Derivations of Design Equations of Batch Reactors

From the book of Fogler:

Consider the general reaction:

aA + bB –> cC + dD

Taking species A as our basis of calculations, we divide the reaction expression

through by the stoichiometric coefficient of species A, in order to arrange the
reaction expression in the form

b c d
A + B –> C + D
a a a

to put every quantity on a “per mole A” basis.

Conversion X = f(t)

moles of A reacted
Moles of A consumed = (moles of A fed)( )
moles of A fed

Moles of A reacted (consumed) = (NA0 )(X)

Moles of A in reactor at time t = (moles of A initially fed to reactor a t=0) – (moles of

A that have been consumed by chemical reaction)

𝐍𝐀 = 𝐍𝐀𝟎 − (𝐍𝐀𝟎 )(𝐗) or 𝐍𝐀 = 𝐍𝐀𝟎 (𝟏 − 𝐗)

When no spatial variations in reaction rate exist, the mole balance on species A for a
batch system reduces to the following equation:

dNA
= rA V
dt

In the general equation above, since reactant A is disappearing, we multiply -1 to

both sides of the equation above to obtain the mole balance for the batch reactor in
the form

dNA
− = (−rA )V
dt

The rate of disappearance of A, −rA , in this reaction might be given by a rate law:

−rA = kCA CB
To determine the length of time the reactants will leave the reactor,

NA = NA0 − NA0 X

with respect to time,

dNa dX
= 0 − NA0
dt dt

and since reactant A is disappearing,

dX
−NA0 = rA V
dt

For a batch reactor, the design equation in differential form is

𝐝𝐗
𝐍𝐀𝟎 = −𝐫𝐀 𝐕
𝐝𝐭

For a constant – volume batch reactor,

1 dNA d(NA /V) dCA

− = = − = −rA
V dt dt dt

For a batch reactor systems in which the volume varies while the reaction is
proceeding, the volume may usually be expressed either as a function of time alone
or of conversion alone, for either adiabatic or isothermal reactors.

dX
Vdt = NA0
−rA V

dX
dt = NA0
−rA V

Integrating,

t X
dX
∫ Vdt = NA0 ∫
0 0 −rA

𝐗
𝐝𝐗
𝐭 = 𝐍𝐀𝟎 ∫
𝟎 −𝐫𝐀 𝐕
 From Perry’s Chemical Engineering Handbook:

Table 7-2 Consecutive and Parallel First-Order Reactions in an Isothermal Constant-

Volume Ideal Batch or Plug Flow Reactor.

The independent variable t is either the batch time of the plug flow residence time.
Reaction Network Material balance Concentration profiles
𝑑𝐶𝑎
A 1 B 2 C = −𝑘1 𝐶𝑎 𝐶𝑎 = 𝐶𝑎0 𝑒 −𝑘1 𝑡
𝑑𝑡
𝑑𝐶𝑏 𝑘1 𝐶𝑎0
= 𝑘1 𝐶𝑎 − 𝑘2 𝐶𝑏 𝐶𝑏 = 𝐶𝑏0 𝑒 −𝑘𝑡 + (𝑒 −𝑘1𝑡 − 𝑒 −𝑘2 𝑡 )
𝑑𝑡 𝑘2 − 𝑘1
𝑑𝐶𝑐
= 𝑘2 𝐶𝑏 𝐶𝑐 = 𝐶𝑎0 + 𝐶𝑏0 + 𝐶𝑐0 − 𝐶𝑎 − 𝐶𝑏
𝑑𝑡
𝑑𝐶𝑎 𝑟
A 1 B = −(𝑘1 + 𝑘2 )𝐶𝑎 𝐶𝑎 = 𝐶𝑎0 𝑒 −(𝑘1 +𝑘2 )
𝑑𝑡
𝑑𝐶𝑏 𝑘1 𝐶𝑎0
A 2 C = 𝑘1 𝐶𝑎 𝐶𝑏 = 𝐶𝑏0 + (1 − 𝑒 (𝑘1 +𝑘2 )𝑡 )
𝑑𝑡 𝑘2 + 𝑘1
𝑑𝐶𝑐
= 𝑘2 𝐶𝑎 𝐶𝑐 = 𝐶𝑎0 + 𝐶𝑏0 + 𝐶𝑐0 − 𝐶𝑎 − 𝐶𝑏
𝑑𝑡
Derivation:

A 1 B 2 C

A 1 B B 2 C
i 𝐴0 𝐵0 𝐵1 𝐶0
∆ −𝑥1 𝑥1 −𝑥2 𝑥2
f A 𝐵1 B C
𝐴0 − 𝐴 = 𝑥1 𝐵1 − 𝐵 = 𝑥2
𝐵1 − 𝐵0 = 𝑥1 𝐶 − 𝐶𝑜 = 𝑥2
𝐴0 − 𝐴 = 𝐵1 − 𝐵0 𝐵1 − 𝐵 = 𝐶 − 𝐶0
𝐵1 = 𝐴0 − 𝐴 + 𝐵0 𝐵1 = 𝐶 − 𝐶0 + 𝐵
𝐴0 − 𝐴 + 𝐵0 = 𝐶 − 𝐶0 + 𝐵
𝐴𝑜 + 𝐵0 + 𝐶0 = 𝐴 + 𝐵 + 𝐶
𝐶𝑎0 + 𝐶𝑏0 + 𝐶𝑐0 = 𝐶𝑎 + 𝐶𝑏 + 𝐶𝑐
Rate equations:

𝑑𝐶𝑎 𝑑𝐶𝑏 𝑑𝐶𝑐

= −𝑘1 𝐶𝑎 = 𝑘1 𝐶𝑎 − 𝑘2 𝐶𝑎 = 𝑘2 𝐶𝑏
𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑪𝒂 :

𝑑𝐶𝑎
= −𝑘1 𝐶𝑎
𝑑𝑡

𝑑𝐶𝑎
= −𝑘1 𝑑𝑡
𝐶𝑎

𝐶𝑎
ln = −𝑘1 𝑡
𝐶𝑎0

𝐶𝑎
= 𝑒 −𝑘1 𝑡
𝐶𝑎0

𝑪𝒂 = 𝑪𝒂𝟎 𝒆−𝒌𝟏 𝒕

𝑪𝒃 :

𝑑𝐶𝑏
= 𝑘1 𝐶𝑎 − 𝑘2 𝐶𝑏
𝑑𝑡

𝑑𝐶𝑏
+ 𝑘2 𝐶𝑏 = 𝑘1 𝐶𝑎
𝑑𝑡

𝑑𝐶𝑏
+ 𝑘2 𝐶𝑏 = 𝑘1 𝐶𝑎0 𝑒 −𝑘1 𝑡
𝑑𝑡

𝐶𝑏 𝑒 𝑘2 𝑡 = 𝐶𝑏0 + ∫ 𝑒 𝑘2 𝑡 𝑘1 𝐶𝑎0 𝑒 −𝑘1 𝑡

𝑘 𝐶
𝐶𝑏 𝑒 𝑘2 𝑡 = 𝐶𝑏0 + 𝑘 1−𝑘𝑎 (𝑒 (𝑘2 −𝑘1 )𝑡 ) + 𝐶 𝐴𝑡 𝑡 = 0, 𝐶𝑏0 = 𝐶𝑏 = 0
2 1

𝑘1 𝐶𝑎0
0= +𝐶
𝑘2 − 𝑘1

−𝑘1 𝐶𝑎0
𝐶=
𝑘2 − 𝑘1

𝑘1 𝐶𝑎0 𝑘1 𝐶𝑎0
𝑒 𝑘2 𝑡 𝐶𝑏 = 𝐶𝑏0 + (𝑒 (𝑘2 −𝑘1 )𝑡 ) −
𝑘2 − 𝑘1 𝑘2 − 𝑘1

𝑘1 𝐶𝑎0 1
(𝑒 𝑘2 𝑡 𝐶𝑏 = 𝐶𝑏0 + (𝑒 (𝑘2 −𝑘1 )𝑡 − 1)) 𝑒 𝑘2𝑡
𝑘2 −𝑘1

𝒌𝟏 𝑪𝒂𝟎
𝑪𝒃 = 𝑪𝒃𝟎 𝒆−𝒌𝟐 𝒕 + (𝒆−𝒌𝟏 𝒕 − 𝒆−𝒌𝟐 𝒕 )
𝒌𝟐 − 𝒌𝟏
𝑪𝒄 :

𝐴𝑡 𝑡 = 0, 𝐶𝑏0 = 𝐶𝑐0 = 0

𝑪𝒄 = 𝑪𝒂𝟎 − 𝑪𝒂 − 𝑪𝒃

Derivation:

A 1 B A 2 C

A 1 B A 2 C
i 𝐴0 𝐵0 𝐴1 𝐶0
∆ −𝑥1 𝑥1 −𝑥2 𝑥2
f 𝐴1 B A C
𝐴0 − 𝐴1 = 𝑥1 𝐴1 − 𝐴 = 𝑥2
𝐵 − 𝐵0 = 𝑥1 𝐶 − 𝐶0 = 𝑋2
𝐴0 − 𝐴1 = 𝐵 − 𝐵0 𝐴1 − 𝐴 = 𝐶 − 𝐶0
𝐴1 = 𝐴0 + 𝐵0 − 𝐵 𝐴1 = 𝐴 + 𝐶 − 𝐶0
𝐴0 + 𝐵0 − 𝐵 = 𝐴 + 𝐶 − 𝐶0
𝐴0 + 𝐵0 + 𝐶0 = 𝐴 + 𝐵 + 𝐶
𝐶𝑎0 + 𝐶𝑏𝑜 + 𝐶𝑐0 = 𝐶𝑎 + 𝐶𝑏 + 𝐶𝑐
Rate Equations:

𝑑𝐶𝑎 𝑑𝐶𝑏 𝑑𝐶𝑐

= −(𝑘1 + 𝑘2 )𝐶𝑎 = 𝑘1 𝐶𝑎 = 𝑘2 𝐶𝑎
𝑑𝑡 𝑑𝑡 𝑑𝑡

𝑪𝒂 :

𝑑𝐶𝑎
= −(𝑘1 + 𝑘2 )𝐶𝑎
𝑑𝑡

𝑑𝐶𝑎
= −(𝑘1 + 𝑘2 )𝑡
𝐶𝑎

𝐶𝑎
ln = −(𝑘1 + 𝑘2 )𝑡
𝐶𝑎0

𝐶𝑎
= 𝑒 −(𝑘1 +𝑘2 )𝑡
𝐶𝑎0

𝑪𝒂 = 𝑪𝒂𝟎 𝒆−(𝒌𝟏 +𝒌𝟐 )𝒕

𝑪𝒃 :

𝑑𝐶𝑏
= 𝑘1 𝐶𝑎
𝑑𝑡

𝑑𝐶𝑏 = 𝑘1 𝐶𝑎 𝑑𝑡

𝐶𝑏 𝑡
∫ 𝑑𝐶𝑏 = 𝑘1 𝐶𝑎0 ∫ 𝑒 −(𝑘1 +𝑘2 ) 𝑑𝑡
𝐶𝑏0 0

−𝑘1 𝐶𝑎0 (𝑘 +𝑘 )𝑡
𝐶𝑏 − 𝐶𝑏0 = 𝑒 1 2 +𝐶
𝑘2 + 𝑘1

𝐴𝑡 𝑡 = 0, 𝐶𝑏 = 𝐶𝑏0 = 0

−𝑘1 𝐶𝑎0
0= +𝐶
𝑘2 + 𝑘1

𝑘1 𝐶𝑎0
𝐶=
𝑘2 + 𝑘1

𝑘1 𝐶𝑎0 (𝑘 −𝑘 )𝑡 𝑘1 𝐶𝑎0
𝐶𝑏 = 𝐶𝑏0 − 𝑒 1 2 +
𝑘2 + 𝑘1 𝑘2 + 𝑘1

𝒌𝟏 𝑪𝒂𝟎
𝑪𝒃 = 𝑪𝒃𝟎 + (𝟏 − 𝒆(𝒌𝟏 +𝒌𝟐 )𝒕 )
𝒌𝟐 + 𝒌𝟏

𝑪𝒄 :

𝐴𝑡 𝑡 = 0, 𝐶𝑏0 = 𝐶𝑐0 = 0

𝑪𝒄 = 𝑪𝒂𝟎 − 𝑪𝒂 − 𝑪𝒃