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Received 25 February 2006; received in revised form 5 July 2006; accepted 4 August 2006
Abstract
A new approximating formula for the Arrhenius integral has been proposed using the Pattern Search Method, which is both reliable and accurate.
Compared with several published Arrhenius integral approximations, the newly proposed formula is superior to the others and is an ideal solution
for the estimation of kinetic parameters from nonisothermal thermogravimetric analysis data.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Arrhenius integral; Nonisothermal kinetics; Kinetic parameters; Pattern Search Method
1. Introduction 2. Theory
The simplest experiment to determine the kinetics of a ther- The differential form of the nonisothermal rate of a solid
mal decomposition is thermogravimetry under nonisothermal reaction can be generally described by,
conditions. Since there are many inherent advantages, integral
dα A
methods have been widely used to determine kinetic parame- = e−(E/RT ) f (α) (1)
ters from nonisothermal thermogravimetric analysis data [1]. dT β
Unfortunately, integral methods involve the integration of the Upon integration, Eq. (1) gives,
Arrhenius function, so called ‘Arrhenius integral’, which has α
dα A T −(E/RT )
no exact analytical solution. A large number of approximate g(α) = = e dT (2)
solutions for the Arrhenius integral, with varying complexity 0 f (α) β 0
and precision, have been published [2]. However, many of these The integral of the right hand side of Eq. (2) is called the
approximations are gross or even inaccurate and do not allow Arrhenius integral. If E/RT is replace by ‘x’ and the integration
proper values for the kinetic parameters to be obtained [3]. In limits are transformed, the above equation becomes,
this work, a new Arrhenius integral approximate formula is
obtained using the Pattern Search Method. It will be shown that AE ∞ e−x
g(α) = dx (3)
the new approximation is reliable and accurate as a solution for βR x x2
the Arrhenius integral. This is written as,
AE
g(α) = p(x) (4)
βR
where p(x) is the exponential integral.
The p(x) function has no exact analytical solution and it is
∗ Corresponding author at: Biomass Energy Engineering Research Center, usually expressed as follows [4]:
School of Agriculture and Biology, Shanghai Jiao Tong University, 2678 Qixin
e−x
Road, Shanghai 201101, PR China. Tel.: +86 21 64783844. p(x) = h(x) (5)
E-mail address: caijunmeng7321@163.com (C. Junmeng). x2
1385-8947/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2006.08.003
16 C. Junmeng et al. / Chemical Engineering Journal 124 (2006) 15–18
x + a ln x + b
h1 (x) = (7)
x + c ln x + d
Table 1
Expressions of some approximations for the Arrhenius integral
T
Author 0
e−(E/RT ) dT p(x)
RT 2
2RT
e−x
2
Coats and Redfern [9] 1− e−(E/RT ) 1−
E E x2 x
RT 2 e−x 1
Gorbachev [10] and Lee and Beck [11] e−(E/RT )
E + 2RT x x+2
RT 2 1 − 2(RT/E) e−x 1 − (2/x)
Li [12] e−(E/RT )
E 1 − 6(RT/E) 2 x2 1 − (6/x2 )
RT 2 1 − 2(RT/E) e−u 1 − (2/x)
Agrawal [13] e−(E/RT )
E 1 − 5(RT/E)2 u2 1 − (5/x2 )
RT 2 1 − 2(RT/E) e−x 1 − (2/x)
Quanyin and Su [14] e−(E/RT )
E 1 − 4.6(RT/E)2 x2 1 − (4.6/x2 )
ET e−(E/RT ) e−x
Zsakó [15]
(E + 2RT )[(E/RT ) − (16(RT )2 /(E2 − 4ERT + 84(RT )2 ))] [x − (16/(x2 − 4x + 84))](x + 2)
RT 2 e−x 1
Wanjun et al. [16] e−(E/RT )
1.00198882E + 1.87391198RT x 1.00198882x + 1.87391198
17
18 C. Junmeng et al. / Chemical Engineering Journal 124 (2006) 15–18