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Background

HJF Systems
Reducible Systems
Stability of Chemical Reaction Networks
Matthew Douglas Johnston
University of Waterloo
October 26, 2008
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
2 HJF Systems
Reaction Graphs
Deciency Zero
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
2 HJF Systems
Reaction Graphs
Deciency Zero
3 Reducible Systems
Uncharacterized systems
Reducible Systems
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
2 HJF Systems
Reaction Graphs
Deciency Zero
3 Reducible Systems
Uncharacterized systems
Reducible Systems
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
Species/Reactants
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
Reactant Complex/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
Product Complex/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
Reaction Constant/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
/
Chemical kinetics is the study of the rates/dynamics resulting from
such reactions.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
In each elementary reaction, a set of reactants reacts at a given
rate to form a product, e.g.
2H
2
+ O
2
k
2H
2
O
/
Chemical kinetics is the study of the rates/dynamics resulting from
such reactions.
To build a mathematical model, we need to make physical
assumptions, e.g.
Uniform distribution (well-mixed);
Temperature and volume are constant;
Law of mass action applies.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
/
2
/
2
/
3
+/
4
/
3
+/
4
/
1
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
k
1
/
2
/
2
k
2
/
3
+/
4
/
3
+/
4
k
3
/
1
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
k
1
/
2
/
2
k
2
/
3
+/
4
/
3
+/
4
k
3
/
1
(
p

(i )
k
i
(
p
+
(i )
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
k
1
/
2
/
2
k
2
/
3
+/
4
/
3
+/
4
k
3
/
1
(
p

(i )
k
i
(
p
+
(i )
Complexes
/
1
/
2

/
3
+/
4
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
k
1
/
2
/
2
k
2
/
3
+/
4
/
3
+/
4
k
3
/
1
(
p

(i )
k
i
(
p
+
(i )
Complexes
/
1
k(1,2)
/
2
k(3,1)

k(2,3)
/
3
+/
4
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
There are two standard ways to index reaction systems: according
to reactions and according to complexes.
Reactions
/
1
k
1
/
2
/
2
k
2
/
3
+/
4
/
3
+/
4
k
3
/
1
(
p

(i )
k
i
(
p
+
(i )
Complexes
/
1
k(1,2)
/
2
k(3,1)

k(2,3)
/
3
+/
4
(
i
k(i ,j )
(
j
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
For the general system
(
p

(i )
k
i
(
p
+
(i )
, i = 1, . . . , r
we have the governing dierential equations
x =
r

i =1
k
i
(z
p
+
(i )
z
p

(i )
)x
z
p

(i )
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
For the general system
(
p

(i )
k
i
(
p
+
(i )
, i = 1, . . . , r
we have the governing dierential equations
x =
r

i =1
k
i
(z
p
+
(i )
z
p

(i )
)x
z
p

(i )
.
We have the following important components:
we sum over r reactions,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
For the general system
(
p

(i )
k
i
(
p
+
(i )
, i = 1, . . . , r
we have the governing dierential equations
x =
r

i =1
k
i
(z
p
+
(i )
z
p

(i )
)x
z
p

(i )
.
We have the following important components:
we sum over r reactions,
k
i
is the reaction rate,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
For the general system
(
p

(i )
k
i
(
p
+
(i )
, i = 1, . . . , r
we have the governing dierential equations
x =
r

i =1
k
i
(z
p
+
(i )
z
p

(i )
)x
z
p

(i )
.
We have the following important components:
we sum over r reactions,
k
i
is the reaction rate,
(z
p
+
(i )
z
p

(i )
) is the reaction vector,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
For the general system
(
p

(i )
k
i
(
p
+
(i )
, i = 1, . . . , r
we have the governing dierential equations
x =
r

i =1
k
i
(z
p
+
(i )
z
p

(i )
)x
z
p

(i )
.
We have the following important components:
we sum over r reactions,
k
i
is the reaction rate,
(z
p
+
(i )
z
p

(i )
) is the reaction vector, and
x
z
p

(i )
=

m
j =1
(x
j
)
z
p

(i )j
is the mass-action term.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
This has the governing dynamics
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
,
where x
1
and x
2
are the concentrations of /
1
and /
2
respectively.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
This has the governing dynamics
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
,
where x
1
and x
2
are the concentrations of /
1
and /
2
respectively.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
This has the governing dynamics
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
,
where x
1
and x
2
are the concentrations of /
1
and /
2
respectively.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
This has the governing dynamics
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
,
where x
1
and x
2
are the concentrations of /
1
and /
2
respectively.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
Consider the (reversible) system
/
1
k
1

k
2
2/
2
.
This has the governing dynamics
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
,
where x
1
and x
2
are the concentrations of /
1
and /
2
respectively.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
What kind of properties does this system have?
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
What kind of properties does this system have?
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
_
=
_
0
0
__
The (positive) equilibrium set is given by
E =
_
x R
2
+
[ x
2
=
_
k
1
k
2
x
1
_
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
What kind of properties does this system have?
_
x
1
x
2
_
= k
1
_
1
2
_
x
1
+ k
2
_
1
2
_
x
2
2
The (positive) equilibrium set is given by
E =
_
x R
2
+
[ x
2
=
_
k
1
k
2
x
1
_
.
For any k
1
, k
2
, x
1
, x
2
we have f(x) S where
S = span
__
1
2
__
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
x
1
x
2
E
(x
0
+S)
Figure: Previous system with k
1
= k
2
= 1.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
x
1
x
2
E
(x
0
+S)
Figure: Previous system with k
1
= k
2
= 1.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
x
1
x
2
E
(x
0
+S)
Figure: Previous system with k
1
= k
2
= 1.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
x
1
x
2
E
(x
0
+S)
Figure: Previous system with k
1
= k
2
= 1.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
The restriction of solutions is a general property:
Theorem
Solutions x(t) are restricted to compatibility classes such that
x(t) (S +x
0
) R
m
+
t 0.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
The restriction of solutions is a general property:
Theorem
Solutions x(t) are restricted to compatibility classes such that
x(t) (S +x
0
) R
m
+
t 0.
We are interested in the following sense of equilibria:
Denition
A mass action system is said to have locally stable dynamics if
there exists a unique positive equilibrium point within each
compatibility class which is asymptotically stable.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
2 HJF Systems
Reaction Graphs
Deciency Zero
3 Reducible Systems
Uncharacterized systems
Reducible Systems
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(
2
(
3
(
4
(
5
(
6
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(2,1)
(
2
(3,1)

(2,4)
(
3
(3,4)
(
4
(
5
(5,6)
(
6
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(2,1)
(
2
(3,1)

(2,4)
(
3
(3,4)
(
4
(
5
(5,6)
(
6
Denition
Connected components of
a reaction graph are called
linkage classes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(2,1)
(
2
(3,1)

(2,4)
(
3
(3,4)
(
4
(
5
(5,6)
(
6
Denition
Connected components of
a reaction graph are called
linkage classes.
This example has two linkage classes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(2,1)
(
2
(3,1)

(2,4)
(
3
(3,4)
(
4
(
5
(5,6)
(
6
Denition
Connected components of
a reaction graph are called
linkage classes.
This example has two linkage classes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
The reaction graph can be considered as a directed graph with
complexes as nodes and reactions as directed connections between
nodes.
For example:
(
1
(2,1)
(
2
(3,1)

(2,4)
(
3
(3,4)
(
4
(
5
(5,6)
(
6
Denition
Connected components of
a reaction graph are called
linkage classes.
This example has two linkage classes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
We will need the following graph theoretical concepts:
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
We will need the following graph theoretical concepts:
Denition
A chemical reaction network is weakly reversible if given a
directed path from (
i
to (
j
, there is a directed path from (
j
to (
i
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
We will need the following graph theoretical concepts:
Denition
A chemical reaction network is weakly reversible if given a
directed path from (
i
to (
j
, there is a directed path from (
j
to (
i
.
Denition
The deciency of a system, , is given by
= n s
where n is the number of complexes, s is the dimension of the
stoichiometric space, and is the number of linkage classes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency:
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5, = 2,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5, = 2,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5, = 2,
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5, = 2, and s = 3.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
The system is weakly reversible.
Compute the deciency: n = 5, = 2, and s = 3.
So = n s = 0, i.e. this is a zero deciency system.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
In 1972, Horn, Jackson and Feinberg presented a result relating the
reaction graph and the stability of mass action systems [1, 2, 3].
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
In 1972, Horn, Jackson and Feinberg presented a result relating the
reaction graph and the stability of mass action systems [1, 2, 3].
Theorem (Zero Deciency Theorem)
If a mass-action system is weakly reversible and has a deciency of
zero then it exhibits locally stable dynamics for all possible rate
constants.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
In 1972, Horn, Jackson and Feinberg presented a result relating the
reaction graph and the stability of mass action systems [1, 2, 3].
Theorem (Zero Deciency Theorem)
If a mass-action system is weakly reversible and has a deciency of
zero then it exhibits locally stable dynamics for all possible rate
constants.
The proof uses the following Lyapunov function:
L(x) =
m

i =1
x
i
(ln x
i
ln x

i
1) + x

i
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
Without even writing down the governing DEs, we know this has
locally stable dynamics!
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Reaction Graphs
Deciency Zero
Example
/
1
k
1

k
2
2/
2
3/
1
k
3
/
3
k
4

k
5
/
1
+ 2/
2
Without even writing down the governing DEs, we know this has
locally stable dynamics!
This result about the dynamics of the system depends solely on
properties of the graph of the system!
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
1 Background
Chemical Reactions
Chemical Reaction Models
Stoichiometric Compatibility Classes
2 HJF Systems
Reaction Graphs
Deciency Zero
3 Reducible Systems
Uncharacterized systems
Reducible Systems
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Are there locally stable systems lying outside of the scope of HJF
systems?
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Are there locally stable systems lying outside of the scope of HJF
systems?
Example
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Are there locally stable systems lying outside of the scope of HJF
systems?
Example
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
x
0
+S
E
x
1
x
2
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Are there locally stable systems lying outside of the scope of HJF
systems?
Example
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
x
0
+S
E
x
1
x
2
Despite this, even the Lyapunov function considered by HJF used
directly fails to prove stability.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We need to consider an alternative approach if we are to prove the
stability of this system.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We need to consider an alternative approach if we are to prove the
stability of this system.
Consider the modied Lyapunov function

L(x) =
m

i =1
c
i
[x
i
(ln x
i
ln x

i
1) + x

i
]
where the c
i
are positive constants.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We need to consider an alternative approach if we are to prove the
stability of this system.
Consider the modied Lyapunov function

L(x) =
m

i =1
c
i
[x
i
(ln x
i
ln x

i
1) + x

i
]
where the c
i
are positive constants.
If we choose c
1
= 2 and c
2
= 1 then
d
dt

L(x) =

L(x) f(x) < 0


for x ,= x

in the compatibility class = asymptotic stability!


Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Using the modied Lyapunov function

L(x) expands the scope of
systems with locally stable dynamics!
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Using the modied Lyapunov function

L(x) expands the scope of
systems with locally stable dynamics!
Can we nd a general class of systems for which the Lyapunov
function

L(x) works?
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Using the modied Lyapunov function

L(x) expands the scope of
systems with locally stable dynamics!
Can we nd a general class of systems for which the Lyapunov
function

L(x) works? ... YES, we can!
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Using the modied Lyapunov function

L(x) expands the scope of
systems with locally stable dynamics!
Can we nd a general class of systems for which the Lyapunov
function

L(x) works? ... YES, we can!
We have called our class of systems reducible systems since it
amounts to reducing complex systems to HJF systems.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Using the modied Lyapunov function

L(x) expands the scope of
systems with locally stable dynamics!
Can we nd a general class of systems for which the Lyapunov
function

L(x) works? ... YES, we can!
We have called our class of systems reducible systems since it
amounts to reducing complex systems to HJF systems.
Former UW graduate student Debbie MacLean also considered
these problems.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Suppose there are b
i
> 0 and c
j
> 0, i = 1, . . . , r , j = 1, . . . , m,
such that for every reactant complex (
l
there is a reaction (and
vice-versa) such that
b
i
c
j
2
(z
j
p
+
(i )
z
j
p

(i )
) = (z
j
l
z
j
p

(i )
), for all i , j .
/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Suppose there are b
i
> 0 and c
j
> 0, i = 1, . . . , r , j = 1, . . . , m,
such that for every reactant complex (
l
there is a reaction (and
vice-versa) such that
b
i
c
j
2
(z
j
p
+
(i )
z
j
p

(i )
) = (z
j
l
z
j
p

(i )
), for all i , j .
/
This equation relates the graph of the original system to a target
system with similar dynamics.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Suppose there are b
i
> 0 and c
j
> 0, i = 1, . . . , r , j = 1, . . . , m,
such that for every reactant complex (
l
there is a reaction (and
vice-versa) such that
b
i
c
j
2
(z
j
p
+
(i )
z
j
p

(i )
) = (z
j
l
z
j
p

(i )
), for all i , j .
/ Original system
This equation relates the graph of the original system to a target
system with similar dynamics.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Suppose there are b
i
> 0 and c
j
> 0, i = 1, . . . , r , j = 1, . . . , m,
such that for every reactant complex (
l
there is a reaction (and
vice-versa) such that
b
i
c
j
2
(z
j
p
+
(i )
z
j
p

(i )
) = (z
j
l
z
j
p

(i )
), for all i , j .
/ Target system
This equation relates the graph of the original system to a target
system with similar dynamics.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Suppose there are b
i
> 0 and c
j
> 0, i = 1, . . . , r , j = 1, . . . , m,
such that for every reactant complex (
l
there is a reaction (and
vice-versa) such that
b
i
c
j
2
(z
j
p
+
(i )
z
j
p

(i )
) = (z
j
l
z
j
p

(i )
), for all i , j .
/
This equation relates the graph of the original system to a target
system with similar dynamics.
The target graph has no purely product complexes - the graph has
been reduced.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Original system and target system have the same dynamics
under the transformation
y(t) = Tx(t)
where T =diagc
1
, . . . , c
m
.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Original system and target system have the same dynamics
under the transformation
y(t) = Tx(t)
where T =diagc
1
, . . . , c
m
.
If the target system is weakly reversible and has zero deciency,
the system is said to be reducible and has locally stable
dynamics for all sets of rate constants.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Original system and target system have the same dynamics
under the transformation
y(t) = Tx(t)
where T =diagc
1
, . . . , c
m
.
If the target system is weakly reversible and has zero deciency,
the system is said to be reducible and has locally stable
dynamics for all sets of rate constants.
Lyapunov function used is

L(x) =
m

i =1
c
i
[x
i
(ln x
i
ln x

i
1) + x

i
]
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
We need to pair
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
We need to pair reactant complexes
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
We need to pair reactant complexes and reactions
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
We need to pair reactant complexes and reactions such that every
reaction occurs between reactant complexes.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Consider our previous system:
Original System
2/
1
+/
2
k
1
/
1
+ 3/
2
/
1
+ 2/
2
k
2
2/
1
Target System
2/
1
+/
2

k
1

k
2
/
1
+ 2/
2
.
We need to pair reactant complexes and reactions such that every
reaction occurs between reactant complexes.
In fact, this is the only possible target graph.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We still need to check the algebraic conditions, i.e. nd
b
1
, b
2
, c
1
, c
2
> 0 such that
b
1
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
b
2
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
.
/
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We still need to check the algebraic conditions, i.e. nd
b
1
, b
2
, c
1
, c
2
> 0 such that
b
1
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
b
2
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
.
/ Original System
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We still need to check the algebraic conditions, i.e. nd
b
1
, b
2
, c
1
, c
2
> 0 such that
b
1
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
b
2
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
.
/ Target System
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
We still need to check the algebraic conditions, i.e. nd
b
1
, b
2
, c
1
, c
2
> 0 such that
b
1
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
b
2
2
_
c
1
0
0 c
2
_ _
1
2
_
=
_
1
1
_
.
/
Can be found by inspection:
b
1
= 1, b
2
= 1, c
1
= 2, c
2
= 1.
The system exhibits locally stable dynamics!
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
There is still much work to be done in this area:
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
There is still much work to be done in this area:
Determining whether large-scale systems are reducible is
computationally cumbersome.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
There is still much work to be done in this area:
Determining whether large-scale systems are reducible is
computationally cumbersome.
Some systems have more than one valid target system.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
There is still much work to be done in this area:
Determining whether large-scale systems are reducible is
computationally cumbersome.
Some systems have more than one valid target system.
There remain systems with locally stable dynamics which are
not reducible.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
Acknowledgements
Thanks everybody for coming out.
I would like to thank my advisor, David Siegel, and the members of
my advisor committee.
This work was made possible by NSERC.
Matthew Douglas Johnston Stability of Chemical Reaction Networks
Background
HJF Systems
Reducible Systems
Uncharacterized systems
Reducible Systems
M. Feinberg. Complex balancing in general kinetic systems.
Archive For Rational Mechanics and Analysis, 49:187-194,
1972.
F. Horn. Necessary and sucient conditions for complex
balancing in chemical kinetics. Archive for Rational Mechanics
and Analysis, 49:172-186, 1972.
F. Horn and R. Jackson. General mass action kinetics. Archive
for Rational Mechanics and Analysis, 47:187-194, 1972.
Matthew Douglas Johnston Stability of Chemical Reaction Networks

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