Law of Mass Action

Law of Mass Action and Oscillation in Nature.
Elio Espejo
School of mathematical sciences UNNC
Elio Espejo (Institute) LMA and Oscillations 1 / 59

What is the Law of mass action?
We consider a very simple irreversible reaction, where two reactants, A and

B, are put together and react to a product C :
k
A + B ! C,
k is the so-called reaction rate.
The law of mass action (LMA) states that the rate of molecular
collisions of two chemical species in a dilute gas or solution is proportional
to the product of the two concentrations.
By convention, the rate constants k, in the reaction diagram are the

proportionality constants.

Examples
Let us denote de concentration of the reactants A and B by a and b

respectively. Thus, the LMA gives
dc
= kab.
dt
Similarly
da
= kab
dt
db
= kab
dt

Reversible reaction
The next step includes a reversible reaction

k+
A+B C
k
with reactions rates κ + and κ . We assume that the split-up of C is

proportional to the present c. The corresponding ODE system is
dc
= k+ ab k 1c
dt
da
= k c k+ ab
dt
db
= k c k+ ab
dt

Background
De…nition 1.Catalysis is the process of increasing the rate of a chemical
reaction by adding a substance known as a catalyst. Catalysts are not
consumed in the catalyzed reaction but can act repeatedly. Often only
very small amounts of catalyst are required.
De…nition 2. An enzyme is a protein that acts as a catalyst in living

organisms, regulating the rate at which chemical reactions proceed without
itself being altered in the process. The molecules upon which enzymes
may act are called substrates, and the enzyme converts the substrates into
di¤erent molecules known as products.
Remark: Some enzymes are used commercially, for example, in the

synthesis of antibiotics. Some household products use enzymes to speed
up chemical reactions: enzymes in biological washing powders break down
protein, starch or fat stains on clothes, and enzymes in meat tenderizer
break down proteins into smaller molecules, making the meat easier to
chew.
Background
In opposite to the kinetics of chemical reactions, in enzyme kinetics there

is a phenomenon of saturation. Even for very high concentrations of the
substrate, the metabolic rate cannot be increase unlimitedly, there is a
maximum value vmax .

Background
The basic enzyme reaction
One of the most basic enzymatic reactions, …rst proposed by Michaelis and
Menten (1913), involves a substrate S reacting with an enzyme E to form
a complex SE with in turn is converted into a product P and the enzyme.
We represent this schematically by
k1 k
S +E SE !2 E + P.
k 1
Here k1 , k 1 and k2 are constant parameter associated with the rates of

reaction. The symbol indicates that the reaction is reversible while the
single arrow ! indicates that the reaction can go only one way.

Background
We denote the concentration of the reactants by lowercase letters
s = [S ] , e = [E ], c = [SE ], p = [P ]
where [ ] denotes concentration. Then the Law of Mass Action leads to

one equation for each reactant
ds
= k1 es + k 1 c,
dt
de
= k1 es + (k 1 + k2 )c
dt
dc
= k1 es (k 1 + k2 )c,
dt
dp
= k2 c.
dt

Background
To complete the mathematical formulation we require initial conditions

which we take here as those at the start of the process which converts S
to P, so
S (0) = s0 , e (0) = e0 , c (0) = 0, p (0) = 0.

Simpli…cation
In the Michaelis Menten mechanism the enzyme E is a catalyst, which only

facilitates the reaction, so its total concentration, free plus combined, is a
constant. This conservation law for the enzyme also comes immediately
from the system of ODEs on adding the 2nd and 3rd equations, those for
the free e and combined c enzyme concentrations, to get
de dc
+ = 0 ) e ( t ) + c ( t ) = e0 .
dt dt

Simpli…cation
Taking into account that the equation for p is decoupled from the other
equations and the conservation law e + c = e0 , we reduce the system of
for ODEs to only two, for s and c, namely,
ds
= k1 (e0 c )s + k 1 c,
dt
dc
= k1 (e0 c )s (k 1 + k2 )c,
dt
or equivalently,
ds
= k1 e0 s + (k1 s + k 1 )c,
dt
dc
= k1 e0 s (k1 s + k 1 + k2 )c,
dt
with initial conditions
s (0) = s0 and c (0) = 0

Simpli…cation
The usual approach to these equations is to assume that the initial stage
of the complex c, formation is very fast after which is essentially at
equilibrium, that is, dc/dt 0 in which case from the equation of c, we
get c in terms of s,
e0 s ( t ) k 1+ k2
c (t ) = , Km =
s ( t ) + Km k1
which substituting into the equation of s gives
ds e0 s
= k1 e0 s + (k1 s + k 1 )c = k1 e0 s + (k1 s + k 1)
dt s + Km
k1 e0 s 2
Km k1 e0 s + k1 e0 s 2 + k 1 e0 s
=
s + Km
k 1 Km k1 k 1 k 1k+ 1
k2
k1 s
= e0 s = e0 s = k2 e0 ,
s + Km s + Km s + Km
where Km is called the Michaelis constant.
Michaelis Menten kinetics
dp
We also get from dt = k2 c,
dp s (t )
= k2 e0 .
dt s ( t ) + Km
Let us put vmax := k2 e0 . Then we conclude that the rate of product

formation v is given by
dp s
v= = vmax . (1)
dt s + Km
=reaction rate
Equation (1) is called the "Michaelis-Menten equation". It gives the

relation between the rate formation of the product P and the concentration
of a substrate. The constant vmax represents the maximum rate achieved
by the system, happening at saturating substrate concentration.

Positive cooperativity
Often enough, enzymes possess more than one binding site. Di¤erent
binding sites may interact: if one site is occupied, the conformation of the
enzyme changes and therewith also the a¢ nity of the enzyme.











Oscillations
A technique to …nd trapping regions

Oscillations

Oscillations

Oscillations

Oscillations

Oscillations

Oscillations

Oscillations
An important remark

Oscillations
Finding periodic solutions

Oscillations

Oscillations

Oscillations
This de…nes a curve in (a, b ) space, as shown in the next …gure
For parameters in the region corresponding to τ > 0, we are guaranteed

that the system has a closed orbit.
Oscillations in nature
Equilibrium in nature


Hormones oscillate, and ecosystem populations oscillate. There are also

thermodynamic oscillations, and oscillations in economic markets.


BZ Computers
The BZ reaction is the basis to design chemical computers, also called a

reaction-di¤usion computers, or Belousov–Zhabotinsky (BZ) computers. It
is an unconventional computer based on a semi-solid chemical "soup"
where data are represented by varying concentrations of chemicals. The
computations are performed by naturally occurring chemical reactions.
In 2020, University of Glasgow researchers created a chemical computer

using 3D-printed parts and magnetic stirrers in order to control the
oscillations of BZ medium.

Mathematical model
The original Belousov-Zhabotinskii reaction (short: BZR) was considered

in detail by R.M. Noyes, R.J. Fields and E. Körös at the University of
Oregon (in the early 1970s), creating a system of 18 reactions and 21
distinct chemical species (and a correspondingly large ODE system).

The Oregonator

The Oregonator

The Oregonator

The Oregonator

The Oregonator

The Oregonator

The Oregonator

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

The Lengyel model

Law of Mass Action

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Law of Mass Action and Oscillation in Nature.

School of mathematical sciences UNNC

Elio Espejo (Institute) LMA and Oscillations 1 / 59

We consider a very simple irreversible reaction, where two reactants, A and

k is the so-called reaction rate.

By convention, the rate constants k, in the reaction diagram are the

Elio Espejo (Institute) LMA and Oscillations 2 / 59

Let us denote de concentration of the reactants A and B by a and b

Elio Espejo (Institute) LMA and Oscillations 3 / 59

The next step includes a reversible reaction

with reactions rates κ + and κ . We assume that the split-up of C is

Elio Espejo (Institute) LMA and Oscillations 4 / 59

De…nition 2. An enzyme is a protein that acts as a catalyst in living

Remark: Some enzymes are used commercially, for example, in the

In opposite to the kinetics of chemical reactions, in enzyme kinetics there

Elio Espejo (Institute) LMA and Oscillations 6 / 59

Here k1 , k 1 and k2 are constant parameter associated with the rates of

Elio Espejo (Institute) LMA and Oscillations 7 / 59

We denote the concentration of the reactants by lowercase letters

where [ ] denotes concentration. Then the Law of Mass Action leads to

Elio Espejo (Institute) LMA and Oscillations 8 / 59

To complete the mathematical formulation we require initial conditions

Elio Espejo (Institute) LMA and Oscillations 9 / 59

In the Michaelis Menten mechanism the enzyme E is a catalyst, which only

Elio Espejo (Institute) LMA and Oscillations 10 / 59

s (0) = s0 and c (0) = 0

Let us put vmax := k2 e0 . Then we conclude that the rate of product

Equation (1) is called the "Michaelis-Menten equation". It gives the

Elio Espejo (Institute) LMA and Oscillations 13 / 59

Elio Espejo (Institute) LMA and Oscillations 14 / 59

Elio Espejo (Institute) LMA and Oscillations 15 / 59

Elio Espejo (Institute) LMA and Oscillations 16 / 59

Elio Espejo (Institute) LMA and Oscillations 17 / 59

Elio Espejo (Institute) LMA and Oscillations 18 / 59

Elio Espejo (Institute) LMA and Oscillations 19 / 59

Elio Espejo (Institute) LMA and Oscillations 20 / 59

Elio Espejo (Institute) LMA and Oscillations 21 / 59

Elio Espejo (Institute) LMA and Oscillations 22 / 59

Elio Espejo (Institute) LMA and Oscillations 23 / 59

Elio Espejo (Institute) LMA and Oscillations 24 / 59

Elio Espejo (Institute) LMA and Oscillations 25 / 59

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Elio Espejo (Institute) LMA and Oscillations 33 / 59

Elio Espejo (Institute) LMA and Oscillations 34 / 59

Elio Espejo (Institute) LMA and Oscillations 35 / 59

This de…nes a curve in (a, b ) space, as shown in the next …gure

For parameters in the region corresponding to τ > 0, we are guaranteed

Elio Espejo (Institute) LMA and Oscillations 37 / 59

Elio Espejo (Institute) LMA and Oscillations 38 / 59

Hormones oscillate, and ecosystem populations oscillate. There are also

Elio Espejo (Institute) LMA and Oscillations 39 / 59

Elio Espejo (Institute) LMA and Oscillations 40 / 59

The BZ reaction is the basis to design chemical computers, also called a

In 2020, University of Glasgow researchers created a chemical computer

Elio Espejo (Institute) LMA and Oscillations 41 / 59

The original Belousov-Zhabotinskii reaction (short: BZR) was considered

Elio Espejo (Institute) LMA and Oscillations 42 / 59