2
0
2019
wu
zha
0
journal
Original
Wu, F.[Fan]
Zhao, Q.[Qinghu]
Tao, L.[Lefu]
Danaci, D.[David]
Xiao, P.[Penny]
Hasan, F. A.[Fatin Abbas]
Webley, P. A.[Paul A.]
J. Chem. Eng. Data
2019
2020-09-29
Solubility of Carbon Monoxide and Hydrogen in Methanol and Methyl Formate: 298-373 K and 0.3-3.3 MPa
In this study, we report the solubility of the gases carbon monoxide (CO) and hydrogen (H2) in methanol and methyl formate using the synthetic isothermal method via total pressure measurement. The motivation for these measurements is to provide data to better understand the reactions occurring during a two-step gas-liquid methanol synthesis method via a methyl formate pathway. Specifically, the solubility of the pairs CO-methanol, CO-methyl formate, H2-methanol and H2-methyl formate were measured at different pressures (0.3 MPa to 3.3 MPa) and temperatures (298 K to 373 K). The solubility of H2 in methanol and methyl formate is lower than that of CO in methanol and methyl formate. The solubility of both H2 and CO in methanol and methyl formate increase with temperature. Thermodynamic properties, including the Gibbs free energy, the enthalpy of dissolution, and the entropy of dissolution were determined and are within expected ranges. The enthalpy of dissolution is positive suggesting stronger solute-solute than solutesolvent interactions. The modified Peng-Robinson Equation of State (PR-EoS) was used to calculate the gas-liquid equilibrium and can successfully correlate and represent the experimental solubility data within an error of 5%.
10.1021/acs.jced.9b00676
12
64
5609-5621
1
InChI=1S/CH4O/c1-2/h2H,1H3
OKKJLVBELUTLKV-UHFFFAOYSA-N
methanol
methyl alcohol
CH4O
1
Commercial source
1
99.9
3
Stated by supplier
2
InChI=1S/C2H4O2/c1-4-2-3/h2H,1H3
TZIHFWKZFHZASV-UHFFFAOYSA-N
methyl methanoate
formic acid, methyl ester
methanoic acid, methyl ester
methyl formate
C2H4O2
1
Commercial source
1
99
2
Stated by supplier
3
InChI=1S/CO/c1-2
UGFAIRIUMAVXCW-UHFFFAOYSA-N
carbon monoxide
CO
1
Commercial source
1
99.995
5
Stated by supplier
4
InChI=1S/H2/h1H
UFHFLCQGNIYNRP-UHFFFAOYSA-N
hydrogen
hydrogen (normal)
H2
1
Commercial source
1
99.999
5
Stated by supplier
5
InChI=1S/CO2/c2-1-3
CURLTUGMZLYLDI-UHFFFAOYSA-N
carbon dioxide
CO2
1
Commercial source
1
99.995
5
Stated by supplier
1
3
1
1
1
Principal objective of the work
EP
EP
8/20/2019
1
Mole fraction
Phase equilibration
3
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Gas
1
Temperature, K
Liquid
2
Pressure, kPa
3
Gas
1
298.15
5
2
241.5
4
1
0.00085
2
1
0.0004
1
298.15
5
2
609.3
4
1
0.00197
3
1
0.0004
1
298.15
5
2
1082
5
1
0.00358
3
1
0.0008
1
298.15
5
2
1587
5
1
0.00553
3
1
0.001
1
298.15
5
2
2101.1
5
1
0.0077
3
1
0.0014
1
298.15
5
2
2616.7
5
1
0.00927
3
1
0.0018
1
298.15
5
2
3148.9
5
1
0.01146
4
1
0.0022
1
322.71
5
2
260.5
4
1
0.00093
2
1
0.0002
1
322.71
5
2
600.5
4
1
0.00238
3
1
0.0006
1
322.71
5
2
1073.7
5
1
0.00415
3
1
0.0006
1
322.71
5
2
1587.6
5
1
0.00642
3
1
0.001
1
322.71
5
2
2109.9
5
1
0.00825
3
1
0.001
1
322.71
5
2
2642
5
1
0.01022
4
1
0.0018
1
322.71
5
2
3167.2
5
1
0.01198
4
1
0.002
1
347.76
5
2
287.8
4
1
0.00109
3
1
0.0004
1
347.76
5
2
598.8
4
1
0.00249
3
1
0.0006
1
347.76
5
2
1075.4
5
1
0.0046
3
1
0.0008
1
347.76
5
2
1591.9
5
1
0.00702
3
1
0.001
1
347.76
5
2
2133.3
5
1
0.0098
3
1
0.0022
1
347.76
5
2
2680.1
5
1
0.01218
4
1
0.0024
1
347.76
5
2
3232.2
5
1
0.01499
4
1
0.003
1
372.9
5
2
508.7
4
1
0.00237
3
1
0.0008
1
372.9
5
2
968.9
4
1
0.00464
3
1
0.0006
1
372.9
5
2
1489.4
5
1
0.00735
3
1
0.001
1
372.9
5
2
2025
5
1
0.0103
4
1
0.0018
1
372.9
5
2
2562.3
5
1
0.01323
4
1
0.0026
1
372.9
5
2
3118
5
1
0.01588
4
1
0.0022
2
3
1
2
1
Principal objective of the work
EP
EP
8/20/2019
1
Mole fraction
Phase equilibration
3
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Gas
1
Temperature, K
Liquid
2
Pressure, kPa
3
Gas
1
299.72
5
2
243
4
1
0.00178
3
1
0.0004
1
299.72
5
2
567.8
4
1
0.00343
3
1
0.0006
1
299.72
5
2
1024.6
5
1
0.00635
3
1
0.0014
1
299.72
5
2
1554.2
5
1
0.00984
3
1
0.0014
1
299.72
5
2
2046.7
5
1
0.01296
4
1
0.0018
1
299.72
5
2
2563
5
1
0.01646
4
1
0.002
1
299.72
5
2
3088.3
5
1
0.01974
4
1
0.0022
1
322.82
5
2
435.6
4
1
0.00251
3
1
0.0006
1
322.82
5
2
950.2
4
1
0.00617
3
1
0.0008
1
322.82
5
2
1522.5
5
1
0.01011
4
1
0.0012
1
322.82
5
2
2031.8
5
1
0.01359
4
1
0.0014
1
322.82
5
2
2554
5
1
0.01773
4
1
0.002
1
322.82
5
2
3097.8
5
1
0.02132
4
1
0.0024
1
347.88
5
2
664.9
4
1
0.00558
3
1
0.0008
1
347.88
5
2
1033.2
5
1
0.00813
3
1
0.001
1
347.88
5
2
1434.5
5
1
0.01118
4
1
0.0012
1
347.88
5
2
1933.3
5
1
0.01481
4
1
0.002
1
347.88
5
2
2474.5
5
1
0.01864
4
1
0.0022
1
347.88
5
2
3027.4
5
1
0.02291
4
1
0.0024
1
372.86
5
2
470.6
4
1
0.00384
3
1
0.0006
1
372.86
5
2
805.5
4
1
0.00669
3
1
0.0008
1
372.86
5
2
1189.5
5
1
0.01031
4
1
0.001
1
372.86
5
2
1678.7
5
1
0.0143
4
1
0.0014
1
372.86
5
2
2205.2
5
1
0.01896
4
1
0.002
1
372.86
5
2
2747
5
1
0.02417
4
1
0.0024
3
4
1
1
1
Principal objective of the work
VVD
TRC
2/20/2020
1
Mole fraction
Phase equilibration
4
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Gas
1
Temperature, K
Liquid
2
Pressure, kPa
4
Gas
1
296.87
5
2
236.8
4
1
0.0004
2
1
0.0002
1
296.87
5
2
616.6
4
1
0.00106
3
1
0.0002
1
296.87
5
2
1102.7
5
1
0.0019
3
1
0.0004
1
296.87
5
2
1607
5
1
0.00273
3
1
0.0004
1
296.87
5
2
2126.9
5
1
0.00361
3
1
0.0008
1
296.87
5
2
2649.1
5
1
0.00453
3
1
0.0008
1
296.87
5
2
3173.9
5
1
0.00537
3
1
0.001
1
320.34
5
2
262.1
4
1
0.0005
2
1
1e-05
1
320.34
5
2
620.9
4
1
0.00115
3
1
0.0002
1
320.34
5
2
1102.1
5
1
0.00208
3
1
0.0002
1
320.34
5
2
1613.7
5
1
0.00306
3
1
0.0004
1
320.34
5
2
2116.5
5
1
0.004
3
1
0.0006
1
320.34
5
2
2647
5
1
0.00498
3
1
0.001
1
348.26
5
2
275.4
4
1
0.00059
2
1
0.0002
1
348.26
5
2
577.7
4
1
0.00124
3
1
0.0002
1
348.26
5
2
1046.2
5
1
0.00223
3
1
0.0004
1
348.26
5
2
1565.2
5
1
0.00334
3
1
0.0006
1
348.26
5
2
2095.2
5
1
0.00452
3
1
0.0006
1
348.26
5
2
2608.2
5
1
0.0056
3
1
0.0008
1
374.85
5
2
841
4
1
0.00211
3
1
0.0006
1
374.85
5
2
1024.1
5
1
0.00257
3
1
0.0004
1
374.85
5
2
1474.5
5
1
0.00368
3
1
0.0004
1
374.85
5
2
1987.7
5
1
0.005
3
1
0.0008
1
374.85
5
2
2521
5
1
0.00638
3
1
0.001
1
374.85
5
2
3047.9
5
1
0.00766
3
1
0.001
4
4
1
2
1
Principal objective of the work
VVD
TRC
2/20/2020
1
Mole fraction
Phase equilibration
4
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Gas
1
Temperature, K
Liquid
2
Pressure, kPa
4
Gas
1
296.63
5
2
238.2
4
1
0.00052
2
1
1e-05
1
296.63
5
2
656.1
4
1
0.00141
3
1
0.0002
1
296.63
5
2
1083.7
5
1
0.00234
3
1
0.0004
1
296.63
5
2
1572.9
5
1
0.00342
3
1
0.0004
1
296.63
5
2
2083.4
5
1
0.00438
3
1
0.0006
1
296.63
5
2
2597.6
5
1
0.0053
3
1
0.0008
1
296.63
5
2
3116.8
5
1
0.00642
3
1
0.0008
1
325.45
5
2
444.6
4
1
0.00117
3
1
0.0002
1
325.45
5
2
1207.8
5
1
0.00318
3
1
0.0002
1
325.45
5
2
1435.9
5
1
0.00377
3
1
0.0004
1
325.45
5
2
1874.5
5
1
0.00487
3
1
0.0004
1
325.45
5
2
2375.8
5
1
0.00628
3
1
0.0006
1
325.45
5
2
2884.7
5
1
0.00771
3
1
0.0008
1
348.38
5
2
462.1
4
1
0.00169
3
1
0.0002
1
348.38
5
2
1126.9
5
1
0.00395
3
1
0.0002
1
348.38
5
2
1436.9
5
1
0.00509
3
1
0.0006
1
348.38
5
2
1840.9
5
1
0.00656
3
1
0.0008
1
348.38
5
2
2303.1
5
1
0.00814
3
1
0.0012
1
348.38
5
2
2828.5
5
1
0.00992
3
1
0.001
1
371.61
5
2
467.2
4
1
0.00237
3
1
0.0002
1
371.61
5
2
658.7
4
1
0.00321
3
1
0.0004
1
371.61
5
2
1098.2
5
1
0.00593
3
1
0.0008
1
371.61
5
2
1538.8
5
1
0.00842
3
1
0.001
1
371.61
5
2
2083.8
5
1
0.01104
4
1
0.0016
1
371.61
5
2
467.2
4
1
0.00237
3
1
0.0002
5
5
1
1
1
Principal objective of the work
EP
EP
8/20/2019
1
Mole fraction
Phase equilibration
5
Liquid
Direct value, X
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
Gas
1
Temperature, K
Liquid
2
Pressure, kPa
5
Gas
1
300.78
5
2
247.7
4
1
0.016
3
1
0.0008
1
300.78
5
2
485.6
4
1
0.0315
3
1
0.0014
1
300.78
5
2
852.6
4
1
0.0551
3
1
0.0013
1
300.78
5
2
1291.5
5
1
0.0843
3
1
0.0017
1
300.78
5
2
1752.8
5
1
0.1164
4
1
0.0021
1
300.78
5
2
2228.1
5
1
0.1506
4
1
0.0026
1
300.78
5
2
2711.9
5
1
0.1847
4
1
0.003
1
322.91
5
2
319.2
4
1
0.0147
3
1
0.0008
1
322.91
5
2
527.6
4
1
0.0244
3
1
0.0014
1
322.91
5
2
912.4
4
1
0.0414
3
1
0.0012
1
322.91
5
2
1356
5
1
0.0614
3
1
0.0016
1
322.91
5
2
1835.3
5
1
0.0839
3
1
0.0021
1
322.91
5
2
2330.8
5
1
0.1081
4
1
0.0021
1
322.91
5
2
2826.8
5
1
0.1338
4
1
0.0029
1
351.33
5
2
317.5
4
1
0.0128
3
1
0.0008
1
351.33
5
2
489.7
4
1
0.0177
3
1
0.0014
1
351.33
5
2
882
4
1
0.0286
3
1
0.0012
1
351.33
5
2
1347.5
5
1
0.0414
3
1
0.0018
1
351.33
5
2
1840.6
5
1
0.0556
3
1
0.0024
1
351.33
5
2
2357.3
5
1
0.0723
3
1
0.003
1
351.33
5
2
2879.7
5
1
0.0908
3
1
0.0035
1
376.36
5
2
622.8
4
1
0.021
3
1
0.0038
1
376.36
5
2
807.8
4
1
0.0251
3
1
0.0003
1
376.36
5
2
1205.7
5
1
0.0338
3
1
0.0016
1
376.36
5
2
1683.6
5
1
0.0448
3
1
0.0022
1
376.36
5
2
2190.8
5
1
0.0553
3
1
0.0028
1
376.36
5
2
2712.8
5
1
0.0695
3
1
0.0034