Russian Journal of Applied Chemistry, Vol. 78, No. 7, 2005, pp. 1064 !1066.

Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 7,

2005, pp. 1085!1087.
Original Russian Text Copyright + 2005 by Blinkova, Eliseev.

PHYSICOCHEMICAL STUDIES

OF SYSTEMS AND PROCESSES

Dissolution of Calcium Carbonate in Aqueous Solutions

of Acetic Acid
E. V. Blinkova and E. I. Eliseev
Ural State Technical University, Yekaterinburg, Russia
Received July 14, 2004; in final form, February 2005

-
Abstract A kinetic equation for the calcium carbonate dissolution, fitting the experimental data to within
8.1%, was obtained. The additional diffusion hindrance caused by the CO2 evolution in the course of the dis-
solution was considered.

To extract zinc from slimes obtained in blast fur-
nace gas treatment, a process based on the acetate
leaching with acetic acid solutions was suggested [1].
The blast furnace slime contains about 6% calcium,
mainly in the form of carbonate [2], which is formed
by the reaction of CaO and CO2 in the gas-conduit
channel of a blast furnace.
Since the slurry from the treatment of blast furnace
gases to remove dust contains calcium oxide and dis-
solved carbon dioxide, calcium carbonate is also
formed in the course of its transportation by the pipe
system. Calcium carbonate in the form of thin crystals
is deposited on the walls of the pipes and causes their
overgrowing. Therefore, the pipelines, which are rela-
tively long, get out of order from time to time. One
of the methods for overcoming this negative phe-
nomenon is the dissolution of salt crystals in a solu-
tion of acetic acid.
To choose proper conditions for this process, it is
necessary to study the calcium carbonate dissolution
in acetic acid solutions. This reaction was not com-
prehensively studied previously.
The acetate method of the calcium carbonate dis-
solution is described by the reaction
CaCO3 + 2C2H4O2 = Ca(CH3CO2)2 + H2O + CO2&. (1)
EXPERIMENTAL
We used a 1 : 3 aqueous solution of analytically
pure acetic acid. The concentration of the CH3COOH
(HAc) solution was determined by potentiometric
titration with NaOH.
The CaCO3 dissolution was studied by the rotating
disc method. The discs were made of white marble,
which, according to the data of the potentiometric
titration, contained 98.9% CaCO3. Samples in the
form of a cylinder (diameter 29 mm) were cut out
from a bulk mineral with a tubular cutter. The discs
were attached to an ebonite cartridge with a silicone
acryl sealant. Prior to each experiment, the disc was
trimmed with an emery paper (fineness 0.2) and flush-
mounted to the cartridge.
The dissolution conditions were varied in the fol-
lowing ranges: temperature, from 283 to 343 K,
CH3COOH concentration in the initial solution, from
0.3 to 3.1 g dm!3, and the disc rotation frequency,
from 3.6 to 18.5 Hz. The process was performed in
a beaker (inner diameter 14 cm).
The content of the dissolved substance was judged
from the content of Ca(II) in the solution. The solu-
tions were analyzed for the Ca(II) content by the
volumetric (complexometric) titration with Acid
Chrome Dark Blue indicator [3], using a plunger
microburet. The analytical error in determining the
Ca(II) concentration did not exceed 1.5%. The experi-
mental time was 3 h.
During the experiment, the rate of the CaCO3 dis-
solution remained virtually constant and increased
with the CH3COOH concentration. The reaction order
with respect to HAc was 0.5.
The dissolution rate was a linear function of the
square root of the rotation frequency n in the fre-
quency range 3.6 318.5 Hz (Fig. 1), which is one
of the essential evidences of a diffusion-controlled
process.
One of the reasons why dissolution is diffusion-
controlled is formation of new (gas) phase [4]. The
diffusion limitations due to CO2 evolution should be

1070-4272/05/7807-1064 + 2005 Pleiades Publishing, Inc.

 DISSOLUTION OF CALCIUM CARBONATE IN AQUEOUS SOLUTIONS
v, mol cm!2 s!1
Fig. 1. Rate of CaCO3 dissolution v vs. rotation frequency
n0.5. Temperature, K: (1) 283, (2) 323, and (3) 343.
less pronounced at low temperature, since the gas
solubility in an aqueous solution is higher under these
conditions [5]. At a higher temperature (343 K), addi-
tional factors affected the rate of the marble dissolu-
tion (especially at n > 14.9 Hz) after 60 min elapsed
from the start of the experiment (Fig. 2). In this case,
the initial linear portion of the kinetic curve was used
for calculating the dissolution rate.
Increasing temperature within 2833343 K increases
the dissolution rate over the entire range of the rota-
tion frequences, i.e., the CaCO3 dissolution is diffu-
sion-controlled (Fig. 3). The temperature dependence
of the dissolution rate of CaCO3 was used to calculate
the apparent activation energy of the process by the
Arrhenius law.
The apparent activation energies calculated at dif-
ferent rotation frequencies were also typical of a dif-
fusion-controlled process over the entire frequency
range.
The discs subjected to the experiment at 343 K had
a convex surface owing to evolution of CO2 in the
course of the dissolution. In the central part of the disc
surface, where the centrifugal force developed in
the rotation is minimal, the most stable CO2 layer
preventing dissolution was accumulated. The part of
the blocked surface increased with the growth of this
layer. Therefore, the dissolution mainly proceeded
in the peripheral zone of the disc.
The effect exerted by the forming gas phase on the
dissolution was eliminated in the presence of a sur-
factant. For this purpose we used a detergent, which,
being a hydrophilizing agent, made the gaseous film
less adhesive to the sample and facilitated its removal
by the centrifugal force. Unlike the experiment per-
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78
1065
c, g dm!3
J, min
Fig. 2. Kinetic curve of CaCO3 dissolution at 343 K and
a disc rotation frequency of 14.9 Hz. (c) Calcium concen-
tration and (J) time; the same for Fig. 4.
formed without surfactant under the similar initial
conditions, the plot of the Ca(II) concentration vs. dis-
solution time was linear (Fig. 4a). This was due to
accessibility of the whole working surface area of
the disc, which ensured the constant process rate. The
rate of the CaCO3 dissolution in the presence of sur-
factant was, however, lower, i.e., the surfactant con-
centrating at the interface created an additional diffu-
sion hindrance.
The same result was obtained by lifting from time
to time the disc over the solution to remove the ac-
cumulating CO2. Under the conditions of vigorous
evolution of CO2 (at 343 K), the dissolution rate
was constant only during the first 60 min and then
markedly decreased. At this moment (90 min after
the start of the experiment), the disc was removed
from the solution for a short time. As a result, the gas
phase was completely removed, and the initial dis-
solution rate was restored (Fig. 4b).
Thus, we obtained a kinetic equation of the CaCO3
dissolution:
v, mol cm!2 s!1
T, K
Fig. 3. Influence of temperature T on the rate of CaCO3
dissolution v. Disc rotation frequency, Hz: (1) 3.6, (2) 6.2,
(3) 9.4, (4) 14.9, and (5) 18.5.
No. 7 2005
1066 BLINKOVA, ELISEEV

c, g dm!3 HAc n exp (!Ea /RT),

v = k cm 0.5
(a)
where v is the specific dissolution rate (mol cm!2 s!1);
k, rate constant [(mol dm!3)0.5 cm!2 s!0.5]; m, reaction
order with respect to HAc (0.5); cHAc, HAc concentra-
tion (mol dm!3); n, disc rotation rate (Hz); Ea, ap-
parent activation energy (J mol!1); R, universal gas
constant (J mol!1 K!1); and T, temperature (K).
From the results of 22 experiments performed
under different conditions, we obtained k = (2.46 +
0.08) 0 10!4 (mol dm!3)0.5 cm!2 s!0.5. The rates of the
c, g dm!3 CaCO3 dissolution calculated from this value were
(b) in satisfactory agreement with the experimental values
(see table).

CONCLUSIONS
(1) At cHAc = 3.1 g dm!3 and 2833343 K, the dis-
solution of CaCO3 in acetic acid is a diffusion-con-
trolled process with an apparent activation energy of
17.2 + 2.6 kJ mol!1.
(2) At 343 K and higher temperatures, the diffu-
sion control of the process may be due to formation
J, min of a gaseous CO2 film on the CaCO3 surface. The
order of the CaCO3 dissolution reaction with respect
Fig. 4. Variation of the CaCO3 dissolution rate due to
blocking of the sample surface by gaseous film: (a) in the
to acetic acid is 0.5.
presence of surfactant and (b) with renewal of the surface. (3) The obtained kinetic equation of the CaCO3
(a) Surfactant concentration, g dm!3: (1) 0.00, (2) 0.025, dissolution is adequate under the following condi-
(3) 0.050, and (4) 0.100; (b) (1) without and (2) with lifting tions: temperature 2833343 K, HAc concentration
the disc.
0.333.1 g dm!3, and rotation rate 3.6 318.5 Hz.
Experimental and calculated rates of CaCO3 dissolution
REFERENCES
T,
n, c , v  108, mol cm!2 s!1 Relative
HAc 1. USSR Inventors Certificate no. 1 092 195.
K Hz g dm!3
experimental calculated error, % 2. Shutikova, V.F., Vychaev, A.V., Larina, T.P, et al.,
Kompleksn. Ispolz. Miner. Syrya, 1991, no. 2, pp. 69!
283 3.6 3.1 6.96 6.78 !2.6 72.
6.2 3.1 9.23 8.90 !3.6 3. Zhivopistsev, V.P., and Selezneva, E.A., Analitiche-
9.4 3.1 10.98 10.96 !0.2 skaya khimiya elementov: Kaltsii (Analytical Chemis-
18.5 3.1 14.22 15.37 8.1 try of Elements: Calcium), Moscow: Nauka, 1975.
283 3.6 0.6 3.11 2.86 !7.9 4. Akselrud, G.A., and Gumnitskii, Ya.M., Zh. Prikl.
Khim., 1986, vol. 59, no. 10, pp. 2185!2189.
3.6 3.1 6.96 6.78 !2.6

283 3.6 3.1 6.96 6.78 !2.6
5. Spravochnik khimika (Chemists Handbook), Nikol-
skii, B.P., Ed., Leningrad: Khimiya, 1964, vol. 3.
343 3.6 3.1 23.32 24.36 4.5 6. Spitsyn, V.I., Pchelkin, V.A., and Goncharov, I.V., Fiz.
Khim., 1961, vol. 137, no. 5, pp. 1158!1161.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 7 2005