Balancing Chemical Reactions,

Even When the Reactions are Not Known

J. M. Haile

1. Introduction

2. Method

3. Example

4. Discussion

Nomenclature

Reference

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Reaction Stoichiometry

Abstract

We demonstrate a method for identifying and balancing any number of

chemical reactions. The procedure is based on the singular-value decomposition
of the formula matrix for the reaction mixture. The method is effective even
when the reactions are not known a priori.

Keywords:

chemical reactions, formula matrix, singular-value

decomposition, stoichiometric coefficients

1. Introduction

Consider a closed chemical reactor from which we draw a sample and find

C species composed of m elements. For example, the sample might contain C = 6

species (CH4, CO2, CO, H2O, H2, and O2) formed from m = 3 elements (C, H,
and O). From this we can form an (m C ) array of integers that specifies the
distribution of elements among species; this array is called the formula matrix A.
In our example,

CH4

O2

CO2 H2O CO

H2

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(1)

Reaction Stoichiometry

From this formula matrix we want to determine (a) the number of independent
chemical reactions, (b) the identities of all possible independent reactions, and (c)
the stoichiometric coefficients for all the reactions in (b).

2. Method

Elemental material balances can be written in the form

A N = b = constants

(2)

where N is a (C 1) vector of mole numbers and b is an (m 1) vector of

elemental abundances. The values of the mole numbers change during the
reaction, but the values for abundances remain constant because elements are
conserved. Values for the entries in b could be known from the initial loading of
the reactor.
The formula matrix A is singular; in fact, it is nearly always rectangular
because the number of species is usually larger than the number of elements.
The rank of A is related to the number of independent reactions R by

R = C rank(A)

(3)

"Balancing" a reaction j = 1, 2, . . . R means finding a (C 1) vector of

stoichiometric coefficients j that satisfies

A j = 0

j = 1, 2, . . . R

Since A is singular, the vector j for any reaction is not unique.

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(4)

Reaction Stoichiometry

In a traditional approach, we would determine rank(A), apply (3) to obtain

the number of independent reactions R , and then find the stoichiometric
coefficients by writing particular reactions and balancing them. Here we show
how to accomplish these tasks simultaneously by, essentially, solving the
homogeneous system (4).
To do so, we first augment A with rows of zeroes below row m, producing
a (C C ) square matrix A. Then we perform a singular-value decomposition of
A,

U W VT

(5)

Routines for performing a singular-value decomposition (SVD) are available in

many mathematical software packages, including MATLAB and Mathematica .
Subroutines are also provided in the book by Press et al. (1986). In (5), U, W, and
V are each square matrices of dimension (C C ). The matrix W is diagonal, and
since A is singular, some diagonal elements of W are zero. In particular,

# nonzero diagonal elements of W = rank(A)

(6)

and by (3),
# zero diagonal elements of W = R

(7)

It may seem inconsistent that the same matrix A satisfies both the
inhomogeneous system of equations (2) and the homogeneous system (4); this is
so, however, because A is singular. The SVD effectively separates these two
possibilities (Press, et al., 1986). The subspace of b that can be reached by the
mapping (2) is called the range of A. For each nonzero diagonal element wkk in

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Reaction Stoichiometry

W, the corresponding column U k in U is an orthonormal basis vector for the

range. Similarly, the subspace of N that maps to zero under (4) is called the
nullspace. For each zero diagonal element wkk in W, the corresponding column
V k in V is an orthonormal basis vector for the nullspace. Vectors in the range
satisfy the elemental conservation laws (2), while vectors in the nullspace balance
the reactions via (4). Thus, vectors in the nullspace represent stoichiometric
coefficients.
Since the nullspace vectors Vk are basis vectors, any linear combination of
them also represents a set of stoichiometric coefficients (i.e., stoichiometric
coefficients are not unique). To obtain all possible sets, we form a (C R ) matrix
P in which each column is one of the nullspace basis vectors V k . Then the
stoichiometric coefficients for the jth reaction can be obtained from

j = P j

(8)

where j is an (R 1) vector of arbitrarily selected scale factors (or weights) for

each reaction j.

3. Example

To illustrate the method, we continue with the formula matrix presented in

(1), which contains C = 6 species and m = 3 elements. We first form the
augmented matrix A by adding three rows of zeroes to A. Then we use the
SVD routine in Press et al. (1986) to find

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Reaction Stoichiometry

0.197 0.265
0.966 0.216
0.166 0.940
0
0
0
0
0
0

5.016 0
0 3.223
0
0
0
0
0
0
0
0

0.810
0.066
0.106
0.418
0.072
0.385

0
0
0
1
0
0

0.944
0.141
0.298
0
0
0

0
0
0
0
0
0
0
0
0
0 1.206 0
0
0
0
0
0
0

0.186
0.583
0.665
0.158
0.374
0.134

0
0
0
0
1
0

0
0
0
0
0
1

0
0
0
0
0
0

0.459 0.315
0
0
0.459 0.495 0.249 0.371
0.115 0.288 0.664 0.093
0.344 0.481 0.166 0.650
0.344 0.535 0.664 0.093
0.574 0.234 0.166 0.650

(9)

(10)

(11)

Note that this is V, not V T . To save space, we display only three significant
figures for the elements in V; in practice, we generally need five significant
figures for reliable results.
According to (7), the number of zero elements on the diagonal in W gives
the number of independent reactions: R = 3. For the zero elements w33, w55,
and w66, the corresponding columns V3, V5, and V6 in V are the basis vectors for
the nullspace. We use these to form a (C R ) matrix P,

0.459
0.459
0.115
0.344
0.344
0.574

0
0.249
0.664
0.166
0.664
0.166

0
0.371
0.093
0.650
0.093
0.650

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(12)

Reaction Stoichiometry

Each column in P is a set of stoichiometric coefficients for one of the three

independent reactions. If subsequent analyses are to be done by computer, then
the columns in P solve our problem: we have identified and balanced the
independent reactions for the given formula matrix (1).
However, if subsequent analyses are to be done by hand, then we may
prefer integers for the stoichiometric coefficients. To obtain integers, we can use
P in (8) with judicious choices for the arbitrary weights . For example, from the
first column of P in (12), we choose scale factors 1T = ( 1/0.115, 0, 0); then (8)
gives 1T = (4, 4, 1, 3, 3, 5), and the balanced reaction is

4CH4 + 4O2

CO2 + 3H2O + 3CO + 5H2

(13)

From the second column in P we choose 2T = (0, 1/0.166, 0); then (8) gives 2T
= (0, 1.5, 4, 1, 4, 1), and the balanced reaction is

3O2 + 2H2O + 8CO

8CO2 + 2H2

(14)

From the third column in P we choose 3T = (0, 0, 1/0.093); then (8) gives 3T =
(0, 4, 1, 7, 1, 7), and the balanced reaction is

4O2 + CO + 7H2

CO2 + 7H2O

(15)

The results (13), (14), and (15) are examples of three independent reactions
provided by the SVD of the formula matrix A given in (1).

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Reaction Stoichiometry

4. Discussion

This procedure is particularly effective when the number of species C is

large; an example is combustion, where it is not unusual for more than 100
species to be involved. But regardless of the number of species, we need only
know the identities of those species to build the formula matrix A. From the
singular-value decomposition of A we obtain the number of independent
reactions, all possible reactions, and all possible sets of stoichiometric coefficient
for those reactions. Further note that the decomposition need only be done once
for any given formula matrix A.
When the number of species C is small, SVD may offer advantages over
balancing by hand. Particularly aggravating are those situations in which one
chemical reaction has more than one set of independent stoichiometric
coefficients. An example is the formation of methane from synthesis gas, which
involves CO and H2 as reactants to form the products CH4 , CO2 , and H2 O.
When balancing by hand, we are tempted to stop after finding one set of
stoichiometric coefficients, forgetting that others might be possible. However,
the SVD method readily finds both independent balances:
4CO + 8H2
3CH4 + CO2 + 2H2O
and
5CO + 7H2
3CH4 + 2CO2 + H2O

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Reaction Stoichiometry

Nomenclature

Formula matrix that shows the distribution of elements among chemical

species in a reaction mixture

Vector of elemental abundances

Number of chemical species in a reaction mixture

Number of elements involved in a reaction mixture

Vector of mole numbers for chemical species

Matrix of elementary stoichiometric coefficients obtained from SVD of A

Number of independent chemical reactions

Matrix obtained from SVD of A and containing orthonormal basis

vectors for the range

Matrix obtained from SVD of A and containing orthonormal basis

vectors for the nullspace

Diagonal matrix obtained from SVD of A

Vector of arbitrarily chosen scale factors for obtaining stoichiometric

coefficients for a particular reaction

Vector of stoichiometric coefficients for a reaction

Reference

W. H. Press, B. P. Flannery, S. A Teukolsky, and W. T. Vetterling, Numerical

Recipes, Cambridge University Press, Cambridge, 1986.

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