2 Prediction of Diffusivities PDF

PREDICTION OF DIFFUSIVITIES
1) Diffusion in gases
Diffusivities are best determined by experimental
measurements.
The diffusivity of some common gases diffusing in
air at 0C and 1 atm (can be obtained from the text
book (McCabe, Smith and Harriott, Appendix 19).
The value of diffusivities can also be predicted using
various empirical equations.
EKC 217: Mass Transfer - Prediction of Diffusivities
The equations developed by Chen and Othmer is:

0.5
1
1
0.01498 T
MA MB
P(TcATcB ) 0.1405(VcA0.4 VcB0.4 ) 2

1.81
DAB
------ (1.50)
where:
DAB = Diffusivity (cm2/s)

T
= Temperature (K)
MA, Mb
= Molecular weights of component A & B
TcA, TcB
VcA, VcB
respectively
= Critical temperatures of A & B respectively (K)
= Critical molar volumes of A & B respectively
(cm3/gmol)
= Pressure (atm)
Another rigorous equation called Chapman-Enskog equation is

used to predict diffusivities:
DAB
0.001858 T
2
P AB
D
1.5
where:
DAB
T
MA, MB
P
AB
D
k
MA MB
M AM B
0.5
------ (1.51)
= Diffusivity (cm2/s)
= Temperature (K)
= Molecular weights of component A & respectively
= Pressure (atm)
= average collision diameter
= collision integral based on the Lennard-Jones potential
= f (kT/AB )
= Boltzmanns constant
= Lennard-Jones force constant for common gases
AB A B
The collision integral, D decreases with increasing T, that makes

DAB increase with more than the 1.5 power of the absolute T.
For diffusion in air at T = 300 1000 K, DAB varies with about T 1.71.8, and T 1.75 can be used to extrapolate from room temperature
data.
Therefore, we can say that:
DAB T 1.75 x 1/P
Hence, the diffusivity at T2 and P2 relative to the standard

temperature and pressure (STP) can be calculated as follows:
1.75
DAB , 2
PSTP T2
DAB , STP
P2 TSTP
------ (1.52)
Eq. (1.51) is relatively complicated to use, and often some of the

constants such as AB are not available of difficult to estimate.
Hence, semi empirical method by Fuller et al. is often preferred:
DAB
1.00 x 10 7 T 1.75 (1 / M A 1 / M B ) 0.5
P A
1/ 3
1/ 3 2
------ (1.53)
where: A = sum of structural volume increments

Eq. (1.53) was obtained by correlating many recent data and uses
atomic values from Table 6.2-2. This method can be used for
mixtures of nonpolar gases or for a polar-nonpolar mixture.
Example 5:
Predict the volumetric diffusivity for benzene in air at 100C and 2
atm by using the rigorous equation (1.51) and by extrapolating from
the published value for 0C and 1 atm.
Solution:
From Appendix 19 (McCabe, Smith and Harriott), the force
constants are as follows:
/k
Benzene
412.3
5.349
78.1
Air
78.6
3.711
29
Thus,
AB
5.349 3.711
4.53
2
AB / k 412.3 x 78.6 180

kT
AB
373
2.072
180
From Appendix 19, D = 1.062.

Substitute values into Eq. (1.51) gives:
DAB
78.1 29
0.001858 x 3731.5
78.1 x 29
2 x 4.532 x 1.062
0.5
0.0668 cm 2 /s
From Appendix 18 at standard temperature and pressure,

DAB 0.299 ft 2 /h 0.0772 cm 2 /s
At 373 K and 2 atm,

1.75
1 373
DAB 0.0772
2 273
0.0666 cm 2 /s
Therefore, agreement with the value calculated from Eq. (1.51)

is very good.
Example 6:
In an oxygen-nitrogen gas mixture at 1 std atm, 25C, the
concentration of oxygen at two planes 2 mm apart are 10 and
20 vol %, respectively. Calculate the flux of diffusion of the
oxygen for the case where:
a) The nitrogen is non-diffusing

b) There is equimolecular counterdiffusion of the two gases.
DO2-N2 at 0C and standard atmospheric pressure

= 1.81 x 10-5 m2/s
10
Solution:
Given:
PT = 1 atm = 1.0133 x 105 N/m2

T = 25C = 298 K
DO2-N2 = 1.81 x 10-5 m2/s (0 C , 1 atm)
Diffusivity of O2-N2 mixture at 25C , 1
atm:
A+B
A
NB = 0
pA1
= 0.2PT
pA2
= 0.1PT
2 mm
1.5
298
DO 2 N 2, 298K 1.81 x 10 x
273
2.06 x 10-5 m 2 /s
5
Component A = O2
Component B = N2
11
pA1 = 0.2 PT
pA2 = 0.1 PT
Then, pB1 = PT 0.2PT = 0.8PT
pB2 = PT 0.1PT = 0.9PT
a) For the case where nitrogen is non-diffusing, Eq. (1.37) is used:
DAB PT
NA
( p A1 p A2 )
RT ( z2 z1 ) pBM
and
pBM
pB 2 pB1
ln( pB 2 / pB1 )
Calculate pBM :
pBM
(0.9 0.8) PT
0.849 PT
ln(0.9 PT / 0.8PT )
12
PT
PT
1.178
pBM 0.849 PT
Substitute the known values into Eq. (1.37):
N O2
DAB PT
( p A1 p A2 )
RT ( z2 z1 ) pBM
2
m
2.06 x 10-5
1.178
5 N
s
0.2 0.1 x 1.0133 x 10

2
Nm
m
(8314
)(298 K)(0.002m)
kmole K
-5 kmole
4.95 x 10
m2 s
13
b) When there is equimolecular counter diffusion of the two gases,

the following equations are applied:
DAB p A1 p A2
JA
RT ( z2 z1 )
DAB pB1 pB 2
JB
RT ( z2 z1 )
Substitute the known values:

2
m
5
5 N
0.2 0.1 x 1.0133 x 10 2
2.06 x 10
s
m
J O2
Nm
8314
(298 K )(2 x 10 3 m)
kmole K
-5 kmole O 2
4.21 x 10
m2 s
14
For nitrogen:
2
m
N
5
2.06 x 10
0.8 0.9 x 1.0133 x 105
s
m
J N2
Nm
8314
(298 K)(2 x 10 3 m)
kmole K
- 4.21 x 10-5 kmole N 2 /m 2 s
15
Exercise: Estimation of Diffusivity of a Gas Mixture

Normal butanol (A) is diffusing through air (B) at 1 atm abs. Using
the Fuller et al. method, estimate the diffusivity DAB for the
following temperatures and compare with the experimental data:
a) For 0C
b) For 25.9C
c) For 0C and 2 atm abs.
Ans:
a) Deviation of +10% from the experimental value (in Table 6.2-1).
b) Deviation of +4% from the experimental value.
c) DAB = 3.865 x 10-6 m2/s
16
2) Diffusion in Small Pores

The diffusion process is called Knudsen diffusion.
Occurs when the pore size is much smaller than the normal mean free
path during gas diffusion in very small pores of a solid, for processes
like adsorption, drying of porous solids or membrane separation.
The diffusivity for a cylindrical pore is:
DK 9700r
where:
T
M
------ (1.54)
DK = Knudsen diffusivity, cm2/s

T = temperature, K
M = molecular weight
r = pore radius, cm
Diffusivity in the pore:

1
1
1
D pore DAB DK
17
------ (1.55)
3) Diffusion in Liquids
A widely used correlation for liquid diffusivity of small molecules,
called Wilke-Chang equation:
DAB 1.173 x 10
where:
DAB
T
B
VA
MB
0.5
(
M
)
T
16
B
------ (1.56)
B V A
0.6
= diffusivity, m2/s
= absolute temperature, K
= viscosity of B in Pa.s
= molar volume of solute as liquid at its normal
boiling point, m3/kgmole (taken from Table 6.3-2)
= association parameter of the solvent
= molecular weight of solvent B (kg/kgmole)
18
Recommended values for :
Water
2.6
Methanol
Ethanol
1.9
1.5
Benzene, heptane and other unassociated solvents
1.0
Eq. (1.56) is valid only at low solute concentrations and does not
apply when the solution has been thickened by addition of highmolecular-weight polymers.
19
20
For water as solute, VA = 0.0756 m3/kgmole.

If other compound is the solute, e.g.: acetone (CH3COCH3) in
water, the value of VA can be calculated by considering the atomic
volumes as given in Table 6.3.2 Atomic and Molar Volumes at the
Normal Boiling Point.
Acetone (CH3COCH3) has 3 carbons, 6 hydrogens and 1 oxygen.
Therefore,
VA = 3(14.8 x 10-3) + 6(3.7 x 10-3) + 1(7.4 x 10-3)

= 0.0740 m3/kgmole
21
22
Example 7:
Predict the diffusion coefficient of acetone (CH3COCH3) in water at
25C and 50C using the Wilke-Chang equation. The experimental
value is 1.28 x 10-9 m2/s at 25C (298 K).
Solution:
From Appendix 9 (McCabe and Thiele textbook), the viscosity of
water at 25C is 0.90x 10-3 Pa.s and at 50C, 0.55 x 10-3 Pa.s. From
Table 6.3-2, for CH3COCH3 with 3 carbons + 6 hydrogens + 1
oxygen,
VA = 3(0.0148) + 6(0.0037) + 1(0.0074) = 0.074 m3/kgmole

23
For water, the association parameter () is 2.6 and MB = 18.02 kg

mass/kgmole.
For 25C, T = 298 K, substituting known values into Eq. (1.56):
DAB 1.173 x 10
0.5
(
M
)
T
16
B
B V A
0.6
(1.173 x 10-16 )(2.6 x 18.02)1/2 (298)
(0.9 x 10-3 )(0.0740) 0.6

1.277 x 10-9 m 2 /s
24
For 50C, T = 323 K:
DAB 1.173 x 10
0.5
(
M
)
T
16
B
B V A
0.6
(1.173 x 10-16 )(2.6 x 18.02)1/2 (323)
(0.55 x 10-3 )(0.0740)0.6

2.25 x 10-9 m 2 /s
Therefore, the predicted diffusivity is very close to the experimental
value.
25
Schmidt number
26
The ratio of the kinematic viscosity to the molecular diffusivity is

known as Schmidt number, Sc.
Sc
------ (1.57)
Similar to Prandtl number:
Pr
cp
------ (1.58)
Sc for gases in air at 0C and 1 atm is given in Appendix 18, range

from 0.5 2.0.
Sc for liquids range from 102 to 105 for typical mixtures.

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PREDICTION OF DIFFUSIVITIES

EKC 217: Mass Transfer - Prediction of Diffusivities

The equations developed by Chen and Othmer is:

P(TcATcB ) 0.1405(VcA0.4 VcB0.4 ) 2

DAB = Diffusivity (cm2/s)

EKC 217: Mass Transfer - Prediction of Diffusivities

Another rigorous equation called Chapman-Enskog equation is

The collision integral, D decreases with increasing T, that makes

DAB T 1.75 x 1/P

Hence, the diffusivity at T2 and P2 relative to the standard

EKC 217: Mass Transfer - Prediction of Diffusivities

Eq. (1.51) is relatively complicated to use, and often some of the

1.00 x 10 7 T 1.75 (1 / M A 1 / M B ) 0.5

where: A = sum of structural volume increments

EKC 217: Mass Transfer - Prediction of Diffusivities

EKC 217: Mass Transfer - Prediction of Diffusivities

EKC 217: Mass Transfer - Prediction of Diffusivities

AB / k 412.3 x 78.6 180

From Appendix 19, D = 1.062.

EKC 217: Mass Transfer - Prediction of Diffusivities

From Appendix 18 at standard temperature and pressure,

At 373 K and 2 atm,

Therefore, agreement with the value calculated from Eq. (1.51)

EKC 217: Mass Transfer - Prediction of Diffusivities

a) The nitrogen is non-diffusing

DO2-N2 at 0C and standard atmospheric pressure

EKC 217: Mass Transfer - Prediction of Diffusivities

PT = 1 atm = 1.0133 x 105 N/m2

EKC 217: Mass Transfer - Prediction of Diffusivities

EKC 217: Mass Transfer - Prediction of Diffusivities

Substitute the known values into Eq. (1.37):

0.2 0.1 x 1.0133 x 10

EKC 217: Mass Transfer - Prediction of Diffusivities

b) When there is equimolecular counter diffusion of the two gases,

Substitute the known values:

EKC 217: Mass Transfer - Prediction of Diffusivities

Exercise: Estimation of Diffusivity of a Gas Mixture

EKC 217: Mass Transfer - Prediction of Diffusivities

2) Diffusion in Small Pores

DK = Knudsen diffusivity, cm2/s

Diffusivity in the pore:

EKC 217: Mass Transfer - Prediction of Diffusivities

Recommended values for :

Benzene, heptane and other unassociated solvents

EKC 217: Mass Transfer - Prediction of Diffusivities

EKC 217: Mass Transfer - Prediction of Diffusivities

For water as solute, VA = 0.0756 m3/kgmole.

VA = 3(14.8 x 10-3) + 6(3.7 x 10-3) + 1(7.4 x 10-3)

EKC 217: Mass Transfer - Prediction of Diffusivities

VA = 3(0.0148) + 6(0.0037) + 1(0.0074) = 0.074 m3/kgmole

For water, the association parameter () is 2.6 and MB = 18.02 kg

(1.173 x 10-16 )(2.6 x 18.02)1/2 (298)

(0.9 x 10-3 )(0.0740) 0.6

EKC 217: Mass Transfer - Prediction of Diffusivities

For 50C, T = 323 K:

(1.173 x 10-16 )(2.6 x 18.02)1/2 (323)

(0.55 x 10-3 )(0.0740)0.6

EKC 217: Mass Transfer - Prediction of Diffusivities

The ratio of the kinematic viscosity to the molecular diffusivity is