting molar conductivity of the electrolyte solution is,
reaction activation energies, Ea, of nucleation and crystal growth
were obtained.
" #
3. Results and discussion jzþ z je2 qL0 F 2 ðjzþ j þ jzþ jÞ
L ¼ L0   pffiffiffi þ k (1)
3  4pε0 εkB 1 þ q 4ph0 NA
2þ
3.1. Determination of electrical conductivity and Mg
concentration
sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
The formation process of Mg(OH)2 crystals is illustrated in Fig. 2, 2e2 NA pffiffi
where; k¼ I (2)
where the control of Mg(OH)2 precipitation is a nucleation and εkB T
growth process related to its critical particle size and is key for
crystallization kinetics. Ions contributing to the electrical conduc- and L0 is the molar conductivity of an infinitely dilute solution, zþ
tivity in the solution reaction process include Mg2þ, OH, Cl, Naþ and z denote cation and anion charges, e is the electronic charge,
and trace amounts of impurities. Since the concentration of the kB is the Boltzmann constant, q ¼ 1/2, NA is Avogadro constant, F is
solutions is low, the electrical conductivity and concentration meet Faraday constant, ε is the dielectric constant of solution, h0 is the
certain functional relationships, such as the FuosseOnsager equa- viscosity of solution, and T is temperature.
tion [16e18]. The typical equations are as follows: I is the ionic strength,

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 Q. Yuan et al. / Materials Chemistry and Physics xxx (2015) 1e9 3

1X
I¼ Ci z2i (3)
2

where Ci is the molar concentration of ions. Therefore, for low

concentration solutions the molar conductivity is a function of ionic
strength I, that is, L ¼ a þ bI, where a and b are constants. In the
Mg(OH)2 reaction system, the electrical conductivity is,

kS ¼ kMgðOHÞ2 þ kNaCl þ kH2 O (4)

where

kMgðOHÞ2 ¼ LMgðOHÞ2 CMg2þ (5)

kNaCl ¼ LNaCl CNaþ (6)

0 200 400 600 800 1000 1200 1400 1600 1800
4
kH2 O ¼ 1:60  10 S=m (7)
þ 
The concentrations of Na and Cl in solution do not change, Fig. 3. Variation of electrical conductivity over time.
and can be calculated from the initial reactant concentrations. Since
the relationship between the electrical conductivity kS and Mg2þ
concentration follows a certain function, the variation of Mg2þ 3.2. Calculation of induction period and specific surface Gibbs
concentration in the crystallization reaction can be obtained by energy function of nucleation
measuring the electrical conductivity. Table 1 shows the experi-
mental conditions used at different temperatures and various According to the definition of relative supersaturation [15,19],
initial concentrations. By measuring electrical conductivity over supersaturation can be written as,
time (Fig. 3), the change in Mg2þ concentration can be followed
(Fig. 4) during the nucleation and growth of the Mg(OH)2. As shown    2
in Fig. 4, the larger the initial concentration (A5-D5) and the higher Mg2þ $ OH  Ksp
S¼ (8)
the reaction temperature, the faster the concentration falls and the Ksp
higher the crystallization rate, indicating that the initial concen-
tration and reaction temperature have a significant effect on the where [Mg2þ] and [OH] are the actual concentrations in solution,
nucleation and crystal growth rates. When the concentration is low Ksp is the equilibrium constant of Mg(OH)2, at different
(A1-D1), the induction period of nucleation becomes longer and the temperatures.
nucleation rate is slow, resulting in a homogeneous nucleation From the nucleation theory on precipitation [9,20], the primary
process. The initial concentrations and induction times at various nucleation process of Mg(OH)2 can be analyzed by the induction
temperatures for Figs. 3 and 4 are given in Table 1. Induction times period of nucleation in solution. An induction period in chemical
vary from a few seconds to several hundred seconds depending on kinetics is the initial slow stage of a chemical reaction, which refers
the solution parameters. As expected, lower concentrations lead to to an interval between an initial formation of supersaturated so-
longer induction times; and higher temperature to shorter times lution and the appearance of precipitate. The induction period can
for the same concentrations (Fig. 5). be defined as [9,21,22],

Table 1
Experimental solution conditions and value of supersaturation and induction period at different temperatures.

Serial Temperature Equilibrium Initial Initial Supersaturation Induction

number (T)/K concentration [Mg2þ]/  104 mol/L [OHd]/  104 mol/L (S) period
(Ksp,T) (tind)/s

A1 288.15 6.53  1013 6.98 13.19 1856.8 290

A2 7.98 15.07 2772.2 83
A3 8.97 16.96 3947.6 59
A4 9.97 18.84 5415.4 44
A5 10.97 20.72 7208.3 27
B1 298.15 5.61  1012 6.86 13.20 211.7 369
B2 7.84 15.07 316.6 79
B3 8.82 16.96 451.2 31
B4 9.80 18.84 619.2 17
B5 10.78 20.72 824.5 7
C1 308.15 8.48  1011 5.88 11.30 21.54 102
C2 6.86 13.19 34.80 50
C3 7.84 15.07 52.44 13
C4 8.82 16.96 75.08 9
C5 9.80 18.84 103.4 6
D1 318.15 3.33  1011 5.88 11.30 7.86 70
D2 6.86 13.19 13.07 15
D3 7.84 15.07 20.00 5
D4 8.82 16.96 28.90 3
D5 9.80 18.84 40.02 2

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Fig. 4. Variation of Mg2þ concentration over time at different temperatures.

tind ¼ tr þ tn þ tg (9)

where, tr is the time required to form the stable molecular clusters,

tn is the time required to form a stable nucleus, and tg is the for-
mation time from the initial tiny particles to the particles whose
sizes can be measured.
The general formula for induction period and nucleus growth
[9,21,23] can be defined as

" #
Nc a0
tind ¼ þ (10)
J ap JGp1

where tind is the induction time, Nc is the number of crystals, a0 is

the volume shape factor, ap is the activity of the solution, J is the
nucleation rate, and G is the activation energy. The nucleation rate,
J, and induction time, tind, have an inverse relationship,

1
tind f (11)
J
Fig. 5. Induction period of nucleation at different temperatures for various magnesium
ion concentrations. The primary nucleation rate can be defined as,

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Fig. 6. Plot of lntind vs 1/(lnS)2 for MgCl2 solutions at different temperatures where
gs(288.15K) ¼ 99.75 mJ/m2,gs(298.15K) ¼ 90.72 mJ/m2, gs(308.15K) ¼ 51.35 mJ/m2, and
gs(318.15K) ¼ 40.47 mJ/m2.

Fig. 7. Induction period of nucleation for different anion sources of magnesium

(T ¼ 298.15 K).
" #
bg3s Vm
2 N f ðqÞ
A
J ¼ A exp  (12)
ðRTÞ3 ðln SÞ2
obtained by plotting the variation of ln(tind) vs (1/lnS)2 using the
where A is a constant under typical conditions, b is the geometric experimental data from Figs. 3 and 4. The plot of ln(tind) vs (1/lnS)2
constant (the value for spherical nucleus is 16p/3), NA is Avogadro shown in Fig. 6 gives a straight line, where the slope denotes the
constant, R is the gas constant, Vm is the molar volume Gibbs function gS. The calculated results are listed in Table 2.
(Vm ¼ 24.7 cm3/mol for Mg(OH)2) [6], S is the supersaturation of the The relationship between lntind and 1/(lnS)2 shows a linear
solution, and f(q) is the heterogeneous nucleation coefficient correlation, which indicates a homogeneous nucleation process
(f(q) ¼ 1, homogeneous nucleation; 0 < f(q) < 1, heterogeneous
nucleation). Substituting (12) into (11), and taking the natural log,
 
bg3s Vm
2 N f ðqÞ 1 2
lnðtind Þ ¼ A
$ þ ln A0 (13)
ðRTÞ3 ln S

At a given temperature then,

bg3s Vm
2 N f ðqÞ
A
B¼ (14)
ðRTÞ3

as a constant, then we can obtain,

 
1 2
lnðtind Þ  (15)
ln S

where the slope line denotes the crystal-solution interfacial tension

or Gibbs free energy per surface area, which is defined as specific
surface Gibbs energy of nucleation, gS.
!1
3
B
gs ¼ RT (16)
bVm NA f ðqÞ
2
Fig. 8. Plot of lntind vs 1/(lnS)2 for different anion sources of magnesium where
T ¼ 298.15 K, gs(CH3COO) ¼ 89.16 mJ/m2, gs(Cl) ¼ 90.72 mJ/m2,
Based on the above equations, the Gibbs function, gS, can be gs ðSO2 2 
4 Þ ¼ 73:53 mJ=m , and gs ðNO3 Þ ¼ 63:01 mJ=m .
2

Table 2
Specific surface Gibbs energy function of nucleation at different temperatures and for various anion sources.

Sources of magnesium Temperature (T)/K Slope (B) Specific surface Gibbs energy function (gs)/mJ m2

MgCl2 288.15 444.02 99.75

MgCl2 298.15 301.47 90.72
MgCl2 308.15 49.53 51.35
MgCl2 318.15 22.02 40.47
Mg(CH3COO)2 298.15 286.22 89.16
MgSO4 298.15 160.52 73.53
Mg(NO3)2 298.15 101.03 63.01

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occurring at the initial stages [9]. The low concentration system
readily forms a uniform particle size distribution of nuclei. In the
actual operation, extending the induction period for nucleation to
create the conditions for homogeneous nucleation is an effective
approach to synthesize a uniform distribution of magnesium hy-
droxide particle sizes [24]. From the results, the specific surface
Gibbs energy of nucleation for Mg(OH)2 is low, suggesting that the
precipitation process favors phase transformation with a short in-
duction period and fast nucleation rate. Moreover, the reaction
temperature has a significant impact on the Gibbs energy function
of nucleation, which leads to the formation of a large quantity of
magnesium hydroxide crystals with small sizes and low crystal-
linity. The precipitation process of magnesium hydroxide results in
a stable colloid, which can inhibit the corresponding industrial
processes such as filtering and drying.
The anions from different sources of magnesium also have an
effect on the nucleation of magnesium hydroxide [5,25e27]. The
MgCl2 solution was substituted with Mg(NO3)2, MgSO4, and
Mg(CH3COO)2 solutions for comparison. The measured values of
the induction period at T ¼ 298.15 K are shown in Fig. 7, and the
corresponding values of Gibbs energy function gS are calculated
from Fig. 8 and are listed in Table 2. The Gibbs free energy is
higher with longer induction times for MgCl2 and Mg(CH3COO)2
solutions. The effect could be attributed to two possible reasons:
(1) the space steric effect, for instance, the Cl ions may chelate
with Mg2þ ions to form complex ions of larger size, while the
CH3COO ions have a relatively large ionic radius, leading to the
space steric effect and extending the induction period; (2) the
transition state stabilization of alkali salts, for example, the
Mg(NO3)2 solution has a minimum value of gS, which could be
ascribed to the instability of molecular clusters Mg(NO3)2$xM-
g(OH)2 formed in the solution.

Fig. 9. SEM images of Mg(OH)2 nucleation process for different time spans: (a) 60 s, (b) 300 s, (c) 600 s, (d) 1200 s, (e) 1800 s, and (f) typical XRD pattern of the sample for 1800 s.

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 Q. Yuan et al. / Materials Chemistry and Physics xxx (2015) 1e9
3.3. Primary nucleation and crystal growth rates
Magnesium hydroxide is easy to precipitate due to its low sol-
ubility [28]. By using the electrical conductivity method, the vari-
ation in concentration can be obtained for the solution effectively,
even for short induction periods. The nucleation kinetics for mag-
nesium hydroxide can be derived from the initial stage of the
concentration versus time plot, while the crystal growth kinetics
can be deduced from the latter stage. Fig. 9aee shows the nucle-
ation process of Mg(OH)2 for different time spans (60, 300, 600,
1200, and 1800 s). At 60 s, an amorphous-like material is obtained
(Fig. 9a). When the reaction time is 300 s, the samples begin
nucleation (Fig. 9b). After 1200 s, a uniform particle size distribu-
tion of magnesium hydroxide is formed (Fig. 9 d and e). Fig. 9f
shows a typical XRD pattern of the sample at 1800 s. The diffraction
peaks can be indexed to the hexagonal structure which matches a
random powder pattern for Mg(OH)2 (JCPDS file no. 7e239) [29].
The significant peak broadening in the XRD pattern, indicates that
the Mg(OH)2 has a small grain size in the nanometer range.
The crystal growth rate can be expressed as,
dm
¼ K0 AðC  C0 Þi (17)
dt
where dm/dt is the crystal yield per unit time, t is the growth time,
K0 is the mass transfer coefficient, A is the surface area of crystal,
and i is the reaction order. In general, the surface area of crystal A is
incorporated into the total reaction coefficient for ease of calcula-
tion. For actual data processing, the crystal growth process is
generally assumed to be a first order reaction [7,8]. In addition, the
Fig. 10. Plot of lnCMg2þ vs t at different temperatures and nucleation rate constant.
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production of precipitated crystals dm/dt are associated with the
consumption of supersaturated solution dC/dt, and the equation
for crystal growth rate becomes,
dc
¼ KðC  C0 Þ (18)
dt
For C ¼ C0eKt, or it can be described in logarithmic form,
ln C ¼ ln C0  Kt (19)
From (19), a plot of lnC vs t, gives a slope of K and intercept lnC0,
from which the crystal growth rate K can be obtained.
3.3.1. Nucleation rate
By plotting lnCMg2þ vs t, the nucleation rate constant can be
obtained from the slope of the linear fit. From Fig. 10, the slope of
the lines varies for the different initial concentrations at the same
temperature; while for similar initial concentrations at different
temperatures, the slope tends to be uniform. This result demon-
strates that the magnesium concentration influences nucleation
rate, which is in agreement with the result for the Gibbs energy
function gS. According to the homogeneous nucleation theory [20],
the critical size of nucleus is,
2ba gs v
r* ¼ (20)
3bv kB T ln S
If the nucleus of magnesium hydroxide is spherical, then bn ¼ 4/
3p, ba ¼ 4p, and n ¼ Ms/NArs. Arranging these relationships into
(20), we get,
8 Q. Yuan et al. / Materials Chemistry and Physics xxx (2015) 1e9

Table 3 time. Due to the hydrophilic property of Mg(OH)2, the crystals are
Nucleation rate constant and crystal growth rate constant at different temperatures. well distributed in low supersaturated solution. The molecular
Rate constant 288.15 K 298.15 K 308.15 K 318.15 K clusters continue growing on the particular crystal phase. In other
Nucleation rate (K1) 0.00203 0.00531 0.00626 0.00727
words, the crystal growth rate depends on the concentration of the
Crystal growth rate (K2) 0.000273 0.001175 0.002188 0.002231 molecular clusters around the crystal growth face, but is not asso-
ciated with the crystal concentration. Consequently, the crystal
growth rate of Mg(OH)2 in this system generally follows the first
order reaction. Fig. 11 shows a good linear relationship between
2gs Ms
r* ¼ (21) lnCMg2þ~t at different temperatures, confirming that the crystal
rs RT ln S growth rate can be described as a first order reaction process.
As seen from (21), the critical size of the nucleus is most influ-
enced by the specific surface Gibbs energy function gS and super-
3.4. Calculation of reaction activation energy Ea
saturation S. At low specific surface energy and high
supersaturation, the critical size of the nucleus r* is small and even
The relationship between the reaction rate constant, K, in
closer to the molecular level, which also explains the “milk of
crystallization kinetics and the absolute temperature, T, can be
magnesia” colloidal phenomena during Mg(OH)2 precipitation
written as follows (Arrhenius eq.),
process [30]. Extending the induction period by controlling the
stable supersaturation S or adding appropriate dopants gives a dln K Ea
uniform particle size distribution of magnesium hydroxide [31,32]. ¼ (22)
dT RT 2
Table 3 shows the nucleation rate constant, which can be deter-
mined by curve fitting at different temperatures, and used to obtain where, Ea is the activation energy of the specific reaction. The in-
the activation energy of nucleation Ea, (plotting lnK vs 1/T). tegral in (22) gives
 
3.3.2. Crystal growth rate Ea
K ¼ A$exp  (23)
In this study, the crystal growth process is denoted by the RT
decrease of solute concentration in solution; that is, crystal growth
rate can be defined as the rate of solute concentration changes over or it can be written in logarithmic form,

Fig. 11. Plot of lnCMg2þ vst at different temperatures and crystal growth rate constant.

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Fig. 12. (a) Activation energy of nucleation Ea,1 and (b) crystal growth Ea,2 obtained by graphical method.
Ea
ln k ¼ ln A 
RT
Therefore, using the Arrhenius equation we obtain a linear
relationship for lnK ~ T1, with a intercept of lnA, and the reaction
activation energy Ea calculated from the slope.
By using the nucleation rate constant and crystal growth rate
constant (see Table 3), the average activation energy of nucleation
Ea,1 and crystal growth Ea,2 obtained from a graphical method
(Fig. 12) are about 15.38 and 6.36 kJ/mol, respectively. As the acti-
vation energy decreases, the reaction rate increases. Thus adding
dopants and/or crystal seeds, changing the reaction temperature, or
controlling the activation energy in different stages are efficient
routes for the synthesis of uniformly distributed nanoparticles by
the precipitation-crystallization method.
4. Conclusion
In summary, the crystallization kinetics for magnesium hy-
droxide formation has been studied by a concentration monitoring
method which measures electrical conductivity to acquire ion
concentrations. The specific surface Gibbs energy of nucleation, gS,
is calculated by measuring the induction period of nucleation. Two
principal factors, namely, reaction temperature and magnesium
salt anions, have the greatest influence on the nucleation of mag-
nesium hydroxide. Moreover, both the nucleation and crystal
growth rates of magnesium hydroxide can be denoted as a first
order reaction equation, from which the reaction rate constant and
the activation energy are obtained.
Acknowledgments
This study was financially supported by the National Natural
Science Foundation of China (Grant # 20971088, #21471102,
#51174138). The authors gratefully acknowledge the support from a
Faculty Research grant (GA9023) at the University of North Texas.
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