Rate Equations of Solid State Reactions. Euclidean and Fractal Models

ACADEMIA ROMN
Rev. Roum. Chim.,

2012, 57(4-5), 491-493
Revue Roumaine de Chimie

http://web.icf.ro/rrch/
Dedicated to Professor Ionel Haiduc

on the occasion of his 75th anniversary
RATE EQUATIONS OF SOLID STATE REACTIONS.

EUCLIDEAN AND FRACTAL MODELS
Eugen SEGAL*
Unversity of Bucharest, Faculty of Chemistry, Department of Physical Chemistry,
4-12 Bd. Regina Elisabeta, Bucharest, RO-70376, Roumania
Received June 2, 2011
The author suggests a comparative analysis of the classical Euclidean rate equations and the fractal ones. The fractal kinetic equations
contain the fractal dimension, property which could be used as a kinetic characteristic of the investigated solid-state reacting system.
INTRODUCTION*
In some previous notes, solid-gas decompositions
limited by nucleation-growth phenomena were
kinetically treated using euclidean as well as fractal
models.1-3 Rigorously valid equations were obtained
for extreme values of the nuclei fractal dimension
and approximate ones for the intermediate ones. The
consideration of the fractal character proves to be
important in order to establish the form of the kinetic
equations. As shown, for the solid-gas decompositions limited by nucleation-growth phenomena, the
fractal rate equations could account for the fractional
values of the time exponent in the integral kinetic
equation t n .
EUCLIDEAN RATE EQUATIONS4-11
Surface controlled reaction
or phase boundary controlled reaction4,5,11
For fast diffusion through the product layer the
chemical change is considered as phase boundary
*
Corresponding author: [email protected]
controlled. Under such conditions the reaction rate

is treated as being directly proportional to the
surface area of the unreacted reactant.
d (V 0 )
= kA
dt
(1)
where V0 is the initial volume of the reacting

particle and the degree of conversion or
d
A
=k
.
dt
V0
(2)
The integral form of equation (2) is:
1 (1 ) n =
with values of n
k
t
r0
(3)
1 1
, and 1 for three, two and one
3 2
dimensional geometry of the reacting particle.
492
Eugen Segal
rate is limited by the diffusion of the component,

A, through the product layer at the interface AB/B.
Anti Jander equation,19
Diffusion controlled reactions

Jander equation
According to Jander12 model the reaction rate
of the component which is covered, A, in a system
of spherical grains with comparable sizes is limited
by the diffusion of the component, B, which covers
through the product layer,AB. The model supposes
that surface of the grain belongs to the reactant and
that the concentrations of the diffusing component
B at the interfaces A/AB and AB/B are constant.
For the kinetics of the reaction between
reactante A and B under the form of compact
powders Jander worked up the following integral
equation:
1
3 2
2kD0
[ 1 (1 ) ] =
r0
(4)
2k
[1 (1 ) ] =
r0
ln t
(5)
1I =
2
(1 )
1
3
2kD0
r0
Gintsling and Braunshtein equation,
(6)
(9)
(10)
All the presented kinetic equations describe

various nonreacted shrinking core models.
Another model is based on continous bulk
absorbtion of the reactant, B, in the reactant, A, the
whole volume of the system changing gradually to
the volume of the product, AB.21-22 Under such
conditions the degree of conversion is given by:
n =
n
n =1
e n kt
(11)
where k is the rate constant given by:
2 D0
r0
(12)
FRACTAL RATE EQUATIONS
As according to the fractal geometry the surface

area of the reaction boundary, A, and the volume
V0 are given by:
D 1
(13)
(14)
V0 = br0
2kD0
2
1 (1 ) =
t
2
3
r0
2
1 + (1 + ) 3 = kt
3
A = ar0
15
2
3
Carter and Valensi equation,
Surface controlled reactions11
Zhuravlev, Lesotkin and Tempelman equation,14
r0
Anti Ginstling Braunstein equation,20
k=
Kroger and Ziegler equation13
3kD0
[(1 + ) 1] 2 =
= 1
where k is the rate constant, D0 the diffusion

coefficient of the reactant B through the layer of
product and r0 is the initial radius of the reactant A.
1
3 2
1
3
(7)
a and b being constants,
d
= (1 )
dt
16-18
2
z ( z 1)(1 ) 3 [1 + ( z 1) ] 3 =
2kD0
r0
D 1
D
(15)
with the fractal dimension is within the range;

(8)
where z is the ratio between the volumes: actual

(real) and ideal (if no change occurs) of the
product layer.
Anti Jander model could be treated as the
reverse of Jander model. Accordingly the reaction
2D3
The integral form of equation (15) is:
1 (1 )
1
D
= kt
(16)
For D=2 and D=3 equation (16) leads to the

integral kinetic equations known as R2 and R3.
Euclidean and fractal models
Diffusion controlled reactions

For 2 D 3 : Ozao and Ochiai using the
obvious relation:
r
r0
= 1 ( )3
d
= [(1 )
dt
2 D
D
Slightly different values of the exponents which

result as consequences of the change of euclidean
dimensions into fractal ones are to be noticed.
CONCLUSIONS
(17)
obtained:
1] 1
(18)
2
(1 ) D + 1 = kt
D
(19)
493
The fractal rate equations are more general with

respect to the euclidean ones.
The fractal rate equations open the perspective
of better quantitative treatment of the kinetic
properties of solid-state reaction mixtures.
and
2
Equation (19) with D=3 turns into:

2
2
(1 ) 3 + 1 = kt
3
(20)
which is a variant of Ginstling-Braunstein

equation.
Using relation (17) as well as the presented
euclidean kinetic equations one obtains:
Jander fractal equation,
1
2kD0t
[1 (1 ) D ] 2 =
r0
(21)
2k ln t
[1 (1 ) ] =
r0
(22)
Zhuravlev fractal equation
[(1 )
1
D
2kD0 t
1] =
2
r0
[(1 ) 1] =
2
5.
6.
7.
8.
9.
11.
12.
13.
14.
(23)
15.
16.
Anti-Jander fractal equation,

1
D
1.
2.
3.
4.
10.
Kroger and Ziegler fractal equation,

!
D 2
REFERENCES
2kD0 t
r0
17.
(24)
18.
19.
Anti Ginstling-Braunstein fractal equation,
20.
1+
2
(1 + )
D
2
D
= kt
(25)
The fractal kinetic equations are valid for the

same systems which use euclidean rate equations.
21.
22.
E. Segal, J. Thermal Anal., 1998, 52, 537.

E. Segal, J. Thermal Anal. Cal., 2000, 61, 979.
E.Segal, J. Thermal Anal. Cal., 2004, 76, 9333.
J. Sestak,V. Satava and W. W.Wendlandt, Thermochim.
Acta, 1973, 7, 333.
J. Sestak, Thermophysical Properties of Solids,
Academia, Praha, 1984, Chapter 8.
P. Jacobs and F. Tompkins, Chemistry of the Solid
State, W.E. Garner(Ed.), Butterworths, London, 1955,
Chapter 7.
K. Hauffe, Reaktionen in und anFesten Stoffen,
Springer-Verlag Berlin, 1955, Chapters 6-8.
B. Delmon, Introduction la Cintique Htrogne,
Editions Technip, Paris, 1969, Chapters 8-12.
P. P. Budnikov and A. M. Ginstling, Reaktzii v
Smesiakh Tberdikh Veshcestv, Gostroizdat, Moskva,
1961, Glava 5.
I. G. Murgulescu, T. Oncescu and E. Segal, Introduction
to Physical Chemistry (in Roumanian), Vol. II,
Publishing House of the Roumanian Academy,
Bucharest,1981, Chapters 39-44.
R. Ozao and M. Ochiai, J. Thermal Anal., 1993, 40, 1331.
W. Jander, Z. Anorg. Allg. Chem., 1927, 163, 1.
C. Kroger and G. Ziegler, Glastech.Ber., 1953, 26, 346;
1954, 27, 199.
V. F. Zhuravlev, I. G. Lesokin and R.G. Tempelman,
J. Appl. Chem. USSR, 1949, 21, 887.
A. M. Ginstling and B. I. Braunshtein, J. Appl. Chem.
USSR, 1950, 23, 1327.
E. R. Carter, J. Chem. Phys., 1961, 34, 2010; 1961, 35,
1137.
J. Haber, Festkorpechemie, V. V. Boldirev and Klaus
Meyer
(Eds.),
VEB
Deutscher
Verlag
fur
Grundstoffindustrie, Leipzig, 1973, p. 221.
G. Valensi, C. R. Acad. Sci., 1936, 202, 309.
W. Komatsu and T. Uemura, Z. Phys. Chem.(Frankfurt),
1970, 72, 59.
I. F. Kononiuk, Geterogennie Khimitceskie Reaktzii i
Reaktzionnaia Sposobnosti, Nauka i Tekhnika, Minsk,
1945, p. 93.
H. Dunwald and C. Wagner, Z .Phys. Chem. B, 1934, 24,
53.
B. Serrin and R. T. Erlickson, J. Chem. Phys, 1941, 9,
742.
494
Eugen Segal

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ACADEMIA ROMN

Rev. Roum. Chim.,

Revue Roumaine de Chimie

Dedicated to Professor Ionel Haiduc

RATE EQUATIONS OF SOLID STATE REACTIONS.

Received June 2, 2011

Corresponding author: [email protected]

controlled. Under such conditions the reaction rate

where V0 is the initial volume of the reacting

The integral form of equation (2) is:

dimensional geometry of the reacting particle.

rate is limited by the diffusion of the component,

Diffusion controlled reactions

Gintsling and Braunshtein equation,

All the presented kinetic equations describe

where k is the rate constant given by:

FRACTAL RATE EQUATIONS

As according to the fractal geometry the surface

Carter and Valensi equation,

Surface controlled reactions11

Zhuravlev, Lesotkin and Tempelman equation,14

Anti Ginstling Braunstein equation,20

Kroger and Ziegler equation13

where k is the rate constant, D0 the diffusion

a and b being constants,

with the fractal dimension is within the range;

where z is the ratio between the volumes: actual

For D=2 and D=3 equation (16) leads to the

Euclidean and fractal models

Diffusion controlled reactions

Slightly different values of the exponents which

The fractal rate equations are more general with

Equation (19) with D=3 turns into:

which is a variant of Ginstling-Braunstein

Zhuravlev fractal equation

Anti-Jander fractal equation,

Kroger and Ziegler fractal equation,

Anti Ginstling-Braunstein fractal equation,

The fractal kinetic equations are valid for the

E. Segal, J. Thermal Anal., 1998, 52, 537.

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