A. Marcilla et al. / J. Anal. Appl.

Pyrolysis 68
/69 (2003) 467
/480 477

d[G1 ]
 k1 [PP]n1 (4)
dt
d[G2 ]
 k3 [PPC]n4 (5)
dt

where n1, n2, n3 and n4 are the reaction orders.

The rate constants k1, k2 and k3 can be expressed by the Arrhenius law:
  
E 1 1
ki ko; i exp(Ei =RT) ko ref; i exp  i  (6)
R T Tref

where Tref is a temperature within the range of significant weight-loss rate (600 K in
this case) that is used to diminish the interrelation among the parameters and help
the optimisation search [35].
Bearing in mind that the weight measured is the addition of the weight
corresponding to all the solid species present, it can be written that:
dw d[PP] d[C] d[PP  C] d[G1 ] d[G2 ]
*     (7)
dt dt dt dt dt dt

Taking into account Eqs. (1)
/(3) or Eqs. (4) and (5):
dw
k1 [PP]n1 k3 [PPC]n4 (8)
dt

Using the initial boundary condition which is, obviously, w /[PP]/[C] /1 and
[PP
/C] /0 when t/0, this equation can be integrated to calculate w (i.e. the
remaining mass fraction).
The previous model has been applied to simultaneously correlate the TG and
DTG curves obtained under dynamic conditions at a heating rate of 10 K min 1,
because, according to Varhegyi and Antal [36], the DTG curves are more sensitive
than the TG curves, and processes can be better observed. In all the calculations, the
objective function (OF) included the TG and DTG data obtained for the different

  
samples of PP with and without catalyst:

XX
((ws; j )exp (ws; j )cal )2 10
j d(ws; j )
dT j j d(ws; j )
dT j

exp

j j j j
OF cal (9)
  
s j d(ws; j ) d(ws; j )
max max
dT exp
dT cal

where j represents the experimental (exp) or calculated (cal) data at temperature Tj

and time tj of the experiment s, and w is the weight fraction, that means the weight at
the time t divided by the initial weight of the sample. The kinetic parameters were
optimised using the tool ‘Solver’ included in the calculation sheet EXCEL 7.0 for
WINDOWS. The integration of the kinetic equations was carried out using the Euler
method.