Module Ii

Module II: Molecular Diffusion
Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

What is molecular diffusion??
❖ Molecule of a species move from a region from a region of higher concentration to that of a lower concentration tending ting to
make the concentration uniform in the medium.
Brownian Motion
of Colloidal
Particles
Mass transfer due to molecular Mass Transfer due to convective

diffusion diffusion
(Slower Process) (Faster Process)

❖ The rate of molecular diffusion is intimately connected with molecular velocity and concentration difference (Driving force)
o Concentration
o Molecular velocity
o Flux
❖ The concentration of a species in a solution can be expressed in variety of ways
o Mass concentration / total mass concentration
o Mass fraction
o Molar concentration / total molar concentration
o Mole fraction

❖ In a gas mixture or liquid solution, the various components or species move with different velocities
❖ Molecular velocity in the microscopic scale
❖ Bulk motion → Caused by a pressure difference
o Mass avg. velocity
o Molar avg. velocity

What do you understand by ‘Flux’??
❖ In mass transfer the term ‘flux’ means the net rate at which a species in a solution passes through a unit area, which is normal to
the direction of diffusion in unit time
o Mass flux o Molar flux o Frame of reference:

i. Coordinate that are fixed in space (Observer is
stationary)
ii. Respect to mass avg. velocity (observer is
moving)
iii. Respect to molar avg. velocity (observer is
moving)

R = 8.314 J/mol-K 𝑃 500 × 103 𝑚𝑜𝑙
𝑐= = = 0.2 × 103 3 = 0.2 𝑘𝑚𝑜𝑙/𝑚3
P = 500 x 103 N/m2 𝑅𝑇 8.314 × 300 𝑚
Basis: 100 kmol of gas mixture
1926.61
kmol Mw Mass Mass 𝑀𝑎𝑣𝑔 = = 19.26 𝑘𝑔/𝑘𝑚𝑜𝑙
(kg) fraction 100
CH4 88 16.04 1411.52 0.732 𝜌 = 𝑐𝑀𝑎𝑣𝑔 = 0.2 × 19.26 = 3.85 𝑘𝑔/𝑘𝑚𝑜𝑙

C2H6 4 30.07 120.28 0.062
C3H8 5 44.09 220.45 0.114
C4H10 3 58.12 174.36 0.090
Total 100 1926.61

Fick’s Law of Diffusion
❖ The basic law of diffusion was expressed by Adolf Fick a psychologist in 1855
o The molar flux of a species relative to an observer moving with the molar
avg. velocity is proportional to the concentration gradient of the species
o If A diffuses in a binary mixture of (A+B), then
❖ Similar to Fick’s law of diffusion the other laws of transport are,

𝑑𝑇
o Fourier’s law of heat conduction (heat transport) 𝑞 = −𝑘
𝑑𝑍
o Newton’s law of viscosity (Momentum transport) 𝑑𝑢𝑥𝑧
𝜏𝑧𝑥 = −𝜇
𝑑𝑧

Diffusion with bulk of mass in motion!!
o 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.
o If circulating currents or eddies are present, then the molecular mechanism will be reinforced, and the total mass
transfer rate may be written as:
Convection term = Eddy diffusion = Molar flux due to convection
𝑚𝑎𝑠𝑠 𝑓𝑙𝑢𝑥 𝑁𝐴 +𝑁𝐵

Mass transfer velocity (molar), U= =
𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐶
Flux of A and B are, 𝑁𝐴 = 𝐶𝐴 𝑢𝐴 𝑎𝑛𝑑 𝑁𝐵 = 𝐶𝐵 𝑢𝐵

Molar flux of A in a binary
mixture with respect to a
stationary observer based on
Fick’s law
Representing bulk Molecular

flow diffusion

o If the concentration of A in a mixture is small i.e., for a dilute solution the contribution of the bulk flow term
become too small, 0

o For gas phase diffusion the above equation may be written in terms of partial pressure too. If the gas mixture is
𝑝 𝑃
assumed to be behaved ideally, 𝐶𝐴 = 𝑅𝑇𝐴 𝑎𝑛𝑑 𝐶 = 𝑅𝑇 , where T is the uniform temperature of the gas in K,
o Both the above equation can also be represented in terms of concentration!!

For ideal gas mixture prove that 𝑫𝑨𝑩 = 𝑫𝑩𝑨 !!

Modes of diffusion
Assumptions:
o Binary gas mixture Diffusion
o Steady state
o Constant area Stagnant

diffusion (NB=0) Counter diffusion
(Absorption
process)
Non-equimolar
Equimolar counter diffusion
counter diffusion (NB=-nNA)
(NB=-NA)
(In chemical
(Distillation reaction)
column)

Diffusion of A through non-diffusing B
o The component B being non-diffusive; 𝑁𝐵 = 0
o For diffusion through a constant area at steady state 𝑁𝐴 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
o Diffusion occurs from a point 𝑧 = 0 (where the partial pressure of A is 𝑝𝐴 = 𝑝𝐴1 ) to the point 𝑧 (𝑝𝐴 = 𝑝𝐴2 )
𝑧
𝐷𝐴𝐵 𝑃 𝑝𝐴2 𝑑𝑝𝐴 𝐷𝐴𝐵 𝑃 (𝑃 − 𝑝𝐴2 ) 𝐷𝐴𝐵 𝑃 𝑝𝐵2
𝑁𝐴 න 𝑑𝑧 = − න 𝑁𝐴 = ln 𝑁𝐴 = ln
0 𝑅𝑇 𝑝𝐴1 𝑝 − 𝑝𝐴 𝑅𝑇𝑧 (𝑃 − 𝑝𝐴1 ) 𝑅𝑇𝑧 𝑝𝐵1

𝐷𝐴𝐵 𝑃 𝑝𝐵2 𝐷𝐴𝐵 𝑃 (pA1 −pA2 ) 𝑝𝐵2
𝑁𝐴 = ln 𝑁𝐴 = ln
𝑅𝑇𝑧 𝑝𝐵1 𝑅𝑇𝑧 (pA1 −pA2 ) 𝑝𝐵1
Here, total pressure P = (𝑝𝐴1 +𝑝𝐵1 ) = (𝑝𝐴2 +𝑝𝐵2 )
𝐷𝐴𝐵 𝑃 (pA1 −pA2 ) 𝐷𝐴𝐵 𝑃 (pA1 −pA2 )

𝑁𝐴 = 𝑁𝐴 =
𝑅𝑇𝑧 (p −p )/ ln 𝑝𝐵2 𝑅𝑇𝑧 𝑝𝐵𝑀
B2 𝐵1 𝑝 𝐵1
𝑝𝐵2
Where, 𝑝𝐵𝑀 = (pB2 − p𝐵1 )/ ln 𝑝𝐵1
log mean partial pressure of B

Equimolar counter diffusion of A and B
o Both A and B diffuses at equal rates but in opposite direction; 𝑁𝐴 = −𝑁𝐵 → (𝑁𝐴 +𝑁𝐵 ) = 0
0
o For diffusion through a constant area at steady state 𝑁𝐴 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
o Diffusion occurs from a point 𝑧 = 0 (where the partial pressure of A is 𝑝𝐴 = 𝑝𝐴1 ) to the point 𝑧 (𝑝𝐴 = 𝑝𝐴2 )
𝐷𝐴𝐵 𝑃
𝑁𝐴 = (p −p )
𝑅𝑇𝑧 A1 A2

Non-equimolar counter diffusion of A and B
o When the mass transfer rates of the two components are unequal and opposite, the process is said to be the non-
equimolar counter diffusion, such a process occurs in a chemical reaction.
Here, 𝑁𝐵 = −𝑛𝑁𝐴
𝑝𝐴 𝐷𝐴𝐵 𝑑𝑝𝐴 1−𝑛 𝑝𝐴 𝐷𝐴𝐵 𝑑𝑝𝐴

𝑁𝐴 = 𝑁𝐴 − 𝑛𝑁𝐵 − 𝑁𝐴 1 − 𝑃 − 1 −=
𝑛 𝑝−
𝐴2
𝑃 𝑅𝑇 𝑑𝑧 𝑃 𝑅𝑇 𝑑𝑧
𝐷𝐴𝐵 𝑃 𝑃− 1−𝑛 𝑝𝐴2

𝑁𝐴 = 𝑃− 1− 𝑙𝑛𝑛 𝑝𝐴2
𝑅𝑇𝑧 (1−𝑛) 𝑃− 1−𝑛 𝑝𝐴1

Multicomponent Diffusion: Maxwell-Stefan approach
o We first use this approach for the analysis of diffusion of a species A in a binary mixture and then extend it to the
case of a multicomponent mixture
o Assumptions: For a non-uniform binary mixture of A and B in which A is diffusing at steady state, the difference
in the partial pressure of A Δ𝑝𝐴 over a small distance Δz is proportional to,
o The molar concentrations of A and B; (𝐶𝐴 𝑎𝑛𝑑 𝐶𝐵 )
o The length of the diffusion path; Δz
o The difference in the velocities of A and B; (uA − uB )

o At a constant temperature and pressure,
−Δ𝑝𝐴 ∝ 𝐶𝐴 𝐶𝐵 Δ𝑧(𝑢𝐴 − 𝑢𝐵 )
Where, 𝐾 ′ is the proportionality
−Δ𝑝𝐴 = 𝐾 ′ 𝐶𝐴 𝐶𝐵 Δ𝑧(𝑢𝐴 − 𝑢𝐵 ) constant
Taking limit, Δ𝑧 → 0,
𝑝
Putting CA + CB = C (total concentration), and 𝐶𝐴 = 𝑅𝑇𝐴 ,

o Now we consider a multicomponent mixture containing n components there will be (n-1) binaries. Thus,
o Dividing both sides by the uniform total molar concentration C, and by RT
𝑅𝑇
o Where 𝐷𝑖𝑗 = 𝐶𝐾′ = diffusivity of the component i in a binary mixture of i and j.
𝑖𝑗

Here, 𝐷𝑖𝑚 is the diffusivity of i

in the mixture

o The diffusivity 𝐷𝑖𝑚 of molecules of component i in the mixture, depends on the mole fractions and fluxes of all the
components.
o Simple results can be obtained in certain limiting cases; for example, if all the components except i are non-
diffusing (𝑁𝑗 = 0, 𝑗 ≠ 𝑖)then the diffusivity of i in the mixture is independent of the flux. So,
where, yj′ is the mole fraction

of the component j in the
mixture on “i-free basis”

𝐷𝐴𝐵 𝑃 (𝑃 − 𝑝𝐴2 )
𝑁𝐴 = ln
𝑅𝑇𝑧 (𝑃 − 𝑝𝐴1 )

Diffusion in a ternary mixture!!
o Let say the components in the mixture are called 1, 2, and 3
o Considering the case of ideal gas where, 𝐷𝑖𝑗 = 𝐷𝑗𝑖 then any of the above three equations can be obtained by adding
the remaining equations as (𝑦1 +𝑦2 + 𝑦3 ) = 1
o Thus, there are only two independent, simultaneous, first-order, linear ODEs (for an n-component mixture there
will be (n-1) equations)

Diffusion in a ternary mixture!!
o Let us consider a ternary mixture of ideal gases in which,
i. Components 1 and 2 diffuse while component 3 is non-diffusing (i.e., 𝑁3 = 0)
ii. Diffusion occurs through a path length 𝑙
o The above two equations can be combined into a single considering 𝐷12 = 𝐷21 and 𝐷32 = 𝐷23

o Now we divide both side of component-1 equation by 𝑁1,and multiply both side of component-2 equation by 𝜉/𝑁2
and subtract. So, we get:

o The above equation can be arranged to the following form
o Boundary condition:
o At 𝑧 = 0, 𝑦1 = 𝑦10 and 𝑦2 = 𝑦20
o At 𝑧 = 𝑙, 𝑦1 = 𝑦1𝑙 and 𝑦2 = 𝑦2𝑙

o The two fluxes 𝑁1 and 𝑁2 cannot be calculated from the above single equation. In order to have another relation,
from component-3 equation; and putting 𝑁3 = 0 (as the component 3 is non-diffusing in this case), 𝐷31 = 𝐷13 and
𝐷32 = 𝐷23 we get,
o Boundary condition:
o At 𝑧 = 0, 𝑦3 = 𝑦30 and at 𝑧 = 𝑙, 𝑦3 = 𝑦3𝑙

Gas phase diffusion coefficient: measurement and prediction
o 𝐷 ≈ 10−5 − 10−4 𝑚2 /𝑠 at room temperature and atmospheric pressure
o The gas phase diffusivity generally varies with,
o Temperature → 𝐷𝐴𝐵 ∝ 𝑇 1.5 𝑡𝑜 1.75
1
o Pressure → 𝐷𝐴𝐵 ∝ 𝑃
1 1
o Molecular weight → DAB ∝ +𝑀
𝑀𝐴 𝐵
o Intermolecular forces in a mixture and is also governed by collisions of the diffusing molecules with other
present in the mixture.
o The rate of collision increases as the mean free path decreases. This is favoured at higher pressure, and
hence the diffusivity of a gas decreases with increasing pressure

Gas phase diffusion coefficient: measurement and prediction
o Twin bulb method
o Stefan tube

Twin-bulb Method
o The total pressure in the bulb remain constant and equal and equimolar counter diffusion occurs through the
connecting tube
o Bulb being large, the concentration or partial pressure components in the bulbs will change rather slowly. Thus, in
the system a pseudo-steady state assumption can be made
o Therefore, at any instant, diffusion through the connecting tube occurs at steady state, the concentration in the bulb
change a little and a new steady state of diffusion is attained simultaneously

o If 𝑎 is the inner cross-section of the connecting tube, 𝑙 is its length, and
𝑝𝐴1 and 𝑝𝐴2 (𝑝𝐴1 > 𝑝𝐴2 ) are the partial pressures of A in the bulbs at
any time 𝑡, the steady state rate of transport of A from bulb 1 to bulb 2
can be written as,
o If 𝐶𝐴1 and 𝐶𝐴2 are the instantaneous concentration of A in the bulbs, the rates of change of these concentrations are
given by the following equations:

o Here 𝐶𝐴1 decreases with time but 𝐶𝐴2 increases. Now combining the above two equations we get,
o We use the following conditions:
o At 𝑡 = 0, 𝑝𝐴1 − 𝑝𝐴2 = 𝑃 − 0 = 𝑃
′ ′
o At 𝑡 = 𝑡 ′ , 𝑝𝐴1 − 𝑝𝐴2 = 𝑝𝐴1 − 𝑝𝐴2

Stefan tube Method
o This method is suitable if, under the given experimental conditions, one of the components (say A) is available as a
volatile liquid and the other component (B) is a gas which is insoluble in A
o Therefore, this can be considered as diffusion of A through non-diffusing B
o The liquid level in the vertical tube will drop very slowly and pseudo-steady state assumption can be considered

o At any time 𝑡, the liquid level be at a distance 𝑧 from the top of the vertical tube,
𝑝𝐴1 be the partial pressure of A at the liquid surface and 𝑝𝐴2 that at the top. The
diffusional flux of A through this distance 𝑧 is given as,
o Let say at small time 𝑑𝑡 the fall in the liquid level is 𝑑z.
𝜌𝐴
o So, the number of moles of A diffuse out = 𝑎 𝑑𝑧 ; therefore, by material balance over the time 𝑑𝑡,
𝑀𝐴

o We use the following conditions:
o At 𝑡 = 0, 𝑧 = 𝑧0
o At 𝑡 = 𝑡 ′ , 𝑧 = 𝑧 ′

Problem: The diffusivity of the vapour of a volatile liquid in air can be conveniently determined by Winkelmann's method in
which liquid is contained in a narrow diameter vertical tube, maintained at a constant temperature, and an air stream is passed
over the top of the tube sufficiently rapidly to ensure that the partial pressure of the vapour there remains approximately zero.
On the assumption that the vapour is transferred from the surface of the liquid to the air stream by molecular diffusion alone,
calculate the diffusivity of carbon tetrachloride vapour in air at 321 K and atmospheric pressure from the experimental data
given in Table below. The vapour pressure of carbon tetrachloride at 321 K is 37.6 kPa and the density of the liquid is 1540
kg/m3. The kilogram molecular volume may be taken as 22.4 m3.

Predictive equations for gas phase diffusivity
o Chapman Enskog equation:
o 𝑇 = absolute temperature (K)

o 𝑀𝐴 , 𝑀𝐵 = molecular weight of components A and B
o 𝑃 = total pressure (atm)
o 𝜎𝐴𝐵 = a characteristic length parameter of the binary (Å)
𝐾𝑇
o Ω𝐷 = Collison integral = 𝑓 𝜖 , where K is the boltzman constant and
𝐴𝐵
𝜖𝐴𝐵 = 𝜖𝐴 𝜖𝐵 0.5

o Fuller, Schettler and Griddings equations:
o 𝑇 = absolute temperature (K)

o 𝑀𝐴 , 𝑀𝐵 = molecular weight of components A and B
o 𝑃 = total pressure (bar)

Molecular diffusion in liquids
o The above equation is valid for both gas and liquid phases. However, unlike ideal gases, the total molar
concentration of a liquid is expected to vary from one point to another
o For the diffusion of A through non-diffusing B,

𝜌
𝐷𝐴𝐵 𝑀 𝑥𝐵2 − 𝑥𝐵1
𝑁𝐴 = 𝑎𝑣
𝑥𝐴1 − 𝑥𝐴2 𝑤ℎ𝑒𝑟𝑒, 𝑥𝐵𝑀 =
𝑧𝑥𝐵𝑀 ln(𝑥𝐵2 /𝑥𝐵1 )
o For equimolar counter-diffusing, o 𝑥𝐴1 and 𝑥𝐴2 are the mole fraction of A at point
𝜌 1 and 2 separated by a distance z.
𝐷𝐴𝐵 𝑀
𝑎𝑣 o In most of the cases the diffusion in the liquid
𝑁𝐴 = 𝑥𝐴1 − 𝑥𝐴2
𝑧 phase occurs at low concentrations. In that
case 𝑥𝐵𝑀 ≅ 1, so that 𝑁𝐴 = 𝐽𝐴

Measurement of liquid phase diffusion coefficient
Diaphragm cell method:
o Diaphragm cell contains two compartments as shown in the Figure. These are
separated by diaphragm. Let the area of the diaphragm is ‘𝑎’ and porosity is ‘𝜀’.
Effective area for diffusion = 𝑎 𝜀

𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑝𝑎𝑡ℎ
Effective diffusion length = 𝑙𝜏 Where, 𝜏 = 𝑑𝑖𝑎𝑝ℎ𝑎𝑟𝑚 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠
o For diffusion in the liquid phase, particularly at low concentration, the bulk flow term can be neglected.
Therefore,

Boundary conditions:
𝑡 = 0, 𝐶𝐴1 = 𝐶𝐴1,0; 𝐶𝐴2 = 𝐶𝐴2,0
𝑡 = 𝑡𝑓, 𝐶𝐴1 = 𝐶𝐴1, 𝑓; 𝐶𝐴2 = 𝐶𝐴2, 𝑓

Unsteady state diffusion
o Considering an element of gas of cross-sectional area, 𝐴 and of thickness 𝛿𝑦 in the direction of mass transfer in
which the concentrations 𝐶𝐴 and 𝐶𝐵 of the components A and B are a function of both position 𝑦 and time 𝑡

For component A,
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑖𝑛 𝑝𝑒𝑟 𝑢𝑖𝑛𝑡 𝑡𝑖𝑚𝑒 ȁ𝑦 − 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑜𝑢𝑡 𝑝𝑒𝑟 𝑢𝑖𝑛𝑡 𝑡𝑖𝑚𝑒 ȁ(𝑦 + 𝛿𝑦) = rate of change of concen𝑡𝑟𝑎𝑡𝑖𝑜𝑛 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑚𝑒𝑛𝑡
𝜕CA 𝜕CA 𝜕 𝜕CA 𝜕𝐶𝐴

−𝐷 + 𝑢𝐹 𝐶𝐴 𝐴 − −𝐷 + 𝑢𝐹 𝐶𝐴 −𝐷 + 𝑢𝐹 𝐶𝐴 𝛿𝑦 𝐴 = 𝛿𝑦𝐴
𝜕𝑦 𝜕𝑦 𝜕𝑦 𝜕𝑦 𝜕𝑡
𝜕𝐶𝐴 𝜕 2 CA 𝜕 𝑢𝐹 𝐶𝐴
⇒ =𝐷 −
𝜕𝑡 𝜕𝑦 2 𝜕𝑦
𝜕𝐶𝐵 𝜕 2 CB 𝜕 𝑢𝐹 𝐶𝐵
Similarly for component B, =𝐷 −
𝜕𝑡 𝜕𝑦 2 𝜕𝑦
Adding the above two equations we get,
𝜕(𝐶𝐴 + 𝐶𝐵 ) 𝜕 2 (𝐶𝐴 + CB ) 𝜕
=𝐷 − 𝐶 + 𝐶𝐵 𝑢𝐹
𝜕𝑡 𝜕𝑦 2 𝜕𝑦 𝐴

𝜕(𝐶𝐴 + 𝐶𝐵 ) 𝜕 2 (𝐶𝐴 + CB ) 𝜕
=𝐷 − 𝐶 + 𝐶𝐵 𝑢𝐹
𝜕𝑡 𝜕𝑦 2 𝜕𝑦 𝐴
Since, for an ideal gas, 𝐶𝐴 + 𝐶𝐵 = 𝐶 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝜕 𝜕𝑢𝐹
0=0− 𝑢𝐹 𝐶 ⇒ =0
𝜕𝑦 𝜕𝑦
Where, uF is therefore independent of y
𝜕𝐶𝐴 𝜕 2 CA 𝜕𝐶𝐴
=𝐷 − 𝑢𝐹
𝜕𝑡 𝜕𝑦 2 𝜕𝑦
For equimolar counter diffusion 𝑢𝐹 = 0

𝜕𝐶𝐴 𝜕 2 CA Fick’s second law for unsteady state
=𝐷
𝜕𝑡 𝜕𝑦 2 diffusion in 1D
Fick’s second law for unsteady state 𝜕𝐶𝐴 𝜕 2 CA 𝜕 2 CA 𝜕 2 CA

=𝐷 + +
diffusion in 3D is given as 𝜕𝑡 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

Diffusion through a varying cross-sectional area
o In many situations the area of diffusion changes along the direction of diffusion, or changes with even time
𝑁𝐴1 = 𝑁𝐴2 = 𝑁𝐴3 𝑁𝐴1 > 𝑁𝐴2 > 𝑁𝐴3

Diffusion in spherical geometry
o Example: evaporation of a drop of water in stagnant air
𝑟𝑠 =radius of the evaporating drop at any instant

of time 𝑡
o Rate of input of A into the thin shell (at 𝑟 = 𝑟) ⇒ 4𝜋𝑟 2 𝑁𝐴 ȁ𝑟
o Rate of output of A from the thin shell (at 𝑟 = 𝑟 + Δ𝑟) ⇒ 4𝜋𝑟 2 𝑁𝐴 ȁ𝑟+Δ𝑟
@stedystate

Dividing both side by Δ𝑟 and taking the limit Δ𝑟 → 0,
So, 𝐴𝑟𝑒𝑎 × 𝐹𝑙𝑢𝑥 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡

o For this particular example water vapor diffuses out, but air does not diffuse (Case: diffusion of A in non-diffusing B)
Here, 𝑁𝐵 = 0
Also,
Therefore,
The above equation can be integrated from 𝑟 = 𝑟𝑠 (surface of the drop) to 𝑟 =∝ (far away from the drop) where 𝑝𝐴 = 𝑝𝐴∝ .
Here, 𝑝𝐴𝑠 is the vapour pressure of water at the temperature of the drop and 𝑝𝐴∝ is the partial pressure of water vapor in
the “bulk air”

o Since W is the constant molar rate of mass transfer, it is equal to the rate of vaporization of the drop at any instant.
Assumption: pseudo-steady state i.e., the drop size changes

Therefore, slowly that the diffusion of water vapour through the
surrounding air occurs virtually at steady state at all the time
If at time 𝑡 = 0, the radius of the drop is 𝑟𝑠0 and at time 𝑡 = 𝑡 ′ it is 𝑟𝑠′ then,

o How much time will be required for complete evaporation of the drop??
𝑟𝑠′ = 0

Diffusion Through a Tapered Tube
o Two large vessels connected by a tapered tube of length 𝐿
o Rate of input of A into the section at z ⇒ 𝜋𝑟 2 𝑁𝐴 ȁ𝑧
o Rate of output of A from the thin section at z + Δz ⇒ 𝜋𝑟 2 𝑁𝐴 ȁ𝑧+Δz
@stedystate

Dividing both side by Δz and taking the limit Δ𝑧 → 0,
For equimolar counter diffusion,
The local radius 𝑟 is related to the axial position 𝑧 by using the property of similar triangles,
Substituting for 𝑁𝐴 and 𝑟, rearranging and integrating within the limits 𝑧 = 0, 𝑝𝐴 = 𝑝𝐴1 and 𝑧 = 𝐿, 𝑝𝐴 = 𝑝𝐴2

Knudsen Diffusion and Surface Diffusion
Knudsen diffusion:
Diffusion in a continuum
o The movement of molecule in a mixture is governed by
molecular velocity as well as collision with other
molecules (this offers resistance)
o If gas diffusion occurs in a very fine pore (<50 nm), Knudsen diffusion
particularly at a low pressure,
“mean free path” >> diameter of the passage

Surface diffusion
Collison with the wall is more frequent
Where,
Knudsen diffusivity, 𝑟𝑝 = radius of the passage
1
8𝑅𝑇 2
𝜈𝑇 = 𝜋𝑀
=average velocity of the molecules by virtue of their thermal
energy
𝑇 = Temperature (K) and 𝑀 =molecular weight

o The flux due to Knudsen diffusion is like that of Fick’s law

Surface diffusion:
o The transport of adsorbed molecules on a surface in the

presence of concentration gradient
o The surface diffusion is visualized to occur by a

“hopping” or “leap-frog” mechanism
Where,
𝑚2 cm 2
𝐷𝑠 = surface diffusion coefficient, in (ranges between 10−4 and 10−5 s )
𝑠
𝐶𝑠 = surface concentration of the adsorbed molecules, in 𝑘𝑚𝑜𝑙/𝑚2

Problems from tutorial/assignment sheet


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Module II: Molecular Diffusion

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Mass transfer due to molecular Mass Transfer due to convective

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

❖ The concentration of a species in a solution can be expressed in variety of ways

o Mass concentration / total mass concentration

o Molar concentration / total molar concentration

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

❖ Molecular velocity in the microscopic scale

❖ Bulk motion → Caused by a pressure difference

o Mass avg. velocity

o Molar avg. velocity

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o Mass flux o Molar flux o Frame of reference:

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

CH4 88 16.04 1411.52 0.732 𝜌 = 𝑐𝑀𝑎𝑣𝑔 = 0.2 × 19.26 = 3.85 𝑘𝑔/𝑘𝑚𝑜𝑙

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o If A diffuses in a binary mixture of (A+B), then

❖ Similar to Fick’s law of diffusion the other laws of transport are,

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Convection term = Eddy diffusion = Molar flux due to convection

𝑚𝑎𝑠𝑠 𝑓𝑙𝑢𝑥 𝑁𝐴 +𝑁𝐵

Flux of A and B are, 𝑁𝐴 = 𝐶𝐴 𝑢𝐴 𝑎𝑛𝑑 𝑁𝐵 = 𝐶𝐵 𝑢𝐵

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Representing bulk Molecular

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o Both the above equation can also be represented in terms of concentration!!

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o Binary gas mixture Diffusion

o Constant area Stagnant

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o The component B being non-diffusive; 𝑁𝐵 = 0

o For diffusion through a constant area at steady state 𝑁𝐴 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Here, total pressure P = (𝑝𝐴1 +𝑝𝐵1 ) = (𝑝𝐴2 +𝑝𝐵2 )

𝐷𝐴𝐵 𝑃 (pA1 −pA2 ) 𝐷𝐴𝐵 𝑃 (pA1 −pA2 )

log mean partial pressure of B

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o For diffusion through a constant area at steady state 𝑁𝐴 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

𝑝𝐴 𝐷𝐴𝐵 𝑑𝑝𝐴 1−𝑛 𝑝𝐴 𝐷𝐴𝐵 𝑑𝑝𝐴

𝐷𝐴𝐵 𝑃 𝑃− 1−𝑛 𝑝𝐴2

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o The molar concentrations of A and B; (𝐶𝐴 𝑎𝑛𝑑 𝐶𝐵 )

o The length of the diffusion path; Δz

o The difference in the velocities of A and B; (uA − uB )

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o Dividing both sides by the uniform total molar concentration C, and by RT

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Here, 𝐷𝑖𝑚 is the diffusivity of i

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

where, yj′ is the mole fraction

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

o Let say the components in the mixture are called 1, 2, and 3

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal

i. Components 1 and 2 diffuse while component 3 is non-diffusing (i.e., 𝑁3 = 0)

ii. Diffusion occurs through a path length 𝑙

Indian Institute of Technology Hyderabad Dr. Ranajit Mondal