Mass transfer

Mass transfer

• Mass transfer is the net movement of a component in a mixture from one

location to the, another location in presence of a difference in concentration or
partial pressure: e.g. evaporation, drying and distillation
• Mass transfer is classified into several parts depending upon the states of matter
such as gas-gas, gas-liquid, gas-solid, liquid-liquid, liquid-solid, and solid-solid
• Mass transfer occurs by two basic mechanism, molecular mass transfer and
convective mass transfer
• Molecular mass transfer involves molecular diffusion by random and
spontaneous microscopic movement of individual molecules in a gas, liquid or
solid due to concentration gradient
• Eddy diffusion by random macroscopic fluid motion is the responsible for the
convective mass transfer
 Diffusion

• Diffusion is defined by the movement of individual molecules through a

substance by virtue of their thermal energy
• The net distance or the average distance the molecules travels between two
collisions is known as the mean free path
• The net distance travel in one direction is given by the rate of diffusion
• Rate of molecular diffusion is very slow and increases with reducing pressure and
increasing temperature
• In a single-phase system the rate of mass transfer due to molecular diffusion is
given by Fick's law of diffusion
 Diffusion

Fick’s law of diffusion

• It defines the diffusion flux of a
component A in an isothermal,
isobaric binary system is proportional
to the concentration gradient in a
particular direction
𝑑𝐶!
𝐽! = −𝐷!"
𝑑𝑦
• The flux of a particular component is
defined as the rate of transport of Concentration gradient of component A
component through unit area normal inducing
mass transfer across area a.
to the transport
 Diffusion
𝑑𝐶!
𝐽! = −𝐷!"
𝑑𝑦
• NA is the rate of mass transfer of component A, 𝑎 is the area across which mass
transfer occurs, 𝐷!" is the binary diffusion coefficient or diffusivity of component
A in a mixture of A and B, CA is the concentration of component A, y is distance,
#$
and ! is the concentration gradient
#%
• 𝐽! has units of amount of material diffused per unit area per unit time
• The negative sign indicates diffusion always occur from higher to lower
concentrations
 Significance of Diffusion

• Scale of mixing- Mixing on a molecular scale relies on diffusion

• Solid phase reaction- Mass transfer within solid particles is usually unassisted by
convection, the only mechanism for intraparticle mass transfer is molecular
diffusion
• Mass transfer across a phase boundary- Oxygen transfer from gas bubbles to
fermentation broth, penicillin recovery from aqueous to organic liquid, and
glucose transfer from liquid medium into mold pellets
• Processes such as osmosis, ultrafiltration, microfiltration, and dialysis works on
the principle of diffusion
 Interphase Mass Transfer

• Film theory or boundary layer explains the mass transfer in turbulent or laminar
flow
• When fluid flows on a surface, the fluid layer adjacent to the surface creates
boundary layer
• If the bulk fluid flows in streamline, rate of mass transfer is controlled by
molecular diffusion
• If the bulk fluid flows in turbulent motion, rate of mass transfer is controlled by
the transport rate across the boundary layer
• There are several models to understand interphase mass transfer such as film
theory, penetration theory and surface renewal theory
 Interphase Mass Transfer

• Film Theory
• The film theory is based on the idea that a fluid film or mass-transfer boundary
layer fluid film forms wherever there is contact between two phases
• Mass transfer across the films occur only through molecular diffusion
• Most of the resistance to mass transfer resides in the liquid films rather than in
the bulk liquid
• The phases are in equilibrium at the plane of contact
• There is no resistance at the interface
 Interphase Mass Transfer

• Two phases: immiscible liquids such as

water and chloroform, and that A is
initially at higher concentration in the
aqueous phase than in the organic
phase
• C&' is the bulk concentration of A in
aqueous phase C&( is bulk the
concentration of A in organic Phase,
C&') is the interfacial concentration of
A in aqueous phaseC&() is the
interfacial concentration of A in organic
phase

Film resistance to mass transfer between two immiscible liquids

 Rate of Mass Transfer

• Rate of mass transfer is directly proportional to the driving force for transfer, and
the area available for the transfer process to take place
Transfer rate ∝ area x driving force
𝑁! ∝ 𝑎(𝐶!* − 𝐶!+ )
𝑁! = 𝐾, 𝑎(𝐶!* − 𝐶!+ )

Where, NA is the volumetric rate of mass transfer of component A, k is the mass

transfer coefficient, a is the area available for mass transfer, CAb is the bulk
concentration of component A away from the phase boundary, and CAi is the
concentration of A at the interface.
 Rate of Mass Transfer

• The inverse of mass transfer coefficient is a measure of the mass transfer

resistance, 𝑅-
𝑅- = 1/ 𝐾,
∆$!
𝑁! = /"
• Convective mass transfer refers to mass transfer occurring in the presence of
bulk fluid motion
• Molecular diffusion will occur whenever there is a concentration gradient,
however, if the bulk fluid is also moving, the overall rate of mass transfer will be
higher due to the contribution of convective currents
 Liquid- solid mass transfer

• Transport of substrates to solid-phase cell or

enzyme catalysts, adsorption of molecules onto
surfaces, such as in chromatography, requires
transport from liquid phase to solid

𝑁! = 𝐾0 𝑎(𝐶!1 − 𝐶!+ )

Where, 𝐶!1 is concentration of A in the bulk liquid,

𝐶!+ is the concentration of A at the phase
boundary, 𝑘2 is the liquid phase mass transfer
coefficient and a is the interfacial area
Concentration gradient for
solid-liquid mass transfer
 Liquid- liquid mass transfer

For two immiscible liquids, the rate of mass transfer will

be
𝑁!' = 𝑘0'𝑎 𝐶!' − 𝐶!'+ − i
𝑁!'= 𝑘0'𝑎 𝐶!' − 𝐶!'+ − (ii)

Where, 𝑘0 is liquid phase mass transfer coefficient and

subscript 1 and 2 refers to the two liquid phases

3!
= 𝐶!' − 𝐶!'+ −(iii)
4#$ ,

3!
4#% ,
= 𝐶!(+ − 𝐶!( −(iv)
Concentration gradient for liquid-liquid mass
transfer
 Liquid-Liquid Mass Transfer
• m, partition coefficient/distribution coefficient is defined as the ratio of solute
concentrations in the two phase

$!$&
𝑚= -(v) 𝑚𝐶!(+ = 𝐶!'+ -(vi) 𝐶!(+ = 𝐶!'+ /m -(vii)
$!%&

• On substituting eq, (vi) and (vii) in eqn. (iii) and (iv), we get,

3! 3! $!$&
= 𝐶!' − 𝑚𝐶!'+ -(viii) = − 𝐶!( -(ix)
4#$ , 5#% , -

• On multiplying and dividing eqn. (iv) and (v) with m, respectively, we get
 Liquid-Liquid Mass Transfer

𝑚𝑁! -(x)
3! $!$ $!$&
= 𝑚𝐶!(+ − 𝑚𝐶!( -5#$'
= -
- - -(xi)
𝑘0(,

Add equation (viii) to (x) and (ix) to (xi) to eliminate the interfacial concentration term

1 𝑚 ' - $!$
𝑁! + = 𝐶!' − 𝑚𝐶!( -(xii) 𝑁! +4 = −𝐶!( -(xiv)
𝐾0', 𝐾0(, 4#$' #%' -

𝐶!'
𝑁! = 𝐾0'𝑎 𝐶!' − 𝑚𝐶!( -(xv) 𝑁! = 𝐾0(𝑎 − 𝐶!( -(xvi)
𝑚

1 1 𝑚 1 1 1
Where, = + and = +
𝐾0', 𝐾0', 𝐾0(, 𝐾0(, 𝑚𝐾0', 𝐾0(,
 Gas- liquid Mass transfer
Rate of Mass transfer of A through the gas
boundary layer is,
𝑁!6 = 𝐾6 𝑎 𝐶!6 − 𝐶!6+ -(i)
Rate of mass transfer of A through the liquid
boundary layer is,
𝑁!0 = 𝐾0 𝑎 𝐶!0+ − 𝐶!0 -(ii)
𝐶!6+
𝐶!2+ =
𝑚
On incorporating above equation in eqn. (i) and(ii)
1 𝑚
𝑁! + = 𝐶!6 − 𝑚𝐶!0 -(iii)
𝑘6 𝑎 𝑘0 𝑎
Concentration gradients for gas-liquid mass
1 1 𝐶!6 transfer.
𝑁! + = − 𝐶!0 -(iv)
𝑚𝑘6 𝑎 𝑘0 𝑎 𝑚
 Gas- liquid Mass transfer

𝑁!6 = 𝐾6 𝑎 𝐶!6 − 𝑚𝐶!0 -(v)

1 1 𝑚
= +
𝐾6, 𝐾6, 𝐾0,
𝐶!6 Where,
𝑁!6 = 𝐾0 𝑎( − 𝐶!0 ) -(vi)
𝑚
1 1 1
= +
𝐾0', 𝑚𝐾6, 𝐾0,
Equation (v) and (vi) can be written as;

𝑁! = 𝐾6 𝑎 𝐶!6 − 𝐶 ∗!6

𝑁! = 𝐾0 𝑎 𝐶 ∗!0 − 𝐶0
 Oxygen Uptake in cell cultures

• The solubility of oxygen in aqueous solutions at ambient temperature and pressure

is 10 ppm
• Oxygen is quickly consumed in aerobic cultures and must be constantly replaced by
sparging
• Rate of oxygen transfer from gas to liquid is,
𝑁! = 𝐾0 a (𝐶 ∗!0 - 𝐶!0 )
Where, 𝑁! is the rate of oxygen transfer per unit volume of fluid (gmol 𝑚89𝑠 8'), 𝐾0 is
the liquid-phase mass-transfer coefficient (𝑚𝑠 8'), a is the gas-liquid interfacial area
per unit volume of fluid (𝑚(𝑚89), 𝐶!0 is the oxygen concentration in the broth (gmol
𝑚89), and 𝐶 ∗!0 is the oxygen concentration in the broth in equilibrium with the gas
phase (gmol 𝑚89)
• The difference (𝐶 ∗!0 - 𝐶!0 ) between the maximum possible and actual oxygen
concentrations in the liquid represents the concentration-difference driving force for
mass transfer
 Factors affecting cellular oxygen demand

• The rate at which oxygen is consumed by cells in fermenters determines the rate at
which it must be transferred from gas to liquid
• Cell species, culture growth phase, and nature of the carbon source in the medium
majorly affects oxygen demand, e.g. rate of oxygen demand is higher when glucose is
used
• Choice of substrate for fermentation can also significantly affects oxygen demand
• In batch culture rate of oxygen uptake varies with time as it depends on the no of cells
present
• Rate of oxygen consumption per cell is called specific oxygen consumption rate, 𝑞: (g g-1
s-1)
𝑄:= 𝑞:𝑥
Where, 𝑄: = volumetric oxygen uptake rate (g l-1 s-1), 𝑥 = cell concentration (g l-1)
 Factors affecting cellular oxygen demand

• When the level of dissolved oxygen in the

medium falls below a certain point, the specific
rate of oxygen uptake depends on the oxygen
concentration in the liquid
• If 𝐶!0 > 𝐶;<+= , 𝑞: is a constant maximum and
independent of 𝐶;<+= ; If 𝐶!0 < 𝐶;<+= , 𝑞: is
linearly dependent on oxygen concentration
• The exact value of 𝐶;<+= depends on the
organism, but under average operating
conditions it usually falls between 5% and 10%
of air saturation
Relationship between specific rate of oxygen
consumption by cells and dissolved-oxygen
concentration
 Oxygen Transfer from gas bubbles to cell

• Several mass-transfer steps are required to transport oxygen from the interior of gas
bubbles to the site of intracellular reaction;
i. Transfer from the interior of the bubble to the gas-liquid interface
ii. Movement across the gas-liquid interface
iii. Diffusion through the relatively stagnant liquid film surrounding the bubble
iv. Transport through the bulk liquid
v. Diffusion through the relatively stagnant liquid film surrounding the cells
vi. Movement across the liquid-cell interface
vii. If the cells are in a floc, clump or solid particle, diffusion through the solid to the
individual cell
viii. Transport through the cytoplasm to the site of reaction
Oxygen Transfer from gas bubbles to cell

Steps for transfer of oxygen from gas bubble to cell

 Oxygen Transfer from gas bubbles to cell
Resistance involved in oxygen transfer
• Relative magnitudes of the various mass-transfer resistances depend on the
composition and rheological properties of the liquid, mixing intensity, bubble size, cell-
clump size, interfacial adsorption characteristics and other factors
i. Transfer through the bulk gas phase in the bubble is relatively fast
ii. The gas-liquid interface itself contributes negligible resistance
iii. The liquid film surrounding the bubbles is a major resistance to oxygen transfer
iv. In a well-mixed fermenter, mass-transfer resistance in the bulk liquid region is
small; however, in viscous broth this resistance plays an important role
v. As single cells are much smaller than gas bubbles, the liquid film surrounding
each cell is much thinner than that around the bubbles and its effect on mass
transfer can generally be neglected
 Oxygen Transfer from gas bubbles to Cell

• When the cells are in clumps, intraparticle resistance is likely to be significant as

oxygen has to diffuse through the solid pellet to reach the interior cells
• Resistance at the cell-liquid interface is generally neglected
• Intracellular oxygen-transfer resistance is negligible because of the small
distances involved
• At steady state rate of oxygen transfer from bubbles must be equal to the rate of
oxygen consumption by cells;
𝑁! = 𝑄:
𝑘0 𝑎(𝐶 ∗!0 − 𝐶!0 ) = 𝑞1 𝑥

• If 𝑘0 𝑎 for a particular system is small, the ability of the reactor to deliver oxygen
to the cells is limited
 Resistance to mass transfer

• For a given set of operating conditions, the maximum rate of oxygen transfer occurs
when the concentration-difference driving force (𝐶 ∗!0 - 𝐶!0 ) is highest i.e. when
𝐶!0 is zero
• Maximum cell concentration of the reactor is,

𝑘0 𝑎𝐶 ∗!0
𝑥-,> =
𝑞1
• If 𝑥-,> estimated from the above equation is lower than the cell concentration
required in the fermentation process, 𝑘0 𝑎 must be improved
• The minimum 𝑘0 𝑎 required to maintain 𝐶!0 > 𝐶;<+= in the fermenter is,

?( >
𝑘0 𝑎;<+= =
($ ∗ !# − $*+&, )
 Oxygen transfer in fermenters

• Bubbles- small bubbles are beneficial because of the increased gas hold-up and
larger interfacial surface-area
• Bubbles with diameters less than 2-3 mm, the bubbles behave as rigid spheres
due to high surface tension and cause no internal gas circulation
• Bubbles with sizes greater than about 3 mm develop internal circulation and
relatively mobile surfaces, depending on liquid properties
• Sparging, stirring and medium properties
• Temperature- Increasing temperature causes C ∗ &@ to drop, so that the driving
force for mass transfer (C ∗ &@ - C&@ ) is reduced
• Antifoam agents
• Gas pressure and oxygen partial pressure
• Presence of cells
 Measurement of 𝑘! 𝑎
Oxygen- balance method (Steady state oxygen balance)
• At steady state, the difference in oxygen flow between inlet and outlet must be equal to
the rate of oxygen transfer from gas to liquid;

1 Where, R is the universal gas constant, 𝐹E , 𝑃!6

𝑁! = { 𝐹E 𝐶!6 − 𝐹E 𝐶!6 }
𝑉0 + 1
is the oxygen partial pressure in the gas and T is
' B- C!. B- C!. absolute
𝑁! = [ − ]
/A# D + D 1 temperature

• Most reliable procedure for measuring and allows determination from a single point
measurement
• Method can also be applied to fermenters during normal operation
• Depends on accurate measurement of gas composition, flow rate, pressure and
temperature
 Measurement of 𝑘! 𝑎

Dynamic method (unsteady state mass balance for

oxygen)
• Advantage- low cost over steady state technique
• The rate of change in dissolved-oxygen concentration
during reoxygenation is equal to the rate of oxygen
transfer from gas to liquid, minus the rate of oxygen
uptake by the cells
𝑑𝐶!0
= 𝑘0 𝑎 𝐶 ∗!0 − 𝐶!0 − 𝑞1 𝑥
𝑑𝑡
• As there is no change in 𝐶!0 with time,
Variation of oxygen tension for dynamic
𝑘0 𝑎 𝐶 ∗!0 − 𝐶!0 = 𝑞1 𝑥 measurement of 𝑘! 𝑎
 Measurement of 𝑘! 𝑎

Where, is final steady dissolved oxygen concentration

On integrating the above equation between 𝑡' and 𝑡(

Sulphite Oxidation
• This method is based on oxidation of sodium sulphite to sulphate in the presence of a
catalyst such as 𝐶𝑢(H
• Usually give higher 𝑘0 𝑎 values than other techniques and hence its application is
discouraged
 Oxygen transfer in large vessels

• In commercial-size reactors (> 10 m3), perfect mixing is difficult to achieve; so the

calculated value of 𝑘0 𝑎 may depend on the position in the tank where the
measurements of CAL are made
• Variation in composition of the gas phase is inevitable as changing static pressure and
continuing dissolution of oxygen reduce the oxygen partial pressure in the bubbles as
they rise
• Significant variation between inlet and outlet oxygen partial pressures affects the
value for C ∗ &@ used in mass-transfer calculations
• Average concentration driving force (C ∗ &@ - CAL) across the system
• A suitable average is the logarithmic-mean concentration difference, (C ∗ &@ - CAL)L

Where subscript (o) and (i)

represent outlet and inlet of
the fermenter
 Problems

Serratia marcescens bacteria are used for production of threonine. The maximum
specific oxygen uptake rate of S. marcescens in batch culture is 5 mmol O2 g-1 h-1.
The bacteria are grown in a stirred fermenter to a cell density of 40 g l-1; kLa under
these circumstances is 0.15 s-1. At the fermenter operating temperature and
pressure, the solubility of oxygen in the culture liquid is 8 x 10-3 kg m-3. Is the rate of
cell metabolism limited by mass-transfer, or dependent solely on metabolic
kinetics? (Ans- 1.20x1089𝑘𝑔𝑚89𝑠 8')
 Problems
A genetically-engineered strain of yeast is cultured in a bioreactor at 30oC for
production of heterologous protein. The oxygen requirement is 80 mmol l-1 h-1; the
critical oxygen concentration is 0.004 mM. The solubility of oxygen in the
fermentation broth is estimated to be 10% lower than in water due to solute
effects. [solubility of O2 (obtained through air sparging) in water at 30oC, 1 atm =
8.05 x 10-3 kg/m3], [solubility of O2 (pure O2) in water at 30oC, 1 atm = 3.84 x 10-2
kg/m3]
(a) What is the minimum mass-transfer coefficient necessary to sustain this
culture if the reactor is sparged with air at approximately 1 atm pressure?
(0.10/s)
(b) What mass-transfer coefficient is required if pure oxygen is used instead of air?
(0.021/s)
 Problems
A 200-liter stirred fermenter contains a batch culture of Bacillus subtilis bacteria at 28oC. Air at
20oC is pumped into the vessel at a rate of 1 vvm; The average pressure in the fermenter is 1
atm. The volumetric flow rate of off-gas from the fermenter is measured as 189 l min-1. The exit
gas stream is analyzed for oxygen and is found to contain 20.1% O2. The dissolved-oxygen
concentration in the broth is measured using an oxygen electrode as 52% air saturation. The
solubility of oxygen in the fermentation broth at 28oC and 1 atm air pressure is 7.8 x 10-3 kg m-3.
[R = 0.000082057 m3 atm K-1 gmol-1]

(a) Calculate the oxygen transfer rate; Determine the value of kLa for the system.
(0.0174gmolm89s8')
(b) The oxygen analyzer used to measure the exit gas composition has been incorrectly
calibrated. If the oxygen content has been overestimated by 10%, what error is associated
with the result for k ? (0.15/s and 0.0289gmolm89s8')
 Problems
The dynamic method is used to measure kLa in a fermenter operated at 30oC. Data
for dissolved-oxygen concentration as a function of time during the re-oxygenation
step is as follows:

Time(s) CAL (% air

saturation)
10 43.5 The equilibrium concentration of oxygen in the broth
15 53.5
is 7.9 x 10 -3 kg m -3. Determine kLa (Ans- 0.069/s)
20 60.0
30 67.5
40 70.5
50 72.0
70 73.0
100 73.5
130 73.5