Research: Science and Education

A Streamlined Approach to Solving Simple and Complex

Kinetic Systems Analytically
John Andraos
Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada

The topic of rate expression derivation for chemical ordinary differential equations (ODEs). This set of equations
reaction schemes in undergraduate and graduate chemical can be solved to obtain the time-dependent evolution of each
kinetics, physical organic, and physical inorganic chemistry chemical species with a boundary constraint defined by the
courses necessarily involves a significant amount of math- initial concentration, or some other measured property, of
ematics. The success of students grasping the methodologies each species at time zero. Marquis Pierre Simon de Laplace
involved and making inferences about the consequences of (17491827) devised an elegant method of solving simultaneous
rate-constant approximations, chemical equilibrium, and rate- ordinary differential equations with boundary constraints that
determining steps largely depends on the studentteacher involves the transformation of these equations into a set of
comfort level in dealing with the language of mathematics. polynomial expressions that can be readily solved by elimi-
Teachers of chemistry may find such a task daunting for a nation or matrix methods. As will be shown (see below),
variety of reasons. Usually the situation exposes the deficiency matrix methods are superior in dealing with reaction schemes
in the mathematical training of chemical educators and the involving combinations of consecutive, cyclic, or branched
students lack of problem-solving skills in realizing how transformations.
concepts learned in one science course may be utilized to full The Laplace transform method is a widely established
advantage in another. The development of this extremely technique for solving simultaneous ordinary linear differential
important critical skill is demanded by the ever growing trend equations (717 ). It is a powerful method owing to its
to interdisciplinary research. The observation that students generality and straightforward implementation despite its
complain often of not seeing the relevance of learning some- unfortunate absence in chemical kinetics and physical organic
thing, particularly in mathematics, to real-world examples inorganic chemistry course syllabuses and in the mainstream
attests to the dilemma and is a direct result of the current education of chemistry undergraduate and graduate students.
and longstanding compartmentalized approach to science A variety of well-known reaction schemes will now be presented
program curricula. This attitude pervades in educators and solved by this technique. Interested readers are encouraged
teaching and students learning styles and results in both
educators and students becoming increasingly dependent on
the results themselves as given in standard texts while sacri-
ficing the knowledge of how such results were obtained in Table 1. Example Reaction Schemes Involving
the first place. The emerging trend of developing cross- Unimolecular Transformations
disciplinary science courses such as the recently described Scheme Rate Equations
Science One and Cooperative Science Option (CSO) offered k d[A]/d t = {k[A]
at the University of British Columbia (1), is a small step in A B
d[B]/d t = k[A]
the right direction in rectifying this situation. k1 d[A]/d t = {k1[A] + k2[B]
In this paper I apply well-established mathematical A B d[B]/d t = k1[A] k2[B]
concepts to the solution of an important chemical problem, k2
namely, the derivation of analytical rate expressions for simple k1 k3 d[A]/d t = {k1[A] + k2[B]
and complex unimolecular and bimolecular chemical reaction A B C d[B]/d t = k1[A] (k2 + k3)[B] + k4[C]
schemes. There are excellent texts available on the subject k2 k4
d[C]/d t = k3[B] k4[C]
(26 ), which give various treatments; however, the approaches k1
taken either involve a mixture of several manipulations, which A B
may appear confusing to the mathematically deficient reader, k2 d[A]/d t = {(k1 + k5)[A] + k2[B] + k6[C]
or give incomplete results. It is the intention here to develop a k5 k3 d[B]/d t = k1[A] (k2 + k4)[B] + k3[C]
k6 k4 d[C]/d t = k5[A] + k4[B] (k3 + k6)[C]
streamlined and accessible approach so as to present the mate-
rial in a simple and unified form and to provide a firm ground- C
ing for students to tackle more complex kinetic examples. k1 k3 d[A]/d t = {k1[A] + k2[B]
A B C d[B]/d t = k1[A] (k2 + k3)[B]
k2
Laplace Transforms Applied to Unimolecular d[C]/d t = k3[B]
k1
Transformations A B
k2 d[A]/d t = {(k1 + k3)[A] + k2[B]
Chemical reaction mechanisms comprised of unimolecu- d[B]/d t = k1[A] (k2 + k4)[B]
lar reactions, such as those given in Table 1, involve elementary k3 k4
d[C]/d t = k3[A] + k4[B]
steps where one chemical species is transformed into another C
either reversibly or irreversibly. A wide variety of schemes is k1 k2 d[A]/d t = {k1[A]
possible including consecutive, cyclic, and branched pathways, A B B d[B]/d t = k1[A] k2[B]
or any combination of these. The series of rate expressions
d[C]/d t = k2[B]
for each chemical species in a scheme represents a set of linear

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 Research: Science and Education

to apply the method to their own research problems and to Definition of Laplace Transform
include it in their course teaching. Before illustrating the
method, preliminary definitions and important properties are The Laplace transform, F(s), of a function f (t) is given
presented. by the integral

Rate Equations for Elementary Steps Fs = exp {s t f t dt (4)
0
For a general elementary irreversible reaction involving
p reactants and q products In this expression the function f (t) is transformed through
k the integral operation into a function of s and is called the
n1X1 + n2X2 + m1Y1 + m2Y2 + inverse Laplace transform of F(s). The shorthand notation
with rate constant k, the corresponding rate laws for disap- describing the relationship between the Laplace transform pair
pearance of reactants and appearance of products are given by is given by

p
F (s) = L{ f (t)} (5a)
= {n i k X j
d Xi nj and
(1a)
dt j=1 f (t) = L{1{F (s)} (5b)

with i = 1, 2, 3, ..., p, and Properties

q Two essential properties applicable to both Laplace
= mi k X j
d Yi nj
(1b) and inverse Laplace transforms are the scaling and linearity
dt j=1
properties. These are given by the relationships
with i = 1, 2, 3, ..., q. For a general elementary reversible L{cf (t)} = cL{ f (t)} (6a)
reaction
and
k1
n1X1 + n2X2 + m1Y1 + m2Y2 + L{1{cf (t)} = cL{1{ f (t)} (6b)
k{1
for the scaling property, where c is any positive- or negative-
with forward and reverse rate constants k1 and k {1, the corre-
valued scaling factor; and by the relationships
sponding rate laws are found by first separating the above
chemical equation into its two constituent directions and L{ f (t) + g(t)} = L{ f (t)} + L{g(t)} (7a)
determining the corresponding rate equations for each chemi- and
cal equation. Hence, for the forward reaction L{1{ f (t) + g(t)} = L{1{ f (t)} + L{1{g(t)} (7b)
k1 for the linearity property. In addition to these, the first-
n1X1 + n2X2 + m1Y1 + m2Y2 +
derivative theorem is given by
eqs 1a and 1b apply, and for the reverse reaction L{ f (t)} = sL{ f (t)} f (0) (8)
k{1
m1Y1 + m2Y2 + n1X1 + n2X2 + which is required for taking the Laplace transform of differ-
ential terms as d[A]/dt appearing in rate expressions. Verifica-
we have
tion of the above expressions is given in various mathematical
p texts (717 ) and the reader is referred to these for further
= n i k {1 Y j
d Xi mj
(2a) reading.
dt j=1
Outline of the Method
with i = 1, 2, 3, ..., p, and
The basic idea of the method is to substitute the difficult
q
= {m i k {1 Y j
d Yi mj task of solving simultaneous ordinary differential equations
(2b) (functions of t) that describe the rate expressions for each
dt j=1
chemical species in a reaction scheme by transforming them
with i = 1, 2, 3, ..., q. into a set of simple polynomial equations (functions of s) using
The pairs of equations 1a2a and 1b2b are then combined the properties given above. Initial conditions are applied and
to give the overall rate law for each reactant species these equations can then be readily solved to obtain Laplace
p p
transform functions corresponding to each chemical species
= {n i k 1 X j + n i k {1 Y j
d Xi nj mj (functions of s). Once these are determined, the desired time-
(3a) dependent function for a given chemical species is found by
dt j=1 j=1
obtaining the corresponding inverse Laplace transform function
where i = 1, 2, 3, ..., p, and the corresponding one for each (a function of t). In practice this is done by simply looking
product species up Laplace transform pairs in extensively compiled tables (18,
q q
19). For most purposes a very small subset of these tables is used.
= {m i k 1 X j + m i k {1 Y j
d Yi nj mj It should be noted that there is a unique correspondence be-
(3b) tween two functions constituting a Laplace transform pair;
dt j=1 j=1
that is, a Laplace transform function is associated with only
where i = 1, 2, 3, ..., q. one inverse Laplace transform function and vice versa.

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Research: Science and Education

The method is illustrated in full detail for the following For convenience the determinant, D, can be written as
reaction scheme D = s(s + 1)(s + 2) (16)
k1 where
A B 1 2 = k2k3 (17a)
k2
k3 1 + 2 = k1 + k2 + k3 (17b)

C
Solving for x (s), y (s), and z (s) yields

with initial conditions [A] = [A] 0, [B] = 0, and [C] = 0 at time a {k 2 0

zero. The corresponding rate laws are given by the following a k2 + s
x s = 1 0 k2 + s 0 = (18)
set of differential equations D s + 1 s + 2
0 0 s
d[A]/dt = {(k1 + k3)[A] + k2[B] (9a)
d[B]/dt = k1[A] k2[B] (9b)
s + k1+ k3 a 0
ak 1
d[C]/dt = k 3[A] (9c) ys = 1 {k 1 0 0 = (19)
Letting D s + 1 s + 2
{k 3 0 s
[A] = x; [B] = y; [C] = z; and [A] 0 = a (10)
leads to simplification of the equations in (9a-c) to and

x(t) + (k1 + k3)x(t) k2 y(t) = 0 (11a) s + k 1 + k 3 {k 2 a

ak 3 k 2 + s
y(t) k1x(t) + k2 y(t) = 0 (11b) zs = 1 {k 1 k2 + s 0 = (20)
D s s + 1 s + 2
{k 3 0 0
z(t) k3x(t) = 0 (11c)
Applying Laplace transforms to eqs 11ac using the properties The corresponding inverse Laplace transforms of x(s),
given in eqs 6a, 7a, and 8 yields y(s), and z(s) found from tables of transforms yield the func-
L{x(t) + (k1 + k3)x(t) k2 y(t)} = 0 (12a) tions x(t), y(t), and z(t):

L{ y(t) k1x(t) + k2 y(t)} = 0 (12b) k 2 1 k

x t =a exp {1t 2 2 exp {2t (21a)
L{z (t) k3x(t)} = 0 (12c) 2 1 2 1
or
sx(s) x(0) + (k1 + k3)x(s) k2 y(s) = 0 (13a) k1
y t =a exp {1t exp {2t (21b)
sy(s) y(0) k1x (s) + k2 y(s) = 0 (13b) 2 1
sz(s) z(0) k3 x(s) = 0 (13c)
k k k k k k
Further applying the initial condition criteria to eqs 13ac z t = a 2 3 + 3 2 1 exp {1t + 3 2 2 exp {2t (21c)
1 2 1 1 2 2 2 1
yields
[s + k1 + k3]x (s) k2 y(s) = a (14a) Finally, the set of equations 21ac can be rewritten in
{k1x (s) + [k2 + s] y(s) = 0 (14b) the familiar form
sz(s) k3 x (s) = 0 (14c) k 2 1 k
A = A exp {1t 2 2 exp {2t (22a)
The set of equations 14ac is solved for x(s), y (s), and 0
2 1 2 1
z(s) using the matrix method. This method is the easiest one
to employ for simultaneous linear equations. Other names k1
for this method include the method of determinants and B = A exp {1t exp {2t (22b)
0
2 1
Cramers method (20). The set of equations 14ac is written
first in matrix form:
k 3 k 2 1 k k
C = A 0 1+ exp {1t + 3 2 2 exp {2t (22c)
s +k 1 +k 3 {k 2 0 x(s) a 1 1 2 2 2 1
{k 1 k2 + s 0 y(s) = 0 (15)
0 using the definitions given in eqs 10 and 17ab.
{k 3 0 s z(s)
Table 2 summarizes the results of common reaction
schemes solved by this method. In the case of the example
The determinant of the left-hand matrix is obtained as follows: involving a reversible reaction between two chemical species
(entry 2 in Table 2), it can be shown that the equilibrium
s +k 1 +k 3 {k 2 0 limit of the ratio of the product and reactant concentrations
D= {k 1 k2 + s 0 = s s 2 + k 1 + k 2 + k 3 s + k 3k 2 is equal to the ratio of the forward and reverse rate constants.
{k 3 0 s Moreover, in the case of the cycle depicted by the fourth entry
in Table 2 it can be shown that the algebraic sum of the loga-

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 Research: Science and Education

Table 2. Reaction Schemes Involving Unimolecular Transformations Solved by the

Laplace Transform Method
Scheme Initial Conditions Rate Equations
k
A B [A]0 = a; [B]0 = 0 A = a exp {kt
B = a 1 exp {kt
k1 a
[A]0 = a; [B]0 = 0 A = k + k exp { k 1 + k 2 t
A B k1+ k2 2 1
k2
ak 1
B = 1 exp { k 1 + k 2 t
k1+ k2

k1 k3 k k k k k k k +k
[A]0 = a; [B]0 = 0; [C]0 = 0 A = a 2 4 1 1 3 4 e {1t 1 3 4 2 e {2t
A B C 1 2 1 2 1 2 2 1
k2 k4
k k 4 1 { t k 4 2 { t
B = ak 1 4 + e 1 + e 2
1 2 1 1 2 2 2 1
C = ak 1k 3 1 + 1 e {1t 1 e {2t
1 2 1 1 2 2 1 2

where
12 = k2k4 + k1k3 + k1k4
1 + 2 = k1 + k2 + k3 + k4
k1 2 { t 22 2 + { t
A B [A]0 = a; [B]0 = 0; [C]0 = 0 A =a + 1 1 e 1 + e 2
k2 1 2 2 1 2 1
k5 k3 k { t k 12 { t
k6 k4 B = a + 1 1 e 1 + e 2
1 2 2 1 2 1
C
k { t k 52 { t
C = a + 5 1 e 1 + e 2
1 2 2 1 2 1
where
= k2 + k3 + k4 + k6; = k2k4 + k2k6 + k3k6;
= k1k4 + k1k6 + k4k5; = k1k3 + k2k5 + k3k5;
12 = + + ; 1 + 2 = + k1 + k5
k1 k3
A = a k + k e {1t k 2 + k 3 2 e {2t
[A]0 = a; [B]0 = 0; [C]0 = 0
A B C 2 1 2 3 1
k2
ak 1
B = e {1t e {2t
2 1
k 1k 3 k 1k 3
C =a 1+ e {1t + e {2t
1 1 2 2 2 1

where
12 = k1k3; 1 + 2 = k1 + k2 + k3
k1
[A]0 = a; [B]0 = 0; [C]0 = 0 A = a k + k e {1t k 2 + k 3 2 e {2t
A B
k2 2 1 2 3 1
ak 1
k3 k4 B = e {1t e {2t
2 1
C k +k
C = a 1 2 4 e {1t 1 4 e {2t
2 1 1 2
where
12 = k1k3 + k2k4 + k3k4; 1 + 2 = k1 + k2 + k3 + k4
k1 k2
A B B [A]0 = a; [B]0 = 0; [C]0 = 0 A = a exp {k 1t
ak 1
B = exp {k 1t exp {k 2t
k2 k1
k2 k1
C =a 1 exp {k 1t exp {k 2t
k2 k1 k1 k2

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Research: Science and Education

Table 3. Reaction Schemes Involving Bimolecular with initial conditions [A]0 = a, [B]0 = b, and [C]0 = 0 at
Transformations as Given in Reference 2 time zero. The corresponding rate laws are given by the
Scheme Initial Conditions Rate Equations following set of differential equations:

A+B
k
C
[A]0 = a; [B]0 = b;
kt = 1 ln a b x d[A]/dt = {k1[A][B] + k {1[C] (25a)
[C]0 = 0 b a b ax
d[B]/dt = {k1[A][B] + k {1[C] (25b)
where x = [C] at time t d[C]/dt = k1[A][B] k {1[C] (25c)
k a
A+B C [A]0 = a; [B]0 = a; A = From eqs 25ac it is readily apparent that
[C]0 = 0 1 + kat
k 1 1 = 2kt d[A]/dt = d[B]/dt = {d[C]/dt (26)
2A B [A]0 = a; [B]0 = 0
ax a whereupon subsequent integration using the boundary con-
where x = [B] at time t ditions leads immediately to the relationships
[A] [A]0 = [B] [B]0 (27a)
rithms of the ratios of product and reactant concentrations
around the cycle is identically zero at equilibrium. [C] = [A]0 [A] (27b)
An important realization is that the method of Laplace Substitution of eqs 27ab into eq 25a and integration over
transforms cannot be applied to chemical systems involving the boundary conditions leads to
bimolecular transformations because there is no distributive
property for product functions; that is, the Laplace transform A + 1 A 0 + 2
of a product of functions does not equal the product of the k 1t 1 2 = ln (28)
A + 2 A 0 + 1
Laplace transforms of those functions:
where
L{ f (t)g (t)} L{f (t)}L{g(t)}
A 0k {1
Differential equations describing bimolecular transformations 12 =
k1
are classified as nonlinear and are generally solved by numerical
methods, with the exception of simple cases (see below), and
which are solved by integration methods. k {1
A point of caution with respect to refs 2 and 3 is that 1 + 2 = A 0 B 0
the tables of transforms given therein do not refer to Laplace k1
transforms according to the formal definition given in eq 4
and stated throughout the mathematical literature (717). The expressions for [B] and [C] are found by replacing [A] in
Rather, they are obtained using the LaplaceCarson transform eq 28 with the appropriate expression defined by eqs 27ab.
given by the analogous definition Thus, the relationships
G(s) = s e0 exp({ st) f (t)dt = LC { f (t)} = sL{ f (t)} (23) B B 0 + A 0 + 1 A 0 + 2
k 1t 1 2 = ln (29a)
Note that use of this definition results in the addition or B B 0 + A 0 + 2 A 0 + 1
omission of terms in the numerators and denominators of
the Laplace transform expressions as appropriate. Scaling and A 0 C + 1 A 0 + 2
linearity properties also hold for the LaplaceCarson trans- k 1t 1 2 = ln (29b)
form; however, the statement of the first-derivative theorem A 0 C + 2 A 0 + 1
differs and is given by
are obtained. The expressions appearing in Table 4 are re-
LC { f (t)} = sG(s) sf (0) (24) written as proper concentrationtime-dependent functions.
There is no practical advantage in using one definition over
Summary
the other.
The powerful utility of Laplace transforms has been
Integral Method Applied to Simple Bimolecular demonstrated for deriving rate expressions for any reaction
Transformations mechanism comprising only unimolecular reactions. The
Capellos and Bielski (2) give rate expressions for a num- method is not applicable to schemes involving bimolecular
ber of bimolecular kinetic schemes as shown in Table 3. A elementary steps; however, integration methods may be used
more complete set of solutions derived in the present work to obtain rate expressions for simple cases. Incorporation of
is shown in Table 4. The method used to arrive at these ex- these techniques in chemical kinetics, physical organic, and
pressions is illustrated in full detail for the scheme physical inorganic chemistry courses should be a great asset
for students understanding of rate expression derivations for
k1
A+B C a wide variety of chemical reactions and reaction mechanism
k{1 phenomena.

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 Research: Science and Education

Table 4. Reaction Schemes Involving Bimolecular Transformations Literature Cited

Solved by the Integration Method
Scheme Initial Conditions Rate Equations 1. Thompson, R. C. Integrating the Sciences in the First
k {1 Year University Curriculum; presented at the 81st
[A]0 = a; [B]0 = b; A = b a b exp b a kt 1
A+B C CSC Conference at Whistler, BC, Canada, May
[C]0 = 0 a
a {1 31June 4, 1998.
B = ab exp a b kt 1
b 2. Capellos, C.; Bielski, B. H. J. Kinetic Systems:
ab Mathematical Description of Chemical Kinetics in So-
C =a +1
b exp b a kt a lution; Wiley: New York, 1972.
k [A]0 = a; [B]0 = a; A = a 3. Rodiguin, N. M.; Rodiguina, E. N. Consecutive
A+B C kta + 1 Chemical Reactions: Mathematical Analysis and De-
[C]0 = 0
B = a velopment; Van Nostrand: Toronto, 1964.
kta + 1
kta
2 4. Moore, J. W.; Pearson, R. G. Kinetics and Mecha-
C = nism; Wiley: New York, 1981.
kta + 1
5. Carpenter, B. K. Determination of Organic Reac-
k
A = a
2A B [A]0 = a; [B]0 = 0 2kta + 1 tion Mechanisms; Wiley: New York, 1984.
2
kta 6. Laidler, K. J. Chemical Kinetics; Harper & Row:
B = New York, 1987.
2kta + 1
7. Debnath, L. Integral Transforms and Their Applica-
k1 1 R2 tions; CRC: Boca Raton, FL, 1995.
A+B C [A]0 = a; [B]0 = b; A =
[C]0 = 0 R 1 8. Guest, P. B. Laplace Transforms and an Introduc-
k2
a b + 1 R a b + 2 tion to Distributions; Ellis Horwood: New York,
B =
R 1 1991.
a + 1 R a + 2 9. Healey, M. Tables of Laplace, Heaviside, Fourier and
C =
1R Z Transforms; W. & R. Chambers: Edinburgh,
1967.
where
ak 2 k 10. Holl, D. L.; Maple, C. G.; Vinograde, B. Intro-
12 = { ; 1 + 2 = b a + 2 ; duction to the Laplace Transform; Appleton-Cen-
k1 k1
tury-Crofts: New York, 1959.
a + 1 {k t
R= e 1 2 1
a + 2 11. Grove, A. C. An Introduction to the Laplace Trans-
form and the Z Transform ; Prentice-Hall:
k1 1 2R Engelwood Cliffs, NJ, 1991.
A+B C [A]0 = a; [B]0 = a; A =
k2 [C]0 = 0 R 1 12. Spiegel, M. R. Applied Differential Equations;
1 R2 Prentice-Hall: Engelwood Cliffs, NJ, 1981.
B =
R 1 13. Robinson, P. D. Fourier and Laplace Transforms;
a + 1 R a + 2 Dover: New York, 1968.
C =
1R 14. Sneddon, I. N. The Use of Integral Transforms;
McGraw-Hill: New York, 1972.
where
ak 2 k 15. Zwillinger, D. Handbook of Differential Equations;
12 = { ; 1 + 2 = 2 ;
k1 k1 Academic: New York, 1989.
a + 1 {2k t
R= 16. Boyce, W. E.; DiPrima, R. C. Elementary Differ-
a + 2 e
1 2 1

ential Equations and Boundary Value Problems;

k1 Wiley: New York, 1986.
2A B [A]0 = a; [B]0 = 0 1 2R
A =
k2 R 1 17. Spiegel, M. R. Schaums Outline Series: Theory and
a + 1 R a + 2 Problems of Laplace Transforms; McGraw Hill: New
B = York, 1991.
2 1R
18. Roberts, G. E.; Kaufman, H. Table of Laplace Trans-
where forms; Saunders: Philadelphia, 1966.
ak 2 k
12 = { ; + = 2 ; 19. Oberhettinger, F.; Badii, L. Tables of Laplace Trans-
2k 1 1 2 2k 1
forms; Springer: New York, 1973.
a + 1 {2k t
R= e 1 2 1
a + 2 20. Grossman, S. I. Elementary Linear Algebra;
Wadsworth: Belmont, CA, 1984.

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