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Mass Transfer

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3.2 Properties of mixtures

3.2.1 Concentration of species

3.2.2 Mass Averaged velocity

3.3 Diffusion flux

3.3.1 Picks Law

3.3.2 Relation among molar fluxes

3.4 Diffusivity

3.4.1 Diffusivity in gases

3.4.2 Diffusivity in liquids

3.4.3 Diffusivity in solids

3.5.1 Diffusion through a stagnant gas film

3.5.2 Pseudo steady state diffusion through a stagnant gas film.

3.5.3 Equimolar counter diffusion.

3.5.4 Diffusion into an infinite stagnant medium.

3.5.5 Diffusion in liquids

3.5.6 Mass diffusion with homogeneous chemical reaction.

3.5.7 Diffusion in solids

from point to point, there is a natural tendency for mass to be transferred,

minimizing the concentration differences within a system. The transport of one

constituent from a region of higher concentration to that of a lower

concentration is called mass transfer.

process that plays a major role in many industrial processes. Examples of such

processes are:

(ii) Removal of pollutants from plant discharge streams by absorption

(iii) Stripping of gases from waste water

(iv) Neutron diffusion within nuclear reactors

1

(v) Air conditioning

Many of air day-by-day experiences also involve mass transfer, for example:

then eventually diffuses to make the concentration uniform.

(ii) Water evaporates from ponds to increase the humidity of

passing-air-stream

(iii) Perfumes presents a pleasant fragrance which is imparted throughout

the surrounding atmosphere.

convection.

Mass transfer always involves mixtures. Consequently, we must account for the

variation of physical properties which normally exist in a given system. When a

system contains three or more components, as many industrial fluid streams

do, the problem becomes unwidely very quickly. The conventional engineering

approach to problems of multicomponent system is to attempt to reduce them

to representative binary (i.e., two component) systems.

and relations which are often used to explain the role of components within a

mixture.

ways. For species A, mass concentration denoted by (A is defined as the mass of

A,mA per unit volume of the mixture.

m

r A = A

------------------------------------ (1)

V

The total mass concentration density ( is the sum of the total mass of the

mixture in unit volume:

2

r = r i

i

unit volume of the mixture.

By definition,

mass of A

Number of moles =

molecular weight of A

m

n A = A

----------------------------- (2)

M A

n r

C A = A

= A

V M A

pA V

n A = [ from Ideal gas law PV = nRT]

R T

n pA

C A = A

=

V R T

where pA is the partial pressure of species A in the mixture. V is the volume of

gas, T is the absolute temperature, and R is the universal gas constant.

C = C i

i

3.2.2 Velocities

3

In a multicomponent system the various species will normally move at different

velocities; and evaluation of velocity of mixture requires the averaging of the

velocities of each species present.

mass-average velocity for a multicomponent mixture defined in terms of mass

concentration is,

r in i r in i

n = i

= i

r i r

i

C i V i

n * = i

C

For most engineering problems, there will be title difference in ( * and ( and so

the mass average velocity, (, will be used in all further discussions.

average velocity is termed as diffusion velocity

The mole fraction for liquid and solid mixture, x A ,and for gaseous mixtures, y A,

are the molar concentration of species A divided by the molar density of the

mixtures.

C

x A = A

(liquids and solids)

C

C

y A = A

(gases).

C

4

(i.e.) x i = 1

i

y i = 1

i

r A

w A =

r

10. The molar composition of a gas mixture at 273 K and 1.5 * 10 5 Pa is:

O2 7%

CO 10%

CO 2 15%

N2 68%

Determine

b) average molecular weight of the gas mixture

c) density of gas mixture

d) partial pressure of O 2.

Calculations:

Let the gas mixture constitutes 1 mole. Then

O2 = 0.07 mol

CO = 0.10 mol

CO 2 = 0.15 mol

N2 = 0.68 mol

O2 = 2 * 16 = 32 g/mol

CO = 12 + 16 = 28 g/mol

CO 2 = 12 + 2 * 16 = 44 g/mol

N2 = 2 * 14 = 28 g/mol

5

O2 = 0.07 * 32 = 2.24 g

CO = 0.10 * 28 = 2.80 g

CO 2 = 0.15 * 44 = 6.60 g

N2 = 0.68 * 28 = 19.04 g

= 30.68 g

2 . 24

O 2 = * 100 = 7 . 30 %

30 . 68

2 . 80

CO = * 100 = 9 . 13 %

30 . 68

6 . 60

CO 2 = * 100 = 21 . 51 %

30 . 68

19 . 04

N 2 = * 100 = 62 . 06 %

30 . 68

Average molecular weight of the gas mixture M =

Number of moles

30 . 68

M = = 30 . 68 g mol

1

PV = nRT

n P

=

V RT

n

= molar density = rm

V

Therefore, density (or mass density) = ( mM

Where M is the molecular weight of the gas.

5

PM 1 . 5 * 10 * 30 . 68

Density = rm M = = kg m

3

RT 8314 * 273

6

= 2.03 kg/m 3

=

7

(

* 1 . 5 * 10

5

)

100

= 0.07 * 1.5 * 10 5

= 0.105 * 10 5 Pa

Just as momentum and energy (heat) transfer have two mechanisms for

transport-molecular and convective, so does mass transfer. However, there are

convective fluxes in mass transfer, even on a molecular level. The reason for

this is that in mass transfer, whenever there is a driving force, there is always a

net movement of the mass of a particular species which results in a bulk motion

of molecules. Of course, there can also be convective mass transport due to

macroscopic fluid motion. In this chapter the focus is on molecular mass

transfer.

The mass (or molar) flux of a given species is a vector quantity denoting the

amount of the particular species, in either mass or molar units, that passes per

given increment of time through a unit area normal to the vector. The flux of

species defined with reference to fixed spatial coordinates, NA is

N A =C A n A ---------------------- (1)

velocity of mixture, (, as

N A = C A (n A -n ) + C A n --------------- (2)

By definition

C i n i

n =n * = i

C

7

C

= (n A -n ) + C i n

A

N A C A i

C i

= C A (n A -n ) + y A C i n i

i

N A = C A (n A - n) + y A (C A n A +C B n B )

= C A (n A - n) + y A (N A +N B )

N A = C A (n A - n) + y A N ----------- (3)

The first term on the right hand side of this equation is diffusional molar flux of

A, and the second term is flux due to bulk motion.

An empirical relation for the diffusional molar flux, first postulated by Fick and,

accordingly, often referred to as Ficks first law, defines the diffusion of

component A in an isothermal, isobaric system. For diffusion in only the Z

direction, the Ficks rate equation is

d C

JA = -D A B

A

d Z

through component B, and dCA / dZ is the concentration gradient in the

Z-direction.

system could be written as

d y

JA = -C D A B

A

----------------- (4)

d Z

8

d y

N A = -C D A B

A

+ y A N --------------- (5)

d Z

N A = J A +y A N

or J A = N A +y A N ----------------------- (6)

Similarly,

J B = N B +y B N -------------------- (7)

By definition N = N A + N B and y A + y B = 1.

Therefore equation (8) becomes,

J A + J B = 0

J A = -J B

d y d y

C D AB

A

= -C D BA

B

--------------- (9)

d z d Z

From y A + y B = 1

dy A = - dy B

D AB = D BA ----------------------------------- (10)

A.

3.4 Diffusivity

9

Ficks law proportionality, D AB, is known as mass diffusivity (simply as

diffusivity) or as the diffusion coefficient. D AB has the dimension of L 2 / t,

identical to the fundamental dimensions of the other transport properties:

Kinematic viscosity, (( = (( / () in momentum transfer, and thermal diffusivity, ( (=

k / ( C ( ) in heat transfer.

In table, some values of DAB are given for a few gas, liquid, and solid systems.

incease with the temperature and vary inversely with pressure. Liquid and solid

diffusivities are strongly concentration dependent and increase with

temperature.

Liquids : 10 6 ------------- 10-9 m2 / sec.

Solids : 5 X 10 14 ------------- 1 X 10-10 m2 / sec.

developed which give approximation, sometimes as valid as experimental

values, due to the difficulties encountered in experimental measurements.

1

D AB (for moderate ranges of pressures, upto 25 atm).

p

And temperature dependency is according to

3

D AB T 2

the diffusivities for the various binary pairs involved in the mixture. The relation

given by Wilke is

10

1

D 1 - mixture =

y 2 y 3 y n

+ + .......... . +

D 1-2 D 1 -3 D 1-n

Where D 1-mixture is the diffusivity for component 1 in the gas mixture; D 1-n is the

diffusivity for the binary pair, component 1 diffusing through component n; and

y n is the mole fraction of component n in the gas mixture evaluated on a

component 1 free basis, that is

y2

y 2 =

y2 + y3 + ....... yn

9. Determine the diffusivity of Co 2 (1), O 2 (2) and N 2 (3) in a gas mixture having

the composition:

The gas mixture is at 273 k and 1.2 * 10 5 Pa. The binary diffusivity values are

given as: (at 273 K)

D 12 P = 1.874 m 2 Pa/sec

D 13 P = 1.945 m 2Pa/sec

D 23 P = 1.834 m 2 Pa/sec

Calculations:

Diffusivity of Co 2 in mixture

1

D =

1m

y

y

2 3

+

D 12 D 13

y 2 0 . 15

where y 2 = = = 0 . 21

y 2 + y 3 0 . 15 + 0 . 565

y 3 0 . 565

y 3 = = = 0 . 79

y 2 + y 3 0 . 15 + 0 . 565

1

Therefore D 1m P =

0 . 21 0 . 79

+

1 . 874 1 . 945

11

= 1.93 m 2.Pa/sec

1 . 93 -5

D 1m = 5

= 1 . 61 * 10 m

2

sec

1 . 2 * 10

1

D =

2m

y

y

1 3

+

D 21 D 23

y 1 0 . 285

Where y 1 = = = 0 . 335

y 1 + y 3 0 . 285 + 0 . 565

(mole fraction on-2 free bans).

and

y 3 0 . 565

y 3 = = = 0 . 665

y 1 + y 3 0 . 285 + 0 . 565

and

D 21 P = D 12 P = 1.874 m2.Pa/sec

Therefore

1

D 2m P =

0 . 335 0 . 665

+

1 . 874 1 . 834

2

= 1.847 m .Pa/sec

1 . 847 -5

D 2m = 5

= 1 . 539 * 10 m

2

sec

1 . 2 * 10

found to be, D 3m = 1.588 * 10 5 m 2/sec.

12

Diffusivity in liquid are exemplified by the values given in table Most of these

values are nearer to 10-5 cm2 / sec, and about ten thousand times shower than

those in dilute gases. This characteristic of liquid diffusion often limits the

overall rate of processes accruing in liquids (such as reaction between two

components in liquids).

industry, diffusion is responsible for the rates of liquid-liquid extraction.

Diffusion in liquids is important because it is slow.

electrolytes ionize in solutions and diffuse as ions. For example, sodium

chloride (NaCl), diffuses in water as ions Na + and Cl-. Though each ions has a

different mobility, the electrical neutrality of the solution indicates the ions must

diffuse at the same rate; accordingly it is possible to speak of a diffusion

coefficient for molecular electrolytes such as NaCl. However, if several ions are

present, the diffusion rates of the individual cations and anions must be

considered, and molecular diffusion coefficients have no meaning.

Diffusivity varies inversely with viscosity when the ratio of solute to solvent ratio

exceeds five. In extremely high viscosity materials, diffusion becomes

independent of viscosity.

Typical values for diffusivity in solids are shown in table. One outstanding

characteristic of these values is their small size, usually thousands of time less

than those in a liquid, which are inturn 10,000 times less than those in a gas.

engineer. For metallurgists, diffusion of atoms within the solids is of more

importance.

which the concentration and molar flux are functions of a single space

coordinate will be considered.

given by Eqn (5) is [section 3.3.1]

13

d y

N A = -C D AB

A

+ y A (N A + N B ) --- (1)

d z

using Arnold diffusion cell. This cell is illustrated schematically in figure.

figure

The narrow tube of uniform cross section which is partially filled with pure liquid

A, is maintained at a constant temperature and pressure. Gas B which flows

across the open end of the tub, has a negligible solubility in liquid A, and is also

chemically inert to A. (i.e. no reaction between A & B).

Component A vaporizes and diffuses into the gas phase; the rate of vaporization

may be physically measured and may also be mathematically expressed

interms of the molar flux.

Consider the control volume S ( z, where S is the cross sectional area of the

tube. Mass balance on A over this control volume for a steady-state operation

yields

z + Dz z

Dividing through by the volume, S(Z, and evaluating in the limit as (Z approaches

zero, we obtain the differential equation

d N A

= 0 ------------------------- (2)

d z

This relation stipulates a constant molar flux of A throughout the gas phase

from Z1 to Z2.

d N B

= 0,

d Z

14

and accordingly, the molar flux of B is also constant over the entire diffusion

path from z1 and z 2.

Considering only at plane z1, and since the gas B is insoluble is liquid A, we

realize that NB, the net flux of B, is zero throughout the diffusion path;

accordingly B is a stagnant gas.

d y

N A = -C D AB

A

+ y A (N A +N B )

d z

Since N B = 0,

d y

N A = -C D AB

A

+ y A N A

d z

Rearranging,

-C D AB d y

N A = A

------------ (3)

1-y A d z

at z = z1 YA = YA1

And at z = z2 YA = yA2

that NA is constant along the diffusion path, by integrating equation (3) we

obtain

Z2 y A2

-d y

N A d z = C D AB

A

Z1 y A1

1-y A

C D AB 1 - y A 2

N A = ln --------------(4)

Z 2 - Z 1 1 - y A1

15

The log mean average concentration of component B is defined as

y B2 - y B1

y B , lm =

y

ln B2

y B1

Since y B =1 - y A ,

(1 - y A 2 ) - (1 - y A 1 ) y A1 - y A2

y B , lm = = ------- (5)

y y

ln A2

ln A2

y A1 y A1

C D ( y A1 -y A2)

N A = AB

-------------------- (6)

Z 2 - z 1 y B , lm

n p

For an ideal gas C = = , and

V R T

p

for mixture of ideal gases y A = A

P

D ( p A1 -p A2)

N A = AB

RT ( z 2 - z1 ) p B , lm

This is the equation of molar flux for steady state diffusion of one gas through a

second stagnant gas.

through another non-diffusing component; absorption and humidification are

typical operations defined by these equation.

The concentration profile (yA vs. z) for this type of diffusion is shown in figure:

16

Figure

12. Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25(C.

Concentration of oxygen at planes 2 mm apart are 10 and 20 volume %

respectively. Nitrogen is non-diffusing.

(a) Derive the appropriate expression to calculate the flux oxygen. Define

units of each term clearly.

(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10

5

m 2/sec.

Solution:

two components, namely that resulting from the bulk motion of A (i.e.), Nx A and

that resulting from molecular diffusion J A:

N A = Nx A + J A ---------------------------------- (1)

d C A

J A = -D AB ----------------------------------------- (2)

d z

d C A

N A = Nx A -D AB ----------------------------- (3)

d z

C d C

N A = (N A + N B )

A

-D AB

A

C d z

Rearranging the terms and integrating between the planes between 1 and 2,

d z C A2 dC A

cD = - C -------------- (4)

AB

A1 N AC -C A (N A + N B )

17

Since B is non diffusing N B = 0. Also, the total concentration C remains

constant. Therefore, equation (4) becomes

z C A2 dC A

= - C

CD AB

A1 N AC -N AC A

1 C -C A2

= ln

N A C -C A1

Therefore,

CD AB C -C A2

N A = ln ---------------------------- (5)

z C -C A1

Replacing concentration in terms of pressures using Ideal gas law, equation (5)

becomes

D AB P t P t -P A2

N A = ln --------------------------- (6)

RTz P t -P A1

where

D AB = molecular diffusivity of A in B

P T = total pressure of system

R = universal gas constant

T = temperature of system in absolute scale

z = distance between two planes across the direction of diffusion

P A1 = partial pressure of A at plane 1, and

P A2 = partial pressure of A at plane 2

Given:

D AB = 1.89 * 10 5 m2/sec

P t = 1 atm = 1.01325 * 10 5 N/m 2

T = 25(C = 273 + 25 = 298 K

z = 2 mm = 0.002 m

P A1 = 0.2 * 1 = 0.2 atm (From Ideal gas law and additive pressure rule)

P A2 = 0.1 * 1 = 0.1 atm

18

N =

(1 . 89 * 10

-5

)(1 . 01325 * 10

5

) ln 1 - 0 .1

A

(8314 )(298 )(0 . 002 ) 1 - 0 .2

= 4.55 * 10 5 kmol/m 2.sec

In many mass transfer operations, one of the boundaries may move with time. If

the length of the diffusion path changes a small amount over a long period of

time, a pseudo steady state diffusion model may be used. When this condition

exists, the equation of steady state diffusion through stagnant gas can be used

to find the flux.

figure

If the difference in the level of liquid A over the time interval considered is only a

small fraction of the total diffusion path, and t0 t is relatively long period of

time, at any given instant in that period, the molar flux in the gas phase may be

evaluated by

C D AB ( y A1 - y A2)

N A = ------------------ (1)

zy B , lm

r A,L d z

N A = -------------------------- (2)

M A d t

r A,L

where is the molar density of A in the liquid phase

M A

under Psuedo steady state conditions, equations (1) & (2) can be equated to

give

19

r A,L d z C D AB ( y A1 -y A2)

= --------------- (3)

M A d t z y B , lm

t rA,L y B , lm M A

Zt

dt = z dz

t =0

C D AB ( y A 1 -y A2) Z t0

yielding

rA,L y B , lm M z 2

- z

2

t =

A

t t0 -------- (4)

C D ( y A1 -y A2)

2

AB

rA,L y B , lm z 2

- z

2

D = t t0

AB

M C (y -y A2) t 2

A A1

of 20mm from the top openend. After 275 hrs at 39.4 (C and a total pressure of

760 mm Hg the level has dropped to 80 mm from the top. Calculate the value of

diffusivity.

Data:

vapor pressure of toluene at 39.4(C = 7.64 kN / m2,

density of liquid toluene = 850 kg/m3

Molecular weight of toluene = 92

(C 6 H6 CH3)

r A, L y Z 2

-Z 2

D =

Blm

t t0 figure

C (y )t

AB

M A A1 - y A2 2

y B2 - y B1

where y B, l m =

y

ln B2

y

B1

y B2 = 1 y A2 y B1 = 1 y A1

20

p A1 7 . 64

y A1 = = (760 mm Hg = 101.3 kN/m2)

P 101 . 3

= 0.0754 y B1 = 1 0.0754 = 0.9246

y A2 = 0 y B = 1 y A2 = 1

1 - 0 . 9246

Therefore y B , lm = = 0 . 9618

1

ln

0 . 9246

5

P 1 . 01325 * 10

C = =

R T 8314 (

* 273 + 39 . 4 )

3

= 0.039 k mol /m

Therefore

850 * 0 . 9618 0 . 08 2

- 0 . 02 2

D =

AB

92 * 0 . 039 * 0 . 0754 ( - 0 )* 275 * 3600

2

= 1.5262 * 10 3 (0.08 2 0.02 2)

= 9.1572 * 10-6 m2/sec.

whose molar latent heats of vaporization are essentially equal, stipulates that

the flux of one gaseous component is equal to but acting in the opposite

direction from the other gaseous component; that is, NA = - NB.

The molar flux NA, for a binary system at constant temperature and pressure is

described by

d y

N A =-C D AB

A

+ y A (N A +N B )

d z

d C

or N A =-D AB

A

+ y A (N A +N B ) ------- (1)

d z

21

d C

N A =-D AB

A

----------------- (2)

d z

For steady state diffusion Equation. (2) may be integrated, using the boundary

conditions:

at z = z1 CA = CA1

and z = z2 CA = CA2

Giving,

Z2 C A2

N A d z = -D AB d C A

Z1 C A1

from which

D

N A = AB

(C A 1 - C A2) ------------------- (3)

z 2 -z 1

n pA

For ideal gases, C A = A

= . Therefore Equation. (3) becomes

V R T

D

N A = AB

(P A1 - P A2) ---------- (4)

R T (z 2 -z 1)

This is the equation of molar flux for steady-state equimolar counter diffusion.

from,

d

(N A ) = 0 (Since NA is constant over the diffusion path).

d z

d C

N A = -D AB

A

.

d z

22

Therefore

d d C

- D AB

A

= 0 .

d z d z

2

d C

or

2

A

= 0.

d z

C -C A1 z-z 1

A

= -------------- (5)

C

A1

-C A2 z 1 -z 2

diffusion.

the partial pressure of methane is p A1 = 55 kPa and at point 2, 0.03 m apart P A2 =

15 KPa. The total pressure is 101.32 kPa, and the temperature is 298 K. At this

pressure and temperature, the value of diffusivity is 6.75 * 10 5m 2/sec.

diffusion.

ii) Calculate the partial pressure at a point 0.02 m apart from point 1.

Calculation:

D

N A =

AB

(p A1 -p A 2 ) --------------------------- (1)

R T z

Therefore;

-5

N A =

6 . 75 * 10

(55 - 15 ) kmol

2

8 . 314 * 298 * 0 . 03 m . sec

-5 kmol

= 3 . 633 * 10

2

m sec

23

And from (1), partial pressure at 0.02 m from point 1 is:

-5

6 . 75 * 10

3 . 633 * 10

-5

= (55 - p A )

8 . 314 * 298 * 0 . 02

p A = 28.33 kPa

11. In a gas mixture of hydrogen and oxygen, steady state equimolar counter

diffusion is occurring at a total pressure of 100 kPa and temperature of 20(C. If

the partial pressures of oxygen at two planes 0.01 m apart, and perpendicular to

the direction of diffusion are 15 kPa and 5 kPa, respectively and the mass

diffusion flux of oxygen in the mixture is 1.6 * 10 5 kmol/m 2.sec, calculate the

molecular diffusivity for the system.

Solution:

D

N A =

AB

(p A1 -p A2 ) ------------------------ (1)

RTz

where

D AB = molecular diffusivity of A in B

R = Universal gas constant (8.314 kJ/kmol.k)

T = Temperature in absolute scale (273 + 20 = 293 K)

z = distance between two measurement planes 1 and 2 (0.01 m)

P A1 = partial pressure of A at plane 1 (15 kPa); and

P A2 = partial pressure of A at plane 2 (5 kPa)

D

1 . 6 * 10

-5

=

AB

(15 -5)

(8 . 314 )(293 )(0 . 01 )

Therefore, D AB = 3.898 * 10 5 m 2/sec

total pressure of 2 atm at 0(C. The diffusion coefficient of the Co2 H2 system

24

under these conditions is 0.275 cm2/sec. If the partial pressure of Co2 is 1.5 atm

at one end of the tube and 0.5 atm at the other end, find the rate of diffusion for:

ii) steady state counter diffusion where N B = -0.75 N A, and

iii) steady state diffusion of Co2 through stagnant H2 (NB = 0)

d y

i) N A = -C D AB

A

+ y A (N A + N B )

d z

Given

NB = - NA

d y A d C A

Therefore N A = -C D AB = -D AB

d z d z

pA

(For ideal gas mixture C A = where pA is the partial pressure of A; such

R T

that p A + p B = P)

Therefore N = -D

(

d p A RT )

A A B

d z

For isothermal system, T is constant

-D AB d p A

Therefore N A =

RT d z

Z P A2

2

D AB

(i.e.) N A d z = - d p A

Z

RT P A1

1

D

N A =

AB

(p A1 - p A2 ) ---------------------------------- (1)

RT z

where Z = Z 2 Z 1

25

-4

N A =

0 . 275 * 10

(1 . 5 * 1 . 01325 * 10

5

- 0 .5 * 1 . 01325 * 10

5

)

8314 * 273 * 0 . 2

-6 k mol

= 6 . 138 * 10

2

m sec

Rate of diffusion = N A S

= 6.138 * 10 6 * ( (0.5 * 10 2) 2

= 4.821 * 10 10 k mol/sec

= 1.735 * 10 3 mol/hr.

d y

ii) N A = -C D AB

A

+y A (N A + N B )

d z

given: N B = - 0.75 N A

d y

Therefore N A = -C D AB

A

+ y A (N A - 0 . 75 N A )

d z

d y A

= -C D A B + 0 . 25 y A N A

d z

d y A

N A - 0 . 25 y A N A = - C D AB

d z

d y A

N A d z = -C D AB

1 - 0 . 25 y A

for constant N A and C

Z y A2

2

d y A

N A d z = - CD AB

Z y A1

1 - 0 . 25 y A

1

d x

=

1

(

ln a +b x )

a +b x b

26

-1

N A z = (- C D AB ) [ln (1 - 0 . 25 y A )]y A 2

y

0 . 25 A1

4 CD AB 1 - 0 . 25 y A 2

N = - ln ---------------------------------- (2)

A

z 1 - 0 . 25 y A 1

Given:

5

p 2 * 1 . 01325 * 10

C = = = 0 . 0893 K mol m

3

R T 8314 * 273

p A1 1 .5

y A1 = = = 0 . 75

P 2

p A 2 0 .5

y A 2 = = = 0 . 25

P 2

Substituting these in equation (2),

-4

4 * 0 . 0893 * 0 . 275 * 10 1 - 0 . 25 * 0 . 25

N A = ln

0 .2 1 - 0 . 25 * 0 . 75

-6 kmol

= 7 . 028 * 10

2

m sec

Rate of diffusion = N A S = 7.028 * 10 6 * ( * (0.5 * 10 2) 2

= 5.52 * 10 10 kmol/sec

= 1.987 * 10 3 mol/hr.

d y

iii) N A = - CD AB

A

+ y A (N A +N B )

d z

Given: N B = 0

d y A

Therefore N A = - CD AB + y A N A

d z

Z y A2

2

d y A

N A d z = - CD AB

Z y A1

1 - y A

1

CD 1 - y

=

AB

ln A2

Z 1 - y

A1

27

-4

0 . 0893 * 0 . 275 * 10 1 - 0 . 25

= ln 1 - 0 . 75

0 .2

-5 kmol

= 1 . 349 * 10

2

m . sec

= 3.814 mol/hr

Here we will discuss problems involving diffusion from a spherical

particle into an infinite body of stagnant gas. The purpose in doing this is to

demonstrate how to set up differential equations that describe the diffusion in

these processes. The solutions, obtained are only of academic interest because

a large body of gas in which there are no convection currents is unlikely to be

found in practice. However, the solutions developed here for these problems

actually represent a special case of the more common situation involving both

molecular diffusion and convective mass transfer.

As an example of such problems, we shall consider the evaporation of

spherical droplet such as a raindrop or sublimation of naphthalene ball. The

vapor formed at the surface of the droplet is assumed to diffuse by molecular

motions into the large body of stagnant gas that surrounds the droplet.

Consider a raindrop, as shown in figure. At any moment, when the radius

Figure

Evaporation of a raindrop

of the drop is r 0, the flux of water vapor at any distance r from the center is given

by

d y

N A = -C D AB

A

+y A (N A +N B )

d r

Here N B = 0 (since air is assumed to be stagnant)

Therefore,

d y A

N A = -C D AB +y A N A

d r

Rearranging,

28

-C D AB d y A

N A = __________ (1)

1-yA d r

The flux N A is not constant, because of the spherical geometry;

decreases as the distance from the center of sphere increases. But the molar

flow rate at r and r + (r are the same.

This could be written as,

A N A = A N A __________ (2)

r r +d r

Substituting for A = 4 ( r 2 in equation (2),

4 p r

2

N A - 4 p r

2

N A = 0

r +d r r

or

r

2

N A - r

2

N A

r +d r r

lim = 0

d r 0 d r

ss

d

(r 2

N A )= 0 __________ (3)

dr

Integrating,

r

2

N A = constant __________ (4)

2

From equation (4), r

2

N A = r 0 N A 0

-r 2

C D AB d y 2

A

= r N A

1-y A

0 0

d r

2 d r d y A

r 0

N A 0 2

= -C D AB 1-y __________ (5)

r A

Boundary condition :

At r = r 0 y A = y AS

And

At r = (y A = y A(

Therefore equation (5) becomes,

1

r 0

2

N A - = [C D AB (

ln 1 - y A )] yy A

0

r r0 AS

Simplifying,

29

C D 1-y A

N =

AB

ln __________ (6)

A 0

r 1 - y A S

0

Time required for complete evaporation of the droplet may be evaluated from

making mass balance.

=

unit time unit time

d 4 rL

4 p r

2

N = - pr 3

0 A 0

dt 3 0

M A

r L d r0

= -4p r0

2

__________ (7)

M A d t

Substituting for N A0 from equation (6) in equation (7),

C D 1 - y A -r L d r

AB

ln = 0

__________ (8)

r 1 - y AS M A d t

0

Initial condition :

When t = 0 r 0 = r 1

Integrating equation (8) with these initial condition,

t - r 1 1

0

=

L

d t r0 d r 0

M C D 1 - y A

0 A AB

ln r 1

1 - y

A S

r 1 r1

2

=

L

t __________ (9)

M 2 C D AB 1 - y A

A

ln

1 - y

A S

Equation (9) gives the total time t required for complete evaporation of spherical

droplet of initial radius r 1.

The problem of combustion of spherical coal particle is similar to

evaporation of a drop with the exception that chemical reaction (combustions)

occurs at the surface of the particle. During combustion of coal, the reaction

C + O2 ( CO 2

cccurs. According to this reaction for every mole of oxygen that diffuses to the

surface of coal (maximum of carbon), react with 1 mole of carbon, releases 1

mole of carbon dioxide, which must diffuse away from this surface. This is a

30

case of equimolar counter diffusion of CO 2 and O 2. Normally air (a mixture of N 2

and O 2) is used for combustion, and in this case N 2 does not takes part in the

reaction, and its flux is zero. i.e. N N = 0 . ( 2

)

The molar flux of O 2 could be written as

d y

N O 2

= -C D O 2 - gas

O 2

+ y O 2

(N O 2

+N CO 2

+ N N 2

)

d r

__________ (1)

Where D O - gas is the diffusivity of O 2 in the gas mixture.

2

Since N N 2

= 0 , and from stoichiometry N O

2

= -N CO 2

, equation

(1) becomes

d y O

= -C

2

N O D O - gas __________ (2)

2 2

d r

For steady state conditions,

d

(r 2

N O 2

)= 0 __________ (3)

d r

Integrating,

2

r

2

N O 2

= constant = r 0

N O 2 s __________ (4)

Where r 0 is the radius of coal particle at any instant, and N O s is the flux of O 2

2

Substituting for N O from equation (2) in equation (4),

2

d y O 2

-r 2

=

2

C D O - gas r 0

N O s __________ (5)

2 2

d r

Boundary condition :

At r = r 0 y O = y O s

2 2

And

At r = y O = y O

2 2

y O

d r 2

2

r 0

N A 0 2

= -C D O 2 - gas d y O 2

r r y O

0 2 s

which yields

31

C D

N O 2 s =

O 2 - gas

(y O 2 s -y O 2 ) __________ (6)

r 0

For fast reaction of O 2 with coal, the mole fraction of O 2 at the surface of particle

iz zero. (i.e.,) y O s = 0 .

2

And also at some distance away from the surface of the particle

y O 2

= y O = 0 . 21 (because air is a mixture of 21 mole % O 2 and 79 mole

2

% N 2)

0 . 21 C D O - gas

=

2

N O s ____________ (7)

2

r 0

Figure

Combustion of a particle of coal

5. A sphere of naphthalene having a radius of 2mm is suspended in a large

volume of shell air at 318 K and 1 atm. The surface pressure of the naphthalene

can be assumed to be at 318 K is 0.555 mm Hg. The D AB of naphthalene in air at

318 K is 6.92 * 10 6 m 2/sec. Calculate the rate of evaporation of naphthalene

from the surface.

Calculation

S N A - S N A = 0 ---------------------------- (1)

r r +d r

dividing (1) by S(r, and taking the limit as (r approaches zero, gives:

d r ( 2

N A )

= 0

d r

Integrating r 2 N A = constant (or) 4 ( r 2 N A = constant

We can assume that there is a film of naphthalene vapor / air film around

naphthalene through which molecular diffusion occurs.

32

d y

N A = - CD AB

A

+ y A (N A +N B )

d r

N B = 0 (since air is assumed to be stagnant in the film)

d y A

N A = - CD AB + y A N A

d r

d y A

N = - CD

d r 1 - y A

A AB

d [ln (1 - y A ) ]

N A = CD AB

d r

p d (ln (1 - ))

2

4 r CD AB y A

W A =

d r

d r

W A = 4 p D AB C d ln (1 - y A )

2

r

Boundary condition:

0 . 555 -4

At r = R y A = = 7 . 303 * 10

760

ln (1 y A) = - 7.3 * 104

At r = ( y A = 0 ln (1-y A) = 0

d r 0

Therefore W A 2

= 4 p D AB C d ln (1 [ - y A )]

R r - 7 .3 * 10

-4

- 1

W A r = 4 p D AB C ln (1[ - y A ) ]0- 7 . 3 * 10 -4

R

1

W A 0 + R = 4 p D AB C [0 + 7 . 3 * 10 -4

]

W A = 4 ( R D AB C * 7.3 * 10 4

33

5

P 1 . 01325 * 10

C = =

Gas cons tan t * T 8314 * 318

= 0.0383 kmol/m 3

= 4.863 * 1012kmol/sec

= 1.751 * 10 5 mol/hr.

Equation derived for diffusion in gases equally applies to diffusion in

liquids with some modifications. Mole fraction in liquid phases is normally

written as x (in gases as y). The concentration term C is replaced by average

r

molar density, .

M av

a) For steady state diffusion of A through non diffusivity B:

N A = constant , N B = 0

D r

N A =

AB

(x A 1 - x A2 )

z x BM M av

where Z = Z 2 Z 1, the length of diffusion path; and

X B 2 -X B 1

X BM =

X B 2

ln X

B 1

N A = - N B = const

D D r

N A =

AB

(C A1 -C A2 ) =

AB

(x A1 -x A 2 )

Z Z M av

4. Calculate the rate of diffusion of butanol at 20(C under unidirectional steady

state conditions through a 0.1 cm thick film of water when the concentrations of

butanol at the opposite sides of the film are, respectively 10% and 4% butanol by

weight. The diffusivity of butanol in water solution is 5.9 * 10 6 cm 2/sec. The

densities of 10% and 4% butanol solutions at 20(C may be taken as 0.971 and

0.992 g/cc respectively. Molecular weight of Butanol (C 4 H 9 OH) is 74, and that

of water 18.

Calculations

34

For steady state unidirectional diffusion,

D AB (x A1 - x A2 )

N A = C

z x B , lm

r

=

M avg

Conversion from weight fraction the Mole fraction:

x =

(0 . 1 74 ) = 0 . 026

A1

(0 . 1 74 + 0 . 9 18 )

x =

(0 . 04 74 ) = 0 . 010

A2

(0 . 04 74 + 0 . 96 18 )

Average molecular weight at 1 & 2:

1

M = = 19 . 47 kg Kmol

1

(0 . 1 74 + 0 . 9 18 )

1

M = = 18 . 56 kg Kmol

2

(0 . 04 74 + 0 . 96 18 )

r (r 1 M 1 + r2 M 2 )

=

M avg 2

0 . 971 19 . 47 + 0 . 992 18 . 56

=

2

= 0.0517 gmol / cm 3

= 51.7 kmol/m 3

x B2 - x B1 (1 - x A2 ) - (1 - x A1 )

x = =

B , lm

(

ln x B 2 x B 1 ) 1 - x

ln A2

1 - x

A1

(i.e.) x =

(1 - 0 . 01 ) - (1 - 0 . 026 )

B , lm

1 - 0 . 01

ln

1 - 0 . 026

35

0 . 016

= = 0 . 982

0 . 0163

D AB r (x A1 - x A2 )

Therefore N A =

2 M avg x B , lm

=

5 . 9 * 10

-6

* 10

-4

* 51 . 7

*

(0 . 026 - 0 . 010 )

-2 0 . 982

0 . 1 * 10

-7 kmol

= 4 . 97 * 10

2

m sec

gmol

= 1 . 789

2

m . hr .

g

= 1 . 789 * 74

2

m . hr .

g

= 132 . 4

2

m . hr .

Absorption operations involves contact of a gas mixture with a liquid and

preferential dissolution of a component in the contacting liquid. Depending on

the chemical nature of the involved molecules, the absorption may or may not

involve chemical reaction.

The following analysis illustrates the diffusion of a component from the

gas phase into the liquid phase accompanied by a chemical reaction in the

liquid phase. Consider a layer of absorbing medium (liquid) as shown in

diagram.

Figure

film, ( is so defined, that beyond this film the concentration of A is always zero ;

that is C A( = 0. If there is very little fluid motion within the film,

d C C

N A =-D AB

A

+

A

(N A +N B ) ____________ (1)

d z C

If concentration of A in the film, C A is assumed small, equation (1) becomes

d C A

N A =-D AB ____________ (2)

d z

The molar flux N A changes along the diffusion path. This change is due to

36

the reaction that takes place in the liquid film. This changes could be written as

d

(N A ) - r A = 0 ____________ (3)

d z

where rA is the rate of disappearance of A. For a first order reaction,

k

A B

-r A = k C A ____________ (4)

with the substitution from equation (4) and (2) in equation (3),

-d d C A

D + k C = 0

d z

AB A

d z

For constant Diffusivity,

2

d C A

-D AB 2

+ k C A = 0 ____________ (5)

d z

which is a second order ordinary differential equation. The general solution to

this equation is

C A =C 1 cos h k z + C 2 sin h k z _______ (6)

D D

AB AB

The constants of this equation can be evaluated from the boundary conditions:

at Z=0 C A = C A0

And at Z=( C A = 0.

The constant C 1 is equal to C A0 , and C 2 is equal to

-C

A0

k d with this substitution equation (6) becomes,

tan h D AB

C A 0 sin h k z

D AB

C A = C A 0 cos h k z -

D AB

tan h k z

D AB

_______ (7)

This equation gives the variation of concentration of A with z (i.e

concentration profile of A in the liquid). The molar flux at the liquid surface can

be determined by differentiating equation (7), and evaluating the derivative

d C A

at z = 0

d z

Differentiating C A with respect to z,

37

C A 0

k cos h k z

d C A D A B D AB

= C A 0

k sin h k z -

d z D A B D AB

tan h k d

D

AB

____________ (8)

Substituting z = 0 in equation (8) and from equation (2),

k d

D C D

N =

AB A 0 AB

____________ (9)

A

Z =0 d

tan h k d

D

AB

For absorption with no chemical reaction, the flux of A is obtained from

equation (2) as

D AB C A

=

0

N ____________ (10)

A d

which is constant throughout the film of liquid. On comparison of equation (9)

and (10), it is apparent that the term k d tan h k d

D D

AB

AB

shows the influence of the chemical reactions. This terms a dimensionless

quantity, is often called as Hatta Number.

In certain unit operation of chemical engineering such as in drying or in

absorption, mass transfer takes place between a solid and a fluid phase. If the

transferred species is distributed uniformly in the solid phase and forms a

homogeneous medium, the diffusion of the species in the solid phase is said to

be structure independent. In this cases diffusivity or diffusion coefficient is

direction independent.

At steady state, and for mass diffusion which is independent of the solid

matrix structure, the molar flux in the z direction is :

d C A

N A =-D AB = constant , as given by Ficks law.

d z

Integrating the above equation,

D AB (C A1 -C A2 )

N A =

z

which is similar to the expression obtained for diffusion in a stagnant fluid with

38

no bulk motion (i.e. N = 0).

In some chemical operations, such as heterogeneous catalysis, an

important factor, affecting the rate of reaction is the diffusions of the gaseous

component through a porous solid. The effective diffusivity in the solid is

reduced below what it could be in a free fluid, for two reasons. First, the tortuous

nature of the path increases the distance, which a molecule must travel to

advance a given distance in the solid. Second, the free cross sectional area is

restricted. For many catalyst pellets, the effective diffusivity of a gaseous

component is of the order of one tenth of its value in a free gas.

If the pressure is low enough and the pores are small enough, the gas

molecules will collide with the walls more frequently than with each other. This

is known as Knudsen flow or Knudsen diffusion. Upon hitting the wall, the

molecules are momentarily absorbed and then given off in random directions.

The gas flux is reduced by the wall collisions.

By use of the kinetic flux is the concentration gradient is independent of

pressure ; whereas the proportionality constant for molecular diffusion in gases

(i.e. Diffusivity) is inversely proportional to pressure.

Knudsen diffusion occurs when the size of the pore is of the order of the

mean free path of the diffusing molecule.

Transient processes, in which the concentration at a given point varies

with time, are referred to as unsteady state processes or time dependent

processes. This variation in concentration is associated with a variation in the

mass flux.

These generally fall into two categories:

i) the process which is in an unsteady state only during its initial

startup, and

ii) the process which is in a batch operation throughout its operation.

In unsteady state processes there are three variables-concentration, time,

and position. Therefore the diffusion process must be described by partial

rather than ordinary differential equations.

Although the differential equations for unsteady state diffusion are easy

to establish, most solutions to these equations have been limited to situations

involving simple geometries and boundary conditions, and a constant diffusion

coefficient.

Many solutions are for one-directional mass transfer as defined by Ficks

second law of diffusion :

39

C A 2 C A

= D AB __________ (1)

t z 2

no bulkmotion contribution, and there is no chemical reaction. This situation is

encountered when the diffusion takes place in solids, in stationary liquids, or in

system having equimolar counter diffusion. Due to the extremely slow rate of

diffusion within liquids, the bulk motion contribution of flux equation (i.e., y A ( N i)

approaches the value of zero for dilute solutions ; accordingly this system also

satisfies Ficks second law of diffusion.

The solution to Ficks second law usually has one of the two standard

forms. It may appear in the form of a trigonometric series which converges for

large values of time, or it may involve series of error functions or related

integrals which are most suitable for numerical evaluation at small values of

time. These solutions are commonly obtained by using the mathematical

techniques of separation of variables or Laplace transforms.

40

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