For liquids of high volatility, A. Stefan (1879) devised a convenient means of measuring the
diffusivity DAB of their vapor A through a stagnant gas B. If the volatile substance A (e.g.
ethyl ether or ethanol) is placed in the lower part of a vertical capillary, then liquid A will
evaporate and, by the mechanism of diffusion, travel to the end of the capillary. Maintaining
the mouth of the capillary at a given composition automatically establishes the concentration
gradient in the capillary, and the falling rate of the meniscus in the capillary provides the rate
of transport. The capillary is placed in an envelope through which air is passed. At the
meniscus the gaseous phase composition is specified by the vapor pressure of liquid A, the
diffusing constituent. At the mouth of the capillary, the gaseous phase is essentially air. The
gradient in the capillary is thus obtained by circulating sufficient air to reduce the substance
A concentration at the mouth to a negligible quantity. The air rate should be low, constant,
and not turbulent. The falling rate of the meniscus can be observed remotely with a
cathetometer.
gas B
(air)
PA2
z=0
PA1
z = z1 at t = 0
z = zt at t
pure liquid A
dy A
+ yA(NA,z + NB,z)
dz
We will assume that air is insoluble in liquid A, it is stagnant (or nondiffusing) and NB,z = 0.
Solving for NA,z give
NA,z(1 yA) = cDAB
NA,z dz = cDAB
0
dy A
cDAB
NA,zdz =
dyA
dz
1 yA
yA2
y A1
dy A
1 y A2
NA,zz = cDABln
1 yA
1 y A1
yB,lm =
we have
ln
1 y A2
y y A2
= A1
y B ,lm
1 y A1
NA,z =
cDAB ( y A1 y A2 )
zy B ,lm
The molar flux is related to the amount of A leaving the liquid by the material balance
NA,z =
dz
cDAB ( y A1 y A2 )
= A, L
zy B ,lm
M A dt
dt
0
A, L
MA
y B ,lm
cDAB ( y A1 y A2 )
zt
z1
zdz
We have
t=
A, L
MA
y B ,lm
cDAB ( y A1 y A2 )
zt2 z12
110
A, L
MA
y B ,lm RT
DAB P ( y A1 y A2 )
y B ,lm RT
zt2 z12 A, L
=
M A DAB ( PA1 PA2 )
2
zt2 z12
Since
yB,lm =
P ( y A1 y A2 )
P
y A1 y A2
=
= B ,lm
ln[(1 y A2 ) /(1 y A1 )]
P
P ln[ P (1 y A2 ) / P (1 y A1 )]
yB ,lm
PB ,lm
=
PA1 PA2
P ( PA1 PA2 )
Therefore
t=
A, L
MA
PB ,lm RT
DAB P ( PA1 PA2 )
zt2 z12
A, L PB ,lm RT
zt2 z12
DAB =
tPM A ( PA1 PA2 ) 2
In this equation
PB,lm = [(P  PA1)  (P  PA2)]/ln [(P  PA1)/(P  PA2)]
PA1 = vapor pressure of liquid A at temperature T.
PA2 = partial pressure of vapor A at the mouth of the capillary.
R = gas law constant.
t = time during which the meniscus fall from z1 to zt.
z1 = distance from the mouth of the capillary to the meniscus at t = 0.
zt = distance from the mouth of the capillary to the meniscus at t.
P = ambient atmospheric pressure
A,L = density of liquid A at T.
111
Example 1.22 A long glass capillary tube, of diameter 0.01 cm, is in contact with water at one end and dry
air at the other. Water vapor evaporates at the wet end within the capillary, and the vapor
diffuses through the capillary toward the dry end. How long is required for one gram of water
to evaporate through this system? The vapor pressure of water is 17.5 mmHg at 20oC, the
temperature at which the entire system is maintained. Take the diffusivity of water vapor in
air at 20oC to be 0.20 cm2/s, and assume that the dry air is at a pressure of 760 mmHg.
Assume that the distance from the wet interface within the capillary to the dry end is always
10 cm. (Ref. An Introduction to Mass and Heat transfer by Stanley Middleman.)
z=L
yAL
z=0
yA0
dy A
+ yA(NA,z + NB,z)
dz
NA,z dz = cDAB
0
y AL
yA0
dy A
1 y AL
NA,zL = cDABln
1 yA
1 y A0
The ambient air is dry so yAL = 0. Vapor pressure of water at 20oC is 17.5 mmHg, therefore
yA0 = 17.5/760 = 0.023. Note: R = 82.057 cm3atm/moloK
NA,z =
cD AB
1
0.20
1
=
= 1.935108 mol/cm2s
ln
ln
L
1 y A0
82.057 293.15 10 1 0.023
1/18
4(1/18)
=
= 9.14109 s
8
N A, z ( Area )
(1.935 10 )( )(0.01^ 2)
102
L2
=
= 250 s.
2(.2)
2 DAB
112
Lo
Pure water
Lw(t)
dy A
+ yA(NA,z + NB,z)
dz
NA,z dz = cDAB
0
dy A
cDAB
NA,zdz =
dyA
dz
1 yA
y AL
yA0
dy A
1 y AL
NA,zL = cDABln
1 yA
1 y A0
The dry air is blow over the top yAL = 0, yA0 = 3.17/101.3 = 0.0313
NA,z =
cD AB
1
ln
L
1 y A0
The molar flux is related to the amount of A leaving the liquid by the material balance
Ac
A,L dLw
M A dt
= AcNA,z = Ac
cD AB
1
ln
L
1 y A0
In this equation, Ac is the cross sectional area of the tube and Lw is the length of the liquid
dL
dL
column. Since w =
, we have
dt
dt
A,L dL
M A dt
cD AB
1
ln
L
1 y A0
K dt =
0
K=
t=
20
10
cDAB M A
A, L
LdL where
ln
1
1
(0.22)(18)
=
ln
= 5.149106 cm2/s
1 y A0 (82.06)(298) 1 0.0313
1
(202 102) = 2.91107 s = 8093 hr
2K
102
L2
td =
=
= 227 s.
2(.22)
2 DAB
At the end of this time the diffusion path can be determine from
227 =
1
(L2 102) => L = (100 + 2275.149106)0.5 = 10.0001 cm
2K
The pseudosteady state assumption is valid since the diffusion path changes very little
during the average time the water molecule travel from the water interface to the top of the
tube.
dC
dx
(1.31)
where S is the surface area normal to the direction of diffusion and D is the bulk solute
diffusivity. For a variety of solutes in dilute aqueous solution at 37oC, the following
correlation can be used to estimate the solute diffusivity from its molecular weight
(1.32)
114
where u A is the instantaneous velocity of the sphere of mass m, u A is the Stokess law drag
force, u A = 6a u A , and F(t) is the random fluctuating force due to the collisions between
the solutes and the solvent molecules. Solving the Langevin stochastic differential equation,
Einstein in 1906 arrived at the following expression for the diffusivity of solutes in dilute
solution
D=
RT
T
=
6 rA N A
6 rA
(1.33)
In this equation, R is the ideal gas constant (8.314 J/moloK), T is the absolute temperature in
o
K, NA is Avogadros number (6.0231023 molecules/mol), is the Boltzmann constant
(1.381016 erg/K), and is the solvent viscosity (g/cmsec). The viscosity of water at 37oC is
0.76cP. Equation (1.33) may be used to estimate the radius, rA, of the solute if its diffusivity
is known. If the diffusivity of the solute is not known, its radius might be estimated from the
molecular weight by the expression
3MW
rA =
4N A
1/ 3
(1.34)
This equation assume that the solute is a solid sphere with density 1 g/cm3.
MW
4
= r A 3
NA
3
Wilke and Chang1have proposed the following correlation to estimate the diffusivity of
nonelectrolytes in an infinitely dilute solution:
0
DAB
7.4 108 ( B M B )1/ 2
=
T
VbA0.6
(1.35)
0
In this equation, DAB
[cm2/s] is the diffusivity of A in very dilute solution in solvent B, MB is
molecular weight of solvent B, T [K] is temperature, [cP] is viscosity of solvent, VbA
[cm3/mol] is solute molar volume at its normal boiling point (for water as solute, VbA = 75.6
cm3/mol), and B is the association factor of solvent B:
B =
1.5 for ethanol as solvent
115
(1.36)
Hayduk and Minhas2 proposed correlations for diffusivity of solutes in infinite dilute solution
depending on the type of solutesolvent system. For solutes in aqueous solutions:
0
DAB
= 1.25108( VbA0.19 0.292)T1.52
(1.37)
9.58
1.12
VbA
0
In this equation, DAB
[cm2/s] is the diffusivity of A in very dilute solution in solvent B, T [K]
is temperature, [cP] is viscosity of solvent, and VbA [cm3/mol] is solute molar volume at its
normal boiling point. For nonaqueous or nonelectrolyte solutions:
0.27
0
AB
= 1.5510
8 VbB
VbA0.42
T 1.29 B0.125
0.92 A0.105
(1.38)
(1.39)
T ln ( Pc /1.013)
Tb
c = 0.9076 1 br
, where Tbr =
1 Tbr
Tc
In this equation, Tc [K] and Pc [bar] are critical temperature and pressure, respectively. The
restrictions for correlation (1.38) are:

Hayduk, W., and B.S. Minhas, Can. J. Chem. Eng., 60, 295 (1982)
116
Example 1.313 Estimate the diffusivity of ethanol (C2H6O) in a dilute solution of water at 288 K using both
WilkeChang equation and HaydukMinhas correlation
Data: Critical volume of ethanol, Vc = 167.1 cm3/mol; viscosity of water at 288 K, = 1.153
cP.
The experimental value for the diffusivity of ethanol in a dilute solution of water at 288 K is
1.0105 cm2/s. The error of the estimate is 0.2% which is not typical.
(b) HaydukMinhas correlation
=
9.58
9.58
1.12 =
1.12 = 0.963
VbA
60.9
0
DAB
= 1.25108( VbA0.19 0.292)T1.52
0
DAB
= 1.25108(60.90.19 0.292)(288)1.52(1.153)0.963 = 0.991105 cm2/s
Example 1.324 Estimate the diffusivity of acetic acid (C2H4O2) in a dilute solution of acetone at 313 K using
both WilkeChang equation and HaydukMinhas correlation using the following data:
Tb, K
Acetic acid 390.4
Acetone
329.2
3
4
T c, K
594.8
508.0
Pc, bar
57.9
47.0
Vc, cm3/mol
171.0
209.0
, cP
0.264
Benitez, J. Principle and Modern Applications of Mass Transfer Operations, Wiley, 2009, p. 26
Benitez, J. Principle and Modern Applications of Mass Transfer Operations, Wiley, 2009, p. 27
117
M
60
58
The experimental value for diffusivity of acetic acid in in a dilute solution of acetone at 313
K is 4.04105 cm2/s. The error of the estimate is 38.5%.
(b) HaydukMinhas correlation for nonaqueous solution
1 Tbr
Tb 329.2
=
= 0.648 c = 7.319 B = 20.0 dyn/cm
Tc
508
Tb 390.4
=
= 0.656 c = 7.91 A = 26.2 dyn/cm
Tc 594.8
For solvent other than water, methanol, or butanol, the organic acid solute should be
considered a dimer with twice the expected value of VbA. Therefore
VbA = 262.4 = 124.8 cm3/mol
For acetone:
VbB = 0.285 VC1.048 = 0.285(209)1.048 = 77.0 cm3/mol
0
DAB
= 1.55108
118
0
AB
8
770.27
= 1.5510
0.42
124.8
3131.29
0.92
0.264
200.125
= 3.84105 cm2/s
0.105
26.2
Example 1.33 A water droplet having a diameter of 0.10 mm is suspended in still air at 50oC, 1.0132105
Pa (1 atm), and 20% relative humidity. The droplet temperature can be assumed to be at 50oC
and its vapor pressure at 50oC is 7.38 kPa.
1) Calculate the initial rate of evaporation of water if DAB of water vapor in air is 0.288
cm2/s.
2) Determine the time for the water droplet to evaporate completely.
Solution T
yd,w d
Tg
Bulk gas phase
yg,w
Droplet surface
The molar flux of water vapor (A) into the air (B) is
NA,r = cDAB
dy A
+ yA(NA,r + NB,r)
dr
In this equation, r is the radial distance from the center of the drop. For still air NB,r = 0, we
have
NA,r =
cDAB dy A
1 y A dr
The system is not at steady state, the molar flux is not independent of r since the area of mass
transfer 4r2 is not a constant. Using quasi steady state assumption, the mass (mole) transfer
rate, 4r2NA,r, is assumed to be independent of r at any instant of time.
WA = 4r2NA,r = 4r2
cDAB dy A
= constant
1 y A dr
WA
y g , w dy
dr
A
= 4 cDAB
2
y
d ,w 1 y
r
A
119
1 y g ,w
1 y g ,w
WA
= 4 cDAB ln
WA = 4RcDAB ln
1 yd , w
1 yd , w
R
This equation provides the moles of water evaporated from the droplet when the radius of the
drop is R.
1) Calculate the initial rate of evaporation of water if DAB of water vapor in air is 0.288
cm2/s.
The initial rate of evaporation occurs when the diameter of the drop is 0.10 mm.
3 atm
82.057 cm .
mol. K
Rg
.005 cm
1 atm
( 50
273 ) K
c = 3.773 10
R g. T
PA
D AB
.288
cm
Mw
cm
7.38
101.32
atm
PA
y dw
WA
mol
4 . . R. c . D AB. ln
y dw = 0.073
y gw
y gw
y dw
.2 .
PA
y gw = 0.015
W A = 4.161 10
3
R A = 4MwRcDAB ln
1 yd , w
dt 3
1 y g ,w
dR
= 4MwRcDAB ln
1 yd , w
dt
D AB
ln
1 y g ,w
1 yd , w
dt = Kdt
120
mol
8
7
4.161 . 10 . 18 = 7.49 10
4AR2
g
s
18
g
mol
D AB
1 y g ,w
ln
RdR = K dt => t =
0
Ri
Ri2
2K
y dw
.0728
D AB.ln
y gw
1
y gw
y dw
.0146
D AB
.288
cm
s
= 0.0175
cm
s
t=
D AB
ln
1 y g ,w
1 yd , w
Ri2
= 0.0052/(21.207105) = 1.04 s
2K
d = 0.21c
f = 0.13d
Fournier, R. L., Basic Transport Phenomena in Biomedical Engineering, Taylor & Francis, 2007, p. 22.
121
We have 6 equations to solve for 6 unknowns a, b, c, d, e, and f. We can reduce the number
of equations to 3 by substituting a = 0.2b, d = 0.21 c, and f = 0.13d to solve for three
unknowns b, c, and e. The three equations are:
6 = b + 2c + 3(0.21c) + e
b + 2.63c + e = 6
1.14b + 7.7346c = 12
6 = 0.45b + c + 3(0.21c) + 2e + 0.130.21c
0.45b + 1.6573c + 2e = 6
The above three equations can be solved using the following Matlab statements:
2.6300
7.7346
1.6573
1.0000
0
2.0000
>> b=[6;12;6]
b=
6
12
6
>> x=A\b
x=
0.4029
1.4921
1.6729
Therefore b = 0.4029, c = 1.4921, e = 1.6729, a = 0.2b = 0.0806, d = 0.21c = 0.3133, and f =
0.13d = 0.0407. The balanced equation for the anaerobic fermentation of glucose by yeast
can then be written as:
C6H12O6 + aNH3 b CH1.74N0.2O0.45 + c C2H5OH + d C3H8O3 + e CO2 + f H2O
C6H12O6 + 0.0806 NH3 0.4029 CH1.74N0.2O0.45 + 1.4921 C2H5OH
+ 0.3133 C3H8O3 + 1.6729 CO2 + 0.0407 H2O
122