One Mass transfer Operations

Unit 1
Mass transfer: concept and theory

1
.

Stirring the water

with a spoon
creates forced
convection.

That helps the

sugar molecules to
transfer to the bulk
water much faster.
Diffusion Convection
(slower) (faster)

2
Diffusion
Solvent B
Solute A

concentration of A concentration of A
is high is low
Mass transfer by diffusion occurs when a component in a
stationary solid or fluid goes from one point to another
driven by a concentration gradient of the component.
Diffusion process can take place in a gas or vapor or in a
liquid, and it can result from the random velocities of the
molecules (molecular diffusion) or from the circulating or
eddy currents present in a turbulent fluid (eddy diffusion).
3
Fick’s First Law of Diffusion

Adolf Fick (1955) first described the molecular diffusion

in an isothermal, isobaric binary system of components A
and B
 According to his idea of molecular diffusion, the molar
flux of a species relative to an observer moving with
molar average velocity is proportional to the concentration
gradient in a certain direction
 eq.1

4
Fick’s First Law of Diffusion

𝑑𝐶 𝐴 concentration

𝐽 𝐴=− 𝐷 𝐴𝐵 gradient of A
in z-direction

𝑑𝑧diffusion coefficient
(mass/moles per
volume per distance)
(or diffusivity) of A in B

diffusion flux of A in relation to the

bulk motion in z-direction
(mass/moles per area per time)
What is the unit of diffusivity?

5
 Unit and Scale of Diffusivity

For dissolved matter in water: D ≈ 10 -5 cm2/s

For gases in air at 1 atm and at room
temperature: D ≈ 0.1 to 0.01 cm 2/s
Diffusivity depends on the type of solute, type
of solvent, temperature, pressure, solution
phase (gas, liquid or solid) and other
characteristics

6
 Unsteady state Diffusion
If the change of concentration of a component A of the diffusive
constituents in a mixture occurs over a time at a point, the Fick’s
law of diffusion at unsteady state condition can be expressed for
Z-direction as:

Both the diffusive and non-diffusive constituents affect the rate

of unsteady state diffusion. The diffusivity at unsteady state
condition can be expressed in terms of activation energy and the
temperature as:

The activation energy (ED) for the diffusion decreases the rate of
diffusion whereas temperature increases the diffusion rate.
7
 Example
Molecular diffusion of Helium in Nitrogen: A mixture of
He and N2 gas is contained in a pipe (0.2 m long) at 298 K
and 1 atm total pressure which is constant throughout. The
partial pressure of He is 0.60 atm at one end of the pipe, and it
is 0.20 atm at the other end. Calculate the flux of He at steady
state if DAB of He-N2 mixture is 0.687 x 10-4 m2/s.
Solution:
Use Fick’s law of diffusion given by equation (1) as

Rearranging equation (1) and integrating gives the following:

8
At steady state, diffusion flux is constant. Diffusivity is
taken as constant
Therefore:
.

DAB is given as 0.687 x 10-4 m2/s

(z2 – z1) is given as 0.2 m
(CA2 – CA1) = ?
 eq. 2
= 5.63 x 10-6 kmol/m2.s

9
Diffusion with bulk of mass in motion:
The Fick's first law of diffusion describes the mass
transfer from the random movement of molecules of a
stationary medium or a fluid in streamline flow. If
circulating currents or eddies are present, then the
molecular mechanism will be reinforced and the total
mass transfer rate may be written as:
Total diffusion = Molecular diffusion + Convection
term (eddy diffusion)
Convection term = Concentration * mass transfer
velocity = CA . V . Molar diffusive flux of A in B

10
Let us use NA to denote the total flux which is diffusion
plus convection for component A.
Total diffusion = NA = JA + CA . V
 eq. 3
 eq. 4
 eq. 5

The above equations is the total diffusion equations in

the form of concentration, mole fraction and pressure.

11
Prove that mutual diffusivities of species A and B
are equal if gas mixture is ideal when total
pressure is constant.
Starting with ficks law and putting it in this equation ,
gives:
 or
For B ,summarizing gives
, from this equation it can be easily shown that:
 DAB =DBA=D Which mean that for a binary gas mixture,
the diffusivity of A in B equals the diffusivity of B in A .

12
 Modes of diffusion

Diffusion

Stagnant
Counter diffusion
Diffusion

Equimolecular Unequimolecular
Counter diffusion Counter diffusion

13
STEADY STATE MOLECULAR DIFFUSION IN
FLUIDS UNDER STAGNANT AND LAMINAR FLOW
CONDITIONS
Steady state diffusion through a constant area
Steady state diffusion through a stagnant gas film
 Assume steady state diffusion in the Z direction without any
chemical reaction in a binary gaseous mixture of species A and B. For
one dimensional diffusion of species A, the Equation of molar flux
can be written as:
, it can be written as
 eq.6

 For the gaseous mixture, at constant pressure and temperature C and

DAB are constant, independent of position and composition.
Also all the molar fluxes are constant in this equation

14
 Therefore the Equation (6) can be integrated between two
boundary conditions as follows:
 at Z = Z1, yA = yA1
at Z = Z2, yA = yA2
where 1 indicates the start of the diffusion path and 2
indicates the end of the diffusion path.
After integration with the above boundary conditions the
Equation for diffusion for the said condition can be
expressed as:
 eq. 7

15
Steady state one dimensional diffusion of A
through non-diffusing B
Evaporation of a pure liquid (A) is at the
bottom of a narrow tube.
Large amount of inert or non-diffusing air (B)
is passed over the top.
Vapour A diffuses through B in the tube.
The boundary at the liquid surface (at point 1)
is impermeable to B, since B is insoluble in
liquid A.
Hence, B cannot diffuse into or away from the
surface.
Therefore, NB = 0 and NA = constant. Therefore:

eq.8
16
For a mixture of ideal gases:
 , and using eq. 2 then the Eq. 8 can be expressed in terms
of partial pressures as:
 eq. 9
Where P is the total pressure and PA1 and PA2 are the
partial pressures of A at point 1 and 2 respectively.
For diffusion under turbulent conditions, the flux is
usually calculated based on linear driving force. For this
purpose the Equation (9) can be manipulated to rewrite it
in terms of a linear driving force. Since for the binary gas
mixture of total pressure P:
; ; ; .

17
Then equation (9) can be written as:

 eq.10

 or eq. 11

Where eq.12

is called logarithmic mean partial pressure of species B.

18
 is known as the drift factor.
 If the drift factor =1 ( this happen when the
concentration of component A being transferred is low)
Then,
 eq.13

19
A schematic concentration profile for diffusion A through
stagnant B is shown in Figure 2.1. The component A diffuses
by concentration gradient, dyA /dZ .
 Here flux is inversely proportional to the distance through
which diffusion occurs and the concentration of the stagnant
gas (PBM ) because with increase in Z and PBM , resistance
increases and flux decreases. 20
 Q1
Diffusion of water through stagnant, non-diffusing air:
Water in the bottom of a narrow metal tube is held at a constant
temperature of 293 K. The total pressure of air (assumed to be
dry) is 1 atm and the temperature is 293 K. Water evaporates
and diffuses through the air in the tube, and the diffusion path
is 0.1524 m long. Calculate the rate of evaporation at steady
state. The diffusivity of water vapour at 1 atm and 293 K is
0.250 x 10-4 m2/s. Assume that the vapour pressure of water at
293 K is 0.0231 atm.

Answer: 1.595 x 10-7 kmol/m2.s

21
Solution: The set-up of Q1 is shown in the
figure. Assuming steady state, equation (14) applies
Air (B)
DAB P
NA = (pA1 - pA2 )
RT(z2 – z1) pB,LM 2

where
z 2 – z1
(pA1 – pA2 )
pB,LM =
ln[(P - pA2 )/ (P - pA1 )]

Data provided are the following: 1

 DAB = 0.250 x 10-4 m2/s;
 P = 1 atm; T = 293 K; Water (A)
 z2 – z1 = 0.1524 m;
 pA1 = 0.0231 atm (saturated vapour pressure);
 pA2 = 0 atm (water vapour is carried away by air at point 2.
22
Substituting the data provided in the equations given, we get
the following:
(0.0231 – 0 )
pB,LM = = 0.988 atm
ln[(1 - 0 )/ (1 – 0.0231 )]

(0.250x10-4 m2/s)(1x1.01325x105 Pa) (0.0231 - 0) atm

NA =
(8314 J/kmol.K) (293 K) (0.1524 m) (0.988 atm)

= 1.595 x 10-7 kmol/m2.s

23
 Question 2
Ammonia gas is diffusing at a constant rate through a layer
of stagnant air 1 mm thick. Conditions are such that the gas
contains 50 percent by volume ammonia at one boundary of
the stagnant layer. The ammonia diffusing to the other
boundary is quickly absorbed and the concentration is
negligible at that plane. The temperature is 295 K and the
pressure atmospheric, and under these conditions the
diffusivity of ammonia in air is 0.18 cm2/s. Estimate the rate
of diffusion of ammonia through the layer.
Solution:

24
 Counter diffusion:
Steady state equimolar counter diffusion
equimolecular counter diffusion: A process where, the mass
transfer rates of the two components are equal and
opposite.
Example: in a distillation column when the molar latent
heats of the two components are the same.
When equimolecular counter diffusion is taking place NB =
- NA, and N=0. Then:

Integrating
 eq.14
25
 Question 3
In an air-carbon dioxide mixture at 298 K and 202.6 kPa,
the concentration of CO2 at two planes (3 mm) apart are 15
vol.% and 25 vol.%. The diffusivity of CO2 in air at 298 K
and 202.6 kPa is 8.2*10-6 m2/s. Calculate the rate of
transfer of CO2 across the two planes, assuming:
a. Equimolecular counter diffusion.
b. Diffusion of CO2 through a stagnant air layer.

Solution:
PA1 = yA1 . PT = 0.15 202.6 = 30.39 kPa
 PA2 = yA2 . PT = 0.25 202.6 = 50.65 kPa
26
27
Unequimolecular counter diffusion
Unequimolecular diffusion: The mass transfer rates of
the two components are unequal and opposite.
Such a process occurs in a chemical reaction.
In this case:
Using this relation with equation 5 gives:

Solving this equation:

 (eq.15)

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 Example
Species A in a gaseous mixture diffuses through a (3 mm)
thick film and reaches a catalyst surface where the reaction
A → 3B
 takes place. If the partial pressure of A in the bulk of the
gas is 8.5 kN/m2 and the diffusivity of A is 2*10-5 m2/s. Find
the mole flux of A, given the pressure and temperature of the
system are 101.3 kPa and 297 K, respectively.

29
30
The effective diffusivity of (A) in the mixture
(DAm)
Considering the transfer of component A through a
stationary gas consisting of components B, C, D, ... etc, if
the total partial pressure gradient can be regarded as being
made up of a series of terms each representing the
contribution of the individual component gases. The mass
transfer rate can be calculated from the previous equations
using the effective diffusivity of A in the mixture (DAm)
(DAm) for stagnant mixture can be calculated using the
following equation :
(17)

31
Example: Nitrogen is diffusing under steady condition
through a mixture of 2% N2, 20% C2H6 , 30% C2H4 and
48% C4H10 at 298 K and 100 kPa.
 The partial pressure of nitrogen at two planes (1 mm )
apart are 13.3 & 6.67 kPa, respectively. Calculate the rate
of N2 across the two planes. The diffusivity of N2 through
C4H10 , C2H6 and C2H4 may be taken as 9.6*10-6 m2/s ,
14.8*10-6 m2/s and 16.3*10-6 m2/s, respectively.

32
33
 Estimating Diffusivity
Diffusivities for different systems could be estimated using the
empirical equations provided in the following slides as well as
those provided in other reference texts available in the library and
other sources and may be found experimentally.
For gases at 1 atm and 298 K:


34
35
 Binary Gas Diffusivity

DAB - diffusivity in cm2/s

P - absolute pressure in bar
Mi - molecular weight
T - temperature in K
Vi - the special diffusion volume coefficient
for component i
DAB is proportional to 1/P and T1.75
36
37
 Example:
Estimate the diffusivity of methanol in air at atmospheric
o
pressure and 25 C.

38
 Diffusivity in Liquids

For very large spherical molecules (A) of 1000 molecular weight or greater
diffusing in a liquid solvent (B) of small molecules:

9.96 x 10-12 T
DAB =
μ VA1/3
applicable for biological solutes such as proteins
DAB - diffusivity in cm2/s
T - temperature in K
μ - viscosity of solution in kg/m s
VA - solute molar volume at its normal boiling point
 in m3/kmol
DAB is proportional to 1/μ and T

39
40
 Diffusivity in Liquids
For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):
1.173 x 10-12 (Φ MB)1/2 T
DAB =
μB VA0.6 applicable for
DAB - diffusivity in cm2/s biological
MB - molecular weight of solvent B solutes
T - temperature in K
μ - viscosity of solvent B in kg/m s
VA - solute molar volume at its normal boiling point in m3/kmol
Φ - association parameter of the solvent, which 2.6 for water,
1.9 for methanol, 1.5 for ethanol, and so on
DAB is proportional to 1/μB and T
41
Example: Estimate the diffusivity of phenol in ethanol at 20°C (293 K).

42
 Diffusivity of Electrolytes in Liquids
For smaller molecules (A) diffusing in a dilute liquid solution of
solvent (B):

8.928 x 10-10 T (1/n+ + 1/n-)

DoAB =
(1/λ+ + 1/ λ-)
DoAB is diffusivity in cm2/s
n+ is the valence of cation
n- is the valence of anion
λ+ and λ- are the limiting ionic conductances in very dilute
solutions
T is 298.2 when using the above at 25oC
DAB is proportional to T
43
Experimental determination of diffusivities
Diffusivities of vapours are
most conveniently determined
by the method developed by
Winkelmann in which liquid is
allowed to evaporate in a
vertical glass tube over the top
of which a stream of vapour-
free gas is passed, at a rate
such that the vapour pressure is
maintained almost at zero.

44
If the apparatus is maintained at a steady temperature,
there will be no eddy currents in the vertical tube and
mass transfer will take place from the surface by
molecular diffusion alone. The rate of evaporation can be
followed by the rate of fall of the liquid surface, and since
the concentration gradient is known, the diffusivity can
then be calculated.

Derive these equations 45

 Example: Calculate the diffusivity of carbon tetrachloride
vapour in air at 321 K and atmospheric pressure from the
experimental data by Winkelmann's method. given in
Table 10.3.

• The vapour pressure of carbon tetrachloride at 321 K is 37.6 kN/m2

and the density of the liquid is 1540 kg/m3. molecular volume may
be taken as 22.4 m3.

46
47
𝐓𝐡𝐞 𝐬𝐥𝐨𝐩𝐞 𝐬 = 0.031ks/mm2 = 3.1 ∗ 107 s/m2

Mwt = 154 kg/kmol , 𝛒𝐋 = 1540 kg/m3

𝐂𝐀 = mole fraction ∗ 𝐂𝐓
𝐂𝐀 =CT*PA/PT
=0.038*37.6/101.3=0.0141kmol/m3
𝐂𝐁𝟏 = 𝐂𝐓 − 𝐂𝐀𝟏
= 0.038 − 0.0141 = 0.0239
𝐂𝐁𝟐 = 𝐂𝐓 − 𝟎 = 0.038
48
 Example:

A small diameter tube closed at one end was filled with acetone to within
18 mm of the top and maintained at 290 K with a gentle stream of air
blowing across the top. After 15000 sec, the liquid level was fallen to
27.5 mm, the vapour pressure of acetone was 21.95 kPa and atmospheric
pressure was 99.75 kPa. Calculate the diffusivity of acetone in air.

Given: the density of acetone is 790 kg/m 3 and the molecular weight of
acetone is 58 kg/kmol.


Solution:


=1.9*10-5m2/s
•

49
 Diffusion through a varying cross-
section area
The mole rate ( N A, kmol /s) through a system of a
varying cross section area is constant.
The mole flux ( NA, kmol/m2.s ) is variable.
Examples: a cone and sphere. 

PA1=PV

𝑘𝑚𝑜𝑙
𝑚𝑜𝑙𝑒 𝑟𝑎𝑡𝑒 𝑁𝐴 𝑠 𝑘𝑚𝑜𝑙
𝑁 𝐴= = = =
𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝐴 𝑚
2 2
𝑚 .𝑠  
NA1 > NA2 > NA3 NA1 = NA2 = NA3 50
Diffusion through a spherical body
The surface area of the sphere

2 𝑑𝐶 𝐴 𝐶 𝐴
𝑁 𝐴=− 4 𝜋 𝑟 𝐷 𝐴𝐵 + ( 𝑁 𝐴+ 𝑁 𝐵)
𝑑𝑟 𝐶𝑇

51
 Case (I): Diffusion through a
stagnant layer :
𝑟1
𝑑𝑟 ( 𝐶 𝑇 −𝐶 𝐴2 )
𝑁 𝐴∫ 2 =− 4 𝜋 𝐷 𝐴𝐵 𝐶 𝑇 ln
𝑟 𝑟
0
( 𝐶 𝑇 −𝐶 𝐴1 )
4 𝜋 𝐷 𝐴𝐵 𝐶 𝑇 ( 𝐶 𝑇 −𝐶 𝐴 2 )
𝑁 𝐴= ln
1 1 ( 𝐶 𝑇 −𝐶 𝐴 1 )
−
𝑟0 𝑟1
𝐷 𝐴𝐵 𝐶 𝑇 ( 𝐶𝑇 − 𝐶 𝐴 2 )
𝑁 𝐴= ln
2
𝑟0
1
(
−
𝑟0 𝑟 1
1
)( 𝐶𝑇 − 𝐶 𝐴 1 )

Mole flux from the sphere surface

52
When the mass transfer from surface to a large distance
compare to the sphere surface (𝐫𝟎):
r1→ ∞ and CA2=0, then
𝐷 𝐴𝐵 𝐶 𝑇 (𝐶𝑇 − 𝐶 𝐴 2 )
𝑁 𝐴= ln
𝑟
2
𝑜
1
(𝑟
−
1
0 ∞ )
( 𝐶 𝑇 −𝐶 𝐴 1 )

𝐷 𝐴𝐵 𝐶 𝑇 ( 𝐶 𝑇 − 𝐶 𝐴 2 )
𝑁 𝐴= ln
𝑟0 (𝐶𝑇 − 𝐶 𝐴 1 )
𝐷 𝐴𝐵 𝑃 𝑇 ( 𝑃 𝑇 − 𝑃 𝐴 2 )
𝑁 𝐴= ln In partial pressure form
𝑟 0 𝑅𝑇 ( 𝑃 𝑇 − 𝑃 𝐴 1) 53
 Example:
A sphere of naphthalene having a radius of 2 mm is
suspended in a large volume of still air at 318 K and 101.3
kPa. The surface temperature of naphthalene can be
assumed to be 318 K and its vapour pressure at this
temperature is 0.555 mmHg. The diffusivity of naphthalene
in air at 318 K is 6.92 * 10-6 m2/s.
Calculate the rate of naphthalene evaporation from surface.
Solution: The sphere is suspended in a large volume of still
air means:

54
 Case (II): Equimolecular Counter
Diffusion :


In case of r1 very large 1/r1=0

55
 Case (III): Unequimolecular Counter
Diffusion

Example: Calculate the rate of burning of carbon particle

2.56 cm radius in an atmosphere of pure oxygen at 1000
K and 1 atm. Assuming a very large blanking layer of
CO2 has formed a round the particle.
At the carbon surface PCO2=1 atm and PO2=0.
At very large radius PCO2=0 and PO2=1 atm.
Given the diffusivity of oxygen in carbon dioxide =
1.032 cm2/s.
56
In case of r very large:

57