Chemical Reactor Engineering

LECTURE 3: INDEPENDENT AND DEPENDENT REACTIONS

ChE 125: Chemical Engineering Reactor Design I

2nd Semester AY 2016 - 2017
Single Reaction Systems:

Species, j: nj  nj ,0   j
Total: Ntot  Ntot ,0  

Multiple Reaction Systems:

Species, j:

Total:
When multiple reactions take place, only a
set of independent reactions should be
considered to determine the species
composition

Multiple Reaction Systems:

Species, j:

Total:
When multiple reactions take place, only a
set of independent reactions should be
considered to determine the species
composition
 Indicates the smallest number of
stoichiometric relations needed to:
a) describe the chemical transformation
b) determine all state variables (e.g. T, P)
Consider:
𝐶𝐻4 + 𝐻2 𝑂 ֞ 𝐶𝑂 + 3𝐻2

𝐶𝐻4 + 𝐻2 𝑂 → 𝐶𝑂 + 3𝐻2 (1)

𝐶𝑂 + 3𝐻2 → 𝐶𝐻4 + 𝐻2 𝑂 (2)

By examination,

𝑅2 = −𝑅1 𝑚=1
𝑘=1
Consider:
𝐶 + 0.5𝑂2 → 𝐶𝑂 (1)

𝐶𝑂 + 0.5𝑂2 → 𝐶𝑂2 (2)

𝐶 + 𝑂2 → 𝐶𝑂2 (3)

By examination,

𝑅1 + 𝑅2 = 𝑅3 𝑚=2
𝑘=1
1. Construct the matrix of the
stoichiometric coefficients for the
chemical reactions.
𝑎1 𝑏1 𝑐1 𝑑1 . . 𝐴1
𝑎2 𝑏2 𝑐2 𝑑2 . . 𝐴2
.
.
𝑎𝑛 𝑏𝑛 𝑐𝑛 𝑑𝑛 . . 𝐴𝑛
1 column for each chemical species
1. Construct the matrix of the
stoichiometric coefficients for the
chemical reactions.
𝑎1 𝑏1 𝑐1 𝑑1 . . 𝐴1
𝑎2 𝑏2 𝑐2 𝑑2 . . 𝐴2
.
.
𝑎𝑛 𝑏𝑛 𝑐𝑛 𝑑𝑛 . . 𝐴𝑛

1 row for each chemical reaction

2. Reduce the matrix into upper triagonal
matrix (i.e. all elements below the
diagonal are zero) using elementary
row operations:
CH 4 O2 CO2 H 2O CO C2 H 6 
 
 1 2 1 2 0 0 
 0 1 2 0 2 0 
 
 0 0 5 3 7 1 
 0 0 0 0 0 0 
 
 0 0 0 0 0 0 
2. Reduce the matrix into upper triagonal
matrix (i.e. all elements below the
diagonal are zero) using elementary
row operations:

a) Interchange any 2 rows

b) Multiply a row by a non-zero constant
c) Add a scalar multiplied row to another
vector
3. After matrix reduction,

number of non – zero rows

number of independent reactions (m)

number of zero rows

number of dependent reactions (k)
4. Select a set of independent reactions.

a) Result of matrix reduction

b) Given chemical reactions
5. Write each of the dependent reactions
as a linear combination of the
independent reactions.

Note: To design chemical reactors, we need

to consider all chemical reactions that
are taking place.

𝑛𝑡𝑜𝑡 = 𝑛𝑚 + 𝑛𝑘
LET: 𝛼𝑘𝑚 = scalar factor relating the kth
dependent rxn to the mth
independent rxn
= multiplier of the mth
independent rxn to obtain the
kth dependent rxn
𝑛

෍ 𝛼𝑘𝑚 (𝜐𝑗 )𝑚 = (𝜐𝑗 )𝑘

𝑚
EXAMPLE 3.1
Carbon disulfide is a common solvent that
is produced by reacting sulfur vapor with
methane. It is produced in a steady – flow
reactor where the ff chemical reactions
take place:

𝐶𝐻4 + 2𝑆 → 𝐶𝑆2 + 2𝐻2 (1)

𝐶𝐻4 + 4𝑆 → 𝐶𝑆2 + 2𝐻2 𝑆 (2)
𝐶𝐻4 + 2𝐻2 𝑆 → 𝐶𝑆2 + 4𝐻2 (3)
SEATWORK 1
Consider the classic mechanism of the reaction
between hydrogen and bromine to form hydrogen
bromide (the asterisks indicate free radicals):

(1)
(2)
(3)
(4)
(5)
 REFERENCES
 Mann, U. (2009). Principles of chemical
reactor analysis and design: new tools for
industrial chemical reactor operations.
Hoboken, NJ: Wiley.
 Hill Jr., C. G. (1977). An introduction to
chemical engineering kinetics & reactor
design. New York: Wiley.
QUESTIONS?