HOMOGENEOUS

REACTION

MK. Rekayasa Biokimia

Smt. Genap 2013/2014

The heart of a typical bioprocess is

the reactor or fermenter

Basic reaction theory:

Reaction thermodynamic how far the

reaction can proceed
Reaction kinetics the rate of reactions

Reaction thermodynamics
Reversible reaction

Closed system
thermodynamics equilibrium is
reached

Reaction thermodynamics
Equilibrium constant, K

[A], [B], [R], [S], ... = equilibrium

concentrations

Reaction thermodynamics
The value of K depends on temperature

Gorxn = the change in standard free energy

per mole
R = universal gas constant
T = absolute temperature

Reaction thermodynamics
standard condition = 1 atm ; 25oC

thermodynamic properties
(other standard condition for biochemical
reactions)

Reaction thermodynamics
Gorxn is equal to the difference in standard
free energy of formation, between
products and reactants

Reaction thermodynamics
G is related to enthalpy, entropy and
absolute T

Exothermic reaction (
K
Endothermic reaction (

negative), T
negative), T

Reaction yield
Yield is the amount of product formed or
accumulated
per amount of reactant provided or
consumed

Reaction rate
-

The reaction rate constant

The reaction order
Elementary reaction
Nonelementary reaction

Reaction rate
Irreversible reaction:
aA + bB yY + zZ
RA = rate of reaction with respect to A
In a closed system:

Reaction rate
In bioprocess engineering, there are three
distinct ways of expressing reaction rate:
Total rate

Volumetric rate

(V =
constant)

Reaction rate

Specific rate, rA, the rate of conversion per

quantity of enzyme (E) or cells (X) involved in the
reaction

Units of rA = s-1 (cell-catalysed reaction)

= kg (unit enzyme)-1 s-1 (enzymecatalysed reaction)
1 unit of enzyme = amount of enzyme which
catalyses conversion of 1 mol substrate per
minute at the optimal condition.

Reaction rate
Alternative expression for spesific reaction
rate:
(volume of the reaction mixture =
constant)

x = cell concentration
e = enzyme concentration

Reaction kinetics
The relationship between rate of reaction
and reactant concentration and
temperature

k = rate constant, dependent of

temperature (Arrhenius)
Order of the overall reaction = (a+b)

Effect of T on Reaction rate

Arrhenius equation:

Plot of the ln k versus 1/T gives a straight

line with slope E/R.

Elementary Reaction

The Half-life

For a first order reaction, the half-life t 1/2 is

calculated as follows.
t1/ 2

0.693
k

For the second order reaction:

[A] at t = t = [A]0
1
1
=
+ kt1/ 2
[A ]0 /2 [A ]o
or t1/ 2 =

1
k[ A ]0

A Pseudo-first Order
Reaction

Example hydration of methyl iodide

CH3I(aq) + H2O(l) CH3OH(aq) + H+(aq) + I-(aq)

Rate = k [CH3I] [H2O]

Since we carry out the reaction in

aqueous solution
[H2O] >>>> [CH3I] [H2O] doesnt change
by a lot

Pseudo-first Order (contd)

Since the concentration of H2O is

essentially constant
Rate = k [CH3I] [constant]
= k`[CH3I] where k` = k [H2O]

The reaction is pseudo first order since it

appears to be first order, but it is
actually a second order process.

The Steady-State
Approximation

Examine the following simple reaction

mechanism
k1

k2

A BP
k 1

Rate v p k 2 B
Rate of product formation, vp,is proportional to the
concentration of an intermediate.

What Is an Intermediate?

B is an intermediate in the above

reqction sequence.

A species formed in one elementary step

of a reaction mechanism and consumed
in one or more later steps.

Intermediates generally small,

indeterminate concentrations.

Applying the Steady State Approximation

(SSA)

Look for the intermediate in the

mechanism.

Step 1 B is produced.
Reverse of Step 1 B is consumed.
Step 2 B is consumed.

d B
k1 A k 1 B k 2 B
dt

The SSA (Contd)

The SSA applied to the intermediate B.

d B
0
dt
k1 A k 1 B k 2 B
k1 A
B
k 1 k 2

SSA The Final Step

Substitute the expression for the

concentration of B into the rate law vp.

d P
k 2 B
dt
d P
k 2 k1
A

dt
k 1 k 2

SSA - Reaction Mechanisms

More examples in using the steady-state approximation
Account for the rate law for the decomposition of N2O5
2 N 2O5 ( g ) 4 NO2 ( g ) O2 ( g )
on the basis of the following mechanism:
k

N 2O5 a NO2 NO3

k a'

NO2 NO3 N 2O5

k

NO2 NO3 b NO2 O2 NO

k

NO N 2O5 c 3NO2

First identify the intermediates

NO and NO3

r k[ N 2O5 ]

SSA - Reaction Mechanisms

k

N 2O5 a NO2 NO3

k a'

NO2 NO3 N 2O5

k

NO2 NO3 b NO2 O2 NO

k

NO N 2O5 c 3NO2
d [ NO]
kb [ NO2 ][ NO3 ] kc [ NO][ N 2O5 ]
dt
d [ NO3 ]
k a [ N 2O5 ] k a' [ NO2 ][ NO3 ] kb [ NO2 ][ NO3 ]
dt
d [ N 2O5 ]
k a [ N 2O5 ] k a' [ NO2 ][ NO3 ] kc [ NO][ N 2O5 ]
31
dt

SSA - Reaction Mechanisms

According to the steady-state approximation, set both rates equal
to zero
d [ NO3 ]
d [ NO]
dt

dt

kb [ NO2 ][ NO3 ] kc [ NO][ N 2O5 ] 0

k a [ N 2O5 ] k a' [ NO2 ][ NO3 ] kb [ NO2 ][ NO3 ] 0

k [ NO][ N 2O5 ]
[ NO3 ] c
kb
[ NO2 ]
kc [ NO][ N 2O5 ]
ka
[ N 2O5 ]
[ NO3 ]
kb
[ NO2 ]
(k a' kb ) [ NO2 ]
k
k a kb
[ N 2O5 ]
ka
[ N 2O5 ]
[ NO3 ] c

kb kc (k a' kb ) [ NO2 ] (k a' kb ) [ NO2 ]

[ NO]

k a kb

kc (k a' kb )

SSA - Reaction Mechanisms

[ NO]

k a kb

kc (k a' kb )

k
k a kb
[ N 2O5 ]
ka
[ N 2O5 ]
[ NO3 ] c

kb kc (k a' kb ) [ NO2 ] (k a' kb ) [ NO2 ]

The net rate of change of concentration of N2O5 is

d [ N 2O5 ]
k a [ N 2O5 ] k a' [ NO2 ][ NO3 ] kc [ NO][ N 2O5 ]
dt

d [ N 2O5 ]
ka
[ N 2O5 ]
k a kb
k a [ N 2O5 ] k a' [ NO2 ]
kc
[ N 2O5 ]
'
'
dt
(k a kb ) [ NO2 ]
k c ( k a kb )

d [ N 2O5 ] k a k a' k a kb k a k a'

k a kb

[
N
O
]

[ N 2O5 ]

2 5
'
'
dt

( k a kb )
( k a kb )

SSA - Reaction Mechanisms

d [ N 2O5 ]
2k k
a b [ N 2O5 ]
dt
k a' kb

because

[ N 2O5 ] 2
r

k a kb

k a'

kb

[ N 2O5 ] k[ N 2O5 ]

It follows that the reaction rate is

r k[ N 2O5 ]

where

k a kb

k a' kb

SSA - Reaction Mechanisms

1.

ka

A B C P
'
ka

2.

3.

kb

d [ P]
k[ A][ B ]
dt