Constant Size Particle: CASE 3.1: Diffusion Through The Boundary Layer Controls The Rate

Constant Size Particle
CASE 3.1: Diffusion through the boundary layer controls the rate
cAg
The conversion of the solid can be expressed as:

N (t = t )
V (t = t )
V (t = t )
XB = 1 B
= 1 B B
= 1 B
N B (t = 0)
B VB (t = 0)
VB (t = 0)
with B: molar density of the solid B
Surface
of particle
Moving reaction
surface
If diffusion through the boundary

layer controls the rate of reaction:
the concentration of the gaseous
reactant at the outer surface of the
particle equals zero.
The flux of the reactant A
through the boundary layer
equals the rate of reaction.
(Same as catalytic reactions)
Concentration of
gaseous reactant A
The conversion can thus be expressed in terms of the

particle radius:
3
V (t = t )
r
XB = 1 B
=1 c
VB (t = 0 )
R
Boundary layer
(gas film)
shrinking
unreacted
core
containing
B(s)
cAg
cAs=cAc
R
rc
rc
A(g) + b B(s) s S(s) + p P(g)

r' A r'B
=
a
b
1 dN B b dN A
S ex dt
Sex dt
The flux of the reactant A

through the boundary layer
equals the rate of reaction.
[Same as catalytic reactions, see previous slides:]
molar flux to the particle surface = reaction rate on surface
WAs = rAs "

Ficks Law:
value zero
If diffusion through the boundary

layer controls the rate of reaction:
the concentration of the gaseous
reactant at the outer surface of the
particle equals zero.
ash
WAs = kc (CAbulk CAsurface)
4 R 2
(Surface Area)
r ' A = k c Sex (C A, g C A,s )

In the case of severe transport limitation through
the boundary layer the concentration of gaseous
A at the external surface, CA,s, of the particle
approximates 0
1 dN B
= b k c C A, g
4 R 2 dt
Rapid reaction, thus zero
The change in the number of moles of the solid B is related to the

volume change of the solid B and hence to the diameter of the
unreacted core.
N B = B V
The number of moles of B:
with B the molar density of the solid B
4
4
dN B = B dV = B d rc3 = B 3rc2 d(rc )

3
3
dN B = B 4 rc2 drc
Substituting this in the relation between the change in the number of
moles of B with time and the concentration of the gaseous reactant A in
the bulk of the fluid:
Separating the variables and integrating yields:
B
R
rC = rC
rc2 drc = b k c C A , g
rC = R
t=t
dt
t =0
t=
B R
3 b k c CA,g
r
1 c
R

CASE 3.2: Diffusion through the Ash Layer controls the rate
shrinking
unreacted
core
containing
B(s)
ash
WAs =flux of A through

exterior of particle
WA=flux of A through
surface at radius r
Concentration of
gaseous reactant A
WAc=flux of A to
reaction surface
rc
rc
B R
3 b k c C A, g
Moving reaction
surface
) = b k c C A, g t
If the particle is completely converted, the radius of the core of

unreacted materials, rc, equals zero.
The time required for complete conversion, t, is thus defined by:
Surface
of particle
3 R 2
Or expressing reaction time (t) as a function of the radius of the

unreacted core:
3
B 4 rc2 drc
r 2 dr
= B 2 c c = b k c C A, g
2
dt
dt
4 R
R
Boundary layer
(gas film)
B rc3 R 3
The concentration of the gaseous A at the reaction surface

(i.e., at the surface of the unreacted core) approaches zero.
Both the gaseous reactant A and the boundary of the
unreacted core move inward toward the centre of the particle.
The shrinkage of the unreacted core is, however, much
slower (ca. 1000 times), than the flux of the gaseous reactant
A (density difference!). Hence, it is reasonable to consider the
concentration gradient of A in the ash layer at any time as
stationary.
The rate of consumption of A is given by the diffusional flux of A:
dN A
= 4 r 2 WA = 4 R 2 WA,s = 4 rc2 WA,c
dt
with
WA = De
dC A
dr
dN A
dC
= 4 r 2 De A
dt
dr
Separating the variables r and CA and integrating over the ash

layer with the appropriate boundary conditions:
dN A
dt
r = rc
r=R
dN A 1 1
= 4 De C A, g
dt rc R
In order to obtain the time dependency, this expression has

to be integrated.
It must be kept in mind that the flux of the gaseous reactant A
(dNA/dt) is related to the change in the number of moles of
the solid B, which is related to the radius of the core of
unreacted material:
dN A 1 dN B B 4 rc2 drc
=
=
dt
b dt
b
dt
C A =0
dr
= 4 De dC A
r2
C A =C A , g
dN A 1 1
= 4 De C A, g
dt rc R
B 4 2 1 1 drc
rc
= 4 D e C A, g
b
rc R dt
Separating the variables and integrating:
rc = rc
b D e C A, g
1 1
rc2 drc =
B
r
R
c
rc = R
t=t
dt
t =0
1 3 1 2 b D e C A, g
1
rc 2
rc R =
t
B
2
3
R
6
t=
B R 2
6 b D e C A, g
The time for complete conversion () is then given when

rc = 0 and therefore:
2
3
r
r
1 3 c + 2 c
R
R
B R2
6 b De CA,g
2
3
t
r
r
= 1 3 c + 2 c

R
R
Substituting conversion of solid B: XB = 1 rc

R
t
= 1 3(1 XB )2 / 3 + 2(1 XB )
Relationship between reaction time and core radius
CASE 3.3: Chemical Reaction Rate controls the rate
Boundary layer
(gas film)
Surface
of particle
Moving reaction
surface
shrinking
unreacted
core
containing
B(s)
ash
The concentration of the gaseous A at the reaction surface

equals the concentration of A in the bulk of the fluid.
Based on unit surface area of unreacted core, the rate of
reaction is given by:
1
4 rc
dN B
b dN A
=
= b k s C A, g
dt
4 rc 2 dt
This is for a first order reaction
Concentration of
gaseous reactant A
And product R
[with ks the first order rate constant based on unit surface area
units m3/(m2 s)].
rc
rc
Writing the change in the number of moles of B in terms

of the radius of the unreacted core:
dN A 1 dN B
=
=
dt
b dt
4 rc
B 4 rc2
B 4 rc2
b
drc
dt
drc
dr
= B c = b k s C A , g
dt
dt
The time required for complete conversion of the solid B,

, (i.e. rc = 0) is thus given by:
B R
b k s C A,g
Separation of variables and integration yields:

rc = rc
drc =
rc = R
b k s C A, g
t=t
t =0
dt
t
r
= 1 c = 1 (1 X B )1 / 3
B
B R
r
t=
(R rc ) =
1 c
b k s C A,g
b k s C A,g R

Constant Size Particle: CASE 3.1: Diffusion Through The Boundary Layer Controls The Rate

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Constant Size Particle

The conversion of the solid can be expressed as:

If diffusion through the boundary

The conversion can thus be expressed in terms of the