Problem 1: Consider the startup of a CSTR under isothermal operation.

We will use
concentration since conversion doesn’t have meaning under unsteady state conditions. We will
also consider only simple reactions, with no change in volumetric flow rates.

The mass balance equation is

d (VC A )
FA−in + V ( rA ) = FA−out +
dt
V V dC A−out
This can be simplified as C A−in + ( rA ) = C A−out + = C A−in + τ ( rA )
Q Q dt

dC A (1 + kτ ) 1
For a first order reaction, the equation is + C A = C A−in . The initial condition is
dt τ τ
that there is no reaction, i.e. CA = CA-out.

 (1+ kτ ) t 
(1+ kτ )
d  e τ C A  (1+ kτ )
Integrating factor is e τ . Therefore,   = C A−in e τ t
t

dt τ
Integrating this, we get
(1+ kτ ) t
C A−in −
CA = + Const × e τ
(1 + k τ )
kτ C A−in
Initial condition gives that Const =
(1 + kτ )

C A−in  −
(1+ kτ ) t 
Therefore, C A =  1 + kτ × e τ

(1 + kτ )  
At infinite time, it will come to the steady state value, as expected. BTW, the 3rd and 4th edition
of the book gives wrong expression.

dC A 1 C − kτ
For zero order reaction, the equation is + C A = A−in
dt τ τ
 t

1
d  eτ C A 
τ
t
  C A−in − kτ τt
The integrating factor is e . Therefore, = e
dt τ
t
−
τ
Integrating this, we get C A = C A−in − kτ + Const × e
Using the initial conditions, Const = kτ .
  −
t

Therefore, C A = C A−in − kτ  1 − e τ  . At very long time, this goes to the steady state solution.
 

For second order reaction, we can solve the equation as shown below.
dC A
CA + τ = C A−in + τ ( −kC A2 )
dt
This can be rearranged as
dC A 1 C
+ kC A2 + C A = A−in
dt τ τ
2
dC A  1  C A−in 1
I.e. +  kC A +  = + 2
dt  2τ k  τ 4τ k

 1 
Let y =  kC A + .
 2τ k 

1 dy C 1 C A−in 1
Then + y 2 = A−in + 2 = A2 where A = + 2 .
k dt τ 4τ k τ 4τ k

1 dy
= ( A2 − y 2 )
k dt
dy
Therefore, = k dt
( A − y2 )
2

1 1  1 1   A+ y 
But =  +  . Hence, ln   = 2 A kt + constant
( A − y ) 2A  A − y A + y 
2 2
 A− y 

 1 
When time = 0, the value of CA = CA-in, and this corresponds to  kC A−in +  = yin
 2τ k 
 A − yin 
Therefore, constant = ln  
 A + yin 
 A − y   A − yin  −2 A kt
From this, we can write that  = e = Be −2 A kt

 A + y   A + yin 

Re arranging this, we get

 1 − Be −2 A kt 
y = A
 1 + Be−2 A kt 
 
  1  C A−in 1
At very long time, this gives y=A, i.e.  kC A− ss +  == + 2
 2τ k  τ 4τ k

C A−in 4τ k 1 1 −1 + 1 + 4τ kC A−in
C A− ss = 2
+ 2 2 − =
k 4τ k 4τ k 2τ k 2τ k

The steady state equation gives, τ kC A2 + C A − C A−in = 0

−1 + 1 + 4τ kC A−in
CA = . Thus, at very long times we confirm that the unsteady state solution
2τ k
approaches the steady state solution