In the Classroom
The Relationship between Stoichiometry and Kinetics
Sidney Toby
Department of Chemistry, Rutgers University, Piscataway, NJ 08854; toby@rci.rutgers.edu
Much attention has been paid in this Journal to the
problem of balancing complex chemical equations (1 ). It is
obvious that if an equation is a composite of two or more
reactions then the overall stoichiometry is ambiguous because
there are an indefinite number of linear combinations of the
equations representing the component reactions. Beyond the
ambiguity of stoichiometry, there is the problem of time
dependence. There is surprisingly little awareness that the
stoichiometry resulting from a complex mechanism may
change with time. Laidler is among the very few who have
pointed out the existence of time-dependent stoichiometry
and given an example (2). In this paper I consider the part
chemical kinetics plays in defining stoichiometry and give a
general method for obtaining the time-dependent stoichi-
ometry of a system consisting of a many-step mechanism.
It is tempting to try to obtain an expression for overall
stoichiometry by simply adding a linear combination of the
reactions in the system. Adding chemical reactions, however,
is fraught with pitfalls because of their time dependence.
Diemente has recently made the important point of distin-
guishing reactions from equations (3). Reactions are signified
by an arrow meaning becomes and their addition may lead
to anomalies, as will be shown shortly, whereas equations are
signified by an equals sign and addition is always valid.
Consider the system of two consecutive reactions
AB (k1)
BC (k2)
The overall reaction may be obtained by simply adding the
two reactions to give
AC
This formulation describes the reaction when it is
complete, regardless of the relative sizes of k1 and k2. It is
not, however, valid before completion, and a more precise
formulation would be
[A]0 = [C]
where the subscripts denote the time dependence.
Now let us consider a system of two parallel reactions
AB (k3)
AC (k4)
In this case, adding the two reactions to obtain an overall
reaction produces an invalid description of the system:
2A B + C (?)
The overall reaction cannot generally be described in this way
because the concentrations of products B and C are not gen-
erally equal but depend on the relative values of k3 and k4. We
can, however, obtain a time-dependent relationship for the
stoichiometry of this system by assuming that the mechanism
188 Journal of Chemical Education Vol. 77 No. 2 February 2000 JChemEd.chem.wisc.edu
consists of elementary steps and then writing the rate laws
d[A]/dt = k3[A] k4[A], d[B]/dt = k3[A], and d[C]/dt = k4[A].
Summing these three rate laws and integrating yields the time-
dependent stoichiometric relationship
[A] + [B] + [C] = [A]0 (1)
where at time zero, [A] = [A]0 and B and C are absent. In a
similar fashion, the time-dependent stoichiometric relationship
for the system described by the reactions above of k1 and k2
can be obtained, and it is also given by eq 1.
The method we have just used for obtaining the overall
stoichiometry of a reacting system from a mechanism of
elementary steps is general and consists of adding a linear
combination of the derivative rate laws in such a way that
(ni d[i]/dt) = 0, where ni is the appropriate stoichiometric
factor for species i, followed by integration.
A slightly more complex example also consisting of two
elementary steps is
A 2B (k5)
A+BC (k6)
and our problem is to find the overall stoichiometry. The rate
laws for A, B, and C are
d[A]/dt = k5[A] + k6[A][B] (2)
d[B]/dt = 2k5[A] k6[A][B] (3)
d[C]/dt = k6[A][B] (4)
Adding 2(eq 2) + eq 3 + 3(eq 4) gives
2d[A]/dt + d[B]/dt + 3d[C]/dt = 0
which, upon integration (assuming that at time zero only
reactant A is present), yields
2[A]0 2[A] = [B] + 3[C]
a result quite different from what might have been expected
by simply adding the reactions of k5 and k6.
A Complex Mechanism
We now consider a more complex real-world example.
The thermal (4 ) or photochemical (5) decomposition of
dimethyldiimide (azomethane, A) may be represented by the
following mechanism:
CH3N=NCH3 CH3 + N2 + CH3 (k7)
CH3 + CH3N=NCH3 CH4 + CH2N=NCH3 (k8)
2CH3 C2H6 (k9)
CH3 + CH2N=NCH3 C2H5N=NCH3 (k10)
CH3 + CH3N=NCH3 (CH3)2NNCH3 (k11)
CH3 + (CH3)2NNCH3 (CH3)2NN(CH3)2 (k12)
 In the Classroom

In this system nitrogen, methane, ethane, methyl-
ethyldiimide (MED), and tetramethylhydrazine (TMH)
are products, and the free radicals CH 3, CH2N =NCH3,
and (CH3)2NNCH3 are intermediates. In the interests of
simplicity, less important reactions such as dimerization of
the heavy radicals have been ignored.
What is the overall stoichiometry of this reaction? We
may easily obtain an apparent answer by adding 3(VII) +
(VIII) + (IX) + (X) + (XI) + (XII), where the roman numerals
represent the number of the reaction assigned to the corre-
sponding rate constant (Bensons notation [6 ]). The interme-
diates cancel and the apparent stoichiometry is then given by
5CH3N=NCH3 3N2 + CH4 + C2H6 +
(5)
C2H5N=NCH3 + (CH3)2NN(CH3)2
This is a balanced reaction but it is chemically mean-
ingless because the experimental ratios of the products are
very different from what is predicted by eq 5; moreover, these
ratios vary with the conditions under which the reaction is
carried out. In fact there is no overall unique stoichiometry
for the decomposition of azomethane. It is, however, possible
to derive unambiguous relationships between reactants and
products by the technique employed above. We first write
the rates of reactant disappearance and product formation.
Next we make the steady-state assumption in the concentrations
of the short-lived intermediates CH3, CH2N=NCH3, and
(CH3)2NNCH3 and then use the steady-state relationships
to eliminate the intermediates from the sum of the reactant
and product rates. The resulting equation may be integrated
to yield unambiguous stoichiometric relationships between
reactants and products.
In the above case the rates of disappearance of reactant
and formation of products are given by
d[A]/dt = k7[A] + k8[CH3][A] + k11[CH3][A]
d[N2]/dt = k7[A]
d[CH4]/dt = k8[CH3][A]
d[C2H6]/dt = k9[CH3]2
d[MED]/dt = k10[CH3][CH2N=NCH3]
d[TMH]/dt = k12[CH3][(CH3)2NNCH3]
Next we recognize that the intermediates CH3, CH2N=NCH3,
and (CH3)2NNCH3 are reactive free radicals with concen-
trations many orders of magnitude lower than those of the
reactants and products. We may therefore make the steady-
state assumption in the concentration of these radicals as
follows:
d[CH3]/dt = 0 = 2k7[CH3][A] k8[CH3][A]
2k9[CH3]2 k10[CH3][CH2N=NCH3]
k11[CH3][A] k12[CH3][(CH3)2NNCH3]
We then eliminate the concentrations of the intermediates
in the expression for d[A]/dt and obtain
d[A]/dt = d[N2]/dt + d[CH4]/dt + d[TMH]
This equation may be easily integrated, and assuming no
products are present at time zero it gives a time-dependent
stoichiometry relating reactant to products
[A]0 [A] = [N2] + [CH4] + [TMH] (6)
In similar fashion, we can eliminate the concentrations
of intermediates in the expression for d[CH3]/dt and obtain
2d[N2]/dt d[CH4]/dt 2[C2H6]/dt
d[MED]/dt 2d[TMH] = 0
which yields another relationship relating the stoichiometry
between products:
2[N2] = [CH4] + 2[C2H6] + [MED] + 2[TMH] (7)
Equations 6 and 7 give valid descriptions of the stoichi-
ometry of the reaction at all times.
Chain Reactions
The stoichiometry of a mechanism that contains a chain
is complex because it will depend on the chain length.
Consider the thermal decomposition of acetaldehyde, which
may be approximated by
CH3CHO CH4 + CO + H2 + C2H6
major products minor products
Taking the slightly simplified mechanism suggested by Laidler
(2) we have
CH3CHO CH3 + CHO (k13)
CHO CO + H (k14)
CH3 + CH3CHO CH4 + CH3CO (k15)
CH3CO CH3 + CO (k16)
H + CH3CHO H2 + CH3CO (k17)
2CH3 C2H6 (k18)
It is a simple matter to add the reactions in such a way
that the intermediates CH3, CHO, H, and CH3CO cancel.
One result is given by (XIII) + (XIV) + (XV) + 2(XVI) +
(XVII) + (XVIII), leading to
3CH3CHO CH4+ 3CO + H2 + C2H6 (?)
which, although a balanced reaction, gives totally wrong
product ratios.
The time-dependent stoichiometry of this system may
be obtained by first writing the rate laws for reactant disap-
pearance (letting CH3CHO Ac) and product formation as
follows:
d[Ac]/dt = k13[Ac] + k15[CH3][Ac] + k17[H][Ac]

d[CH2N=NCH3]/dt = 0 = d[CH4]/dt = k15[CH3][Ac]

k8[CH3][A] k10[CH3][CH2N=NCH3] d[CO]/dt = k14[CHO] + k16[CH3CO]
d[(CH3)2NNCH3]/dt = 0 = d[C2H6]/dt = k18[CH3]2
k11[CH3][A] k12[CH3] [(CH3)2NNCH3] d[H2]/dt = k17[H][Ac]

JChemEd.chem.wisc.edu Vol. 77 No. 2 February 2000 Journal of Chemical Education 189

In the Classroom
We now write the steady-state formulation for the concen-
trations of the intermediates CH3, CHO, CH3CO, and H
and obtain the relationships
d[CH3CHO]/dt = d[C2H6]/dt + d[CH4]/dt + d[H2]/dt
d[CO]/dt = 2d[CH3CHO]/dt d[CH4]/dt 2d[H2]/dt
These two equations may be integrated to give, respectively,
[CH3CHO]0 [CH3CHO] = [C2H6] + [CH4] + [H2]
2[CH3CHO]0 2[CH3CHO] = [CO] + [CH4] + 2[H2]
and then may be combined to give the stoichiometric relation
between reactant and all products
3[CH3CHO]0 3[CH3CHO] = [CO] + 2[CH4] + [C2H6] + 3[H2]
A reacting system containing a long chain forms an ex-
ception to the prohibition against adding reactions because
non-chain processes may be ignored. A reasonable approxi-
mation may be obtained by recognizing that steps k15 and
k16 form a chain sequence and if the chains are long, addition
of these two steps leads to
CH3CHO CH4 + CO
which gives the approximate overall stoichiometry when
acetaldehyde decomposes via long chains. The accuracy of
this approximation will depend on the length of the chain.
Zero-Order Reactions
A zero-order reaction gives rise to a different kind of
stoichiometry. We take as an example the deergrass system,
a nonchemical mechanism that can give rise to damped
oscillations (7 ).
EG
(earth yields grass; zero-order rate constant k19)
190 Journal of Chemical Education Vol. 77 No. 2 February 2000 JChemEd.chem.wisc.edu
D+GD+D
(deer eat grass and multiply; 2nd-order rate constant k20)
DC
(deer die; 1st-order rate constant k21)
The appropriate rate laws are
d[G]/dt = k19 k20[D][G]
d[D]/dt = k20[D][G] k21[D]
d[C]/dt = k21[D]
Adding these equations eliminates [D], [G], and [C] and gives
d[G]/dt + d[D]/dt + d[C]/dt = k19
which may be integrated to give
[G] + [D] + [C] = [G]0 + [D]0 + k19 t (8)
Equation 8 implies that the total concentrations on the left
side will increase linearly with time and with no limit. In a
chemical system, as Ball has pointed out, initial reactant
concentrations will set a limit to the total products formed
(8). Put another way, a closed chemical system cannot react
indefinitely via zero order kinetics: eventually the order will
change.
Literature Cited
1. See, for example, letters in J. Chem. Educ. 1996, 73, 1129; 1997,
74, 1256; 1998, 75, 285.
2. Laidler, K. J. Chemical Kinetics, 3rd ed.; Harper & Row: New
York, 1987.
3. Diemente, D. J. Chem. Educ. 1998, 75, 319.
4. Paquin, Y.; Forst, W. Int. J. Chem. Kinet. 1973, 5, 691.
5. Durban, P. C.; Marshall, R. M. Int. J. Chem. Kinet. 1980, 12,
1031.
6. Benson, S. W. The Foundations of Chemical Kinetics; McGraw-
Hill: New York, 1960.
7. Toby, S. Chem. Educator 1996, 1(4).
8. Ball. D. W. J. Chem. Educ. 1998, 75, 917.