MT 1
MT 1
MT 1
in
1
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
ρ A = ------------------------------------ (1)
V
The total mass concentration density ρ is the sum of the total mass of the mixture
in unit volume:
ρ = ∑ρ i
i
By definition,
2
mass of A
Number of moles =
molecular weight of A
m
n A = A ----------------------------- (2)
M A
nA ρ
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
3.2.2 Velocities
∑ ρ iν i ∑ ρ iν i
ν = i = i
∑ ρ i ρ
i
3
By similar way, molar-average velocity of the mixture ν * is
∑C i V i
ν * = i
C
For most engineering problems, there will be title difference in ν * and ν and so
the mass average velocity, ν, 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
ρ A
wA =
ρ
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%
4
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
5
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 = ρ m
V
Therefore, density (or mass density) = ρ mM
Where M is the molecular weight of the gas.
PM 1.5 * 10 5 * 30.68
Density = ρ 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
6
N A =C Aν A ---------------------- (1)
N A = C A (ν A −ν ) + C A ν --------------- (2)
By definition
∑ C iν i
ν =ν * = i
C
Therefore, equation (2) becomes
CA
N A = C A (ν A −ν ) + ∑C i ν i
C i
= C A (ν A −ν ) + y A ∑C i ν i
i
N A = C A (ν A − ν) + y A (C A ν A +C B ν B)
= C A (ν A − ν) + y A (N A +N B )
N A = C A (ν A − ν) + 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
7
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 A N --------------- (5)
dZ
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)
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 dy B
CD AB = −CD BA --------------- (9)
dz dZ
From yA+yB=1
dy A = - dy B
D AB = D BA ----------------------------------- (10)
8
This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in
A.
3.4 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
9
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
′ y 2 0.15
where y 2 = = = 0.21
y 2 +y3 0.15 + 0.565
y3
y 3′ =
0.565
= = 0.79
y 2 +y3 0.15 + 0.565
10
1
Therefore D 1m P =
0.21 0.79
+
1.874 1.945
= 1.93 m 2.Pa/sec
1.93
D 1m = = 1.61 * 10 − 5 m 2 sec
1.2 * 10 5
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
5
1.2 * 10
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.
11
3.4.2 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.
12
3.5.1 Diffusion through a stagnant gas film
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
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.
13
From equation (1) (of section 3.5)
dy A
NA = −CD AB + y A (N A + N B)
dz
Since N B = 0,
dy A
NA = −CD AB + y A N 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 ,
14
(1 − y A2 ) − (1 − y A1 ) y A1 − y A2
y B, lm = = ------- (5)
ln ln
y A2 y A2
y A1 y A1
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.
The concentration profile (yA vs. z) for this type of diffusion is shown in figure:
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:
15
Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is made up of
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)
dCA
J A = −D AB ----------------------------------------- (2)
dz
dCA
N A = Nx A − D AB ----------------------------- (3)
dz
(
NA = NA + NB ) CCA − D AB
dCA
dz
Rearranging the terms and integrating between the planes between 1 and 2,
dz C A2 dC A
= −
∫ cD
AB
∫C A1 N C − C N + N
A A A 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
16
Replacing concentration in terms of pressures using Ideal gas law, equation (5)
becomes
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 = 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
NA =
(
1.89 * 10 − 5 )(1.01325 * 10 5 ) 1 − 0.1
ln
(8314 )(298 )(0.002) 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.
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,
17
at any given instant in that period, the molar flux in the gas phase may be
evaluated by
CD AB (y A1 − y A2 )
N A = ------------------ (1)
zy B, lm
ρ A,L dz
N A = -------------------------- (2)
M A dt
ρ 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
ρ A,L dz CD AB (y A1 − y A2 )
= --------------- (3)
M A dt zy B, lm
t ρ A,L y B, lm M A
Zt
∫ dt = C D ∫ z dz
t =0 AB (y A1 − y A2 ) Zt 0
yielding
ρ A,L y B, lm M z 2
− z 2
t =
A t t0 -------- (4)
CD AB ( y A1 − y A2 ) 2
This shall be rearranged to evaluate diffusivity DAB as,
ρ 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
18
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)
ρ A, L y Blm Z 2
−Z 2
D AB = t t0
M A C y ( A1 −y A2 ) t 2
figure
y B 2 − 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
19
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
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.
20
Concentration profile in these equimolar counter diffusion may be obtained from,
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 z−z1
A
= -------------- (5)
C A1
−C A2 z1 −z 2
Calculation:
NA =
D AB
RT z
(p A 1 − p A 2 ) --------------------------- (1)
21
Therefore;
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 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:
NA =
D AB
RTz
(p A1 − p A2 ) ------------------------ (1)
where
D AB
1.6 * 10 − 5 = (15 − 5)
(8.314 )(293 )(0.01)
22
Therefore, D AB = 3.898 * 10 –5 m 2/sec
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 (p A 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
23
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+bx = ln (a + b x )
b
( −1
N A z = − C D AB )
ln 1 − 0.25 y [ ( )]
y A2
A y
0.25 A1
24
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
25
kmol
= 1.349 * 10 − 5
m 2 . sec
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
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 + δr are the same.
This could be written as,
26
AN A = AN A __________ (2)
r r +δ r
where A = surface area of sphere at r or r + δr.
Substituting for A = 4 π r 2 in equation (2),
4π r 2
NA − 4π r 2
NA = 0
r +δ r r
or
2 2
r NA − r NA
r +δ r r
lim = 0
δ r →0 δr
ss
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∞
r r0 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.
27
d 4 ρ
4 π r 02 N A 0 = − πr3 L
dt 3 0
M A
ρ d r0
= − 4 π r0 2 L __________ (7)
MA dt
Substituting for N A0 from equation (6) in equation (7),
C D AB 1 − y A − ρ 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 − ρ 1 1 0
∫d t = M
L
∫r0 d r0
0 A C D AB 1− y A∞ r1
ln
1− y
AS
ρ 1 r 12
t =
L
__________ (9)
M A 2 C D AB 1− y A∞
ln
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
28
Since N N
2
= 0 , and from stoichiometry N O 2 = − N CO 2 , equation
(1) becomes
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 NA 0 ∫ = − C D O 2 − gas ∫ d yO2
2
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)
29
0.21 C D O 2 − gas
NO2s = ____________ (7)
r0
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
dividing (1) by Sδr, and taking the limit as δr approaches zero, gives:
(
d r 2N A )=0
dr
Integrating r 2 N A = constant (or) 4 π 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
dr 1 − y A
N A = CD AB
[ (
d ln 1 − y A )]
dr
30
W A = Rate of evaporation = 4 π r 2 N A R = constant.
WA =
4π r 2
( (
CD AB d ln 1 − y A ))
dr
WA ∫
dr
2
= 4 π 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 ∫ = 4 π D AB C
2
R r − 7.3 *10 − 4
∞
WA
− 1 0
[ (
r = 4 π D AB C ln 1 − y A − 7.3 *10 − 4 )]
R
WA
1
0 + R = 4 π D AB C 0 + 7.3 * 10
−4
[ ]
W A = 4 π 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
31
N A = constant , N B = 0
ρ
NA=
D AB
(
x A1 − x A2 )
z x BM M av
where Z = Z 2 – Z 1, the length of diffusion path; and
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 ρ
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 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
NA =
D AB
C
(x A1 − x A2 )
z x B, lm
where C is the average molar density.
ρ
=
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:
32
1
M1 = = 19.47 kg Kmol
(0.1 74 + 0.9 18 )
1
M2 = = 18.56 kg Kmol
(0.04 74 + 0.96 18 )
ρ
=
(
ρ1 M1 + ρ 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 2 − x B1 (1 − x A2 ) − (1 − x A1)
x B,lm = =
(
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 ρ (
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 .
33
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
N A = − D AB
dCA
dz
+
CA
C
(N A + N B ) ____________ (1)
34
The constant C 1 is equal to C A0 , and C 2 is equal to
− C A0
k δ 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
dCA
at z = 0
dz
Differentiating C A with respect to z,
k k
C A0 cos h z
dCA D AB D AB
= C A0 k sin h k z −
dz D AB D AB
tan h k δ
D AB
____________ (8)
Substituting z = 0 in equation (8) and from equation (2),
k δ
D AB C A 0 D AB
NA = ____________ (9)
Z= 0 δ
tan h k D δ
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 δ
which is constant throughout the film of liquid. On comparison of equation (9) and
(10), it is apparent that the term k δ tan h
k δ shows
D AB D AB
the influence of the chemical reactions. This terms a dimensionless quantity, is
often called as Hatta Number.
35
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 :
dCA
N A = − D AB = constant , as given by Fick’s law.
dz
Integrating the above equation,
(
D AB C A1 − C A2 )
NA =
z
which is similar to the expression obtained for diffusion in a stagnant fluid with no
bulk motion (i.e. N = 0).
36
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 Fick’s
second law of diffusion :
∂C A ∂2 C A
= D AB __________ (1)
∂t ∂z2
This partial differential equation describes a physical situation in which there is
no bulk–motion 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 Fick’s second law of diffusion.
The solution to Fick’s 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.
37