Determination of Rate Equation

Reference: Chemical Reaction Engineering, Octave Levenspiel, Wiley

1) Concentration dependence at fixed T.

2) Temperature dependence of k.

Reactors:
(1) Batch/Non-flow: (a) Constant Volume, (b) Variable Volume
(2) Flow: (a) Backmix, (b) Plug flow

 Homogeneous reactions: Batch Reactor is used

 Heterogeneous reactions: Flow reactor is used.

Batch Reactors

(a) Constant Volume Batch Reactor: A B

cA = nA/V , cA0 = nA0/V

nA0 = Initial no. of moles of A

V = Volume of fluid

nA = No. of moles of A at time t

cA = Concentration of A at time t

cA0 = Initial concentration of A

XA = Fractional Conversion of A
1
Concentration, cA (mol/L)

XA = (nA0 - nA)/nA0 0.8

= (nA0/V - nA/V)/(nA0/V) 0.6

0.4
= (cA0 - cA)/CA0
0.2
= 1 – (cA/ cA0)
0
cA = cA0(1 - XA) 0 2 4 6 8 10 12
Time, t (min)

(A) Integral method of determination of rate equation

(B) Differential method of determination of rate equation
1
(A) Integral method of determination of rate equation:
6
(i) General Procedure 5
Step1: Guess a rate equation 4

F(cA)
- rA = - dcA/dt = kf(cA) 3
2
1
Step2: - dCA/f(cA) = kdt 0
0 1 2 3 4 5 6 7 8 9 10
Time, t (min)
cA t
d cA
Step3:-−∫ f ¿ ¿ ¿ = F(cA) = k ∫ dt = kt
c A0 0

F(cA) = kt
cA
dcA
F(cA) = −∫
cA 0 f (c A )

Step4: F(cA) is plotted against t.

Step5: Check if experimental data fall on a straight line.

i. If yes, the assumed rate equation is correct.
ii. If not, choose a new rate equation and repeat the steps.

a) For Zeroeth Order Reaction

- dcA/dt = k  cA0 - cA = kt  F(cA) = cA0 - cA

b) For First Order Reaction

- dcA/dt = kcA  -ln cA/cA0 = kt  F(cA) = - ln cA/cA0

c) For Second Order Reaction

- dcA/dt = k(cA)2  1/cA – 1/cA0 = kt  F(cA) = 1/cA – 1/cA0

d) For mth order reaction [m≠1]:

cA
d CA
-∫ = kt
c A0 C mA

c 1−m
A –c 1−m
A 0 = (m-1)kt [m≠1]  F(cA) = (c 1−m
A –c 1−m
A 0 )/(m-1)

2
3
 e) m=2, bimolecular reaction A + B → C; CA = CA0(1-XA)
dc A dc
-rA= -( ) = -( B ) = kcAcB
dt dt

No. of moles of A & B consumed per unit volume = cA0XA = cB0XB

d XA
-rA = cA0( ) = k(cA0 – cA0XA)(cB0 – cA0XA)
dt

Let M= cB0/cA0
d XA
-rA= cA0( ) = kc 2A 0 (1-XA) (M-XA)
dt
XA t
d XA
∫ ( 1−X ) (M − X ) = cA0 k ∫ d t
0 A A 0

XA
1 1 1
∫ (M −1)
0
[ −
1−X A M −X A ]
d XA = cA0 kt

1
(M −1)
[-ln ¿ ¿XA)¿0X + ln ¿ ¿M-XA)¿0X ] = cA0 kt
A A

1
¿ – ln M – ln (1−X A )] = cA0 kt
(M −1)

( M −X A )
ln M ( 1−X ) = (M-1) kcA0 t
A

1
As M → ∞ ln
1−X A = cB0 kt

cA
- ln(1-XA) = - ln c = cB0 kt = k’t
A0

The equation approaches first order.

Order f(cA) F(cA)

0 1 cA0 – cA

1 cA - ln cA/cA0

2 c A2 1/cA – 1/cA0
4
M (≠1) c Am (c 1−m
A –c 1−m
A 0 )/(m-1)
(ii) Half-Life Period Method

It is the time needed for the reactant concentration to drop to 50% of its initial
value.

A number of experimental runs are carried out at different initial concentrations,

c A 0.

m=1
1
-ln c A /c A 0 = kt 0.9
0.8

Concentration, cA (mol/L)
At t =t 1/ 2, c A =c A 0 /2 0.7
cA0 0.6
1
-ln 2 = -ln 2 = kt 12 0.5
cA 0.4
0.3
t1/2 = ln k/2 0.2
0.1
0
0 0.5 1 1.5 2 2.5 3 3.5 4
m=2 t
Time,
1/2 t (min)
1 1
c A c A 0 = kt
-

2 1
At t = t 12 t
c A 0 c A 0 = k 1/ 2
-

1 1
t 1/ 2 = .
c A0 k

m=m

c A1−m -c A 01−m = (m-1).kt

¿ - c A 01−m = (m-1).kt 1/ 2

c A 01−m[ 2m−1 – 1] = (m-1).kt 1/ 2

m −1
t 1/ 2 = 2 – 1 . c A 01−m
k (m−1)

ln t 1/ 2 = (1-m) ln c A 0 + ln k '

' 2m −1 – 1
k =
k (m−1)
5
ln t 1/ 2 = (1-m) ln c A 0 + ln k '
m<1 m>1 m =1
ln t1/2 is plotted vs lncA0. 5
4.5
Slope = 1-m 4
 m is obtained from the slope 3.5
3
 k is obtained from the intercept

ln t1/2
2.5
2
1.5
1
0.5
0
0 1 2 3 4 5 6 7 8 9 10
ln cA0

Summary of Integral Methods:

(A) General Procedure:

cA
dcA
F(cA) = −∫
cA 0 f (c A )

m f(cA) F(cA)
1 cA -ln cA / cA0
2 cA2 1/ cA – 1 / cA0

2 (Bimolecular) cA cB [1/(m-1)cA]*ln[M-XA/M(1-XA)]
m cA m [1/(m-1)][cA 1-m - cA0 1-m ]

(B) Half-life Period:

m t1/2

1 ln 2/ k
m (2m-1 -1)/[k(m-1)].cA0 1-m