Oxygen absorption in lungs

Inhaled air passes through larynx, trachea, bronchi and

finally into alveoli. Oxygen is transferred through the
walls of each alveolus into blood flowing in the capillaries
surrounding alveolus.

We want to find oxygen transfer rate in the lungs for

𝑐𝑐 𝑐𝑚2
a normal adult in . Diffusivity of oxygen in blood is ~1.8 × 10−5 ,
𝑚𝑖𝑛 𝑠
There are about 480 million alveoli, volume of each alveolus is
6 3 𝑐𝑚2
4.2 × 10 𝜇𝑚 , interfacial area is 30 ,
𝑐𝑚3
𝑚𝑜𝑙
Henry’s law is 𝑝 𝑎𝑡𝑚 = 7.6 × 105 𝑐 assume,
𝑐𝑐
oxygen concentration in bulk blood to be zero.
𝐷 𝑝
Mass transfer rate is: 𝑘𝑐 𝐴𝑐1𝑖 = 𝐴
𝑙 𝐻
−5𝑐𝑚2
1.8 × 10 𝑠 𝑐𝑚2 1𝑚3 106 𝑐𝑚3 0.21 𝑎𝑡𝑚
6 6 3
= × 30 × 480 × 10 × 4.2 × 10 𝜇𝑚 × × × 𝑎𝑡𝑚 𝑐𝑐
0.01 𝑐𝑚 𝑐𝑚3 1018 𝜇𝑚3 1𝑚3 7.6 × 105
𝑚𝑜𝑙
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑐𝑐 𝑠 310 𝑐𝑐
= 3 × 10−5 = 3 × 10−5 × 22400 × 60 × = 46
𝑠 𝑠 𝑚𝑜𝑙 𝑚𝑖𝑛 273 𝑚𝑖𝑛

Oxygen absorption in normal adults at rest is roughly 300 mL/min! How do we reconcile this fact with above
calculation?
 Absorption of SO2 in water: Which phase controls mass transfer?
We wish to analyze dissolution of SO2 from its dilute mixture in air into water. The mass transfer coefficients of SO2 in air and
water are 𝑘𝑐′ = 3.4 𝑐𝑚Τ𝑠 and 𝑘𝑐 = 1.5 × 10−3 𝑐𝑚Τ𝑠 , respectively. The Henry’s law constant for SO2 is 𝐻 = 840 𝑎𝑡𝑚 𝑐𝑐Τ𝑚𝑜𝑙 .
Temperature is 30 oC.
′
Find overall mass transfer coefficient Equate fluxes in air and water phases: 𝑘𝑐′ 𝑐1′ − 𝑐1𝑖 = 𝑘𝑐 𝑐1𝑖 − 𝑐1

′ ′
The equilibrium relation with the given Henry’s constant can be rearranged to relate 𝑐1𝑖 and 𝑐1𝑖 : 𝑐1𝑖 = 𝑚𝑐1𝑖 Find 𝑚

𝐻 840 𝑎𝑡𝑚 𝑐𝑐ൗ𝑚𝑜𝑙

𝑚= = = 0.034
𝑅𝑇 82.1 𝑎𝑡𝑚 𝑐𝑐ൗ
𝑚𝑜𝑙 𝐾 × 303 𝐾

1 1
Eliminate interfacial concentrations to find overall mass transfer coefficient, 𝐾𝑐 = 𝑘 + 𝑚𝑘′ Find value of 𝐾𝑐 and resistances
𝑐 𝑐
of water and air phases

𝐾𝑐 = 1.48 × 10−3 𝑐𝑚Τ𝑠 𝑤𝑎𝑡𝑒𝑟 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 1.48 × 10−3 𝑐𝑚Τ𝑠 Transfer of SO2 is completely controlled by
= × 100 = 98.7%
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 1.5 × 10−3 𝑐𝑚Τ𝑠 water phase; air phase resistance is negligible

Draw concentration profiles in the water and air films

𝑐1𝑖

𝑝1 𝑝1𝑖

AIR SIDE WATER SIDE

𝑐1
We conduct an experiment on dissolution of sulphur dioxide (SO2) from air into water. The concentration of dissolved SO2
is measured with respect to time. Sketch the concentration of SO2 (y-axis) versus time (x-axis)

𝑆𝑂2
𝑡𝑖𝑚𝑒, 𝑠

Write a differential equation that describes evolution of concentration of SO2 in water. Take pressure of SO2 in air to be
𝑝 𝑎𝑡𝑚 , temperature of the system to be 𝑇 𝐾 .

𝑑𝑐1 𝑝 Overall mass transfer coefficient, 𝐾𝑐 , can be obtained from the slope of
𝑉 = 𝐾𝑐 𝐴
𝑑𝑡 𝐻 above plot during the initial stages of dissolution as: 𝐾𝑐 =
𝑉 × 𝑠𝑙𝑜𝑝𝑒×𝐻
𝐴𝑝

Dilute aqueous NaOH

We add sodium hydroxide to water to make a dilute aqueous solution of NaOH

It is known that SO2 reacts instantaneously and irreversibly with NaOH according to: SO2 + 2 NaOH Na2SO3 + H2O

We wish to analyse the effect of addition of sodium hydroxide to rate of absorption of SO2
Write a differential equation that describes change in concentration of NaOH (2) in water. Take pressure of SO2 in air to be
𝑝 𝑎𝑡𝑚 , temperature of the system to be 𝑇 𝐾 .

𝑑𝑐2 𝑝 𝑠𝑙𝑜𝑝𝑒 × 𝐻 × 𝑉

𝑁𝑎𝑂𝐻
𝑉 = −2𝐾𝑐𝑟 𝐴 𝐾𝑐𝑟 =
𝑑𝑡 𝐻 2𝐴𝑝

We gradually increase NaOH concentration and obtain 𝑘𝑟′ for several

[NaOH]
𝑡𝑖𝑚𝑒, 𝑠

Below Table summarizes results of these experiments Record your observations

[NaOH], mol/L
• Mass transfer coefficient rises with [NaOH]
MTC with NaOH
MTC without NaOH • Mass transfer coefficient plateaus off at higher [NaOH]
0.0 1
0.01 1.4
We want to explain these results using film theory of mass transfer
0.1 4.5
0.5 16
2.0 16
 Analysis of mass transfer with chemical reaction using film theory
Consider a reaction between gas species (1) and liquid species (2) Species Species Species
1 +𝜈 2 ⟶ 3

• For a system limited by liquid phase resistance, a reactive liquid is added to enhance the mass transfer in the liquid
phase.

• Gas film does not offer any resistance to mass transfer

• It is assumed that the reaction between dissolved gas and reactive liquid is instantaneous, that is, they cannot co-exist. The
liquid film shown below reflects this statement.

The diffusive flux of species 1 to the reaction front must equal the
diffusive flux of species 2, adjusted by the stoichiometric factor, 𝜈.
𝐷1
Using Fick’s law of diffusion, flux of species 1 to the front is: 𝑛1 = 𝑧
𝑐1𝑖 − 0

2 𝐷
Reaction front Similarly, diffusive flux of species 2 to the front is: 𝑛2 = 𝑙−𝑧 𝑐2𝐿 − 0

How are the two fluxes related? 𝜈𝑛1 = 𝑛2

𝜈𝐷1 𝑐1𝑖 𝑙
Find 𝑧. Reaction front is located at 𝑧 = 𝜈𝐷 from the interface
1 𝑐1𝑖 +𝐷2 𝑐2𝐿
𝑧
𝑧=𝑙 Substitute 𝑧 in equation for 𝑛1 and rearrange in the following form:
𝑧=0 Liquid film
𝐷1
𝑛1 = 1+ 𝑐1𝑖 − 0
𝑙
 Enhancement of mass transfer coefficient with chemical reaction
𝐷1 𝐷2 𝑐2𝐿 𝐷1 𝐷 𝑐2𝐿 𝐷 𝑐2𝐿
𝑛1 = 1+ 𝑐1𝑖 − 0 Mass transfer coefficient with reaction, 𝑘𝑐𝑟 = 1 + 𝜐𝐷2 = 𝑘𝑐 1 + 𝜐𝐷2
𝑙 𝜐𝐷1 𝑐1𝑖 𝑙 1 𝑐1𝑖 1 𝑐1𝑖
𝑘𝑐𝑟 𝐷 𝑐2𝐿
Enhancement factor: 𝑘𝑐
= 1 + 𝜐𝐷2
1 𝑐1𝑖

[NaOH], mol/L MTC with NaOH

MTC without NaOH
We want to look at experimental results on SO2 absorption
0.0 1
0.01 1.4
• Enhancement rises with [NaOH] 0.1 4.5
0.5 16
• Why does enhancement does not rise beyond 16?
2.0 16

Gas film controlled

Liquid film
controlled
Reaction front right
at the interface
Reaction front Reaction front
𝑐1

𝑐1𝑖 = 0
𝑧=0 𝑧=𝑙 Liquid film thins No liquid film
Liquid film Gas film
[NaOH] increases
 Tutorial 4
We wish to analyze dissolution of SO2 from its dilute mixture in air into aqueous solutions of sodium hydroxide. The mass
transfer coefficients of SO2 in air and water are 𝑘𝑐′ = 3.4 𝑐𝑚Τ𝑠 and 𝑘𝑐 = 1.5 × 10−3 𝑐𝑚Τ𝑠 , respectively. The Henry’s law constant for
SO2 is 𝐻 = 840 𝑎𝑡𝑚 𝑐𝑐Τ𝑚𝑜𝑙 . Temperature is 30 oC. Find overall mass transfer coefficient. Diffusion coefficient of SO2 in water is
2 2
1.9 × 10−5 𝑐𝑚 Τ𝑠 and diffusion coefficient of NaOH in water is 2.1 × 10−5 𝑐𝑚 Τ𝑠 .

1: SO2
SO2 + 2NaOH Na2SO3 + H2O
2: NaOH

Write equation for mass transfer flux in gas phase,

SO2 concentration in bulk gas is 𝑐1′ and
′
interfacial gas concentration is 𝑐1𝑖
′
Mass transfer flux in gas phase is 𝑁1 = 𝑘𝑐′ 𝑐1′ − 𝑐1𝑖

Write equation for mass transfer flux in liquid phase,

SO2 concentration in bulk liquid is 0 and 𝑧=0 𝑧=𝑙
Liquid film
its interfacial concentration is 𝑐1𝑖 𝐷2 𝑐2𝐿
𝑘𝑐𝑟 𝐷2 𝑐2𝐿 𝑘𝑐′ 𝑐1′ − 𝑘𝑐 ൗ𝜐𝐷
1
Mass transfer flux in liquid phase is 𝑁1 = 𝑘𝑐𝑟 𝑐1𝑖 − 0 =1+ Find interfacial concentration, 𝑐1𝑖 𝑐1𝑖 = ′
𝑘𝑐 𝜐𝐷1 𝑐1𝑖 𝑘𝑐 + 𝑚𝑘𝑐
𝜐𝐷1 𝑘𝑐′ 𝑐1′
Critical concentration of NaOH at which reaction front is located right at the interface is 𝑐2𝐿 = 𝑘𝑐 𝐷2

′ ′ 𝑐1′
Equilibrium at the interface: 𝑐1𝑖 = 𝑚𝑐1𝑖 , 𝑚 = 0.034 Substitute 𝑐1𝑖 in 𝑘𝑐′ 𝑐1′ − 𝑐1𝑖 , simplify and arrange the equation as 𝑁1 = 𝐾𝑐𝑟 −0
𝑚
 Tutorial 4
𝐷2 𝑐2𝐿 𝐷 𝑐
1+ 2 2𝐿′
1+ ൘𝜈𝐷 𝑐 ′ 𝑐1′ 𝜈𝐷1 𝑐1
1 1 Overall mass transfer coefficient with reaction is 𝐾𝑐𝑟 =
𝑁1 = −0 1 1
1 1 𝑚 +
𝑘𝑐 𝑚𝑘′𝑐
+
𝑘𝑐 𝑚𝑘𝑐′

𝐾𝑐𝑟 𝐷 𝑐2𝐿
Overall mass transfer coefficient with reaction is 𝐾𝑐
= 1 + 𝜈𝐷2 ′
1 𝑐1

Find the flux of SO2 from a gas containing 0.2 vol% of SO2 if a) [NaOH] = 0.1 M and b) [NaOH] = 1.0 M. Temperature is 40 oC
and pressure is 1.5 atm

𝜐𝐷1𝑘𝑐′ 𝑐1′ 1.5×0.2

Critical [NaOH] is: 𝑐2𝐿 = 𝑐1′ = 100×82.1×313 = 1.2 × 10−7 𝑚𝑜𝑙Τ
𝑐𝑐
𝑘𝑐 𝐷2

2
2 × 1.9 × 10−5 𝑐𝑚 ൗ𝑠 × 3.4 𝑐𝑚Τ𝑠 × 1.2 × 10−7 𝑚𝑜𝑙ൗ𝑐𝑐
𝑐2𝐿 = 2
= 0.5 𝑀
1.5 × 10−3 𝑐𝑚Τ𝑠 × 2.1 × 10−5 𝑐𝑚 ൗ𝑠

𝐷 𝑐
1+ 2 2𝐿൘ 1+2.1×10
−5 ×0.1×10−3
𝑐1′ 𝜈𝐷1 𝑐′1 𝑐1′ ൗ
2×1.9×10−5 ×1.2×10−7 1.2×10−7 𝑚𝑜𝑙
Flux at [NaOH] = 0.1 M is 𝐾𝑐𝑟 = 1 1 = 1 1 = 2.4 × 10−6
𝑚 + ′ 𝑚 −3 + 0.034 𝑐𝑚2 𝑠
𝑘𝑐 𝑚𝑘𝑐 1.5×10 0.034×3.4

𝑐1′ 𝑐1′ 1.2×10−7 𝑚𝑜𝑙

Flux at [NaOH] = 1.0 M is 𝐾𝑐𝑟 = 𝑘𝑐′ = 3.4 × = 1.2 × 10−5 , maximum flux that can be achieved for
𝑚 𝑚 0.034 𝑐𝑚2 𝑠
the given conditions
 Tutorial 4
Variation of overall mass transfer coefficient with [NaOH]

Overall mass transfer

𝑘𝑐′
• At no or low [NaOH],

Liquid film
coefficient

controlled
overall MTC equals liquid side coefficient
Gas film
• At high [NaOH],
controlled
overall MTC equals gas side coefficient

[NaOH]
𝑘𝑐

Problem 2
A chemical plant produces methanol (CH3OH) from natural gas (CH4). This gas contains 16000 parts per million (ppm) of H2S, a
poison for the catalyst, which reforms CH4 to CO and H2. H2S is to be removed to 100 ppm to retain catalyst activity for
sufficiently long time. Aqueous solutions of diethanol amine are to be used for removal of H2S. 1 mole of amine reacts 1 mole
of H2S to form a complex compound. CH4 is available at 16 bar pressure and 30 oC. Determine concentration of amine in
water such that the process is gas controlled. 1 ppm means 1 mole of H2S in one million moles of CH4.
 CHECK YOUR UNDERSTANDING

• When are reactive liquids added for absorption of a gas? If the process is gas controlled? Or liquid controlled?
• How does film theory explain enhancement of mass transfer upon addition of a reactive liquid? Explain by
drawing concentration profiles in the films
• What is the limit to which mass transfer coefficient can be increased by adding a reactive liquid?
Draw concentration profiles at this limit.
• Write an equation to find mass transfer flux when the limit in above question is reached