Lecture 9: Multiple Reactions in Series

Two First-Order Reactions in Series

A Æ B Æ C, or

(R1) A Æ B, − rA1 = k1C A ,

(R2) B Æ C, − rB1 = k 2 C B

Lets model this in a Liquid-Phase Batch Reactor.

dC A
V = −k1C AV
dt

dC B
V = + k1C AV − k 2 C BV
dt

dCC
V = k 2 CCV
dt

We can solve this analytically – the first equation can be solved by itself.

⎛C ⎞
ln⎜⎜ A ⎟⎟ = −k1t , or C A = C AO e − k1t
⎝ C AO ⎠

Now, substitute into the next equation:

dC B
+ k 2 C B = k1C AO e − k1t
dt

If we multiply both sides by e k 2t , then we get

dC B
e k 2t + k 2 C B e k2t = k1C AO e − k1t e k2t , or
dt

d
dt
( )
C B e k2t = k1C AO e (k 2 − k1 )t . We can solve this by separation of variables,

CB e k 2t

( ) ∫k C
t

∫ d CBe 2 =
k t
1 AO e (k 2 − k1 )t dt
C BO e 0 t =0

1
C B e k 2t − C BO =
k 2 − k1
e(
k1C AO (k 2 − k1 )t
)
− 1 , or

C B = C BO e − k2t +
k 2 − k1
(
k1C AO −k1t
e − e − k 2t )

Now that we’ve solved for the concentration of B as a function of reaction time, we can
maximize the concentration of B by solving for

dC B
dt
* kC
k 2 − k1
( * *
)
= 0 = − k 2C BO e − k 2t + 1 AO − k1e − k1t + k 2 e − k 2t , and if CBO = 0, then

1 ⎛k ⎞
t* = ln⎜⎜ 1 ⎟⎟
k 2 − k1 ⎝ k 2 ⎠

which is the reaction time to maximize CB. Identical analysis can be done for a PFR, in
which case we find that the residence time to maximize CB,exit is:

1 ⎛k ⎞
τ* = ln⎜⎜ 1 ⎟⎟ .
k 2 − k1 ⎝ k 2 ⎠

If we want to see how the maximum B concentration changes with conversion,

CB
=
k1
C AO k 2 − k1
(
e − k1t − e − k2t , where )

CA
= 1 − e − k1t , and 1 − X A = e − k1t , and t = − ln (1 − X A ) ; substituting …
1
X A = 1−
C AO k1

1 ⎛⎜ ln (1− X ) ln (1− X ) ⎞
k2
CB ⎟
= e − e k1
C AO k ⎜ ⎟
2
−1⎝ ⎠
k1
⎛ ln (1− X )
1
k2
ln (1− X ) ⎞
⎜e − e k1 ⎟
k2 ⎜ ⎟
−1⎝ ⎠
~ C CB CB k1
S D /U = B = = =
CC C AO − C A − C B C AO X A − C B 1 ⎛⎜ ln (1− X )
k2
ln (1− X ) ⎞
XA − e − e k1 ⎟
k2 ⎜ ⎟
−1⎝ ⎠
k1

2
 CB
~ C CB CB C AO
S D /U = B = = =
C C C AO − C A − C B C AO X A − C B C
XA − B
C AO

1 ⎛⎜ ln (1− X ) ln (1− X ) ⎞
k2
~ CB CB 1 CB 1 ⎟
YD / U = = = = e − e k1
C AO − C A C AO X A X A C AO X A k 2 ⎜ ⎟
−1⎝ ⎠
k1

Lets plot this up and see what it looks like:

0.9

0.8

0.7

0.6 k2/k1 = 10
k2/k1 = 5
0.5
CB/CAO

k2/k1 = 2

0.4 k2/k1 = 0.5

k2/k1 = 0.2
0.3 k2/k1 = 0.1

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
XA

3
 1.2

0.8 k2/k1 = 10
k2/k1 = 5
k2/k1 = 2
YB

0.6
k2/k1 = 0.5
k2/k1 = 0.2
0.4 k2/k1 = 0.1

0.2

0
0 0.2 0.4 0.6 0.8 1
XA

100

90

80

70
k2/k1 = 10
60 k2/k1 = 5
k2/k1 = 2
SB

50
k2/k1 = 0.5
40 k2/k1 = 0.2
k2/k1 = 0.1
30

20

10

0
0 0.2 0.4 0.6 0.8 1
XA

4
In general, we can see that for k1 >> k2, we can get a very high conversion of A before we
start significantly losing B.

What if we have a second-order reaction, followed by a first-order reaction?

A Æ B Æ C, or

(R1) A Æ B, − rA1 = k1C A ,

(R2) B Æ C, − rB1 = k 2 C B2

Lets model this in a Liquid-Phase Batch Reactor.

dC A
V = −k1C AV
dt

dC B
V = + k1C AV − k 2 C B2V
dt

dCC
V = k 2 C B2V
dt

We can solve this analytically – the first equation can be solved by itself.

⎛C ⎞
ln⎜⎜ A ⎟⎟ = −k1t , or C A = C AO e − k1t
⎝ C AO ⎠

Now, substitute into the next equation:

dC B
+ k 2 C B2 = k1C AO e − k1t
dt

Ugh… at this point we can either delve deeper into differential equations to find a
solution to this, or we can use polymath to do the heavy lifting for us. Lets rest upon the
mercyful fact that this is not a graduate level course, and use the computer instead…

Lets have polymath solve the above set of equations, given k1 = 1 s-1, k2 = 1 L.mol-1s-1.
That will give us concentration vs. time results. Lets convert that data to conversion,
dimensionless concentration of B, yield and selectivity to generate the same plots as
before.

~ C ~ CB
S D / U = B , and YD / U = .
CC C AO − C A

5
Since we’re using polymath, we can rapidly crank through multiple order cases, for the
general system,

A Æ B Æ C, or

(R1) A Æ B, − rA1 = k1C An ,

(R2) B Æ C, − rB1 = k 2 C Bm

14

12 n=1,m =2
n=1,m =3
10 n=1,m =1/2
Selectivity to B

n=1,m =1/4
8

0
0.5 0.6 0.7 0.8 0.9 1
Conve rs ion of A

1
n=1,m =2
0.9
n=1,m =3
0.8 n=1,m =1/2
0.7 n=1,m =1/4

0.6
Yield of B

0.5

0.4

0.3

0.2

0.1

0
0.5 0.6 0.7 0.8 0.9 1
Conve rs ion of A

6
 1
n=1,m =2
0.9
n=1,m =3
0.8 n=1,m =1/2
0.7 n=1,m =1/4

0.6
CB/CAO

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
Conve rs ion of A

We can again draw some general conclusions from this theoretical analysis:

First, we can see that as the ratio of n/m decreases (undesired consecutive reaction is of
higher order than first reaction), our maximum achievable Yield and Selectivity increases,
for a given conversion.

Secondly, we see that as the ratio of k2/k1 decreases (undesired consecutive reaction is
slower than first reaction), our maximum achievable Yield and Selectivity increases. As
before, the ratio of k2/k1 is dictated by operating temperature, as follows:

⎡ E ⎤
exp ⎢− A 2 ⎥
k 2 k 2o
= ⎣ RT ⎦ = exp ⎡− E A 2 + E A1 ⎤ = exp ⎡ E A1 − E A 2 ⎤ . From inspection, if
⎡ E ⎤ ⎢ RT RT ⎥ ⎢ RT ⎥
k1 k1o
exp ⎢− A1 ⎥ ⎣ ⎦ ⎣ ⎦
⎣ RT ⎦

EA1 > EA2, the exponential term is positive, and we decrease k2/k1 by increasing T.

EA1 < EA2, the exponential term is negative, and we decrease k2/k1 by decreasing T.

This matches the strategy for maximizing yield and selectivity of parallel reactions via
temperature selection.

7
Discussion of Complex Reaction Networks
Example 1: Series-Parallel Selectivity and the “shunt” reaction

For the hydrogenation of phenylacetylene, we have both series and parallel reactions of
the form:

k1 +H2 k3
Styrene
+H2
Phenylacetylene Ethylbenzene
k2
+H2

If we run this reaction in excess hydrogen, we can assume that hydrogen concentration is
constant throughout, and we get the following pseudo-kinetics:

(R1): A Æ B, r1=k1CA

(R2): A Æ C, r2=k2CA

(R3): B Æ C, r3=k3CB

And if we model this in as a liquid-phase Plug-Flow Reactor, we get

dFA dC A dC A
= vo = = −k1C A − k 2 C A
dV dV dτ

dFB dC B dC B
= vo = = + k1C A − k 3C B
dV dV dτ

dFC dCC dCC

= vo = = k 2 C BV + k1C A
dV dV dτ

We can try to solve this analytically, noting that the mole-A balance is a stand-alone
differential equation (thanks to irreversible kinetics).

dC A
= −(k1 + k 2 )C A , and C A = C AO e − (k1 + k 2 )t
dτ

8
 = + k1C AO exp[− (k1 + k 2 )τ ] − k 3 C B , which can be solved via integrating factors again.
dC B
dτ

+ k 3C B = + k1C AO exp[− (k1 + k 2 )τ ]

dC B
dτ

dC B
(C B exp[k 3τ ]) = + k1C AO exp[− (k1 + k 2 − k 3 )τ ]
dτ

k1C AO {exp[− (k1 + k 2 − k 3 )τ ] − 1}

CB = −
k1 + k 2 − k 3 exp[k 3τ ]

We can again take the derivative of this equation w.r.t. residence time, and find the
optimal reactor size for maximizing the outlet concentration of desired intermediate, B.

d d ⎛ k1C AO {exp[− (k1 + k 2 − k 3 )τ ] − 1} ⎞

CB = 0 = ⎜ ⎟⎟ = ????
dτ dτ ⎜⎝ k1 + k 2 − k 3 exp[k 3τ ] ⎠

We can also follow through and solve for CC. Instead of doing this via the differential
mole balance, lets look at the book-keeping, and realize that for this specific case of a
mole-neutral set of reactions,

CC = CAO – CA - CB, and

k1C AO {exp[− (k1 + k 2 − k 3 )τ ] − 1}

CC = C AO − C AO exp[− (k1 + k 2 )τ ] +
k1 + k 2 − k 3 exp[k 3τ ]

If we take the derivative of CC w.r.t. residence time, and then look at the initial rate of
change in CC,

⎛ − (k1 + k 2 ) exp[− (k1 + k 2 )0] + ⎞

dCC ⎜ ⎟
= C AO ⎜ ⎟
⎜ k + k − k {(− k1 − k 2 ) exp[(− k1 − k 2 )0] − (− k 3 ) exp[− k 3 0]}⎟
k1
dτ τ =0
⎝ 1 2 3 ⎠

⎛ − (k1 + k 2 ) + ⎞
dCC ⎜ ⎟
= C AO ⎜ k1 ⎟ = C AO (− (k1 + k 2 ) + k1 ) = C AO k 2 .
dτ τ =0 ⎜ k + k − k {− k1 − k 2 + k 3 }⎟
⎝ 1 2 3 ⎠

We could have gotten this from an easier way, via inspection of the original differential
equation,

9
dCC
= k 2 C BO + k1C AO = k1C AO
dτ τ =0

This is markedly different than the case of purely series selective reactions, where

dC C
= k 2 C BO = 0 .
dτ τ =0

So, we’ve uncovered another test of experimental data : If the initial rate of appearance of
final product, C, is zero, then we do not have a shunt reaction (no parallel selectivity).

Okay, how about reversible reactions? Lets look at the Wei-Prater Reaction:

k1 B k3

A C
k2

(R1f): A Æ B, r1f=k1fCA

(R1r): B Æ A, r1r=k1rCB

(R2f): A Æ C, r2f=k2fCA

(R2r): C Æ A, r2r=k2rCC

(R3F): B Æ C, r3=k3fCB

(R3R): C Æ B, r3=k3rCC

And if we model this in as a liquid-phase Plug-Flow Reactor as before, we get

⎛ ⎞ ⎛ ⎞
dC A C
= − k1 f ⎜ C A − B ⎟ − k 2 f ⎜ C A − CC ⎟
dτ ⎜ K 1,eq ⎟ ⎜ K 2,eq ⎟
⎝ ⎠ ⎝ ⎠

⎛ ⎞ ⎛ ⎞
dC B C
= + k1 f ⎜ C A − B ⎟ − k 3 f ⎜ C B − CC ⎟
dτ ⎜ K 1,eq ⎟ ⎜ K 3,eq ⎟
⎝ ⎠ ⎝ ⎠

10
dC C ⎛ C ⎞ ⎛ ⎞
= k2 f ⎜ C A − C ⎟ − k 3 f ⎜ C B − CC ⎟
dτ ⎜ K 2,eq ⎟ ⎜ K 3,eq ⎟
⎝ ⎠ ⎝ ⎠

We can solve this analytically – it is a classic example of solving systems of coupled,

first-order differential equations in chemical engineering. A complete treatment of this
reaction appears in most textbooks, including Varma and Morbidelli (1997).

We can re-arrange these equations via expansion and subsequent collection of like terms,

dC A CB CC
= − k1 f C A − k 2 f C A + k1 f + k2 f
dτ K 1,eq K 2,eq
dC B CB CC
= k1 f C A − k 3 f C B − k 1 f + k3 f
dτ K 1,eq K 3,eq
dCC CC CC
= k 2 f C A + k3 f C B − k3 f − k2 f
dτ K 3,eq K 2,eq

⎡ k1 f k2 f ⎤
⎡ dC A ⎤ ⎢− k1 f − k 2 f ⎥
⎢ dτ ⎥ ⎢ K 1,eq K 2,eq ⎥ ⎡C ⎤
⎢ dC ⎥ ⎢ k1 f k3 f ⎥ ⎢ A⎥
⎢ B ⎥ = ⎢ + k1 f − − k3 f ⎥ ⋅ ⎢C B ⎥
⎢ dτ ⎥ ⎢ K 1,eq K 3,eq ⎥ ⎢C ⎥
⎢ dC B ⎥ ⎢ k2 f k3 f ⎥ ⎣ C ⎦
⎢ dτ ⎥ ⎢ + k 2 f + k3 f − − ⎥
⎣ ⎦
⎢⎣ K 2,eq K 3,eq ⎥⎦

Which can be solved for the corresponding Eigenfunctions and Eigenvalues.

However, for this class, lets go ahead and rely upon Polymath to crunch the numbers for
us, expecially if the orders are other than unity.

(polymath code 2).

11
Another Complex Reaction Chemistry: Dry Reforming of Methane

k1
CH4 +2O2 CO2 +2H2O
k2
CH4+2H2O CO2 +4H2

Methane combusts to produce steam; steam reforms methane to hydrogen and CO2.

Species Initial Rxn 1 Rxn 2 Final

CH4 (A) FAO - FAOXA1 - FAOXA2 FAO(1-XA1-XA2)
O2 (B) FAOΘB - 2 FAOXA1 0 FAO(ΘB- 2 XA1)
CO2 (C) FAOΘC + FAOXA1 + FAOXA2 FAO(ΘC + XA1+ XA2)
H2O (D) FAOΘD + 2 FAOXA1 - 2 FAOXA2 FAO(ΘD+ 2 XA1- 2 XA2)
H2 (E) FAOΘE 0 + 4 FAOXA2 FAO(ΘE+ 4 XA2)

Lets assume this is a gas-phase, catalytic reaction that follows Langmuir-Hinshelwood

kinetics over a CuO/SiO2 catalyst.

k1 p A p B2 k1 p A p D2
r1 = , and r = , and
1 + K 1 p A + K 2 p B2 1 + K 1 p A + K 2 p D2
2

FAO (1 − X A1 − X A2 )
pA = P ,
FAO (1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )

FAO (Θ B − 2 X A1 )
pB = P ,
FAO (1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )

(Θ D + 2 X A1 − 2 X A2 )
pD = P .
(1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )
In a Fluidized Bed Reactor, we can draw the following mole balances for the first two
species, recognizing that there are two reactions, so we’ll need two mole balances.

dFA
= 0 = FAO − FA − r1V − r2W
dt

dFB
= 0 = FBO − FB − 2r2W
dt

12
And after substitution, we get:

dFA
= 0 = FAO X A1 + FAO X A2
dt

k1 P 3 (1 − X A1 − X A 2 )(Θ B − 2 X A1 )
2

−k P 3 (1 − X A1 − X A 2 )(Θ D + 2 X A1 − 2 X A 2 )
2

(1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )3 1 (1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )3
−W
⎡(1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )3 + K 1 P(1 − X A1 − X A 2 )(1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )2 ⎤
⎢ ⎥
⎢+ K P 2 (Θ − 2 X )2 (1 + Θ + Θ + Θ + Θ + 2 X ) ⎥
⎢
⎣
2 B A1 B C D E A2
(1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 ) ⎦ 2 ⎥

(1 − X A1 − X A2 )(Θ D + 2 X A1 − 2 X A2 )2
k1 P 3
dFB (1 + Θ B + Θ C + Θ D + Θ E + 2 X A2 )3
= 0 = +2 FAO X A1 − 2 W
dt ⎡(1 + Θ B + Θ C + Θ D + Θ E + 2 X A 2 )3 ⎤
⎢ ⎥
⎢+ K 1 P(1 + Θ B + Θ C + Θ D + Θ E + 2 X A 2 ) (1 − X A1 − X A 2 ) ⎥
2

⎢ 2⎥
⎢⎣+ K 2 P (1 + Θ B + Θ C + Θ D + Θ E + 2 X A 2 )(Θ D + 2 X A1 − 2 X A 2 ) ⎥⎦
2

So far, we have three unknowns – Volume, XA1, XA2. If this was a reactor modeling
problem, we’d be given reactor volume, and we could solve these equations for XA1, XA2.
If this was a reactor sizing problem, we’d be given a target conversion (usually XA), and
be asked to solve for XA1, XA2, then the volume.

Note that while this algebra may seem a bit hairy, it is still the exact same procedure as
before; just stay calm and walk your way through the algebra, and you’ll get the solution.

Note that this is an Isochoric (constant volume), Isobaric (constant pressure) system –
thus the outlet flow rate changes with conversion to account for change in moles with
reaction.

13