ABOUT THE INTERRELATION BETWEEN TGA KINETIC PARAMETERS

A.Marcilla*, J.C. Garca-Quesada and R. Ruiz. Chemical Engineering Department University of Alicante. Apdo. 99, E-03080 Alicante, Spain. Tlf.: +34 965 90 34 00 - Ext. 3789, Fax: +34 965 90 38 26, *E-mail: antonio.marcilla@ua.es
ABSTRACT
The study of thermogravimetric curves is commonly used to elucidate the likely processes involved during pyrolysis, as well as to determine the corresponding kinetic parameters. One of the main problems found in the determination of such parameters is their ability to couple each other in such way that different sets of kinetic parameters can properly describe similar conversion degree curves once a kinetic model has been selected. In order to diminish the effect of the interrelation between kinetic parameters, procedures based on the utilisation on different heating rates are suggested. This topic has been treated extensively in bibliography, where most of the authors specially pay attention to the compensation effect between activation energy and preexponential factor [1-3], while there is another factor to have in mind: the reaction order. When speaking about kinetic parameters interrelation, the compensation effect of the whole kinetic triplet should be considered: activation energy, preexponential factor and conversion degree function considered (given by a certain kinetic model). Depending of the values adopted by the kinetic triplet, a different fit quality can be observed. Thus, the actual compensation effect between kinetic parameters should be represented in four dimensional charts; for example, if the reaction order model was considered, the four dimensional charts should represent any variable which could represent the quality of the fit (as a variation coefficient) versus the activation energy-preexponential factor-reaction order. Due to the impossibility of the construction of 4D graphs, 3D charts can be used alternatively. In this case, three different alternative 3D charts can be used, since they can represent the variation coefficient versus two of the kinetic parameters (keeping the third as a constant). Those zones of the 3D charts with the lowest variation coefficient should correspond to the set of kinetic parameters which compensate each other in order to represent a certain conversion degree curve. In the present work, the interrelation between the kinetic triplet has been studied.

ACKNOWLEDGEMENTS
The authors of the work wish to thank financial support provided by the Spanish Comisin de Investigacin Cientfica y Tecnolgica de la Secretara de Estado de Educacin, Universidades, Investigacin y Desarrollo and the European Community (FEDER refunds) (CICYT CTQ2004-02187) and by the Generalitat Valenciana (project GRUPOS03/159).

REFERENCES
1. J. G. Rocha Poc H. Furlan and R. Giudici. A Discussion on Kinetic Compensation Effect and Anisotropy, J. Phys. Chem. B 106,, ( 2002) 4873-4877. 2. Andrew K. Galwey. Perennial problems and promising prospects in the kinetic analysis of nonisothermal rate data, Thermochimica Acta 407, (2003) 93103. 3. M. E. Brown, A. K. Galwey. The significance of compensation effects appearing in data published in Computational aspects of kinetic analysis: ICTAC project, 2000, Thermochimica Acta 387 (2002) 173 183.

RESULTS
Different reference conversion data have been generated at different heating rates using the reaction order model and the same set of kinetic parameters: preexponential factor(ln A =6), activation energy (Ea/R=60 kJ/mol) and reaction order (n=1). Afterwards, new sets of curves were generated by using different sets of kinetic parameters. Reference curves and generated curves were compared by calculating the error between the reference and the generated curves:

Error ir ig
i

The width of that valley also gives information about the compensation effect. The part of the surface under a certain value of error (considered as good for a good correlation of reference data) gives the likely combination of kinetic parameters which describes adequately the system studied. Although this path of minimum error follows apparently a flat surface, it is a curved surface with a minimum. That minimum corresponds to the set of kinetic parameters which gives the best correlation of the reference data (i.e. those used for generate them). The analysis has been applied to multi heating rate analysis (data not shown), observing a marked narrowing of the surfaces with the number of heating rates used. The study of the shape of the surface could be used with experimental data in order to achieve kinetic analysis.

Depending on the parameter kept as constant, a different type of graph can be obtained. The 3D graphs show surfaces with a valley. Those zones with the lowest error in the valley constitute a path in the surface, reflecting the compensation effect between kinetic parameters, since it corresponds to the zone where a set of kinetic parameters better reproduce the reference curve.

1.4 1.3 1.2 1.1 1 0.9 0.8 0.7 0.6 0.5 0.4 5.8 5.9 6.0 ln A (s-1) 6.1 6.2

9000 8500 8000

Ea/R (K-1)

7500 7000 6500 6000

100

5500 5000 4.0 5.0 6.0 ln A (s-1) 7.0 8.0

0.16
80

0.12 0.1

Error

Error

0.14

60

40

0.08 0.06

20 0 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

100

0.07

0 20 40 60 80 100

Error
0.06

0.04 0.02 0 0.5 0.7 0.9 n

0.03 0.02
9 20 7 0 9000 8000 7000 4 6000 5000 3 5 6 8

Error

80 0 20 40 60 80 100

0.05
Error

Error

60

0.04

1.1

1.3

1.5

40

ln A (s-1)

Ea=60 kJ/mol

0.01 0 4.0 5.0 6.0

ln A (s-1)

(s

-1 )

n=1

Ea/R (K

-1)

ln

7.0

8.0

1.4 1.3 1.2 1.1 1 0.9 0.8 0.7 0.6 7150

0.20 0.15
Error
ln A=constant Ea=constant n=constant

0.10 0.05 0.00 0.6 0.8 1.0 n 1.2 1.4

7200

7250 Ea/R (s-1)

7300

7350

100

80

0.18

Error

60

0.16 0.14

40 0 20 40 60 80 100

0.12

20

Error

Error

0.1 0.08 0.06 0.04 0.02 0 0.6 0.8 1 n 1.2 1.4

0 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 10000

CONCLUSIONS
In the present work a procedure for evaluation of the compensation effect between kinetic analysis has been suggested. This method is based on the study of the shape of surfaces obtained by comparing reference conversion degree curves with conversion degree curves obtained by a kinetic parameters sweep. That difference, calculated as an error, is represented in 3D graphs, shows surfaces with a trajectory of minimum error. This trajectory shows a point of minimum error, which determines the best set of kinetic parameters to reproduce the reference curves.

ln A=6 /A (s-1)

9000

8000

7000

6000

5000

Ea/R (K-1)