Spherical steady-state diffusion with heterogeneous 1st order

reaction

Lecture [ 16 ]

There are two opposite extremes for this type of system:

Diffusion-controlled: The reaction at the surface is fast compared to

the diffusion rate of species to/from the surface

Reaction-controlled: The diffusion rate of species to/from the surface

is fast compared to the rate of reaction at the surface .

Diffusion-controlled example combustion of a carbon particle using air

3

C (s) + 2.5 O2 (g) 2 CO2 (g) + CO (g)

carbon particle
radius = R
differential element
r r+dr

O2
CO2 , CO
Let A = O2 B = CO2 C = CO D= N2

mass balance on O2 (A) for the differential volume : (OUT IN = 0) :

4r 2 N A ( r )

(16.1)
integration of this expression between r=R and r=r gives:

2
R r 4r N A( r ) r 0

N A(r) r 2 N A(R ) R 2

1
2
r

N A(r) N A(R ) R 2

(16.2)

Spherical steady-state diffusion with heterogeneous 1st order reaction

Lecture [ 16 ]

3 C (s) + 2.5 O2 (g) 2 CO2 (g) + CO (g)

A
B
C
The reaction stoichiometry gives the following flux relationships:

N A(r)
2.5

N B( r )
2

N C( r )

D= N 2

N D(r ) 0

re-arranging to:

N B ( r ) 0.80 N A ( r )

N C ( r ) 0.40 N A ( r )

Ficks 1st law, for a 4-constituent system:

N A ( r ) N A ( r ) N B ( r ) N C ( r ) N D ( r ) y A D AM .c

y A
r

(16.3)

eliminating NB(r), NC(r) and ND(r):

N A ( r ) N A ( r ) 0.8 N A ( r ) 0.4 N A ( r ) y A D AM .c

N A(r)

D AM .c y A
1 0.2 y A r

y A
r

(16.4)

boundary conditions are as follows:

at r=R

this reaction is assumed to be very fast (essentially instantaneous), and so at

the surface of the particle we can say yA = 0

at r=

far from the particle there is only pure air, so yA() = 0.21

Spherical steady-state diffusion with heterogeneous 1st order reaction

Lecture [ 16 ]

Integration of equation 16.4, using equation 16.2 to substitute for N A(r):

R N A(R )
2

R N A(R )
2

yA ( )

D AM c
y
1 0.2 y A A

1
r D AM c
r2

1
R N A(R )
r

1
r
r2

yA ()

(16.5)

y A
1 0.2 y A

D AM c
ln 1 0.2 y A
0.2

N A ( R ) 5 ln 1 0.2 y A ( )

0.21

D AM c
D
c
0.206 AM
R
R

(16.6)

It is often of practical interest to be able to calculate the rate at which the particle
disappears with time.
This can be done using a mass balance on the carbon particle in pseudo-steady state,
then integrating the expression over time. Now we are saying that R is =f(t):

moles carbon in particle

carbon
4R 3
4Carbon R 2 R


t
t 0.001 M carbon 3
0.001 M Carbon t (16.7)
3
3
mol
1 kg m m

s kg / g g mol

And considering the O2 flux together with the reaction stoichiometry:

mols carbon 3 4R 2 molar flux O2 1.2(4R 2 N A( R )) (16.8)

t
2.5
mol
mol
2

m .

2
s

m s

Spherical steady-state diffusion with heterogeneous 1st order reaction

Lecture [ 16 ]

And so, combining equations 16.6, 16.7, and 16.8:

4Carbon R 2 R
D c

1.2(4R 2 ) 0.206 AM
0.001 M Carbon t
R

Integrating, and noting that MA = 12:

R ( t t )

337 Carbon

. RR
0
D AM c
R ( t 0 )
t

2
337 Carbon
. R (2t 0 ) R ( t )
2D AM c

(16.9)

The concentration profile, i.e. yA = f(r) , for this case with fast reaction can be
generated using equation 16.5, but now integrating between and r, instead of
between and R :

R N A(R )
2

1
r
r2

yA()

yA ( r )

D AM .c
y
1 0.2 y A A

(16.10)

The result of the previous integration (between and R ), given in equation 16.6,
can be used to substitute for NA(R) in equation 16.10:

5 ln 1 0.2 y A ( ) D AM .c r

0.21

D AM .c

r
5 ln 1 0.2 y A ( ) R 2
r
r

0.21

yA ( r )

yA ( r )

y A
1 0.2 y A

y A
1 0.2 y A
4

Spherical steady-state diffusion with heterogeneous 1st order reaction

1
5 ln 1 0.2 y A ( ) R
r

ln 1 0.2 y A ( )

1
ln 1 0.2 y A yy AA (( r ))
0.2

R
ln 1 0.2 y A ( ) ln 1 0.2 y A ( r )
r

ln 1 0.2 y A ( r ) ln 1 0.2 y A ( ) 1
r

1 0.2 y A ( r )

1 0.2 y

R
1 r

A()

y A ( r ) 5 1 0.2 y A ( )

Lecture [ 16 ]

yA(r)

(16.11)

Note that the profile doesnt depend of the absolute magnitude of R, just the ratio R/r.
This means that the concentration profile moving radially away from the particle does not
change as the particle shrinks with time ( i.e. R gets smaller).

yA()
0.21
t
0
0

R(t)

R(t=0)

Spherical steady-state diffusion with heterogeneous 1st order reaction

Lecture [ 17 ]

Reaction-controlled example again, combustion of a carbon particle using air

3

C (s) + 2.5 O2 (g) 2 CO2 (g) + CO (g)

carbon particle
radius = R
differential element
r r+dr

O2
CO2 , CO
Let A = O2 B = CO2 C = CO D= N2

RA N A( R ) k c A( R )
Expressing the rate expression for NA(R) in terms of mole fractions:

N A ( R ) k c y A ( R )

(17.1)

mol
m mol

2
m s
s m3

Now use equations 17.2 and 17.4 (i.e the same method as given in lecture 17) to
generate an expression for yA(r) = f(r) :

N A(R )

1
r
r2

ya ( )

NA (R )

D AM c
y
1 0.2 y A A

(17.2)

k c

This is identical to equation 17.5, except that the lower limit of the RHS integral, y A(R), is now
not zero, and instead we have used equation 19.1 to provide a value for it.
The lower integration limit is now a function of N A(R).

Spherical steady-state diffusion with heterogeneous 1st order reaction

integrating:

D AM c 1 0.2 y A ( )
ln
0.2R
1 0. 2 N A ( R )
ck

N A(R )

(17.3)

in many practical cases it is found that:

0.2

N A(R )
ck

Lecture [ 17 ]

N A(R )

ln 1 0.2

c.k

1 so we can use just the first term of

the Taylor Series expansion for

Definition of the required

Taylor series:

xn
ln 1 x
n 1 n

Equation 17.3 becomes:

N A(R )
N A(R )

N A(R )

D AM c

ln 1 0.2 y A ( ) ln 1 0.2
0. 2 R
ck

0.2 N A ( R )
D AM c

ln
1

0
.
2
y

A()
0. 2 R
ck

N A(R )

D AM .c
ln 1 0.2 y A ( )
D AM

0.2R 1

kR

Consider further that

Damkhler number

Da

kL
D AB

( m / s )( m)
m2 / s

(17.4)

yA() << 1 (i.e. dilute system)

we can also use just the first term of

the Taylor Series expansion for

ln 1 0.2 y A

to simplify equation 17.4

Spherical steady-state diffusion with heterogeneous 1st order reaction

Equation 17.4 becomes:

N A(R )

N A(R )

D AM .c

ln 1 0.2 y A ( )
D AM

0.2R 1

D AM .c
D

0.2R 1 AM
kR

( 1) 2

0.2 y

A ()

(17.4)

Lecture [ 17 ]

Definition of the required

Taylor series:

ln 1 x 1
n 1

n 1

xn
n

D AM .c
y A ( ) (17.5)
D

R 1 AM
kR

For this case with finite reaction rate, the concentration profile, i.e. yA = f(r) , can be
generated using equation 17.2, but now integrating between and r, instead of between
and R :

R N A(R )
2

1
r
r2

R 2 N A(R )
r

yA ( )

yA ( r )

D AM c
y
1 0.2 y A A

(17.6)

D AM c
ln 1 0.2 y A yy AA (( r ))
0.2

1
D
c

ln 1 0.2 y A yy AA (( r ))
R 2 N A ( R ) 0 AM
r
0.2

R2
D
c
N A ( R ) AM
ln 1 0.2 y A ( ) ln 1 0.2 y A ( r )
r
0 .2

(17.7)

The result of the previous integration (between and R ) given in equation 17.5
can be used to substitute for NA(R) in equation 17.7:

Spherical steady-state diffusion with heterogeneous 1st order

reaction
R2
D AM c 1 0.2 y A ( )
(17.7)
N A(R )
ln

r
0.2
1

0
.
2
y

A ( r )

Lecture [ 17 ]

R 2 D AM c y A ( )
D AM c 1 0.2 y A ( )

ln

D AM
r
0.2
1

0
.
2
y

A ( r )

R 1

kR

1 0.2 y A ( )
R 0.2 y A ( )

ln

D AM
r
1

0
.
2
y

A
(
r
)

kR

R 0.2 y A ( )
exp

D
r

1 AM

kR

1 0.2 y A ( )

1 0.2 y A ( r )

yA(r)

R 0.2 y A ( )
1 0.2 y A ( r ) 1 0.2 y A ( ) exp
D
r

1 AM

kR

y A ( r ) 5

1 0.2 y A ( ) exp R 0.2 yDA ( )

r

1 AM

kR

yA()
0.21

(17.8)
0
0

R(t)

R(t=0)

Spherical steady-state diffusion with heterogeneous 1st order reaction

Lecture [ 17 ]

Homogeneous 1st order reaction systems:

Define reaction rate in terms of a reaction volume:
RA = -k[cA]
Define dimensionless Thiele modulus:

k
DAB / L2

L2 / DAB

1/ k

reaction rate
diffusion rate

k has units of 1/s

kL2
D AB

(1 / s )(m 2 )
m2 / s

time to diffuse
time to react

Heterogeneous 1st order reaction systems:

Define reaction rate in terms of a reaction surface:
NA = -k[cA]
Define dimensionless Damkhler number:

Da

k' / L
reaction rate

D AB / L2 diffusion rate

Da

k has units of m/s

k' L
DAB

( m / s )( m)
m2 / s

L2 / DAB time to diffuse

Da

L / k'
time to react

10