Heterogeneous non catalytic reactions

• solid – fluid (liquid, gas)

 Dissolution of solids (e.g. MgCO3(s) + HNO3(l))
 Chemical Vapor Deposition (SiH4(g)  Si(s) + 2H2)
 Sublimation (U(s) + 3 F2(g)  UF6(g))
 Reduction of solid oxides (NiO(s) + H2(g)  Ni(s) + H2O(g))
 Metals oxidation (Zn(s) + O2(g)  ZnO(s))
 Catalytic reactions

• liquid – gas
 Dissolution with chemical reaction
Cl2(s) + 2NaOH(l)  NaOCl(l) + NaCl(l) + H2O(l)
3NO2(g) + H2O(l)  2HNO3(l) + NO(g)

• solid – solid
 CoO(s) + Al2O3(s)  CoAl2O4(s)

Heat and mass transfer phenomena affect global reaction rate.

Heterogeneous gas-solid reactions
Silicon thermal oxidation is by far most
Si(s) + O2(g)  SiO2(s) important for silicon devices. It is the key
process in modern silicon integrated circuit
technology.
 Kinetics of gas-solid heterogeneous reaction

Si(s) + O2(g)  SiO2(s)

 cO2  cO2
2
porous
 D
s
O2 SiO2
t x
2

Si

Air (O2)
O2

cO2 ( x )  N O 2 flux density of O2 in gas phase(mol.m-2.s-1)

(D)
co J O2 flux density of O2 in SiO2 layer (mol.m-2.s-1)
c1
Convection + Diffusion k cO 2 coefficient of mass transfer of O (m.s-1)
2
rS  kc 2
N O 2  k cO 2 [ c1  c o ] c2
2 -1
D O 2 diffusion coefficient of O2 in SiO2 (m .s )
s

rS of chemical reaction (mol. m-2.s-1)

rate
x diffusion

dc O 2 [ c 2  c1 ]
 D  D O2
(D) s s
J

O2 O2
dx
 Steady state

N O 2  J O 2   O 2 rs
(D)

[ c 2  c1 ]
k cO 2 [ c1  c o ]  D O 2   kc 2
s

  D O2 
s

k cO 2  k  
  
c1 a c2 calculation :  
c1  s
co
D O2
k .k cO 2  ( k cO 2  k )
 s
D O2  s
D O2 
 k cO 2   c1  c 2  k cO 2 c o
 
s

 
D O2
  c2 
k cO 2
 co
s
D
s
 s

O2
D O2 D O2 k .k  ( k cO 2  k )

cO 2

 c1   k   c2  0
   
  SiO2 layer thickness and Si conversion :

reaction rate
 1 1 1 
2
M S iO 2
     co t
 S iO 2
s
co  k cO 2 k  2 D O2
rs 
1  (t ) 1  SiO d
  rS 
 o M S iO  Si
2

M dt
s
   o X Si  o=
SiO 2 2
k cO 2 D k
 S iO
O2
2 M Si 2

M SiO 2 , M Si ,  SiO 2 ,  Si Molar weights and densities of SiO2 a Si  o Initial thickness of Si slab
 3 limiting cases
1. Rate determining step is the external mass transfer of oxygen towards interface (gas - SiO2)

cO2 ( x ) 
1  1 1 M SiO 2
 ,   rs  k cO 2 c o ,   k cO c o t co c1
 SiO
s 2
k cO 2 D O2
k cO 2 k 2
c2
x
2. Rate determining step is the internal mass transfer of oxygen in porous SiO2 layer

s 
 1  1 D O2 M SiO 2 cO2 ( x )
   rs   
s c1
, co , 2 D co t co
  SiO
s s O2
D O2
k cO 2 D O2
k 2

c2
x
3. Rate determining step is chemical reaction taking place on the interface (SiO2 - Si)

cO2 ( x ) 
1  1 1 M SiO 2 c1
 ,   rs  kc o ,   kc o t co
 SiO
s
k D O2 k k cO 2 2

Discussion: rS = f(composition), rS = f(temperature) c2

x
 External heat and mass transfer

Combustion of the spherical carbon particle

Conditions in the immediate region of an interface between phases are hard to explore experimentally. In such
situations it is helpful to develop a mathematical model of the process starting with the known basic facts. The result of
the analysis is then compared with those experimental measurements which it is possible to make. Good agreement
suggests that the model may have been realistic.
—T. K. Sherwood, R. L. Pigford, and C. R. Wilke (1975)
Oxygen molar flux at steady state

Energy flux at steady state

Surface temperature and concentration of oxygen
S
Two balance equations for unknown c1 , T S
Multiple steady state solutions as in
the case of CSTR!
Example
Heterogeneous gas-liquid reactions
Kinetics of gas-liquid reactions

C O2(g ) C O 2 (l )  C O 2 (l )  A 

H C O3(l )  O H (l )  B 
  
C O 2 (l )  O H (l )
  2
H C O3(l )  O H (l ) C O3(l )  H 2O (l )

Interface

C O 2 ( l )   O H ( l )  produkty rV  k c C O 2 c O H   m ol.m -3
.s
-1

Gas Liquid
J A ( z   z ) S L  J A ( z ) S L  rV  zS L
J B ( z   z ) S L  J B ( z ) S L   rV  zS L

dc A
J A  DA
dz
dc B
J B   DB
dz

2
d cA
PC O 2 DA  k c A c B  0
c  H CO2 c
* * 2
C O 2 ,G CO2 ,L dz
RT 2
d cB
DB 2
  k c A c B  0
dz
 2
d cA
DA 2
 k c A c B  0
dz
2
d cB
DB 2
  k c A c B  0
dz

Boundary conditions
dc B dc A dc B
z  0 : c A  c A,L ,
eq

dz
0 or z  0;  D A
dz
   
 k cA , G c A , G  c A ,G  k cA ,G c A ,G  H A c A ( z  0) ,
*

dz
0

dc A
z   L : SLDA  k c A c B , L  V L  S L  L  , c B  c B , L
dz

Dimensionless form
z cC O2 cA cO H  cB
x , Y1   , Y2  
L
eq eq
c C O2 , L
c A,L
cO H  , L cB ,L

2
2
d Y1 d Y2
  H a Y1Y 2  0
2
 H a Y1Y 2  0
2
2
dx
2 dx
dY 2 dY1  V 
x  1;   H a Y1  L  1  , Y 2  1
2
x  0; Y1  1, 0
dx dx  S L L 

k  cB D A k  cB D A eq
D A c A,L
Ha     k A,L  D A /  L
o

DA /  L
o
k A,L D B cB ,L
 Numerical solution gives to us concentration profiles

We get the overall rate of CO2 absorption by integration of local rate

VL
1   dc  
eq
S L D A c A , L  d Y1 
RA  
VL
 rV dV    S L D A  A    VL R A
 dz  z  0  V L L
   RA
0   dx  x  0
Limiting situations

eq eq
D A c A,L 3 D A c A,L 2 Ha  3
   10    10
D B cB ,L D B cB ,L