Studies in Gas-Solid Reactions: Part I.

A Structural
Model for the Reaction of Porous Oxides with a
Reducing Gas
J . S Z E K E L Y AND J . W. EVANS

A structural model is presented for describing the reaction of a porous metal oxide pellet
with a reducing gas. It is suggested that the pellet is made up of a large number of grains
and the overall rate of reaction is computed by summing the contributions of all these individual grains. The model thus incorporates structural parameters, such as grain size,
porosity (pore size distribution) and allows a quantitative assessment of the role played
by these quantities in determining the rate of progress of the reaction.
r e a c t i o nH
of porous m e t aE
l oxide a g g r e g a t e s with a
T
r e d u c i n g gas is of c o n s i d e r a b l e t e c h n o l o g i c a l i m p o r taslce arid has c o n s e q u e n t l y r e c e i v e d a g r e a t deal of
attention. A l a r g e p r o p o r t i o n of t h e s e studies was c o n c e r n e d with iron oxide r e d u c t i o n but many o t h e r s y s t e m s have a l s o been e x t e n s i v e l y studied.
Most of the i n v e s t i g a t o r s to data have i n t e r p r e t e d
t h e i r r e s u l t s by using a s u i t a b l e v a r i a n t of the " s h r i n k ing c o r e m o d e l " . 1"8 T h i s m o d e l , sketched s c h e m a t i c a l l y in Fig. 1 is based on the a s s u m p t i o n that a f t e r
s o m e r e a c t i o n had o c c u r r e d the solid p h a s e c o n s i s t s of
an u n r e a c t e d c o r e , s u r r o u n d e d by a r e a c t e d s h e l l .
T h e s e two z o n e s a r e s e p a r a t e d by a s h a r p phase bounda r y w h e r e the c h e m i c a l r e a c t i o n takes p l a c e . As the
r e a c t i o n p r o c e e d s , the r e a c t e d s h e l l expands and diffusion of the r e a c t a n t s and p r o d u c t s through this r e g i o n
may b e c o m e one of the r a t e l i m i t i n g f a c t o r s .
The shrinking c o r e m o d e l {model based on " t o p o c h e m i c a l r e a c t i o n s " ) has been r e m a r k a b l y s u c c e s s f u l
for the i n t e r p r e t a t i o n of e x p e r i m e n t a l r e s u l t s ; in g e n e r a l , the equations b a s e d on this r e p r e s e n t a t i o n d e s c r i b e d the o v e r a l l r a t e in t e r m s of a " ' d r i v i n g f o r c e "
and t h r e e s e t s of r e s i s t a n c e s , n a m e l y :
i) Gas phase m a s s t r a n s f e r .
if) Diffusion of r e a c t a n t s and p r o d u c t s through the
reacted shell.
iii) C h e m i c a l r e a c t i o n o c c u r r i n g at the i n t e r f a c e
s e p a r a t i n g the r e a c t e d and the u n r e a c t e d r e g i o n s .
Of t h e s e q u a n t i t i e s , the gas phase m a s s t r a n s f e r
c o e f f i c i e n t and the r a t e of p o r e diffusion may be p r e d i c t e d , o r at least e s t i m a t e d . The p a r a m e t e r s c h a r a c t e r i z i n g the c h e m i c a l k i n e t i c s , h o w e v e r , have to be
m e a s u r e d e x p e r i m e n t a l l y . Indeed, the f o r m of the r a t e
equation and the n u m e r i c a l v a l u e s of the r a t e constant
s e r v e d as the p r i n c i p a l a d j u s t a b l e p a r a m e t e r s which
i l l o w e d the m a t c h i n g of e x p e r i m e n t a l and " t h e o r e t i c a l "
results.
While the shrinking c o r e model has been v e r y widely
ased, it s u f f e r s f r o m two m a j o r s h o r t c o m i n g s :
a) The i m p o r t a n t p o s t u l a t e of " t o p o c h e m t c a l r e a c t i o n " , i . e . , the e x i s t e n c e of a s h a r p boundary between

the r e a c t e d and u n r e a c t e d z o n e s is not u n i v e r s a l l y

supported by e x p e r i m e n t a l e v i d e n c e . In t h e i r study of
h e m a t i t e r e d u c t i o n , G r a y and H e n d e r s o n ~ found that the
r e d u c e d and u n r e a c t e d s e c t i o n s w e r e s e p a r a t e d by a
t r a n s i t i o n z o n e , which contained both totally r e d u c e d
and only p a r t i a l l y r e d u c e d g r a i n s . S i m i l a r findings
w e r e r e p o r t e d by W e i s z and Goodwin t~ in t h e i r i n v e s tigation c o n c e r n e d with the c o m b u s t i o n of c a r b o n d e p o s i t s in p o r o u s c a t a l y s t s .
b) P e r h a p s the m o s t s e r i o u s drawback of the s h r i n k Lag c o r e m o d e l is the fact that s t r u c t u r a l e f f e c t s , such
as p o r o s i t y , g r a i n s i z e , and so forth, a r e i m p l i c i t l y
i n c o r p o r a t e d in the c h e m i c a l r a t e constant and do not
a p p e a r e x p l i c i t l y . It follows that any m e a s u r e m e n t
m a d e of r e d u c t i o n k i n e t i c s is n e c e s s a r i l y s p e c i f i c to
a given m a t e r i a l o r even to a given batch of m a t e r i a l ,
and no unique r e a c t i o n p a r a m e t e r s can be a s s i g n e d to
a given o r e o r s i n t e r . The shrinking c o r e model p r o v i d e s little guidance on the r o l e played by s t r u c t u r a l
p a r a m e t e r s in d e t e r m i n i n g the o v e r a l l r e a c t i o n r a t e .

INREACTED CORE

//
'

J. SZEKELY is Professor of Chemic-,d Engineering and Director,

Center for Process Metallurgy at the State University at Buffalo, BuD
falo, N.Y.J.W. EVANS, formerly Graduate Student in Chemical Engineering at the State University of New York at Buffalo, is now with the
Ethyl Corp., Baton Rouge, La.
Manuscript submitted July 24, 1970.
METALLURGICALTRANSACTIONS

I/C.EM,CA
_ REACT,ONAT
/ ' T.E P.ASE .OONDARY
REACTED ZONE
- P O R E DIFFUSION

II

GAS PHASE MASS TRANSFER

OF REACTANTS AND PRODUCTS

Fig. t--Schematic represen~tion oftheshrinkingcore model.

VOLUME 2, JUNE 1971-1691

T h e s e a p p a r e n t s h o r t c o m i n g s of the topochemical a s s u m p t i o n prompted a n u m b e r of r e c e n t studies,~x-x4 of

which the work r e p o r t e d by Ishida and W e n " is p r o b ably the most noteworthy. T h e s e a u t h o r s r e g a r d e d the
p o r o u s solid m a t r i x as a homogeneous medium and des c r i b e d the g a s - s o l i d r e a c t i o n in t e r m s of a " h o m o geneous rate c o n s t a n t . " This r e p r e s e n t a t i o n led to a
diffuse r e a c t i o n front but s t i l l would not allow the a
p r i o r i p r e d i c t i o n of the r e a c t i o n r a t e s in t e r m s of
structural considerations.
F i n a l l y , in a r e c e n t paper the a u t h o r s proposed a
s t r u c t u r a l model ts for the r e a c t i o n between a s e m i infinite porous m e d i u m and a g a s e o u s r e a c t a n t .
Through this model it was p o s s i b l e to identify s o m e
of the significant s t r u c t u r a l p a r a m e t e r s , but the g e o m e t r y chosen precluded d i r e c t c o m p a r i s o n with m e a s urements.
The work r e p o r t e d in the p r e s e n t s e r i e s of p a p e r s
w a s u n d e r t a k e n with a view of developing a s t r u c t u r a l
model which can be c o m p a r e d d i r e c t l y with e x p e r i m e n t a l m e a s u r e m e n t s . The u l t i m a t e o b j e c t i v e of the i n v e s tigation is to define the p h y s i c a l c r i t e r i a that affect the
r e a c t i v i t y of porous s o l i d s , and hence to define the
o p t i m a l conditions for effecting t h e s e r e a c t i o n s .
In P a r t I we s h a l l p r e s e n t a m a t h e m a t i c a l m o d e l ,
which is a f u r t h e r development of that d e s c r i b e d in the
e a r l i e r p u b l i c a t i o n , and in the s u b s e q u e n t P a r t II the
p r e d i c t i o n s b a s e d on the model w i l l be c o m p a r e d with
e x p e r i m e n t a l m e a s u r e m e n t s o b t a i n e d , using the s y s t e m NiO-H2.
FORMULATION
Let us c o n s i d e r a s p h e r i c a l pellet of the solid r e a c t a n t , made up of a l a r g e n u m b e r of s p h e r i c a l g r a i n s
of u n i f o r m r a d i u s , r s , Let the p o r o s i t y of the s a m p l e
be P , and the d i s t a n c e from the c e n t e r ( m a c r o s c o p i c
r a d i a l coordinate) be d e s i g n a t e d by R . The s a m p l e is
b r o u g h t into contact with a g a s , A , with which it r e a c t s
to form a solid product and a g a s e o u s product, B.
The following m a j o r a s s u m p t i o n s a r e made:
i) The i n i t i a l physical s t r u c t u r e is m a i n t a i n e d
throughout the r e a c t i o n , and
ii) the r e a c t i o n of each g r a i n p r o c e e d s f r o m the
o u t s i d e toward the c e n t e r , so that the position of the
r e a c t i o n front w i t h i n e a c h g r a i n exhibits s p h e r i c a l
s y m m e t r y - - t h i s b e h a v i o r may be d e s c r i b e d as the m i c r o s c o p i c s h r i n k i n g c o r e . Thus the r a t e at which each
g r a i n r e a c t s is p r o p o r t i o n a l to the s u r f a c e a r e a of
the r e a c t i o n front at any given t i m e . The r a d i u s of
this m i c r o s c o p i c r e a c t i o n front is designated by r ,
which is a function of t i m e and o f R ( i . e . , r a d i a l p o s i tion within the sample).
The model d e s c r i b e d above is sketched in Fig. 2
w h e r e it is seen that the r e a c t a n t gas is t r a n s f e r r e d
f r o m the bulk gas s t r e a m , diffuses between the g r a i n s
and then through a solid product l a y e r within each
g r a i n and r e a c t s at the s p h e r i c a l r e a c t i o n i n t e r f a c e .
The product gas thus g e n e r a t e d diffuses back through
the solid product l a y e r and between the g r a i n s before
u n d e r g o i n g a m a s s t r a n s f e r step into the bulk gas
stream.
At this stage it may be w o r t h w h i l e to c o m m e n t
b r i e f l y on the a p p r o p r i a t e n e s s of t h e s e a s s u m p t i o n s .
A s s u m p t i o n i) is r e s t r i c t i v e , n o n e t h e l e s s it is thought
1692-VOLUME2, JUNE t971

to be valid for a r a n g e of p r a c t i c a l c o n d i t i o n s . It is
a g r e e d that s i n t e r i n g o r a g g l o m e r a t i o n of the reduced
phase will o c c u r in many i n s t a n c e s , hut it is suggested
that these m o r e c o m p l e x s i t u a t i o n s a r e best d e s c r i b e d
in t e r m s of an a p p r o p r i a t e l y modified model.
A s s u m p t i o n ii) is thought to r e p r e s e n t a r e a s o n a b l e
a p p r o x i m a t i o n to r e a l i t y , at least in a m a c o r s c o p i c
sense.
Let us now p r o c e e d by stating the a p p r o p r i a t e cons e r v a t i o n equations for the g a s e o u s r e a c t a n t s and
products.
A m a s s b a l a n c e on component A yields the following
d i f f e r e n t i a l equation d e s c r i b i n g diffusion of A between
the g r a i n s :
D_s a (R a C A / - ( 1 - ~ O ) p , . ~ = 0
R "~ a--R-\_.z ~R /

ill

where
P m = t r u e m o l a r d e n s i t y of r e a c t a n t solid.

= r a t e of d i s a p p e a r a n c e of g a s e o u s r e a c t a n t p e r
mole of i n i t i a l solid r e a c t a n t .
DJi = the effective diffusivity of the gaseous r e a c t a n t
between the g r a i n s of the porous solid.
CA = m o l a r c o n c e n t r a t i o n of the g a s e o u s r e a c t a n t in

the i n t e r s t i c e s between the g r a i n s .

A s i m i l a r equation may be w r i t t e n for the g a s e o u s
product:
R a 8R

8R

w h e r e n s is the m o l e s of B f o r m e d by the r e a c t i o n of
one mole of A. Subsequently, n s w i l l be taken a s u n i t y ,

Bulk gas

s/ream

Fig. 2--Schematic representation of the structural model.

METALLURGICAL TRANSACTIONS

but the modification to account for o t h e r v a l u e s of n s

is s t r a i g h t f o r w a r d .
Eqs. [1] and [2] a r e valid for e q u i m o l a r c o u n t e r diffusion (the p r e s e n t case) o r w h e r e diffusion b e t w e e n
the g r a i n s is purely of the K n u d s e n type. It is to be
noted that no a c c u m u l a t i o n t e r m s a p p e a r in the two
e q u a t i o n s , thus the ' q u a s i - s t e a d y s t a t e ' a s s u m p t i o n is
i m p l i c i t in this f o r m u l a t i o n . The q u a s i - s t e a d y s t a t e
a s s u m p t i o n is r e a d i l y justified on p h y s i c a l g r o u n d s
b e c a u s e the amount of g a s e o u s r e a c t a n t within the
p o r e s is negligible, c o m p a r e d with the net input and
the r a t e of r e a c t i o n .
Before we can p r o c e e d f u r t h e r , the r e a c t i o n t e r m ,
has to be r e l a t e d to the c o n c e n t r a t i o n of the r e a c t a n t s and products and also the r a t e of p r o g r e s s of the
r e a c t i o n front, within the g r a i n s at a p a r t i c u l a r l o c a tion, R 9
We shall make the following f u r t h e r a s s u m p t i o n s :
lit) The r e a c t i o n between the gas and the solid is of
f i r s t o r d e r in both the f o r w a r d and r e v e r s e d i r e c t i o n s ,
and
iv) t h e r e is n e g l i g i b l e r e s i s t a n c e due to diffusion
through the product l a y e r w i t h i n the g r a i n s ; thus the
c o n c e n t r a t i o n at the r e a c t i o n s u r f a c e within a g r a i n is
identical with that in the i n t e r s t i c e s at the s a m e r a d i a l
coordinate.
The a s s u m p t i o n r e g a r d i n g f i r s t o r d e r k i n e t i c s is
r e s t r i c t i v e , n o n e t h e l e s s it will apply to many s y s t e m s ,
in p a r t i c u l a r it will hold as a r e a s o n a b l e a p p r o x i m a tion in the v i c i n i t y of e q u i l i b r i u m , i . e . , in the mixed
c o n t r o l r e g i m e s . N o n l i n e a r k i n e t i c e x p r e s s i o n s could
be r e a d i l y a c c o m m o d a t e d but in view of the much
l a r g e r demand on c o m p u t e r t i m e this p o s s i b l e r e f i n e m e n t was not i n c o r p o r a t e d at this stage.
A s s u m p t i o n iv) is thought to be r e a s o n a b l e for s m a l l
g r a i n s as the diffusion path through the (porous} g r a i n s
is v e r y much s m a l l e r than the diffusion path through
the bulk of the porous solid.
With these a s s u m p t i o n s , ill) and iv), the a d v a n c e meat of the r e a c t i o n front within a g r a i n is w r i t t e n a s :
dt

Prn

R ~ a-~-

w h e r e k is the c h e m i c a l r e a c t i o n r a t e c o n s t a n t and KE
is the e q u i l i b r i u m c o n s t a n t .
g, the r e a c t i o n t e r m , may now be r e a d i l y r e l a t e d to
the a d v a n c e m e n t of the r e a c t i o n front within a g r a i n ,
as follows:
F o r the e a s e w h e r e one mole of A r e a c t s with one
mole of solid,* we have:
*Ready allowance could be made for other stoidaiometries through the use of
aa appropriate constant of proportionality.

4 ~ r z" d r
(C _ C_~)
- ~ P m = 4 nr2k
A
KE

Pmrs

A -

[5]

KE

On s u b s t i t u t i n g for 9 f r o m Eq. [5] into Eq. [1] and [2]

we obtain:

OR

3R /

METALLURGICAL TRANSACTIONS

rs

(\ CA

prnr~

"I-~E

and Eq. [3] b e c o m e s :

dr(rs,R)
dt

k (C A - K~E)
Pm

[9]

C l e a r l y , this additional s o p h i s t i c a t i o n would be a p p r o p r i a t e only if a c c u r a t e i n f o r m a t i o n w e r e a v a i l a b l e on

the g r a i n size d i s t r i b u t i o n .
INITIAL

AND

BOUNDARY

CONDITIONS

The initial and boundary conditions for the governing

Eqs. [3], [6], and [7] have to express the following
physical c o n s t r a i n t s :
a) the initial position of the r e a c t i o n front within
each g r a i n , i . e . , that no r e a c t i o n had taken place b e fore t = 0
b) the fact that the c o n c e n t r a t i o n p r o f i l e s a r e s y m m e t r i c a l about the c e n t e r of the p e l l e t , and
c) the continuity of the m o l a r fluxes at the outer
s u r f a c e of the pellet, i . e . , diffusive flux a c r o s s the
o u t e r s u r f a c e of the pellet = couvective flux through
the " g a s f i l m " s u r r o u n d i n g the pellet.
T h e s e boundary c o n d i t i o n s a r e given in Eqs. [10]
through [14]:
r = r s for a t l R at t = 0

[10]

~CA = 0 a t R = 0
OR

[11]

~cz

[12]

D~4 ~

= o

~R

D[3 ~
3R

air

= h(CA o

CA) a t R =Ro

[13]

= h(CB o - CB) a t R =Ro

[14]

w h e r e Ro is the r a d i u s of the s p h e r i c a l s a m p l e , h is
the m a s s t r a n s f e r coefficient from the bulk gas s t r e a m
to the solid s a m p l e , CAo and CBo a r e the c o n c e n t r a t i o n s
of the g a s e o u s r e a c t a n t and product in the bulk gas
stream.
CORRECTION

--017]

[4]

Thus

....

~-

H e r e m e n t i o n may be made of a m o r e g e n e r a l case

where the g r a i n s a r e not of u n i f o r m size. Let
f ( r s) 9 d r s be the weight fraction of g r a i n s with r a d i i
between r s and ~rs + d r s) and a s s u m e t h a t f is independent of R . Now

~R

A - KE

aRJ

KE

FOR

NONI~K)THERMAL

BEHAVIOR

In general, the temperature

of the pellet will differ
from that of the gas stream, because of the heat generated or absorbed by the chemical reaction. For
relatively small heats of reaction ready allowance
may be made for non-isothermality,
by assuming that
the pellet is at uniform temperature
at any given
time; ~6 then the unsteady state heat balance yields the
following:
V O L U M E 2, J U N E 1 9 7 1 - - t 6 9 3

dT
dt

H de
Cp dt

3
Ro(1 - P) pmCp

[ht(T - TE) + ea(T ~ - T~)]

[15]

w ith

T = TE at t = 0

[16]

w h e r e T and T E a r e the pellet and e n v i r o n m e n t t e m p e r a t u r e s in absolute u n i t s , H is the heat of r e a c t i o n ,

and the other q u a n t i t i e s a r e defined in the list of
symbols.
F r o m the knowledge of d ~ / d t the pellet t e m p e r a t u r e
may thus be computed and the p r o p e r t y v a l u e s m a y
then be evaluated at this c o r r e c t t e m p e r a t u r e . F o r the
p r a c t i c a l s y s t e m to be c o n s i d e r e d in P a r t H, this c o r r e c t i o n amounted only to a m a x i m u m of about 20 ~ to
30~ so that the p r i n c i p a l effect was confined to the
reaction rate constant.
Eqs. [3], [6], [7], and [15], together with the bounda r y conditions contained in Eqs. [10] through [14]
r e p r e s e n t a complete s t a t e m e n t of the p r o b l e m . The
s u b s e q u e n t m a n i p u l a t i o n of these equations and the
n u m e r i c a l technique used for t h e i r solution is d i s c u s s e d in the s u b s e q u e n t section.
THE TECHNIQUE OF SOLUTION
Rearrangement of the Equations
The governing equations may be rearranged on noting
that in the absence of coupled fluxes Eqs. [6] and [7]
are not independentand one of them may be eliminated
by the followingprocedure:
Stoichiometry dictates that:

On i n t e g r a t i n g Eq. [18] o n c e , with r e s p e c t to R , and

using Eq. [17 ] yields a f t e r a f u r t h e r i n t e g r a t i o n :

(DA
[20]
CB = CAo + \ D ~ - 1) CARo-- CA 9 D~,
DB
Thus on s u b s t i t u t i o n Eqs. [3] and [6] to [7] a r e t r a n s -

formed to Eqs. [20] and [21], respectively.

k {CA(l+

R z

rs

the quantity [1 - (r 3/ r s ) ] may be c o n s i d e r e d a local e x tent o f r e a c t i o n and will be designated ~. Thus the
right side of Eq. [21] is the weighted a v e r a g e value of
O/.

c is not a function of R , but is, of c o u r s e , a function

of t.
The N u m e r i c a l Solution
In o r d e r to put the governing equations in a finite
d i f f e r e n c e f o r m , let us e s t a b l i s h a t w o - d i m e n s i o n a l
grid in R and t, d e s i g n a t i n g the mesh spacing in R by
AR and the t i m e step by At.
The values of R at the v a r i o u s grid points wilt be
designated by s u b s t i t u t i n g a p p r o p r i a t e n u m e r i c a l
v a l u e s into the index i of the q u a n t i t y R i , which now
denotes d i s c r e t e v a l u e s of the s p a t i a l coordinate. The
index i is so chosen that:
i = 1

atR =0

i=n

air

=Ro

dt

Pm

DBKE]

KE

w h e r e the s u b s c r i p t s i denote v a l u e s of the a p p r o p r i a t e

v a r i a b l e s at r a d i u s R i .
If the values of CAi w e r e known a s a function of
t i m e , the set of equations r e p r e s e n t e d by Eq. [251
could be r e a d i l y i n t e g r a t e d , e . g . by the Runge-Kutta
method.
In o r d e r to obtain CAi , let us r e c a l l Eq. [22], which
may be w r i t t e n a s follows:

[ R 2 OR

[24]

[19]

which is valid for all v a l u e s of R .

CB may now be e x p r e s s e d with the aid of Eqs. [17]
and [19] to obtain:

dr

Ro~

The index of any m e s h value of R differs from its

n e i g h b o r s by unity.
Eq. [21] may now be r e p l a c e d by n equations of the
type

f u r t h e r m o r e on c o m b i n i n g Eqs. [6] and [7] we have:

D~4 (Constant - Ca ) = D~ CB

In generating a solution, we seek values of CA (and

also CB) and r , for all values of R and t. However, in
order to compare the computed results with experimental data, it is convenientto define a quantity,
termed the extent of reaction which bears a direct
relationship to experimentally measured weight change
of the specimen.
The overall extent of reaction e may be expressed
as follows :

R=Ri

rs

The left hand side of Eq. [26] may be e x p r e s s e d in a

finite d i f f e r e n c e form a s :

aR/

0R

1694-VOLUME2, JUNE 1971

[221

~R]

-~-~

+ 2R

[CAi__1 - 2CAi + Cai+l ]

Ri
+

~R

~ AR2

L2",J

MFTALL:URCICALTRANSACTIONS

~Read physical /
parameters /

[ ?:=':i:,o:'"~ .I
I COIl PROPS tO store

initial

physical parameters

co,,

Aux,4 io co.~a,, i
initial

[concentration praf es J
-

Call RKSTEP 1o advance

Call AUXI4 to compute
solution by one time 1 I concentration profiles
step
, ,['--'1 at each RUNGE-KUTTA
[
|
derivative evaluation
89
Call AUXI4 to coml~te concentration
profiles a t e ~
of t me step

Call SIM,IMZ to find"]

new reaction extent
t

Coil TEMP to find 'I

new temperatur s
[

Solution may now proceed as follows:

I) Starting with given initial values of r i and computing the initial values of CAi, the position of the reaction front is advanced by one time step through the
integration of Eq. [25].
2) The resultant new values of r i may then be substituted into Eqs. [29], [30], and [31] which then yield
n simultaneous equations for CAi, i = 1, 2, 3, . . . n.
3) The new values of CAi are then used for advancing
the reaction front by a further time step.
The actual computation was performed on the Control
Data Corporation 6400 computer at the State University
of New York at Buffalo, using Fortran IV. The numerical solution of Eq. [26] was performed by a subroutine
labeled AUX14. Calling parameters for AUX14 were
the n values of R i and of r i together with the value of
and for the physical properties h, P, k, D~, D~,
K E , CAo and ,rs . The n values of CAi constituted the
output from the subroutine.
Another subroutine, RKSTEP, advanced the solution
of Eq. [23] by one time step using the fourth order
Runge-Kutta technique. This subroutine had as input
parameters the present n values of r i and CA i, together
w i t h k, Pm , D ~ , D~ , KE , CAo , and the s i z e of the t i m e
s t e p . T h e new v a l u e s f o r r i c o n s t i t u t e d the output. F o r
f u r t h e r c o m p u t a t i o n a l d e t a i l s the r e a d e r is r e f e r r e d
to the t h e s i s upon w h i c h t h i s p a p e r is b a s e d . ~7
A b l o c k d i a g r a m of the c o m p u t e r p r o g r a m is shown
in F i g . 3.

Coil PROPS to find

propert ies
at new temperature

COMPUTED

Fig. 3--Block diagram of the computer program.

H e r e R i a r e s e l e c t e d s u c h that t h e m e s h s p a c i n g (AR)
is u n i f o r m . On r e a r r a n g e m e n t E q . [27] m a y be w r i t t e n

as:

%__

~i CAo

[28]

3(1 - P ) r } R } k
~xi = "
, 3
DA r s

[29]

KE

where

E q . [28] h o l d s f o r a l l the i n t e r n a l g r i d p o i n t s , i . e . ,
i = 2, 3 , 4 . . . .
( n - 1).
The boundary conditions are also readily expressed
in a f i n i t e d i f f e r e n c e f o r m , t h u s we h a v e :

3 CA, - 4 CA2 + CAa = 0

[30]

and

CAn_2- 4CA,,_ 1 + (3 + 2'~)CAn = 2~CAo

[31[

( r e p i n c i n g E q . [13 ])

RESULTS

In view of the numerical procedure used for solving

the governing equations, numerical values were required for the parameters appearing in the equations.
These quantities may be divided into two groups,
namely:
a) Parameters which are readily available for a
given application, or at least, may be easily calculated.
b) Parameters, the evaluation of which required
further measurement.
a) Pellet size,Ro, porosity, P, molar density of the
solid gaseous reactant and product concentrations, CAo,
C ~ , and the gas film heat and mass transfer coefficients, ht and h, fall in this first category and therefore no further comment will be made on the techniques
used for their evaluation.
b) The parameters that are not very readily measured or evaluated are the reaction rate constant, k,
I
the effective diffusion coefficients, D~4, D B , and the
grain size, r s , or the grain size distribution.
Of t h e s e q u a n t i t i e s , h, the reaction rate constant has
to be m e a s u r e d e x p e r i m e n t a l l y ; k w i l l d e p e n d on t e m p e r a t u r e and on the c o n d i t i o n o e the s u r f a c e , but w i l l
no l o n g e r be a f f e c t e d by the m a c r o s t r u c t u r e o f the
solid.
D'A and D~, the effective diffusion coefficients, d e pend on the t o r t u o s i t y and a r e m a d e up of t h e K n u d s e n
d i f f u s i o n c o e f f i c i e n t and the m o l e c u l a r d i f f u s i v i t y .
On d e n o t i n g t h e s e by D~4K and DBK r e s p e c t i v e l y , D~
m a y be e s t i m a t e d by the B o s a n q u e t i n t e r p o l a t i o n
formula:

where
= ~3h~A-9 AR
METALLURGICAL TRANSACTIONS

[32]

1
m~

[331

D~4B + D A K
VOLUME 2, JUNE 1971-1695

CHEMICAL

REACTION

CONTROL

INTERNAL

DIFFUSION
Extent

Extent

I-O

I.o

Radial Variation
of Extent of
Reaction ( ~ ) :

Radial Variation
of Extent of
Reaction ( = ) :

Cone,

CONG.

Co

Co

Occurs :

0
Ro
Distance from Centre
Low Temperatures
High Porosities
Small Spheres

Fig. 4--Typical plot of the local extent of reaction and of the

concentration profile for chemical control.
The m o l e c u l a r diffusion coefficient may be e s t i m a t e d
from the m o l e c u l a r t h e o r y of g a s e s , and the K n u d s e n
diffusion coefficient may also be e s t i m a t e d if the pore
s i z e d i s t r i b u t i o n (grain s i z e d i s t r i b u t i o n ) and the p o r o s i t y a r e known.
A l t e r n a t i v e l y , D.~ may be m e a s u r e d e x p e r i m e n t a l l y
through both the r e a c t e d and u n r e a c t e d m a t r i c e s .
F i n a l l y , r s , the g r a i n size m a y be e i t h e r m e a s u r e d
d i r e c t l y by e l e c t r o n m i c r o s c o p y , o r X - r a y diffraction
t e c h n i q u e s ; a l t e r n a t i v e l y , a value for r s may be deduced from pore size d i s t r i b u t i o n m e a s u r e m e n t s .
It is s t r e s s e d that the effective diffusion coefficient
and the g r a i n size may be s t r o n g l y i n t e r r e l a t e d if the
component due to Knudsen diffusion is s i g n i f i c a n t .
A f u r t h e r , m o r e detailed d i s c u s s i o n will be p r e s e n t e d
in P a r t ]I of the paper r e g a r d i n g the t e c h n i q u e s a v a i l able for e s t i m a t i n g and m e a s u r i n g D ~ , k and r s .
In view of the v e r y large n u m b e r of p a r a m e t e r s that
have to e n t e r the computation, any set of computed
r e s u l t s will' be specific to a p a r t i c u l a r , given a p p l i c a tion. At this stage it is thought d e s i r a b l e , to defer the
p r e s e n t a t i o n of detailed computed c u r v e s to P a r t II of
the p a p e r and to confine o u r s e l v e s to a d i s c u s s i o n of
the g e n e r a l f e a t u r e s of the solution.
F i g s . 4 to 6 show s k e t c h e s of the c o n c e n t r a t i o n p r o files and of the s p a t i a l d i s t r i b u t i o n of a , the extent of
r e a c t i o n , at some i n t e r m e d i a t e t i m e s , c o r r e s p o n d i n g
to v a r i o u s types of a s y m p t o t i c b e h a v i o r .
The p r o f i l e s of a and of C A , sketched in Fig. 4, c o r r e s p o n d to s y s t e m s w h e r e the o v e r a l l r a t e is c o n t r o l l e d
by c h e m i c a l k i n e t i c s ; in p r a c t i c a l s i t u a t i o n s c h e m i c a l
k i n e t i c s tend to c o n t r o l at low t e m p e r a t u r e s , at high
p o r o s i t i e s , and in the c a s e of s m a l l p e l l e t s . Inspection
of Fig. 4 shows that both the c o n c e n t r a t i o n and a p r o files a r e u n i f o r m .
Fig. 5 shows s y s t e m s w h e r e i n t e r n a l diffusion is the
r a t e c o n t r o l l i n g step, which is r e a l i z e d at high t e r n 1696-VOLUblE 2, JUNE 1971

I-

0
Ro
Distance from Centre

0
Re
Distance from Centre

Concentration
Profile :

CONTROL

Concentration
Profile :

o
o
R=
Distance from Centre

Occurs :

High Temperatures
Low Porosities
Large Spheres
Towards End of Reaction
Fig. 5--Typical plot of the local extent of reaction and of the
concentration profile for pore diffusion control.
M I X E D (chemical reaction 4- internal diffusion) C O N T R O L
Extent
I.o

Radial Variation
of Extent of
Reaction ( ~ ) :

/
o

I
0
Ro
Distance from Centre

!b

Conc. T

Profile :

o '
O

Re

Distance from Centre

Fig. 6--Typical plot of the local extent of reaction and of the
concentration profile for mixed control.

p e r a t u r e s , low p o r o s i t i e s , and for l a r g e p e l l e t s . It is

s e e n that the profile of c~ u n d e r g o e s a step change f r o m
unity to zero at some i n t e r m e d i a t e v a l u e of R , which of
c o u r s e , c o r r e s p o n d s to a s h a r p r e a c t i o n boundary. Inspection of the c o n c e n t r a t i o n profile shows that g r a dients in c o n c e n t r a t i o n a r e confined to a region between
Ro and the r e a c t i o n f r o n t , i . e . , to the r e a c t e d shell.
F i n a l l y , the b e h a v i o r of a r e g i m e of mixed c o n t r o l
(chemical r e a c t i o n + i n t e r n a l diffusion) is sketched in
Fig. 6. It is seen that the p r o f i l e of a is a smooth
c u r v e , a significant p o r t i o n of which f a l l s between 0
and 1; it follows that this s i t u a t i o n c o r r e s p o n d s to a
METAL[.URGICAL TRANSACTIONS

E
o!V

,b

,~

~o ' ,%

~o'

,2o

TIME (Minutes)

Fig. 7--Plot of the overall extent of reaction against time for

nickel oxide reduction with hydrogen. The numbers on the
curves correspond to:
No.
1
2
3
4

Temp, ~
299
301
303
293

R0, cm
0.770
1.178
0.800
1.128

P, Initial
0.729
0.734
0.384
0.384

dLffuse r e a c t i o n zone. The c o n c e n t r a t i o n p r o f i l e shown

a l s o r e f l e c t s this b e h a v i o r .
I n s p e c t i o n of F i g s . 4 to 6 shows that a s h a r p r e a c t i o n
front e x i s t s only in one p a r t i c u l a r c a s e , when the p r o c e s s is c o n t r o l l e d e n t i r e l y by i n t e r n a l diffusion; in a l l
o t h e r c a s e s the r e a c t i o n zone w i l l c o n s i s t of a diffuse
r e g i o n , the width of which Ls d e t e r m i n e d by the r e l a t i v e
magnitude of the v a r i o u s p a r a m e t e r s .
Since F i g s . 4 to 6, like all p r e c e d i n g i l l u s t r a t i o n s ,
w e r e s k e t c h e s of computed b e h a v i o r , it may be of int e r e s t to show a c t u a l computed r e s u l t s . This is done
in Fig. 7 on a plot of the o v e r a l l extent of r e a c t i o n
a g a i n s t t i m e . The p a r t i c u l a r s y s t e m c o n s i d e r e d is in
the i n t e r m e d i a t e r e g i m e w h e r e both diffusion and
c h e m i c a l k i n e t i c s a r e s i g n i f i c a n t . The f o u r c u r v e s
shown indicate that both p o r o s i t y and p e l l e t s i z e have
a significant effect on the o v e r a l l r e a c t i o n r a t e .

DISCUSSION
In the p a p e r an a l t e r n a t i v e is p r o p o s e d to the c o n v e n t i o n a l " s h r i n k i n g c o r e " m o d e l , e x t e n s i v e l y used
for d e s c r i b i n g the r e d u c t i o n k i n e t i c s of solid, p o r o u s
metal oxides.
The m o d e l p r e s e n t e d in the p a p e r d e s c r i b e s the
o v e r a l l r a t e of the r e a c t i o n by s u m m i n g the c o n t r i b u tions f r o m the individual g r a i n s that make up the p o r ous solid m a t r i x .
On a s s u m i n g that the solid s t r u c t u r e is not modified
in the c o u r s e of the r e a c t i o n , the s y s t e m is r e p r e sented by two s e t s of s i m u l t a n e o u s d i f f e r e n t i a l e q u a t i o n s , one s e t d e s c r i b i n g the r e a c t i o n of individual
l a y e r s of solid g r a i n s , and the o t h e r d e s c r i b i n g the
diffusion of r e a c t a n t s and p r o d u c t s within the porous
matrix.
A s a t i s f a c t o r y n u m e r i c a l s c h e m e was d e v e l o p e d for
the solution of t h e s e e q u a t i o n s , and thus c u r v e s w e r e
g e n e r a t e d giving the a p p r o p r i a t e t r a n s i e n t c o n c e n t r a tion p r o f i l e s and the extent of r e a c t i o n with t i m e .
METALLURGICALTRANSACTIONS

The potential a t t r a c t i v e n e s s of the p r e s e n t model is

twofo ld :
a) The p r o f i l e s g e n e r a t e d for the local extent of r e a c t i o n a r e in q u a l i t a t i v e a g r e e m e n t with e x p e r i m e n t a l
findings; a c e r t a i n combination of c i r c u m s t a n c e s can
lead to diffuse r e a c t i o n z o n e s , w h e r e a s t h e r e a r e conditions (when p o r e diffusion c o n t r o l s ) w h e r e the r e a c t e d and u n r e a c t e d zones a r e s e p a r a t e d by a sharp
r e a c t i o n boundary.
b) A m o r e significant f e a t u r e of the m o d e l is that it
i n c o r p o r a t e s s t r u c t u r a l p a r a m e t e r s , such as p o r e
diffusion c o e f f i c i e n t , g r a i n s i z e , p o r o s i t y , and the like,
into the o v e r a l l r e a c t i o n s c h e m e . T h e s e q u a n t i t i e s
may be m e a s u r e d independently, and if a d e q u a t e i n f o r m a t i o n is a v a i l a b l e on the c h e m i c a l k i n e t i c s , it should
be p o s s i b l e to p r e d i c t the b e h a v i o r of c e r t a i n s y s t e m s
from purely physical measurements.
A b e t t e r u n d e r s t a n d i n g of the r o l e played by s t r u c t u r a l p a r a m e t e r s in the o v e r a l l r e a c t i o n s c h e m e could
lead us to s p e c i a l t e c h n i q u e s , o r to the m o d i f i c a t i o n of
e x i s t i n g t e c h n i q u e s of s o l i d s p r e p a r a t i o n with a view
of a c h i e v i n g o p t i m a l p e r f o r m a n c e of the r e a c t o r unit
in which they a r e p r o c e s s e d . U l t i m a t e l y , t a i l o r - m a d e
s t r u c t u r e s may be evolved to suit a g i v e n , p a r t i c u l a r
gas-solid reaction.
It is noted, that in its p r e s e n t state the m o d e l is
r e s t r i c t i v e , b e c a u s e of the a s s u m p t i o n m a d e for the
r e t a i n m e n t of the o r i g i n a l s t r u c t u r e .
Within the f r a m e w o r k of the m o d e l , a l l o w a n c e s could
be m a d e for s t r u c t u r a l changes o c c u r r i n g in the c o u r s e
of the r e a c t i o n . The i n c o r p o r a t i o n of t h e s e f a c t o r s ,
through a d d i t i o n a l e q u a t i o n s , is quite s t r a i g h t f o r w a r d
in concept but would, of c o u r s e , i n c r e a s e the c o m p l e x i t y
of c o m p u t a t i o n . At p r e s e n t t h e r e is not enough i n f o r m a tion a v a i l a b l e on s i n t e r i n g k i n e t i c s for m e t a l - m e t a l
oxide s y s t e m s of i n t e r e s t to make such an e f f o r t w o r t h w h i l e . N o n e t h e l e s s , future w o r k both in the a u t h o r s '
l a b o r a t o r y and e l s e w h e r e , could tend to the c o n s t r u c t i o n
of m o r e g e n e r a l m o d e l s .
ACKNOWLEDGMENTS
The a u t h o r s wish to thank the New York State S c i e n c e
and T e c h n o l o g y Foundation for p a r t i a l support of this
i n v e s t i g a t i o n . Thanks a r e also due to the t r u s t e e s of
the C. C. F u r n a s F e l l o w s h i p f o r the support of J . W. E.
during the a c a d e m i c y e a r 1969-70.
LIST O F S Y M B O L S

CA, CB

G a s e o u s r e a c t a n t and product m o l a r
c o n c e n t r a t i o n s within p o r e s

CA~ , CBo

Gas c o n c e n t r a t i o n s in bulk g a s s t r e a m

CARo

R e a c t a n t gas c o n c e n t r a t i o n at p e l l e t
surface

Cp

M o l a r s p e c i f i c heat of p e l l e t

D~4 , D~

E f f e c t i v e d t f f u s i v i t i e s of g a s e o u s r e a c tant and product within p o r o u s p e l l e t

Total h e m i s p h e r i c a l e m i s s i v i t y of
pellet

G r a i n s i z e d i s t r i b u t i o n function

Rate of d i s a p p e a r a n c e of g a s e o u s r e a c tant p e r m o l e of initial solid r e a c t a n t

VOLUME 2, JUNE 1971-1697

Heat

of reaction

Mass

ht

Heat

Chemical

KE

Equilibrium

rl s

Stoichiometry

transfer
transfer

Porosity

Radial

coefficient

rate

within

spherical

Radius of reaction front within grain

rs

Radius of grain

Pellet temperature

TE

Environment temperature

Time
Letters

extent

1 6 9 8 - V O L U M E 2, JUNE 1971

molar

density

of solid

reactant

constant

REFERENCES

coefficient

Radius of pellet

Local

True

of reaction

constant

coordinate

Greek

P D1

extent

constant

pellet
Ro

Overall

Stefan-Boltzmann

coefficient

reaction

of reaction

1. S. Yagi and D. Kunii: Proc. 5th lnterm. Syrup. on Combustion, 1955, p. 231.
2. W. M. McKewan: ?'rang TMS-AIME, 1962, vol. 224, p. 2.
3. H. W. St. Clair: Trans. TMS-AIME, 1965, vol. 233, p. 1145.
4. W. K. Lu and G. Bitsianes: Trahx TMS-AIME, 1966, vot. 236, p. 531.
5. R. H. Spitzer, F. S. Manning, and W. O. Philbrook: Trans. TMS-ADtE, 1966,
vol. 236, p. 1715.
6. J. Shen and J. M. Smith: Ind. Eng. Chem. FundaTnentals, 1965, vol. 4, p. 293.
7. M. lshida and C. Y. Wen: Chem. Eng. ScL, 1968, vol. 23, p. 125.
8. G. S. G. Bevetidge and P. J. Goldie: Chem. Eng. Sci., 1968. vot. 23, p. 913.
9. N. B. Gray and J. Henderson: Trans. TMS~41ME, 1966, vol. 236, p. 1213.
10. P. B. Weisz and R. D. Goodwin: J. Catalysis, 1963, voL 2, p. 397.
11. J. M. Amman and C. C. Watson: Chem. Eng. Sci, 1962, vol. 17, p. 323.
12. D. T. Lacey, J. H. Bowen, and K. S. Basden: Ind. Eng. Chem. Fundamentals,
1965, vol. 4, p. 275.
13. A. K. Lahiri and V. Seshadri: J. Iron Steel Inst., 1968, vol. 206, p. 1118.
14. M. Ishida and C. Y. Wen: At~ Inst. Chem. Eng. J., 1968, voi. 14, p. 311.
15. J. Szekely and J. W. Evans: Chem. Eng. ScL, 1970, vol. 25, pp. 1095-1107.
16. D. Luss and N. R. Amundson: Ant Inst. Chem. Eng. J., 1969, vol. 15. p. 194.
17. J. W. Evans: Ph.D. Dissertation, State University of New York at Buffalo,
1970.

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