Basic Knowledge of Mass Transfer

Molecular Diffusion

Molecular diffusion is the movement of component molecules in a mixture under the

influence of a concentration difference in the system (Bailey, 2009). Diffusion of molecules
occurs in the direction required to destroy the concentration gradient. If the gradient is
maintained by constantly supplying material to the region of high concentration and
removing it from the region of low concentration, diffusion will be continuous. This situation
is often exploited in mass-transfer operations and bioreaction system.

Fick’s law of diffusion:

Assume that mass transfer of A occurs across area a perpendicular to the direction of
diffusion. In single-phase systems, the rate of mass transfer due to molecular diffusion is
given by Fick's law of diffusion, which states that mass flux is proportional to the
concentration gradient:

JA= NA/a = -DAB dCA/dy

Ja is the mass flux of component A, N a is the rate of mass transfer of component A, a

is the area across which mass transfer occurs, .-DAB is the binary diffusion coefficient or
diffusivity of component A in a mixture of A and B, Ca is the concentration of component A,
and y is distance, d C A / dy is the concentration gradient, or change in concentration of A
with distance.

Role of Diffusion in Bioprocessing

Mixing. As discussed before, turbulence in fluids produces bulk mixing on a scale

equal to the smallest eddy size. Within the smallest eddies, flow is largely streamline so that
further mixing must occur by diffusion of fluid components. Mixing on a molecular scale
therefore completely relies on diffusion as the final step in the mixing process.

Solid-phase reaction. In biological systems, reactions are sometimes mediated by

catalysts in solid form, e.g. clumps, flocs and films of cells and immobilized-enzyme and –
cell particles (Bailey, 2009). When cells or enzyme molecules are clumped together into a
solid particle, substrates must be transported into the solid before reaction can take place.
Mass transfer within solid particles is usually unassisted by bulk fluid convection; the only
mechanism for intraparticle mass transfer is molecular diffusion. As the reaction proceeds,
diffusion is also responsible for removing of product molecules away from the site of
reaction, this will be discussed more fully in heterogeneous bioreaction kinetics. When
reaction is coupled with diffusion, the overall reaction rate can be significantly reduced if
diffusion is low.

Mass transfer across a phase boundary. Mass transfer between phases occurs often
in bioprocesses. Oxygen transfer from gas bubbles to fermentation broth, penicillin recovery
from aqueous to organic liquid, and glucose transfer from liquid medium into mould pellets
are typical examples (Doran, 2013). When different phases come into contact, fluid velocity
near the phase interface is significantly decreased and diffusion becomes crucial for mass
transfer across the phase interface.

Film Theory

The two-film theory is a useful model for mass transfer between phases. Mass transfer
of solute from one phase to another involves transport from the bulk of one phase to the
phase boundary or interface, and then from the interface to the bulk of the second phase. The
film theory is based on the idea that a fluid film or mass-transfer boundary layer forms
wherever there is contact between two phases (Doran, 2013). According to the film theory,
turbulence in each fluid dies out at the phase boundary. A thin film of relatively stagnant
fluid exists on either side of the interface; mass transfer through this film is affected solely by
molecular diffusion. The concentration of A changes near the interface as indicated in Figure
below, CAI i is the
interfacial concentration of A in the aqueous phase; CA2 i is the interfacial concentration of
A in the organic phase. Most of the resistance to mass transfer resides in the liquid films
rather than in the bulk liquid. For practical purposes it is generally assumed that there is
negligible resistance to transport at the interface itself; this is equivalent to assuming that the
phases are in equilibrium at the plane of contact. The difference between CA1 i and CA2 i at
the interface accounts for the possibility that, at equilibrium, A may be more soluble in one
phase than in the other. For example, ifA were acetic acid in contact at the interface with both
water and chloroform, the equilibrium concentration in water would be greater than that in
chloroform
by a factor of between 5 and 10. CAI i would then be significantly higher than CA2i.
Mass Transfer Equation

Rate of mass transfer is directly proportional to the driving force for transfer, and the
area available for the transfer process to take place, that is: Transfer rate ∝ transfer area
×driving force (Geankoplis, 2012).

The proportional coefficient in this equation is called the mass transfer coefficient, so
that: Transfer rate = mass-transfer coefficient × transfer area × driving force

NA= ka∆CA = ka(CAo-CA1)

Liquid-Solid Mass Transfer

Mass transfer between a moving liquid and a solid is important in biological

processing in a variety of applications. Transport of substrates to solid-phase cell or enzyme
catalysts has already been mentioned. Adsorption of molecules onto surfaces, such as in
chromatography, requires transport from liquid phase to solid; liquid-solid mass transfer is
also important in crystallization as molecules move from the liquid to the face of the growing
crystal. Conversely, the process of dissolving a solid in liquid requires liquid-solid mass
transfer directed away from the solid surface.

The concentration of A at the phase boundary is CAi; the concentration of A in the

bulk liquid outside the film is CAo. If a is the liquid-solid interfacial area per unit volume, the
volumetric rate of mass transfer can be determined from the equation:

NA = kL a ( CAo - GAi )
where k L is the liquid-phase mass-transfer coefficient

Liquid-liquid Mass Transfer

 Liquid-liquid mass transfer between immiscible solvents is most often encountered in
the product-recovery stages of bioprocessing. Organic solvents are used to isolate antibodies,
steroids and alkaloids from fermentation broths; two-phase aqueous systems are used in
protein purification.

The rate of mass transfer NA in each liquid phase can be obtained:

NA1 = kL1 a (CA1 - CA1i) and NA2 = kL2 a (CA2i - CA2)

At steady state, there is no accumulation of component A at interface or anywhere in

the system component. A transported through liquid 1 must be transported through phase 2,
that is NA1 = NA2=NA.

If CA1i and CA2i are equilibrium concentrations, they can be related using the
distribution coefficient m.

These two Eqs indicate that the rate of mass transfer between two phases is not
dependent simply on the concentration difference; the equilibrium relationship is also an
important factor. The driving force for transferring component A out of liquid 1 is the
difference between the bulk concentration CA1 and the concentration of component A in
liquid 1 which would be in equilibrium with concentration CA2 in liquid 2.

Gas-Liquid Mass Transfer

The rate of mass transfer of component A through the gas boundary layer is:

The rate of mass transfer of component A through the liquid boundary layer is:

If we assume that equilibrium exists at the interface, CAGi and CALi can be related. For
dilute concentration of most gases and for a wide range of concentration for some gases,
equilibrium concentration in the gas phase is a linear function of liquid concentration.
Therefore

The overall gas-phase mass-transfer coefficient KG is defined by:

The overall liquid-phase mass-transfer coefficient KL is defined as:

When solute A is very soluble in the liquid, for example, ammonia, the liquid-phase
resistance is small compared with that posed by the gas interfacial film, therefore

Conversely, if component A is poorly soluble in the liquid, e.g. oxygen, the liquid-phase
mass-transfer resistance dominates and kG a is much larger than kL a, thus:

References:

Bailey, J. S. (2009). Biochemical Engineering. Singapore: Alkem Company (S) Pte Ltd.
Doran, P. M. (2013). Bioprocess Engineering Principles. Singapore: Elsevier Ltd.

Geankoplis, C. J. (2012). Principles of Transport Processes and Separation Processes. New

Jersey: Pearson Education, Inc.

Mohamad Hekarl Uzir & Mashitah Mat Don. (2007). Biochemical Engineering. Retrieved
from http://chemical.eng.usm.my/notes/HEKARL/notes/ekc471_notes.pdf

Perry, R. H. (1997). Perry's Chemical Engineers' Handbook 7th Edition. United States of
America: The McGraw-Hill Companies, Inc.