Chemical reactions on solid surfaces Chapter | 8 323

TABLE 8.4 Some Examples of LHHW rate expressions.

Overall reaction Mechanism/controlling step Rate expression
1. Isomerization A + σ  A ⋅σ C A − CB /K eq
r = kACσ
A B
(
1+ K A /Keq + KB CB )
A ⋅σ  B ⋅σ C A − CB /K eq
r = ksK ACσ
1+ K AC A + KBCB

B ⋅σ  B + σ KeqC A − CB
r = kBCσ
(
1+ K A + KBK eq C A )
2. Decomposition A + σ  A ⋅σ C A − CBCC /Keq
(Double site) r = kACσ
1+ K ACBCC /Keq + KBCB + KC CC
A B+ C

A ⋅σ + σ  B ⋅σ + C ⋅σ C A − CBCC /Keq
r = ksK ACσ2
(1+ K AC A + KBCB + KCCC )2
B ⋅σ  B + σ KeqC A − CBCC
r = kBCσ
KBKeqC A + (1+ K AC A + KC CC ) CC

C ⋅σ  C + σ KeqC A − CBCC
r = kC Cσ
KC KeqC A + (1+ K AC A + KBCB ) CB

3. Decomposition A + σ1  A ⋅σ1 C A − CBCC /Keq

(Dual site) r = kACσ 1
1+ K ACBCC /Keq + KBCB
A B+ C

A ⋅σ1 + σ 2  B ⋅σ1 + C ⋅σ 2
r=
(
ksK ACσ 1Cσ 2 KeqC A − CBCC )
(1+ K AC A + KBCB ) (1+ KCCC )
B ⋅σ1  B + σ1
r=
(
kBCσ 1 KeqC A − CBCC )
KBKeqC A + (1+ K AC A ) CC

C ⋅σ 2  C + σ 2 KeqC A − CBCC
r = kC Cσ 2
KC KeqC A + CB

4. Bimolecular (double site)

A +B C +D
A + σ  A ⋅σ
r=
(
kACσ C ACB − CC CD /Keq )
−1
K AKeq CC CD + (1+ KBCB + KC CC + KDCD ) CB

B + σ  B ⋅σ
r=
(
kBCσ C ACB − CC CD /Keq )
−1
KBKeq CC CD + (1+ K AC A + KC CC + KDCD ) C A

A ⋅σ + B ⋅σ  C ⋅σ + D ⋅σ
r=
(
ksK AKBCσ2 C ACB − CC CD /Keq )
(1+ K AC A + KBCB + KCCC + KDCD )2
C ⋅σ  C + σ
r=
(
kC Cσ KeqC ACB − CC CD )
KC K eqC ACB + (1+ K AC A + KBCB + KDCD ) CD

D ⋅σ  D + σ
r=
(
kDCσ KeqC ACB − CC CD )
KDKeqC ACB + (1+ K AC A + KBCB + KC CC ) CC

(Continued)
324 Bioprocess Engineering

TABLE 8.4 Some Examples of LHHW rate expressions. (Cont.)

Overall reaction Mechanism/controlling step Rate expression
5. Bimolecular
(dissociative)
A 2 + 2σ  2A ⋅ σ
r=
( −2
kA2Cσ2 C 1/A22CB2 − CC2CD2Keq )
2
 12 −1 
1
A2 + B  C + D K A2K eqCC CD + (1+ KBCB + KC CC + KDCD ) CB 
2  
B + σ  B ⋅σ
r=
(
kBCσ C 1/A22CB − CC CD /Keq )
−1
KBKeq (
CC CD + 1+ K A2C A2 + KC CC + KDCD C 1/A22 )
A ⋅σ + B ⋅σ  C ⋅σ + D ⋅σ
r=
(
ksK 1/A22KBCσ2 C 1/A22CB − CC CD /K eq )
(1+ )
2
K A2C A2 + KBCB + KC CC + KDCD

C ⋅σ  C + σ
r=
(
kC Cσ KeqC 1/A22CB − CC CD )
(
KC KeqC CB + 1+ K A2C A2 + KBCB + KDCD CD
1/ 2
A2 )
D ⋅σ  D + σ
r=
(
kDCσ K eqC 1/A22CB − CC CD )
(
KDK eqC 1/A22CB + 1+ K A2C A2 + KBCB + KC CC CC )
6. Bimolecular (Dual site)
A +B C +D
A + σ1  A ⋅σ1
r=
(
kACσ 1 C ACB − CC CD /Keq )
−1
K AK eq CC CD + (1+ KC CC ) CB

B + σ 2  B ⋅σ 2
r=
(
kBCσ 2 C ACB − CC CD /Keq )
−1
KBKeq CC CD + (1+ KDCD ) C A

A ⋅σ1 + B ⋅σ 2  C ⋅σ1 + D ⋅σ 2
r=
(
ksK AKBCσ 1Cσ 2 C ACB − CC CD /Keq )
(1+ K AC A + KCCC ) (1+ KBCB + KDCD )
C ⋅σ1  C + σ1
r=
(
kC Cσ 1 KeqC ACB − CC CD )
KC KeqC ACB + (1+ K AC A ) CD

D ⋅σ 2  D + σ 2
r=
(
kDCσ 2 K eqC ACB − CC CD )
KDK eqC ACB + (1+ KBCB ) CC

7. Bimolecular
(Eley–Rideal)
A + σ  A ⋅σ
r=
(
kACσ C ACB − CC /Keq )
A +B C (1+ KCCC ) CB + K AKeq−1CC
(B not adsorbing) A ⋅σ + B  C ⋅σ
r=
(
ksK ACσ C ACB − CC /Keq )
1+ K AC A + KC CC

C ⋅σ  C + σ KeqC ACB − CC
r = kC Cσ
1+ K eqC ACB + K AC A

and the fraction of sites occupied by A and B are given by

K BC B
θ B = K BC Bθ =
1 + K BC B + K s−1K BC B (8.124)
K s−1K BC B
θ A = K s−1θ B = .
1 + K BC B + K s−1K BC B (8.125)
Substituting Eqs. (8.123) and (8.125) into Eq. (8.117), we obtain
k AC A − k− A K s−1K BC B C − k A−1k− A K s−1K BC B
r = Cσ −1
= k ACσ A . (8.126)
1 + K BC B + K s K BC B 1 + K BC B + K s−1K BC B