SUBJECT :- CHEMICAL PROCESS TECHNOLOGY- 2 (3340503)

SEMESTER :- 4TH SEM (DIPLOMA CHEMICAL ENGINEERING)

CHAPTER :- MOLECULAR DIFFUSION IN FLUIDS (UNIT 2)

 Syllabus Topics:
 Molecular and Eddy diffusion
 Rate of diffusion in Fluids
 Molar flux, diffusivity and concentration gradient in Fluids
 Applications of diffusion in Fluids
 Derivation of diffusivity equation (DAB=DBA)
 Effect of concentration, Temperature and pressure on diffusivity
 General equation for steady state molecular diffusion in fluids for laminar flow
 Molecular diffusion in gases
 Derive Equation for Steady state diffusion of
A. Component A through non diffusing B.
B. Equimolar counter current diffusion of A and B
 Empirical equation of diffusivity of gases

 Molecular Diffusion:
 Molecular diffusion is defined as or concerned with the movement of individual component
(molecules) through a substance due to their thermal energy.
 The average distance the molecules travels between collision is it’s mean free path and average
velocity is dependent upon the temperature.

 Turbulent/ eddy Diffusion:

 The mechanical agitation has produced rapid movement of relatively large chunks or eddies
of fluid, which is in turbulent motion, this method of solute transfer is known as eddy or
turbulent diffusion.

 Mechanism of Mass Transfer:

 It can be increased by increasing temperature or by reducing temperature or by reducing
pressure. This theory can be applied to liquid also but the diffusion rate will be lower, because
number of molecules per unit volume will be more.

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  The phenomenon of molecular diffusion leads to uniform concentration of component in
solution.

Molecular diffusion Eddy diffusion

 It is the movement of individual molecule  When Eddy or chunks of fluid rapidly
from one phase to another. move to create uniform concentration is
called Eddy diffusivity or Turbulent
diffusivity.
 It is slow.  It is fast.
 It is important for fluid moving in laminar  It is for fast moving fluid and agitated
flow or stagnant flow. fluid.
 Useful in measuring Diffusivity.  Useful in measuring Mass Transfer
Diffusivity.

 Diffusivity or diffusion coefficient

 Diffusivity is defined as the ratio of the flux to the corresponding concentration gradient.
 The dimensions of the diffusivity are L2/ θ and its SI units are m2/s.
 The diffusivity of any component is a measure of its diffusive mobility and is a function of the
temperature, pressure, nature and concentration of the other components.

 Fick's law of diffusion

 A relation between the flux of the diffusing substance and the concentration gradient
responsible for molecular diffusion- mass transfer was first proposed by FICK in 1855 and is
therefore referred to as Fick's first law of diffusion.
 The flux of diffusing components A (diffusion flux of A) in Z direction in a binary mixture of A
and B is proportional to the molar concentration gradient.
 So Fick's law of diffusion for a binary mixture for steady state diffusion can be expressed as
𝑑𝐶𝐴
𝐽𝐴 ∝ ( )
𝑑𝑧
𝑑𝐶𝐴
𝐽𝐴 = −DAB ( )
𝑑𝑧
 Where, JA = molar flux of components A
 DAB is the proportionality constant known as the molecular diffusivity for diffusion co-efficient
for component 'A' diffusing through 'B'.
 The negative sign indicates that diffusion occurs in the direction of a drop in concentration.

 Derivation of the equation of diffusivity (𝐃𝐀𝐁 = 𝐃𝐁𝐀 )

 For Binary Gas Mixture

𝑁𝐴 + 𝑁𝐵 = 𝑁 … (1)

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  𝑁𝐴 is the movement of ‘A’ is made up of two parts, that resulting from the bulk motion N and
the fraction 𝑋𝐴 of N which is A that resulting from diffusion 𝐽𝐴 :
 𝑁𝐴 = Flux due to diffusion + Flux due to bulk flow [Velocity of bulk flow* Concentration]
𝑁𝐴 + 𝑁𝐵
∴ 𝑁𝐴 = 𝐽𝐴 + ( ) CA … (2)
𝐶𝐴 + 𝐶𝐵
𝑑𝐶𝐴 𝑁𝐴 + 𝑁𝐵
∴ 𝑁𝐴 = −DAB ( ) + ( ) CA
𝑑𝑧 𝐶𝐴 + 𝐶𝐵
𝑑𝐶𝐴 𝑁𝐴 + 𝑁𝐵
∴ 𝑁𝐴 = −DAB ( ) + ( ) CA … (3)
𝑑𝑧 𝐶𝑇

 Similarly for B,

𝑑𝐶𝐵 𝑁𝐴 + 𝑁𝐵
∴ 𝑁𝐵 = −DBA ( ) + ( ) CB … (4)
𝑑𝑧 𝐶𝑇

 Addition of equation (3) and (4)

𝑑𝐶𝐴 𝑁𝐴 + 𝑁𝐵 𝑑𝐶𝐵 𝑁𝐴 + 𝑁𝐵
∴ (𝑁𝐴 + 𝑁𝐵 ) = [−DAB ( ) + ( ) CA ] + [−DBA + ( ) CB ] … (5)
𝑑𝑧 𝐶𝑇 𝑑𝑧 𝐶𝑇

 On rearranging, we get

𝑑𝐶𝐴 𝑑𝐶𝐵 𝑁𝐴 + 𝑁𝐵
(𝑁𝐴 + 𝑁𝐵 ) = −DAB ( ) − DBA ( ) + ( ) (CA + CB ) … (6)
𝑑𝑧 𝑑𝑧 𝐶𝑇

 We have, CA + CB = 𝐶𝑇 … (7)

𝑑𝐶𝐴 𝑑𝐶𝐵 𝑁𝐴 + 𝑁𝐵
∴ (𝑁𝐴 + 𝑁𝐵 ) = −DAB ( ) − DBA ( ) + ( ) (𝐶𝑇 ) … (8)
𝑑𝑧 𝑑𝑧 𝐶𝑇
𝑑𝐶𝐴 𝑑𝐶𝐵
∴ DAB ( ) = −DBA ( ) … (9)
𝑑𝑧 𝑑𝑧
 Now differentiating equation (7) w.r.t. z, we get

𝑑𝐶𝐴 𝑑𝐶𝐵
=− … (10)
𝑑𝑧 𝑑𝑧
𝑑𝐶𝐴
 Adding the value from equation (10) into (9)
𝑑𝑧

𝑑𝐶𝐵 𝑑𝐶𝐵
∴ − DAB ( ) = −DBA ( ) … (11)
𝑑𝑧 𝑑𝑧
∴ DAB = DBA … (12)

 Hence proved, DAB = DBA

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 Steady State Molecular Diffusion in fluids at rest and in laminar flow.
 To the case of diffusion only in the z direction with 𝑁𝐴 & 𝑁𝐵 constant (steady state)

dCA CA
NA = −DAB ( ) + ( ) (NA + NB ) … (12)
dz CT

N A C T − CA (N A + N B ) dCA
∴ = −DAB ( ) … (13)
CT dz

 Applying integration within limits: Z= Z1 ; CA = CA1

Z= Z2 ; CA = CA2
CA2 z2
− dCA 1
∫ = ∫ dz … (14)
CA1 N A CT − CA (N A + N B ) CT DAB z1

1 C 1 z
∴ ln[NA CT − CA (NA + NB )]CA2 = [z]z21 … (15)
(N A + N B ) A1 CT DAB
1
∴ [ln{ NA CT − CA2 (NA + NB )} − ln{ NA CT − CA1 (NA + NB )}]
(N A + N B )
1
= (z − z1 ). . . (16)
CT DAB 2

1 NA CT − CA2 (NA + NB ) 1
∴ ln ( )= (z) … (17)
(N A + N B ) NA CT − CA1 (NA + NB ) CT DAB

1 CT DAB NA CT − CA2 (NA + NB )

∴ × × ln ( ) = 1 … (18)
(N A + N B ) z NA CT − CA1 (NA + NB )

 Multiplying both sides by NA ,

NA CT DAB NA CT − CA2 (NA + NB )

NA = × × ln ( ) … (19)
(N A + N B ) z NA CT − CA1 (NA + NB )

N A CT (NA + NB )CA2
NA CT DAB −
(N A + N B )CT (N A + N B )CT
NA = × × ln ( ) … (20)
(N A + N B ) z N A CT (NA + NB )CA1
(N A + N B )CT − (N A + N B )CT

NA C
NA CT DAB − A2
(N A + N B ) CT
NA = × × ln ( ) … (21)
(N A + N B ) z NA CA1
−
(N A + N B ) CT

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 Molecular Diffusion in Gases
 From ideal gas law, 𝑃𝑡 𝑉 = 𝑛𝑡 𝑅𝑇,
𝑃𝑡 𝑛𝑡
= = 𝐶𝑡 … (22)
𝑅𝑇 𝑉
 We have, 𝑛𝐴 + 𝑛𝐵 = 𝑛𝑡

𝐶𝐴 + 𝐶𝐵 = 𝐶𝑡
𝑛𝐴 𝑛𝐵
= +
𝑉 𝑉
𝑛𝐴 + 𝑛𝐵 𝑛𝑡
∴ 𝐶𝑡 = =
𝑉 𝑉
 From Raoult’s law, [PA = yA*Pt]
𝑃𝐴2 𝐶𝐴2
∴ = 𝑦𝐴2 = … (23)
𝑃𝑡 𝐶𝑡
 From the equation (21)
𝑁𝐴 CA2
𝑁𝐴 DAB 𝐶𝑡 −
(𝑁 + 𝑁𝐵 ) 𝐶𝑇
𝑁𝐴 = × × ln ( 𝐴 ) … (24)
(𝑁𝐴 + 𝑁𝐵 ) 𝑧 𝑁𝐴 CA1
(𝑁𝐴 + 𝑁𝐵 ) − 𝐶𝑇

𝑁𝐴 PA2
𝑁𝐴 DAB 𝑃𝑡 −
(𝑁 + 𝑁𝐵 ) 𝑃𝑡
𝑁𝐴 = × × ln ( 𝐴 ) … (25)
(𝑁𝐴 + 𝑁𝐵 ) 𝑅𝑇 𝑁𝐴 PA1
(𝑁𝐴 + 𝑁𝐵 ) − 𝑃𝑡
𝑁𝐴
𝑃 − PA2
(𝑁𝐴 + 𝑁𝐵 ) 𝑡
𝑁𝐴 DAB 𝑃𝑡 𝑃𝑡
𝑁𝐴 = (𝑁 × × ln ( 𝑁𝐴 ) … (26)
𝐴 + 𝑁𝐵 ) 𝑅𝑇 𝑃 −P
(𝑁𝐴 + 𝑁𝐵 ) 𝑡 A1
𝑃𝑡
𝑁𝐴
𝑃 − PA2
𝑁𝐴 DAB 𝑃𝑡 (𝑁𝐴 + 𝑁𝐵 ) 𝑡
𝑁𝐴 = × × ln ( ) … (27)
(𝑁𝐴 + 𝑁𝐵 ) 𝑅𝑇 𝑁𝐴
(𝑁𝐴 + 𝑁𝐵 ) 𝑃𝑡 − PA1
𝑃𝐴2 𝑃𝐴1
 In Equation (25), by replacing value of 𝑎𝑠 𝑦𝐴2 & 𝑎𝑠 𝑦𝐴1 , we get
𝑃𝑡 𝑃𝑡

𝑁𝐴
𝑁𝐴 DAB 𝑃𝑡 − yA2
(𝑁𝐴 + 𝑁𝐵 )
𝑁𝐴 = × × ln ( ) … (28)
(𝑁𝐴 + 𝑁𝐵 ) 𝑅𝑇 𝑁𝐴
(𝑁𝐴 + 𝑁𝐵 ) − yA1

 We have, 𝑃𝐴1 + 𝑃𝐵1 = 𝑃𝑡 ⇒ 𝑃𝐵1 = 𝑃𝑡 − 𝑃𝐴1

𝑃𝐴2 + 𝑃𝐵2 = 𝑃𝑡 ⇒ 𝑃𝐵2 = 𝑃𝑡 − 𝑃𝐴2

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 CASE – 1: Steady state diffusion of A through non-diffusing/ stagnant B:
 Example, Ammonia (A) were being absorbed from air (B) in H2O
 For the steady state diffusion of an ideal gas A through a stagnant gas B, we have:
𝑁𝐵 = 0 & 𝑁𝐴 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑁𝐴 𝑁𝐴
∴ = = 1 … (𝑎)
(𝑁𝐴 + 𝑁𝐵 ) 𝑁𝐴

 We have equation (27),

𝑁𝐴
𝑃 − PA2
𝑁𝐴 DAB 𝑃𝑡 (𝑁𝐴 + 𝑁𝐵 ) 𝑡
𝑁𝐴 = × × ln ( )
(𝑁𝐴 + 𝑁𝐵 ) 𝑅𝑇𝑍 𝑁𝐴
(𝑁𝐴 + 𝑁𝐵 ) 𝑃𝑡 − PA1

 By using value of equation (a) above equation reduces to,

DAB 𝑃𝑡 𝑃𝑡 − PA2
𝑁𝐴 = 1 × × ln ( ) … (28)
𝑅𝑇𝑍 𝑃𝑡 − PA1

 We have,
𝑃𝐴1 + 𝑃𝐵1 = 𝑃𝑡 ⇒ 𝑃𝐵1 = 𝑃𝑡 − 𝑃𝐴1
𝑃𝐴2 + 𝑃𝐵2 = 𝑃𝑡 ⇒ 𝑃𝐵2 = 𝑃𝑡 − 𝑃𝐴2
 Putting value of PB1 & PB2 in equation (28), we get
DAB 𝑃𝑡 PB2
𝑁𝐴 = × ln ( ) … (29)
𝑅𝑇𝑍 PB1

 We have, 𝑃𝐴1 + 𝑃𝐵1 = 𝑃𝐴2 + 𝑃𝐵2

 On re-arranging, 𝑃𝐴1 − 𝑃𝐴2 = 𝑃𝐵2 − 𝑃𝐵1
𝑃𝐴1 − 𝑃𝐴2
∴ =1
𝑃𝐵2 − 𝑃𝐵1
DAB 𝑃𝑡 𝑃𝐴1 − 𝑃𝐴2 PB2
∴ 𝑁𝐴 = × ln ( ) … (30)
𝑅𝑇𝑍 𝑃𝐵2 − 𝑃𝐵1 PB1
DAB 𝑃𝑡 𝑃𝐴1 − 𝑃𝐴2
∴ 𝑁𝐴 = × … (31)
𝑅𝑇𝑍 𝑃𝐵,𝑀

 Where, 𝑃𝐵,𝑀 is the log 𝑚𝑒𝑎𝑛 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐵.

𝑃𝐵2 − 𝑃𝐵1
𝑃𝐵,𝑀 =
P
ln ( B2 )
PB1
 Here, the flux is proportional to the concentration difference expressed in terms of partial
pressure of A and inversely proportional to the distance Z and the concentration of the stagnant

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 gas 𝑃𝐵,𝑀 . With increase in the Z and 𝑃𝐵,𝑀 , resistance to diffusion increases and therefore, flux
decreases.

 CASE – 2: Steady State Equimolar Counter Current Diffusion of A and B

 For Equimolar counter diffusion,
𝑁𝐴 = −𝑁𝐵 … (a)
We have the equation (3)

𝑑𝐶𝐴 𝑁𝐴 + 𝑁𝐵
𝑁𝐴 = −DAB ( ) + ( ) CA
𝑑𝑧 𝐶𝑇

 By using relation (a), above equation reduce to,

𝑑𝐶𝐴
∴ 𝑁𝐴 = −DAB ( )+0
𝑑𝑧
𝑃𝐴
 Putting, = 𝐶𝐴
𝑅𝑇

−DAB 𝑑𝑃𝐴
∴ 𝑁𝐴 = ( )
𝑑𝑧 𝑅𝑇
 Rearranging and integrating above equation within limits, Z= Z1 ; PA = PA1
Z= Z2 ; PA = PA2
𝑧2 𝑃𝐴2
𝑁𝐴 𝑅𝑇
∴ ∫ 𝑑𝑧 = − ∫ 𝑑𝑃𝐴
DAB 𝑧1 𝑃𝐴1

 We get,

𝑁𝐴 𝑅𝑇
∴ [𝑧]𝑧𝑧2 = −[𝑃𝐴 ]𝑃𝑃𝐴2
DAB 1 𝐴1

𝑁𝐴 𝑅𝑇
∴ (𝑧2 − 𝑧1 ) = −(𝑃𝐴2 − 𝑃𝐴1 )
DAB

𝑁𝐴 𝑅𝑇
∴ 𝑍 = (𝑃𝐴1 − 𝑃𝐴2 )
DAB

 Rearranging the above equation, we get

DAB
∴ 𝑁𝐴 = (𝑃𝐴1 − 𝑃𝐴2 )
𝑅𝑇𝑍

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 Empirical equation for Diffusivities of gas:
 Diffusivity or diffusion coefficient, DAB is property of the system depends upon temperature,
pressure and nature of the component.

1 1 1 1
10−4 (1.084 − 0.249 √ + ) T 3/2 √ +
𝑀A 𝑀B 𝑀A 𝑀B
DAB =
𝑃t (𝑟𝐴𝐵 )2 ƒ (𝐾𝑇 /(ε𝐴𝐵 ) )

 Where,
DAB = Diffusivity (m2/s)
T = Absolute temperature.
MA & MB = molecular weight of A & B.
Pt = Absolute Pressure
rAB = molecular separation of collision
εAB = Energy of molecular attraction
K = Boltzmann constant

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