Académique Documents
Professionnel Documents
Culture Documents
June 1955
K*
gn
===
e
jy
u =
u* =
uom =
Ap
1253
LITERATURE CITED
operations are advanced, increasing need arises for diffusion coefficients of gases and vapors. I n view of the scarcity of
reliable experimental data, methods of predicting such information assume a useful role. The general objective of this paper is
to review critically the existing methods for estimation of diffusivities. An effort has been made to establish therelativeaccuracy
of various procedures by comparison of calculated results with a
body of selected experimental data.
REVIEW OF PREVIOUS CORRELATIONS
As used in this paper, the diffusion coefficient is the proportionality constant in the rate equation for mass transfer in absence
of convection or other modes of transfer, defined as follows for
unidirectional diffusion:
R
T
x
temperature, K.
distance in direction of diffusion
ci
1.47T~,
(4)
1.47F(TB,TB,)~
(5)
1254
mm
Oo5
004
LINES O F CONSTANT
0 03
V A L U E S O F A F O R XI.O
A
002
001
0
002003 0 0 5
001
01
02 03
MOLECULAR
WEIGHT
05
RATIO,
IO
2 0 30
50
MI
M2
according to
The numerical constant, B , is equal t o 9.2916 X
theory.
The collision integral, W(I)(I),has been calculated by Hirschfelder, Bird, and Spotz as a function of k T / . Representative
values are listed in Table I.
should be evaluated according to their respective potential functions. The labor involved is formidable and as yet this has not
been accomplished.
The term A in Equation 6 is a correction factor, a small quantity usually less than 0.03, which varies with gas composition.
Detailed equations for A have been given (8, 9). A is a complicated function of mole fraction, molecular weights, viscosities,
the first approximation to the diffusion coefficient, and additional
functions of k T / e I 2 . However, these equations are so lengthy
that their use may not be justified for many engineering calculations, particularly when the force constants have been estimated.
As a first approximation to A for a given gas system it is suggested
that A values for mole fractions of each component equal to zero
be obtained and an average value calculated, assuming A t o be
linear in mole fraction. Values of A a t zero mole fraction are preRented in Figure 1. This procedure is not completely satisfactory, as A may deviate considerably from a linear function, but
it should accomplish a major part of the correction. This procedure was adopted in subsequent applications of Equation 6.
ESTIMATION OF FORCE CONSTANTS FOR SIMILAR
MOLECULES
Both ~ / and
k r , may be calculated from knowledge of gas viscosity a t two temperatures by solving the equation for viscosity
(9).
107 =
(9)
Table I.
kT/
v/w(2)(2
k T; / r )
w'')(l;k T / m )
0.3596
0.4432
0.5432
0.6301
0.7023
0.7613
0.8523
0.9172
0.9657
1.036
1.085
1.222
1.550
1.714
2.095
1.331
1.033
0.8335
0.7197
0.6479
0.6991
0.5373
0.4998
0.4745
0.4418
0.4211
0.3712
0.2878
0.2585
0.2085
12
dZ
(12)
and
1.92Tm
(10)
(11)
(8)
For collisions between a polar and a nonpolar molecule, modified forms of equations are suggested ( 1 4 ) . With these modifications Equation 6 applies t o systems containing a polar and a nonpolar component. However, the energy of interaction among
polar molecules, valence-unsaturated molecules, and cigarshaped molecules is very different from that between nonpolar
molecules. Before Equation 6 may be considered strictly applicable to systems containing such molecules, the collision integral
/IC = 0.75Tc
(13)
/ k = 1.21Tb
(14)
0.833V:'a
(15)
June 1955
Table 11.
System
Air-benzene
Air-ethyl alcohol
Air-ethyl ether
Air-diphenyl
Air-I2
Air-nitrobenzene
Air-n-heptadecane
Air-n-hexadecane
Air-n-octadecane
Air-n-octane
Air-mater
COz-ethyl alcohol
COa-ethyl ether
C0z-Hz
C 02- C H4
C02-Nz
COz-NZO
COz-CsHs
co2-I120
CO-CZHI
CO-Hi
CO-Nz
co-01
Freon 12-benzene
Freon 12-ethanol
Freon 12-mater
He-A
He-benzene
He-ethyl alcohol
He-Ne
He-nitrobenzene
He-Hz
He-HzO
H2-NHa
Hn-A
Hz-benzene
Ha-CClr
Hi-CzHa
Hz-ethyl alcohol
Hz-CZHI
Hg-ethyl ether
HI-HC1
H2-CHI
H2-h-i
Hz-h-20
Hz-02
Ha-CaHE
H2-SO2
HrHz0
h-2-NH1
Kz-CzHa
Nz-Hs
N2-I*
N2-NO
N2-02
NzO-CsHe
Os-NHz
02-benzene
Oz-CCh
02-C2H4
NHs-C1H4
A-Ne
CsHs-CzHe
CzHs-CHI
Temp., O K.
298
298
293
49 1
298
298
298
298
298
298
298
273
273
273.2
273.2
288
298
298
297.7
273
273
288
273
298
298
298
273.2
298
298
293
298
293
298
293
293.2
273
296
273
340
293
293
294
273 2
293
273 2
273 2
300
273
293
293
300
288
273
293
273
298
293
296
298
293
293
293
293
293
Exptl. Diffusion
Coefficient Sq
Cm./Sec. (at i
Atm.)
0.0962
0.135
0.0896
0.160
0.0834
0.0868
0.423
0.0405
0.0397
0.0602
0.260
0.0693
0,0541
0,550
0.153
0.158
0.117
0.0863
0.164
0.151
0.622
0.211
0.185
0.0385
0,0475
0.105
0.641
0.384
0.494
1.23
0.372
1.64
0.908
0.849
0.770
0.317
0.345
0.439
0.578
0.483
0.354
0.795
0.626
1.205
0.535
0.697
0.450
0.483
0.850
0 241
0.187
0,743
0 070
0.232
0 181
0.086
0.253
0.0939
0.0731
0.182
0.177
0.329
0.085
0.163
Table 111.
1255
qp&f;"
Gas
T O , A. from Viscosity
3.617
97.0
2.624
315
3.418
124.0
5.270
440
3,996
190
COZ
3.590
110.3
co
CClr
327
5.881
230
4.418
CzHa
391
4.455
C2H30H
600
Diphenyl
6.223=
350b
5,424'"
Ethyl ether
205
4.232
CzHa
288 b
Freon 12
5,llOd
6.03
2.70
Helium
800
7.9235
n-Heptadecane
33.3
2.968
H2
HC1
360
3.305
550
4.982
Iodine
136.5
3.882
CHI
35.7
Neon
2.80
539 b
Nitrobenzene
4.931"
NO
119
3.47
91.5
3.681
N2
220
3.879
NzO
8200
n-Octadecane
7.963a
320
n-Octane
7.451
113.2
3.433
0 2
Propane
5.061
254
252
4,290
SO2
Water
363
2.655
356d
2.649e
All values obtained from viscosity are taken from Hirschfelder, Bird, and
Spotz ( a ) , unless otherwise noted. A mole complete table is presented b y
Hirschfelder, Curtiss, and Bird (IS).
Values estimated from diffusion data.
b Values estimated from T c .
C Values estimated from boiling temperature.
d (6). e ( 9 4 ) .
Air
Ammonia
Argon
Benzene
30
20
0
1.0
05
;
03
e 02
l-
io1
0
-I
DEVIATION
200 %
005
003
01
0 2 03 05
10
OBSERVED D, SQ C M / S E C
003005
Examination of data as in the case of e l k suggested an alternative method of estimation of ro based on molal volume a t the
normal boiling point, which may be expressed as:
ro = 1.18V1ia
(17)
20
30
1256
.v
2.0
v
cn 1.0
\
0.5
.0.3
rn
0
Q
0.2
0.2
0.1
0.1
0.3
0.4
0.5
0.7
0.6
0.8
09
a
0.05
Figure 5.
0.03
003 005 01
0.2 0.3 0.5
IO
OBSERVED D, SQ GM/SEC.
2 0 3.0
2,0c
H.B.S. M E T H O D
calculations with observed data. Average and maximum deviations between calculation and experiment are summarized in
Table IV for all methods.
It is of interest to compare the three methods with respect t o
the effect of temperature on the diffusion coefficient. The equation of Gilliland is theoretically at variance with the Arnold and
the Hirschfelder, Bird, and Spotz equations. The two latter
methods consider possible molecular interaction upon collision
and therefore in principle should give more satisfactory results.
This conclusion is borne out by the relatively meager experimental evidence available. Table V shows the temperature behavior
of the carbon dioxide-air system over a range of 293 to 1500' K.,
as observed by Kilbanova, Pomerantsev, and Frank-Kamenetskil
(16). Results calculated by each method, assuming the value a t
293' K. to be correct, are also given. The Arnold and the
Hirschfelder, Bird, and Spotz methods agree closely, probably
within the limits of experimental error, while the Gilliland equation gives low values a t higher temperatures.
O
DEVIATION = 7.0 %
0.1
0.2 0.3 0.5
1.0 2.0 3.0
OBSERVED 0, SQ. CM. / S E C .
0.030.05
Ay. %
Method
1 Gilliland
2 Arnold
3 Hirschfelder, Bird and Spotz,
e / k and r o from viscosity
4 T O from T c / p ? , (Eq. le), e l k
from viscosity
5 T O from V ( E a . 17),r / k from
viscosity
6 ro from V. (Eq. 151, a/k from
viscosity
7 TO from V (Eq. 17), e / k = 1.21
Equation
1
Tb (Eq. 14)
Deviation
Max. ,%
As a means of studying deviations of Equation 6 from experimental results, values of the constant B were computed for each
system given in Table I11 which would make the equation agree
with experiment. Force constants were based on viscosity.
Various attempts were made t o relate these values of B to properties of the systems. As shown in Figure 5 , there appears to be
some correlation of the constant with the molecular weight group
[Mhky2]
'".
Deviation
20.0
8.4
46.8
20.5
7.0
21.4
10.1
31.3
10.3
24.9
11.8
32.7
12.0
31.0
B = 10.7
- 2.46 ML;Mfz]
lI2
12
13
14
15
18
3.9
16.0
18
9.4
32.7
18
7.0
21.9
18
1o.a
37.6
1.8
5.4
26.0
Table V.
T,
K.
293
400
18
7.2
24.9
18
5.1
20.5
600
800
1000
1300
18
7.7
24.5
1500
0.555
0.915
1.32
1.97
2.45
0.543
0.905
1.28
1.97
2.49
0.523
0.883
1.28
1.97
2.52
0.448
0.690
0.970
1.42
1.77
..
June 1955
3 .O
1251
3.0
2.0
2.0
1.0
i
V
c; 0.5
v)
o-0.3
0
W
5i
-I
3
Ya
0.2
0.1
0.05
0.03
0.030.05 0.1
OBSERVED
D,
SQ. GM. / S E C
1.0
SQ.CM./SEC
OBSERVED D,
20 3.0
7 = viscosity, gram/cm.-sec.
Subscripts 1 and 2 denote components 1 and 2, respectively.
REFERENCES
DISCUSSION
dington, 1939.
(7) Gilliland, E. R., IND.
ENQ.CHEM.,26, 681 (1934).
(8) Hirschfelder, J. O., Bird, R. B., and Spota, E. L., Chem. Rev., 44,
205 (1949).
(9) Hirschfelder; J. O., Bird, R. E., and Spotz, E. L., J . Chem. Phys.,
16. 968 (1948).
,
(10) Hirsohfelder, J. O., Bird, R. E., and Spotz, E. L., Trans. Am.
SOC.Mech. Enors., 71, 921 (1949).
\ - - -
RECEIVED
for review June
1 , 1954.
ACCEPTED
December 4, 1954.