2
0
2017
hai
doh
0
journal
Original
Haidl, J.[Jan]
Dohnal, V.[Vladimir]
J. Chem. Eng. Data
2017
2020-09-29
Dilute Vapor Absorption: A New Accurate Technique for Measurement of the Limiting Activity Coefficient of Water in Hydrophobic Solvents of Lower Volatility
An accurate experimental method for the determination of the limiting activity coefficient of water in hydrophobic solvents was described theoretically; the pertinent apparatus was built and its performance was duly verified. The method is based on continuously saturating the solvent by a gas stream of a constant and known humidity up to the attainment of the steady state and subsequent determination of the water content in the solvent by Karl Fischer titration. Using this new method, accurate values of the limiting activity coefficient of water were determined in eight selected solvents. The measurements were carried out at several temperatures and from these data the infinite dilution dissolution enthalpy and entropy of water in the solvents were evaluated. They both exhibit highly positive values reflecting the breakage of the hydrogen bonding network of water upon its dissolution in the solvents. Prediction of the water limiting activity coefficients was further attempted using the Modified UNIFAC method and found to fail dramatically, the calculated values being lower than the experimental ones by a factor ranging from 2 to 10. General lack of reliable limiting water activity coefficient data and their unreliable prediction indicate the significance of both the new method and the acquired data.
Infinite dilution
Dissolution enthalpy
Aromatic ethers
Aromatic halogenates
Water
10.1021/acs.jced.7b00114
9
62
2713-2720
1
InChI=1S/C2HCl3/c3-1-2(4)5/h1H
XSTXAVWGXDQKEL-UHFFFAOYSA-N
trichloroethene
1,1,2-trichloroethylene
trichloroethylene
C2HCl3
1
Commercial source
1
99.5
3
Stated by supplier
2
99.5
3
Gas chromatography
2
InChI=1S/C7H8/c1-7-5-3-2-4-6-7/h2-6H,1H3
YXFVVABEGXRONW-UHFFFAOYSA-N
toluene
methylbenzene
C7H8
1
Commercial source
1
99.5
3
Stated by supplier
2
99.6
3
Gas chromatography
3
InChI=1S/C7H8O/c1-8-7-5-3-2-4-6-7/h2-6H,1H3
RDOXTESZEPMUJZ-UHFFFAOYSA-N
anisole
anisol
methoxybenzene
methyl phenyl ether
phenoxymethane
phenyl methyl ether
C7H8O
1
Commercial source
1
99.7
3
Stated by supplier
2
99.9
3
Gas chromatography
4
InChI=1S/C8H10O/c1-2-9-8-6-4-3-5-7-8/h3-7H,2H2,1H3
DLRJIFUOBPOJNS-UHFFFAOYSA-N
ethoxybenzene
benzene, ethoxy-
ethyl phenyl ether
phenetole
C8H10O
1
Commercial source
1
99
2
Stated by supplier
2
99
3
Gas chromatography
5
InChI=1S/C7H7BrO/c1-9-7-4-2-6(8)3-5-7/h2-5H,1H3
QJPJQTDYNZXKQF-UHFFFAOYSA-N
1-bromo-4-methoxybenzene
4-bromomethoxybenzene
anisole, p-bromo-
p-bromoanisole
C7H7BrO
1
Commercial source
1
99
2
Stated by supplier
2
99.5
3
Gas chromatography
6
InChI=1S/C7H5F3/c8-7(9,10)6-4-2-1-3-5-6/h1-5H
GETTZEONDQJALK-UHFFFAOYSA-N
(trifluoromethyl)benzene
.alpha.,.alpha.,.alpha.-trifluorotoluene
benzene, (trifluoromethyl)-
benzenyl fluoride
benzotrifluoride
benzylidyne fluoride
phenylfluoroform
trifluoromethylbenzene
C7H5F3
1
Commercial source
1
99
2
Stated by supplier
2
99.8
3
Gas chromatography
7
InChI=1S/C6H5Cl/c7-6-4-2-1-3-5-6/h1-5H
MVPPADPHJFYWMZ-UHFFFAOYSA-N
chlorobenzene
monochlorobenzene
phenyl chloride
C6H5Cl
1
Commercial source
1
99.5
3
Stated by supplier
2
99.9
3
Gas chromatography
8
InChI=1S/C6H5Br/c7-6-4-2-1-3-5-6/h1-5H
QARVLSVVCXYDNA-UHFFFAOYSA-N
bromobenzene
phenyl bromide
C6H5Br
1
Commercial source
1
99.5
3
Stated by supplier
2
99.9
3
Gas chromatography
9
InChI=1S/H2O/h1H2
XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
H2O
1
Commercial source
1
99.9
3
Estimated by the compiler
1
1
1
9
1
Principal objective of the work
EP
EP
3/14/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Pressure, kPa
Liquid
99
2
2
Mole fraction
9
Liquid
0
1
1
Temperature, K
Liquid
1
278.15
5
1
1200
2
1
126
1
283.15
5
1
978
3
1
102
1
288.15
5
1
806
3
1
84
1
293.15
5
1
663
3
1
69
1
298.15
5
1
524
3
1
54
1
303.15
5
1
441
3
1
45
2
2
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
283.15
5
1
620
2
1
57
1
293.15
5
1
423
3
1
39
1
303.15
5
1
300
1
1
27
1
313.15
5
1
214
3
1
19
1
318.15
5
1
184
3
1
16
1
323.15
5
1
155
3
1
14
3
3
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
95.3
3
1
8.3
1
303.15
5
1
84.4
3
1
7.3
1
308.15
5
1
75.8
3
1
6.6
1
313.15
5
1
68.8
3
1
6
1
318.15
5
1
61.7
3
1
5.3
1
323.15
5
1
55.9
3
1
4.8
1
328.15
5
1
50
3
1
4.3
4
4
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
110
4
1
9.6
1
303.15
5
1
97
3
1
8.5
1
308.15
5
1
87.3
3
1
7.6
1
313.15
5
1
77.7
3
1
6.8
1
318.15
5
1
69.9
3
1
6.1
1
323.15
5
1
62.7
3
1
5.4
5
5
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
119.2
4
1
10.5
1
303.15
5
1
105.9
4
1
9.3
1
308.15
5
1
93.7
3
1
8.2
1
313.15
5
1
83.3
3
1
7.3
1
318.15
5
1
74.1
3
1
6.4
1
323.15
5
1
65.5
3
1
5.7
6
6
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
362
3
1
33
1
303.15
5
1
302
3
1
27
1
308.15
5
1
256
3
1
23
1
313.15
5
1
218
3
1
20
1
318.15
5
1
181
3
1
16
1
323.15
5
1
155
3
1
14
7
7
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
376
3
1
34
1
303.15
5
1
318
3
1
29
1
308.15
5
1
271
3
1
24
1
313.15
5
1
235
3
1
21
1
318.15
5
1
202
3
1
18
1
323.15
5
1
177
3
1
16
8
8
1
9
1
Principal objective of the work
BDH
TRC
3/13/2017
1
Activity coefficient
Chemical equilibration / Heterogeneous equilibration
9
Liquid
Direct value, X
Pure liquid solute
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Mole fraction
9
Liquid
0
1
2
Pressure, kPa
Liquid
100
1
1
Temperature, K
Liquid
1
298.15
5
1
367
3
1
33
1
303.15
5
1
311
3
1
28
1
308.15
5
1
264
3
1
24
1
313.15
5
1
226
3
1
20
1
318.15
5
1
189
3
1
17
1
323.15
5
1
164
3
1
15