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Molecular Diffusion

11/30/2018 PE 311 1

Introduction to Mass Transfer Operations

The transport or migration of one constituent from a

region of higher concentration to that of a lower

concentration is known as mass transfer.

Mass transfer operations depend on molecules

diffusing from one distinct phase to another and are

based upon differences in the physicochemical

properties of the molecules, such as vapour pressure

or solubility.

For interphase mass transfer, there is a concentration

gradient between bulk and interface, however under

steady state, at interface equilibrium is assumed.

11/30/2018 PE 311 2

Introduction to Mass Transfer Operations

A group of operations for separating the components

of mixtures is based on the transfer of material from

one homogeneous phase to another.

These methods is covered by the term mass transfer

operations which include techniques like:

gas absorption and stripping,

liquid-liquid extraction and leaching,

distillation,

Humidification,

drying and crystallization

11/30/2018

PE 311 3

Concentrations & Flux

The concentration of particular species is expressed in

variety of ways. In mass transfer operation, the

concentration gradient is the driving force when other

driving forces (temperature, pressure gradients, etc.)

are kept constant.

The actual driving force for mass transfer to occur is to

create gradient of chemical potential (between two

points) which is a function of all external forces.

11/30/2018 PE 311 4

Concentrations & Flux

The concentration gradients are generally

expressed in terms of:

mass concentration of component,

molar concentration of component

mass or mole fraction of species.

11/30/2018 PE 311 5

Mass Concentration

Amount of a particular species in a mixture is

defined by the mass of that species per unit

volume, i.e. partial density.

Wi mass of species i in the mixture

i ...........(1)

V Volume of mixture

The mass density of the mixture itself, , is the

total mass of all species per unit volume;

therefore,

1 W1 W2 Wn

Wi ... i ............(2)

V i V V V

PE 300 - Lecture Series 6

Mass Fraction

The relative amount of species i in the mixture

may be described by the mass of i per unit mass

of the mixture,

mass of species i Wi i V i

mi ............(3)

mass of mixture Wtot V

i in the mixture

Leading into:

i

i mi i 1 0 mi 1.............(4)

PE 300 - Lecture Series 7

Molar Concentration

Expressing the concentration of species i in

the mixture in terms of moles rather than

mass gives:

mass of i Wi

moles of i molecular weight of i M i 1 Wi i

ci .........(5)

volume V V Mi V Mi

The molar concentration of the mixture, c, is

the total number of moles for all species per

unit volume; thus,

Wi

i moles of i i M i Wi i

c ci ........(6)

V V i V Mi i Mi i

Mole Fraction

The mole fraction of species i, xi, is the

number of moles of i per mole of mixture

Wi Wi

moles of i Mi M i V ci

xi ............(7)

Wi Wi V c

moles of mixture

i M i M

i i

And ci

i xi i c 1 0 xi 1.................(8)

Molecular Weight

The molecular weight of the mixture is the

number of kg of mixture per kmol of mixture:

M ..........(9)

From Equation (5) and (6) c

1 1

M .........(10)

c c

i

i

i i 1

i M i M

mi

M i i i i

Wi

i i V Wi 1 M i ci

M i

M i xi M i .........(11)

c c c PE 300i - Lecture

V cM Series

i i c i 10

Mixture compositions and species fluxes

Mole fraction may be converted to mass

fraction using the following relations:

xi M i xi M i

mi ......(12)

M xk M k

k

And mi M mi M i

xi ...........(13)

Mi xk / M k

k

Ni N A ci ..........(14)

where NA is Avogadro's number, 6.02214 x 1026

molecules/kmol. PE 300 - Lecture Series 11

Ideal gases

Combine the preceding relations with the ideal

gas law.

For any individual component, i, we may write

the partial pressure, Pi, exerted by i as

pi i Ri T ..........(15)

Ro

Where Ri ..............(16)

Mi

Resulting into

Ro

pi i Ri T M i ci T ci Ro T .........(17)

Mi

PE 300 - Lecture Series 12

Ideal gases

Giving pi p

c ci .........(18)

i i Ro T Ro T

p pi ...........(19)

i

ci pi pi

And xi .........(20)

c c Ro T p

Fluxes

The flux is defined as the rate of transport of species i

per unit area in a direction normal to the transport.

The flux is calculated with respect to a fixed reference

frame. The molar flux of species i can be represented

as :

11/30/2018 PE 311 14

Fluxes

The units of molar and mass fluxes are moles/m2.s

and mass/m2.s. Sometimes it is convenient to

interpret the total flux of species i with respect to an

arbitrary reference frame rather than a fixed set of

reference frame.

The molar flux of species i based on arbitrary

reference velocity Uo is defined as:

Similarly mass flux of species based on arbitrary

reference velocity Uo is denoted by:

11/30/2018 PE 311 15

Example - 1

The most important mixture that we deal with

is air. Its mass composition is: N2 = 0.7556, 02 =

0.2315, Ar = 0.01289, trace gases < 0.01.

Determine xO2, pO2, cO2 and O2 for air at 1 atm.

11/30/2018 PE 311 16

Mass Transfer Classification

Mass Transfer

Diffusion Transfer

11/30/2018 PE 311 17

Molecular Diffusion

Molecular diffusion or molecular transport can be

defined as the transfer or movement of individual

molecules through a fluid by means of the random

individual movements of the molecules.

The diffusion of molecules when the whole bulk fluid

is not moving but stationary; the diffusion of

molecules is due to a concentration gradient

11/30/2018 PE 311 18

Molecular Diffusion Process

11/30/2018 PE 311 19

Fick’s Law of Diffusion

Fick's First Law of Diffusion states that the net

flux of a molecular/mass species A or B is

proportiona1 to the negative gradient of the

concentration of that species, expressed as:

dx A

J A * C DAB x A C DAB ...........(28)

dx

dm A

or j A * DAB m A DAB ...........(29)

dx

For ideal gas

p 1 dp A

J A* DAB x A DAB ...........(30)

R T R T dx

PE 300 - Lecture Series 20

Fick’s Law of Diffusion

By comparing the transport laws in

concentration form one sees quantitatively the

molecular-transport analogy

Momentum

du du d u d u

........(31)

dx dx dx dx

Nm d u kg m 1 kg

3 v 3 v 3

m dx m s m m s

Nm m3 s m m m3 s m 2

v 3 kg 2 3

m kg s m kg s

PE 300 - Lecture Series 21

Fick’s Law of Diffusion

Heat

Q cp d c p T d c p T

q

dT

dT ......(32)

A dx dx c cp dx dx

p

Q W d c p T kg J K J

q 2 3 4

A m dx m kg K m m

W m4 J 1 m4 m2

2

m J s m2 J s

dC A

J A DAB ..........(33)

dx

Mass kg dC A kg 1

J A 2 DAB DAB 3

m s dx m m

kg m

4

m2

DAB 2

m s kg s

PE 300 - Lecture Series 22

Fick’s Law of Diffusion

GASES LIQUIDS

Kinematic viscosity, [m2/s]

-5

1 to 5 x 10 0.1 to 2 x 10-5

Thermal Diffusivity, c p [m2/s] 1.5 to 7 x 10- 0.1 to 2 x 10-7

5

5 9

Dimensionless Quantities

Kinematic Vis cos ity c p 0.7 to 1.0 1.0 to 10

Pr andtl number

Thermal Diffusivity

Kinematic Vis cos ity 1.0 to 10 10 to 104

Schmidt number

Mass Diffusivity D

Thermal Diffusivity Schmidt Number 1.0 to 10 102 to 104

Lewis number

Mass Diffusivity Pr andtl Number D

Example -2

A mixture of He and N2 gas is contained in a pipe at

298 K and 1 atm total pressure which is constant

throughout. At one end of the pipe at point 1 the

partial pressure pA1 of He is 0.6 atm and at the other

end 0.2 m pA2 = 0.2 atm. Calculate the flux of He at

steady state if DAB of the He-N2 mixture is 0.687 x 10-4

m2/s.

Convection Mass Transfer

When a fluid flowing outside a solid surface in forced

convection motion, rate of convective mass transfer is given by:

N A k c (c L1 c Li )

kc - mass transfer coefficient (m/s)

cL1 - bulk fluid conc.

cLi - conc of fluid near the solid surface

Kc depend on:

1. system geometry

2. Fluid properties

3. Flow velocity

Equimolar Counter Diffusion

Consider two gases A and B at constant total pressure

P in two large chamber connected by a tube.

equal to the net moles of B to the left.

11/30/2018 PE 311 26

Example 3

Ammonia gas (A) is diffusing through a uniform

tube 0.10 m long containing N2 gas (B) at 1.0132 x

105 Pa pressure and 298 K. The diagram is similar to

Fig. 6.2-1. At point 1, pA1 = 1.013 x 104 Pa and at point

2, pA2 = 0.507 x 104 Pa. The diffusivity DAB = 0.230 x

10-4 m2/s.

(a) Calculate the flux J*A at steady state

(b) Repeat for J*B

GENERAL CASE FOR DIFFUSION OF GASES A AND

B PLUS CONVECTION

Up to now we have considered Fick's Law of diffusion

in a stationary fluid

There has been no net movement or convective flow of

the entire phase of binary mixture A and B

The diffusion flux occurred because of the

concentration gradient

This flux can be converted to a velocity of diffusion of

A

GENERAL CASE FOR DIFFUSION OF GASES

A AND B PLUS CONVECTION

11/30/2018 PE 311 29

For equimolar counterdiffussion, NA=-NB ,

then NA=J*A=-NB=-J*B

Example 4

Water in the bottom of a narrow metal tube is held at a

constant temperature of 293 K. The total pressure of air

(assumed dry) is 1.01325 x 105 Pa (1.0 atm) and the

temperature is 293 K (20 °C). Water evaporates and

diffuses through the air in the tube, and the diffusion

path z2-z1 is 0.1524 m (0.5 ft) long. The diagram is

similar to Fig. 6.2-2a. Calculate the rate of evaporation

at steady state in lb mol/h.ft2 and kg mol/s.m2. The

diffusivity of water vapor at 293 K and 1 am pressure is

0.250 x 10-4 m2/s. Assume that the system is

isothermal. Use SI and English units.

Example 5

A sphere of naphthalene having a radius of 2.0

mm is suspended in a large volume of still air at

318 K and 1.101325 x 105 Pa (1 atm). The

diffusivity of the naphthalene at 318 K is 6.92 x

10-6 m2/s.

Calculate the rate of evaporation of

naphthalene from the surface.

DIFFUSION COEFFICIENTS FOR GASES

Experimental determination of diffusion

coefficients

One method is to evaporate a pure liquid in a

narrow tube with a gas passing over the top

The fall in liquid level is measured with time and

diffusivity calculated

• Experimental diffusivity data

The values range from about

PREDICTION OF DIFFUSIVITY FOR GASES

First prediction using kinetic theory of gases

It is assumed that there are no attractive or

repulsive force between molecules

The derivation uses mean free path, which is the

average distance that a molecules has travelled

between collisions

and average velocity of molecules is

Example 6

Normal butanol (A) is diffusing through air (B)

at 1 atm abs. Using the Fuller et al. method,

estimate the diffusivity DAB for the following

temperatures with the experimental data:

(a) For 0 °C.

(b) For 25.9 °C.

(c) For 0 °C and 2.0 atm abs.

MOLECULAR DIFFUSION IN

LIQUIDS

Diffusion of solutes in liquids is very

important in many industrial processes

especially in such separation as

Liquid-liquid extraction(solvent extraction)

Gas Absorption

Distillation

MOLECULAR DIFFUSION IN LIQUIDS

The rate of molecular diffusion is in liquids is slightly

slower than in gases

Molecules in liquids are very close together compared to

a gas

Molecules of the diffusing solute A will collide with

molecules of liquid B more often

They diffuse more slowly than in gases

The diffusion coefficient in a gas will be of the order of

magnitude of about 100000 times greater than in gas

However the flux in a gas is not that much greater, being

only about 100 times faster

EQUATIONS FOR DIFFUSION IN

LIQUIDS

Equimolar counter diffusion

The equation is similar to that of gas at

steady state

Where

Equimolar counter diffusion

Example 7

Diffusion of A through non diffusing B

This is the most important case of diffusion in liquids

Example is a dilute solution of propionic acid (A) in a

water (B) solution contacted with toluene

Only the propionic acid (A) diffuses through the water

phase to the boundary and to the toluene

The toluene – water interface is a barrier to diffusion of B

and Nb = 0

If gas equation is rewritten in terms of concentrations we

obtain the equation for liquids at steady state

Diffusion of A through non

diffusing B

Example 8

Diffusion in Solids

Rates of diffusion of gases are generally slower than

rates in liquids and gases.

Mass transfer in solids is quite important in chemical

processes such as:

Diffusion and catalytic reaction in solids catalysts

Separation of fluids by membranes

Diffusion of gases through polymer films used in packaging

Treating of metals at high temperatures by gases

11/30/2018 PE 311 50

Diffusion in Solids

Transport in solids can be broadly classified into:

Diffusion that follow Fick’s Law ( structure of the solid is not

important)

Diffusion in porous solids (actual structure and void

channels are important)

11/30/2018 PE 311 51

STEADY MASS DIFFUSION THROUGH A WALL

Many practical mass transfer problems involve the diffusion of a species through a

plane-parallel medium that does not involve any homogeneous chemical reactions under

one-dimensional steady conditions.

diffusion resistance of

the wall

52

The rate of mass diffusion through a plane wall is

proportional to the average density, the wall area, and the

concentration difference across the wall, but is inversely

proportional to the wall thickness.

the wall in s/kmol

53

Steady one-dimensional mass transfer

through nonreacting cylindrical and

spherical layers

On a molar basis

54

Noting that 1 kmol of an ideal gas at the

standard conditions of 0°C and 1 atm

occupies a volume of 22.414 m3, the

volume flow rate of the gas through the

wall by diffusion can be determined

from

55

Example 9

11/30/2018 PE 311 56

H/W 2

Discuss the analogy between heat, mass and

momentum transfer

11/30/2018 PE 311 57

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