C03 09/29/2010 Page 88

88 Chapter 3 Mass Transfer and Diffusion

concentration c is constant through the film, where

z, cm xN2 xH2 yN2;cm/s yH2;cm/s
c ¼ cA þ cB ð3-20Þ
0 (End 1) 0.800 0.200 0.0351 0.1435
by differentiation, 5 0.617 0.383 0.0465 0.0749
dc ¼ 0 ¼ dcA þ dcB ð3-21Þ 10 0.433 0.567 0.0663 0.0506
15 (End 2) 0.250 0.750 0.1148 0.0383
Thus, dcA ¼ dcB ð3-22Þ

From (3-3a), (3-3b), (3-15), and (3-22), Note that species velocities vary along the length of the tube, but at
any location z, yM ¼ 0. For example, at z ¼ 10 cm, from (3-8),
DAB DBA yM ¼ ð0:433Þð0:0663Þ þ ð0:567Þð0:0506Þ ¼ 0
¼ ð3-23Þ
dz dz
Therefore, DAB ¼ DBA. This equality of diffusion coeffi-
cients is always true in a binary system. §3.1.4 Unimolecular Diffusion (UMD)
In UMD, mass transfer of component A occurs through stag-
nant B, resulting in a bulk flow. Thus,
EXAMPLE 3.1 EMD in a Tube.
NB ¼ 0 ð3-24Þ
Two bulbs are connected by a straight tube, 0.001 m in diameter and
0.15 m in length. Initially the bulb at End 1 contains N2 and the bulb N ¼ NA ð3-25Þ
and
at End 2 contains H2. Pressure and temperature are constant at 25 C
and 1 atm. At a time after diffusion starts, the nitrogen content of the
Therefore, from (3-12),
gas at End 1 of the tube is 80 mol% and at End 2 is 25 mol%. If the dxA
binary diffusion coefficient is 0.784 cm2/s, determine:
N A ¼ xA N A  cDAB ð3-26Þ
dz
(a) The rates and directions of mass transfer in mol/s which can be rearranged to a Fick’s-law form by solving
(b) The species velocities relative to stationary coordinates, in cm/s for NA,

Solution cDAB dxA cDAB dxA

NA ¼  ¼ ð3-27Þ
ð1  xA Þ dz xB dz
(a) Because the gas system is closed and at constant pressure and
temperature, no bulk flow occurs and mass transfer in the con-
necting tube is EMD. The factor (1  xA) accounts for the bulk-flow effect. For a
The area for mass transfer through the tube, in cm2, is A ¼ mixture dilute in A, this effect is small. But in an equimolar
3.14(0.1)2=4 ¼ 7.85  103 cm2. By the ideal gas law, the mixture of A and B, (1  xA) ¼ 0.5 and, because of bulk
P
total gas concentration (molar density) is c ¼ PT ¼ ð82:06Þð298Þ
1
¼ flow, the molar mass-transfer flux of A is twice the ordinary
5
4.09  10 mol/cm . Take as the reference plane End 1 of the
3
molecular-diffusion flux.
connecting tube. Applying (3-18) to N2 over the tube length, For the stagnant component, B, (3-13) becomes
cDN2 ;H2   dxB
nN2 ¼ ðxN2 Þ1  ðxN2 Þ2 A 0 ¼ xB N A  cDBA ð3-28Þ
z2  z1 dz
ð4:09  105 Þð0:784Þð0:80  0:25Þ dxB
¼ ð7:85  103 Þ or xB N A ¼ cDBA ð3-29Þ
15 dz
¼ 9:23  109 mol/s in the positive z-direction
Thus, the bulk-flow flux of B is equal to but opposite its dif-
nH2 ¼ 9:23  109 mol/s in the negative z-direction
fusion flux.
(b) For EMD, the molar-average velocity of the mixture, yM , is 0. At quasi-steady-state conditions (i.e., no accumulation of
Therefore, from (3-9), species velocities are equal to species species with time) and with constant molar density, (3-27) in
diffusion velocities. Thus, integral form is:
Z z Z
J N2 nN2 cDAB xA dxA
yN2 ¼ ðyN2 ÞD ¼ ¼ dz ¼  ð3-30Þ
cN2 AcxN2 z1 N A xA1 1  xA
9:23  109 which upon integration yields
¼
½ð7:85  103 Þð4:09  105 ÞxN2 

cDAB 1  xA
¼
0:0287
in the positive z-direction NA ¼ ln ð3-31Þ
xN2 z  z1 1  xA1

0:0287
Thus, the mole-fraction variation as a function of z is
Similarly, yH2 ¼ in the negative z-direction  
xH2 N A ðz  z1 Þ
xA ¼ 1  ð1  xA1 Þexp ð3-32Þ
Thus, species velocities depend on mole fractions, as follows:
cDAB
C03 09/29/2010 Page 89

§3.1 Steady-State, Ordinary Molecular Diffusion 89

Figure 3.1b shows that the mole fractions are thus nonlinear Solution
in z.
The total vapor concentration by the ideal-gas law is:
A more useful form of (3-31) can be derived from the defi-
nition of the log mean. When z ¼ z2, (3-31) becomes P 1
c¼ ¼ ¼ 4:09  105 mol/cm3

 RT ð82:06Þð298Þ
cDAB 1  xA2
NA ¼ ln ð3-33Þ (a) With z equal to the distance down from the top of the beaker, let
z2  z1 1  xA1
z1 ¼ 0 at the top of beaker and z2 ¼ the distance from the top of
The log mean (LM) of (1  xA) at the two ends of the stag- the beaker to gas–liquid interface. Then, initially, the stagnant
nant layer is gas layer is z2  z1 ¼ Dz ¼ 0.5 cm. From Dalton’s law, assum-
ing equilibrium at the liquid benzene–air interface,
ð1  xA2 Þ  ð1  xA1 Þ
ð1  xA ÞLM ¼ p 0:131
ln½ð1  xA2 Þ=ð1  xA1 Þ xA1 ¼ A1 ¼ ¼ 0:131; xA2 ¼ 0
ð3-34Þ P 1
xA1  xA2
¼ 0:131
ln½ð1  xA2 Þ=ð1  xA1 Þ ð1  xA ÞLM ¼ ¼ 0:933 ¼ ðxB ÞLM
ln½ð1  0Þ=ð1  0:131Þ
Combining (3-33) with (3-34) gives
From (3-35),
cDAB ðxA1  xA2 Þ cDAB ðDxA Þ

NA ¼ ¼ ð4:09  106 Þð0:0905Þ 0:131
z2  z1 ð1  xA ÞLM ð1  xA ÞLM Dz NA ¼ ¼ 1:04  106 mol/cm2 -s
0:5 0:933
cDAB ðDxA Þ ð3:35Þ
¼
ðxB ÞLM Dz N A ðz  z1 Þ ð1:04  106 Þðz  0Þ
(b) ¼ ¼ 0:281 z
cDAB ð4:09  105 Þð0:0905Þ
From (3-32),
xA ¼ 1  0:869 exp ð0:281 zÞ ð1Þ
EXAMPLE 3.2 Evaporation from an Open Beaker.
Using (1), the following results are obtained:
In Figure 3.2, an open beaker, 6 cm high, is filled with liquid ben-
zene (A) at 25 C to within 0.5 cm of the top. Dry air (B) at 25 C
and 1 atm is blown across the mouth of the beaker so that evaporated z, cm xA xB
benzene is carried away by convection after it transfers through a
0.0 0.1310 0.8690
stagnant air layer in the beaker. The vapor pressure of benzene at
0.1 0.1060 0.8940
25 C is 0.131 atm. Thus, as shown in Figure 3.2, the mole fraction
of benzene in the air at the top of the beaker is zero and is deter- 0.2 0.0808 0.9192
mined by Raoult’s law at the gas–liquid interface. The diffusion 0.3 0.0546 0.9454
coefficient for benzene in air at 25 C and 1 atm is 0.0905 cm2/s. 0.4 0.0276 0.9724
Compute the: (a) initial rate of evaporation of benzene as a molar 0.5 0.0000 1.0000
flux in mol/cm2-s; (b) initial mole-fraction profiles in the stagnant
air layer; (c) initial fractions of the mass-transfer fluxes due to
molecular diffusion; (d) initial diffusion velocities, and the species These profiles are only slightly curved.
velocities (relative to stationary coordinates) in the stagnant layer; (c) Equations (3-27) and (3-29) yield the bulk-flow terms, xANA
(e) time for the benzene level in the beaker to drop 2 cm if the spe- and xBNA, from which the molecular-diffusion terms are
cific gravity of benzene is 0.874. obtained.
Neglect the accumulation of benzene and air in the stagnant
layer with time as it increases in height (quasi-steady-state
assumption). xiN Ji
Bulk-Flow Flux, Molecular-Diffusion
mol/cm2-s  106 Flux, mol/cm2-s  106
Air 1 atm
25°C z, cm A B A B
xA = 0 0.0 0.1360 0.9040 0.9040 0.9040
Mass
transfer 0.5 cm 0.1 0.1100 0.9300 0.9300 0.9300
z
xA = PAs /P 0.2 0.0840 0.9560 0.9560 0.9560
Interface
0.3 0.0568 0.9832 0.9832 0.9832
6 cm 0.4 0.0287 1.0113 1.0113 1.0113
Liquid 0.5 0.0000 1.0400 1.0400 1.0400
Benzene

Note that the molecular-diffusion fluxes are equal but opposite

Beaker
and that the bulk-flow flux of B is equal but opposite to its molec-
ular diffusion flux; thus NB is zero, making B (air) stagnant.
Figure 3.2 Evaporation of benzene from a beaker—Example 3.2.
C03 09/29/2010 Page 90

90 Chapter 3 Mass Transfer and Diffusion

(d) From (3-6), The binary diffusivities, DAB and DBA, are called mutual
N N A 1:04  10 6 or binary diffusion coefficients. Other coefficients include
yM ¼ ¼ ¼ ¼ 0:0254 cm/s ð2Þ DiM , the diffusivity of i in a multicomponent mixture; Dii, the
c c 4:09  105
self-diffusion coefficient; and the tracer or interdiffusion
From (3-9), the diffusion velocities are given by
coefficient.
Ji Ji In this chapter and throughout this book, the focus is on
yi d ¼ ¼ ð3Þ
ci xi c the mutual diffusion coefficient, which will be referred to as
From (3-10), species velocities relative to stationary coordinates the diffusivity or diffusion coefficient.
are
yi ¼ yid þ yM ð4Þ §3.2.1 Diffusivity in Gas Mixtures
Using (2) to (4), there follows As discussed by Poling, Prausnitz, and O’Connell [2], equa-
tions are available for estimating the value of DAB ¼ DBA in
yi d Ji gases at low to moderate pressures. The theoretical equations
Molecular-Diffusion Species based on Boltzmann’s kinetic theory of gases, the theorem of
Velocity, cm/s Velocity, cm/s corresponding states, and a suitable intermolecular energy-
z, cm A B A B potential function, as developed by Chapman and Enskog,
predict DAB to be inversely proportional to pressure, to increase
0.0 0.1687 0.0254 0.1941 0 significantly with temperature, and to be almost independent of
0.1 0.2145 0.0254 0.2171 0 composition. Of greater accuracy and ease of use is the empiri-
0.2 0.2893 0.0254 0.3147 0 cal equation of Fuller, Schettler, and Giddings [3], which
0.3 0.4403 0.0254 0.4657 0 retains the form of the Chapman–Enskog theory but utilizes
0.4 0.8959 0.0254 0.9213 0 empirical constants derived from experimental data:
0.5 1 0.0254 1 0
0:00143T 1:75
DAB ¼ DBA ¼ 1=2 P 1=3 P 1=3 ð3-36Þ
Note that yA is zero everywhere, because its molecular- P M AB ½ð V ÞA þ ð V ÞB 2
diffusion velocity is negated by the molar-mean velocity.
where DAB is in cm2/s, P is in atm, T is in K,
(e) The mass-transfer flux for benzene evaporation equals the rate
of decrease in the moles of liquid benzene per unit cross section 2
M AB ¼ ð3-37Þ
area of the beaker. ð1=M A Þ þ ð1=M B Þ
P
Using (3-35) with Dz ¼ z, and V ¼ summation of atomic and structural diffusion vol-
cDAB ðDxA Þ r dz umes from Table 3.1, which includes diffusion volumes of sim-
NA ¼ ¼ L ð5Þ ple molecules.
z ð1  xA ÞLM M L dt

Separating variables and integrating, Table 3.1 Diffusion Volumes from Fuller, Ensley, and Giddings
Z t Z z2 [J. Phys. Chem.,73, 3679–3685 (1969)] for Estimating Binary Gas
r ð1  xA ÞLM
dt ¼ t ¼ L z dz ð6Þ Diffusivities by the Method of Fuller et al. [3]
0 M L cDAB ðDxA Þ z1

where now z1 ¼ initial location of the interface and z2 ¼ location of Atomic Diffusion Volumes
the interface after it drops 2 cm. and Structural Diffusion-Volume Increments
The coefficient of the integral on the RHS of (6) is constant at C 15.9 F 14.7
0:874ð0:933Þ H 2.31 Cl 21.0
¼ 21;530 s/cm2
78:11ð4:09  105 Þð0:0905Þð0:131Þ O 6.11 Br 21.9
N 4.54 I 29.8
Z z2 Z 2:5 Aromatic ring 18.3 S 22.9
z dz ¼ z dz ¼ 3 cm2 Heterocyclic ring 18.3
z1 0:5

From (6), t ¼ 21,530(3) ¼ 64,590 s or 17.94 h, which is a long time Diffusion Volumes of Simple Molecules
because of the absence of turbulence.
He 2.67 CO 18.0
Ne 5.98 CO2 26.7
Ar 16.2 N2O 35.9
§3.2 DIFFUSION COEFFICIENTS Kr 24.5 NH3 20.7
(DIFFUSIVITIES) Xe 32.7 H2O 13.1
H2 6.12 SF6 71.3
Diffusion coefficients (diffusivities) are defined for a binary
D2 6.84 Cl2 38.4
mixture by (3-3) to (3-5). Measurement of diffusion coeffi-
N2 18.5 Br2 69.0
cients involve a correction for bulk flow using (3-12) and
O2 16.3 SO2 41.8
(3-13), with the reference plane being such that there is no
Air 19.7
net molar bulk flow.