ABOUT THE INTERRELATION BETWEEN 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. 3003, Fax: +34 965 90 38 26, *E-mail: antonio.marcilla@ua.es

INTRODUCTION
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 [1-4], 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 energypreexponential 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, considering the reaction order model.

THE COMPENSATION EFFECT

Compensation effect between kinetic parameters can also be observed by analysing the shape of the valley obtained in the 3D surfaces. Although activation energy and pre-exponential factor show the more marked dependence, as already reported in bibliography [1-4], a compensation effect can also be observed between these variables and the reaction order in Figure 5.

V.C. contour profiles: Compensation effect between kinetic parameters

7600
7600

6.3

7500
7500

6.2

7400

7400
6.1

0.00 0.02 0.04 0.06 0.08 0.10

Ea/R (K-1)

7300

7200

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16

Ea/R (K-1)

7300

7200

7100

7100

0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040

6.0

5.9

7000

7000

5.8

6900 0.96 0.98 1.00 1.02 1.04

6900 5.7 5.8 5.9 6.0 6.1 6.2 6.3

5.7 0.96 0.98 1.00 1.02 1.04

ln A (s-1)

ln A (s-1)

Figure 5

INFLUENCE OF THE NUMBER OF HEATING RATES USED

As commented above, multi heating rates analysis is usually suggested in order to reduce parameter interaction. However, the question that arises concerns about the number of different heating rates to use in kinetic analysis. In the present study different cases have been analysed, considering different heating rates between 0.5-40C/min. The influence of the number of heating rates in the shape of the surfaces VC-Ea-lnA has been studied.
1 heating rate 2 heating rates 4 heating rates

RESULTS
0.18 0.16 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.14 0.12 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.16 0.14 0.12
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 0.24 0.22 0.20 0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 7600 7500 7400

Different reference conversion have been generated at different heating rates using the reaction order model and the same set of kinetic parameters: preexponential factor(ln A =), activation energy (Ea/R=) 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 a variation coefficient: 2 i mod el1 i mod el 2 V .C. i N 2 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 V.C. 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.

V.C.

V.C.

0.08 0.06 0.04 0.02 0.00 7600 7500 5.9 7300 7200 5.8 7100 7000 6900 5.7 6.3 6.2 6.1

0.08 0.06 0.04 0.02 0.00 7600 7500 5.9 7300 7200 5.8 7100 7000 6900 5.7 6.3 6.2 6.1

V.C.

0.10

0.10

-1 )

-1 )

(s

(s

ln

7400

7400

ln

7300

7200

5.8 7100 7000 6900 5.7

Ea/R

(K-1)

Ea/R (K-1)

Ea/R

(K-1)

6 heating rates

10 heating rates

0.18 0.16 0.14 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.12

0.18 0.16 0.14 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.12

V.C.

0.08 0.06 0.04 0.02 0.00 7600 7500 5.9 7300 7200 5.8 7100 7000 6900 5.7 6.3 6.2 6.1

V.C.

0.10

0.10 0.08 0.06 0.04 0.02 0.00 7600 7500 5.9 7300 7200 5.8 7100 7000 6900 5.7 6.3 6.2 6.1 6.0 7400

-1 )

(s

6.0

ln

7400

Ea/R

(K-1)

E/R (

K-1)

Figure 6

Type I. Reaction order constant

0.18 0.16 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.14 0.12

Although these surfaces seem to have a track of minimum variation coefficient, they actually have a minimum which correspond to the right set of kinetic parameters. It is shown as an example in Figure 4 for the Type I of 3D charts. It is also worth metionning that the width of the valley also represent the sensitibity of the fit quality with the kinetic parameters considered. This sensitibity is associated to the uncertainty in the determination of a given kinetic parameter. The narrowest valley, the lower uncertainty in the determination of the kinetic parameters. Thus, according to Figures 1-3, the fit quality is very sensible to activation energy and in minor degree to preexponential factor and reaction order. Although these surfaces seem to have a track of minimum variation coefficient, where the variation coefficient is apparently constant, they are actually paraboloids with a minimum, which correspond to the right set of kinetic parameters. It is shown as an example in Figure 4 for the Type I of 3D charts.

As expected the width of the valley, is markedly reduced when increasing the number of heating rates to be considered, but even for 10 different heating rates, the surface obtained still shows a quite wide valley, thus indicating that compensation effect and interaction between kinetic parameters is not fully avoided when using multi-heating rate analysis.

V.C.

0.10 0.08 0.06 0.04 0.02 0.00 7600 7500 5.9 7300 7200 5.8 7100 7000 6900 5.7 6.3 6.2 6.1

7400

Ea/R

(K-1)

ln

(s

6.0

-1 )

Figure 1

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 CTQ200402187) and by the Generalitat Valenciana (project GRUPOS03/159).

Type II. Preexponential factor constant

0.12 0.10 0.08 0.00 0.02 0.04 0.06 0.08 0.10

V.C.

0.06 0.04 0.02 0.00 1.04 1.02 1.00 0.98 0.96 7600 7500 7400 7300 6900 7000 7100 7200

( Ea/R

) K-1

REFERENCES
1. N. Liu, R. Zong, L. Shu, J. Zhou, W. Fan. Kinetic Compensation Effect in Thermal Decomposition of Cellulosic Materials in Air Atmosphere, 2. J. G. Rocha Poc H. Furlan and R. Giudici. A Discussion on Kinetic Compensation Effect and Anisotropy, J. Phys. Chem. B 2002, 106, 4873-4877. 3. Andrew K. Galwey. Perennial problems and promising prospects in the kinetic analysis of

Figure 2

Type III. Activation energy constant

Type III. Activation energy constant

0.05

0.04 0.00 0.01 0.02 0.03 0.04

0.03

V.C.

0.02 0.01 0.00 5.7

1.04 1.02 1.00 0.98 5.8 5.9 0.96 6.0 6.1 6.2 6.3

nonisothermal rate data, Thermochimica Acta, 407, (2003) 93103.

n

4. M. E. Brown, A. K. Galwey. The significance of compensation effects appearing in data published in Computational aspects of kinetic analysis: ICTAC project, 2000,
Figure 4

ln A (s-1)

Figure 3

Thermochimica Acta 387 (2002) 173183.

ln

(s -1 )

ln

5.9

(s

6.0

6.0

6.0

-1 )

6.3 6.2 6.1

ln

A (s

) -1