Chapter 3-Internal Mass Transfer Resistance

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Internal Mass-Transfer Resistance

In order to derive an equation that shows how the mass-transfer


resistance affects the effectiveness of an immobilized enzyme, let’s make
a series of assumptions as follows:
1. The reaction occurs at every position within the immobilized enzyme,
and the kinetics of the reaction are of the same form as observed for
free enzyme.
2. Mass transfer through the immobilized enzyme occurs via molecular
diffusion.
3. There is no mass-transfer limitation at the outside surface of the
immobilized enzyme.
4. The immobilized enzyme is spherical.
The model developed by these assumptions is known as the distributed
model.
Internal Mass-Transfer Resistance

First we derive a differential equation which describes the relationship


between the substrate concentration and the radial distance in an
immobilized enzyme. The material balance for the spherical shell with
thickness dr as shown in Figure 3.3 is
Internal Mass-Transfer Resistance

For a steady-state condition:


dCS/dt = 0
Where: dCS/dt is the change of substrate concentration
After opening up the brackets and simplifying by eliminating all terms
containing dr2 or dr3, we obtain the second order differential equation:

Eq. (3.11) can be solved by substituting a suitable expression for rS. Let’s
solve the equation first for the simple cases of zero-order and first-
order reactions, and for the Michaelis-Menten equation.
Internal Mass-Transfer Resistance

Zero-order Kinetics: Let’s assume that the rate of substrate consumption


is constant (zero order) with respect to substrate concentration as

This is a good approximation when KM << CS for Michaelis-Menten


kinetics, in which case k0 = rmax.
By substituting Eq. (3.12) into Eq. (3.11), we obtain

The boundary conditions for the solution of the preceding equation are
Internal Mass-Transfer Resistance

Eq. (3.13) becomes


Internal Mass-Transfer Resistance

Therefore, the solution of Eq. (3.13) is

Eq. (3.20) is only valid when CS > 0. The critical radius, below which CS is
zero, can be obtained by solving

The actual reaction rate according to the distribution model with zero
order is (4/3) π (R3 RC3)k0. The rate without the diffusion limitation is
(4/3) π R3k0. Therefore, the effectiveness factor, the ratio of the actual
reaction rate to the rate if not slowed down by diffusion, is
Internal Mass-Transfer Resistance

First-order Kinetics: If the rate of substrate consumption is a first-


order reaction with respect to the substrate concentration,

By substituting Eq. (3.23) into Eq. (3.11) and converting it to


dimensionless form, we obtain

where
Internal Mass-Transfer Resistance

and φ is known as Thiele’s modulus, which is a measure of the reaction


rate relative to the diffusion rate.
Eq. (3.24) together with the boundary conditions

determines the function C’S(r’).


In order to convert Eq. (3. 24) to a form which can be easily solved, we set
so that the differential equation becomes
Internal Mass-Transfer Resistance

Now the general solution of this differential equation is

Since xS must be bounded as approaches zero according to the first


boundary condition, we must choose C1 = 0. The second boundary
condition requires that C2 = 1/sinh3 φ , leaving

which shows how the substrate concentration changes as a function of


the radial distance in an immobilized enzyme.

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