Int. J. Miner. Process.

80 (2006) 27 – 34
www.elsevier.com/locate/ijminpro

Dissolution kinetics of natural magnesite in lactic acid solutions

Feray Bakan, Oral Laçin ⁎, Bahar Bayrak, Hanifi Saraç
Department of Chemical Engineering, Atatürk University, 25240 Erzurum, Turkey
Received 19 October 2005; received in revised form 20 January 2006; accepted 22 January 2006
Available online 28 February 2006

Abstract

In this study, the dissolution of magnesite particles in aqueous lactic acid solutions was investigated in a batch reactor
employing the parameters of stirring speed, particle size, temperature and acid concentration. The shrinking core model was
evaluated to determine the effect of particle size, temperature and concentration. It was also found that the stirring speed did not
change the dissolution. Consequently, it was determined that the dissolution rate is controlled by surface chemical reaction. The
activation energy of the process was determined to be 50.3 kJ mol− 1.
© 2006 Elsevier B.V. All rights reserved.

Keywords: magnesite; lactic acid; chemical dissolution; kinetics

1. Introduction ammonium chloride at constant pH and it was concluded

Several studies have been performed to determine the
dissolution rate of magnesite. Dissolution kinetics of
magnesite mineral in aqueous sulfur dioxide was studied
by Abali et al. (1992) who found that the dissolution rate
is controlled by surface reaction. Kurtbaş et al. (1992)
studied the reaction kinetics of natural magnesite with
hydrochloric acid and found that the dissolution rate was
controlled by chemical reaction. In another study, the
dissolution kinetics of magnesite mineral with Cl2 gas in
aqueous media was investigated by Özbek et al. (1999)
who determined that the dissolution process is controlled
by surface reaction in the temperature range of 12–40°C
and film diffusion for range of 40–70°C. Raschman
(2000) studied the leaching of calcined magnesite using
⁎ Corresponding author. Atatürk Üniversitesi, Mühendislik Fakültesi
Kimya Mühendisliği Bölümü, 25240, Erzurum, Turkey. Tel.: +90
4422314554; fax: +90 442 2360957.
E-mail addresses: olacin@atauni.edu.tr, olacin69@yahoo.com
(O. Laçin).
0301-7516/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2006.01.005
that the leaching process is controlled by the chemical
reaction of MgO with H+ ions at the liquid–solid
interface and by pore diffusion. Demir et al. (2003)
investigated the leaching kinetics of magnesite in citric
acid solutions and it was found that the dissolution rate
was controlled by chemical reaction. Dissolution of
magnesite in acetic acid solutions was investigated by
Laçin et al. (2005) and it was determined that the dis-
solution of natural magnesite was controlled by chemical
reaction. Raschman and Fedorockova (2004) researched
the inhibiting effect of hydrochloric acid concentration
on the dissolution rate of magnesium oxide during the
leaching of dead-burned magnesite and they found that
the dissolution of MgO is controlled by chemical re-
action. Although magnesite dissolution was studied in a
variety of acidic media ranging from hydrochloric acid to
citric acid no study was found concerning the dissolution
kinetics of magnesite in lactic acid solutions.
Lactic acid (2 hydroxypropionic acid), the most widely
occurring carboxylic acid in nature, is produced commer-
cially for use in pharmaceuticals and foods, in leather
28 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34
Table 1
Chemical analysis of the magnesite
Component Wt.%
MgO 47.30
CaO 0.43
Fe2O3 0.25
SiO2 0.40
Loss of ignitation (at 850°C) 51.62
tanning and textile dyeing, and in making plastics, solvents,
inks, and lacquers. Although it can be prepared by chemical
synthesis, production of lactic acid by fermentation of
glucose and other substances is a less expensive method
(Srivastava et al., 2004). Magnesium lactate is the
magnesium salt of lactic acid, is produced for food,
pharmaceutical, refractory, textile, and cosmetic industries.
The dissolution kinetics of a solid compound depends
on the processes taking place at the solid–liquid
boundary. The processes are complex and involve both
chemical reactions and mass transfer. The solid–liquid
reaction can occur at the surface of the solid in the film
around the solid or in the liquid bulk phase. Different
steps, such as mass transfer, chemical reaction and charge
transfer can determine the dissolution rate. The classical
models used for solid–liquid reactions are the shrinking
particles and shrinking core models. The shrinking core
model has been suggested by many authors to be valid for
leaching of magnesite (Markus et al., 2004).
In this study, the dissolution kinetics of magnesite in
lactic acid solutions was examined according to the
shrinking core models, and the best fitted equation to the
experimental data was determined.
2. Experimental
The magnesium carbonate ore used in the present
study was supplied from a region of Erzincan–Refahiye
Fig. 1. X-ray diffractogram of the magnesite ore.
Table 2
The parameter values for dissolution of magnesite in lactic acid
Parameter Value
Temperature (°C) 30, 40, 50, 60a, 70
Acid concentration (mol L− 1) 1.0, 1.5a, 2, 2.5, 3, 4
Particle size (μm) 1425, 725, 512, 338a, 215, 153
Stirring speed (rpm) 500, 600a, 700, 800
a
The constant values used when the effect of other parameters was
investigated.
in Turkey. After crushing and washing, the ore was
ground and then sieved to different size fractions 1425,
725, 512, 338, 215 and 153μm using ASTM standard
sieves. The chemical analysis was carried out by the
standard gravimetric and volumetric methods (Furmann,
1963). The analytical results were given in Table 1.
X-ray diffraction patterns of the magnesite ore were
obtained using a Rigaku 2000 JCPDS DMAX
(29-1490) diffractometer (XRD) with CuKα radiation
(30 kV and 30 mA and automatic monochromator) at a
scanning rate 2è of 2° min− 1 (Fig. 1).
Lactic acid, HC3H5O3-2-hydroxy-d-propanoic acid,
used for leaching experiments was reagent grade
(90 wt.% solution in water from Merck Chemicals).
The dissolution process was carried out in a 500-
mL cylinder glass batch reactor heated by a thermostat
for keeping reactor contents at a constant temperature,
equipped with a digital controlled mechanical stirrer,
thermometer and a condenser to prevent losses by
evaporation (Bayrak et al., in press). For each
experiment, 250mL volume of lactic acid at a definite
concentration was transferred into the reactor at the
required temperature. The reaction was initiated by the
addition of a small amount of magnesite, at time t = 0,
while stirring the contents of the reactor at a certain
speed. An amount of sample of the reaction mixture
was withdrawn from the reactor at appropriate time
intervals, filtered immediately and the Mg+ 2 content in
 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34 29

the solution was analyzed complexometrically by
EDTA at the medium of buffer solution (about
pH = 10) (Gülensoy, 1974). For each experimental
condition, the experiment was repeated twice, and
the arithmetic average of the result of the two
experiments was used in the kinetic analysis. The
dissolution tests were performed as a function of
several parameters, their range and values are given in
Table 2.
3. Results and analysis
Reactions between magnesite and lactic acid can be
written as follows:
2HC3 H5 O3ðaqÞ ↔2Hþ
ðaqÞ þ 2C3 H5 O3 ðaqÞ
1−
MgCO3ðsÞ þ 2Hþ þ2
ðaqÞ →MgðaqÞ þ CO2ðgÞ þ H2 OðlÞ
MgCO3ðsÞ þ 2HC3 H5 O3 ðaqÞ→Mgþ2 ðaqÞ
þ 2C3 H5 O1−
3 ðaqÞ þ CO 2ðgÞ þ H O
2 ðlÞ
To investigate the effect of the particle size on the
dissolution rate, experiments were carried out using five
different particle sizes of the sample ranging from 1425
to 153μm. As seen in Fig. 2, the dissolution rate
increases with decrease in particle size of magnesite
used, which can be attributed to increase of the contact
surface, on which the main dissolution reaction occurs,
with the decrease of the particle size per amount of the
solid.
The effect of the temperature on the dissolution rate
was studied using five different reaction temperatures in
the range of 30–70 °C. Fig. 3 shows that increasing the
reaction temperature increases the dissolution rate, as
expected from the exponential dependence of the rate
constant in the Arrhenius equation.
To observe the effect of stirring speed on the
dissolution rate, experiments were carried out using
four different stirring speeds in the range of 500–
800 rpm. As seen from the experimental results given in
Fig. 4, the dissolution rate is practically independent of
the stirring speed.
In order to investigate the effect of the lactic acid
ð1Þ concentration on the dissolution rate, some experiments
were performed with six different lactic acid concentra-
tions in the range of 1.0–4.0 M. The experiments
ð2Þ
showed that the dissolution rate increases by increasing
the acid concentration until 2.0 M of the lactic acid
concentration and more increase in acid concentration
ð3Þ caused decreasing rate as can be seen in Fig. 5(a) and
(b). It could be attributed that the intensity of negative
effect of water, the solvent, decrease after a certain value
of acid concentration, was more dominant than that of
positive effect of increase of acid concentration. Again,
when the acid concentration exceeded a definite value,
the number of hydrogen ions in the medium might
decrease due to decrease of water amount more and
more. In addition, this behavior could be explained by
the fact that as the acid concentration in the medium is

1,0
1425 µm
725 µm
512 µm
0,8 338 µm
215 µm
153 µm

0,6
XMg (%)

0,4

0,2

0,0
0 10 20 30
Reaction time (min)

Fig. 2. Effect of particle size on the dissolution of magnesite.

30 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34

1,0
30 °C
40 °C
50 °C
0,8
60 °C
70 °C

0,6
XMg (%)

0,4

0,2

0,0
0 10 20 30 40 50 60 70
Reaction time (min)

Fig. 3. Effect of temperature on the dissolution of magnesite.

increased, the appearance rate of the product increases
and as the product reacted to the saturation value near
the solid particle, it forms a sparingly soluble product
film layer around the particle. Consequently, the
dissolution process slowed down after 2.0M of acid
concentration (Imamutdinova, 1967). But, the leaching
kinetics was essentially investigated for the concentra-
tion range of 1.0–2.0 M.
The rate of reaction between a solid and a fluid can
be expressed according to the heterogeneous reaction
models. In the model, when ash is not formed, the
reacting particle will shrink during reaction and finally
disappear. According to this model the following three
steps are considered to occur in succession during
reaction (Levenspiel, 1999).
1. Diffusion of the fluid reactant from the main body of
the fluid film to the surface of the solid.
2. Reaction on the surface between the fluid reactant
and the solid.

1,0
500 rpm
600 rpm
0,8 700 rpm
800 rpm

0,6
XMg (%)

0,4

0,2

0,0
0 10 20 30 40 50 60 70
Reaction time (min)

Fig. 4. Effect of stirring speed on the dissolution of magnesite.

 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34 31

(a)
1,0

1.0 M
1.5 M
0,8 2.0 M

0,6
XMg (%)

0,4

0,2

0,0
0 10 20 30 40
Reaction time (min)
(b)
1,0
2.0 M
2.5 M
0,8 3.0 M
4.0 M

0,6
XMg (%)

0,4

0,2

0,0
0 10 20 30 40
Reaction time (min)

Fig. 5. (a) Effect of acid concentration on the dissolution of magnesite for 1.0–2.0M. (b) Effect of acid concentration on the dissolution of magnesite
for 2.0–4.0 M.

3. Diffusion of the products in reaction from the surface fluid film does not act as a rate-controlling step. So,
of the solid through the fluid film back into the main the experimental data have been applied to the step 2
body of the fluid. Note that the ash layer is absent and of shrinking core models. However the variation of
does not show any resistance. CA is too big to neglect during the reaction so, CA
cannot be accepted constant in the Eq. (4) and this
According to the steps given above a heteroge- model is modified as follows:
neous reaction may be controlled by these steps. The Z rC Z t
fact that the dissolution rate was independent of the −qB drC ¼ bkS CA dt ð4Þ
stirring speed indicates that the diffusion through the R 0
32 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34

where, 0.9899. In order to confirm the results of these

statistical analyses, the experimental data for each
 
NB0 NB0 parameter were analyzed by the graphical methods.
CA ¼ CA0 1− XB and M ¼ If the left hand of Eq. (7) is called as C, the plot of C
VbCA0 VbCA0
0:024molMgCO3 vs. time is shown in Fig. 6 for the reaction temperatures
¼ ¼ 0:13 ð5Þ (30–70 °C). The apparent rate constants were evaluated
0:25L  0:5  1:5M
Z XB Z t from the slopes of the straight lines.
dXB 3dbdkS dCA0 From Arrhenius equation kterm was known as:
¼ d dt ð6Þ
0 ð1−XB Þ2=3 d ð1−MXB Þ qB dR 0
k ¼ k0 e−EA =RT ð8Þ
It is too hard to solve Eq. (6) analytically so this
equation was solved numerically with MATLAB 7.0 As shown Fig. 7, the plot of lnk vs. 1 / T was obtained
Package Program and the integrated rate expression is for the each value of the temperature and the following
values are calculated:
−2:19lnðð1−XB Þ1=3 þ 1:91Þ
EA ¼ 50:3kJd mol−1 ; k0 ¼ 1:8  106 s−1
þ 1:09lnðð1−XB Þ2=3 −1:91ð1−XB Þ1=3
 Thus, Eq. (7) could be given as:
þ 3:657Þ−3:79arctanð0:58ð1:05ð1−XB Þ1=3 −1Þ
3dbdkS dCA0
¼ dt ð7Þ
q dR −2:19lnðð1−XB Þ1=3 þ 1:91Þ
|fflfflfflfflfflfflfflfflBffl{zfflfflfflfflfflfflfflfflffl}
k þ 1:09lnðð1−XB Þ2=3 −1:91ð1−XB Þ1=3


The plugging of all the experimental data into the
integral rate was tested by multiple regressions using
Statistica 7.0 Package Program, and the multiple
regression coefficients obtained for integral rate
expression were calculated. In the calculations, it was
seen that the very high value of regression coefficient
correcting the rate expression was for surface reaction
control (step2). The coefficient value was calculated as
þ 3:66Þ−3:79arctanð0:58ð1:05ð1−XB Þ1=3 −1Þ
−50:3
¼ 1:8  106 e RT dt ð9Þ
The activation energy of a diffusion controlled
process is characterized to be from 4.18 to 12.55 kJ/
mol, while for a chemically controlled process it is
usually greater than 41.84 kJ/mol (Abdel-Aal, 2000).

2,2
30°C
2,0
40°C
1,8 50°C
60°C
1,6 70°C
1,4

1,2
C

1,0

0,8

0,6

0,4

0,2

0,0
0 10 20 30 40 50 60 70
Reaction time (min)

Fig. 6. C vs. time for various reaction temperatures.

 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34 33

-3
-3,2
-3,4
-3,6
-3,8
-4
-4,2
lnk (s-1)

-4,4
-4,6
-4,8
-5
-5,2
-5,4
-5,6
-5,8
2,914 3,002 3,095 3,193 3,299

1/Tx103 (K-1)

Fig. 7. Arrhenius plot for the dissolution of magnesite.

Such a value for the activation energy indicates that
the leaching of magnesite with lactic acid solutions is
controlled by surface chemical reaction.
4. Conclusions
The dissolution kinetics of magnesite in lactic acid
solutions was studied. On the basis of the results of this
study, the following conclusions can be expected:
• The rate of dissolution of magnesite in lactic acid was
independent of stirring speed, which indicates that
the reaction is not controlled by the diffusion in the
liquid phase.
• The dissolution kinetics follows a shrinking core
model with the surface chemical reaction as the rate-
controlling step. The activation energy of the reaction
was 50.3kJmol− 1 and the reaction rate was very
sensitive to the temperature in the range of 30–70°C.
• Increasing the lactic acid concentration increases
magnesite dissolution in the range of 1.0–2.0 M and
decreases it in the range of 2.0–4.0 M.
• By the decreasing in particle size of magnesite, the
dissolution rate increases.
Nomenclature
b Stoichiometric coefficient of solid B
CA Concentration of acid reactant, mol L− 1
CA0 Initial concentration of acid reactant, mol L− 1
EA Activation energy, kJ mol− 1
k Reaction rate constant, s− 1
k0 Frequency or pre-exponential factor, s− 1
ks Rate constant for surface reaction, m s− 1
NB0 Initial moles of solid reactant
R Initial particle radius, m
R Universal gas constant, J mol− 1 K− 1
rC Radius of unreacted core, m
t Time, s
T Temperature, K
V Reaction volume, L− 1
ρB Molar density of solid reactant, mol L− 1
XB Fraction of B converted, the conversion
XMg Fraction of Mg converted.
References
Abali, Y., Çolak, S., Ekmekyapar, A., 1992. Magnezit Mineralinin
Sulu Ortamda SO2 Gazı ile Çözünme Kinetiği. Doğa: Turk. J. 16,
319–324 (in Turkish).
Abdel-Aal, E.A., 2000. Kinetics of sulfuric acid leaching of low-grade
zinc silicate ore. Hydrometallurgy 55, 247–254.
Bayrak, B., Lacin, O., Bakan, F., Saraç, H., (in press). Investigation of
Dissolution Kinetics of Natural Magnesite in Gluconic Acid
Solutions. Chemical Eng. J. (Available online 3 February 2006).
Demir, F., Dönmez, B., Çolak, S., 2003. Leaching kinetics of mag-
nesite in citric acid solutions. J. Chem. Eng. Jpn. 36 (6), 683–688.
Furmann, N.H., 1963. Standard Methods of Chemical Analysis.
D.Van. Nastrand Company, 6th ad., New Jersey.
Gülensoy, H., 1974. Kompleksometrik Titrasyonlar ve Kompleksome-
trinin Temelleri. Fatih Yayınevi, İstanbul, Turkey.
Imamutdinova, V.M., 1967. Kinetics of dissolution of borates in
mineral acid solutions. Zh. Prikl. Khim. 11, 2593–2596.
Kurtbaş, A., Ekmekyapar, A., Çolak, S., 1992. Doğal Manyezitin HCl
Çözeltileriyle Heterojen Reaksiyon Kinetiği. Doğa: Turk. 16,
90–94 (in Turkish).
34 F. Bakan et al. / Int. J. Miner. Process. 80 (2006) 27–34
Laçin, O., Dönmez, B., Demir, F., 2005. Dissolution kinetics of natural
magnesite in acetic acid solutions. Int. J. Miner. Process. 75,
91–99.
Levenspiel, O., 1999. Chemical Reaction Engineering, 3rd Edition.
John Wiley and Sons Inc., New York.
Markus, H., Fugleberg, S., Valtakari, D., Salmi, T., Murzin, D.Y.,
Lahtinen, M., 2004. Kinetic modeling of a solid–liquid reaction:
reduction of ferric iron to ferrous iron with zinc sulphide. Chem.
Eng. Sci. 59, 919–930.
Özbek, H., Abali, Y., Çolak, S., Ceyhun, İ., Karagölge, Z., 1999.
Dissolution kinetics of magnesite mineral in water saturated by
chlorine gas. Hydrometallurgy 00, 1–13.
Raschman, P., 2000. Leaching of calcined magnesite using ammonium
chloride at constant pH. Hydrometallurgy 56, 109–123.
Raschman, P., Fedorockova, A., 2004. Study the inhibiting effect of
acid concentration on the dissolution rate of magnesium oxide
during the leaching of dead-burned magnesite. Hydrometallurgy
71, 403–412.
Srivastava, A., Narayanan, N., Roychoudhury, P.K., 2004. L (+) lactic
acid fermentation and its product polymerization. Electron. J.
Biotechnol. 7 (2).