Chap. 8 Reaction Kinetics

(1) Definition of reaction rate

The change of number of component i with time is define as the rate
of reaction:
1 dN i
ri = * (Based on unit volume of reactor)
V dt
dCi
= (V = constant)
dt
e.g. A + 2 B → C , V = cons.
dCC dC dC
rC = , rB = − B , rA = − A
dt dt dt

(2) Homogeneous reactions

ri = f ( state of system ) = f ( T, P, component )

∵ homogeneous, P = constant

→ ri = f ( T, component )

(3) Rate equation

1. Single & multiple reactions:
a. single rxn: A → B or A + B → C + D
b. multiple rxn:
(i) Series rxn: A → B → C
(ii) Parallel rxn: A → B
A→C
2. Elementary & nonelementary rxns:
Elementary reactions: rate equation corresponds to the
stoichiometic equation.
e.g. A + 2 B ⎯⎯→
K
C , − rA = k * C 1A * C B2 , where k: rate constant

1 Edited by Prof. Yung-Jung Hsu

 

Nonelementary reactions: rate equation isn’t related to the

stoichiometic equation.
C A2
e.g. 2 A ⎯⎯→
K
3B , − rA = k , where k: rate constant
CB

3. Order of reaction:
− rA = k * C Aa * C Bb * CCc * C Dd , a + b + c + d = n

For A: of order a, for B: of order b

Overall: of order n

4. Expression of rate equation:

a. elementary rxns: A → B or A + B → C + D
A + 2 B ⎯⎯→
K
3C

− rA = k * C A * C B2 , − rB = k * C A * C B2 , rC = k * C A * C B2

→ − rA = −rB = rC (wrong!!)

∵ stoichiometic equation.

→ − rA = k * C A * C B2

− rB = k ' * C A * C B2 , k ' = 2k

rC = k '' * C A * C B2 , k '' = 3k

b. nonelementary rxns:
Choose suitable mechanism
By rate-limiting step method. 速率決定步驟

[O2 ][O] [O ]
1 is at equilibrium, K =
∵○ ⇒ [O] = K 3
[O3 ] [O2 ]

2 is the rate-determine step, − RO 3 = k3 [O][O3 ] = k '

[O3 ]2
∵○
[O2 ]

2 Edited by Prof. Yung-Jung Hsu

 

(4) Temperature dependence

1. Rate equation: ri = f (T, component), P=const.

= k* f (component) →k~T
By Arrhenius Law:
k = k0 * exp[− E ] , where k0: frequency factor
RT
E: activation energy
2. How to find E, k0?
E
From k = k0 * exp[− E RT ] → ln k = ln k0 −
RT
Plot lnk vs. 1/T

(5) Equilibrium constant & rate constant

Consider a “reversible” reaction at constant volume:

dC A
− rA = − = kC A − k −1CB * CC (A 濃度隨時間變化之量)
dt
If the reaction is at equilibrium, the rate of change of concentration of
dC A
A will be zero ⇒ = 0 帶入上式
dt

⇒ kC A, E − k −1CB , E * CC , E = 0

k C * CC , E
⇒ −1
= B, E =K
k C A, E
CB , E * CC , E k
⇒K , where K is equilibrium constant & K = −1
C A, E k

3 Edited by Prof. Yung-Jung Hsu

 

(6) Interpretation of reaction data → to find k

1. Unimolecular irreversible 1st-order reaction:
A⎯⎯→
k
P , V=constant
dC A dC A
− rA = − = kC A ⇒ = k * dt
dt CA
dC A C
⇒ −∫ = ∫ k * dt ⇒ − ln A = kt
CA t

C A0 C 0 C A0
A

2. Pseudo 1st-order reaction:

A+ B ⎯
⎯→k
P , with B excess (V=const.)
dC A
− rA = − = kC A * CB
dt

If B is excess ⇒ CB ≅ CB 0 >> C A (超過 20 倍)

dC A
− = kC A * CB 0
dt
C
− ln A = kCB 0 * t
C A0
ln C A = − kCB 0 * t + ln C A0

3. Irreversible 2nd-order reaction:

Type I: 2 A ⎯⎯→
k
P
dC A dC A
⇒∫ = − k ∫ dt
2 CA t
− rA = − = kC A 2
dt C A0 C 0
A

4 Edited by Prof. Yung-Jung Hsu

 

1 1
⇒ = + kt
C A C A0

Type II: A + B ⎯⎯→

k
P
dC A
− rA = − = kC A * C B
dt
Q C A − C A0 = C B − C B 0
⇒ C B = C A + C B 0 − C A0

a. if C A0 = C B 0 ⇒ C A = C B

dC A 2
− rA = − = kC A ……type I
dt

b. if C A0 ≠ C B 0

dC A
− rA = − = kC A * (C A + C B 0 − C A0 )
dt
C C
⇒ ln A − ln B = −k (C B 0 − C A0 )t
C A0 CB 0
C A CB0
⇒ ln[ * ] = −k (C B 0 − C A0 )t
C B C A0

4. Irreversible nth-order reaction & n ≠ 1 :

nA ⎯ ⎯→k
P
dC
− rA = − A = kC A
n

dt
⇒ ln(−rA ) = ln k + n ln C A

5 Edited by Prof. Yung-Jung Hsu

 

Then plot ln(−rA ) vs. ln C A :

6 Edited by Prof. Yung-Jung Hsu