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ORIGINAL ARTICLE
KEYWORDS
Calcium carbonate;
Thermogravimetric analysis;
Thermal decomposition;
Kinetic;
Organic acid
Abstract By means of thermogravimetric analysis (TGA), inuences of organic acids such as citric
acid, oxalic acid and tartaric acid on decomposition process and thermal behaviors of calcium carbonate were investigated in non-isothermal condition. Experiments were conducted from the ambient temperature to 1273 K at a heating rate of 10 K min1. Moreover, the kinetic parameters
(activation energy and pre-exponential factor) of the mixtures of calcium carbonate and organic
acids were determined using the CoatsRedfern method. It is indicated that the decomposition process of calcium carbonate containing different organic acids includes three or four weight loss processes. In the zone of 370450 C, energy is released due to the combustion of organic products
decomposed from organic salts, and energy increases with the increase of molecular weight of
organic acid. Activation energy of the samples containing citric acid, oxalic acid and tartaric acid
is decreased by 34.9%, 28.8% and 31.9%, respectively. The results may be used to provide a useful
basis for further applying industrial wastes containing different organic acids in cement industries
with high-efciency.
2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.
1. Introduction
The thermal decomposition of calcium carbonate particles in
raw meal has been the subject of intensive study over the years
due to its importance in the output and heat consumption of
cement clinker of cement industry. A number of researchers
* Corresponding author. Tel.: +86 27 87661567; fax: +86 27
87160951.
E-mail address: lxggroup@163.com (X.-G. Li).
Peer review under responsibility of King Saud University.
1878-5352 2013 Production and hosting by Elsevier B.V. on behalf of King Saud University.
http://dx.doi.org/10.1016/j.arabjc.2013.09.026
Please cite this article in press as: Li, X.-G. et al., Decomposition kinetic characteristics of calcium carbonate containing organic
acids by TGA. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.09.026
X.-G. Li et al.
Figure 1
Please cite this article in press as: Li, X.-G. et al., Decomposition kinetic characteristics of calcium carbonate containing organic
acids by TGA. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.09.026
3
T/
100
TG /%
TG / %
95
90
30
130
230
330
430
530
630
730
830
930
-0.1
-0.6
85
-1.1
80
-1.6
75
Calcium carbonate+citric acid
70
65
-2.1
-2.6
-3.1
-3.6
Calcium carbonate
60
Calcium carbonate
-4.1
55
-4.6
50
0
100
200
300
400
500
600
700
800
900
1000
T/
-5.1
(a) TG curve
TG-DTG curve of the mixtures containing organic acid and calcium carbonate.
fa 1 a
2.00
1.50
1.00
0.50
T/
0.00
DSC / mW/mg
Figure 2
-0.50
-1.00
-1.50
100
200
300
400
500
600
700
800
900
1000
Please cite this article in press as: Li, X.-G. et al., Decomposition kinetic characteristics of calcium carbonate containing organic
acids by TGA. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.09.026
X.-G. Li et al.
Table 1
Thermal behaviors of the mixtures containing organic acid and calcium carbonate.
No.
Peak
C
CC
CC
CC
CO
CO
CO
CT
CT
CT
Heat
Heat
Heat
Heat
Heat
Heat
Heat
Heat
Heat
Heat
absorption
absorption
evolution
absorption
absorption
evolution
absorption
absorption
evolution
absorption
Tpeak/C
Decomposition process
792.8
120.1
464.4
787.9
151.1
452.8
788.3
126.2
441.0
785.8
R1decomposition of CaCO3
R2dehydration of Ca3(C6H5O7)24H2O; decomposition of C6H8O7
R3decomposition of Ca3(C6H5O7)2 and combustion of products
R1
R4dehydration of Ca(COO)2H2O; decomposition of H2C2O4
R5decomposition of Ca C2O4 and combustion of products
R1
R6decomposition of C4H6O6
R7decomposition of CaC4H4O6 and combustion of products
R1
Notes: C Calcium carbonate; CC Calcium carbonate + citric acid; CO Calcium carbonate + oxalic acid; CT Calcium carbonate + tartaric acid.
Table 2
No.
CC
CO
CT
Table 3
No.
R1(+)
R2(+)
R3()
R4(+)
R5()
R6(+)
R7()
DQ
998.3
1129
881.9
13.1
226.4
15.8
43.0
31.6
92.4
785.0
1101.8
821.1
Thermal analysis of the decomposition of mixture containing organic acid and calcium carbonate.
DH/kJ kg1
Temperature/C
C
CC
CO
CT
Initial
Peak
Final
Mixture
CaCO3
600
645
620
596
792.8
787.9
783.4
785.8
829
824
820
815
1296.0
784.98
1101.77
821.05
1296.0
998.3
1129.0
881.9
180.2
117.3
128.1
122.7
Decrease/%
13.6
6.2
7.4
6.9
21.4
2.4
6.9
Combined with the results of peak temperature of decomposition, heat absorption or evolution and activation energy,
the incorporation of organic acids can decrease the heat consumption of decomposition of calcium carbonate.
4. Conclusions
The decomposition process contains three or four phases with
weight loss, but there is only one weight loss during the decomposition of calcium carbonate at 600850 C. The differences
among the mixtures are represented before the zones at
600 C. Also the nal weight loss of the mixtures increases to
a certain degree with the incorporation of organic acids.
In the zone of 370450 C, energy is released due to the
combustion of organic products decomposed from organic
salts, and energy increases with the increase of molecular
weight of organic acid.
The activation energy of the mixtures containing citric acid,
oxalic acid and tartaric acid decreases 34.9%, 28.8% and
31.9%, respectively. The results agree with that of the change
of decomposition temperature of the mixtures. And there is a
linear connection between the activation energies and preexponential factors (lnA = 0.1168E 7.7472).
Please cite this article in press as: Li, X.-G. et al., Decomposition kinetic characteristics of calcium carbonate containing organic
acids by TGA. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.09.026
Please cite this article in press as: Li, X.-G. et al., Decomposition kinetic characteristics of calcium carbonate containing organic
acids by TGA. Arabian Journal of Chemistry (2013), http://dx.doi.org/10.1016/j.arabjc.2013.09.026