2.

DIFFUSION
11 July 2022 07:47

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---------- Table of Content ----------

 INTRODUCTION
○ IMPORTANT PARAMETERS
 TYPES OF DIFFUSION OR TYPES OF MASS TRANSFER
○ MOLECULAR MASS TRANSFER
○ CONVECTIVE MASS TRANSFER | EDDY MT | TURBULENT MT
 EFFECT OF RESISTANCE OR BARRIER ON MMT AND CMT
 MOLECULAR AVERAGE VELOCITY
 MASS AVERAGE VELOCITY
 FLUX
○ DIFFUSION VELOCITY
○ Concept of flux
 GENERAL FUNDAMENTAL EQUATION OF MASS TRANSFER/DIFFUSION
 FICK'S FIRST LAW
 FICK'S SECOND LAW
○ ANALOGIES
 Summary
 MODES OF DIFFUSION
○ Case 1 : A diffusing through B - Non diffusion
○ CALCULATION OF THE FLUX IN TEARM OF LOGARITHMIC DRIVING FORCE
 FLUX
  Summary
 CONCENTRATION PROFILE
○ In tearm of pressure
○ Case 2 : Counter diffusion
○ EQUIMOLAR COUNTER DIFFUSION
○ CALCULATION OF FLUX BY USING EQUIMOLAR COUNTER DIFFUSION
 Flux Calculation
 Summary
 CONCENTRATION PROFILE
○ UNEQUIMOLAR COUNTER DIFFUSION :
 STEFAN TUBE EXPERIMENT | MEASUREMENT OF DIFFUSION COEFFICIENT
 DIFFUSION THROUGH VARYING AREA
○ Concept of Flux Calculation with Varying Area
 DIFFUSION THROUGH NAPHTHALENE BALL
○ TIME REQUIRED TO COMPLETE THE EVAPORATION OF NAPHTHALENE BALL
○ Summary
 CONCEPT OF MULTICOMPONENT DIFFUSIVITY
○ Concept of 'A' free basis
 Diffusivity using 'A' free basis Concept
 VARIATION OF DIFFUSIVITY
○ Case 1 : For Gases
○ Case 2 : For Liquid
○ Case 3 : For Solid
 Knudsen Diffusion

-----------------------------------------------------------------------------------------------------------------

INTRODUCTION
---------
 " Net momentum of molecules from higher concentration region to lower concentration
region by virtue(गुण) of their thermal energy. "
- Diffusion is a mass transfer phenomenon that causes the distribution of a chemical species to become
more uniform in space as time passes.

 Examples of diffusion in everyday life :

 You can smell perfume because it diffuses into the air and makes its way into your nose.
 Cigarette smoke diffuses into the air.
 A few crystals of potassium permanganate in water will diffuse and turn the water purple.
 Leave a soda bottle open and the carbon dioxide bubble will diffuse and leave it flat.
 A tea bag placed in a cup of hot water will diffuse into the water.
 Aroma of food diffuses into the air and smell reaches you
 Oxygen and carbon dioxide diffuse to and from blood to the body cells.
 In leaves, oxygen from the leaf cells diffuses out to the air.
 Alloys are examples of diffusion, as in copper being diffused in a copper alloy.
 Heat is diffused during heat conduction, such as a mug getting hot when a hot liquid is placed in it.

 IMPORTANT PARAMETERS : ---------

1. Concentration :
- Here two types of concentration is
(1) Mass concentration (Mass density) :
𝐦𝐢 𝐤𝐠
𝛒𝐢 = (𝑚 = mass of the specie 'i' and V = volume of the specie 'i')
𝐕 𝐦𝟑

(2) Molar concentration (Molar density) :

𝐧𝐢 𝐦𝐨𝐥𝐞
𝐂𝐢 = (𝑛 = number of moles of the specie 'i' and V = volume of the specie 'i')
𝐕 𝐦𝟑

(3) Total Concentration :

𝐂𝐓 = ∑ 𝐂𝐢
 - Gases => assume : ideal gas
PV = nRT
𝐧 𝐏
𝐂𝐢 = =
𝐕 𝐑𝐓

PA
- For component A : CA = (PA = Partial pressure of component A)
RT

P
- For system (Total) : CT = RTT (PT = Total pressure of system)

- From these CA = CT . xA (for liquid) | CA = CT . yA (for gas)

(XA , yA is the mole fration of componrnt A in liquid and vapor repectively)

TYPES OF DIFFUSION OR TYPES OF

MASS TRANSFER
---------
(Type - 1) Molecular mass transfer | Conductive mass transfer | Molecular diffusion | Conductive diffusion.
This type of mass transfer or diffusion is occur at molecular level.

(Type - 2) Convective mass transfer | Convective diffusion | Eddy mass transfer | Eddy diffusion | Turbulent
mass transfer | turbulent diffusion
- This type of mass transfer or diffusion is occur at macroscopic level.

 MOLECULAR MASS TRANSFER : ---------

" Mass transfer / diffusion occur in a stagnate medium (v = 0)."

 NOTE : (i) It occurs in a stagnate medium (Velocity and Reynold's number is ZERO).
(ii) It is very slow Mass Transfer.
(iii) It is microscopic phenomenon.
 QUE : Why it is very slow molecular mass transfer ?
Ans : By kinetic theory of gases :

- Very slow because net momentum by molecule is very less.

QUE : How to increase Molecular mass transfer?

Ans :
- Two ways the increase of MMT :
(1) Increase Temperature :
Temperature increase ---> Kinetic energy increase ---> Velocity increase ---> Net momentum increase --->
MMT increase.
(2) Decrease Pressure :
Decrease in pressure ---> decrease in collision ---> increase in mean free path (λ) ---> Net momentum
increase ---> MMT increase.

 Example : Here P1 = 10 bar and P1 = 5 bar

 CONVECTIVE MASS TRANSFER | EDDY MT | TURBULENT MT : ---------

" Mass transfer occurs in a moving medium. "

 QUE : Without any molecular mass transfer, convective mass transfer is possible ?
Ans : YES.
- Molecular mass transfer is mainly due to the concentration difference.
- If we take system which have constant concentration all-over then may be temperature difference or
Buoyancy effect convective mass transfer possible.

- Mathematical way : flux NA = CA uA .

- Here CA = concentration, is constant but uA = velocity, could be anything.

EFFECT OF RESISTANCE OR BARRIER

ON MMT AND CMT
---------

 Experiment 1 : For MMT (Molecular mass transfer)

- In first case no barrier is present on cup of water and in second case we put barrier of 0.1mm air film on cup
of water then the flux is decrease 600 time of first case.
- Result : Barrier reduce molecular mass transfer rate.

 Experiment 2 : Salt Water Experiment

 Objective : How convective mass transfer is faster than molecular mass transfer.
 - Here water placed on brine is very carefully.
 First beaker(MMT) results :
- After 10 year : 87% of final concentration.
- After 28 year : 99 - 100% of final solution.

- In second beaker stirrer is placed and rotate at 22 rpm.

 Second beaker(CMT) results :
- After 60 sec (1min) : 99 - 100% of final concentration reach.

MOLECULAR AVERAGE VELOCITY

---------
- It is denoted by U or V.
 Formula 1 :
∑ Ci ui
U= ∑ Ci
(Ci = concentration of specie 'i')

mol m
× m
m3 sec
- Unit : mol =
sec
m3

- For Binary system A and B :

∑ Ci ui
U= ∑ Ci

CA uA + CB uB
∴U =
CA +CB

 Formula 2 : Where ∑ Ci = CT
∑ Ci u i
∴U =
CT

 Formula 3 :
 Ci Ci
U=∑ ui yi =
CT CT
∴U = ∑ yi ui

 All Formulas :
∑ 𝐂𝐢 𝐮𝐢 𝐂𝐀 𝐮𝐀 + 𝐂𝐁 𝐮𝐁 ∑ 𝐂𝐢 𝐮𝐢
U= ∑ 𝐂𝐢
| U= 𝐂𝐀 +𝐂𝐁
| U= 𝐂𝐓
| U = ∑ 𝐲𝐢 𝐮𝐢

MASS AVERAGE VELOCITY

---------
- It is denoted by 'u'.
∑ 𝛒𝐢 𝐮 𝐢
u= ∑ 𝛒𝐢
- Where ; u =mass average velocity
ρi = mass density or mass concentration
ui = velocity of species 'i'.

 About Density (𝛒𝐢 ) :

mi
ρi =
V

 If ideal gas mixture :

PV = nRT
weight ×RT
∴PV =
Molecular weight

w P × Molecular weight
∴ρ= =
V RT

P Mwt.
∴ρ= RT

- In tearm of concentration :
ρ = C × Mwt.

- For multi component system :

ρi = Ci × Mi

- If in the question given data in mol%, how to draw out?

ρi = CT × yi × Mi
 All Density (𝛒) formulas :
𝐦𝐢 𝐏 𝐌𝐰𝐭.
𝛒𝐢 = | 𝛒= | 𝛒 = C×Mwt. --> 𝛒𝐢 = 𝐂𝐢 × 𝐌𝐢 | 𝛒𝐢 = 𝐂𝐓 × 𝐲𝐢 × 𝐌𝐢
𝐕 𝐑𝐓
---------------------------------------------------------------------------------------------------------------
QUE : If gaseous mixture(N2 , H2 , Ar) has mole% (40%, 40%, 20%) respectively and velocity (vN2 = 00.06
m m m
,v =
sec H2
0.1 sec, Ar = 0.003 sec ) then findout :
(i) molar average velocity.
(ii) mass average velocity.
(iii) volume average velocity.
Ans :
(i) molar average velocity.
U = ∑ yi ui

∴U = yN uN2 + yH uH2 + yAr uAr

2 2

∴U = (4×0.06) + (0.4×0.1) + (0.2×0.003)

𝐦
∴U = 0.0646
𝐬𝐞𝐜

(ii) mass average velocity.

C
∑ ρi ui ∑ Ci ×Mi ×ui ∑ i ×Mi ×ui Ci
C
u= = = T
C = yi
∑ ρi ∑ Ci ×Mi ∑ i ×Mi CT
CT
∑ yi ×Mi ×ui
∴u = ∑ yi ×Mi

yN ×MN2 ×uN2 + yH ×MH2 ×uH2 + yAr ×MAr ×uAr

∴u = 2 2
yN MN2 + yH MH2 + yAr MAr
2 2

(0.40×28×0.06) +(0.40×2×0.1) +(0.20×40×0.003)

∴u =
(0.40×0.06) +(0.40×0.1) +(0.20×0.003)

𝐦
∴u = 0.039 𝐬𝐞𝐜

(iii) volume average velocity.

- Volume average velocity and Molar average velocity both are same. (Vol% = Mole%)
-------------------------------------------------------------------------------------------------------------

FLUX
---------
 " Amount of substance or quantity (mass, energy, momentum) passes per unit area per unit time is
called flux. "
Unit : .
, .

○ About Area : Area will consider which is perpendicular to the direction of the flow.

 Types of flux :
(i) Molar flux = concentration (𝐂𝐢 ) × diffusion velocity (𝐕𝐝 )
kmol m kmol
= × =
m3 s m2 .s

(ii) Mass flux = density (𝛒) × diffusion velocity (𝐕𝐝 )

kg m kg
= × =
m3 s m2 .s

 DIFFUSION VELOCITY : ---------

 Case 1 : V --> When observer at stationary position.

𝐕𝐝 = (𝐮𝐀 - 0)

 Case 2 : V --> When observer moving with bulk average velocity.

𝐕𝐝 = (𝐮𝐀 - 𝐔)
∑ Ci ui
- U = Molar Average velocity U = ∑ Ci

CA uA + CB uB
- For binary system : U =
CA +CB

 Concept of flux : ---------

 NA = Concentration × diffusion velocity (Vd ) = CA × (uA - 0) = 𝐂𝐀 . 𝐮𝐀
NA flux = when observer at stationary position.

 JA = Concentration × diffusion velocity (Vd ) = 𝐂𝐀 × (𝐮𝐀 - 𝐔)

JA flux = when observer moving with bulk average velocity or relative velocity.
 - Both are molar flux.

GENERAL FUNDAMENTAL EQUATION

OF MASS TRANSFER/DIFFUSION
---------
 Derivation :
CA uA + CB uB
- For binary system : U = NA = CA . uA
CA +CB
NA + NB
∴U=
CT

- JA = CA × (uA - U)
NA + NB
∴ JA = CA × uA -
CT

CA
∴ JA = CA u A − (NA + NB )
CT

CA
- As we know that NT = NA + NB and if liquid misture; = xA
CT

∴ JA = NA − xA NT

𝐍 𝐀 = 𝐍 𝐓 𝐱 𝐀 + 𝐉𝐀

- where;
NT xA = due to Bulk diffusion | JA = due to molecular diffusion / due to concentration difference.
- This is the general fundamental equation of mass transfer.

 Case 1 : If no bulk diffusion OR no convective mass transfer

- NA = NT xA + JA (NT xA = 0)

∴ 𝐍𝐀 = 𝐉𝐀 purly molecular diffusion

 Case 2 : If no concentration gradient

- NA = NT xA + JA (JA = 0)
 ∴ 𝐍𝐀 = 𝐮𝐀 . 𝐂𝐀 = 𝐍𝐀 𝐱 𝐀 when concentration is same everywhere in system

- There is diffusion because of velocity of molecules.

 Point to be noted :
 Case : If system dilute (xA --> 0)
- NA = NT xA + JA (NT xA = 0)

𝐍 𝐀 = 𝐉𝐀

 This case occur in (i) Diluted system, (ii) No convective MT, (iii) Film MT, (iv) MT in solid.
- For component A : NA = NT xA + JA

- For component B : NB = NT xB + JB

- NA + NB = NT (xA + xB ) + JA + JB

∴ NT = NT (xA + xB ) + JA + JB [NA + NB = NT | xA + xB = 1]
∴ 1 = 1 + JA + JB
∴ JA + JB = 0

∴ ∑ 𝐉𝐢 = 𝟎

 In 4 cases you will see N = J

(1) In Dilute system.
(2) Equimolar counter diffusion.
(3) Mass transfer in solid.
(4) Film theory.

FICK'S FIRST LAW

---------
- It just tells about the idea of flux.
- Fick's law talk about steady state diffusion because of concentration difference only at constant
temperature and pressure.
 - Flux due to molecular diffusion.
- CA = f(z) , CA ≠ f(z,t)

 Statement :
" Molar flux of species(A) relative to observer moving with bulk average velocity is directly
proportional to concentration gradient exist in the particular direction(in the direction of concentration
decrease) at isothermal and isobaric system. "

dCA
- Mathematical statement : JA Z ∝
dZ
𝐝𝐂𝐀
𝐉𝐀 𝐙 = − 𝐃𝐀𝐁 𝐝𝐙

- Where
DAB = mass diffusivity.
dCA
= Concentration gradint in the direction(Z) of decreasing concentration.
dZ
JA Z = flux in Z-direction.

 Meaning of 𝐉𝐀 𝐙 tearm :

- Here slop is negative.

∂CA
JA Z = − DAB ∂Z

CA 2 − CA 1
JA Z = − DAB Z2 − Z1
(CA 2 − CA 1 is nagative tearm)

- (−) meaning ----> concentration decreases in the Z - direction.

 Concept of 𝐃𝐀𝐁 :
 It is diffusivity of A in (A & B) mixture.
 It is experimental quantity.
 It tells about the idea of easy of diffusion
 DAB more ------> easy of mass transfer or easy of diffusion.

 Unit of Diffusivity :
kmol mol
kmol mol ∂C m3 m3
JA Z OR = − DAB A OR
m2 .sec m2 .sec ∂Z m m

kmol
×m m2 𝐦𝟐
m2 .sec
DAB = kmol = | 𝐃𝐀𝐁 =
sec 𝐬𝐞𝐜
m3

 Significance of diffusivity :
m2 m2
DAB = sec = m × sec
(velocity)

If DAB is more ----> movement more ----> mass transfer more.

FICK'S SECOND LAW

---------
 Here CA = f(z,t)
 Fick's law talk about unsteady state mass transfer/diffusion.
 Large application in pharmaceutical Industry.

𝛛𝐂𝐀 (𝐳,𝐭) 𝛛𝟐 𝐂 𝐀
= 𝐃𝐀𝐁 𝟐
𝛛𝐭 𝛛𝐙

 ANALOGIES : ---------

dCA m2
(1) Fick's Law of diffusion : JA Z = − DAB DAB = Mass Diffusivity
dZ sec

dT
(2) Fourier Law of heat transfer : Q̇ x = −K dX

kJ J
kJ J K dTρCp m3 m3
 Q̇ x OR = − OR
m2 .sec m2 .sec ρCp dX m m

d(TρCp )
=−α
dX
 𝐊 𝐦𝟐
𝛂= = Thermal Diffusivity
𝛒𝐂𝐩 𝐬𝐞𝐜

dVx
(3) Newton's law of viscosity for Momentum Transfer : τXY = − μ dy

(τXY = velocity of component / fluid in X-direction which change in y-direction)

μd(Vx .ρ)
- τXY = −
ρ dy

d(Vx .ρ)
=−ν×
dy

𝛍 𝐦𝟐
𝛎 = = Kinematic Viscocity OR Momentum Diffusivity
𝛒 𝐬𝐞𝐜

 Summary : ---------
d
Rate of quantity = Diffusivity × [Quantity]
dZ

𝐝𝐂𝐀
(1) Fick's Law of diffusion : 𝐉𝐀 𝐙 = − 𝐃𝐀𝐁
𝐝𝐙

𝐝(𝐓𝛒𝐂𝐩 )
(2) Fourier Law of heat transfer 𝐐̇𝐱 = − 𝛂
𝐝𝐗

𝐝(𝐕𝐱 .𝛒)
(3) Newton's law of viscosity for Momentum Transfer : 𝛕𝐗𝐘 = − 𝛎 × 𝐝𝐲

(4) when two miscible liquid are present together the we talk about both Fick's laws.

MODES OF DIFFUSION
---------
- There are two types of mode of diffusion
 Case 1 : A diffusing through B - Non diffusion (Stagnant)
 Objective : To calculate flux.

 Why we calculate flux ?

- To design the system.
- To optimize the system.
- To control the system.

 Derivation :
- At z1 ---> yA , xA 1 , CA 1 , PA 1
1
- At z2 ---> yA , xA 2 , CA 2 , PA 2
2

 Assumption :
(1) Steady state diffusion.
(2) NA ≠ f(z).
(3) Isothermal and Isobaric condition.
(4) No chemical reaction.

 Form Fundamental Equation :

NA = NT . xA + JA

- Here in case 1 : NB = 0
So NA + NB = NT
NA = NT

NA = NA . xA + JA

dCA
- From Fick's 1st Law : JA Z = − DAB
dZ

dCA
∴ NA = NA . xA − DAB dZ

∂CA
∴ NA (1 − xA ) = − DAB ∂Z

CA
- As we know that : xA = => CA = xA .CT
CT

∂CA ∂xA
CT is constant : = CT
∂Z ∂Z

∂xA
∴ NA (1 − xA ) = − DAB CT
∂Z

Z= Z x =x ∂xA
∴ ∫Z= Z 2 NA ∂Z = ∫x A= x A 2 (− DAB CT )
1 A A1 (1 − xA )

x dxA
∴ NA (Z2 − Z1 ) = − DAB CT ∫x A 2
A 1 (1 − xA )

1 − xA 2
∴ NA (Z2 − Z1 ) = (DAB CT ) ln
1 − xA 1
 D C 1 − xA 2
∴ NA = (Z AB− ZT ) ln 1 − xA 1
2 1

Z(distance between two points) = (Z2 − Z1 )

𝐃𝐀𝐁 𝐂𝐓 𝟏 − 𝐱𝐀 𝟐
∴ 𝐍𝐀 = 𝐥𝐧
𝐙 𝟏 − 𝐱𝐀 𝟏

(2) In case in question data given in tearm of concentrations CA 1 and CA 2

CA 2
DAB CT 1−
CT
NA = Z
ln CA 1
1− C
T

𝐃𝐀𝐁 𝐂𝐓 𝐂𝐓 − 𝐂𝐀 𝟐
∴ 𝐍𝐀 = 𝐥𝐧
𝐙 𝐂𝐓 − 𝐂𝐀 𝟏

(3) If data available in tearm of partial pressure PA1 , PA2

PA
1− 1
DAB CT PT
NA = Z
ln PA
1 − P2
T

𝐃𝐀𝐁 𝐂𝐓 𝐏𝐓 − 𝐏𝐀 𝟐
∴ 𝐍𝐀 = 𝐙
𝐥𝐧 𝐏𝐓 − 𝐏𝐀 𝟏

(4) If data available in tearm of mole fraction in gas yA , yA

1 2

𝐃𝐀𝐁 𝐂𝐓 𝟏 𝐲𝐀 𝟐
∴ 𝐍𝐀 = ln
𝐙 𝟏 𝐲𝐀 𝟏

 Summary : A diffusion B Non-diffusion

𝐃𝐀𝐁 𝐂𝐓 𝟏 − 𝐱𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 𝟏 − 𝐲𝐀 𝟐
(1) 𝐍𝐀 = 𝐍𝐓 . 𝐱 𝐀 + 𝐉𝐀 | (2) 𝐍𝐀 = 𝐥𝐧 | (3) 𝐍𝐀 = 𝐥𝐧
𝐙 𝟏 − 𝐱𝐀 𝟏 𝐙 𝟏 − 𝐲𝐀 𝟏

𝐃𝐀𝐁 𝐂𝐓 𝐂𝐓 − 𝐂𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 𝐏𝐓 − 𝐏𝐀 𝟐 𝐏𝐓
(4) 𝐍𝐀 = 𝐥𝐧 | (5) 𝐍𝐀 = 𝐥𝐧 (where 𝐂𝐓 = )
𝐙 𝐂𝐓 − 𝐂𝐀 𝟏 𝐙 𝐏𝐓 − 𝐏𝐀 𝟏 𝐑𝐓

 Why we deriving above formulas ?

d A
Reason : because we can not measure easily and accuretly, it is varying at avery point.
 CALCULATION OF THE FLUX IN TEARM OF LOGARITHMIC DRIVING FORCE
---------
 Why we are calculating logarithmic mean driving force?
Reason : because whenever things (like temperature, concentration, partial pressure, composition, etc.)
changes with length then we can accurately measure driving force in tearm of logarithmic mean.

 Binary system : (1) PT = PA 1 + PB 1 = constant (2) PT = PA 2 + PB 2 = constant

𝐏𝐁 𝟐 − 𝐏𝐁 𝟏
 In tearm of pressure : 𝐏𝐁𝐥𝐦 = 𝐏𝐁
𝐥𝐧 𝐏 𝟐
𝐁𝟏

𝐂𝐁 𝟐 − 𝐂𝐁 𝟏
 In tearm of pressure : 𝐂𝐁𝐥𝐦 = 𝐂𝐁 𝟐
𝐥𝐧
𝐂𝐁 𝟏

𝐗𝐁𝟐 − 𝐗𝐁𝟏
 In tearm of pressure : 𝐗 𝐁𝐥𝐦 = 𝐗𝐁𝟐
𝐥𝐧
𝐗𝐁𝟏

𝐘𝐁 𝟐 − 𝐘𝐁 𝟏
 In tearm of pressure : 𝐘𝐁𝐥𝐦 = 𝐘𝐁 𝟐
𝐥𝐧
𝐘𝐁 𝟏

 FLUX : ---------
 For liquid mass fraction :

XB 2 − XB 1
XBlm = XB 2
[xA 1 + xB 1 = 1, xA 2 + xB 2 = 1]
ln
XB 1

(1 − XA 2 ) − (1 − XA 1 )
∴ XBlm = (1 − XA )
ln (1 − X 2 )
A1

1 − XA 2 XA 1 − XA 2
∴ ln 1 − XA 1
= XBlm

DAB CT 1 − xA 2 DAB CT XA 1 − XA 2
∴ NA = Z
ln 1 − xA 1
= Z
× XBlm

𝐃𝐀𝐁 𝐂𝐓 ∆𝐗 𝐀
∴ 𝐍𝐀 = .
𝐙 𝐗 𝐁𝐥𝐦

𝐃𝐀𝐁 𝐂𝐓 ∆𝐘𝐀
 Similarly for gaseous mass fraction : 𝐍𝐀 = .𝐘
𝐙 𝐁𝐥𝐦
 For pressure :

PB 2 − PB 1
PBlm = PB 2
[PA 1 + PB 1 = PT , PA 2 + PB 2 = PT ]
ln
PB 1

(PT − PA 2 ) − (PT − PA 1 )
∴ PBlm = (PT − PA )
ln (P − P 2 )
T A1

PT − PA 2 PA 1 − PA 2
∴ ln =
PT − PA 1 PBlm

DAB CT PT − PA 2 DAB CT PA 1 − PA 2
∴ NA = Z
ln PT − PA 1
= Z
× PBlm

𝐃𝐀𝐁 𝐂𝐓 ∆𝐏𝐀
∴ 𝐍𝐀 = .
𝐙 𝐏𝐁𝐥𝐦

 For concentration :

CB 2 − CB 1
CBlm = CB 2
[CA 1 + CB 1 = CT , CA 2 + CB 2 = CT ]
ln CB 1

(CT − CA 2 ) − (CT − CA 1 )
∴ CBlm = (CT − CA 2 )
ln
(CT − CA 1 )

CT − CA 2 CA 1 − CA 2
∴ ln CT − CA 1
= CBlm

DAB CT CT − CA 2 DAB CT CA 1 − CA 2
∴ NA = ln = ×
Z CT − CA 1 Z CBlm

𝐃𝐀𝐁 𝐂𝐓 ∆𝐂𝐀
∴ 𝐍𝐀 = 𝐙
.𝐂
𝐁𝐥𝐦

 Summary : --------- A diffusion B Non-diffusion

𝐃𝐀𝐁 𝐂𝐓 𝟏 − 𝐱𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 ∆𝐗 𝐀
(1) 𝐍𝐀 = 𝐙
𝐥𝐧 𝟏 − 𝐱𝐀 𝟏
| 𝐍𝐀 = 𝐙
.𝐗
𝐁𝐥𝐦

𝐃𝐀𝐁 𝐂𝐓 𝟏 − 𝐲𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 ∆𝐘𝐀

(2) 𝐍𝐀 = 𝐙
𝐥𝐧 𝟏 − 𝐲𝐀 𝟏
| 𝐍𝐀 = 𝐙
.𝐘
𝐁𝐥𝐦

𝐃𝐀𝐁 𝐂𝐓 𝐂𝐓 − 𝐂𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 ∆𝐂𝐀

(3) 𝐍𝐀 = 𝐥𝐧 | 𝐍𝐀 = .
𝐙 𝐂𝐓 − 𝐂𝐀 𝟏 𝐙 𝐂𝐁𝐥𝐦
 𝐃𝐀𝐁 𝐂𝐓 𝐏𝐓 − 𝐏𝐀 𝟐 𝐃𝐀𝐁 𝐂𝐓 ∆𝐏𝐀
(4) 𝐍𝐀 = 𝐙
𝐥𝐧 𝐏𝐓 − 𝐏𝐀 𝟏
| 𝐍𝐀 = 𝐙
.𝐏
𝐁𝐥𝐦

 CONCENTRATION PROFILE ---------

 Mathematical Approach :

- Rate of mass in - Rate of mass out + generation = Accumulation

- Here we pre assume that steady state | T & P constant | There is no chemical reaction
So that generation and accumulation is 0.

∴Rate of mass in - Rate of mass out = 0

Kg
∴(NA × A) ( × m2 ) − (NA × A)Z+∆Z = 0
m2 .sec

∴ (NA × A)Z − (NA × A)Z+∆Z = 0

(NA ×A)Z − (NA ×A)Z+∆Z

∴ limZ→0 =0
∆Z

d
∴ dZ [ANA ] = 0 (Area is constant )

d
∴ [NA ] = 0
dZ

∴ 𝐍𝐀 = Constant (At area is constant)

- From basis fundamental equation

NA = NT .xA + JA
 ∂yA
∴ NA = NT .yA − DAB CT ∂Z

∂yA
∴ NA = NT .yA − DAB CT ∂Z

∂yA
∴ NA (1−yA ) = − DAB CT
∂Z

(− DAB CT ) ∂yA
∴ NA = .
∂Z (1−yA )

d
- Now ; [NA ] = 0
dZ

∂ (− DAB CT ) ∂yA
∴ ∂Z ∂Z
. (1−y ) =0
A

- We pre assumed that diffusion(− DAB ) and CT both are constant.

∂ ∂yA
∴ ∂Z ∂Z(1−yA )
=0

∂ ∂yA
∴∫ = ∫0
∂Z ∂Z(1−yA )

∂ ∂yA
∴∫ = ∫ C1
∂Z ∂Z(1−yA )

∂y
A
∴ ∫ ∂Z(1−y = ∫ C1 ∂Z
A)

− 𝐥𝐧{𝟏 − 𝐲𝐀 } = 𝐂𝟏 Z + 𝐂𝟐

- Boundary Condition 1 : yA = yA | Z = Z1
1
- Boundary Condition 2 : yA = yA | Z = Z2
2

- − ln 1 − yA = C1 Z1 + C2 ---------------------- (1)
1

- − ln 1 − yA = C1 Z2 + C2 --------------------- (2)
1

- Equation (1) − Equation (2) :

ln 1 − yA − ln 1 − yA = C1 Z1 + C2 − C1 Z2 − C2
2 1

∴ ln 1 − yA − ln 1 − yA = C1 (Z1 − Z2 )
2 1

1−yA
ln 2
1−yA
∴ C1 = 1
Z1 − Z2

(1) − ln 1 − yA = C1 Z1 + C2
1

1−yA
ln 2
1−yA
∴ − ln 1 − yA = 1
Z1 + C2
1 Z 1 − Z2

∴ −(Z1 − Z2 ) ln 1 − yA = Z1 ln(1 − yA ) − ln(1 − yA ) + C2 (Z1 − Z2 )

1 2 1

∴ − Z1 ln 1 − yA + Z2 ln 1 − yA = Z1 ln(1 − yA ) − Z1 ln(1 − yA ) + C2 (Z1 − Z2 )

1 1 2 1

Z2 Z1
∴ ln 1 − yA = ln 1 − yA + C2 (Z1 − Z2 )
1 2

Z
1 (1−yA ) 2
∴ C2 = ln Z
1
Z1 − Z2 (1−yA ) 1
2

- Put the value of C1 & C2 ;

1−yA
ln 1−y 2 Z
(1−yA ) 2
A1 1
∴ − ln 1 − yA = Z+ ln 1
Z
Z1 − Z 2 Z1 − Z2 (1−yA ) 1
2

𝐙 𝐙𝟏
𝟏 𝐲𝐀 𝟏 𝐲 𝐀 𝟐 𝐙𝟐 𝐙𝟏
∴𝟏 𝐲𝐀 𝟏
= 𝟏 𝐲𝐀 𝟏
For A
 Proof : − ln 1 − yA = C1 Z + C2
1 − yA = e−(C1 Z + C2 )
yA = 1 − e−(C1 Z + C2 )
Nature of this profile is Exponential.

Case 2 : Counter diffusion

---------

 EQUIMOLAR COUNTER DIFFUSION :

 CALCULATION OF FLUX BY USING EQUIMOLAR COUNTER DIFFUSION

 Meaning of equimolar counter diffusion : A and B both are diffusing but in opposite direction. (𝐍𝐀 = - 𝐍𝐁 )

 Note : NA = - NB | NT = 0 | Ex : Distillation

 Flux Calculation :
- Form general fundamental equation of diffusion :
NA = NT XA + JA
𝐍 𝐀 = 𝐉𝐀 (Because of NA = - NB ; NT = 0)

- In this case mass transfer occur by purely molecular diffusion and no bulk motion.
- By using Fick's first law :
∂CA
JA = − DAB
∂Z

∂yA CA
JA =−∴ DAB CT ∂Z
∵ CT
= yA

∂yA
∴ NA = JA = − DAB CT
∂Z

 Assumptions : NA ≠ f(Z)| steady state M. T. | Isothermal & Isobaric | No chemical reaction

∴ NA (∂Z) = (− DAB CT ) ∂yA

 Z=Z2 y=yA
2
∴ NA (∂Z) = (− DAB CT ) ∂yA
Z=Z1 y=yA
1

∴ NA (Z2 − Z1 ) = − DAB CT [y2 - y1 ] (Z = Z2 − Z1 )

𝐃𝐀𝐁 𝐂𝐓
∴ 𝐍𝐀 = . ∆𝐲𝐀
𝐙

 Case : in tearm of mass fraction in liquid.

𝐃𝐀𝐁 𝐂𝐓
𝐍𝐀 = 𝐙
. ∆𝐱 𝐀

 Case : in tearm of pressure.

DAB CT
NA = Z
. ∆yA (∆PA = PT . ∆yA )

DAB PT ∆PA
NA = .
RTZ PT

𝐃𝐀𝐁
𝐍𝐀 = . ∆𝐏𝐀
𝐑𝐓𝐙

 Case : in tearm of concentration.

DAB CT
NA = . ∆xA (∆CA = CT . ∆xA )
Z

DAB CT ∆CA
NA = .
Z CT

𝐃𝐀𝐁
𝐍𝐀 = . ∆𝐂𝐀 NA = K ∆CA (K = Mass transfer coefficient)
𝐙

 Summary : ---------

𝐃𝐀𝐁 𝐃𝐀𝐁 𝐂𝐓
(1) 𝐍𝐀 = . ∆𝐂𝐀 (3) 𝐍𝐀 = . ∆𝐲𝐀
𝐙 𝐙

𝐃𝐀𝐁 𝐃𝐀𝐁 𝐂𝐓
(2) 𝐍𝐀 = . ∆𝐏𝐀 (4) 𝐍𝐀 = . ∆𝐱 𝐀
𝐑𝐓𝐙 𝐙

 CONCENTRATION PROFILE : ---------

 We know that NA = constant

 dNA DAB CT
dZ
=0 ∵ NA = Z
. ∆yA

d ∆yA
∴ DAB CT . = 0
dZ dZ

d dyA
∴ = 0
dZ dZ

d dyA
∴ = 0
dZ dZ

dyA
∴ = C1
dZ

∴ 𝐲𝐀 = 𝐂𝟏 Z + 𝐂𝟐 (same as Y = mX + C)

- Therefore we can say that profile is linear.

 Boundary conditions :
- Boundary Condition 1 : yA = yA | Z = Z1
1

- Boundary Condition 2 : yA = yA | Z = Z2
2

yA = C1 Z1 + C2 ------------- (1)
1

yA = C1 Z2 + C2 ------------- (2)
2

- Equation (1) − Equation (2) :

yA − yA = C1 Z1 + C2 − C1 Z2 − C2
1 2

∴ yA − yA = C1 (Z1 − Z2 )
1 2

yA − yA
∴ C1 = 1 2
Z1 − Z2

(1) yA = C1 Z1 + C2
1

yA − yA
∴ yA = 1 2
Z + C2
1 Z1 − Z2 1
 ∴ yA Z1 − yA Z2 = yA Z1 − yA Z1 + C2 (Z1 − Z2 )
1 1 1 2

yA Z1 − yA Z2
∴ C2 = 2 1
Z1 − Z2

 Final result : profile

𝐲𝐀 − 𝐲𝐀 𝟏 𝐙 − 𝐙𝟏
=
𝐲𝐀 𝟏 − 𝐲𝐀 𝟐 𝐙𝟏 − 𝐙𝟐

 Case : in tearm of pressure :

PA PA 1
PT
− PT Z − Z1
PA 1 PA 2 =
− Z1 − Z2
PT PT

𝐏𝐀 − 𝐏𝐀 𝟏 𝐙 − 𝐙𝟏
=
𝐏𝐀 𝟏 − 𝐏𝐀 𝟐 𝐙𝟏 − 𝐙𝟐

 Profile : ---------

yA − yA yA − yA
∴ yA − yA = 1 2
.Z- 1 2
. Z1
1 Z1 − Z2 Z 1 − Z2

 Y = MX + C

yA − yA
- M= 1 2
= (M = - ive; beacause of Z1 − Z2 < 0)
Z1 − Z2

--------------------------------------------------------------------------------------------------------------
 Profile Based Problem :
 Ethanol(A) is diffusing through air(B) under steady state condition, with air non diffusing at temperature
313 K and pressure 101.3 KPa. The partial pressure of ethanol at two planes 5 mm apart 8 KPa. The
diffusivity of ethanol in air is 1.45 × 10 .
Calculate :
The mole fraction of Ethanol as the function of the distance along the direction of diffusion. The use of
result to evaluate the mole fraction at the center of diffusion path.
Solution :

 Method 1 :
Z−Z1
1−yA Z2 −Z1
1−yA
= 2
1−yA 1−yA
1 1

- Z1 = 0, Z2 = 5mm, Z = 2.5 mm

PA 1 8
- yA = PT
=
101.3
= 0.07897
1
PA 2 4
- yA = PT
=
101.3
= 0.03948
2

2.5−0
1−yA 1−0.039485−0
1−0.07897
= 1−0.07897

𝐲𝐀 = 0.059

 Method 2 :
NA = Constant (At area is constant)

- From basis fundamental equation

NA = NT .xA + JA

∂yA
∴ NA = NT .yA − DAB CT
∂Z
 ∂yA
∴ NA = NT .yA − DAB CT ∂Z

∂yA
∴ NA (1−yA ) = − DAB CT
∂Z

(− DAB CT ) ∂yA
∴ NA = .
∂Z (1−yA )

d
- Now ; [NA ] = 0
dZ

∂ (− DAB CT ) ∂yA
∴ ∂Z ∂Z
. (1−y ) =0
A

- We pre assumed that diffusion(− DAB ) and CT both are constant.

∂ ∂yA
∴ ∂Z ∂Z(1−yA )
=0

∂ ∂yA
∴∫ = ∫0
∂Z ∂Z(1−yA )

∂ ∂yA
∴∫ = ∫ C1
∂Z ∂Z(1−yA )

∂y
A
∴ ∫ ∂Z(1−y = ∫ C1 ∂Z
A)

− ln 1 − yA = C1 Z + C2

 − ln 1 − yA = C1 Z1 + C2
1

∴ − ln{1 − 0.07897} = C1 (0) + C2

∴ C2 = 0.08226

 − ln 1 − yA = C1 Z2 + C2
2

∴ − ln{1 − 0.03948} = C1 (5) + (0.08226)

∴ C1 = - 0.008395
 − ln 1 − yA = C1 Z + C2
∴ − ln 1 − yA = (- 0.008395)(2.5) + 0.08226

∴ − ln 1 − yA = (- 0.008395)(2.5) + 0.08226

1
∴ = e0.0612725
1−yA

∴ 1 − yA = 0.9405669

∴ 𝐲𝐀 = 0.059
----------------------------------------------------------------------------------------------------------------

 UNEQUIMOLAR COUNTER DIFFUSION : ---------

 Assumptions :
- Amount of mole of A transfer to the B ≠ Amount of mole of B transfer to the A
- Moles of B transfer to the A ≠ 0
(1) Steady state diffusion.
(2) NA ≠ f(z).
(3) Isothermal and Isobaric condition.
(4) No chemical reaction.
NB = -K NA [K(constant) ≠ (1,0)]

- From general fundamental equation of mass transfer :

NA = NT XA + JA (NB = -K NA )
∴ NA = (NA + NB )XA + JA
∂xA
∴ NA = (NA - K NA )XA − DAB CT ∂Z

∂xA
∴ NA {1 − (1 − K)XA } = − DAB CT
∂Z

DAB CT . ∂xA
∴ NA ∂Z = − {
1−(1−K)XA }

Z X DAB CT . ∂xA
∴ ∫Z 2 NA ∂Z = ∫X A 2 − {1−(1−K)XA }
1 A1

DAB CT 1−(1−K)XA 2
∴ NA (Z2 − Z1 ) = ln
(1−K) 1−(1−K)XA 1

N
DAB CT 1− 1− − B XA 2
NA
∴ NA (Z2 − Z1 ) = N ln N
1− − B 1− 1− − B XA 1
NA NA
 NA + NB NA
1− X
NA NA A 2 NA + NB
∴ NA (Z2 − Z1 ) = DAB CT ln NA + NB × NA
NA + NB 1− X
NA A 1 NA + NB

NA
NA − XA 2
NA + NB
∴ NA Z = DAB CT ln NA
NA + NB − XA 1
NA + NB

𝐍𝐀
𝐍𝐀 𝐃𝐀𝐁 𝐂𝐓 𝐍𝐀 𝐍𝐁
𝐗𝐀𝟐
∴ 𝐍𝐀 = 𝐥𝐧 𝐍𝐀
𝐍𝐀 𝐍𝐁 𝐙 𝐗𝐀𝟏
𝐍𝐀 𝐍𝐁

 Case 1 : NB = 0

𝐃𝐀𝐁 𝐂𝐓 𝟏 𝐗𝐀𝟐
𝐍𝐀 = 𝐥𝐧
𝐙 𝟏 𝐗𝐀𝟏

In chemical Reaction : A ---> 3B

NA NB
=
−1 +3
NB = -3NA

NA
NA DAB CT − XA 2
NA + NB
NA = NA + NB Z
ln NA
N +
− 1

NA
NA DAB CT NA + −3NA
− XA 2
NA = ln NA
NA + −3NA Z − XA 1
NA + −3NA

1
1 DAB CT − XA 2
NA = −2 Z
ln −2
1
− XA 1
−2

𝐃𝐀𝐁 𝐂𝐓 𝟏 𝟐𝐗 𝐀 𝟐
𝐍𝐀 = 𝟐𝐙
𝐥𝐧 𝟏 𝟐𝐗 𝐀 𝟏

PA 2 CA 2 PA 1 CA 1
XA 2 = PT
= CT
| XA 1 = PT
= CT

○ STEFAN TUBE EXPERIMENT | MEASUREMENT OF DIFFUSION COEFFICIENT

---------

 Assumptions :
 (1) Steady state diffusion. | Binary system.
(2) NA (flux) ≠ f(z).
(3) Isothermal and Isobaric condition.
(4) No chemical reaction.

- Here air is present in large amount (D >> d) (PA 2 = 0 : Assume).

- Here process is unsteady state because of decreases in hight with respect to time.
- Here in above figure (t0 - t) is very large as conpaer to (Z0 - Zt = z) thats why z is negligible.
- So that this process is called pseudo steady state process.

 Concept of pseudo steady state :

- Things (height, size, rate) are changes with respect to time very slow that phenomenon is called pseudo
steady state.

 By A diffusing B not diffusing :

DAB CT 1 − yA
NA = ln 2
Z 1 − yA
1

z ρA 1 − yA t
∴ ∫z t − . z dz = DAB CT ln 2
∫t dt [here (−) because of decreasing in height]
0 mA 1 − yA 0
1

z0 = Initial height, zt = Final height

ρA zt 2 − z0 2 1 − yA
∴− = DAB CT ln 2
× (t − 0)
mA 2 1 − yA
1

𝛒𝐀 (𝐳𝟎 𝟐 𝐳𝐭 𝟐 )
∴ 𝐃𝐀𝐁 = 𝟏 𝐲𝐀 𝟐
𝟐𝐦𝐀
𝐂𝐓 𝐥𝐧 .(𝐭 𝟎)
𝟏 𝐲𝐀 𝟏
 DIFFUSION THROUGH VARYING AREA
---------

 Varying area geometries :

- Objective : Calculation of flux in different - different kind of geometries.

 Concept of Flux Calculation with Varying Area : ---------

- Mass Balance :
Rate of mass in - Rate of mass out = Accumulation

- At steady state :
(NA Ar ) at r − (NA Ar ) at r + ∆r = 0

(NA Ar ) at r − (NA Ar ) at r + ∆r
∴ lim
∆r→0 ∆r

d
∴ [NA Ar ] = 0
dr

𝐍𝐀 𝐀 𝐫 = Constant = w (Rate of Diffusion)

 Concept : Flux × Area = Constant = w

 NA Ar = Constant

𝐍𝐀 𝟏 𝐀 𝐫 𝟏 = 𝐍𝐀 𝟐 𝐀 𝐫 𝟐

 CASE 1 : For Sphere (AS = 4πr2 )

N1 A1 = N2 A2

∴ N1 × 4πr1 2 = N2 × 4πr1 2

𝟐
𝐍𝟐 𝐫𝟏
𝐍𝟏
= 𝐫𝟐

 CASE 2 : For Cylinder (AS = 2πrL)

N1 A1 = N2 A2

∴ N1 × 2πr1 L = N2 × 2πr2 L

𝐍𝟐 𝐫𝟏
=
𝐍𝟏 𝐫𝟐

- If say Curved surface; then surface area is 2πrL

- If say Total surface area; then 2πrL + πr2 + πr2

 CASE 3 : Flate Plate of wall

 N1 A1 = N2 A2

𝐍𝟏 = 𝐍𝟐

DIFFUSION THROUGH NAPHTHALENE

BALL
---------

 Assumption :
1 1
(1) r2 >>>> r1 => r <<<< r
2 1
(2) Pseudo steady state process.
(3) Isothermal and Isobaric.
(4) No chemical reaction.
(5) A(Naphthalene ball) diffusing B(Air) not diffusing.

 Derivation : From basic equation of mass transfer or diffusion.

NA = NT yA + JA

DAB dPA
Where JA = −
RT dr

DAB dPA
∴ NA (1 − yA ) = −
RT dr

P
Where yA = PA (PA is a partial paressure)
T

P DAB dPA
∴ NA 1 − PA= − RT dr
T

DAB PT dPA
∴ NA dr = −
RT (PT −PA )
 - We know that NA × Ar = wA = Constant

w
NA = 4πrA2

r wA P DAB PT dPA
∴ ∫r 2 dr = ∫P A 2 −
1 4πr2 A1 RT (PT −PA )

wA 1 1 DAB PT PT −PA 2
∴ − = ln
4π r1 r2 RT PT −PA 1

1 1
- Where r <<<r
2 1

w DAB PT PT −PA 2
∴ 4πrA = RT
ln PT −PA 1
1

- r1 divided both the sides;

wA DAB PT PT −PA 2
∴ = ln
4πr1 2 RTr1 PT −PA 1

𝐃𝐀𝐁 𝐏𝐓 𝐏𝐓 −𝐏𝐀 𝟐
∴ 𝐍𝐀 (𝐚𝐭 𝐫 = 𝐫 ) = 𝐥𝐧 here 𝐏𝐀 𝟐 <<< 𝐏𝐀 𝟏
𝟏 𝐑𝐓𝐫𝟏 𝐏𝐓 −𝐏𝐀 𝟏

- In general we can say

𝐃𝐀𝐁 𝐏𝐓 𝐏𝐓 −𝐏𝐀 𝟐
𝐍𝐀 (𝐚𝐭 𝐫 ) = 𝐥𝐧 here 𝐏𝐀 𝟐 <<< 𝐏𝐀 𝟏
𝐑𝐓𝐫 𝐏𝐓 −𝐏𝐀 𝟏

 TIME REQUIRED TO COMPLETE THE EVAPORATION OF

NAPHTHALENE BALL : ---------

DAB PT PT −PA 2
NA (at r ) = RTr
ln PT −PA 1
 kg
ρA dr m3 m kmol
- Here NA = − = kg × = m2 .sec
mA dt sec
kmol

ρA dr DAB PT PT −PA 2
∴− = ln
mA dt RTr PT −PA 1

ρA DAB PT PT −PA 2
∴− mA
r.dr = RTr
ln PT −PA 1
. dt

ρA 0 DAB PT PT −PA 2 t
∴− ∫r r. dr = ln . ∫t=0
f
dt
mA 1 RTr PT −PA 1

- Divide both the side by r1 ;

1 ρA r1 2 DAB PT PT −PA 2
∴ × − × 0 − = ln × tf
r1 mA 2 RTr1 PT −PA 1

DAB PT PT −PA 2
- We know that NA (at r = r ) = ln
1 RTr PT −PA 1

𝛒 𝐀 𝐫𝟏 𝟏
∴ 𝐭 𝐟 = 𝟐𝐦𝐀
× 𝐍𝐀 (𝐚𝐭 𝐫 𝐫 )
𝟏

- Where ;
ρA = density of naphthalene ball
mA = molecular weight of Naphthalene ball
r1 = radius of Naphthalene ball.

- In general form :

𝛒𝐀 𝐫 𝟏
𝐭 𝐟 = ×
𝟐𝐦𝐀 𝐍𝐀 (𝐚𝐭 𝐫 )

--------------------------------------------------------------------------------------------------------------
QUE : Two naphthalene ball is given with data D1 = 15 cm, D2 = 55 cm and mass & density of both the
balls is same then find out the time required for complete evaporation t1 & t2 . Here mass transfer
1
coefficient K ∝ 3 .
r2
Solution :

ρ A r1 1
tf = ×
2mA NA (at r = r )
1
 NA = K. Driivng force
- Here Driving force is same then NA ∝ K
1
∴ NA ∝ 3
r2

5
r
∴ tf ∝ 3 => tf ∝ r 2
r2

5 5
5
t1 r21 D21
∴ = = = (3) = 15.8
2
t2 r2 D2

---------------------------------------------------------------------------------------------------------------
 Summary : ---------
DAB PT PT −PA 2
NA (at r ) = RTr
ln PT −PA 1
here PA 2 <<< PA 1

ρA r 1
tf = ×
2mA NA (at r)

CONCEPT OF MULTICOMPONENT
DIFFUSIVITY
---------

𝟏 − 𝐲𝐀
𝐃𝐀−𝐌𝐢𝐱 = 𝐲𝐢
∑
𝐃𝐀−𝐢

- Here A, B, C and D are the components of mixture, where diffusivity of B, C and D components is known and
moles of all components is known.
- Objective is to find the diffusivity of component A in the mixture.

𝟏 − 𝐲𝐀
𝐃𝐀−𝐌𝐢𝐱 = 𝐲𝐁 𝐲 𝐲
+ 𝐂 + 𝐃
𝐃𝐀−𝐁 𝐃𝐀−𝐂 𝐃𝐀−𝐃

 Concept of 'A' free basis : ---------

- Assume the moles of A=20mol, B=10mol, C=5mol, D=10mol.

20 10 5 10
- Mole fraction : yA = , yB = ,y = ,y =
45 45 C 45 D 45
 Calculate the mole fraction of 'C' on 'A' free basis (𝐲𝐂 ′ ) :

𝐦𝐨𝐥𝐞 𝐨𝐟 𝐂
𝐲𝐂 ′ = 𝐦𝐨𝐥𝐞 𝐨𝐟 𝐂+𝐦𝐨𝐥𝐞 𝐨𝐟 𝐁+𝐦𝐨𝐥𝐞 𝐨𝐟 𝐃

- In numerator and denominator divided by total mole;

mole of C
∴ yC ′ = Total mole
mole of C+mole of B+mole of D
Total mole

yC
∴ yC ′ =
yC + yB + yD

- We know yA + yB + yC + yD = 1

𝐲𝐂
𝐲𝐂 ′ =
𝟏 − 𝐲𝐀
--------------------------------------------------------------------------------------------------------------
 We calculate based on data :
- A=20mol, B=10mol, C=5mol, D=10mol.
20 10 5 10
- Mole fraction : yA = , yB = ,y = ,y = .
45 45 C 45 D 45

5
yC
yC ′ = = 45
20 = 0.2
1 − yA 1 − 45

mole of C 5
yC ′ = = = 0.2
mole of C+mole of B+mole of D 5+10+10
--------------------------------------------------------------------------------------------------------------
 Diffusivity using 'A' free basis Concept : ---------

1 − yA
DA−Mix = yB y y
+ C + D
DA−B DA−C DA−D

1
∴ DA−Mix = yB yC yD
1 − yA 1 − yA 1 − yA
+ +
DA−B DA−C DA−D

𝟏
𝐃𝐀−𝐌𝐢𝐱 = 𝐲𝐁 ′ 𝐲 ′ 𝐲 ′
+ 𝐂 + 𝐃
𝐃𝐀−𝐁 𝐃𝐀−𝐂 𝐃𝐀−𝐃

- Where yB ′ , yC ′ , yD ′ are the mole fraction on 'A' free basis.

 𝐃𝐀−𝐌𝐢𝐱 𝐂𝐓 𝟏 − 𝐲𝐀 𝟐
Flux 𝐍𝐀 = 𝐙
𝐥𝐧 𝟏 − 𝐲𝐀 𝟏

 Assumption : If we find the diffusivity of component 'i' then the diffusivity of other than 'i' component is
ZERO means NJ = 0. you can only find the flux of component 'i'.

---------------------------------------------------------------------------------------------------------------
QUE : Nitrogen is diffusing under steady condition through a mixture of 5% N2 , 15% C2 H6 , 40%C2 H4 and
40% C4 H10 at 298 k and 100 kPa. The partial pressure of the nitrogen at two planes (5mm) apart are 16.3
& 6.67 kPa, respectively. Calculate the flux of N2 accros the two planes. The diffusivity of N2 through C4 H10 ,
2 2 2
−6 m −6 m −6 m
C2 H6 and C2 H4 may be taken as 8.6 × 10 , 16.8 × 10 and 19.3 × 10 , respectively.
sec sec sec
Solution :
1 1 m2
- DA−Mix = = 0.15 0.4 0.4 = 1.24 × 10−5
yC H ′
2 6 +
yC H ′
2 4 + yD ′ 1 −0.05 + 1 −0.05 + 1 −0.05
sec
DN −C H
2 2 6
DN −C H
2 2 4
DN −C H
2 4 10 16.8 × 10−6 19.3 × 10−6 8.6 × 10−6

DN2 −Mix PT P T − P N2
- Flux NN2 = ln 2
RT.Z P T − P N2
1

1.24 × 10−5 × 100 100 −6.67

∴ NN2 = −3 ln
8.314×298 ×5×10 100 −16.3

∴ NN2 = 1.000979992 × 10−4 × 0.108902622

∴ 𝐍𝐍𝟐 = 1.09 × 𝟏𝟎−𝟓

--------------------------------------------------------------------------------------------------------------

VARIATION OF DIFFUSIVITY
---------
- Diffusivity is the mainly function of Temperature (major), Pressure(major in Gas), Viscosity(major in Liquid),
Molecular weight, Nature of substance.

 Case 1 : For Gases

𝐓𝐱
𝐃𝐀𝐁 ∝
𝐏𝐓 𝐦𝐨𝐥𝐞𝐜𝐮𝐚𝐥𝐫 𝐰𝐞𝐢𝐠𝐡𝐭

- Typically region of x ---> 1.25 to 1.75.

 3
- Other than GATE exam relation is not given then use DAB ∝ T . 2

𝐦𝟐
- Typically order 𝐃𝐀𝐁 ≈ 𝟏𝟎−𝟑 to 𝟏𝟎 −𝟓
𝐬𝐞𝐜

 Analysis of result :
- Pressure constant and temperature ↑ ----> kinetic energy ↑ ----> velocity of molecule ↑ ----> diffusivity (m
m
× ↑) ↑ ----> Rate of mass transfer ↑ .
s

- If pressure ↓ ----> number of collison ↓ ----> net momentum ↑ ----> DAB ↑ ----> Rate of mass transfer ↑.

𝟏
- Rate of mass transfer ∝ 𝐃𝐀𝐁 ∝
𝐏 𝐓
-----------------------------------------------------------------------------------------------------------
QUE : The diffusivity of argon in nitrogen at and 4 atm pressure is. What would be the diffusivity of in argon
at and 8.5 atm?
Solution :
Tx
DAB ∝
PT molecualr weight

D2 P1
∴ ∝
D1 P2

D2 4
∴ ∝
D1 8.5

∴ 𝐃𝟐 = 0.47 𝐃𝟏
---------------------------------------------------------------------------------------------------------------
 Case 2 : For Liquid ---------

𝐓
𝐃𝐀𝐁 ∝ 𝛍 × 𝐌𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐰𝐞𝐢𝐠𝐡𝐭

𝟐
- Typically order 𝐃𝐀𝐁 ≈ 𝟏𝟎 −𝟕 −𝟗 𝐦
to 𝟏𝟎
𝐬𝐞𝐜

 Case 3 : For Solid

𝐃𝐬 ∝ √ 𝐓

𝐦𝟐
- Typically order 𝐃𝐀𝐁 ≈ 𝟏𝟎−𝟏𝟏 to 𝟏𝟎 −𝟏𝟑
𝐬𝐞𝐜
 - We can observed mass transfer in solid when, this solid comes contect with liquid and gases but negligible
mass transfer observed in solid - solid phenomenon.
- Ex : Drying, Adsorption, Membrane separation.

 Knudsen Diffusion : ---------

- Here in experiment pore diameter is less than the 50nm.

- Distance of molecule until Collison with another molecule and change the path and velocity, that distance is
called mean free path (λ).

- In this experiment 𝛌 > diameter of pore.

 Note : mass transfer within the solid occurs due to molecular diffusion or molecular mass transfer.
𝐉𝐀 = 𝐍 𝐀
 Calculation of flux (𝐃𝐊 ) :

𝛛𝐂𝐀
𝐍 𝐊 = − 𝐃𝐊 𝛛𝐙

- From literature we can observe

𝟐
𝐃𝐊 = 𝐫𝐩 𝐯𝐓
𝟑

- Where; rp = radius of pour or capillary.

vT = average velocity of molecules.
𝟏
𝟖𝐑𝐓𝟐
𝐯𝐓 =
𝛑𝐦

J
- Where; R = universal gas constant 8.314
mol.K
m = Molecular weight
T = absolute temperature.

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