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Molecular diffusion of volatile-

liquid vapors into air
a a a
K. C. Kwon , Yoonkook Park , C. M. Simmons ,
a b
G. L. Tibere & T. H. Ibrahim
a
Department of Chemical Engineering , Tuskegee
University , Tuskegee, Alabama, USA
b
Chemical Engineering Department , American
University of Sharjah , Sharjah, UAE
Published online: 09 Sep 2010.

To cite this article: K. C. Kwon , Yoonkook Park , C. M. Simmons , G. L. Tibere &

T. H. Ibrahim (2003) Molecular diffusion of volatile-liquid vapors into air, Chemical
Engineering Communications, 190:11, 1449-1467, DOI: 10.1080/714909153

To link to this article: http://dx.doi.org/10.1080/714909153

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 Chem. Eng. Comm., 190: 1449
1467, 2003
Copyright # Taylor & Francis Inc.
ISSN: 0098-6445 print/1563-5201online
DOI: 10.1080/00986440390240740

MOLECULAR DIFFUSION OF VOLATILE-LIQUID

VAPORS INTO AIR
Downloaded by [Washington University in St Louis] at 09:01 06 October 2014

K. C. KWON
YOONKOOK PARK
C. M. SIMMONS
G. L. TIBERE
Department of Chemical Engineering,
Tuskegee University,Tuskegee, Alabama, USA

T. H. IBRAHIM
Chemical Engineering Department,
American University of Sharjah, Sharjah, UAE

Diffusion coefficients of vapors diffused into stagnant air were determined at

room temperature and atmospheric pressure. Experimental data on diffusion
coefficients were obtained from the steady-state open-tube evaporation
method modified for this study. No fresh air is passed over the top end of a
diffusion tube, and amounts of volatile liquids evaporated in the diffusion
tube are measured with a balance rather than a change of the liquid level in a
diffusion tube. Experimental molecular diffusion coefficients are obtained by
applying experimental data of mass losses of volatile liquids versus evaporation
durations to a diffusion equation developed suitable for the novel open-tube
evaporation method. Three main experimental errors of the novel open-tube
evaporation method are described in detail. Predicted diffusion coefficients
are calculated with the Wilke-Lee method and compared with experimental
values obtained from this diffusion study.

Keywords: Molecular diffusion coefficient; Diffusion equation; Open-tube

evaporation method; Experimental errors

Received 5 December 2000; in final form 9 December 2001.

Address correspondence to K. C. Kwon, Department of Chemical Engineering, Room
514, Engineering Building, Tuskegee University, Tuskegee, AL 36088, USA. E-mail:
kwonk@tusk.edu

1449
 1450 K. C. KWON ET AL.

INTRODUCTION
Molecular mass transfer of toxic gases and vapors of industrial solvents
into air are widely investigated to study air pollution control and envir-
onmental emissions of volatile vapors. Rates of absorption, adsorption,
drying, distillation, and condensation occurring in various industrial
processes in the chemical, petroleum, and gas industries are dependent on
diffusion of processed gaseous chemicals (Berezhnoi and Semenov, 1997).
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The extensive use of the term ‘‘diffusion’’ in the chemical engineering

literature refers to the net transport of material within a single phase in
the absence of mixing. Binary diffusion coefficients, a property of the
binary system, are dependent on temperature, pressure, and the nature of
the binary components. Both experiment and theory have shown that the
driving forces of diffusion are pressure gradients, temperature gradients,
and concentration gradients (Reid et al., 1987). Diffusion coefficients of
gaseous organic chemicals utilized in industrial applications are impor-
tant 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 liquid
vapors. The following experimental methods have been used frequently.
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 airstream is passed over the top end of
the diffusion tube (Coulson and Richardson, 1984). This method is
widely used to determine diffusion coefficients 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-path tube for given evaporation dura-
tions at a constant temperature and pressure. In the diffusion tube, a
mass transfer of the vapor of the liquid takes place from the surface of the
liquid in the diffusion tube by molecular diffusion alone (Nirdosh et al.,
2000) at constant temperature and pressure. Slow losses of the liquid by
evaporation are obtained by the change in the liquid level in the diffusion
tube (Nirdosh et al., 2000).
Determinations of diffusion coefficients by the closed-tube method
are usually quite reliable. 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
 EXPERIMENTAL DIFFUSION EQUATION 1451

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. A significant uncertainty is slight dependence of the
diffusivity on the mixture composition. A composition of a vapor-gas
mixture is assumed to be independent of diffusion coefficients for the
open-tube evaporation method (Berezhnoi and Semenov, 1997). How-
ever, the composition plays a significant role in determining diffusion
coefficients for this closed-tube method.
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The apparatus of the two-bulb method consists of two glass bulbs

with volumes V1 and V2 connected by a capillary of cross-sectional area
A and length L whose volume is small compared to the glass bulb V1 and
the glass bulb V2. Pure gas A is added to the glass bulb V1 and pure gas B
to the glass bulb V2 at the same pressures. The valve is opened, diffusion
proceeds for the given time, the valve is closed, and the mixed contents of
each chamber are sampled separately (Geankoplis, 1983). The determi-
nations of the diffusion coefficients by the two-bulb method have
uncertainties similar to those of the closed-tube method. The accuracy of
this method, however, is about the same as that of the closed-tube
method. The two-bulb method is capable of yielding reliable diffusivities
if care is taken to optimize the geometry of the apparatus and to make
corrections when necessary (Marrero and Mason, 1972).
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 causes the dispersion of the pulse. As the pulse emerges from
the tube outlet, measurements of the dispersion lead to values of DAB
(Marrero and Mason, 1972). The advantages of the gas chromatography
method are as follows. Determinations of the diffusion coefficients can be
completed in a matter of minutes. Once the carrier gas is kept at a desired
temperature and pressure, it is possible to inject a number of sample
pulses into the gas to disperse a sample gas in the long hollow tube.
Another advantage is that this method is used to study dense gas mix-
tures (Marrero and Mason, 1972). The disadvantages of the method are
that maintaining a laminar flow is difficult at high pressures, and the
corrections for the end effects should be taken into account. The most
important advantage of this method is that diffusion coefficients can be
rapidly and correctly determined.
Prior to diffusion, a barrier separates a liquid from a gas for the
interferometric method. At the instant of removing the barrier, unsteady-
state evaporation begins in an open cylinder. Shifts of interference bands
with time are photographed with a high-speed camera and a neon lamp.
The main advantage is the fact that the interferometric method eliminates
the need to measure the rates of mass transfer. However, the main
 1452 K. C. KWON ET AL.

limitation of this method is caused by the diffusion cell, which allows

measuring binary diffusion coefficients of vapors of volatile liquids dif-
fused only into air at atmospheric pressure and room temperature
(Berezhnoi and Semenov, 1997).
The point source method (Marrero and Mason, 1972) was developed
especially for the determination of diffusion coefficients at high tem-
peratures. A trace amount of gas is introduced through a fine hypodermic
tube into a carrier gas flowing in the same direction. The tracer spreads
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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 a sample probe located at various distances downstream of
the tracer inlet. Electrical heat allows the temperature to increase to
1200 K.
The open-tube evaporation method has been employed for this
study. It is difficult to recognize the change in the liquid level in a dif-
fusion tube in the conventional open-tube evaporation method for short
evaporation duration. A novel open-tube evaporation method was
developed to overcome this limitation. In this study, amounts of volatile
liquids evaporated in the diffusion tube are measured with a balance
rather than a change of the liquid level in the diffusion tube, without
passing fresh air over the top end of the diffusion tube. Surprisingly, our
novel method has proven to be not only reliable and accurate but also
simple and easy to carry out. Nonetheless, this method is restricted to
narrow ranges of temperatures and is strongly dependent on the volatility
of the liquid being tested (Marrero and Mason, 1972).

THEORY
Diffusion coefficients for a vapor 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, is 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 tube. The vaporization rate of the liquid A is
described in the following equation, based on Fick’s first law in which
diffusion of the vapor of the liquid A through the stagnant or nondiffusing
gas B occurs at steady state (Geankoplis, 1983; Welty et al., 1984). The
mole fraction of the vapor of the liquid A is assumed to be negligible at the
top end of the diffusion tube in developing the diffusion equation:

PDAB
1 
NAz ¼ ln : ð1Þ
RTz 1
yAo
 EXPERIMENTAL DIFFUSION EQUATION 1453

A pseudo-steady-state diffusion of the liquid A through the stagnant

gas B is assumed, since the length of the diffusion path does not change
significantly over a short time period. The molar flux of the vapor A,
NAz, is also described in terms of the amount of the liquid A vaporized, as
shown in the following equation:

rA dz
NAz ¼ : ð2Þ
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MA dt

Substituting Equation (1) into Equation (2) and integrating the combined
equation produces the following equation:

rA RT
t¼ ðz2
z2o Þ: ð3Þ
2PDAB MA lnð1=ð1
yAo ÞÞ

The amount of the liquid A vaporized for the vaporization duration t is

obtained from the following equation (see Figure 1):

z ¼ zo þ ðmo
mÞ=SrA : ð4Þ

Figure 1. Diffusion tube with moving liquid level.

 1454 K. C. KWON ET AL.

Substituting Equation (4) into Equation (3) produces the following

equation:

rA RT
m
m
mo
m
o
t¼ 2zo þ : ð5Þ
2PDAB MA lnð1=ð1
yAo ÞÞ SrA SrA

Several models (Hines and Maddox, 1985; Mason and Monchick,

1962; Bird et al., 1960) have been developed to predict diffusion coeffi-
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cients of both gases and volatile liquid vapors. The Wilke-Lee method
(Treybal, 1980), as shown in Equation (6), is used in predicting diffusion
coefficients of the chosen systems in this study. This method is recom-
mended exclusively for mixtures of nonpolar gases or polar gas with a
nonpolar gas:

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
10
4 1:084
0:249 1=MA þ 1=MB T 3=2 1=MA þ 1=MB
DAB ¼ : ð6Þ
PðrABn Þ2 fðkT=eAB Þ

EXPERIMENTAL PROCEDURE

The experimental setup (see Figure 2) of the novel open-tube evaporation

method modified for this study consists of a glass tube, a balance
(Gardner and Preston, 1992), a caliper, and a thermometer. Diffusion
tubes of various diameters were chosen for this study, namely, tubes with
the following cross-sectional areas and lengths, respectively: 1.4957 cm2
and 12.6 cm; 11.2221 cm2 and 4.9 cm; 4.2638 cm2 and 4.9 cm; 0.9677 cm2
and 9.8 cm; 0.5217 cm2 and 7.3 cm; and 1.5690 cm2 and 14.9 cm. Various
liquids (see Table I) were selected for diffusion experiments.
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 constant temperature, and an airstream is passed over the
top end of the diffusion tube. Slow losses of the liquid by evaporation are
obtained by changes in the liquid level in the diffusion tube. Our novel
open-tube experimental method is completely different from the con-
ventional open-tube method. In this study, slow losses of the liquid by
evaporation were determined by reading weight 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.
A diffusion tube was partially filled with a liquid. The initial diffu-
sion-path length, the initial distance from the top end of the diffusion
tube to the liquid level in the diffusion tube, was measured. The top
 EXPERIMENTAL DIFFUSION EQUATION 1455
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Figure 2. Schematic diagram of an experimental setup.

window of the balance remained open. The tube, partially filled with a
known amount of the volatile liquid to a known level in the diffusion
tube, was placed on a balance. The balance was reset, and then a stop-
watch was started, after the inside wall of the diffusion tube was dried for
approximately 5 min. The temperature was recorded. Loss amounts of
the liquid due to evaporation were recorded at random evaporation time
intervals for 10
100 min.

CALCULATIONS
Equation (5) was rearranged to obtain the following diffusion equation
(see Equation (7)) with evaporation durations as an independent variable
and left-hand side values of the diffusion equation containing loss
amounts as a dependent variable. The slope term of the diffusion equa-
tion contains properties such as the molecular weight and density of a
liquid vaporized, the experimental temperature and pressure, and the
mole fraction of vapor at the liquid surface in the diffusion-path tube:

m
m
mo
m 2PDAB MA lnð1=ð1
yAo ÞÞ

o
2zo þ ¼ t: ð7Þ
SrA SrA rA RT
 Downloaded by [Washington University in St Louis] at 09:01 06 October 2014

Table I Experimental Diffusion Coefficients of Vapors in Air Compared with Predicted and Literature Values at Atmospheric Pressure

1456
Binary diffusion coefficient, cm2/s
Diffusion path, Evaporation area, Deviation % from
Liquid vapor cm cm2 Temperature (C) Experimental Literature Predicted predicted values

Acetic acid 6.07 1.4957 24.7 0.0972 0.1209 0.1142 714.9

Acetic acid 2.4 1.4957 25 0.1048 0.1211 0.1144 78.4
Acetone 1.5 1.4957 24.3 0.0997 0.1103 0.1099 79.3
Acetone 6.43 1.4957 26.1 0.1113 0.1135 0.1127 71.2
Acetone 1.56 1.5690 25.2 0.0993 0.1115 0.1104 710.1
Acetone 3.61 1.5690 25.1 0.1102 0.1114 0.1104 70.2
Acetone 6.03 1.5690 25.5 0.1084 0.1117 0.1107 72.1
Acetone 9.52 1.5690 25.5 0.1088 0.1117 0.1107 71.7
Acetone 12.81 1.5690 25.6 0.1060 0.1117 0.1107 74.2
n-Butanol 0.95 1.4957 24.8 0.0804 0.0865 0.0896 710.2
n-Propanol 1.95 1.4957 24.8 0.1047 0.0997 0.1027 2.0
Ethanol 1.15 1.4957 24.9 0.1306 0.1347 0.1227 6.5
Methanol 1.3 1.4957 24.8 0.1685 0.1590 0.1574 7.1
Carbon disulfide 2.65 1.4957 25.2 0.1071 0.1072 0.1117 74.2
Diethylamine 2.75 1.4957 25.2 0.0929 0.0897 3.5
Benzene 2.05 1.4957 23.7 0.0930 0.0956 0.0932 70.2
Ethyl acetate 2.15 1.4957 25.3 0.0881 0.0867 0.0858 2.6
n-Heptane 1.83 1.4957 24.7 0.0691 0.0724 0.0724 74.6
n-Heptane 2.45 1.4957 24.8 0.0723 0.0724 0.0725 70.3
n-Heptane 3.97 1.4957 25 0.0728 0.0725 0.0726 0.3
n-Heptane 5.45 1.4957 25.7 0.0747 0.0728 0.0728 2.5
n-Heptane 4.1 11.2221 24.6 0.0729 0.0724 0.0725 0.6
 Downloaded by [Washington University in St Louis] at 09:01 06 October 2014

n-Heptane 4.1 4.2638 26 0.0727 0.0729 0.0734 70.9

n-Heptane 4.1 1.4957 25.7 0.0726 0.0728 0.0730 70.5
n-Heptane 4.1 0.9677 25.5 0.0744 0.0727 0.0726 2.4
n-Heptane 4.1 0.5217 25.6 0.0768 0.0727 0.0729 5.3
n-Heptane 1.34 1.5690 25.2 0.0651 0.0734 0.0728 710.6
n-Heptane 3.66 1.5690 25.2 0.0712 0.0734 0.0728 72.2
n-Heptane 6.73 1.5690 25.2 0.0716 0.0734 0.0728 71.6
n-Heptane 9.47 1.5690 25.2 0.0724 0.0734 0.0728 70.5
n-Heptane 12.8 1.5690 25.1 0.0760 0.0734 0.0728 4.4
n-Hexane 5.84 1.4957 26 0.0836 0.0821 0.0805 3.9
Methylene chloride 1.35 1.4957 25 0.0909 0.0904 0.1074 715.3
Methylene chloride 6.10 1.4957 26.2 0.1090 0.1043 0.1082 0.7
Methylene chloride 1.74 1.5690 25.5 0.0945 0.1039 0.1078 712.3
Methylene chloride 3.51 1.5690 25.5 0.1074 0.1039 0.1078 70.4
Methylene chloride 6.26 1.5690 25.5 0.1118 0.1039 0.1078 3.7
Methylene chloride 9.28 1.5690 25.5 0.1101 0.1039 0.1078 2.1
Methylene chloride 12.8 1.5690 25.5 0.1081 0.1039 0.1078 0.3
Isooctane 5.63 1.4957 24.2 0.0675 0.0530 0.0672 0.4
Isooctane 4.1 1.4957 25.1 0.0675 0.0532 0.0678 7 0.6
Toluene 2.55 1.4957 24 0.0854 0.0852 0.0826 3.3

1457
 1458 K. C. KWON ET AL.

Loss amounts of a liquid A due to evaporation measured with a

balance were recorded at random evaporation durations. These experi-
mental data were applied to Equation (7) to obtain the value of a slope
through the linear least squares method, as shown in Figure 5. Diffusion
coefficient values can be calculated from slope values. The properties of
the liquid A such as the density rA and the molecular weight MA (Perry
and Chilton, 1973), the experimental temperature and pressure, and the
mole fraction yAo of the vapor A at the liquid surface of the liquid A in a
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diffusion tube were substituted into the slope value of the diffusion
equation to calculate a diffusion coefficient value. The vapor pressure of
the liquid A at the liquid surface in the diffusion-path tube was obtained
from the Antonie equation (Felder and Rousseau, 1986; Dean, 1992) to
calculate the mole fraction yAo of the vapor A at the liquid surface in the
diffusion tube.
Experimental diffusion values obtained from this study, as shown in
Table I, are compared with literature diffusion values (Coulson and
Richardson, 1984; Geankoplis, 1983; Reid and Sherwood, 1966; Bennett
and Myers, 1962; Berezhnoi and Semenov, 1997) and predicted diffusion
values of vapors of volatile liquids were calculated with Equation (6).

RESULTS AND DISCUSSIONS

Some experimental diffusion coefficients from this study are compared
with literature values as well as predicted values, as shown in Table I.

Figure 3. Amounts of n-heptane evaporated for various evaporation durations at various

lengths of diffusion path, using a 1.41 cm diameter diffusion tube.
 EXPERIMENTAL DIFFUSION EQUATION 1459
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Figure 4. Evaporation rates of volatile liquids at various diffusion lengths of the 1.41 cm
diameter glass tube over 24.7
25.7 C.

Figure 5. Loss amounts of liquid n-heptane due to its evaporation into air at various eva-
poration durations and various initial lengths of diffusion path (zo) under atmospheric
pressure.
 1460 K. C. KWON ET AL.

Diffusion experiments by evaporating liquid n-heptane, acetone, and

methylene chloride were conducted to find out effects of initial lengths of
diffusion path on their diffusion coefficients into air. The range of the
diffusion-path length is 1.3
12.8 cm. Amounts of n-heptane evaporated
were plotted at various evaporation durations and various lengths of
diffusion path, using a 1.41 cm diameter diffusion tube (see Figure 3). The
evaporation rates obtained from Figure 3 were plotted against the dif-
fusion lengths (see Figure 4). Figure 4 shows that evaporation rates
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decrease exponentially with increased diffusion-path lengths.

Amounts of n-heptane liquid evaporated in a diffusion tube decrease
with increased lengths of diffusion path for a given diffusion duration.
These data were applied to the developed diffusion equation (see Equa-
tion (7)), and values of the left-hand side of the diffusion equation con-
taining evaporated amounts of n-heptane liquid as a dependent variable
were plotted against evaporation durations as an independent variable.
Amounts of n-heptane liquid evaporated in the diffusion tube decrease
with increased lengths of diffusion path for a given diffusion duration,
and evaporation rates of liquids decrease exponentially with increased
lengths of diffusion path. However, the slope values of the straight lines
of n-heptane, computed with the linear least squares method, appear to
be nearly the same (see Figure 5). Diffusion values of n-heptane are
expected to be nearly the same, independent of diffusion-path length,
since diffusion values of n-heptane into air are computed with slope
values of these straight lines. These results indicate that diffusion coef-
ficients of n-heptane diffused into air are independent of initial lengths of
diffusion path at a given diffusion temperature.
The diffusion values of vapors of n-heptane, acetone, and methylene
chloride into air, calculated from the slope values of the straight lines,
were plotted against the diffusion lengths. Diffusion values of vapors of
n-heptane, acetone, and methylene chloride appear to be not affected
significantly with lengths of diffusion path above around 4 cm length of
diffusion path, although acetone and methylene chloride are very volatile
at room temperature in comparison with n-heptane (see Figure 6).
The following temperature equation is obtained from evaporation
rates and natural convection heat transfer coefficients (Holman, 1997;
Smith et al., 2001) on the outside wall of a diffusion tube. Bulk tem-
peratures of air-vapor mixtures in the diffusion tube at various diffusion
lengths were obtained from bulk temperatures of air around the outside
wall of the diffusion tube, using Equations (8)
(10). Differences between
bulk temperatures of air around the outside wall of the diffusion tube and
bulk temperatures of air-vapor mixture in the diffusion tube were plotted
against lengths of diffusion path, using experimental diffusion data of
n-heptane, acetone, and methylene chloride. Differences between bulk
temperatures of air around the outside wall of the diffusion tube and bulk
 EXPERIMENTAL DIFFUSION EQUATION 1461
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Figure 6. Effects of diffusion-path length on diffusion of vapors into stagnant air in the tem-
perature range of 24.7
25.7 C.

temperatures of air-vapor mixtures in the diffusion tube decrease expo-

nentially with increased length of diffusion path, as shown in Equation (8),
where the second term may be negligible in comparison with the first
term:
 0:8
q q lnðDDoi Þ
T1o
T1i ¼ þ ; ð8Þ
1:42pDo L0:75 2pkL

q ¼n
~DHv ; ð9Þ

~ ¼ ðmo
mÞ=t:
n ð10Þ

The Wilke-Lee equation (see Equation (6)) was applied to estimate

experimental errors in calculating diffusion coefficient values due to
cooling effects by evaporation of volatile liquids, since differences
between bulk temperatures of air around the outside wall of a diffusion
tube and bulk temperatures of air-vapor mixtures in the diffusion tube
were computed from Equation (8). Bulk temperatures of air around the
outside wall of the diffusion tube and bulk temperatures of vapor-air
mixtures in the diffusion tube were substituted into the Wilke-Lee
equation to obtain the following error equation (see Equation (11)).
Error percentages of diffusion values, based on diffusion values evaluated
at bulk temperatures of air around the outside wall of the diffusion tube,
were calculated with the error equation. Error percentages of diffusion
 1462 K. C. KWON ET AL.

values, based on diffusion values evaluated at bulk temperatures of air

around the outside wall of the diffusion tube, decrease with increased
diffusion-path lengths, as shown in Figure 7. More volatile liquids such
as acetone and methylene chloride require longer diffusion lengths than
less volatile liquids such as n-heptane and isooctane to obtain reasonably
accurate diffusion values with lower error percentages:

   1:5 !
DABi
DABo T1i
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Error  100 ¼  100 ¼
1  100: ð11Þ

DABo T1o

No fresh air flows across the top end of a diffusion tube. No cor-
rection on the length of the diffusion path was made in calculating dif-
fusion values with raw data. Errors of diffusion values are expected to
increase with decreased length of the diffusion path, because mole frac-
tions of a vapor at the top end of the diffusion path are neglected without
flowing fresh air over the top end of the diffusion path. Errors of diffu-
sion values may increase with decreased boiling points of volatile liquids
at a given diffusion-path length. Experimental diffusion values of vapors
into stagnant air, DABe, were obtained with raw data and Equation (12),
where yAt, mole fraction of vapors at the top end of the diffusion path, is
assumed to be negligible. Corresponding predicted diffusion values of
vapors into stagnant air, DABp, may be obtained with raw data and
Equation (13), where yAt, mole fraction of vapors at the top end of the
diffusion path, is not negligible.

Figure 7. Error percentages of diffusion values at various diffusion-path lengths, evaluated

at temperature differences between air and vapor-air mixture.
 EXPERIMENTAL DIFFUSION EQUATION 1463

Equation (14) can be derived from Equations (12) and (13). Mole
fractions of vapors at the top end of a diffusion path were obtained by
substituting both experimental diffusion values and predicted diffusion
values into Equation (14). Ratios of mole fractions of vapors at the top
end of the diffusion path to those at the bottom end of the diffusion path
for n-heptane, acetone, and methylene chloride were obtained at various
lengths of diffusion path, as shown in Figure 8. Ratios of mole fraction of
vapors at the top end of the diffusion path to those at the bottom end of
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the diffusion path appear to level off at around 4 cm length of diffusion

path, independent of their volatility. These observations may suggest that
reasonably accurate diffusion values can be obtained without flowing air
across the top end of a diffusion path and correcting lengths of diffusion
path by choosing a proper initial length of diffusion path. More volatile
liquids such as acetone and methylene chloride require longer lengths of
diffusion path than less volatile liquids such as n-heptane and isooctane
to obtain diffusion values of accuracy similar to those of less volatile
liquids:

m
m
mo
m 2PDABe MA lnð1=ð1
yAo ÞÞ

o
2zo þ ¼ t; ð12Þ
SrA SrA rA RT

m
m
mo
m 2PDABp MA lnðð1
yAt Þ=ð1
yAo ÞÞ

o
2zo þ ¼ t; ð13Þ
SrA SrA rA RT

Figure 8. Ratios of mole fractions of vapors at the top end to those at the bottom end of a
diffusion path at various lengths of diffusion path.
 1464 K. C. KWON ET AL.

 
  DABeD
DABp
1 ABp
yAt ¼ 1
: ð14Þ
1
yAo

Diffusion experiments with liquid n-heptane were conducted to find

out effects of evaporation areas on its diffusion coefficients into air,
as shown in Table I. The cross-sectional areas of the diffusion tubes for
these diffusion experiments are 0.5217 cm2, 0.9677 cm2, 1.4957 cm2,
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4.2637 cm2, and 11.2221 cm2. The initial length of diffusion path for these
experiments is 4.1 cm over the temperature range of 24.6
26 C.
Diffusion values of vapors of n-heptane appear to be not affected
significantly with cross-sectional areas of diffusion path, although slight
radial temperature distributions and axial temperature distributions may
be expected in large evaporation areas such as 11.2221 cm2 and
4.2638 cm2 in comparison with small evaporation areas such as 0.5217 cm2
and 0.9677 cm2. These results indicate that diffusion coefficients of n-
heptane diffused into air appear to be independent of evaporation areas.
Experimental diffusion values of various vapors into air were com-
pared with predicted diffusion values and literature diffusion values, as
shown in Table I. The results suggest that the experimental technique
yields reasonable agreement between the experimental values and the
predicted values. Although the results from this method are rather pre-
cise, it is also important to notice the limitations on this particular
diffusivity method. To obtain a good agreement between experimental
coefficients and predicted diffusion coefficients, a proper length and a
proper diameter of a diffusion tube are selected, depending on the
volatility of a chosen liquid.

CONCLUSIONS
This novel open-tube evaporation method is a simple and easy way to
obtain reasonable diffusion values. Experimental diffusion coefficients of
the vapor of a liquid into air in this study were obtained from amounts of
the liquid evaporated for evaporation durations with a balance rather
than changes in the liquid level in a diffusion tube versus evaporation
durations. No fresh air was passed over the top end of a diffusion tube in
this study. Experimental diffusion values of vapors diffused into air,
calculated by applying experimental diffusion data to the newly devel-
oped diffusion equation, appear to be reasonably agreeable with pre-
dicted values as well as literature values.
Our diffusion experiments clearly demonstrate the following new
facts. Several series of experiments with liquid n-heptane, acetone, and
methylene chloride were conducted to find out effects of initial lengths of
diffusion path on their diffusion coefficients into air. These results
 EXPERIMENTAL DIFFUSION EQUATION 1465

indicate that diffusion coefficients of these liquids’ vapors diffused into

air appear to be independent of initial lengths of diffusion path.
Diffusion values of vapors of n-heptane appear to be not affected
significantly with cross-sectional areas of diffusion path, although slight
radial temperature distributions and axial temperature distributions may
be expected in large evaporation areas such as 11.2221 cm2 and
4.2638 cm2 in comparison with small evaporation areas such as 0.5217 cm2
and 0.9677 cm2. These results indicate that diffusion coefficients of
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n-heptane diffused into air appear to be independent of evaporation areas.

Three main experimental errors of the novel open-tube evaporation
method are described in detail. The first experimental error source is
attributed to neglecting mole fractions of vapors at the top end of a
diffusion tube. The second experimental error source is attributed to
neglecting slight differences between bulk temperatures of air around the
outside wall of a diffusion tube and bulk temperatures of air-vapor
mixture in the diffusion tube due to heat of vaporization. Longer lengths
of diffusion path result in less experimental error, since the above two
experiment errors decrease exponentially with increased lengths of dif-
fusion path. However, longer diffusion lengths may be attributed to
increased experimental errors for less volatile liquids with high boiling
points, since lower loss amounts of less-volatile liquids result in increased
errors of measuring loss amounts with a balance.

NOMENCLATURE
DAB diffusivity, m2/s for Equation (6) and cm2/s for Equation (5)
DABe experimental diffusion values of vapors into stagnant air, cm2/s
DABi diffusion values at bulk temperature of a vapor-air mixture in a diffusion tube
DABo diffusion values at air bulk temperature around the outside wall of a diffusion
tube
DAbp predicted diffusion values of vapors into stagnant air, cm2/s
Di inside diameter of a diffusion tube, m
Do outside diameter of a diffusion tube, m
f (kT/eAB) collision function
k Boltzmann’s constant
L length of diffusion path, m
m amount of the liquid A in a diffusion tube at an evaporation duration t, g
MA molecular weight of a vapor A
MB molecular weight of a gas B
mo initial amount of the liquid A in a diffusion tube, g
mo 7 m loss amount of the liquid A due to evaporation for the evaporation duration t, g
NAz flux of the vapor A at steady state
P atmospheric pressure, atm for Equation (5), N/m2 for Equation (6)
q heat loss rate due to heat of vaporization, watt
R ideal gas constant, 82.0545 atm-cm3/g-mole-K for Equation (5)
rAB molecular separation at collision, rAB ¼ (rA þ rB)/2
S cross-sectional area of a diffusion tube, cm2
 1466 K. C. KWON ET AL.

T absolute temperature, K
t diffusion duration, s or min
T 1i bulk temperature of vapor-air mixture in the diffusion tube,  C or K
T 1o bulk temperature of air around the outside wall of the diffusion tube,  C or K
yAo mole fraction of the vapor A at the liquid surface in a diffusion tube at T and P
yAt mole fraction of vapor at the top end of the diffusion tube
z length of diffusion path, cm
zo initial length of diffusion path, cm
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eAB energy of molecular attraction, eAB ¼ (eAeB)1/2

rA density of the liquid A at T, g/cm3
DHv heat of vaporization, j/g
k thermal conductivity of a wall of a diffusion tube, w/m- C
ñ evaporation rate of a volatile liquid, g/s

ACKNOWLEDGMENTS
The authors thank Chemical Engineering students for conducting
experiments and obtaining 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 article. The
Tuskegee University Title III program — faculty development program
supports this research project.

REFERENCES
Bennett, C. O. and Myers, J. E. (1962). Momentum, Heat, and Mass Transfer,
McGraw-Hill, New York, 436
437.
Berezhnoi, A. N. and Semenov, A.V. (1997). Binary Diffusion Coefficients of
Liquid Vapors in Gases, Begell House, New York.
Bird, R. B., Stewart, W. E., and Lightfoot, E. N. (1960). Transport Phenomena,
John Wiley, New York.
Carmichael, L. T., Sage, B. H., and Lacey, W. N. (1955). Diffusion coefficients in
hydrocarbon systems: n-hexane in the gas phase of the methane-, ethane-,
and propane -n-hexane systems, AIChE J., 1(3), 385
390.
Coulson, J. M. and Richardson, J. F. (1984). Chemical Engineering, 3rd ed.,
Pergamon Press, New York, 275.
Dean, J. A. (1992). Lange’s Handbook of Chemistry, 14th ed., McGraw-Hill, New
York.
Felder, R. M. and Rousseau, R. W. (1986). Elementary Principles of Chemical
Processes, John Wiley, New York.
Gardner, P. J. and Preston, S. R. (1992). Binary gaseous diffusion coefficients for
iodine helium and in argon, J. Chem. Eng. Data, 37, 500
502.
Geankoplis, C. J. (1983). Transport Processes and Unit Operations, Allyn and
Bacon, Boston, 383.
 EXPERIMENTAL DIFFUSION EQUATION 1467

Hines, A. L. and Maddox, R. N. (1985). Mass Transfer Fundamentals and

Applications, Prentice-Hall, Englewood Cliffs, New Jersey, 19
25.
Holman, J. P. (1997). Heat Transfer, 8th ed., McGraw-Hill, New York.
Marrero, T. R. and Mason, E. A. (1972). Gaseous diffusion coefficients, J. Phys.
Chem. Ref. Data, 1(1) 3
118.
Mason, E. A. and Monchick, L. (1962). Transport properites of polar-gas mix-
tures, J. Chem. Phys., 36, 2746
2757.
Monfort, J. P. and Pellegatta, J. L. (1991). Diffusion coefficients of the halo-
Downloaded by [Washington University in St Louis] at 09:01 06 October 2014

carbons CCl2F2 and C2Cl2F4 with simple gases, J. Chem Eng. Data, 36,
135
137.
Nirdosh, I., Garred, L. J., and Baird, M. H. I. (2000). Low-cost mass transfer
experiments, Chem. Eng. Edu., 34, 158
161.
Perry, R. H. and Chilton, C. H. (1973). Chemical Engineer’s Handbook, 5th ed.,
McGraw-Hill, New York.
Reid, R. C., Prausnitz, J. M., and Poling, B. E. (1987). The Properties of Gases
and Liquids, 4th ed., McGraw-Hill, New York.
Reid, R. C. and Sherwood, T. K. (1966). The Properties of Gases and Liquids: Their
Estimation and Correlation, 2nd ed., McGraw-Hill, New York, 534
535.
Smith, J. M., Van Ness, H. C., and Abbott, M. M. (2001). Introduction to Chemical
Engineering Thermodynamics, 6th ed., McGraw-Hill, New York.
Tang, F. T. and Hawkes, S. (1984). Diffusion of propane in helium, J. Chem. Eng.
Data, 29, 124
126.
Treybal, R. E. (1980). Mass-Transfer Operations, McGraw-Hill, New York,
31
33.
Welty, J. R. Wicks, C. E., and Wilson, R. E. (1984). Fundamentals of Momentum,
Heat, and Mass Transfer, John Wiley, New York, 523
533.