Chapter 3

Kinetics

3.1 Chemical kinetics

One unit of chemical species A comes into contact with one unit of species B to produce
one unit of another species C. We write
A + B æ C.
The symbols on the left side of the arrow are the reactants and the one on the right is the
product. We use the same letters to denote the concentrations of these species. According
to the above description, the concentrations change in time as
dA dB dC
= =≠ .
dt dt dt
If we let r denote the rate of the reaction, then we can also write the above derivatives as
dA dB dC
= ≠r, = ≠r, = r.
dt dt dt
The rate of the reaction r depends on several factors, most importantly on the concentra-
tions of the reactants. Thus r is some function r(A, B). Furthermore, we have
r(0, 0) = 0
r(A, 0) = 0 ’A
r(0, B) = 0 ’B
since both reactants are necessary for the reaction. Differentiating the last two equations,
we see that
ˆr ˆ2r
(0, 0) = 0, (0, 0) = 0
ˆA ˆA2
ˆr ˆ2r
(0, 0) = 0, (0, 0) = 0
ˆB ˆB 2
Therefore, if we were to write a Taylor series of the function r about the point (0, 0), we
would obtain
ˆr ˆr 1 ˆ2r 1 ˆ2r ˆ2r
r(A, B) = r(0, 0)+A· (0, 0)+B· (0, 0)+ A2 · 2 (0, 0)+ B 2 · (0, 0)+AB· (0, 0)+· · ·
ˆA ˆB 2 ˆA 2 ˆB 2 ˆA ˆB

42
CHAPTER 3. KINETICS 43

2
where the first nonzero term on the right is the mixed derivative ˆA ˆB (0, 0), since all
ˆ r

the derivatives before it are zero by the above considerations. Therefore, a first term
approximation to the rate function r is
r = kAB
ˆ2r
where the constant k is ˆA ˆB (0, 0). This argument is the basis for many models involving
interacting species.
We can use the same principle for other reactions as well. Consider the reaction
2A æ C
where two A’s come together to form a C. This can be seen as a special case of the reaction
A+B æ C where A and B are the same species. Hence, in this case the rate of the reaction
has the form r = kA2 .
Similarly, for the reaction
–A + —B æ “C + ”D (3.1)
the rate would be r = kA– B — . Namely, the reaction rate depends on the products of the
concentrations of the reactants with exponents coming from the coefficients in the reaction.
These coefficients are called the stoichiometric coefficients.

3.1.1 The law of mass action

Generalizing this concept leads to what is known as the Law of Mass Action.
Law of Mass Action
1. For the reaction
–A + —B + · · · + ŸK æ products,
the rate is
r = kA– B — · · · K Ÿ
where k is a rate constant.
2. The rate of change of the concentration of a species X, with stoichiometric coefficient
‹ is
dX
= ±‹r
dt
where the + is used when X is a product and the ≠ when X is a reactant.
3. For a system of reactions, the rates add.
As an example, the rate for the reaction (3.1) is r = kA– B — and the kinetic equations are
dA
= ≠–r = ≠–kA– B —
dt
dB
= ≠—r = ≠—kA– B —
dt
dC
= “r = “kA– B —
dt
dD
= ”r = ”kA– B —
dt
CHAPTER 3. KINETICS 44

To complete the formulation one needs to supply the initial conditions A(0) = A0 , B(0) =
B0 , C(0) = C0 , D(0) = D0 .

3.1.2 Conservation laws

Note that if we multiply the first equation above by — and the second one by – and subtract,
we obtain
dA dB d
— ≠– = (—A ≠ –B) = 0
dt dt dt
which means that the quantity —A ≠ –B is a constant. Using the initial conditions, we
have
—A(t) ≠ –B(t) = —A0 ≠ –B0 , t Ø 0.
Similarly, by combining the C and A equations, we obtain
“A(t) ≠ –C(t) = “A0 ≠ –C0 ,
and from the D and A equations
”A(t) ≠ –D(t) = ”A0 ≠ –D0 .
These equations are called conservation laws since they refer to quantities that remain
constant in time in a changing system. They are useful for expressing one variable in terms
of another one, thus reducing the number of equations to be solved. For example, by the
above conservation laws we can write
B(t) = B0 + —(A(t) ≠ A0 )/–
C(t) = C0 + “(A0 ≠ A(t))/–
D(t) = D0 + ”(A0 ≠ A(t))/–.
Hence, solving for A(t) is enough to determine the remaining variables. Substituting for B
into the differential equation for A, we get a first-order ODE
3 4—
dA — —
= ≠–kA– B0 ≠ A0 + A(t) . (3.2)
dt – –
Such first order equations can usually be solved by techniques such as separation of vari-
ables.
If two quantities are conserved, clearly their sum is also conserved. The same goes
also for any linear combination (as well as some nonlinear combinations). Therefore, con-
servation laws are not unique. the aim is not to find all conservation laws, but a set
of independent laws from which the others can be derived. There is a simple test for
determining if a set of conservation laws are independent:
Independence Test. A set of conservation laws are independent if each law contains a
species that does not appear in the other laws.

3.1.3 Steady states

Steady states (also called equilibrium states) are special solutions of a system that are
constant in time. To find them, we set the time derivatives of the variables to zero. For
example, in (3.2) the steady states are A = 0 and A = A0 ≠ –B0 /—.
CHAPTER 3. KINETICS 45

3.1.4 Examples
Example 3.1. A æ 2C
The rate of the reaction is r = kA. The kinetic equations are
dA
= ≠kA
dt
dC
= 2kA
dt
Since dt
d
(2A + C) = 0, a conservation law is given by 2A(t) + C(t) = 2A0 + C0 . Hence,
C(t) = 2A0 + C0 ≠ 2A(t). The steady states are found by setting the derivatives equal
to zero, which gives A = 0. From the conservation law, the corresponding value for C is
C = C0 + 2A0 . Hence, the reaction continues until A is exhausted and the amount of C
has increased by 2A0 .
Example 3.2.

A⌦C +D
A + B æ 2A + C

The first line represents a reversible reaction and is actually a shorthand for two reactions

AæC +D and C +D æA

We therefore have three reactions in total. Each reaction has its own reaction rate. For
the reversible reactions we represent the rates by r1 and r≠1 , and the last reaction’s rate
is denoted r2 . These rates are determined by the Law of Mass Action as

r1 = k1 A
r≠1 = k≠1 CD
r2 = k2 AB.

Next we write the kinetic equation for each species, adding the rates as per the Law of
Mass Action:
dA
= ≠r1 + r≠1 ≠ r2 + 2r2
dt
= ≠k1 A + k≠1 CD + k2 AB

Note that in the third reaction, species A is both a reactant and a product (such a reaction
is called an autocatalytic reaction since A is used to produce more of itself); therefore, the
rate in each direction is determined separately and added. The kinetic equations for the
other species are found similarly:
dB
= ≠k2 AB
dt
dC
= k1 A ≠ k≠1 CD + k2 AB
dt
dD
= k1 A ≠ k≠1 CD.
dt
CHAPTER 3. KINETICS 46

We can also derive the conservation laws

d
(A + 2B + C) = 0 =∆ A + 2B + C = A0 + 2B0 + C0
dt
d
(A + B + D) = 0 =∆ A + B + D = A0 + B0 + D0 .
dt
Consequently, the system can be reduced to two equations
dA
= ≠k1 A + k≠1 (– ≠ A ≠ 2B)(— ≠ A ≠ B) + k2 AB
dt
dB
= ≠k2 AB
dt
where – = A0 +2B0 +C0 and — = A0 +B0 +D0 . As for the steady states, from the equation
for B we have that either A = 0 or B = 0. If A = 0, then from the equation for A we find
that either C = 0 or D = 0. If C = 0, the conservation laws give B = B0 + 12 (A0 + C0 )
and D = D0 + 12 (A0 ≠ C0 ). Other cases can be calculated similarly.

3.2 General formulation

Consider m distinct species X1 , . . . , Xm involved in n reactions
m
ÿ m
ÿ
–ij Xi æ —ij Xi , j = 1, . . . , n. (3.3)
i=1 i=1

A species can appear in a reaction as a reactant or product or both, depending on whether

–ij and —ij is zero or not. The stoichiometric coefficients –ij , —ij are assumed to be non-
negative. Using the Law of Mass action, the jth reaction has reaction rate rj equal to
m
Ÿ
rj = kj
–ij
Xi
i=1

where kj is the rate constant. The kinetic equation for species Xi is

ÿn
d
Xi = (—ij ≠ –ij )rj .
dt j=1

Let X = (X1 , X2 , . . . , Xm )€ be the vector of concentrations and r = (r1 , r2 , . . . rn )€ be the

vector of reaction rates. Then the last equation can be written in matrix form as
d
X = Sr, (3.4)
dt
where S is the stoichiometric matrix with elements Sij = —ij ≠ –ij . Note that S an m ◊ n
matrix; its size is (#species)◊(#reactions).
Example 3.3. For the reactions

2X1 æ 4X2
X2 æ 3X1 + X3
CHAPTER 3. KINETICS 47

the stoichiometric matrix is Q R

≠2 3
c d
S = a 4 ≠1 b
0 1
and the rate vector is A B
k1 X12
r= .
k2 X2
Therefore, the kinetic equations are
Q R Q R
X ≠2 3 A B
d c 1d c 2
d k1 X1
aX2 b = a 4 ≠1 b .
dt k2 X2
X3 0 1
A conservation law for (3.3) has the form
d
(a1 X1 + a2 X2 + · · · + am Xm ) = 0 (3.5)
dt
for some constants aj to be determined. Hence,
a1 X1 (t) + a2 X2 (t) + · · · + am Xm (t) = a1 X10 + a2 X20 + · · · + am Xm0
where Xj0 is the initial concentration of Xj . We can also write this in vector form as
a€ X(t) = a€ X0
where a = (a1 , . . . , am )€ and X0 = (X10 , . . . , Xm0 )€ . Multiplying (3.4) on the left by a€ ,
we obtain
dX
a€ = a€ Sr.
dt
Since a is a constant vector,
dX d
a€ = (a€ X).
dt dt
Also, since a€ Sr is a scalar, it is equal to its transpose, that is,
a€ Sr = r€ S€ a.
So, the conservation law (3.5) corresponds to
d €
0= (a X) = r€ S€ a. (3.6)
dt
Therefore, any nonzero vector a that satisfies
S€ a = 0 (3.7)
yields a conservation law.
Let N (S€ ) denote the null space of S€ . If N (S€ ) contains only the zero vector, then
there are no conservation laws of the form (3.7). Otherwise, let {a1 , . . . , ak } be a basis for
N (S€ ). Then each basis vector produces a conservation law, which is independent of the
laws obtained from the laws obtained from the other basis vectors. Moreover, since the
{a1 , . . . , ak } is a basis, any conservation laws coming from (3.7) can be written in terms of
the laws coming from the basis vectors. We summarize in the next theorem.
CHAPTER 3. KINETICS 48

Theorem 3.1 (Null Space Theorem). The basis vectors of S€ correspond to independent
conservation laws of the system.
Example 3.4. Continuing the last example, equation (3.7) takes the form
Q R
A B a1 A B
≠2 4 0 c d 0
aa2 b = ,
3 ≠1 1 0
a3

which can be solved by any convenient way. For example, the first row implies a1 = 2a2 , and
using this in the second row gives a3 = ≠5a2 . Alternatively, we can form the augmented
matrix and do row reducing:
A B A B
≠2 4 0 0 1 ≠2 0 0
æ ,
3 ≠1 1 0 0 5 1 0

which again gives a1 = 2a2 and a3 = ≠5a2 . Hence, all vectors of the form (2a2 , a2 , ≠5a2 )€
are solutions. In other words, a1 = (2, 1, ≠5)€ is a basis for the null space. The corre-
sponding conservation law is

2X1 (t) + X2 (t) ≠ 5X3 (t) = 2X10 + X20 ≠ 5X30 .

Remark We should note that the criterion (3.7) derived from (3.6) is not completely
equivalent to (3.6). Indeed, while (3.7) implies (3.6), it is possible that (3.6) may be
satisfied without (3.7) being true. This means that there may be occasions where
there are more conservation laws than given by (3.7). As an example, consider the
system of reactions

A æ 3B
A æ 2C.

The rate vector is r = (k1 A, k2 A)€ = A(k1 , k2 )€ and the transpose of the stoichio-
metric matrix is A B
≠1 3 0
S =
€
.
≠1 0 2
Then
r€ S€ = A(≠k1 ≠ k2 , 3k1 , 2k2 ).
It can be seen that the vector a =(6, 2, 3)€ satisfies r€ S€ a = 0 as well as S€ a = 0,
so we could find it by solving (3.7). It corresponds to the conservation law 6A + 2B +
3C = const. Note that the null space N (S€ ) has dimension one (since S€ has rank
two), so this conservation law is all we could possibly find by solving (3.7). There is,
however, another independent conservation law, which is

3k1 A + (k1 + k2 )B = constant.

It corresponds to the vector ā = (3k1 , k1 + k2 , 0)€ , which depends on the rate con-
stants. Note that S€ ā ”= 0, so a is not in the null space of S€ . Nevertheless,
r€ S€ ā = 0, so it also corresponds to a conservation law.
CHAPTER 3. KINETICS 49

3.3 Stability
Consider the vector differential equation
dx
= f (x), (3.8)
dt
where x œ Rn and f : Rn æ Rn is a continuously differentiable function. For example,
the kinetic equations (3.4) are in this form since the rate vector is a function of the xi ’s.
A steady state (equilibrium) solution xs is a constant solution of (3.8), so it satisfies
the algebraic equation f (xs ) = 0. Hence, if the system starts from the initial condition
x(0) = xs , then x(t) = xs for all t > 0.
The concept of stability is about what happens to solutions starting from nearby initial
conditions. A steady state is said to be stable if all solutions starting from sufficiently near
initial conditions stay close to xs for all t > 0. A steady state is said to be asymptotically
stable if it is stable and in addition all solutions starting from sufficiently near near initial
conditions converge to xs . A steady state is said to be unstable if it is not stable. Roughly
speaking, in any neighborhood of an unstable equilibrium xs one can always find an initial
point such that the corresponding solution leaves the neighborhood of xs .
Since stability is about solutions close to the steady state, one can use perturbation
arguments to derive conditions for its stability and instability. Hence, suppose the initial
condition is
x(0) = xs + Áv
where v is some vector and Á is a small scalar. Expand the corresponding solution in a
power series
x(t) ≥ x0 (t) + Áx1 (t) + Á2 x2 (t) + · · ·
and substitute in (3.8). Then,

x0Õ + Áx1Õ + Á2 x2Õ + · · · = f (x0 + Áx1 + Á2 x2 + · · · )

= f (x0 ) + Df (x0 ) · (Áx1 + Á2 x2 + · · · ) + · · ·

where the last line is obtained by a Taylor series expansion of f around x0 . Recall that
Df denotes the Jacobian matrix of f , whose components are
ˆfi
[Df ]ij = .
ˆxj

The initial condition is expanded similarly:

x0 (0) + Áx1 (0) + Á2 x2 (0) + · · · = xs + Áv

The O(1) terms give

x0Õ = f (x0 ), x0 (0) = xs
whose solution in the steady state x0 = xs .
The O(Á) terms give
x1Õ = Df (x0 ) · x1 , x1 (0) = v
CHAPTER 3. KINETICS 50

This is a linear differential equation, so we seek exponential solutions of the form x1 (t) =
e⁄t v. (The appearance of v is due to the initial condition.) Substituting into the O(Á)
equation, we have
⁄e⁄t v = Df (x0 ) · e⁄t v
The exponential terms can be cancelled since they are never zero. Using the fact that
x0 = xs and defining the matrix A = Df (x0 ) = Df (xs ), we have

Av = ⁄v.

Therefore, the exponent ⁄ must be an eigenvalue of A = Df (x0 ) = Df (xs ). If the real

part of ⁄ is negative, then x1 (t) = e⁄t v æ 0, so the solution x(t) = xs + x1 (t) æ xs and
the steady state xs is asymptotically stable. On the other hand, if the real part of ⁄ is
positive, then x1 (t) = e⁄t v grows in magnitude and the solution x(t) = xs + x1 (t) moves
away from xs , so xs is unstable. We summarize the result in the next theorem.

Theorem 3.2. The steady state xs is asymptotically stable if all the eigenvalues of the
Jacobian matrix Df (xs ) have negative real parts, and it is unstable if at least one eigenvalue
of Df (xs ) has positive real part.

The problem of determining the stability of the steady state is thus reduced to finding
the eigenvalues of the Jacobian matrix evaluated at the steady state. In fact, the exact
values of the eigenvalues are not needed, we only need the signs of their real parts. For
one-dimensional systems, the criterion is simply whether the sign of the derivative f Õ (xs )
is negative or positive. For two dimensional systems, the Jacobian is a real 2 ◊ 2 matrix
so the two eigenvalues are either both real, or they are a complex conjugate pair. Recall
that the product of the eigenvalues of a matrix equals its determinant, and the sum of the
eigenvalues equals its trace (the sum of the diagonal elements). If both eigenvalues are real,
then the stability condition is that they should both be negative, which implies that their
sum is negative and their product is positive. On the other hand, if the two eigenvalues are
complex conjugate, then the stability condition is that the real parts should be negative,
which implies that their sum is negative and their product is positive (the product of a
complex conjugate pair cannot be negative since it equals the square of the magnitude of the
complex number). In both cases, we conclude the the steady state of a 2-dimensional system
is asymptotically stable if the Jacobian matrix has positive determinant and negative trace.

Example 3.5. xÕ = x3 ≠ 4x. Here, f (x) = x3 ≠ 4x = x(x2 ≠ 4), so the equilibrium points
(steady states) are x = 0, ±2. Furthermore, f Õ (x) = 3x2 ≠ 4, f Õ (±2) > 0 and f Õ (0) < 0.
Therefore, the points x = ±2 are unstable and x = 0 is asymptotically stable.

Example 3.6. The system

xÕ = x(2 ≠ x ≠ y)
yÕ = x ≠ y

has two equilibrium points: (0, 0) and (1, 1). The Jacobian matrix is
A B
2 ≠ 2x ≠ y ≠x
Df = .
1 ≠1
CHAPTER 3. KINETICS 51

For the equilibrium point at (0, 0):

A B
2 0
Df (0, 0) =
1 ≠1
which has eigenvalues 2 and ≠1. Therefore, (0, 0) is unstable. For the equilibrium at (1, 1) :
A B
≠1 ≠1
Df (1, 1) =
1 ≠1
which has eigenvalues ≠1 ± i. Therefore, (1, 1) is asymptotically stable. Since this is
a 2-dimensional system, the same conclusions can be obtained without calculating the
eigenvalues. Hence, since Df (0, 0) has positive trace (0, 0) must be unstable. Df (1, 1) has
negative trace and positive determinant, so (1, 1) is asymptotically stable.

3.4 Disease modeling

One of the earliest models of disease dynamics was given by Kermack and McKendrick in
1927. These compartmental models (called SIR and SIRS) can be derived using the law of
mass action. The “reactions” are
S + I æ 2I
IæR
RæS
The first line says that if a susceptible individual comes in contact with an infected indi-
vidual, (s)he is also infected. The second line says that infected individuals recover at a
certain rate. The last line is relevant if the immunity wears off after recovering from the
infection (SIRS model); it is absent in the SIR model.
The kinetic equations are
dS
= ≠k1 SI + k3 R
dt
dI
= k1 SI ≠ k2 I
dt
dR
= k2 I ≠ k3 R
dt
(In the SIR model the reaction constant k3 is zero since immunity is permanent and recov-
ered individuals do not get infected again.) In the following, we assume k3 > 0.
By adding the equations we arrive at the conservation law
d
(S + I + R) = 0.
dt
This merely says that the total population N = S + I + R is constant. Substituting
R = N ≠ S ≠ I into the first equation reduces the system to
dS
= ≠k1 SI + k3 (N ≠ S ≠ I)
dt
dI
= k1 SI ≠ k2 I
dt
CHAPTER 3. KINETICS 52

To find the steady states we set all derivatives to zero. The second equation implies
that either I = 0 or S = k2 /k1 . For I = 0, the first equation gives S = N since k3 ”= 0.
Hence (N, 0) is a steady state and corresponds to the absence of any infected individuals
(disease-free equilibrium). (By the conservation law, the value of R is also zero at this
equilibrium point.)
On the other hand, for S ú = k2 /k1 , the first equation gives

k3 (N ≠ k1 )
k2
Iú = ,
k1 + k3

which is positive if k3 > 0 and N > kk21 . In this case, (S ú , I ú ) is also a steady state, called the
endemic equilibrium. For a given population size N , the endemic equilibrium exists only
if k1 is sufficiently larger than k2 , that is, infection rate is sufficiently larger than recovery
rate. Note that in the SIR model (i.e., when k3 = 0) there is no endemic equilibrium state.
To determine the stability of the steady states (see Section ??) we calculate the Jacobian
matrix A B
≠k1 I ≠ k3 ≠k1 S ≠ k3
Df = .
k1 I k1 S ≠ k2
At the disease-free equilibrium,
A B
≠k3 ≠k1 N ≠ k3
Df (N, 0) =
0 k1 N ≠ k2

The eigenvalues are ≠k3 and k1 N ≠ k2 . So, the disease-free equilibrium is asymptotically
stable if k3 > 0 and N < k2 /k1 and unstable if N > k2 /k1 .
At the endemic equilibrium,
A B
≠k1 I ú ≠ k3 ≠k2 ≠ k3
Df (S , I ) =
ú ú
k1 I ú 0

The trace is ≠(k1 I ú + k3 ) < 0 and the determinant is = k1 I ú (k2 + k3 ) > 0 whenever
I > 0. Hence, the endemic equilibrium is stable when it exists (i.e., when I ú > 0).
ú

3.5 Michaelis-Menten enzyme kinetics

Many chemical and biological systems depend on enzymes to catalyze one or more of their
component reactions. The exact mechanisms are often not well-understood and may be
quite complicated. A simple description is given by the Michaelis-Menten model in 1913.
The assumption is that an enzyme (E) will bind to a substrate (S), forming a complex
(C). The enzyme within the complex will then either modify the substrate and release it
as a new species (P ), or else it will release the substrate unchanged:

S+E ⌦C
C æ P + E.
CHAPTER 3. KINETICS 53

The kinetic equations can be found by the Law of Mass Action:

dS
= ≠k1 SE + k≠1 C
dt
dE
= ≠k1 SE + k≠1 C + k2 C
dt
dC
= k1 SE ≠ k≠1 C ≠ k2 C
dt
dP
= k2 C
dt
Typical initial conditions are that we start with S and E (just substrate and enzyme), with
no C or P , that is,

S(0) = S0 , E(0) = E0 , C(0) = 0, P (0) = 0.

Conservation Laws: One can easily see the conservation laws

d
(E + C) = 0
dt
d
(S + C + P ) = 0.
dt
Thus, E + C = E0 and S + C + P = S0 . Substituting E = E0 ≠ C and P = S0 ≠ S ≠ C,
we reduce the system to two equations
dS
= ≠k1 E0 S + (k≠1 + k1 S)C (3.9)
dt
dC
= k1 E0 S ≠ (k2 + k≠1 + k1 S)C. (3.10)
dt
Steady states: To find the steady states, we set both derivatives to zero, which yields
C = S = 0. (To see this, add the right hand sides of the above two equations to find
≠k2 C = 0, which implies C = 0, then the first equation implies S = 0.)
Nondimensionalization: For the S variable, we use the initial condition to nondimen-
sionalize and define:
S(t)
s(t) = .
S0
We cannot do the same with C because the initial condition C0 is zero. Instead, we make
use of the conservation law E + C = E0 , which shows that C can vary from 0 up to E0 .
Hence, we define
C(t)
c(t) = .
E0
Substituting into (3.9)–(3.10) gives

ds
S0 = ≠k1 E0 S0 s + (k≠1 + k1 S0 s)E0 c
dt
dc
E0 = k1 E0 S0 s ≠ (k2 + k≠1 + k1 S0 s)E0 c.
dt
CHAPTER 3. KINETICS 54

Dividing both equations by k1 E0 S0 yields

1 ds (k≠1 + k1 S0 s)
= ≠s + c
k1 E0 dt k1 S0
1 dc (k2 + k≠1 + k1 S0 s)
=s≠ c.
k1 S0 dt k1 S0
To simplify the notation, we denote µ = k≠1 /(k1 S0 ) and Ÿ = (k2 + k≠1 )/(k1 S0 ) and write
1 ds
= ≠s + (µ + s)c
k1 E0 dt
1 dc
= s ≠ (Ÿ + s))c.
k1 S0 dt
Finally, we rescale time by defining · = k1 E0 t to obtain
ds
= ≠s + (µ + s)c (3.11)
d·
dc
Á = s ≠ (Ÿ + s)c (3.12)
dt
where
E0
Á= .
S0
Furthermore, the initial conditions are
s(0) = 1, c(0) = 0.
The physical problem tells us that Á is small, since a very small amount of enzyme
suffices to catalyze the reaction. Therefore, we have a singular perturbation problem,
which we will solve by perturbation methods.
Outer expansion. We expand the solution in asymptotic series as s(· ) ≥ s0 (· )+Ás1 (· )+
· · · and c(· ) ≥ c0 (· ) + Ác1 (· ) + · · · and substitute into (3.11)-(3.12). Then O(1) terms give
ds0
= ≠s0 + (µ + s0 )c0
d·
0 = s0 ≠ (Ÿ + s0 )c0 .
From the second equation we solve
s0 (· )
c0 (· ) = (3.13)
Ÿ + s0 (· )
and substitute into the first equation:
ds0 s0
= ≠s0 + (µ + s0 )
d· Ÿ + s0
≠Ÿs0 ≠ s20 + µs0 + s20
=
Ÿ + s0
s0
= (µ ≠ Ÿ)
Ÿ + s0
s0
= ≠⁄
Ÿ + s0
CHAPTER 3. KINETICS 55

where we have defined ⁄ = Ÿ ≠ µ. (Note that ⁄ = Ÿ ≠ µ = k2 /(k1 S0 ) > 0; hence the

reason for defining ⁄ with a minus sign.) We can solve the resulting differential equation
by separating variables and integrating:
⁄ ⁄
Ÿ + s0
ds0 = ≠⁄ d·
s0
which gives the implicit solution

Ÿ ln s0 + s0 = ≠⁄· + A (3.14)

for some integration constant A.

Inner expansion. Note that the outer solution (3.13) does not satisfy the initial condi-
tion c(0) = 0. Hence there must exist an initial layer near · = 0 where c sharply moves
from zero to the value given by (3.13). To see what happens for small values of · , we use
the scaling
·
·¯ = .
Á
We will designate the solutions in this region as s̄ and c̄. Equations (3.11)-(3.12) become
ds̄
= Á(≠s̄ + (µ + s̄)c̄)
d¯
·
dc̄
= s̄ ≠ (Ÿ + s̄)c̄
d¯
·
with initial conditions s̄(0) = 1, c̄(0) = 0. We expand the solutions in asymptotic series
· ) ≥ s̄0 (¯
s̄(¯ · )+Ás̄1 (¯
· )+· · · and c̄(¯
· ) ≥ c̄0 (¯
· )+Ác̄1 (¯
· )+· · · and substitute into the differential
equation. The O(1) terms give the system
ds̄
=0
d¯
·
dc̄
= s̄0 ≠ (Ÿ + s̄0 )c̄0
d¯
·
with s̄0 (0) = 1 and c̄(0) = 0. The first equation has the solution

s̄0 = 1

and substituting into the second one gives the linear equation
dc̄0
= 1 ≠ (Ÿ + 1)c̄0
d¯·
which has the solution
1
c̄0 (¯
·) = (1 ≠ e≠(Ÿ+1)¯· ).
Ÿ+1
Matching. The solution coming out of the initial layer must be the same as the solution
going into the initial layer. Thus, we have the requirements

lim s̄0 (¯
· ) = lim s0 (· )
·¯æŒ · æ0+

lim c̄0 (¯
· ) = lim c0 (· )
·¯æŒ · æ0+
CHAPTER 3. KINETICS 56

The first requirement gives A = 1. The second condition is already satisfied.

Composite solution. We add the inner and outer solutions and subtract their common
part. In other words,

s(· ) ≥ s0 (· ) + s̄0 (¯
· ) ≠ s0 (0)
c(· ) ≥ c0 (· ) + c̄0 (¯
· ) ≠ c0 (0).

Therefore, the composite asymptotic solution is

s(· ) ≥ s0 (· )
s0 (· ) 1 ≠(Ÿ+1)· /Á
c(· ) ≥ ≠ e
Ÿ + s0 (· ) Ÿ + 1

where s0 is found by solving

Ÿ ln s0 + s0 = ≠⁄· + 1.
Michaelis-Menten model is an example of a fast-slow system, where one variable (in this
case c) changes much faster compared to the other variable during part of its evolution.