Mass transfer operations - 1

DR.A.V.RAGHAVENDRA RAO
In the last class

Dimensionless numbers in Mass Transfer

𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑣𝑒 𝑚𝑎𝑠𝑠 (𝑚𝑜𝑙𝑎𝑟) 𝑓𝑙𝑢𝑥
𝑆ℎ =
𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑢𝑥 𝑓𝑜𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑎 𝑠𝑡𝑎𝑔𝑛𝑎𝑛𝑡 𝑚𝑒𝑑𝑖𝑢𝑚 𝑜𝑓 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 "z"

𝑘𝑐 𝑙 𝑘𝐿 𝑙
𝑆ℎ = or
𝐷𝐴𝐵 𝐷𝐴𝐵

𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦
𝑆𝑐ℎ𝑚𝑖𝑑𝑡 𝑛𝑢𝑚𝑏𝑒𝑟 𝑆𝑐 =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦

µ
ൗ
𝑆𝑐 =
𝐷𝐴𝐵

µ
𝑆𝑐 =
𝐷𝐴𝐵
 𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑣𝑒 𝑚𝑎𝑠𝑠 𝑓𝑙𝑢𝑥 𝑘𝐿 𝑐 𝑘𝐿
𝑆𝑡𝑀 = = =
𝑓𝑙𝑢𝑥 𝑑𝑢𝑒 𝑡𝑜 𝑏𝑢𝑙𝑘 𝑓𝑙𝑜𝑤 𝑣𝑐 𝑣

𝑆ℎ
𝑆𝑡𝑀 =
𝑅𝑒. 𝑆𝑐

𝑘𝐿 𝑙
𝐷𝐴𝐵 𝑘𝐿
𝑆𝑡𝑀 = =
𝑣𝑙 µ 𝑣
µ 𝐷𝐴𝐵

𝑓𝑙𝑢𝑥 𝑑𝑢𝑒 𝑡𝑜 𝑏𝑢𝑙𝑘 𝑓𝑙𝑜𝑤 𝑜𝑓𝑡ℎ𝑒 𝑚𝑒𝑑𝑖𝑢𝑚

𝑃𝑒𝑀 =
𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑒 𝑓𝑙𝑢𝑥 𝑎𝑐𝑟𝑜𝑠𝑠 𝑎 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 "𝑙"

𝑣 𝑐 𝑣𝑙 µ
𝑃𝑒𝐻 = = = = 𝑅𝑒. 𝑆𝑐
𝐷𝐴𝐵
𝑐 µ 𝐷𝐴𝐵
𝑙
𝐶𝑜𝑙𝑏𝑢𝑟𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟

𝑆ℎ 𝑓
𝑆𝑡𝑀 . 𝑆𝑐 0.67 = 𝑗𝐷 = 1/3
= 0.023 𝑅𝑒 −0.2 =
𝑅𝑒. 𝑆𝑐 2
 Analogies
1. Reynolds analogy
2. Chilton-Colburn analogy or Colburn analogy

𝑓
= 𝑆𝑡𝐻 = 𝑆𝑡𝑀
2

𝐶𝑜𝑙𝑏𝑢𝑟𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟

𝑓
𝑆𝑡𝐻 . 𝑃𝑟 0.67 = 𝑗𝐻 = 0.023 𝑅𝑒 −0.2 =
2

𝐶𝑜𝑙𝑏𝑢𝑟𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟

𝑓
𝑆𝑡𝑀 . 𝑆𝑐 0.67 = 𝑗𝐷 = 0.023 𝑅𝑒 −0.2 =
2
Problems Related to

1. Reynolds analogy
2. Chilton-Colburn analogy or Colburn analogy
3. Correlations for Mass Transfer correlations
Interphase mass transfer
The process of mass transfer from the bulk of one phase to the interphase surface and then from
interphase to the bulk of another phase is called interphase mass transfer.

As an example, consider absorption of SO2 from air in to water. In this case SO2 diffuses through air and
then passes through interface between the air and water and finally, diffuses through water.

Here mass transfer occurs in each phase because of concentration gradient till an equilibrium is
reached ( i.e. chemical potential of the component becomes same in both phases). The equilibrium
concentrations in gas and liquid phase, yA and xA (mole fractions) are measured.

If we inject additional SO2 in the air, a new set of equilibrium concentrations will be established with
higher concentrations in both phases.

Like the above we collect more equilibrium data and if we draw yA Vs xA the graph gives rise an
equilibrium curve for a given temperature and pressure.

For another system like (NH3 – air – Water) the curve will be different.
For dilute solutions equilibrium curve can be approximated to be a straight line. The equilibrium
relation in such cases may be expressed by Henry's law equation at low concentrations.

𝑝𝐴 = 𝐻𝑥𝐴
where H is equal to Henry's constant in atmosphere/ mole fraction

𝑝𝐴 𝐻
= 𝑦𝐴 = 𝑥 = 𝐻′𝑥𝐴
𝑝𝑡 𝑝𝑡 𝐴

where H' is Henry's law constant in mole fraction gas / mole fraction liquid.

It can be observed that H' depends on total pressure whereas H does not depends on total pressure.
 Two – film resistance theory :
Consider the mass transfer of a solute A from the bulk of a gas phase to the bulk of a liquid phase.

As shown in above figure, the concentration of A in the main body of gas is yAG mole fraction and it falls to yAi
at the interface.

In the liquid, the concentration falls from xAi at the interface to xAL in the bulk liquid.
According to the Lewis and Whitman (1924) there is no resistance to solute across the interface separating the
phases.

Only diffusional resistances are residing in the fluids. This concept is called two-resistance theory.
The equilibrium concentrations yAi, xAi are obtained from systems equilibrium distribution curve.
yAi, xAi are equilibrium concentrations.
For steady state mass transfer, the rate at which A reaches the interface from the gas must be equal to the
rate at which it diffuses to the bulk liquid. So that no accumulation or depletion of A at the interface occurs.

Therefore, the mass transfer flux of A in terms of mass transfer film coefficient for each phase can be written
as

𝑁𝐴 = 𝑘𝑦 𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 𝑘𝑥 𝑥𝐴𝑖 − 𝑥𝐴𝐿

𝑦𝐴𝐺 − 𝑦𝐴𝑖 𝑘𝑥
= −
𝑥𝐴𝑖 − 𝑥𝐴𝐿 𝑘𝑦

yAi = f (xAi)
Overall mass transfer coefficients

Usually, the solute concentrations in the bulk fluids can be determined by sampling and
analysing. But sampling at interface is impossible.
Sampling procedure can give yAG and xAi but not yAi and xAi which are important to determine rate
of mass transfer.

The equilibrium distribution curve for the system is

unique at fixed temperature and pressure.

Point P represents the bulk concentrations xAL and yAG.

Bulk concentrations are measured easily. yA* and xA*

are measured as good as measuring xAL and yAG.

The entire two-phase mass transfer effect can be measured in terms of overall mass transfer
coefficient.
𝑁𝐴 = 𝐾𝑦 𝑦𝐴𝐺 − 𝑦𝐴∗
From figure
𝑦𝐴𝐺 − 𝑦𝐴∗ = 𝑦𝐴𝐺 − 𝑦𝐴𝑖 + 𝑦𝐴𝑖 − 𝑦𝐴∗

= 𝑦𝐴𝐺 − 𝑦𝐴𝑖 + 𝑚′ 𝑥𝐴𝑖 − 𝑥𝐴𝐿 ---- (1)

𝑦𝐴𝑖 − 𝑦𝐴∗
𝑓𝑟𝑜𝑚 𝑔𝑟𝑎𝑝ℎ , = 𝑚′ → 𝑦𝐴𝑖 − 𝑦𝐴∗ = 𝑚′ 𝑥𝐴𝑖 − 𝑥𝐴𝐿
𝑥𝐴𝑖 − 𝑥𝐴𝐿
We have

𝑁𝐴 = 𝑘𝑦 𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 𝑘𝑥 𝑥𝐴𝑖 − 𝑥𝐴𝐿 (𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑙𝑜𝑐𝑎𝑙 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡)

𝑁𝐴
= 𝑦𝐴𝐺 − 𝑦𝐴𝑖
𝑘𝑦

𝑁𝐴
= 𝑥𝐴𝑖 − 𝑥𝐴𝐿
𝑘𝑥

𝑁𝐴
= 𝑦𝐴𝐺 − 𝑦𝐴∗
𝐾𝑦
 𝑁𝐴 𝑁𝐴 𝑁𝐴
= + 𝑚′
𝐾𝑦 𝑘𝑦 𝑘𝑥

1 1 1
= + 𝑚′ −− −(2)
𝐾𝑦 𝑘𝑦 𝑘𝑥
Overall resistance = gas phase resistance + liquid phase resistance

Similarly xA* is the measure of yAG and overall coefficient is defined as

𝑁𝐴 = 𝐾𝑥 𝑥𝐴∗ − 𝑥𝐴𝐿

𝑥𝐴∗ − 𝑥𝐴𝐿 = 𝑥𝐴∗ − 𝑥𝐴𝑖 + 𝑥𝐴𝑖 − 𝑥𝐴𝐿

𝑦𝐴𝐺 − 𝑦𝐴𝑖
𝑥𝐴∗ − 𝑥𝐴𝐿 = + 𝑥𝐴𝑖 − 𝑥𝐴𝐿
𝑚"

𝑁𝐴 𝑁𝐴 𝑁𝐴
= +
𝐾𝑥 𝑚"𝑘𝑦 𝑘𝑥

1 1 1
= + −− −(3)
𝐾𝑥 𝑚"𝑘𝑦 𝑘𝑥
The equations 2 and 3 leads to the following relationships among mass transfer coefficients

1ൗ
𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑔𝑎𝑠 𝑝ℎ𝑎𝑠𝑒 𝑘𝑦
=
𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑏𝑜𝑡ℎ 𝑝ℎ𝑎𝑠𝑒𝑠 1ൗ
𝐾𝑦
1ൗ
𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒 𝑘𝑥
=
𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑏𝑜𝑡ℎ 𝑝ℎ𝑎𝑠𝑒𝑠 1ൗ
𝐾𝑥
𝑝𝐴𝐺 − 𝑝𝐴∗ = 𝑝𝐴𝐺 − 𝑝𝐴𝑖 + 𝑝𝐴𝑖 − 𝑝𝐴∗

= 𝑝𝐴𝐺 − 𝑝𝐴𝑖 + 𝑚′ 𝑐𝐴𝑖 − 𝑐𝐴∗ ---- (1)

We have
𝑁𝐴 = 𝑘𝐺 𝑝𝐴𝐺 − 𝑝𝐴𝑖 = 𝑘𝐿 𝑐𝐴𝑖 − 𝑐𝐴𝐿 )

𝑁𝐴
= 𝑝𝐴𝐺 − 𝑝𝐴𝑖
𝑘𝐺

𝑁𝐴
= 𝑐𝐴𝑖 − 𝑐𝐴𝐿
𝑘𝐿

𝑁𝐴
= 𝑝𝐴𝐺 − 𝑝𝐴∗
𝐾𝐺

𝑁𝐴 𝑁𝐴 ′
𝑁𝐴
= + 𝑚
𝐾𝐺 𝑘𝐺 𝑘𝐿

1 1 1
= + 𝑚′ −− −(2)
𝐾𝐺 𝑘𝐺 𝑘𝐿
Similarly cA* is the measure of pAG and overall
coefficient is defined as

𝑁𝐴 = 𝐾𝐿 𝑐𝐴∗ − 𝑐𝐴𝐿

𝑐𝐴∗ − 𝑐𝐴𝐿 = 𝑐𝐴∗ − 𝑐𝐴𝑖 + 𝑐𝐴𝑖 − 𝑐𝐴𝐿

𝑝𝐴𝐺 − 𝑝𝐴∗
𝑐𝐴∗ − 𝑐𝐴𝐿 = + 𝑐𝐴𝑖 − 𝑐𝐴𝐿
𝑚"

𝑁𝐴 𝑁𝐴 𝑁𝐴
= +
𝐾𝐿 𝑚"𝑘𝐺 𝑘𝐿

1 1 1
= + −− −(3)
𝐾𝐿 𝑚"𝑘𝐺 𝑘𝐿
The equations 2 and 3 leads to the following relationships among mass transfer coefficients

1ൗ
𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑔𝑎𝑠 𝑝ℎ𝑎𝑠𝑒 𝑘𝑦
=
𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑏𝑜𝑡ℎ 𝑝ℎ𝑎𝑠𝑒𝑠 1ൗ
𝐾𝑦
1ൗ
𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝ℎ𝑎𝑠𝑒 𝑘𝑥
=
𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑏𝑜𝑡ℎ 𝑝ℎ𝑎𝑠𝑒𝑠 1ൗ
𝐾𝑥
Case 1: Gas film controlling

For highly soluble gases, for example ammonia in water HCl in water, resistance in liquid film will
be very small compare to resistance in gas film. In other words, liquid film mass transfer coefficients
are very large compare to gas film mass transfer coefficients.

Overall resistance ≈ resistance by gas film.

In such cases m' is very small (equilibrium is flat). A very small concentration difference in gas will
provide a very large concentration difference in liquid.

1 1
≈ 𝑜𝑟 𝑦𝐴𝐺 − 𝑦𝐴∗ ≈ 𝑦𝐴𝐺 − 𝑦𝐴𝑖
𝐾𝑦 𝑘𝑦

In such cases the mass transfer rates can not be increases by increasing rates in liquid film by
agitation of liquid film, rather mass transfer rates can be increased by increasing rates in gas phase,
by decreasing gas film resistance.
Case 2: Liquid film controlling

For less soluble gases, such as oxygen or nitrogen in water, resistance in gas film is very
small compare to resistance in liquid film. In other words, gas film mass transfer
coefficients are very large compare to liquid film mass transfer coefficients.

Overall resistance ≈ resistance by liquid film.

In such cases 𝑚" is very large (equilibrium is vertical). A very large concentration
difference in gas will provide a very small concentration difference in liquid.

1 1
≈ 𝑜𝑟 𝑥𝐴∗ − 𝑥𝐴𝐿 ≈ 𝑥𝐴𝑖 − 𝑥𝐴𝐿
𝐾𝑥 𝑘𝑥

In such cases the mass transfer rates cannot increases by increasing rates in gas film.
Rather mass transfer rates can be increased by influencing the liquid coefficient by
agitation of liquid film.
For cases where kx and ky are not nearly equal, the relative size of the ratio of kx/ky and of m'
(or m") which will determine the location of the controlling mass transfer resistance.

It is useful to note that the effect of temperature is much larger for liquid phase mass transfer
coefficients than for those for gases. Consequently, a large effect of temperature on overall
coefficient, when it is determined experimentally, is fairly clear indication that the controlling
mass transfer resistance is in the liquid phase.
In an experimental study of absorption of ammonia by water in a wetted wall column the overall gas
phase mass transfer coefficient, KG was estimated as 2.72 x 10-4 kmol/m2s atm. At one point in the
column the gas contained 10 mol % ammonia and the liquid phase concentration was 6.42 x 10-2
kmol NH3/m3 of solution. Temperature is 293 K and the total pressure is 1 atm. 85 % of the resistance
to mass transfer lies in gas phase. If Henry’s law constant is 9.35 x 10-3 atm.m3/kmol, calculate the
individual film coefficient and the interfacial composition.

Solution

KG = 2.72 x 10-4 kmol/m2s atm

Resistance
1 1 𝑚2 𝑠 𝑎𝑡𝑚
= = 3676.47
𝐾𝐺 2.72 𝑋 10−4 𝑘𝑚𝑜𝑙
1 1 𝑚2 𝑠 𝑎𝑡𝑚
= 0.85 𝑋 = 3125
𝑘𝐺 𝐾𝐺 𝑘𝑚𝑜𝑙
We know that
1 1 𝑚
= +
𝐾𝐺 𝑘𝐺 𝑘𝐿

m = Henry’s constant = 9.35 x 10-3 atm.m3/kmol

By substituting the values of KG, kG and m we can obtain kL

kL =1.695 x 10-5 m/s

We shall now calculate the interfacial concentration from the following relation

𝑁𝐴 = 𝐾𝐺 𝑝𝐴𝐺 − 𝑝𝐴∗

= 𝑘𝐺 𝑝𝐴𝐺 − 𝑝𝐴𝑖

= 𝑘𝐿 𝐶𝐴𝑖 − 𝐶𝐴𝐿

𝑦𝐴𝐺 = 0.1
𝑘𝑚𝑜𝑙 𝑁𝐻3
𝐶𝐴𝐿 = 6.42 𝑋 10−2
𝑚3 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑝𝐴𝐺 = 𝑦𝐴𝐺 𝑋 𝑝𝑡 = 0.1 𝑋 1 = 0.1 𝑎𝑡𝑚

𝑝𝐴𝑖 = 𝑚 𝐶𝐴𝑖

𝑁𝐴 = 𝑘𝐺 𝑝𝐴𝐺 − 𝑝𝐴𝑖 = 𝑘𝐿 𝐶𝐴𝑖 − 𝐶𝐴𝐿

 𝑘𝐺 𝐶𝐴𝑖 − 𝐶𝐴𝐿
=
𝑘𝐿 𝑝𝐴𝐺 − 𝑚 𝐶𝐴𝑖

𝐶𝐴𝑖 − 6.42 𝑋 10−2

8.88 =
0.1 − 9.35 x 10−3 𝐶𝐴𝑖

𝑘𝑚𝑜𝑙
𝐶𝐴𝑖 = 1.6593
𝑚3

𝑝𝐴𝑖 = 𝑚 𝐶𝐴𝑖 = 9.35 x 10−3 𝑋 1.6593 = 0.0155 𝑎𝑡𝑚

Problem
The equilibrium distribution of a solute A between air and water at low concentration at a particular
temperature is given as y = 1.2 x
At certain point in a mass transfer device the concentration of solute A in the bulk air is 0.04 mole
fraction and that in the bulk aqueous phase is 0.025. In which direction does the transport of solute A
occur (i.e. from gas to liquid or from liquid to gas)? Calculate the overall gas phase and the overall
liquid phase driving forces for mass transfer?
At the same point the local individual mass transfer coefficients for the transport of A are,
ky = 7.2 kmol/h.m2.y and kx = 4.6 kmol/h.m2.x. Calculate a. the interfacial concentrations in both
the gas phase and the liquid phase b. the overall mass transfer coefficients, Kx and Ky and c. the local
mass flux, NA. which resistance controls the role of mass transfer?

Bulk concentration of A in gas phase yAG = 0.04; equilibrium relation: y = 1.2 x

The corresponding equilibrium liquid phase concentration,

𝑦𝐴𝐺 0.04
𝑥𝐴∗ = = = 0.0333
1.2 1.2

The actual concentration of the solute in the bulk liquid is xAL = 0.025 which is less than the
equilibrium value. Therefore, the transport of the solute A will occur from the gas phase to the liquid
phase.
The overall driving force:
On gas phase basis, 𝑦𝐴𝐺 − 𝑦𝐴∗ = 0.04 − 1.2 x𝐴𝐿 = 0.04 − 1.2 0.025 = 0.01

On liquid phase basis, 𝑥𝐴∗ − x𝐴𝐿 = 0.0333 − 0.025 = 0.0083

Given, ky = 7.2 kmol/h.m2.y and kx = 4.6 kmol/h.m2.x

At steady state, the local overall flux is

𝑁𝐴 = 𝑘𝑦 𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 𝑘𝑥 𝑥𝐴𝑖 − x𝐴𝐿

7.2 0.04 − 𝑦𝐴𝑖 = 4.6 𝑥𝐴𝑖 − 0.025

𝐼𝑛𝑡𝑒𝑟𝑓𝑎𝑐𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛𝑠 𝑎𝑟𝑒 𝑖𝑛 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚, 𝑦𝐴𝑖 = 1.2 𝑥𝐴𝑖

Solving the above two equations, the interfacial concentrations are

xAi = 0.03044 and yAi = 0.03653

b. The overall gas phase coefficient,

1 1 𝑚′ 1 1.2
= + = + = 0.1389 + 0.2609 = 0.3998
𝐾𝑦 𝑘𝑦 𝑘𝑥 7.2 4.6

Ky = 2.501 kmol/h.m2.y

The overall liquid phase coefficient,

1 1 1 1 1
= + = + = 0.1157 + 0.2174 = 0.3331
𝐾𝑥 𝑚"𝑘𝑦 𝑘𝑥 1.2 (7.2) 4.6

Kx = 3.0002 kmol/h.m2.x
c.
kmol
𝑁𝐴 = 𝑘𝑦 𝑦𝐴𝐺 − 𝑦𝐴𝑖 = 7.2 0.04 − 0.03653 = 0.025
m2 . ℎ
The controlling resistance:
Fraction of the total mass transfer resistance in the gas-phase
1ൗ
𝑘𝑦 0.1389
= = 0.347
1ൗ 0.3998
𝐾𝑦
Fraction of the total mass transfer resistance in the liquid-phase
1ൗ
𝑘𝑥 0.2174
= = 0.653
1ൗ 0.3331
𝐾𝑥
So the mass transfer resistances are comparable in magnitude and neither of them can be said to be
controlling.
Theories of mass transfer

Various theories are proposed to explain the mechanism of turbulent mass transfer and
developing for expressions for the mass transfer coefficient theoretically.

1. Film theory (Whitman 1923)

➢ Nernst (1904) proposed that near the interface there exists a stagnant film towards the liquid
at gas-liquid interface.
➢ This stagnant film is hypothetical, since we do not know the details of the velocity profile near
interface
➢ The basic concept is the resistance to diffusion is due to this stagnant film
➢ Mass transfer occurs through this film at steady state

𝑑𝑐 𝑐𝐴 𝑐𝐴
𝑁𝐴 = −𝐷𝐴𝐵 𝑑𝑧𝐴 ( the bulk flow term 𝑁, in 𝑁𝐴 = 𝐽𝐴 + 𝑁 is small when mass transfer
𝑐 𝑐
occurs at low concentrations
Steady state mass balance over an elementary volume of thickness z

Rate of input of solute at z = 𝑁𝐴 ȁ𝑧

Rate of output of solute at z+z = 𝑁𝐴 ȁ𝑧+z

Rate of accumulation is zero

Rate of accumulation = Rate of input - Rate of output

𝑁𝐴 ȁ𝑧 − 𝑁𝐴 ȁ𝑧+z = 0

𝑁𝐴 ȁ𝑧 − 𝑁𝐴 ȁ𝑧+z
lim =0
∆𝑧→ ∝ ∆𝑧

𝑑𝑁𝐴
=0
𝑑𝑧

𝑑 𝑑𝑐𝐴
−𝐷𝐴𝐵 =0
𝑑𝑧 𝑑𝑧

𝑑 2 𝑐𝐴
=0
𝑑𝑧 2
Integrate the above for the following boundary conditions

𝑐𝐴 = 𝑐𝐴𝑖 𝑤ℎ𝑒𝑛 𝑧 = 0

𝑐𝐴 = 𝑐𝐴𝑏 𝑤ℎ𝑒𝑛 𝑧 = 𝛿

𝑧
𝑤𝑒 𝑔𝑒𝑡 𝑐𝐴 = 𝑐𝐴𝑖 − 𝑐𝐴𝑖 − 𝑐𝐴𝑏
𝛿

Hence according to film theory concentration profile in stagnant film is linear

𝑑𝑐𝐴
Molar flux through film 𝑁𝐴 = −𝐷𝐴𝐵 𝑑𝑧
𝐷𝐴𝐵 𝑐𝐴𝑖 − 𝑐𝐴𝑏
𝑁𝐴 =
𝛿

𝐷𝐴𝐵
𝑘𝐿 =
𝛿

In this film transport is governed by molecular diffusion

There for Fick’s law describes flux through film
 𝑑 2 𝑐𝐴
=0
𝑑𝑧 2

𝑑𝑐𝐴
=𝐴
𝑑𝑧
𝑐𝐴 𝑧
න 𝑑𝑐𝐴 = 𝐴 න 𝑑𝑧
𝑐𝐴𝑖 0

𝑐𝐴 − 𝑐𝐴𝑖 = 𝐴𝑧 −−− −(1)

𝑐𝐴𝑏 𝛿
න 𝑑𝑐𝐴 = 𝐴 න 𝑑𝑧
𝑐𝐴𝑖 0

𝑐𝐴𝑖 − 𝑐𝐴𝑏 = − 𝐴 𝛿 −−− − 2

𝑐𝐴𝑖 − 𝑐𝐴𝑏
𝐴= −
𝛿

𝑐𝐴 = 𝑐𝐴𝑖 + 𝐴𝑧

𝑧
𝑐𝐴 = 𝑐𝐴𝑖 − 𝑐𝐴𝑖 − 𝑐𝐴𝑏
𝛿
Assumptions :

1. Mass transfer occurs purely by molecular diffusion through the stagnant film layer. Beyond this film
concentration is same due to well mixing of fluid.
2. Mass transfer through the film occurs at steady state

Limitations:

1. Effective diffusion coefficient is seldom constant since some turbulence occurs and enters in the
film.
2. It does not visualize a realistic physical picture regarding the mechanism of mass transfer at
phase boundary
Penetration theory

This theory was proposed by Higbie (1935)

In many situations, the time of exposure of a fluid to mass transfer is short, so that the concentration
gradient of the film theory, characteristic of steady state would not have time to develop

Higbie explained as a bubble of gas rises through a liquid which absorbs the gas

A particle of the liquid b, initially at the top of the bubble, is in contact with the gas for the time ,
required for the bubble to rise a distance equal to its diameter while the liquid particles slips along
the surface of the bubble.

An extension to the case, where the liquid may be in turbulent motion, an eddy b rising from
turbulent depth of the liquid and remaining exposed for a time  to the action of gas.

In this theory, the time of exposure is taken as constant for all such eddies or particles of liquid
Initially, the concentration of dissolved gas in the eddy is uniformly CA0

When the eddy is exposed to the gas at the surface the concentration in the liquid at the gas liquid
interface is CAi ,which may be taken as equilibrium solubility of the gas in the liquid

It is assumed that equilibrium is immediately attained by the surface layers that a process of unsteady
state molecular diffusion then occurs and that the element is remixed after a fixed interval of time.

Assumptions;

1. Unsteady state mass transfer occurs as long as it is in contact with the bubble

2. Equilibrium exists at gas liquid interface

3. Each of liquid elements stays in contact with gas for the same period of time.
Diffusion of A away from the interface the Fick’s second law (z – direction) reduces to

𝜕𝑐𝐴 𝑑2 𝑐𝐴 𝜕𝑐𝐴 𝑑2 𝑐𝐴 𝑑2 𝑐𝐴
=𝐷 { =𝐷 ቀ 𝑑𝑥 2 + +
𝜕𝑡 𝑑𝑧 2 𝜕𝑡 𝑑𝑦 2
𝑑2 𝑐𝐴
ቁ }
𝑑𝑧 2

Boundary conditions
t = 0 Z > 0 𝑐𝐴 = 𝑐𝐴𝑏
t > 0 Z = 0 𝑐𝐴 = 𝑐𝐴𝑖
t > 0 Z = ∞ 𝑐𝐴 = 𝑐𝐴𝑏
𝑐𝐴𝑖 = concentration at interface
𝑐𝐴𝑏 = concentration in the bulk phase

Solving the above eqution and proceeding for average flux

𝐷𝐴𝐵
𝑁𝐴𝑣𝑔 = 2 𝑐𝐴𝑖 − 𝑐𝐴𝑏
𝜋𝜃
𝑘𝐿 𝑎𝑣𝑔 𝛼 𝐷𝐴𝐵
Surface – renewal theory

Danckwerts (1951) pointed out that Higbie theory with its constant time of exposure of the eddies of
the fluid at the surface is a special case of what may be more realistic picture, where eddies
exposed for varying lengths of time.

The liquid at the interface is then a mosaic of elements of different exposure time histories.
If “S” is the fractional rate of replacement of elements Danckwerts found

𝑁𝐴𝑣𝑔 = 2 𝑐𝐴𝑖 − 𝑐𝐴𝑏 𝐷𝐴𝐵 𝑆

𝑘𝐿 𝑎𝑣𝑔 = 𝐷𝐴𝐵 𝑆

Assumptions
1. The liquid elements at the interface are being randomly swapped by fresh elements from bulk
2. At any moment, each of the liquid elements at the surface has some probability of being
substituted by fresh element
3. Unsteady state mass transfer takes place to an element during its stay at the interface.
 Unit – 3
Equipment for gas-liquid
operations
 Gas-Gas : Practically not realized

Gas-Liquid: Distillation, Absorption,

Humidification

CLASSIFICATION Gas-Solid: Adsorption, Drying

OF
MASS TRANSFER OPERATIONS
Liquid –Liquid: Liquid Liquid Extraction

Liquid - Solid : Leaching, Adsorption,

Crystallization

Solid –Solid : Practically not realized

These operations involve interphase mass transfer and require intimate contact among the phases.

The main purpose of the equipment for interphase mass transfer is to provide intimate contact of the
immiscible phases.

At the same time the pressure drop through the equipment and hence the power requirement should be as low
as possible

Equipment

Continuous Batch

A high degree of turbulent mixing is created properly disperse one phase into the other. This helps
in generating a large interfacial area of contact as well as in increasing the mass transfer coefficient.
 Batch Continuous
1. Unsteady state operation 1. Steady state operation
2. Simple in construction with small 2. Complex in construction with more
instrumentation instrumentation
3. Low investment cost and high operating 3. High investment cost and low operating
cost cost
4. Difficult to maintain same quality of the 4. Once equipment is reached steady state,
product in all batches produces same quality of the product
5. Flexibility in production ( can be used 5. Not so flexible in production
for different types of product production) 6. Production capacity is high
6. Production capacity is low
 Designed and fabricated according to
the requirements of the client; these
Custom built types of equipment cannot be readily
purchased from the market
Equipment
Proprietary equipment is designed by the
Proprietary manufacturer to meet performance
specifications made by the user. Pumps,
compressors, valves, piping

Gas is dispersed in the liquid in the form of

Gas dispersed bubbles. For example: bubble columns,
agitated vessels, tray towers,
Equipment
Liquid is dispersed in the form of droplets
Liquid or discontinuous films in a continuous gas
dispersed phase. For example: wetted wall column,
spray towers, packed towers, venturi
scrubber
Gas dispersed

Sparged vessel Agitated vessel Tray column

Liquid Dispersed: Packed column

Wetted wall column Spray column

Tray and packed columns are most widely used for gas-liquid contacting - namely for gas
absorption, stripping, distillation.

Tray Columns
A tray tower primarily consists of a vertical cylindrical shell and a set
of 'tower internals' that include
1. Trays or plates on which the gas-liquid contact occurs
2. Arrangements for flow of the liquid from one tray to the lower one
through the down comer
3. Inlet and outlet nozzles for the two phases

In a gas absorption application, the liquid enters the top tray through
a nozzle. It flows across each tray and flows into the lower tray through
a 'downcomer’.

The gas flows upwards and vigorously bubbles through the liquid on a
tray, forming a turbulent 'gas-liquid dispersion' in which bubble
breakage and coalescence occur continuously.
An average depth of the dispersion is maintained on a tray.

Mass transfer from the gas to the liquid (or from the liquid to the gas)
phase occurs depending on the direction of the driving force.

In 'gas absorption', the solute gets transported from the gas to the liquid
phase; the reverse occurs in stripping.

The gas then leaves the froth or dispersion and enters the next upper tray.
The liquid flows across a tray and then over a 'weir' to enter into the
downcomer.

The downcomer is a region near the wall, separated by a 'downcomer

plate', in which the bubbles get disengaged from the liquid

In this way, countercurrent and stage-wise gas liquid contact takes place in
the tower. Each tray acts as a stage in which the liquid flowing down from
the upper tray and the gas flowing up from the lower tray come into
contact; the tower acts as a cascade.
The number of equilibrium stages (ideal trays) required for a given
separation is determined solely from material balances and equilibrium
considerations

The stage efficiency and therefore the number of real trays is determined
by mechanical design and the conditions of operation.

We will briefly discuss the constructional and operational features of a tray

tower and tower internals.
Tray and packed columns are most widely used for gas-liquid contacting - namely for gas
absorption, stripping, distillation.

Tray Columns
A tray tower primarily consists of a vertical cylindrical shell and a set
of 'tower internals' that include
1. Trays or plates on which the gas-liquid contact occurs
2. Arrangements for flow of the liquid from one tray to the lower one
through the down comer
3. Inlet and outlet nozzles for the two phases

In a gas absorption application, the liquid enters the top tray through
a nozzle. It flows across each tray and flows into the lower tray through
a 'downcomer’.

The gas flows upwards and vigorously bubbles through the liquid on a
tray, forming a turbulent 'gas-liquid dispersion' in which bubble
breakage and coalescence occur continuously.
An average depth of the dispersion is maintained on a tray.

Mass transfer from the gas to the liquid (or from the liquid to the gas)
phase occurs depending on the direction of the driving force.

In 'gas absorption', the solute gets transported from the gas to the liquid
phase; the reverse occurs in stripping.

The gas then leaves the froth or dispersion and enters the next upper tray.
The liquid flows across a tray and then over a 'weir' to enter into the
downcomer.

The downcomer is a region near the wall, separated by a 'downcomer

plate', in which the bubbles get disengaged from the liquid

In this way, countercurrent and stage-wise gas liquid contact takes place in
the tower. Each tray acts as a stage in which the liquid flowing down from
the upper tray and the gas flowing up from the lower tray come into
contact; the tower acts as a cascade.
The number of equilibrium stages (ideal trays) required for a given
separation is determined solely from material balances and equilibrium
considerations

The stage efficiency and therefore the number of real trays is determined
by mechanical design and the conditions of operation.

We will briefly discuss the constructional and operational features of a tray

tower and tower internals.
The Shell

The shell is usually made of a metal or an alloy. Plastic shells are also used
sometimes. The material is selected on the basis of corrosiveness of the
fluids, temperature and pressure conditions, and cost.

If the shell diameter is small, it may be made of several flanged sections in

order that the trays may be fitted into it and maintained, when necessary,
by opening it. Tray towers of diameter less than 1 metre are rarely used.

On the other extreme, towers as big as 10 metre in diameter are known to

be in use. Shell thickness is calculated by using a standard vessel design
code (for example, ASME Section VllI; IS 2825).
A tower is generally 'skirt-supported' on concrete foundations.

The support should be strong enough to take the column weight, the liquid
load and the wind stress.

The seismic factor at the particular location is also needed to be

considered during column and support design. Since the bending
moment due to wind load is maximum at the tower bottom, it is a common
practice to use different wall thicknesses for different sections of the shell.

The bottom section has the maximum thickness and the upper sections
have gradually smaller thicknesses. This strategy substantially reduces the
weight, and hence the cost of the shell.
The Tray

A 'tray' has two major functions:

1. It allows the gas to flow through the holes or passages; the gas
vigorously bubbles through the liquid to form a 'gas-liquid
dispersion'. The tray holds the dispersion on it.
2. The trays separate the column into a number of compartments
each of which constitutes a stage.

Mass transfer between the phases occurs on a tray. Therefore, the

trays as a whole constitute the heart of a column.

The performance of a column depends upon the performance of

the trays.

Trays are also called 'plates'. There are quite a few types of trays in
use.

1. Bubble cap tray

2. Sieve tray
3.Valve tray
The bubble-cap tray
A bubble cap consists of two major
components-a bell-shaped 'cap' and a
'riser' (also called a 'chimney’).

The riser is inserted through a hole on the

tray floor and the bell-shaped cap is bolted
to it.

The riser is a piece of tube with a flared or

expanded bottom end. In fact, the riser
acts as the vapour passage and also holds
the cap.

The caps and the risers are made of low

carbon steel, stainless steel or any other
suitable material that can withstand the
environment within the tower.

Caps are arranged on a tray on equilateral

triangular pitch with rows normal to the
direction of liquid flow. Bubble caps
generally range from 1 inch to 6 inches in
diameter.
Sieve Tray This is the simplest type of tray in which the bubble caps
are replaced by holes or perforations for entrance of the
gas into the liquid.

The vapour passes up through perforations in the plate;

and the liquid is retained on the plate by the vapour flow.
At low flow-rates liquid will "weep" through the holes,
reducing the plate efficiency.

The holes are of relatively small diameter - usually

ranging from 1/8 to 1/2 in. This is why the name 'sieve
tray' (also called 'perforated tray’)

For clean services, use of a hole diameter 3/8 in. is

common.

However, for liquids that foul or cause deposition use of a

hole diameter 1/2 in.

For vacuum services 1/8 in can be used.

Small holes enhance tray capacity, reduce entrainment, reduce weeping, promote froth regime
operation and exhibit better mass transfer characteristics.
The valve tray
The valve tray is a relatively new class of tray that provides variable
area for the gas or vapour flow depending upon the flow rate or
'throughput'. This is why it is called 'valve tray’.

A valve tray is a proprietary tray. Different types of valve trays are

made by different companies.

A common valve tray has sufficiently large punched holes on the tray
floor, each fitted with a movable disk, generally circular. A disk has
guides that can slide vertically up or down along the thickness of the
tray floor.

The opening for the gas flow changes in this way, but the disk is
always held in the same vertical line. As the gas flow increases, the
disk is automatically raised. It settles down at a low vapour rate to
prevent 'weeping’.

The guides or retaining legs are bent at the end so that the disk does
not pop up or gets detached even at a large vapour rate.
The trays do not easily acquire deposits from dirty liquids, polymers
or other solids because of the up and down motion of the disk and the
guides.Valve units are, therefore, self-cleaning.

The valve tray is a good choice for highly fouling services. In addition,
they offer lower pressure drop than the bubble-cap type and
generally they are cheaper than the latter type.

A few problems common to all kinds of valve trays are (i) mechanical
wear and corrosion because of continuous movement of the valve
legs, and (ii) sticking of the disk on the tray if there is sticky deposition
on the tray.

In a common valve tray layout, 12 to 16 valves per ft2 of tray area are
accommodated.

Because of high flexibility, high turndown ratio and relatively low cost,
valve trays are now widely used for gas absorption and distillation.
Downcomers and weirs

The 'downcomer' is a passage through which the liquid

flows down from one tray to the next below.

The desired depth of the gas-liquid dispersion is

maintained on a tray by using a 'weir' in the form of a
vertical plate.

The liquid, along with some dispersed gas or vapour

bubbles, overflows the weir and enters the 'downcomer'
or the 'downspout’.

Disengagement of the gas as bubbles occurs in the

upper region of a downcomer. The lower region contains
clear liquid that enters the lower tray.
The downcomer must provide sufficient residence time
for gas-liquid disengagement.

The residence time is usually 3 to 5 seconds. However for

a foaming liquid, considerably higher residence time
and therefore a larger downcomer volume has to be
provided.

The 'clear liquid' velocity in the downcomer normally

ranges between 0.3 and 0.5 ft/s. This value may vary
depending upon the liquid properties.

The weir length may vary from 60 to 80% of the tower

diameter; the downcomer area correspondingly varies
from 5 to 15% of the tray area. A weir height of 1 to 2
inches is generally maintained.
Nozzles
A tower for contacting a liquid and a vapour (or a gas)
should be provided with a few nozzles for feed entry
(both gas and liquid), entry of reflux at the top and of the
reboiler vapour return at the bottom (in a distillation
column), and for product withdrawal from the tower.

The primary criterion of a feed nozzle design is to ensure

that the feed is introduced with minimum splashing or
jetting (the velocity of liquid feed in the nozzle should not
exceed 1 m/s). The feed should be evenly distributed
and mixed with internal liquid or vapour.

Mist Eliminator
Even under normal operating conditions, a little
entrainment of liquid in the upflowing vapour may occur.
In order to prevent entrainment in the vapour leaving the
top tray, a pad made of wire mesh or a pack of suitably
bent and spaced thin sheets is fitted above it.

The droplets are retained after they strike the surface of

the pad. Such a device is called 'mist eliminator' or a
'demister'