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Mass Transfer and Convective Mass Transfer
Mass Transfer and Convective Mass Transfer
2
Many of air day-by-day experiences also involve mass transfer, for example:
(i) A lump of sugar added to a cup of coffee eventually dissolves and 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.
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.
In order to understand the future discussions, let us first consider definitions and
relations which are often used to explain the role of components within a mixture.
mA
A ------------------------------------ (1)
V
The total mass concentration density is the sum of the total mass of the mixture
in unit volume:
i
i
By definition,
3
mass of A
Number of moles
molecularweight of A
m
n A A ----------------------------- (2)
M A
nA
C A A
V M A
pA V
n A [ from Ideal gas law PV = nRT]
RT
nA p
C A A
V RT
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
1.2.2 Velocities
i i i i
i i
i
i
4
By similar way, molar-average velocity of the mixture * is
C i V i
* 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.
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.
CA
x A (liquids and solids)
C
CA
y A (gases).
C
The sum of the mole fractions, by definition must equal 1;
(i.e.) x i 1
i
y i 1
i
A
wA
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%
5
Determine
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
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
6
Weight of gas mixture
Average molecular weight of the gas mixture M
Number of moles
30.68
M 30.68 g mol
1
Assuming that the gas obeys ideal gas law,
PV = nRT
n P
V RT
n
molar density m
V
Therefore, density (or mass density) = mM
Where M is the molecular weight of the gas.
PM 1.5 * 10 5 * 30.68
Density m M kg m 3
RT 8314 * 273
= 2.03 kg/m 3
7
100
* 1.5 * 10 5
= 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
7
N A C A A ---------------------- (1)
N A C A ( A ) C A --------------- (2)
By definition
C i i
* i
C
Therefore, equation (2) becomes
CA
N A C A ( A ) C i i
C i
C A ( A ) y A C i i
i
N A C A ( A ) y A (C A CA B B)
C A ( A ) y A (N A N B )
N A C A ( A ) 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 Fick’s first law, defines the diffusion of
component A in an isothermal, isobaric system. For diffusion in only the Z
direction, the Fick’s rate equation is
dC A
JA D AB
dZ
8
A more general flux relation which is not restricted to isothermal, isobasic system
could be written as
dy A
J A C DA B ----------------- (4)
dZ
dy A
N A C DA B y AN --------------- (5)
dZ
NA J A y AN
or J A N A y AN ----------------------- (6)
Similarly,
J B N B y B N -------------------- (7)
J A J B N A N B (y A y B) N ---------- (8)
By definition N = N A + N B and y A + y B = 1.
Therefore equation (8) becomes,
JA+JB=0
J A = -J B
dy A dyB
CD AB C D BA --------------- (9)
dz dZ
From yA+yB=1
dy A = - dy B
D AB = D BA ----------------------------------- (10)
9
This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in
A.
1.4 Diffusivity
In table, some values of DAB are given for a few gas, liquid, and solid systems.
1
D AB (for moderate ranges of pressures, upto 25 atm).
p
And temperature dependency is according to
3
D AB T 2
10
Diffusivity of a component in a mixture of components can be calculated using
the diffusivities for the various binary pairs involved in the mixture. The relation
given by Wilke is
1
D 1 mixture
y 2 y 3 y n
.......... .
D1 2 D1 3 D1 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 y 3 ....... y n
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 2 Pa/sec
D 23 P = 1.834 m 2 Pa/sec
Calculations:
Diffusivity of Co 2 in mixture
1
D 1m
y 2 y 3
D 12 D 13
y2 0.15
where y 2 0.21
y2 y3 0.15 0.565
y3
y 3
0.565
0.79
y2 y3 0.15 0.565
11
1
Therefore D 1m P
0.21 0.79
1.874 1.945
= 1.93 m 2.Pa/sec
1.93
D 1m 5
1.61 * 10 5 m 2 sec
1.2 * 10
Diffusivity of O 2 in the mixture,
1
D 2m
y 1 y 3
D 21 D 23
y1 0.285
Where y 1 0.335
y1 y3 0.285 0.565
(mole fraction on-2 free bans).
and
y3
y 3
0.565
0.665
y1 y3 0.285 0.565
and
D 21 P = D 12 P = 1.874 m 2.Pa/sec
Therefore
1
D 2m P
0.335 0.665
1.874 1.834
= 1.847 m 2.Pa/sec
1.847
D 2m 1.539 * 10 5 m 2 sec
1.2 * 10 5
By Similar calculations Diffusivity of N 2 in the mixture can be calculated, and is
found to be, D 3m = 1.588 * 10 –5 m 2/sec.
12
1.4.2 Diffusivity in liquids:
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).
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.
13
1.5.1 Diffusion through a stagnant gas film
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
This relation stipulates a constant molar flux of A throughout the gas phase from
Z1 to Z2.
dN B
0,
dZ
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.
14
dy A
NA CD AB y A (N A N B)
dz
Since N B = 0,
dy A
NA CD AB y AN A
dz
Rearranging,
CD AB dy A
NA ------------ (3)
1 y A dz
Z2 y A2
dy A
N A d z C DAB 1 y A
Z1 y A1
CD AB 1 y A2
NA ln --------------(4)
Z 2 Z 1 1 y A1
y B2 y B1
y B, lm
ln
y B2
y B1
Since y B 1 y A ,
15
(1 y A2 ) (1 y A1 ) y A1 y A2
y B, lm ------- (5)
ln ln
y y
y A1 y A1
A2 A2
C D AB ( y A1 y A2 )
N A -------------------- (6)
Z 2 z1 y B, lm
n p
For an ideal gas C , and
V RT
pA
for mixture of ideal gases y A
P
Therefore, for an ideal gas mixture equation. (6) becomes
N
D AB (p A1 p A2 )
A
RT ( z2 z1) p B, lm
This is the equation of molar flux for steady state diffusion of one gas through a
second stagnant gas.
(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:
16
N A Nx A J A ---------------------------------- (1)
dCA
J A D AB ----------------------------------------- (2)
dz
dCA
N A Nx A D AB ----------------------------- (3)
dz
NA NA NB CCA D AB ddCzA
Rearranging the terms and integrating between the planes between 1 and 2,
dz C A2 dC A
cD C
AB
A1
N AC C A N A N B -------------- (4)
z C dC A
C A2
CD AB A1 N C N C
A A A
1 C C A2
ln
NA C C A1
Therefore,
CD AB C C A2
NA ln ---------------------------- (5)
z C C A1
Replacing concentration in terms of pressures using Ideal gas law, equation (5)
becomes
17
D AB P t P t P A2
NA 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 = 25C = 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
NA
1.89 * 10 5 1.01325 * 10 5 1 0.1
ln
83142980.002 1 0.2
–5 2
= 4.55 * 10 kmol/m .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.
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
18
CD AB (y A1 y A2 )
N A ------------------ (1)
zy B, lm
A,L dz
N A -------------------------- (2)
M A dt
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
A,L dz CD AB ( y A1 y A2 )
--------------- (3)
M A dt zy B, lm
t A,L y B, lm M A
Zt
dt C D z dz
t 0 AB (y A1 y A2 ) Z t 0
yielding
A,L y B, lm M z 2
z 2
t A t t0 -------- (4)
C D AB ( y A1 y A2 ) 2
This shall be rearranged to evaluate diffusivity DAB as,
A,L y B, lm z 2
z 2
D t t0
M A C ( y A1 y A2 ) t
AB
2
1. A vertical glass tube 3 mm in diameter is filled with liquid toluene to a
depth 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.
19
Data:
vapor pressure of toluene at 39.4C = 7.64 kN / m2,
density of liquid toluene = 850 kg/m3
Molecular weight of toluene = 92
(C 6 H6 CH3)
A, L y Blm Z 2
Z 2
D AB t t0
MAC y A1 y A2 t 2
y B2 y B1
where y B, l m
y B2
ln
y B1
y B2 = 1 – y A2 y B1 = 1 – y A1
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
P 1.01325 * 10 5
C
RT 8314 * 273 39.4
= 0.039 k mol /m3
Therefore
20
The molar flux NA, for a binary system at constant temperature and pressure is
described by
dy A
N A CD AB y A (N A N B )
dz
dC A
or N A D AB y A (N A N B ) ------- (1)
dz
dC A
N A D AB ----------------- (2)
dz
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
NA d z D AB dC A
Z1 C A1
from which
D
N A AB (C A1 C A2 ) ------------------- (3)
z 2 z1
nA p
For ideal gases, C A A . Therefore Equation. (3) becomes
V RT
D AB
N A (P A1 P A2 ) ---------- (4)
R T ( z 2 z 1)
This is the equation of molar flux for steady-state equimolar counter diffusion.
21
d
(N A ) 0 (Since NA is constant over the diffusion path).
dz
d CA
N A D AB .
dz
Therefore
d d CA
D 0.
d z
AB
dz
2
d CA
or
2
0.
dz
C C A1 zz1
A
-------------- (5)
C A1
C A2 z1 z 2
Calculation:
NA
D AB
RT z
p A 1 p A 2 --------------------------- (1)
Therefore;
22
6.75 * 10 5
NA 55 15 kmol
8.314 * 298 * 0.03 m 2 . sec
kmol
3.633 * 10 5
m 2 sec
6.75 * 10 5
3.633 * 10 5
8.314 * 298 * 0.02
55 p A
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 20C. 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:
NA
D AB
RTz
p A1 p A2 ------------------------ (1)
where
D AB
1.6 * 10 5 15 5
8.3142930.01
Therefore, D AB = 3.898 * 10 –5 m 2/sec
23
2. A tube 1 cm in inside diameter that is 20 cm long is filled with Co 2 and H2 at a
total pressure of 2 atm at 0C. The diffusion coefficient of the Co2 – H2 system
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:
i) N A C D AB
dy
dz
A
y A N A N B
Given
NB = - NA
dy A dCA
Therefore N A C D AB D AB
dz dz
pA
(For ideal gas mixture C A where pA is the partial pressure of A; such
RT
that p A + p B = P)
d pA RT
Therefore N A D A B
dz
For isothermal system, T is constant
D AB d p A
Therefore N A
RT dz
Z2 P A2
D AB
(i.e.) N A d z d pA
Z1 RT P A1
NA
D AB
RT z
p A1 p A2 ---------------------------------- (1)
where Z = Z 2 – Z 1
24
NA
0.275 * 10 4
8314 * 273 * 0.2
1.5 * 1.01325 * 10 5 0.5 * 1.01325 * 10 5
k mol
6.138 * 10 6 2
m sec
Rate of diffusion = N A S
ii) N A C D AB
dy
dz
A
y A N A N B
given: N B = - 0.75 N A
Therefore N A C D AB
dy
dz
A
y A N A 0.75 N A
dy A
C D AB 0.25 y A NA
dz
dy A
N A 0.25 y A N A C D AB
dz
dy A
N A d z C D AB
1 0.25 y A
for constant N A and C
Z2 y A2
dy A
N A d z CD AB
Z1 y A1 1 0.25 y A
dx 1
a b x b ln a b x
1
N A z C D AB
ln 1 0.25 y
y A2
A y
0.25 A1
25
4 CD AB 1 0.25 y A 2
NA ln ---------------------------------- (2)
z 1 0.25 y A 1
Given:
p 2 * 1.01325 * 10 5
C 0.0893 K mol m 3
RT 8314 * 273
p A 1 1.5
y A1 0.75
P 2
p A2 0.5
y A2 0.25
P 2
Substituting these in equation (2),
iii) N A CD AB
dy
dz
A
y A N A N B
Given: NB = 0
dy A
Therefore N A CD AB y A NA
dz
Z2 y A2
dy A
N A d z CD AB
Z1 y A1 1 y A
CD AB 1 y A2
ln
Z 1 y A1
0.0893 * 0.275 * 10 4 1 0.25
ln 1 0.75
0 .2
26
kmol
1.349 * 10 5
m 2 . sec
Rate of diffusion = 1.349 8 10 –5 * * (0.5 * 10 –2) 2
N A C D AB
dy
dr
A
y A N A N B
Here N B = 0 (since air is assumed to be stagnant)
Therefore,
dy A
N A C D AB y A NA
dr
Rearranging,
C D AB d y A
NA __________ (1)
1 y A dr
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,
AN A AN A __________ (2)
r r r
where A = surface area of sphere at r or r + r.
Substituting for A = 4 r 2 in equation (2),
27
4 r 2
NA 4 r 2
NA 0
r r r
or
2 2
r NA r NA
r r r
lim 0
r 0 r
d
dr
r 2
NA 0 __________ (3)
Integrating,
2
r N A constant __________ (4)
2
r C D AB d y A
r 02 N A 0
1 y A dr
dr dy A
r 02 N A 0 C D AB __________ (5)
r 2 1 y A
Boundary condition :
At r = r 0 y A = y AS
And
At r = y A = y A
Therefore equation (5) becomes,
r 02 NA 0
1
C D AB ln 1 y A yy A
rr0 AS
Simplifying,
C D AB 1 y A
NA 0 ln __________ (6)
r0 1 y A S
Time required for complete evaporation of the droplet may be evaluated from
making mass balance.
28
d r0
4 r0 2 L
__________ (7)
MA dt
Substituting for N A0 from equation (6) in equation (7),
C D AB 1 y A L d r0
ln __________ (8)
r0 1 y AS MA dt
Initial condition :
When t = 0 r 0 = r 1
Integrating equation (8) with these initial condition,
t 1 1 0
d t M
L
r0 d r0
C D AB 1 y A
ln
0 A r1
1 y
AS
1 r 12
t
L
__________ (9)
M 2 C D AB 1 y A
ln
A
1 y
AS
Equation (9) gives the total time t required for complete evaporation of spherical
droplet of initial radius r 1.
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
N O 2 C D O 2 gas
d yO2
dr
y O 2 N O 2 N CO 2 N N 2
__________ (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
29
d yO2
N O 2 C D O 2 gas __________ (2)
dr
For steady state conditions,
d
dr
r 2
NO2 0 __________ (3)
Integrating,
r 2
N O 2 constant r 02 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
at the surface of the particle.
Substituting for N O from equation (2) in equation (4),
2
d yO2
r 2
C D O 2 gas r 02 N O 2 s __________ (5)
dr
Boundary condition :
At r r 0 yO2 yO2s
And
At r yO2 yO2
With these boundary condition, equation (5) becomes
y O2
dr
r 02 N A 0 2
C D O 2 gas d yO2
r0 r y O2s
which yields
NO2s
C D O 2 gas
r0
y O2s yO2 __________ (6)
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
yO2 y O 0.21 (because air is a mixture of 21 mole % O 2 and 79 mole
2
% N 2)
30
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
dividing (1) by Sr, and taking the limit as r approaches zero, gives:
d r 2N A 0
dr
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.
N A CD AB
dy
dr
A
y A N A N B
N B = 0 (since air is assumed to be stagnant in the film)
dy A
N A CD AB y A NA
dr
d yA
N A CD AB
dr1 y A
N A CD AB
d ln 1 y A
dr
WA
4 r 2
CD AB d ln 1 y A
dr
31
WA
dr
2
4 D AB C d ln 1 y A
r
Boundary condition:
0.555
At r = R y A 7.303 * 10 4
760
ln (1 – y A) = - 7.3 * 10 –4
At r = yA = 0 ln (1-y A) = 0
d ln 1 y A
0
dr
Therefore W A 2
4 D AB C
R r 7.3 *10 4
WA
1
r 4 D AB C ln 1 y A 7.3 *10 4
0
R
WA
1
0 R 4 D AB C 0 7.3 * 10
4
W A = 4 R D AB C * 7.3 * 10 –4
P 1.01325 * 10 5
C
Gas cons tan t * T 8314 * 318
= 0.0383 kmol/m 3
32
X B 2 X B1
X BM
X
ln B 2
X B 1
b) For steady – state equimolar counter diffusion :
N A = - N B = const
D AB
NA
D AB
Z
C A1 C A2
Z M av
x A1 x A 2
4. Calculate the rate of diffusion of butanol at 20C 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 20C 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
NA
D AB
C
x A1 x A2
z x B, lm
where C is the average molar density.
M avg
Conversion from weight fraction the Mole fraction:
x A1
0.1 74 0.026
0.1 74 0.9 18
x A2
0.04 74 0.010
0.04 74 0.96 18
Average molecular weight at 1 & 2:
1
M1 19.47 kg Kmol
0.1 74 0.9 18
1
M2 18.56 kg Kmol
0.04 74 0.96 18
33
1 M1 2 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 B,lm
x B 2 x B1
1 x A2 1 x A1
ln x B 2 x B1 1 x A2
ln
1 x A1
(i.e.) x B,lm
1 0.01 1 0.026
1 0.01
ln
1 0.026
0.016
0.982
0.0163
Therefore N A
D AB
x A1 x A2
2 M avg x B, lm
5.9 * 10 6 * 10 4 * 51.7
*
0.026 0.010
0.1 * 10 2 0.982
kmol
4.97 * 10 7
m 2 sec
gmol
1.789
m 2 .hr .
g
1.789 * 74
m 2 . hr .
g
132.4
m 2 . hr .
34
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).
N A D AB
dCA
dz
CA
C
N A N B ____________ (1)
35
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
dCA
at z 0
dz
Differentiating C A with respect to z,
C A0 k cos h k z
dCA D AB D AB
C A0 k sin h k z
dz D AB D AB
tan h k
D AB
____________ (8)
Substituting z = 0 in equation (8) and from equation (2),
k
D AB C A 0 D AB
NA ____________ (9)
Z 0 k
tan h
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
which is constant throughout the film of liquid. On comparison of equation (9) and
(10), it is apparent that the term k tan h k shows
D AB D AB
the influence of the chemical reactions. This terms a dimensionless quantity, is
often called as Hatta Number.
36
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 :
dCA
N A D AB constant , as given by Fick’s law.
dz
Integrating the above equation,
NA
D AB C A1 C A2
z
which is similar to the expression obtained for diffusion in a stagnant fluid with no
bulk motion (i.e. N = 0).
37
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 Fick’s
second law of diffusion :
C A 2 C A
D AB __________ (1)
t z 2
2.1 Introduction
2.2 Convective Mass Transfer coefficient
2.3 Significant parameters in convective mass transfer
2.4 The application of dimensional analysis to Mass Transfer
2.4.1 Transfer into a stream flowing under forced convection
2.4.2 Transfer into a phase whose motion is due to natural convection
2.5 Analogies among mass, heat, and momentum transfer
2.5.1 Reynolds analogy
2.5.2 Chilton – Colburn analogy
2.6 Convective mass transfer correlations
2.6.1 For flow around flat plat
2.6.2 For flow around single sphere
2.6.3 For flow around single cylinder
2.6.4 For flow through pipes
2.7 Mass transfer between phases
2.8 Simultaneous heat and mass transfer
2.8.1 Condensation of vapour on cold surface
2.8.2 Wet bulb thermometer
38
2.1 Introduction
Our discussion of mass transfer in the previous chapter was limited to molecular
diffusion, which is a process resulting from a concentration gradient. In system
involving liquids or gases, however, it is very difficult to eliminate convection from
the overall mass-transfer process.
1. Mass transfer takes place only in a single phase either to or from a phase
boundary, as in sublimation of naphthalene (solid form) into the moving
air.
In the first few section we will see equation governing convective mass transfer in
a single fluid phase.
In the study of convective heat transfer, the heat flux is connected to heat
transfer coefficient as
Q A q h t s t m -------------------- (4.1)
N A k c C As C A -------------------- (4.2)
The molar flux N A is measured relative to a set of axes fixed in space. The
driving force is the difference between the concentration at the phase boundary,
CAS (a solid surface or a fluid interface) and the concentration at some arbitrarily
defined point in the fluid medium, C A . The convective mass transfer coefficient
kC is a function of geometry of the system and the velocity and properties of the
fluid similar to the heat transfer coefficient, h.
39
Dimensionless parameters are often used to correlate convective transfer data.
In momentum transfer Reynolds number and friction factor play a major role. In
the correlation of convective heat transfer data, Prandtl and Nusselt numbers are
important. Some of the same parameters, along with some newly defined
dimensionless numbers, will be useful in the correlation of convective mass-
transfer data.
The molecular diffusivities of the three transport process (momentum, heat and
mass) have been defined as:
Momentum diffusivity ----------------------------- (4.3)
k
Thermal diffusivity --------------------------- (4.4)
Cp
and
Mass diffusivity D AB --------------------------- (4.5)
It can be shown that each of the diffusivities has the dimensions of L 2 / t, hence, a
ratio of any of the two of these must be dimensionless.
Momentum diffusivity Cp
Pr ------------------------ (4.6)
Thermal diffusivity K
Momentum diffusivity
Sc -------------- (4.7)
Mass diffusivity D AB D AB
The ratio of the molecular diffusivity of heat to the molecular diffusivity of mass is
designated the Lewis Number, and is given by
Thermal diffusivity k
Le ------------- (4.8)
Mass diffusivity D AB C p D AB
40
Let us consider the mass transfer of solute A from a solid to a fluid flowing past
the surface of the solid. For such a case, the mass transfer between the solid
surface and the fluid may be written as
N A k c C As C A ---------------------- (4.1 a)
Since the mass transfer at the surface is by molecular diffusion, the mass
transfer may also described by
dCA
N A D AB ------------------------- (4.9)
dy y 0
When the boundary concentration, CAs is constant, equation (4.9) may be written
as
N A D AB
d C A C As ---------------------- (4.10)
dy y 0
Equation (4.1a) and (4.10) may be equated, since they define the same flux of
component A leaving the surface and entering the fluid
k c C A s C A D AB
d
dy
C A C As ---------------
y 0
(4.11)
kc
d C A C As d y
D AB C A C A y 0
-------------------- (4.12)
kc L
d C A C As d y y 0
C A S C A L
----------------- (4.13)
D AB
41
The right hand side of equation (4.13) is the ratio of the concentration gradient at
the surface to an overall or reference concentration gradient; accordingly, it may
be considered as the ratio of molecular mass-transport resistance to the
convective mass-transport resistance of the fluid. This ratio is generally known as
the Sherwood number, Sh and analogous to the Nusselt number Nu, in heat
transfer.
There are two important mass transfer processes, which we shall consider, the
transfer of mass into a steam flowing under forced convection and the transfer of
mass into a phase which is moving as the result of natural convection associated
with density gradients.
Consider the transfer of mass from the walls of a circular conduit to a fluid flowing
through the conduit. The mass transfer is due to the concentration driving force
C As – C A .
These variables include terms descriptive of the system geometry, the flow and
fluid properties and the quantity of importance, k c.
42
1 DABa b D c k c ---------------------------- (4.17)
a
L2 M
b
L
1
t 3 L c --------------------------- (4.18)
L t
L: 0 = 2a – 3b + c + 1
t : 0=–a–1
M: 0=b
kc D
Thus 1 which is the Sherwood number.
D AB
The other two groups could be determined in the same manner, yielding
D
2 --------------------------- (4.19)
D AB
and 3 S c -------------------------------- (4.20)
D AB
which is termed as Schmidt Number
D D
2
Re ----------------- (4.21)
3 D AB D AB
which is the Reynolds Number
43
Sh Re, Sc --------------------------- (4.22)
Natural convection currents develop if there exists any variation in density within
the fluid phase. The density variation may be due to temperature differences or
to relatively large concentration differences.
kc L
1 Nu, the Nusselt number ---------------------- (4.27)
D AB
D AB 1
, the reciprocal of Schmidt number --------
2 Sc
(4.28)
L3 g A
and 3 ------------------------------- (4.29)
D AB
44
D AB L 3 g A
2 3
D AB
L3 g A
Gr AB -------------------------- (4.30)
2
Sh Gr AB , Sc ---------------------------- (4.31)
Analogies among mass, heat and momentum transfer have their origin either in
the mathematical description of the effects or in the physical parameters used for
quantitative description.
To explore those analogies, it could be understood that the diffusion of mass and
conduction of heat obey very similar equations. In particular, diffusion in one
dimension is described by the Fick’s Law as
dCA
J A D AB ------------------------------ (4.32)
dz
dT
q k --------------------------------- (4.33)
dz
d
----------------------------- (4.34)
dz
Where is the momentum flux (or shear stress) and is the viscosity of fluid.
At this point it has become conventional to draw an analogy among mass, heat
and momentum transfer. Each process uses a simple law combined with a mass
or energy or momentum balance.
45
In this section, we shall consider several analogies among transfer phenomenon
which has been proposed because of the similarity in their mechanisms. The
analogies are useful in understanding the transfer phenomena and as a
satisfactory means for predicting behaviour of systems for which limited
quantitative data are available.
The similarity among the transfer phenomena and accordingly the existence of
the analogies require that the following five conditions exist within the system
2. There is no mass or energy produced within the system. This implies that
there is no chemical reaction within the system
5. The velocity profile is not affected by the mass transfer. This implies there
should be a low rate of mass transfer.
The first recognition of the analogous behaviour of mass, heat and momentum
transfer was reported by Osborne Reynolds in 1874. Although his analogy is
limited in application, it served as the base for seeking better analogies.
Reynolds postulated that the mechanisms for transfer of momentum, energy and
mass are identical. Accordingly,
kc h f
-------------------------------- (4.35)
C p 2
46
2.5.2 Chilton – Colburn Analogy
Because the Reynold’s analogy was practically useful, many authors tried to
extend it to liquids. Chilton and Colburn, using experimental data, sought
modifications to the Reynold’s analogy that would not have the restrictions that
Prandtl and Schmidt numbers must be equal to one. They defined for the j factor
for mass transfer as
kc
jD Sc 2 3 --------------------------- (4.36)
23
j H St Pr ----------------------------- (4.37)
Nu h
where St is Stanton number =
Re Pr C p
Based on data collected in both laminar and turbulent flow regimes, they found
f
jD jH ----------------------------- (4.38)
2
This analogy is valid for gases and liquids within the range of 0.6 < Sc < 2500
and 0.6 < Pr < 100.
The Chilton-Colburn analogy has been observed to hold for many different
geometries for example, flow over flat plates, flow in pipes, and flow around
cylinders.
13. A stream of air at 100 kPa pressure and 300 K is flowing on the top surface
of a thin flat sheet of solid naphthalene of length 0.2 m with a velocity of 20
m/sec. The other data are:
Calculate:
(a) the overage mass transfer coefficient over the flat plate
(b) the rate of loss of naphthalene from the surface per unit width
47
Note: For heat transfer over a flat plate, convective heat transfer coefficient for
laminar flow can be calculated by the equation.
Nu 0.664 Re1L 2 Pr 1 3
Solution:
Nu 0.664 Re1L 2 Pr 1 3
The analogous relation for mass transfer is
where
Rate of loss per meter width = (1.4024 * 10 –7) (0.2) = 2.8048 * 10 –8 kmol/m.sec
= 0.101 gmol/m.hr.
48
Extensive data have been obtained for the transfer of mass between a moving
fluid and certain shapes, such as flat plates, spheres and cylinders. The
techniques include sublimation of a solid, vapourization of a liquid into a moving
stream of air and the dissolution of a solid into water.
These data have been correlated in terms of dimensionless parameters and the
equations obtained are used to estimate the mass transfer coefficients in other
moving fluids and geometrically similar surfaces.
Using the definition of j factor for mass transfer on equation (4.39) and (4.40) we
obtain
These equations may be used if the Schmidt number in the range 0.6 < Sc <
2500.
7. If the local Nusselt number for the laminar boundary layer that is formed over a
flat plate is
Nu x 0.332 Re 1x 2 Sc 1 / 3
a) Re L = 100 000
b) Re L = 1500 000
49
The transition from laminar to turbulent flow occurs at Re x = 3 * 10 5.
Derivation:
L
k c dx
By definition : k c o
L
dx
o
kc x xv
and Nu x ; Re x ; Sc ;
D AB D AB
For Re L = 100 000 ; (which is less than the Reynolds number corresponding to
Transition value of 3 * 10 5)
1
L xv 1 D AB
0.332
2
Sc 3 dx
x
k c o
L
12
v
0.332 Sc 13
L
dx
D AB
L o x1 2
12
0.332 v L
Sc 1 3 D AB x 1 2 o
1
L
2
kcL
(i.e.) 0.664 Re L1 2 Sc 1 3 [answer (a)]
D AB
Lt L
d x
0.332 Re 1 2 Sc 1 3 d x 0.0292 Re 45 13
Sc
x
x x
x
k D AB o L t
c
L
where L t is the distance from the leading edge of the plane to the
transition point where Re x = 3 * 10 5.
50
12 Lt 45 L
d x
0.332 Sc1 3 v dx
0.0292 Sc1 3
v
15
o x
1 2
Lt x
k c D AB
L
45
kcL 0.0292 45 L V
0.664 Re1t 2 Sx 1 3 Sc 1 3 x
Lt
D AB 45
0.664 Re 1t 2 Sc 1 3 0.0365 Sc 1 3 Re Re
45
L
45
t
kcL
0.664 Re 1t 2 Sc 1 3 0.0365 Re L4 5 Sc 1 3 0.0365 Ret4 5 Sc 1 3
D AB
where Re t = 3 * 10 5
Correlations for mass transfer from single spheres are represented as addition of
terms representing transfer by purely molecular diffusion and transfer by forced
convection, in the form
Sh Sh o C Re m Sc n
---------------------- (4.43)
Sh 2 C Re m Sc 1 3 -------------------------- (4.44)
For mass transfer into liquid streams, the equation given by Brain and Hales
23
Sh 4 1.21 PeAB 12
-------------------------- (4.45)
correlates the data that are obtained when the mass transfer Peclet number, Pe
AB is less than 10,000. This Peclet number is equal to the product of Reynolds
and Schmidt numbers (i.e.)
Pe AB Re Sc ---------------------------------- (4.46)
For Peclet numbers greater than 10,000, the relation given by Levich is useful
51
Sh 1.01 Pe1AB
3
--------------------------- (4.47)
correlates the data for mass transfer into gases for at Reynold’s numbers ranging
from 2 to 800 and Schmidt number ranging 0.6 to 2.7.
Sh 2 0.59 Gr AB Sc 1 4 ----------------------- (4.49)
6. The mass flux from a 5 cm diameter naphthalene ball placed in stagnant air at
40C and atmospheric pressure, is 1.47 * 10 –3 mol/m 2. sec. Assume the vapor
pressure of naphthalene to be 0.15 atm at 40C and negligible bulk concentration
of naphthalene in air. If air starts blowing across the surface of naphthalene ball
at 3 m/s by what factor will the mass transfer rate increase, all other conditions
remaining the same?
For spheres :
Calculations:
kc L
Sh where L is the characteristic dimension for sphere L =
D AB
Diameter.
Sc
D AB
52
Dv
Rc
Mass flux, N A K c c ------------------------------(1)
also N = K G p A
kc
Therefore K G
RT
Given:
mol Kc
N 1.47 * 10 3 pA
2 RT
m . sec
k c 0.15 mol
0 1.47 * 10 3 * 10 4
RT 1 cm 2 . sec
1.47 * 10 7
kc * 82.06 * 273 40
0.15
= 0.0252 cm/sec
k c = 2.517 * 10 –4 m/sec ------------------------------(3)
Estimation of D AB:
From (2),
2.517 * 10 4 * 5 * 10 2
2 (since v = 0)
D AB
And
k c * 5 * 10 2
0.5 0.33
5 * 10 2 * 3 * 1.123 1.8 * 10 5
2 0.6
6.2925 * 10 6 5 1.123 * 6.2925 * 10 6
1.8 * 10
53
7946 k c = 2 + 0.6 * (96.74) * (1.361)
( 4) N A2 0.0102
40.5
(3 ) N A1 2.517 * 10 4
Therefore, rate of mass transfer increases by 40.5 times the initial conditions.
Several investigators have studied the rate of sublimation from a solid cylinder
into air flowing normal to its axis. Bedingfield and Drew correlated the available
data in the form
k G P Sc 0.56
Gm
0.281 Re / 0.4 ------------------------ (4.50)
Mass transfer from the inner wall of a tube to a moving fluid has been studied
extensively. Gilliland and Sherwood, based on the study of rate of vapourization
of nine different liquids into air given the correlation
p B, l m
Sh 0.023 Re 0.83 Sc 0.44 -------------- (4.51)
P
Where p B, lm is the log mean composition of the carrier gas, evaluated between
the surface and bulk stream composition. P is the total pressure. This expression
has been found to be valid over the range
Linton and Sherwood modified the above relation making it suitable for large
ranges of Schmidt number. Their relation is given as
54
Sh 0.023 Re 0.83 Sc 1 3 --------------------- (4.52)
Sh = 0.62 Re ½ Sc 1/3
D2
Where Re and is the angular speed in radians/time.
Calculations:
N A = k c (C As – C A ) -------------------------------- (2)
Given:
Sh = 0.62 Re ½ Sc 1/3
1 1
kc D D 2
2 3
(i.e.) 0.62 ------------------ (3)
D AB D AB
1 rotation = 2 radian
Therefore 20 rotation per minute = 20 * 2 radian/min
20
* 2 radian sec
60
For water = 1 g/cm 3 = 1 centipoise = 0.01 g/cm.sec.
55
From (3),
1 1
2 3
k c 0.62 D
AB
D AB
1 1
40 60 * 1 2 0.01 3
0.62 * 1.0 * 10 5 *
0.01 1 * 1.0 * 10 5
= 8.973 * 10 –4 cm/sec.
From (2),
N A = 8.973 * 10 –4 (0.003 – 0)
= 2.692 * 10 –6 g/cm 2.sec
From (1),
N A S = N A * (2r 2)
= 2.692 * 10 –6 * (2 * 1.5 2)
= 3.805 * 10 –5 g/sec
= 0.137 g/hr.
56
Equation (1) is analogous to that in heat transfer, where the individual
coefficients h are related to the overall coefficient U.
From equation (1),
1 1 1
_____________ (2)
k c1 k c2 Kc
In equation (1), the potential for mass transfer is exposed in terms of
composition. However, this is not always the most convenient way to express it.
For example, if fluid 1 is a gas and fluid 2 a liquid, as in gas absorption, the
potential in gas phase is often expressed in terms of partial pressures, while that
in the liquid phase may be expressed in terms of concentrations. The expression
for the molar flux is then written for the individual phases as:
N A K p P AG P Ai K c C Ai C AL __________
(3)
where
k p = individual mass transfer coefficient for the gas phase with the
potential defined in terms of partial pressures.
P AG , C AL = partial pressure and concentration of A in the bulk gas and liquid
phases, respectively.
P Ai , C Ai = partial pressure and concentration of A, respectively, at the interface.
57
In many system, mass transfer resistance is mainly in one phase. For example,
gases such as nitrogen and oxygen do not dissolve much in liquids. Their
Henry’s law constant H is very large, thus K c k c is a good approximation. In
this case, the liquid phase controls the mass transfer press since mass transfer is
slowest there.
58
where M A is the molecular weight of the diffusing constituent A. H 1 and H 2 are
enthalpies of the vapor at plane 1 and liquid at plane 2.
From equation (1) and (2)
q h l T 2 T 3 h c T 1 T 2 N A M A H 1 H 2 ________ (3)
The molar flux NA is calculated by diffusion through stagnant gas model as
C D AB d y A
NA
1 y A dZ
substituting the appropriate limits, the integral form of equation is
C D AB avg y A1 y A2
NA
Z 2 Z 1 y B, lm __________ (4)
The another example of simultaneous heat and mass transfer is that taking place
in wet-bulb thermometer. This convenient device for measuring relative humidity
of air consists of two conventional thermometer, one of which is clad in a cloth
nick wet with water. The unclad dry-bulb thermometer measures the air’s
temperature. The clad wet-bulb thermometer measures the colder temperature
caused by evaporation of the water.
We want to use this measured temperature difference to calculate the
relative humidity in air. This relative humidity is defined as the amount of water
actually in the air divided by the amount at saturation at the dry-bulb temperature.
To find this humidity, we can write equation for the mass and energy fluxes as:
N A k c C Ai C A k y y Ai y A
__________ (1)
and
q h Ti T __________ (2)
where C Ai and C A are the concentrations of water vapor at the wet bulb’s
surface and in the bulk of air, y Ai and y A are the corresponding mole fractions ; Ti
is the wet-bulb temperature, and T is the dry-bulb temperature. It can be noted
that y Ai is the value at saturation at Ti.
In the air-film surroundings the wet-bulb, the mass and energy fluxes are
coupled as
N A q __________ (3)
where is the latent heat of vaporization of water.
Thus,
ky y Ai y A
h T Ti
Rearranging,
ky
Ti T
h
y Ai y A __________ (4)
From Chilton – colbum analogy,
59
jH = jD
h kc
Pr 3 Sc 3
2 2
or __________ (5)
2
Cp
For gas Pr 1 and Sc 1.
Therefore equation (5) becomes,
kc 1
(as k y C k y = k c)
h Cp
Therefore equation (4) becomes
Ti T
Cp
y Ai y A
where Cp is the bumid heat of air. By similar method, the other industrial
processes of importance involving simultaneous heat and mass transfer such as
humidification and drying can be analysed.
14. Air at 1 atm is blown past the bulb of a mercury thermometer. The bulb is
covered with a wick. The wick is immersed in an organic liquid (molecular weight
= 58). The reading of the thermometer is 7.6 C. At this temperature, the vapor
pressure of the liquid is 5 kPa. Find the air temperature, given that the ratio fo
heat transfer coefficient to the mass transfer coefficient (psychrometric ratio) is 2
kJ/kg. Assume that the air, which is blown, is free from the organic vapor.
Solution:
For simultaneous mass and heat transfer, heat flux q and mass flux N A are
related as
q N A ----------------------------------------- (1)
N A k Y Y' Y ' ---------------------------------- (2)
where
k Y = mass transfer coefficient
Y' = mass ratio of vapor in surrounding air at saturation; and
Y’ = mass ratio of vapor in surrounding air.
q h T T ----------------------------------- (3)
60
where
h = heat transfer coefficient;
T = wet bulb temperature of air; and
T = dry bulb temperature of air.
Substituting for N A and q from equation (2) and equation (3) in equation (1),
h T T' k y T' Y '
T T
Y' Y ' --------------------------------------------- (4)
h kY
T 7.6
3600.1038 0 18.69
2
T = 18.69 + 7.6 = 26.29C
Temperature of air = 26.29C.
61