Diffusion of some Hydrocarbons in Air: a Regularity in the Diffusion

Coefficients of a Homologous Series1

ROBERT
W. ELLIOTT~
AND HARRY
WATTS
Research Department, Dorv Chemical of Canada, Limited, Sarnia, Ontario
Received March 17, 1971

Diffusion coefficients in air at 298.2 "K and I atm pressure are reported for ethane, ethene, ethyne, cyclo-
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propane, propene, propadiene, propyne, butane, I-butene, 2-methylpropene, cis-2-butene, trans-2-butene,

1,3-butadiene, I-butyne, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, and 1-pentene.
A linear relationship, valid for alkanes and alkenes, has been found between the diffusion coefficient and
the reduced molecular weight of the members of a homologous series and air.
Diffusion coefficients calculated by ten prediction equations were generally lower than those observed.

Les coefficients de diffusion dans l'air a 298.2 "K et sous une pression de une atmosphere sont rapportes
pour l'ethane, Pethene, l'ethyne, le cyclopropane, le propkne, le propadiene, le propyne, le butane, le butene-I,
le methyl-2 propene, le butkne-2 cis, le butine-2 trans, le butadiine-1,3, le butyne-I, le methyl-2 butane, le
dimethyl-2,2 propane, le cyclopentane et le pentine-I.
Une relation lineaire, valable pour les alcanes et les alcenes, existe entre le coefficient de diffusion et la
masse mol6culaire reduite des membres d'une sirie homologue et l'air.
Les coefficients de diffusion, calculCs a partir de dix equations de prediction, sont generalement plus bas
que ceux observes.
Canadian Journal of Chemistry, 50,31(1972)
For personal use only.

Introduction molecular forces, and those aimed at obtaining

Measurements of gaseous diffusion coeffi-
cients are of great value for both theoretical and
practical reasons. The detailed kinetic theory of
gases relates the diffusion coefficient in a binary
mixture to the intermolecular forces acting
between the diffusing species (1). In principle, it
is possible to calculate a diffusion coefficient
from intermolecular forces. However, knowl-
edge of intermolecular forces is far from com-
plete; hence data necessary for this calculation
must be obtained from measurements of some
other property, such as viscosity, which can also
be related to intermolecular forces. Alternately,
data on diffusion coefficients may be used to give
information on intermolecular forces (2). The
practical need in engineering design for reason-
able values of diffusion coefficients has produced
a rash of semi-empirical prediction equations.
Most of these are soundly based on theory, but
have been forced to empiricism because of our
incomplete knowledge of intermolecular forces.
Dichotomy of interest has divided diffusion
coefficient measurements into two groups, those
aimed at gaining greater understanding of inter-
'Contribution No. 190.
'Present address: The International Nickel Company of
Canada Limited, J. Roy Gordon Research Laboratory,
Sheridan Park, Clarkson, Ontario.
data on systems of practical importance. Most
studies of gaseous diffusion have been frag-
mentary and few systematic investigations of
related systems have been made. Recent notable
exceptions have been the investigations of noble
gas mixtures by Van Heijningen, Harpe, and
Beenakker (2) and the diffusion of 147 com-
pounds in air by Lugg (3).
In this paper we report the results of a
systematic investigation of the diffusion of some
hydrocarbons in air. These results have revealed
a regularity in the diffusion coefficients of a
homologous series that has apparently not been
previously observed.
Experimental
The apparatus and experimental techniques have been
described previously (4, 5). All data were corrected to
I atm pressure and 25 "C as before. In an attempt to refine
techniques two possible sources of experimental error were
investigated. Previously it had been considered that the
effect of small atmospheric pressure fluctuations would be
negligible from the point of view of their effect upon the
magnitude of the diffusion coefficient. However, if the
atmospheric pressure fell steadily during an experiment the
rate of loss of diffusing gas from the cell would be enhanced,
due to expansion of the cell contents, and if it rose steadily
during an experiment the rate of loss would be lowered, due
to contraction of the cell contents. If this effect were sig-
nificant, then experiments performed with a steady pressure
 CANADIAN JOURNAL OF CHEMISTRY. VOL. 50, 1972

TABLE1. Diffusion coefficients a t 298.2 "K

Infrared Diffusion coefficients in cm2 s-'

frequency No. of
Compound (cm-I) data Experimental Calculated
Ethane
Ethene
Ethyne
Cyclopropane
Propene
Propadiene
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Propyne
Butane
1-Butene
2-Methylpropene
cis-2-Bu tene
trans-2-Butene
1,3-Butadiene
I-Butyne
2-Methylbutane
2,2-Dimethylpropane
Cyclopentane
1-Pentene

drop would give diffusion coefficients showing positive cients of the alkenes, ethene, propene, 1-butene,
deviations from the mean of a set and those performed with and 1-pentene, are all higher-than those for the
For personal use only.

a steady pressure increase would show negative deviations.

Statistical analysis of experiments in which these conditions
obtained showed no such systematic trend in the diffusion
coefficients. We therefore conclude that any effect of small
systematic atmospheric pressure changes during an experi-
ment is negligible.
The frequencies of the i.r. absorption bands used to follow
concentration changes in the diffusion cell lay near the OH
stretching vibration frequency of water, consequently
changes in atmospheric humidity during an experiment
might effect the results due to changes in atmospheric
absorbance in the reference beam of the i.r. spectrophotom-
eter used to follow concentration changes in the cell.
Consequently the relative humidity of the room was mea-
sured during experiments. Analysis of results showed no
trend in diffusion coefficient with humidity.
Materials
The compounds studied were pure grade (99 mol% or
better) and were obtained from the following sources:
ethane, propene, n-butane, 2-methylpropene, 1-butene, cis-
2-butene, trans-2-butene, 1,3-butadiene, 2-methylbutane,
1-pentene, and cyclopentane (95 m o l x ) , Phillips Petroleum
Company; ethyne, cyclopropane, propadiene, propyne,
1-butyne, and 2,2-dimethylpropane, Matheson of Canada,
Ltd.; ethylene, Imperial Oil, Limited.
Results and Discussion
Table 1 gives the mean observed diffusion
coefficients in air of the c o m ~ o u n d sstudied
together with their root-mean-square deviations,
the number of data obtained, and the i.r. fre-
quency used to follow concentration changes of
the diffusing gas. Inspection of the data reveals
some systematic trends. The diffusion coeffi-
corresponding alkanes. Propane and n-pentane
were determined previously (5) and have the
values 0.1 144 f 0.0015 and 0.0856 f 0.0035 cm2
s-', respectively. Propadiene and 1,3-butadiene
have higher diffusion coefficients than the cor-
responding alkenes. The values for cyclopropane
and cyclopentane are both higher than the re-
spective straight chain alkanes quoted above.
Lugg (3) reported that the diffusion coefficients
of chain isomers of many substituted alkanes
was in the order iso > n. This order is observed
with pentane but not with butane. Beatty (6)
observed that the binary diffusion coefficient
for the system 2,2-dimethylpropane-pentane
was higher than the self diffusion coefficient of
pentank; consistent with this we find the dif-
fusion coefficients in air to be ordered 2,2-
dimethylpropane > pentane. We also note a
significant difference between the cis and trans
isomers of 2-butene.
Diffusion coefficients were calculated from
the detailed kinetic theory equation (1) as in
previous work (4, 7) and from nine other pre-
diction equations using modified versions of the
computer programmes of Jarvis and Lugg (8).
The equations used are named in order of de-
creasing accuracy of their predictions, together
with the root-mean-square deviations in cm2 s-'
of the predicted from our experimental results:
Wilke-Lee (9), f0.0087; Slattery-Bird (lo),
 I ELLIOTT AND WATTS: DIFFUSION OF SOME HYDROCARBONS IN A I R
I 33
I f0.0092; the kinetic theory equation (I),
I
f 0.0105; Chen-Othmer (1 1), f0.0106; Fuller,
Schettler, and Giddings (l2), f0.0122; Hirsch-
felder, Bird, and Spotz (l3), f0.0141; Othmer-
Chen (l4), f 0.0147; Andrussow (15), f 0.0202;
Gilliland (16), f0.0220; and Arnold (17),
k0.0414. In general, all of these equations pre-
dicted diffusion coefficients lower than the
experimental values, and none was completely
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successful in arranging the diffusion coefficients

of isomers in the correct order. Indeed the
equations of Gilliland (16), Andrussow (1 5), and
Fuller, Schettler, and Giddings (12) are unable
to distinguish between isomers at all!
If good data for its use were available, the
kinetic theory equation should be superior to
the other equations because of its sound theoret-
ical basis. In our calculations we used tabulated
values of the Lennard-Jones potential param-
eters for the hydrocarbons obtained from
I viscosity measurements (I), where available;
where these data were not available they were
REDUCED MOL W T

I FIG. 1. Linear plots of diffusion coefficient in air at

For personal use only.

estimated from critical properties listed by
Kudchadkar, Alani, and Zwolinski (1 8) by the
method of Stiel and Thodos (19). Where critical
properties were not available they were esti-
mated by standard methods (19). Potential
/ parameters for the mixture were calculated
from those for the pure components as before
(7) using the Hudson-McCoubrey combining
rules (20) and ionization potentials as follows:
,I ethane, ethene, ethyne, propene, propadiene,
propyne, 1-butene, 1,3-butadiene, and 1-butyne
from Herzberg (21), butane, 2-methylpropene,
cis-2-butene, trans-2-butene from Bernecker and
Long (22), 2-methylbutane, 2,2-dimethylpro-
pane, and cyclopentane from Lorquet (23),
cyclopropane from Cermak (24), and 1-pentene
from Honig (25). It is probably this estimation
of data that causes the kinetic theory equal ion
to be slightly inferior to the Wilke-Lee and
Slattery-Bird equations for the present systems.
In Fig. 1 are plotted the observed diffusion
coefficients against the reduced molecular weight
of each system, defined by
I
where M A is the mean molecular weight of air
I
and M H is the molecular weight of the hydro-
carbon. Data for the n-alkanes and n-alkenes
25 "C against reduced molecular weight for the diffusion of
n-alkanes, Q ; n-alkenes, H ; and n-alkynes, A.The inter-
section of lines for alkanes and alkenes is marked +.
gave good straight lines. A least square fit to the
equation :
gave values for the slope m, intercept c, intercept
on the p axis, correlation coefficients, and
standard deviations of experimental value of 9
from the fitted line listed in Table 2. The
probability of obtaining these values of the cor-
relation coefficients by chance alone is less than
0.01, indicating that the data are well represented
by a linear relationship (26). To increase the
number of data used in this calculation we
included our previous values for methane (4)
and propane (5) and Lugg's values for hexane
and octane (3).
The intercepts of these lines on the reduced
molecular weight axis are very close to the mean
molecular weight of air, 28.967. This is con-
sistent with the limit of p + M A as M H+ a,
and the expectation that 9 + 0 as M H+ co.
Figure 1 shows that the lines for the n-alkanes
and n-alkenes intersect close to the point for
methane. This would imply that, as far as dif-
fusion is concerned, methane can be regarded
as the first member of the alkene series. No
 CANADIAN JOURNAL OF CHEMISTRY. VOL. 50, 1972

TABLE
2. Values for least squares fit to eq. 3

p axis Standard Correlation

Hydrocarbon m c intercept deviation coefficients
n-alkanes 0.3344 0.01206 27.73 0.0062 -0.9945
n-alkenes 0.3261 -0.01130 28.85 0.001 -0.9996

linear correlation was observed with the alkynes 2. R. J. J. VAN HEIJNINGEN, J. P. HARPE,and J. J. M.
but our data are insufficient to draw any con- BEENAKKER. Physica, 38, 1 (1968).
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 181.64.164.190 on 09/24/17

3. G. A. LUGG. Anal. Chem. 40, 1072 (1968).

clusion about the trend of diffusion coefficient
with reduced molecular weight in this series.
The kinetic theory equation can be written in
the form
where Tis the absolute temperature and Q(T*)
is a collision integral at a reduced temperature
of T* = kT/&,, and el, and a,, are molecular
interaction parameters characteristic of a 1-2
interaction; b is a constant, and k is the Boltz-
mann constant. The implications of eqs. 2 and 3
For personal use only.
4. M. C o w l ~ a n dH. WATTS. Can. J. Chem. 49,74 (1971).
5. R. F. BARRand H . WATTS. J. Chem. Eng. Data. In
press.
6. J. W. BEATTY. J. Chem. Phys. 51,4673 (1969).
7. H. WATTS. Can. J. Chem. 49,67 (1971).
8. M. W. JARVIS and G. A. LUGG. Report 318, Depart-
ment of Supply, Australian Defence Scientific Service,
Defence Standards Laboratories, Maribyrnong, Vic-
toria, Australia.
9. C. R. WILKEand C. Y. LEE. Ind. Eng. Chem. 47, 1253
(1955).
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(1962).

12. E. N. FULLER,P. D. SCHETTLER, and J. C. GIDDINGS.

are that aIz2Q(T*) varies in a systematic, but
not simple, way with reduced molecular weight
for a homologous series. The discovery of this
regularity in diffusion coefficients points to the
need for further experimental work on other
homologous series and to the need for further
theoretical work. Analysis of literature data,
now in progress, indicates that the linear
variation of diffusion coefficient with reduced
molecular weight is a general phenomenon for
other classes of compounds (27).
We suggest that our linear relationship may
be used for the empirical prediction of diffusion
coefficients and predict the following for 9 in
cm2 s - I : heptane, 0.0635; nonane, 0.0495; dec-
ane, 0.0442. We might expect that the value for
heptane in air would be reliable because it is an
interpolated value and it will be interesting to
see if future measurement bears out these
predictions.
1. J. 0. HIRSCHFELDER, C. F. CURTISS,and R. B. BIRD.
Molecular theory of gases and liquids. John Wiley and
Sons, Inc., New York. 1954.
Ind. Eng. Chem. 58, 19 (1966).
13. J. 0.HIRSCHFELDER, R. B. BIRD, and E. L. SPOTZ.
Trans. Am. Soc. Mech. Eng. 71,921 (1949).
14. D. F. OTHMERand H. T. CHEN. Ind. Chem. Eng.,
Prod. Res. Dev. 1,249 (1962).
15. L. ANDRUSSOW.Z. Elecktrochem. 54, 566 (1950).
16. E. R. GILLILAND.Ind. Eng. Chem. 26, 681 (1934).
17. J. H. ARNOLD. Ind. Eng. Chem. 22, 1091 (1930).
18. A. P. KUDCHADKER, G. H. ALANI,and B. J. ZWOLINSKI.
Chem. Rev. 68, 659 (1968).
19. R. C. REIDand T. K. SHERWOOD.The properties of
gases and liquids. 2nd ed. McGraw-Hill, New York.
1966.
20. G. H. HUDSON and J. D. MCCOUBREY.Trans. Faraday
SOC.56, 761 (1960).
21. G. HERZBERG.Molecular spectra and molecular struc-
ture, Vol. 111. Electronic spectra and electronic structure
of polyatomic molecules. Van Nostrand, Princeton,
New Jersey. 1966.
22. R. R. BERNECKER and F. A. LONG. J. Phys. Chem. 65,
1566 (1961).
23. J. C. LORQUET. Adv. Mass Spectrosc. 3, 443 (1966).
24. V. CERMAK.Coll. Czeck. Chem. Comm. 33, 2739
(1968).
25. R. E. HONIG. J. Chem. Phys. 16, 105 (1948).
26. W. VOLK. Applied statistics for engineers. McGraw-
Hill, New York, New York. 1958.
27. R. W. ELLIOTTand H . WATTS. Nature. In press.