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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).
1093-0191/04/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S1093-0191(03)00039-X
668
ts
rART
z2 yz2o.
2PDABMA ln1y1yyAo..
(1)
669
ization duration t is obtained from the following equation (see Fig. 1).
zszoq
moym.
(2)
SrA
rART
2PDABMAln1y1yyAo..
B moym EB
=C
D
SrA
FC2zoq
GD
moym E
F
SrA G
(3)
DAB s
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
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
Vapor
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
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
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.
(6)
(7)
Ayks1.21Tb
(8)
rABs(rAqrB)y2
(9)
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)
674
Table 5
Experimental, predicted, and literature value of diffusion coefficients
Vapora
Temperature
(8C)
Experimental
DAB (cm2 ys) and
its deviation (%)
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
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)
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.
Fig. 5. Comparison of experimental pseudo-binary diffusion coefficient values of normal alcohols with literature values and predicted
values at atmospheric pressure.
676
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.
677
678
T:
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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