On the Stoichiometry of Chemically Reacting Materials

RAY M. BOWEN

Communicated by R. ARIS & C. TRUESDELL

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
2. Balance of Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3. Vector Space Structure and the Main Results . . . . . . . . . . . . . . . . . . . 116
4. Component Representations . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5. Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

1. Introduction
It is well known that in a mixture of 9/chemically reacting materials the num-
ber of independent chemical reactions is not arbitrary. The mathematical represen-
tation of these reactions constitutes a part of chemistry known as stoichiometry.
This topic has been discussed by several authors at various levels of generality.
One of the better discussions has been given by ARIS 1. The presentation given here
differs from that of ARIS in that I have adopted a mathematical description that
renders the results component free, and, more importantly, I obtain my results
directly from well known postulates of balance of mass for a mixture rather than
from equivalent, but more obscure, statements about the meaning of reaction
equations 2. I have made an effort to present clear definitions of the terms: chemi-
cal reaction, independent chemical reaction, reaction rate and extent of reaction.
A proof of the Law of Definite Proportions is also given.

2. Balance of Mass
For a mixture of 9~ reacting materials with diffusion, the axiom of balance of
mass for the a th constituent is 3

p ~= -div(p~ u~)+ p "~, (1)

where p~ is the density of the a th constituent,

p= ~p~
4=1

is the density of the mixture, ca=pJp is the concentration of the a th constituent,

us is the diffusion velocity of the a th constituent and ~ is the rate of supply of
mass to the a th constituent resulting from chemical reactions. The concentrations
1 Ares [1]. See also Ares [8].
2 See, for example, Ares [1], Section 3.
3 TRUESDELL& TOUPIN[2], Section 159.
 Stoichiometry of Reacting Materials 115

and diffusion velocities satisfy the equations

91 9/
~c,=1 and ~p.u.=O. (2)
a=l a=l

Naturally, (1) and (2) imply that

Y~ ~.--o. (3)
a=l

Equation (3) is a statement of conservation of mass for the mixture.

Equation (1) is not sufficient to reflect all that can be said regarding the con-
servation of mass in a mixture. In most physical circumstances, it is permissible to
assert that the atomic substances making up the constituents are indestructible.
This postulate takes the form 4
91
t"~'~./rn~ a = l . . . . . 92[ (4)
a=l

where m" is the molecular weight of the a th constituent, t"~ is a nonnegative integer
representing the number of moles of the a th atomic substance in the a th constituent
and 91 denotes the number of atomic substances making up the constituents. If
w" denotes the atomic weight of the ath atomic substance, then
91
m"=~t"~w ~, a = l . . . . . 9~. (5)
~t=l

Usually the matrix (t"~) has rank ~, where ~ < min (91, ~). If this is the case, we
can write (4) and (5) in the forms

~S"~,/rn"=O, a=l,...,~, and m"=~S"~ff~ ~, a=1,...,9~, (6)

tt=l r

where the N~ are molecular weights obtained by eliminating the dependent columns
of (t",) and, of course, (S"~) has rank ~. The details of this elimination are not
important here. It is convenient to introduce the molar concentration o9, and the
molar supply &, defined by
(0a = ca/m a and & . = ~<,/m <'. (7)

Equations (1), (2)1, (6) and (3) then become

1
div (p. u.) + &., (8)
p m"
91
m"o.=l, (9)
am1
91
S", &. = O, = 1, ..., ~ , (10)
a=l

m " = E sacral r a = 1..... 9l (11)

a:=1
4 TRUESDELL & TOUPIN [2], S e c t i o n 1 5 9 A .

8*
116 R.M. BOWEN:

and
91
m*&,=0. (12)
a=l

3. The Vector Space Structure and the Main Results

Consider an 9/dimensional vector space q / w i t h inner product. If (e~, ..., e~)
is the basis of q/, then equations (8) through (12) can be written

~b=a+&, (13)
m . oJ = 1, (14)

f,.&=O, ~=1,...,~, (15)

m = E m* e . = Z m~f, (16)
a=l at=l
and
m. &=0, (17)
where
91
co = y~ o~o eL (18)
a=l

1 .
a = -- a = ~ l - ~ dlv (p, ua) e*, (19)

& = Z &, e" (20)

tt=l
and
91
L = E S*~ e,. (21)
a=l

Naturally (e 1, ..., e ~) is the reciprocal basis of ~ The vector space og shall be

referred to as the constituent space. We are primarily interested in a subspace of q/
defined as follows:
Definition 1. The reaction subspaee ~e"is the set of all vectors x in og such that 5

x.f,=O, ~ = 1 .... , ~ .

Since the vectors ( f l . . . . . f~) are linearly independent, they generate a sub-
space of q/. This subspace is the orthogonal complement ~e"z of "f', and we can
write q / a s
og = ~ ~ ~r177 (22)

where dim ~ e ' • and dim q e ' = 9 l - ~ =~R.

Consider an endomorphism S: ag ~ q/defined by

S x = Z (x. f~) f " (23)

s The name "reaction subspace" was apparently first introduced by Ares.

 Stoichiometry of Reacting Materials 117

for all vectors x in ~/, where (f~ . . . . . f~) is the reciprocal basis of ~ • It is not
difficult to show that S is a symmetric endomorphism that satisfies the equation 6
S 2 = S. (24)
Equation (24) asserts that S is an orthogonal projection of q/ on ~ • along ~ .
If I denotes the identity mapping on q/, then the endomorphism P: q / ~ q/defined
by
P=I-S (25)
is an orthogonal projection of q / o n ~ along ~ •
Theorem 1. The atomic substances are indestructible if and only if ~ is in the
reaction subspace ~e'.
The proof of this theorem follows directly from (15). Equivalent versions of
(15) are
P&=~ (26)
and
S~=0. (27)
Since & is in r I shall call & the reaction vector. Another important observation
is that
P m = 0. (28)

This result follows from (16), (23), and (25).

Theorem 2.
m. & = 0 . (29)
This result is trivial since & is in ~ and, by (28), m is in ~ • Theorem 2 simply
states that conservation of mass for the mixture is implied by indestructibility of
the atomic substances. Thus (17) is not an independent statement.
It is useful at this point to give a definition of the term chemical reaction as it
applies to the discussion given here.
Definition 2. A chemical reaction is a one dimensional subspace of the reaction
space yr.
Def'mition 3. A collection of chemical reactions { ~ , ~2 . . . . . ~a} in ~ are said
to be independent if
yt
n E ~ = (0}, g = 1. . . . . oq. (30)
/t 4:ct
Since ~ has dimension 9t, there is a limit on the number of independent chemical
reactions in ~ .
Theorem 3. In a mixture of 9l reacting materials there are only 91 =g l -
independent chemical reactions.
Since dim ~r = 91, there exists a direct sum decomposition of ~e" into 91 inde-
pendent chemical reactions 7. This decomposition shall be written
~r =~/r ~)~r @ "'" ~)"g'~. (31)
6 GREtra [3], Section 11.11.
7 M o s x o w , SAMPSON & MEYER [4], Chapter 13, Section 3.
118 R.M. BOWEN:

Remark. Since every vector in 3e" is orthogonal to 3e';, every vector in ~ ,

# = 1, ..., 91, is orthogonal to Y " . Therefore, each chemicalreaction 3~'~, It = 1..... 9t,
is orthogonal to 3e'-t.
By virtue of the properties of direct sum decompositions, any vector x in 3v"
has a unique decomposition of the form
91
x = ~ xu, (32)
~=1

where x~ is a vector in ~ . If, in addition, xl, x2 . . . . . x~ are non-zero elements of

~ , ~ , ..., -/r~, respectively, then they are linearly independent. By application of
these results, we have
Theorem 4. Given the decomposition of ~ into 91 independent chemical reac-
tions, the reaction rector ~ has a unique decomposition into 91 reaction rates j~,
# = 1, ..., 91, such that
&= ~j~. (33)
#=1

Theorem 4 represents one of the more important results of stoichiometry. It

assigns a clear meaning to the words reaction rate and shows how these rates
generate the reaction vector ~.
Remark. If we define the 91 projections (not necessarily orthogonal) Pu: q / ~ ug,
# = 1 . . . . , 91, by
e~ x = x~ (34)
for all x in q/, then
ju=PzfJ, # = 1 . . . . . 91. (35)
It is possible to show that
91
P = ~ P~ (36)
and
P~ p,, = ~P~ if ~ = v (37)
t0 if p ~ v .

In other words P is the direct sum of Px, P2 . . . . and P~. Equation (35) is interesting
since it gives an explicit expression for the #th reaction rate in terms of the reaction
^

v e c t o r to.
Chemical reactions are often characterized by parameters known as extents
of reaction or degrees of reaction a. The vehicle for the introduction of these para-
meters is the Law of Definite Proportions 9. A proof of this law will now be given.
A critical assumption in this proof is the absence of diffusion. This assumption
achieves locally what the classical treatments achieve globally when they assume
the system is closed 1~
Theorem 5. In the absence of diffusion, r is in the reaction subspace q/'.
8 DE DONDER [5].
9 PRIGOGINE & DEFAY [6], C h a p t e r I, Section 4.
10 Professor C. TRUESDELL h a s pointed o u t to m e t h a t T h e o r e m s 5 a n d 6 a n d their corollaries
remain valid when diffusion is present if a is in -/r.
 Stoichiometry of Reacting Materials 119

This result follows from Theorem 1 and (13) with a = 0 . The mathematical
statement of this theorem is
P~=~. (38)
Corollary. I f ~o~ is the value of ~o at some reference time, then o~- e~~ is in the
reaction subspace ~e'.
This result follows by integration of (38). The result is
P(m - ~o~ = o~- ~o~ (39)
The vector e J - m ~ shall be called the extent of reaction vector. Since oJ must satisfy
the condition (14), (39) implies that o)~ must be so selected that
m . co~ = 1. (40)

Also, since o~-eJ ~ is in f ' , we can apply again the logic leading to Theorem 4 and
assert
T h e o r e m 6 (Law of Definite Proportions). Given the decomposition of ~e" into 91
independent chemical reactions, the extent of reaction vector, o~-oJ ~ has a unique
decomposition into 91 vectors r l . . . . . ~91 such that
91
o~-oJ~ ~ ~.. (41)
#=1
The vector ~. is the extent of the #th reaction. Equations (41) and (34) imply
that
~. = P . ( o J - oJ~ (42)

Equation (42) should have clear geometric meaning. It asserts that the extent of
the #th reaction is the projection of the extent of reaction vector onto the #th
chemical reaction.
Corollary.
~, = J r , # = 1, ..., 9t. (43)

The proof of this corollary follows from (13) (with a =0) (33), (35) and (42).

4. C o m p o n e n t Representations
The usual applications of the results of the last section require writing these
results in components. These component expressions are well known in physical
chemistry il. It follows from (23) and (25) that

P gu = gu, /1 = 1 . . . . . 91, (44)

where (gl . . . . . g91)is a basis for 3rr. The reciprocal basis to (gt, ..., g~) is (gl, ..., g91).
Since we are attempting to obtain component versions of the results of section 3,
we must make a choice of the subspaces 3r i, 3~2, ..., 3r~. One possible choice is
to take "Uu to be the subspace generated by g~. Since the vectors (gl, ..., g91) are
linearly independent, the resulting chemical reactions are independent. Also, we
11 PRIGOGINE~ DEFAY[6], Chapter I, Sections 5 and 6.
120 R.M. BOWEN:

can write the reaction rate j , in the form 12

j~=g~j~. (45)
Theorem 7.
&, = ~ P,~j,, a = 1, ..., 91, (46)
g=l
where
P~=e,.g ~, /~=1 . . . . . 91, a = l . . . . . ~/. (47)

Proof. From (45), (20) and (33) we find that

91 81
~ e*= ~ j . g". (48)
a=l /t=l

Equation (48) immediately implies (46) since e*. eb = 6~,.

The matrix (P,U) is usually called the stoichiometric matrix. It is not difficult
to show from (23), (25) and (47) that
81
P e~= E P~ g," (49)
/t=l

Therefore, the stoichiometric matrix is the matrix of the orthogonal projection P

with respect to the bases (ex, ..., e81) and (gl . . . . , g~).
Theorem 8.
~ s~eff=0, ~ = 1 , . . . , ~ , # = 1 , ..., 91. (50)
a=l

Proof. Since q/" and 3e"• are orthogonal complelnents,

g".f~=O, ~ = 1 , . . . , ~ , # = 1 , ..., 91.
Therefore, by using (47) and (21), we obtain (50).
Theorem 9.
9/
~P~m*=O, # = 1 , ..., 91. (51)
tt=l

Equation (51) is just (28) expressed in components. It can also be obtained directly
by multiplying (50) by ~ and making use of (6)2.
Remark. I f . / / i s the chemical symbol for the a th constituent, then (50) represents
a

the conditions implied by balancing the R reaction equations

91
P,~ ,/r = 0, # = 1. . . . . 9t. (52)
a=l a

In the absence of diffusion, Theorem 6 and its corollary imply that

81
o9,- co,0 = ~ P~ ~u, a = 1. . . . . 9/, (53)
#=1

12 The summationconventionis not being used in this article.Therefore,there is no summation

implied by the repeated indices in (45).
 Stoichiometry of Reacting Materials 121

where
~=g"~ and ~=j#. (54)

Remark. In order to apply (46) it is necessary to know the elements of the

stoichiometric matrix. Obviously, any matrix of rank 91 that satisfies (50) repre-
sents an acceptable stoichiometric matrix. The most common procedure used by
physical chemists to determine (P,") is in effect to select the 91 subspaces "/P~,... , ~
such that (30) is satisfied and that each subspace is orthogonal to ~ • Knowledge
of these 91 subspaces then allows the calculation of the matrix (Po") form (47).
To a chemist the "selection of the 91 subspaces" involves the assumption, based
upon his experience, that 91 independent chemical reactions are taking place.
The 91 reactions are independent if, when written in the form of (52), (P,")
has rank 91. The requirement that each subspace ~ . . . . , ~ is orthogonal to ~e-z
is satisfied by balancing each reaction equation. In this fashion, the matrix (P,")
can be read off from (52). Naturally, each reaction determines only the correspond-
ing elements of (Pa") within a non-zero constant. In the process of writing the
reaction equations, chemists usually regard certain of the constituents in a given
reaction as products of the reaction and the remaining ones as reactants. These are
distinguished in (52) by taking the coefficients P,~ to be nonnegative for the pro-
ducts and nonpositive for reactants 13. Without additional information into the
reaction mechanisms, this procedure for determining (P,") must be regarded as
not having any more significance than any other choice of (P,").
HOOYMAN 14 has proposed a prescription for determining the stoichiometric
matrix that has some computational advantages. HOOYMAN'S method, in effect,
is to take the 91 vectors (g~, g2 . . . . . g~) equal to 91 vectors taken from the collec-
tion (e 1. . . . , e~). As can be seen from (47), this choice determines 912 elements of
(PaU), 91(~t-1) of which are zero and 91 of which are unity. The remaining
(91-91) 91 = ~ 91 elements of (PoU) can then, in principle, be computed from (50).
The only problem that might arise in this calculation is that the choice of the 91 vec-
tors in (el . . . . . e~) might not be consistent with (50). However, since (S*~) has
rank 6, some acceptable choice of the vectors (ex . . . . . e~) is always possible. For
the purposes of this discussion, assume that an acceptable choice is

gu=ee§ /x= 1, ..., 91. (55)

In this case, (47) implies that

P~+,~=~, c t , # = l . . . . . 9t, (56)

and (46) becomes
j~=&~+,, p = 1, ..., 91. (57)

HOOYMAN'S procedure has the advantage that each reaction rate is equal to the
molar supply of some constituent. In many applications, HOOYMAN'S method is
essentially the same as the first method described.

13 PRIGOGINE& DEFAY[6], Chapter I, Section 4.

14 HOOYMAN[7].
122 R.M. BOWEN:

5. Example
In order to illustrate some of the ideas of this paper, consider a mixture of
five constituents as follows:
-M=H20(S),
1
9- ~ = H 2 0 (/),
2
.M=H20(g),
3
.~--H2
4.
and
~'ff~O 2 .
5

The letters s, l and g denote the solid, liquid and gaseous phases of water respec-
tively. The atomic substances making up the mixture are obviously H and O. If
ct = 1 corresponds to H and a =2 to O, then (5) becomes

m l = 2 w l + l w 2,
m 2 = 2 W l + l w 2,
m a = 2 w I + 1 w2, (58)
and m4=2wt +Ow2
mS=Ow~ +2w 2.
Therefore,

Since (t"~) from (59) has rank 2, then 9.I = ~ =2 and (S"~) and (t",) coincide. There-
fore, there are 9 2 - ~ = 3 independent chemical reactions in this mixture. Note, in
passing, that if we omit H2 and 02 from the mixture, the resulting matrix (t"~)
would have a rank of unity. This affords a possible example when ~ 4=9.I. Returning
to (59), we see from (21) that
f l = 2 e l +2e2 +2ea + 2 e ,
and (60)
f2=el +e2 +ea + 2es.
The reaction subspace ~e" is a three dimensional subspace of q/generated by any
three linearly independent vectors (gl, g2, ga) that are orthogonal to f l and f2.
As was mentioned in Section 4, one method of characterizing the reaction sub-
space is simply to assume certain chemical reactions. For example, we might take
the three reactions to be
H20(s)=H20(I),
n20(/)=H20(g) (61)
and H 2 0 ( g ) = H 2 + 890 2 .
 Stoichiometry of Reacting Materials 123

As written, these three equations are balanced, and thus (50) is satisfied. If we
regard the terms on the right as products, then the stoichiometric matrix is

(P,~) =
- 1 1 0 00 i]
0 - 1 1 . (62)
0 0-1 1

From (47) the reciprocal base vectors of ~ are given by

91
gU=EP~e~ (63)
a=l

For this example, it follows then that

g l = _el +e2,
g2= _ e 2 + e 3 (64)
and g3= _ca+e4+ 89 e s.

By use of (62) and (46) the molar supplies are given by

~t = --Jl,
~)2 =Jl --J2'
6~33----J2--J3' (65)
and ~4- =J3
~5= 89
If one does not want to assert in advance the reactions taking place, HOOYMAN'S
method can be used to compute (Pa"). In order to apply this method take, for
example,
gl----el,
and g2 = e2 (66)
g3 = e3"
Then, by (47),
i o o e, 1 es 1]
(P,~)= 1 0 P42 p52I . (67)
0 1 P43 Ps3j

equivalent to

i 0 0 /341 P5 1]
1 0 P42 P52[
o 1 p3 p53]
[21]
The unknown elements of (P.") can now be calculated from (50), which, by (59), is

=0. (68)

Expanding (68) yields

P41-~e4.2=e43= - 1
(69)
/'51 =P52 = P53 = - 31.
124 R.M. BOWEN:Stoichiometry of Reacting Materials

Therefore,
1 0 0 -1 1~
(Pf)= 1 0 -1 . (70)
0 1 -1 -

The molar supplies in this case are given by

t~l = J l ,
(D2 = J 2 ,
~03 =J3 , (71)
64 = --Jl --J2--J3
and ^ 1 9 1 9 1 9
~ --~Jl--2J2--~33"
The basis of q/" in this case is, by (63) and (70),
g l = e l _ e 4 89
g2 = e2 -- e 4 -- 89e 5 (72)
and g 3 = e 3 _ e 4 _ 8 9 5.

Therefore, the reaction subspace is completely determined. Of course, the basis

defined by (72) is related to the one defined by (64) by a change of basis in 3e'.
The reaction equations corresponding to (72) can be written down f r o m (52)
and the stoichiometric matrix (70) for this example. They are

H 2 0 (s) = H 2 + 89 2 ,
and H 2 0 (I) = H 2 + 89 2 (73)
H20(g) =H2 + 89

Acknowledgments. The research reported here was supported by the U.S. Atomic Energy
Commission while I was employed on the summer staff of the Sandia Laboratory.

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3. Gm~tm, W.H., Linear Algebra, 2nd Ed. Berlin-Gfttingen-Heidelberg: Springer 1963.
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Rice University
Houston, Texas
(Received October 27, 1967)