Advances in Environmental Research 8 (2004) 667678

Pseudo-binary molecular diffusion of vapors into air

K.C. Kwon*, T.H. Ibrahim, YoonKook Park, C.M. Simmons
Department of Chemical Engineering, 517 Engineering Building, University Avenue, Tuskegee University, Tuskegee, AL 36088,
USA
Accepted 4 April 2003

Abstract
A novel open-tube evaporation method was developed to determine the experimental diffusion coefficients of the
vapors of various liquids diffused into air. The mass losses of the volatile liquids chosen for this study were measured
with a balance rather than changes in the level of the liquid in a diffusion tube for various evaporation durations and
no fresh air was passed over the top end of the diffusion path by forced convection, as opposed to the conventional
open-tube evaporation method. A diffusion equation was developed which is suitable for the novel open-tube
evaporation method. The experimental diffusion coefficient values obtained from the novel experimental diffusion
methods were in reasonable agreement with the diffusion coefficient values predicted with both the Wilke-and-Lee
method and the Fuller et al. method. The experimental diffusion coefficients of n-heptane diffused into air are
independent of the lengths and the evaporation areas of the diffusion paths chosen for this study. The experimental
diffusion coefficients of normal alcohols and hydrocarbons in air decrease with increased number of carbon atoms in
their molecular formulas. The overall root mean squares of deviation of the diffusion values of this experimental
study from those predicted with the Wilke-and-Lee method and the Fuller et al. method are 5.8 and 6.0%, respectively.
2003 Elsevier Science Ltd. All rights reserved.
Keywords: Molecular diffusion coefficient; Diffusion equation; Open tube evaporation method; Students t distribution

1. Introduction
Molecular mass transfer of toxic gases and vapors of
industrial solvents into air is widely investigated to
study air pollution control and environmental emissions
of volatile vapors. Rates of absorption, adsorption,
drying, distillation and condensation occurring in various industrial processes within the chemical, petroleum
and gas industries are dependent on diffusion of processed gaseous chemicals (Berezhnoi and Semenov,
1997). The extensive use of the term diffusion in the
literature refers to the net transport of material within a
single phase in the absence of convective mixing. Binary
diffusion coefficients are dependent on temperature,
pressure and the nature of the binary components. Both
experiment and theory have shown that the driving
*Corresponding author. Tel.: q1-334-727-8976; fax: q1334-724-4188.
E-mail address: kwonk@tusk.edu (K.C. Kwon).

forces of diffusion are pressure gradients, temperature

gradients and concentration gradients (Reid et al.,
1987). Diffusion coefficients of vapors of various organic chemicals utilized in industrial applications are important in understanding transport mechanisms in industrial
processes (Monfort and Pellegatta, 1991).
Many experimental methods (Coulson and Richardson, 1984; Berezhnoi and Semenov, 1997; Marrero and
Mason, 1972) have been employed in determining
diffusion coefficients of both gases and vapors. Diffusion coefficients of the vapor of a volatile liquid diffused
into air are most conveniently determined by the open
tube evaporation method (Carmichael et al., 1955). In
this method, a volatile liquid is partially contained in a
vertical diffusion tube with a narrow diameter, maintained at a constant temperature, and an air stream is
passed over the top end of the diffusion tube (Coulson
and Richardson, 1984) by forced convection. This
method is widely used to determine diffusion coeffi-

1093-0191/04/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1093-0191(03)00039-X

668

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

cients of vapors of various liquids dispersed into a

stagnant gas, which fills the rest of the diffusion tube.
A diffusion coefficient is determined from experimental
data of slow losses of a liquid in the diffusion tube for
a given evaporation duration at a constant temperature
and pressure. In the diffusion tube, mass transfer of the
vapor of the liquid takes place from the surface of the
liquid by molecular diffusion alone (Nirdosh et al.,
2000) at constant temperature and pressure. Slow losses
of the liquid by evaporation are determinal from the
change in the liquid level in the diffusion tube (Nirdosh
et al., 2000).
The closed-tube method (Geankoplis, 1983; Marrero
and Mason, 1972) is usually quite reliable in determining diffusion coefficients of gases. The essential characteristics of this method are a variation of mixture
composition with time and position throughout a long
tube closed at both ends. Gas mixtures are initially
separated in the closed tube then interdiffused at constant temperature and pressure (Marrero and Mason,
1972). The diffusion time is controlled by an opening
mechanism at the middle of the tube. The composition
changes are measured as a function of time, either
continuously or after a definite period of diffusion.
Gas chromatography (Monfort and Pellegatta, 1991;
Tang and Hawkes, 1984) is a method in which a trace
amount of a gas is injected as a pulse in a carrier gas
flowing through a long hollow tube. The combined
action of molecular diffusion and the parabolic velocity
profile of the carrier gas cause the dispersion of the
pulse. As the pulse emerges from the tube outlet,
measurements of the dispersion lead to values of molecular diffusion (Marrero and Mason, 1972)
The interferometric method (Berezhnoi and Semenov,
1997) uses a barrier, which separates a liquid from a
gas prior to diffusion. At the instant of removing the
barrier between the liquid and the gas, unsteady-state
evaporation begins in an open cylinder. Shifts of interference bands with time are photographed with a highspeed camera and a neon lamp.
The point source method (Marrero and Mason, 1972)
was developed especially for the determination of diffusion coefficients at high temperatures. A trace amount
of a gas is introduced through a fine hypodermic tube
into a carrier gas flowing in the same direction. The
tracer spreads by diffusion through the carrier gas, which
has characteristics of steady-state laminar flow with a
flat velocity profile. The mixture composition is measured by means of a sample probe located at various
distances downstream of the tracer inlet. Electrical heat
allows the temperature to increase to 1200 K.
Changes in the liquid level in a diffusion tube for
short evaporation duration are hardly measurable with
the conventional open-tube evaporation method.
Amounts of volatile liquids evaporated in the diffusion
tube in this study were measured with a balance rather
than changes of the liquid level in the diffusion tube to

overcome this limitation of the conventional open-tube

evaporation method. No fresh air was passed over the
top end of the diffusion tube by forced convection
during the diffusion experiments, but natural convection
at the top end of the diffusion path might cause air to
move slightly in laminar flow. The novel open-tube
evaporation method and a newly developed diffusion
equation suitable for the novel open-tube evaporation
method were employed to determine diffusion coefficients of the vapors of various volatile liquids diffused
into air. Surprisingly, our novel open-tube evaporation
method has proven to be reliable and accurate in
addition to being easy and simple for experimentation.
Nonetheless, this method is restricted to narrow ranges
of temperatures, and strongly dependent on the volatility
of the liquid being tested (Marrero and Mason, 1972).
2. Theory
Diffusion coefficients of vapors of volatile liquids
can be experimentally measured in a diffusion tube. The
diffusion tube is partially filled with a neat volatile
liquid A at a constant temperature and atmospheric
pressure. The inside and the outside of the diffusion
tube, partially-filled with the neat volatile liquid A, are
surrounded with a gas B having a negligible solubility
in the liquid A. The liquid A vaporizes and diffuses
through the stagnant gas phase B in the diffusion path
of the diffusion tube. The vaporization rate of the liquid
A is described in Ficks first law, in which diffusion of
the vapor of the liquid A through the stagnant or nondiffusing B occurs at steady-state (Geankoplis, 1983).
The mole fraction of the vapor of the liquid A is
assumed to be negligible at the top end of the diffusion
path of the diffusion tube in developing a diffusion
equation. In this study, atmospheric air was chosen as
stagnant gas phase. Air is considered as a single substance, since the constituents of the air in the diffusion
path remain in fixed proportions and the air in the
diffusion path is almost stagnant.
A pseudo-steady state diffusion of the vapor of liquid
A through the stagnant gas B is assumed, since the
length of the diffusion path does not change significantly
over a short period of time. The molar flux of the vapor
A in the diffusion path is also described in terms of the
amount of the liquid A vaporized. The following diffusion equation (Geankoplis, 1983) is developed under
the above-mentioned assumptions.

ts

rART
z2 yz2o.
2PDABMA ln1y1yyAo..

(1)

The amount of the liquid A vaporized for the vapor-

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

669

Fig. 2. Schematic diagram of an experimental set-up.

Fig. 1. Diffusion tube with moving liquid level.

ization duration t is obtained from the following equation (see Fig. 1).
zszoq

moym.

(2)

SrA

Substituting Eq. (2) into Eq. (1) produces the following

equation.
ts

rART
2PDABMAln1y1yyAo..
B moym EB

=C
D

SrA

FC2zoq
GD

moym E
F
SrA G

(3)

Several models (Bird et al., 1960; Hines and Maddox,

1985; Mason and Monchick, 1962) have been developed
to predict diffusion coefficients of both gases and vapors
of volatile liquids. The Wilke and Lee method (Treybal,
1980) as shown in Eq. (4) and the Fuller et al. method
(Reid et al., 1987) were used to predict diffusion
coefficients of the systems chosen for this study. The
Wilke-and-Lee method is exclusively recommended for
mixtures of non-polar gases or a polar gas with a nonpolar gas.

DAB s

constant temperature, and an air stream is passed over

the top end of the diffusion tube by forced convection.
Slow losses of a liquid by evaporation are determined
from changes in the liquid level in the diffusion tube.
Our novel open-tube experimental method is different
from the conventional open-tube method. In this study,
slow losses of the liquid by evaporation were determined
by measuring continuously losses of the liquid in the
open diffusion tube with a balance rather than measuring
changes in the liquid level in the diffusion tube. No
fresh air was passed over the top end of the diffusion
tube during diffusion experiments by forced convection,
as opposed to the conventional open-tube evaporation
method.
The experimental set-up (see Fig. 2) of the novel
open-tube evaporation method consists of a diffusion
tube, a balance (Gardner and Preston, 1992), a barometer and a thermometer. The following glass test tubes
of various diameters and lengths were utilized to obtain
experimental data of losses of a liquid by evaporation
for various evaporation durations. (1) 1.38-cm diameter

10y41.084y0.249y1yMAq1yMB.T3y2y1yMAq1yMB
PrAB.2 fkTyAB.

(4)
3. Experimental set-up and procedure
In the conventional open tube evaporation method, a
volatile liquid is partially contained in a vertical diffusion tube with a narrow diameter, maintained at a

Fig. 3. Loss amounts of liquids by evaporation at various evaporation durations under atmospheric pressure.

670
Table 1
Calculations of the mole fraction of the vapor of a liquid at the surface of the liquid in a diffusion tube with Antoine equation and experimental pseudo binary diffusion coefficients

Acetic acid
Acetic acid
Acetone
Acetone
n-Butanol
n-Propanol
Ethanol
Methanol
Carbon disulfide
Diethylamine
Benzene
Ethyl acetate
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-hexane
Methylene chloride
Methylene chloride
Isooctane
Isooctane
Toluene

zo (cm)

6.07
2.4
1.5
6.43
0.95
1.95
1.15
1.3
2.65
2.75
2.05
2.15
1.83
2.45
3.97
5.45
4.1
4.1
4.1
4.1
4.1
5.84
1.35
6.1
5.63
4.1
2.55

S (cm2)

1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
11.2221
4.2638
1.4957
0.9677
0.5217
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957

T (8C)

24.7
25
24.3
26.1
24.8
24.8
24.9
25
25.2
25.2
23.7
25.3
24.7
24.8
25
25.7
24.6
26
25.7
25.5
25.6
26
25
26.2
24.2
25.1
24

SV=104 cm2ymin

5.627
6.036
125.0
152.2
2.928
10.54
29.91
60.81
206.3
166.0
51.05
57.46
30.38
31.92
32.44
35.72
31.89
33.67
33.49
33.95
35.25
123.8
227.7
303.7
35.36
35.62
16.16

MA

60.05
60.05
58.08
58.08
74.12
60.09
46.07
32.04
76.13
73.14
78.11
88.1
100.2
100.2
100.2
100.2
100.2
100.2
100.2
100.2
100.2
86.17
84.94
84.94
114.22
114.22
92.13

rA (gycm3)

1.049
1.049
0.792
0.792
0.81
0.804
0.789
0.792
1.261
0.712
0.879
0.901
0.684
0.684
0.684
0.684
0.684
0.684
0.684
0.684
0.684
0.659
1.336
1.336
0.692
0.692
0.866

P (mmHg)

763.0
763.3
766.6
762.3
763.8
763.3
766.6
762.3
763.3
763.3
766.3
762.5
761.7
761.7
761.7
762.3
765
765.6
760.7
760.7
760.7
762.3
762.5
762.3
763
760.7
765

Antoine parameter
A

7.80307
7.80307
7.02447
7.02447
7.4768
7.84767
8.04494
7.87863
6.94279
5.8016
6.90565
7.09808
6.9024
6.9024
6.9024
6.9024
6.9024
6.9024
6.9024
6.9024
6.9024
6.87776
7.4092
7.4092
6.81189
6.81189
6.95334

1651.2
1651.2
1161
1161
1362.39
1499.21
1554.3
1473.11
1169.11
583.3
1211.033
1238.71
1268.115
1268.115
1268.115
1268.115
1268.115
1268.115
1268.115
1268.115
1268.115
1171.53
1325.9
1325.9
1257.84
1257.84
1343.943

225
226
224
224
178.77
204.64
222.65
230
241.59
144.1
220.79
217
216.9
216.9
216.9
216.9
216.9
216.9
216.9
216.9
216.9
224.366
252.6
252.6
220.74
220.74
219.377

yAo

DAB (cm2 ys)

0.0203
0.0220
0.2911
0.3164
0.0080
0.0270
0.0761
0.1658
0.4764
0.2975
0.1169
0.1269
0.0591
0.0594
0.0600
0.0621
0.0586
0.0628
0.0622
0.0616
0.0619
0.2072
0.5632
0.5907
0.0622
0.0652
0.0353

0.0975
0.0968
0.1008
0.1117
0.0815
0.1051
0.1318
0.1690
0.1078
0.0934
0.0938
0.0884
0.0693
0.0725
0.0730
0.0777
0.0734
0.0725
0.0727
0.0744
0.0769
0.0834
0.0881
0.1095
0.0678
0.0653
0.0859

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

Vapor

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

671

Table 2
Experimental diffusion coefficients and their deviations of various vapors, using the Students t distribution with the 95% confidence
interval and the (ny1) degrees of freedom
Vapor

zo (cm)

S (cm2)

T (8C)

Experimental DAB
(cm2ys) and its
deviation (cm2 ys)

Experimental DAB
(cm2ys) and its
deviation (%)

Acetic acid
Acetic acid
Acetone
Acetone
n-butanol
n-propanol
Ethanol
Methanol
Carbon disulfide
Diethylamine
Benzene
Ethyl acetate
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-hexane
Methylene chloride
Methylene chloride
Isooctane
Isooctane
Toluene

6.07
2.4
1.5
6.43
0.95
1.95
1.15
1.3
2.65
2.75
2.05
2.15
1.83
2.45
3.97
5.45
4.1
4.1
4.1
4.1
4.1
5.84
1.35
6.1
5.63
4.1
2.55

1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957
11.2221
4.2638
1.4957
0.9677
0.5217
1.4957
1.4957
1.4957
1.4957
1.4957
1.4957

24.7
25
24.3
26.1
24.8
24.8
24.9
25
25.2
25.2
23.7
25.3
24.7
24.8
25
25.7
24.6
26
25.7
25.5
25.6
26
25
26.2
24.2
25.1
24

0.0975"0.0096
0.0968"0.0082
0.1008"0.0004
0.1117"0.0005
0.0815"0.0023
0.1051"0.0030
0.1318"0.0045
0.1690"0.0012
0.1078"0.0013
0.0934"0.0013
0.0938"0.0005
0.0884"0.0016
0.0693"0.0009
0.0725"0.0009
0.0730"0.0006
0.0777"0.0009
0.0734"0.0009
0.0725"0.0005
0.0727"0.0007
0.0744"0.0009
0.0769"0.0015
0.0834"0.0005
0.0881"0.0002
0.1095"0.0011
0.0678"0.0009
0.0653"0.0005
0.0859"0.0044

0.0975"9.9
0.0968"8.5
0.1008"0.4
0.1117"0.4
0.0815"2.8
0.1051"2.9
0.1318"3.4
0.1690"0.7
0.1078"1.2
0.0934"1.4
0.0938"0.5
0.0884"1.8
0.0693"1.4
0.0725"1.4
0.0730"0.9
0.0777"1.2
0.0734"1.3
0.0725"0.6
0.0727"0.9
0.0744"1.3
0.0769"1.9
0.0834"0.6
0.0881"0.3
0.1095"1.0
0.0678"1.5
0.0653"0.8
0.0859"5.2

tube with a cross-sectional area of 1.4957 cm2 and a

length of 12.6 cm, (2) tube with a cross-sectional area
of 11.2221 cm2 and a length of 4.9 cm, (3) tube with
a cross-sectional area of 4.2638 cm2 and a length of 4.9
cm, (4) a tube with a cross-sectional area of 0.9677
cm2 and a length of 9.8 cm, and (5) a tube with a
cross-sectional area of 0.5217 cm2 and a length of 7.3
cm.
The tube was partially filled with a liquid. The initial
length of the diffusion path, the initial distance from
the top end of the diffusion tube to the liquid level in
the diffusion tube was measured. The top window of
the balance remained open for air to be passed over by
natural convection. The tube, partially filled with a
known amount of the liquid to a known level in the
tube was placed on the balance. The balance was reset
and a stopwatch started, after the inside wall of the tube
was dried for 5 min. The temperature of the liquid and
atmospheric pressure were measured with a thermometer
and a barometer. Loss amounts of the liquid by evaporation were measured with the balance at random time
intervals for 1045 min.

4. Calculations
Eq. (3) is rearranged to obtain Eq. (5) with evaporation durations as an independent variable and left-side
values of Eq. (5) containing loss amounts of liquid A
as a dependent variable.
B moym E

C
D

SrA
B

F
G

=C2zoq
D

moym E 2PDABMAln1y1yyAo..
Fs
t
SrA G
rART

(5)

Loss amounts of liquid A by evaporation were measured at random evaporation durations. These experimental data were applied to both sides of Eq. (5), and then
BB m ym E B
m ym EE
o
F=C2zoq o
FF
independent variables CC
SrA GG
DD SrA G D
against dependent variables (t) were plotted on a graph
to
obtain
the
value
of
the
slope
B 2PD M
E
ln
1y
1yy

AB
A
Ao..
C
F through the linear least
D
G
rART

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

672

Table 3
Estimation of the binary diffusion coefficients for the various vapors using Wilke and Lee method*
Vapor

T
(8C)

BP
(8C)

P
(mmHg)

Vapor
Ayk

Vapor
rA

rAB

AByk

kTyAB

f(kTyAB)

Predicted DAB
(cm2ys)

Acetic acid
Acetic acid
Acetone
Acetone
n-butanol
n-propanol
Ethanol
Methanol
Carbon disulfide
Diethylamine
Benzene
Ethyl acetate
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-hexane
Methylene chloride
Methylene chloride
Isooctane
Isooctane
Toluene

24.7
25.0
24.3
26.1
24.8
24.8
24.9
25.0
25.2
25.2
23.7
25.3
24.7
24.8
25.0
25.7
24.6
26.0
25.7
25.5
25.6
26.0
25.0
26.2
24.2
25.1
24.0

118.1
118.1
56.5
56.5
117
97.8
78.4
64.7
46.3
55.5
80.1
77.1
98.4
98.4
98.4
98.4
98.4
98.4
98.4
98.4
98.4
69
40
40
99.3
99.3
110.8

763.0
763.3
766.6
762.3
763.8
763.3
766.6
762.3
763.3
763.3
766.3
762.5
761.7
761.7
761.7
762.3
765.0
765.6
760.7
760.7
760.7
762.3
762.5
762.3
763.0
760.7
765.0

473.4
473.4
398.9
398.9
472.1
448.9
425.4
408.8
386.5
397.7
427.4
423.8
449.6
449.6
449.6
449.6
449.6
449.6
449.6
449.6
449.6
414.0
378.9
378.9
450.7
450.7
464.6

0.4826
0.4826
0.4954
0.4954
0.5542
0.5114
0.4599
0.3932
0.4769
0.5686
0.5403
0.5668
0.6443
0.6443
0.6443
0.6443
0.6443
0.6443
0.6443
0.6443
0.6443
0.6136
0.4895
0.4895
0.6724
0.6724
0.5791

0.4268
0.4268
0.4333
0.4333
0.4627
0.4412
0.4155
0.3822
0.4240
0.4699
0.4557
0.4689
0.5077
0.5077
0.5077
0.5077
0.5077
0.5077
0.5077
0.5077
0.5077
0.4923
0.4303
0.4303
0.5217
0.5217
0.4751

192.9
192.9
177.1
177.1
192.6
187.8
182.9
179.3
174.3
176.8
183.3
182.5
188.0
188.0
188.0
188.0
188.0
188.0
188.0
188.0
188.0
180.4
172.6
172.6
188.2
188.2
191.1

1.544
1.546
1.680
1.690
1.547
1.586
1.630
1.662
1.712
1.688
1.620
1.635
1.585
1.585
1.586
1.590
1.584
1.591
1.590
1.589
1.589
1.658
1.728
1.735
1.580
1.585
1.555

0.5980
0.5977
0.5741
0.5725
0.5975
0.5902
0.5825
0.5771
0.5690
0.5729
0.5844
0.5817
0.5906
0.5905
0.5903
0.5896
0.5907
0.5893
0.5896
0.5898
0.5897
0.5777
0.5664
0.5653
0.5914
0.5905
0.5959

0.1078
0.1080
0.1088
0.1108
0.0891
0.1022
0.1217
0.1571
0.1113
0.0905
0.0924
0.0875
0.0724
0.0724
0.0725
0.0728
0.0720
0.0726
0.0729
0.0728
0.0729
0.0805
0.1070
0.1079
0.0672
0.0678
0.0820

The values of B yk and rB for air used are 78.6 K and 0.3711 nm, respectively.

squares method (Johnson and Leone, 1964), as shown

in Fig. 3. The density rA and the molecular weight MA
(Perry and Chilton, 1973) of the liquid A, and the mole
fraction yAo of the vapor of the liquid A at the surface
of the liquid A in a diffusion tube, the diffusion
temperature, and atmospheric pressure were substituted
B 2PD M
ln1y1yyAo.. E
AB
A
F to
into the slope value C
D
G
rART
calculate the experimental pseudo-binary diffusion coefficient of the liquid A diffused into the stagnant air in
the diffusion path. The diffusion coefficients obtained
by Eq. (5) are shown in Tables 1 and 2.
The saturated vapor pressure at the surface of liquid
A in a diffusion tube was obtained with the temperature
of the liquid A and the Antoine equation (Dean, 1992;
Felder and Rousseau, 1986). Saturated vapor pressures
of liquids are dependent on their temperatures alone,
and independent of humidity of air according to the
Antoine equation (see Eq. (6)). The mole fraction (yAo)
of the vapor of the liquid A at the surface of the liquid
A in the diffusion tube can be obtained by dividing the
saturated vapor pressure of the liquid A with atmospheric pressure, as shown in Table 1. Fluctuations of
both temperature and atmospheric pressure are consid-

ered to be almost negligible during relatively short

experimental durations in comparison with the conventional open tube evaporation method.
PSs10AyByCqT..

(6)

The Wilke-and-Lee method (see Eq. (4)) and its

parameter equations, as shown in Eq. (7) through Eq.
(11), were used to predict the diffusion values of the
vapors of the volatile liquids chosen for this study. Eq.
(7) and Eq. (8) were used to calculate the value of rA
and the value of Ayk of the vapor of liquid A,
respectively. Air is considered as a single substance,
since the constituents of the air in a diffusion path
remain in fixed proportions and the air in the diffusion
path is almost stagnant. The value of rB and the value
of Byk of air were not calculated for this study, but
were obtained from the literature (Treybal, 1980). The
value of rB and the value of Byk of air are 0.3711 nm
and 78.6 K, respectively.
rAs1.18v1y3

(7)

Ayks1.21Tb

(8)

rABs(rAqrB)y2

(9)

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

673

Table 4
Literature diffusion coefficients of various vapors diffused into air from the references
Vapor

Temperature
(8C)

Literature value
DAB (cm2 ys)

Ref.

Acetic acid
Acetic acid
Acetone
Acetone
n-butanol
n-propanol
Ethanol
Methanol
Carbon disulfide
Diethylamine
Benzene
Ethyl acetate
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane
n-hexane
Methylene chloride
Methylene chloride
Isooctane
Isooctane
Toluene

24.7
25
24.3
26.1
24.8
24.8
24.9
25
25.2
25.2
23.7
25.3
24.7
24.8
25
25.7
24.6
26
25.7
25.5
25.6
26
25
26.2
24.2
25.1
24

0.1207
0.1209
0.1110
0.1120
0.0865
0.1000
0.1347
0.1591
0.1046
0.0000
0.0956
0.0867
0.0724
0.0724
0.0725
0.0728
0.0724
0.0729
0.0728
0.0727
0.0727
0.0820
0.1037
0.1043
0.0530
0.0532
0.8518

Geankoplis, 1983
Geankoplis, 1983
Berezhnoi and Semenov, 1997
Berezhnoi and Semenov, 1997
Geankoplis, 1983; Treybal, 1980
Coulson and Richardson, 1984
Reid et al., 1987; Hines and Maddox, 1985
Coulson and Richardson, 1984
Berezhnoi and Semenov, 1997
Not available
Geankoplis, 1983; Bennett and Myers, 1962
Treybal, 1980
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Reid et al., 1987
Geankoplis, 1983; Reid et al., 1987
Berezhnoi and Semenov, 1997
Berezhnoi and Semenov, 1997
Berezhnoi and Semenov, 1997
Berezhnoi and Semenov, 1997
Geankoplis, 1983

AByksw(Ayk)(Byk)x1y2

(10)

f(kTyAB)s0.7375(kTyAB)y0.4857

(11)

The value of rAB and the value of AByk were

calculated with Eq. (9) and Eq. (10), respectively. The
value of f(kTyAB) was obtained with Eq. (11), which
was developed from the collision function figure (Treybal, 1980). Table 3 shows the calculated parameter
values of the Wilke-and-Lee method and its predicted
diffusion coefficients of the various vapors chosen for
this study.
The literature diffusion coefficients (see Table 4)
were obtained from the publications (Geankoplis, 1983;
Berezhnoi and Semenov, 1997; Treybal, 1980; Coulson
and Richardson, 1984; Reid et al., 1987; Hines and
Maddox, 1985; Bennett and Myers, 1962). The predicted diffusion coefficients and the literature diffusion
coefficients of the vapors of the volatile liquids were
compared with the experimental diffusion coefficients
obtained from the novel open-tube evaporation method,
as shown in Table 5.
5. Results and discussion
The experimental and predicted pseudo-binary diffusion coefficients of the vaporair systems chosen for

this study at atmospheric pressure are shown in Tables

1, 3 and 5. Table 4 shows the literature diffusion values
of the vapors of the liquids obtained from the
publications. The experimental pseudo-binary diffusion
values from this study were compared with the literature
diffusion values as well as the predicted diffusion
values, as shown in Table 5 and Figs. 4, 5 and 9.
The experimental pseudo-binary diffusion coefficients
of the normal alcohols in air were plotted against the
number of carbon atoms in their molecular formulas, as
shown in Fig. 5. The result indicates that the experimental pseudo-binary diffusion coefficients of the normal alcohols in air decrease with increased number of
carbon atoms in their molecular formulas. This result is
in good agreement with the fact that heavier molecules
have larger collision diameters and larger energy of
molecular attractions, as shown in Eq. (4).
A series of experiments with liquid n-heptane were
conducted to find out effects of initial lengths of a
diffusion path on its pseudo-binary diffusion coefficients
into air, as shown in Figs. 6 and 7. These results indicate
that the pseudo-binary diffusion coefficients of n-heptane diffused into air are almost independent of the
initial length of the diffusion path. This fact may justify
the assumption that mole fractions of vapors of liquids
at the top end of the diffusion path are negligible.

674

Table 5
Experimental, predicted, and literature value of diffusion coefficients
Vapora

Temperature
(8C)

Experimental
DAB (cm2 ys) and
its deviation (%)

Predicted DAB (cm2 ys)

Wilke and Lee
method

Fuller et al.
method

6.07
2.4
1.5
6.43
0.95
1.95
1.15
1.3
2.65
2.75
2.05
2.15
1.83
2.45
3.97
5.45
4.1
4.1
4.1
4.1
4.1
5.84
1.35
6.1
5.63
4.1
2.55

24.7
25
24.3
26.1
24.8
24.8
24.9
25
25.2
25.2
23.7
25.3
24.7
24.8
25
25.7
24.6
26
25.7
25.5
25.6
26
25
26.2
24.2
25.1
24

0.0975"9.9
0.0968"8.5
0.1008"0.4
0.1117"0.4
0.0815"2.8
0.1051"2.9
0.1318"3.4
0.1690"0.7
0.1078"1.2
0.0934"1.4
0.0938"0.5
0.0884"1.8
0.0693"1.4
0.0725"1.4
0.0728"0.9
0.0775"1.2
0.0734"1.3
0.0725"0.6
0.0727"0.9
0.0744"1.3
0.0769"1.9
0.0834"0.6
0.0881"0.3
0.1095"1.0
0.0678"1.5
0.0653"0.8
0.0859"5.2

0.1078
0.1080
0.1088
0.1108
0.0891
0.1022
0.1217
0.1571
0.1113
0.0905
0.0924
0.0875
0.0724
0.0724
0.0725
0.0728
0.0720
0.0726
0.0729
0.0728
0.0729
0.0805
0.1070
0.1079
0.0672
0.0678
0.0820

0.1041
0.1043
0.1053
0.1064
0.0894
0.1023
0.1224
0.1597
0.1054
0.0895
0.0889
0.0871
0.0704
0.0704
0.0705
0.0708
0.0703
0.0709
0.0708
0.0707
0.0707
0.0770
0.1033
0.1040
0.0653
0.0656
0.0801

Literature
DAB (cm2 ys)

0.1207
0.1209
0.1110
0.1120
0.0865
0.1000
0.1347
0.1591
0.1046
0.0000
0.0956
0.0867
0.0724
0.0724
0.0725
0.0728
0.0724
0.0729
0.0728
0.0727
0.0727
0.0820
0.1037
0.1043
0.0530
0.0532
0.8518

Deviationb
Wilke and Lee
method

Fuller et al.
method

y10.6
y11.6
y7.9
0.8
y9.3
2.8
7.7
7.0
y3.2
3.1
1.5
1.0
y4.5
0.1
0.4
6.1
1.9
y0.1
y0.3
2.2
5.2
3.5
y21.5
1.5
0.9
y3.8
4.5
6.0c

y6.8
y7.7
y4.5
4.7
y9.7
2.7
7.1
5.5
2.2
4.2
5.2
1.5
y1.6
2.9
3.2
8.6
4.2
2.2
2.6
5.0
8.1
7.7
y17.3
5.0
3.7
y0.5
6.8
5.8c

The evaporation area was 1.4957 cm2 in all runs except es11.2221 cm2, fs4.2638 cm2, gs0.9677 cm2, and hs0.5217 cm2.
(experimental valuepredicted value)yexperimental value=100%.
c
The overall root mean square of deviation percentage of the experimental diffusion values from those predicted with Wilke and Lee method (Treybal, 1980) and Fuller et al.
method (Reid et al., 1987).
b

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

Acetic acid
Acetic acid
Acetone
Acetone
n-butanol
n-propanol
Ethanol
Methanol
Carbon disulfide
Diethylamine
Benzene
Ethyl acetate
n-heptane
n-heptane
n-heptane
n-heptane
n-heptanee
n-heptane f
n-heptane
n-heptaneg
n-heptaneh
n-hexane
Methylene chloride
Methylene chloride
Isooctane
Isooctane
Toluene

Diffusion
path (cm)

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

675

Fig. 4. Comparison of experimental pseudo-binary diffusion coefficient values of vapors of various liquids with literature values
and predicted values at atmospheric pressure.

The experimental pseudo-binary diffusion coefficients

of n-heptane in air obtained from this study were plotted
against evaporation temperatures as shown in Fig. 8.
This observation shows that the pseudo-binary diffusion
coefficients of n-heptane diffused into air increase with
increased evaporation temperatures inspite of the narrow
evaporation temperature range of 2426 8C at atmospheric pressure. These observations also agree with the
Wilke-and-Lee method.
The experimental pseudo-binary diffusion coefficients
of the normal hydrocarbons in air were plotted against

the number of carbon atoms in their molecular formulas

as shown in Fig. 9. This fact suggests that experimental
pseudo-binary diffusion coefficients of normal hydrocarbons in air decrease with increased number of carbon
atoms in their molecular formulas. This result is also
well known and follows directly the fact that heavier
molecules have larger collision diameters and larger
energy of molecular attractions, as shown in Eq. (4).
A series of diffusion experiments with liquid nheptane were conducted to find out effects of evaporation areas on its pseudo-binary diffusion coefficients

Fig. 5. Comparison of experimental pseudo-binary diffusion coefficient values of normal alcohols with literature values and predicted
values at atmospheric pressure.

676

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

Fig. 6. Loss amounts of liquid n-heptane by evaporation at

various evaporation durations and various initial lengths of diffusion path (zo) under atmospheric pressure.

Fig. 7. Effects of diffusion-path length on diffusion of n-heptane vapor into stagnant air in the temperature range of 24.7
25.7 8C.

Fig. 8. Pseudo-binary diffusion coefficients of n-heptane at various evaporation temperatures.

Fig. 9. Comparison of experimental pseudo-binary diffusion

coefficient values of normal hydrocarbon with literature values
and predicted values at atmospheric pressure.

Fig. 10. Loss amounts of liquid n-heptane by evaporation with

various evaporation areas (S) and the initial 4.1 cm diffusionpath length (zo) at atmospheric pressure.

Fig. 11. Pseudo-binary diffusion coefficients of n-heptane with

various evaporation areas at room temperature and atmospheric
pressure.

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

into air, as shown in Figs. 10 and 11. These results

indicate that the pseudo-binary diffusion coefficients of
n-heptane diffused into air are independent of the
evaporation areas chosen for this study. These observations may suggest that changes in concentrations of
vapors in the radial direction in a diffusion path do not
occur.
The predicted diffusion coefficients of the various
vapors into air were also calculated with the Fuller et
al. method (Reid et al., 1987), as shown in Table 5.
The overall root mean square (Spiegel, 1961) of deviation of the diffusion values obtained with the novel
open-tube evaporation method from those predicted with
the Wilke-and-Lee method (Treybal, 1980) is 6.0%,
whereas it is 5.8% with the Fuller et al. method. Both
methods seem to predict very closely the pseudo-binary
diffusion coefficients of the vapors of the various liquids
chosen for this study.
The overall results suggest that the experimental
diffusion values obtained from the novel open-tube
evaporation method are in reasonable agreement with
the diffusion values predicted with both methods.
Although air contains some moisture and moisture
contents in air vary, the value of rB and the value of
Byk of air were obtained from the literature (Treybal,
1980) in order to calculate the predicted pseudo-binary
diffusion coefficients of the vapors into air with the
Wilke and Lee method. The value of rB and the value
of Byk of air from the literature (Treybal, 1980) are
0.3711 nm and 78.6 K, respectively. Although the results
from the novel open-tube evaporation method are rather
precise, it is also important to notice the limitations of
the novel open-tube evaporation method. It is recommended that disturbance of air surrounding the evaporation apparatus be minimized to obtain a good
agreement between experimental diffusion coefficients
and predicted diffusion coefficients. The novel opentube evaporation method is restricted to narrow ranges
of temperatures, and strongly dependent on the volatility
of a liquid being tested (Marrero and Mason, 1972).
6. Conclusions
The experimental diffusion coefficients of the vapors
of the liquids into air in this study were obtained from
the evaporated amounts of the liquids measured with a
balance rather than changes in the liquid level in a
diffusion tube for various evaporation durations. No
fresh air was passed over the top end of the diffusion
tube by forced convection during diffusion experiments,
as opposed to the conventional open-tube evaporation
method. The experimental diffusion coefficient values
obtained with the novel open-tube evaporation method
and the newly developed diffusion equation are reasonably agreeable with the predicted diffusion coefficient

677

values. This novel open-tube evaporation method turned

out to be simple and convenient in determining experimental diffusion coefficients of vapors of liquids into
air at atmospheric pressure.
The pseudo-binary diffusion coefficients of n-heptane
diffused into air are almost independent of the initial
lengths of the diffusion paths chosen for this study. This
observation indicates that mole fractions of vapors of
liquids at the top end of the diffusion paths are negligible. The pseudo-binary diffusion coefficients of nheptane diffused into air were also independent of the
evaporation areas chosen for this study, suggesting that
changes in concentrations of vapors in the radial direction in the diffusion paths do not occur. The pseudobinary diffusion coefficients of n-heptane diffused into
air increase with increased evaporation temperatures in
spite of the narrow temperature range of 2426 8C at
atmospheric pressure. These results agree with the Wilke
and Lee method.
The experimental pseudo-binary diffusion coefficients
of the normal alcohols in air decrease with increased
number of carbon atoms in their molecular formulas.
The experimental pseudo-binary diffusion coefficients
of the normal hydrocarbons in air decrease with
increased number of carbon atoms in their molecular
formulas. This result agrees with the fact that heavier
molecules have larger collision diameters and larger
energy of molecular attractions, as shown in Wilke-andLee method.
The overall root mean square (Spiegel, 1961) of
deviation of the diffusion values of this experimental
study from those predicted with the Wilke-and-Lee
method (Treybal, 1980) is 6.0%, whereas with the Fuller
et al. method it is 5.8%. Both methods predict very
closely the pseudo-binary diffusion values of the vapors
of various liquids chosen for this study.
7. Nomenclature
A, B, C: Parameters of Antonie equation
BP:
Boiling temperature of a liquid at
atmospheric pressure
Diffusion coefficient of a vapor A diffused
DAB:
into air, m2 ys for Eq. (4) and cm2 ys for Eq.
(5)
Molecular weight of A, kgykmol
MA:
Molecular weight of B, kgykmol
MB:
P:
Atmospheirc pressure, atm for Eq. (5), Nym2
for Eq. (4)
Saturated vapor pressure of a liquid at T 8C,
PS:
mmHg
R:
Ideal gas constant, 82.0545 atm-cm3 yg-mle-K
for Eq. (5)
S:
Cross-sectional area of a diffusion tube, cm2
SV:
Slope value of the diffusion equation

678

K.C. Kwon et al. / Advances in Environmental Research 8 (2004) 667678

T:

Absolute vaporization temperature, K for Eqs.

(4) and (5) and 8C for Eq. (6)
Normal boiling point of a liquid, K
Tb:
f(kTyAB): Collision function
m:
Amount of the liquid A in a diffusion tube at
evaporation duration t, g
Initial amount of the liquid A in a diffusion
mo:
tube, g
moym: Loss amount of the liquid A due to
evaporation for the evaporation duration t, g
rAB:
Molecular separation at collision, rABs(rAq
rB)y2, nm
t:
Evaporation duration, min
Mole fraction of the vapor A at the liquid
yAo:
surface in a diffusion tube at T and P
z:
Length of diffusion path, cm
Initial length of diffusion path, cm
z o:
AB:
Energy of molecular attractionsyAB
rA:
Density of the liquid A at T, gycm3
k:
Boltzmanns constant
v:
Molar volume of a liquid at normal boiling
point, m3ykg-mole

Acknowledgments
The authors thank for Chemical Engineering students
to conduct experiments and obtain experimental data
for this research project. The authors also thank Dr
Nader Vahdat, Dr Dennis Likens and the anonymous
reviewers for comments and suggestions on this paper.
The Tuskegee University Title III program-faculty
development program supports this research project.
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