Effect of Mass Transfer Resistance

Enzymes
- are MACROMOLECULAR BIOLOGICAL CATALYST. The molecules upon which
enzymes may act are called substrates and the enzyme converts the substrate into different
molecules. It increases the reaction rate by lowering the activation energy.
Immobilized Enzymes
- Attached to an inert, insoluble material called matrix – such as calcium alginate, agar, k
–carrageenan, polyacrylamide and collagen. For example, with the use of calcium alginate. It is
produced by reacting of sodium alginate solution and enzyme solution with calcium chloride.
- Increased resistance to changes in conditions such pH or temperature.

Immobilization of an enzyme transforms a homogeneous (soluble) catalyst into a

heterogeneous (insoluble) system. While this technique often improves enzyme stability and
allows for its retention within a continuous reactor, it also introduces mass transfer effects that
require careful design consideration. Carrier binding techniques introduce external mass transfer
effects between the liquid phase and the solid surface. Entrapment methods fix the enzyme in a
polymeric matrix, creating internal mass transfer effects that are diffusion processes.

Factors affecting the mass transfer of the substrate:

 Properties of immobilized enzymes whether it is porous or non porous matrix. The
matrix can be a particle, a membrane, or a fiber.
 Properties of the bulk fluid (density, viscosity)
 Dynamic characteristic of the bulk fluid (velocity field)
 Properties of the solute (diffusivity)

Rate-Determining Step
- it is the slowest step of a chemical reaction that determines the speed (rate) at which the overall
reaction proceeds.
- In catalytic reaction, the overall rate of reaction is equal to the rate of the slowest step in the
mechanism.
NON-POROUS MATRIX
Damköhler Number (Da)
• For Surface (Bound) Immobilization such as
Adsorption and Covalent Bonding.
• The rate of enzymatic reaction rate depends on the
relative rate of the reaction rate and the diffusion
rate, which is characterized by Damköhler number:
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Da =
𝐷𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
Da>>1 – reaction rate is greater than diffusion rate.
Therefore, the enzymatic reaction is diffusion limited.
Da<<1 – diffusion rate is greater than reaction rate

POROUS MATRIX

Steps in a Heterogeneous Porous Catalytic Reaction

1.) Mass transfer of A to surface
2.) Diffusion of A from pore mouth to internal catalytic surface
3.) Adsorption of A onto catalytic surface
4.) Reaction on surface
5.) Desorption of product B from surface
6.) Diffusion of B from pellet interior to pore mouth
7.) Diffusion of B from external surface to the bulk fluid (external diffusion)

Note: 1,2,7&6 are diffusion steps while 3,4&5 are reaction steps
External Diffusion
Mass transfer of the substrate from the bulk fluid to the external surface of the
catalyst.
Internal Diffusion
When the internal diffusion is the rate-determining step, the overall rate will be
unaffected by the rate of external diffusion. Conversely, whatever the fluid velocity
outside the pores, it will not affect the velocity of fluid inside the immobilized enzyme.

Diffusion rate vs Reaction rate

Diffusion rate > Reaction rate
• Concentration of the substrate at the immediate vicinity of the active sites are almost the
same from the bulk fluid
• Diffusion steps do not affect the overall rate of the reaction

Diffusion rate < Reaction rate

• Mass transport affects the overall reaction rate

Effectiveness Factor, 𝜼, for Porous Matrix

-it is defined as the ratio of reaction rate with diffusion limitation and reaction rate without
diffusion limitation.
𝒅𝒊𝒇𝒇𝒖𝒔𝒊𝒐𝒏 𝒓𝒂𝒕𝒆
𝒏=
𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆
Ways to eliminate mass transfer resistance
Diffusion resistances can be eliminated by using small enzyme particle sizes, a high
degree of turbulence around the particles and high substrate concentration.

Particle Sizes
• It should be small as possible to facilitate particle integrity, resistance to compression
and nature of particle recovery of the system.

Maximization of reaction rate

Maximum reaction rate is determined by the enzyme activity and concentration in the
support.

High enzyme content:

• High enzyme activity per unit reaction volume
• low effectiveness factor.
• Reaction rate is greater than diffusion rate
Low Enzyme Content
• Low enzyme activity per unit reaction volume
• High effectiveness factor
• Diffusion rate is greater than reation rate
Electrostatic Effect
• When enzymes are immobilized in a charged matrix, as a result of a change in the
microenvironment of the enzyme, the apparent bulk pH optimum of the immobilized
enzyme will shift from that of soluble enzyme.
• Electrostatic Effect is describe by the pH – activity profile and is given by:
zFψ
𝛥pH = pH𝑖 − pH𝑒 = 0.43
RT
Where:
z = charge (valence) on the substrate, F = faradays constant, ψ = electrostatic potential
R = universal gas constant & T = temperature

• Change in pH will result in alteration of intrinsic enzyme activity and ionic constituents.

Steric Effect
• Enzyme activity toward a high-molecular weight substrate is usually reduced upon
immobilization due to steric hindrance.
• Low – molecular substrate – it is easy for a substrate to penetrate the active sites of the
immobilized enzymes.
References
 Stryer L, Berg JM, Tymoczko JL (2002). Biochemistry (5th ed.). San Francisco: W.H.
Freeman. ISBN 0-7167-4955-6.
 Radzicka A, Wolfenden R (January 1995). "A proficient enzyme". Science. 267 (5194):
90–931
 Elements of Chemical Reaction Engineering by Fogler
 Bioprocess Engineering Principles by Pauline M. Duran