KINETICS & REACTOR DESIGN - EXAMPLE#12

Column 1 Column 2
Reactant A Decomposes in a batch reactor (A → Products). The
Time Concentration
Composition of A in the reactor is measured at various times with results
t s (s) CA mol/lit
shown in the following columns 1 and 2. Find a rate equation to represent
0 CA0 = 10
the data.
20 8
40 6
(a) Use Fractional-Life method. 60 5
(b) Use Integral method. 120 3
(c) Use Differential method. 180 2
300 1

Solution part a:

F1−n − 1 1−n F1−n − 1

tF = ( ) CA0 → Log (t F ) = Log ( ) + (1 − n)LogCA0
(n − 1)k (n − 1)k

F1−n − 1
Log (t F ) = Y , Log ( ) = B , (1 − n) = α , LogCA0 = X
(n − 1)k

We don’t have a reactor so we have to use a simulation technic with (Concentration-Time) data
given.

We then draw the smooth curve:

C(A)-t
12

10

8
C(A)

0
0 50 100 150 200 250 300 350
t
Using the smooth curve and connecting the lines from 𝐶𝐴0 and 𝐶𝐴 then calculating the difference
between them we get the 𝑡0.8 of every data given.

CA0 CA = CA0 t = 0.8

We Choose F = 0.8 10 10 × 0.8 = 8 0 → 18.5 → t 0.8 = 18.5 s

5 4 59 → 82 → t 0.8 = 23 s

2 1.6 180 → 215 → t 0.8 = 35 s

In Fractional-Life time analysis, we no longer deal with point data and use the optimized curve.

We need to make a table containing X, Y, XX, XY, SX , SY , SXY , SXX data.

X = LogCA0 Y = Log(t 0.8 ) XX XY

Log10 = 1 Log18.5 = 1.27 1 1.27

Log5 = 0.7 Log23 = 1.36 0.49 0.952
Log2 = 0.3 Log35 = 1.54 0.09 0.462
SX = 2 SY = 4.17 SXX = 1.58 SXY = 2.684

Note: N=3

N(SXY ) − (SX )(SY ) (SY )(SXX ) − (SX )(SXY )

α= → α = −0.4 , B= = 1.649
N(SXX ) − (SX )2 N(SXX ) − (SX )2

0.8(1−1.4) − 1 lit 0.4

→ α = −0.4 → 1 − n = −0.4 → n = 1.4 , → 10B = → k = 0.005
0.4k mol0.4 s
Second method we can use is:

F1−n −1
We put CA0 = 10 , t 0.8 = 18.5 s → Log (t F ) = Log ( (n−1)k ) + (1 − n)LogCA0

0.8(1−1.4) − 1 lit 0.4

→ Log18.5 = Log ( ) + (1 − 1.4)Log10 → k = 0.005
0.4k mol0.4 s

Solution part b:

CA t
−dCA −dCA ∫ −dCA
−rA = kCAn → = kCAn → = kdt → ∫ ( ) = ∫ kdt
dt V=constant C n CAn
A CA 0 0

CA1−n − CA1−n
→ 0
= kt → CA1−n − CA1−n = (n − 1)kt n≠1
(n − 1) 0

CA1−n − CA1−n
0
=Y , (n − 1)t = X , k=α

and

CA
− ln ( ) = kt n=1
C A0

When both the degree and the rate constant are unknown, we have to guess.

n = 0.4 → CA1−0.4 − CA1−0.4

0
= (0.4 − 1)kt

CA1−0.4 − CA1−0.4
0
= Y , (0.4 − 1)t = X , k = α

We then use linear regression with excel and get 𝑅 2 which shows the exactness of our line and if
is equal to 1 shows that it is the best possible (n) and ideal.
After using regression we get the data:

𝑛 𝑅2
0.5 0.978
0.8 0.9958
0.95 0.0974
1.2 0.99378
1.4 0.99951
1.43 0.9996
1.45 0.99955
1.5 0.9990

The optimum 𝑅 2 is at n=1.43

If we use: CA1−n − CA1−n

0
= (n − 1)kt , n=1.43

𝑡=20 ,𝐶𝐴 =8,𝐶𝐴0 =10

𝑛 = 1.43 → CA1−1.43 − CA1−1.43
0
= (1.43 − 1)kt →

8−0.43 − 10−0.43 = (0.43)20𝑘 → 𝑘 = 0.00435

 Solution part c:

−rA = kCAn → ̅̅̅A̅

Log (−rA ) = Logk + nLogC
Log

̅̅̅A̅ = X
Log (−rA ) = Y , Logk = B , n = α , LogC

ΔCA CAi + CAi+1

−rA = − , ̅̅̅A̅)i =
(C
Δt 2

−rA ̅̅̅A̅)i
(C ̅̅̅A̅ = X
LogC Log (−rA ) = Y XX XY

8 − 10 10 + 8
− = 0.1 =9 Log 9 = 0.95424 −1 0.91057 −0.95424
20 − 0 2
6−8 8+6
− = 0.1 =7 Log 7 = 0.85450 −1 0.73017 −0.85450
40 − 20 2
5−6 6+5
− = 0.05 = 5.5 Log 5.5 = 0.74036 −1.3010 0.54813 −0.96320
60 − 40 2
3−5 5+3
− = 0.033 =4 Log 4 = 0.60205 −1.4814 0.36246 −0.89187
120 − 60 2
2−3 3+2
− = 0.0166 = 2.5 Log 2.5 = 0.39794 −1.77989 0.15835 −0.70828
180 − 120 2
1−2 2+1
− = 0.0083 = 1.5 Log 9 = 0.17609 −2.0809 0.03100 −0.36642
300 − 180 2

− − SX = 3.72518 SY = −8.64319 SXX = 2.74068 SXY = −4.73851

Note: N=6

N(SXY ) − (SX )(SY ) (SY )(SXX ) − (SX )(SXY )

α= → α = −0.4 , B= = −2.34918
N(SXX ) − (SX )2 N(SXX ) − (SX )2

α = 1.4693 → n = 1.4693

𝐵 −2.34918
𝑙𝑖𝑡 0.4693
B = 𝐿𝑜𝑔𝑘 → 10 = 𝑘 → 𝑘 = 10 = 0.00447
𝑚𝑜𝑙 0.4693 . 𝑠