Vapor Pressure Predictions of Multi-Functional Oxygen-Containing Organic Compounds With

SUPPLEMENTARY MATERIAL

Vapor pressure predictions of multi-functional oxygen-containing organic compounds with COSMO-RS

Bernd Schröder*1, Michal Fulem2, Mónia A. R. Martins1

1 Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

2 Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28, Prague 6, Czech Republic

*e-mail:

SM 1. Available phase transition literature data used for deriving subcooled liquid vapor pressures according eq.4.

Compound / Tfus/ K / / kJ·mol˗1 / as/
J·mol˗1·K˗1 / bs/
J·mol˗1·K˗2 / al/
J·mol˗1·K˗1 / bl/
J·mol˗1·K˗2
2,2,3,3-Tetramethylbutane / 373.94 ± 0.05 [A,B] / 7.5404 ± 0.00669
[A,B] / 37.176473 [B] / 0.677945 [B] / 32.020112 [B] / 0.656753 [B]
Pentanedioic acid / 371 ± 0.264 [B] / 23 ± 0.141
[B,C] / -23.63951 a[B] / 0.653196 a[B] / 224.042857 [B] / 0.217321 [B]
2,2-Dimethyl-1-propanol / 328.20 ± 2.94b [B,D] / 2.9 ± 0.2
[B,D] / -72.75017 [B] / 0.961436 [B] / 60.011204 [B] / 0.638496 [B]

a – derived from heat capacity at saturation pressure for the phase transition (Crystal 1, Gas)

b – assigned error reflects deviations in available experimental data

[A] Scott et al., 1952

Scott, D. W.; Douslin, D. R.; Gross, M. E.; Oliver, G. D.; Huffman, H. M., 2,2,3,3-Tetramethylbutane: Heat Capacity, Heats of Transition, Fusion and Sublimation, Vapor Pressure, Entropy and Thermodynamic Functions. J. Am. Chem. Soc., 1952, 74, 883-887.

[B] derived from evaluated TDE data

[C] derived from Steele et al., 2002

Steele, W. V.; Chirico, R. D.; Cowell, A. B.; Knipmeyer, S. E.; Nguyen, A., Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for 1,4-Diisopropylbenzene, 1,2,4,5-Tetraisopropylbenzene, Cyclohexanone Oxime, Dimethyl Malonate, Glutaric Acid, and Pimelic Acid. J. Chem. Eng. Data, 2002, 47, 725-739.

[D] Straka et al., 2007

Straka, M.; van Genderen, A.; Růžička, K.; Růžička, V., Heat Capacities in the Solid and in the Liquid Phase of Isomeric Pentanols, J. Chem. Eng. Data, 2007, 52, 794-802.

SM 2. Parameter of the pV expansion equation (eq.6) used in the calculation of solid vapor pressures, as obtained from TDE. Parameter a4…a8 are omitted (zero).

Compound / <T>/ K / a1 / a2 / a3
2,2,3,3-Tetramethylbutane / 273.15 to 373.944 / 54.852 / -6885.5 / -5.39725
Pentanedioic acid / 338 to 371 / 34.2198 / -14343.4 / -0.245536
2,2-Dimethyl-1-propanol / 274.2 to 328.2 / 30.5361 / -6753.77 / -1.35608

SM 3. Critically evaluated solid and liquid vapor pressures, pS and pL, at T = 298.15 K, for the compounds treated with eq.5.

Compound / log(pS/ kPa) / log(pL/ kPa)
2,2,3,3-Tetramethylbutane / 0.437 / 0.722
Pentanedioic acid / -6.640 / -6.050
2,2-Dimethyl-1-propanol / 0.068 / 0.107

SM 4. COSMO-RS predictions from the BP-TZVPD-FINE method, regarding all relevant conformers, plotted versus critically evaluated (subcooled) liquid vapor pressures, pL, at T = 298.15 K. Captions are valid for both plots.

SM 5. COSMO-RS parameter for the predicted vapor pressures fitted to the Antoine equation ln(p) = A – B / (T + C) (ln(p)/ [kPa]).

BP-TZVP, all conformers / BP-TZVPD-FINE, all conformers / BP-TZVP, most stable conformer / BP-TZVP-FINE, most stable conformer
A / B / C / A / B / C / A / B / C / A / B / C
Non-oxygenated hydrocarbons
Cyclohexane / 14.783449 / 3229.8452 / -19.310029 / 15.877268 / 3868.857646 / -0.25752 / 14.783445 / 3229.845 / -19.31 / 15.877265 / 3868.857646 / -0.25751891
1,1-Dimethylcyclopentane / 15.191877 / 3625.0425 / -19.198341 / 16.105638 / 4101.933841 / -0.25093 / 15.191875 / 3625.042 / -19.1983 / 16.105635 / 4101.933841 / -0.2509289
trans-1,3-Dimethylcyclopentane / 15.326803 / 3743.6026 / -19.518609 / 16.138222 / 4148.079489 / -0.28089 / 15.326805 / 3743.603 / -19.5186 / 16.138225 / 4148.079489 / -0.28089138
2,2-Dimethylpentane / 15.529222 / 3515.5353 / -21.438082 / 16.268444 / 4008.72271 / -0.25684 / 15.529225 / 3515.535 / -21.4381 / 16.268445 / 4008.72271 / -0.2568352
1,1-Dimethylcyclohexane / 15.420489 / 3977.4392 / -19.0985 / 16.456634 / 4579.819682 / -0.23152 / 15.419985 / 3976.922 / -19.0964 / 16.456275 / 4579.664863 / -0.23253377
cis-1,2-Dimethylcyclohexane / 15.455137 / 4000.536 / -19.271301 / 16.482721 / 4609.220895 / -0.25192 / 15.455135 / 4000.536 / -19.2713 / 16.482725 / 4609.220895 / -0.25192448
2,2,4-Trimethylpentane / 15.800651 / 3830.5187 / -21.201923 / 16.495007 / 4287.583087 / -0.26225 / 15.800655 / 3830.519 / -21.2019 / 16.495005 / 4287.583087 / -0.26225143
2,3,4-Trimethylpentane / 15.771975 / 3803.3054 / -21.461295 / 16.532533 / 4333.191228 / -0.26723 / 15.771975 / 3803.305 / -21.4613 / 16.532535 / 4333.191228 / -0.2672265
2,2,3,3-Tetramethylbutane / 15.535813 / 3607.2364 / -21.193444 / 16.446372 / 4235.512097 / -0.27071 / 15.535815 / 3607.236 / -21.1934 / 16.446375 / 4235.512097 / -0.2707053
Alcohols
1,2-Propanediol / 18.166924 / 4887.457 / -72.375553 / 19.539658 / 5984.537389 / -44.0808 / 17.957595 / 4908.136 / -69.477 / 19.043575 / 5841.94622 / -44.9414339
2-Butanol / 16.020221 / 3546.906 / -69.960536 / 17.628885 / 4406.723104 / -45.2997 / 16.312245 / 3537.569 / -68.0214 / 17.976875 / 4545.675312 / -42.2983901
2-Methyl-1-propanol / 16.75171 / 3678.8713 / -70.556848 / 18.396795 / 4736.286926 / -38.6134 / 16.705365 / 3697.029 / -69.5169 / 18.266105 / 4715.951967 / -38.0442095
1-Butanol / 17.210707 / 3961.7138 / -69.497584 / 18.61598 / 5021.130035 / -33.4708 / 17.108435 / 3920.564 / -68.7476 / 18.580225 / 4997.980858 / -33.2303846
1,4-Butanediol / 19.901187 / 6091.9418 / -61.930645 / 20.638025 / 7431.778575 / -20.6139 / 19.663235 / 6031.973 / -60.6298 / 20.395655 / 7398.997341 / -16.4224931
2,3-Butanediol / 17.78592 / 4937.2626 / -68.944387 / 19.816395 / 6485.789423 / -23.6349 / 17.644505 / 4894.592 / -66.9422 / 19.335765 / 6155.542462 / -25.1206912
1,3-Butanediol / 18.966262 / 5687.7924 / -62.824169 / 20.352202 / 7192.942802 / -22.7818 / 18.643315 / 5544.917 / -62.1912 / 20.324335 / 7.28E+03 / -1.61E+01
1,2-Butanediol / 18.267899 / 5057.9894 / -71.861694 / 19.179907 / 5867.108515 / -44.735 / 18.195945 / 5096.902 / -69.7534 / 19.332325 / 6141.127855 / -33.8102127
1,5-Pentanediol / 19.795998 / 6017.1004 / -75.836565 / 22.317193 / 7866.133701 / -40.1613 / 21.364585 / 6342.791 / -72.0428 / 22.999875 / 8476.115644 / -31.1012411
1-Pentanol / 17.488111 / 4289.3607 / -68.446457 / 19.316897 / 5634.264546 / -28.8261 / 17.090995 / 4085.887 / -68.7004 / 19.191805 / 5556.308421 / -30.21801
Cyclohexanol / 16.629787 / 4199.2846 / -65.256324 / 18.31101 / 5091.837263 / -41.5978 / 16.480145 / 4394.106 / -61.8174 / 18.943365 / 5840.956107 / -31.1906726
1-Hexanol / 17.741462 / 4618.3208 / -67.454826 / 18.966793 / 5586.846107 / -35.2218 / 17.635225 / 4570.502 / -66.7726 / 19.207225 / 5745.413178 / -32.5095465
2-Methyl-2-pentanol / 16.499901 / 3993.8975 / -66.724024 / 17.335372 / 4455.337183 / -51.1196 / 16.522155 / 4021.366 / -65.9477 / 16.620475 / 4113.475907 / -54.2605891
2,3-Dimethyl-2-butanol / 16.304168 / 3843.5984 / -66.387923 / 17.010947 / 4252.02466 / -53.2062 / 16.319415 / 3864.035 / -66.7579 / 17.017935 / 4242.401145 / -53.634167
2-Methyl-2,4-pentanediol / 18.919414 / 5907.647 / -62.908898 / 21.075718 / 7826.550868 / -16.9518 / 18.569305 / 5789.671 / -60.622 / 20.189065 / 7219.178454 / -25.3704356
2-Methyl-cis-cyclohexanol / 15.855631 / 4245.5125 / -62.241451 / 17.40696 / 5029.344164 / -44.1477 / 15.683265 / 4172.43 / -61.1863 / 16.949585 / 4749.581323 / -48.6553767
1,2,3-Propanetriol / 18.364731 / 5610.236 / -74.383918 / 19.171922 / 6236.785432 / -57.827 / 18.491295 / 5442.693 / -66.771 / 20.229255 / 6274.781598 / -57.5738368
2,2-Dimethyl-1-propanol / 16.375842 / 3706.6931 / -68.837517 / 17.352675 / 4273.940544 / -49.6805 / 16.252165 / 3646.12 / -68.1602 / 17.631745 / 4415.298748 / -46.9126668
2-Pentanol / 16.733336 / 3909.5989 / -70.044634 / 18.358163 / 4898.832773 / -41.7964 / 16.615555 / 3879.364 / -69.4668 / 18.193885 / 4857.474106 / -41.9413829
1,2-Pentanediol / 17.945124 / 5071.5982 / -74.694676 / 19.557852 / 6316.377862 / -34.2645 / 18.466885 / 5389.326 / -69.3284 / 19.946265 / 6642.353911 / -25.8685411
3-Hexanol / 16.555499 / 4041.0879 / -66.150859 / 17.606323 / 4704.194436 / -46.4993 / 16.567295 / 4036.845 / -66.2349 / 17.045575 / 4421.023249 / -50.8415136
1,6-Hexanediol / 20.698522 / 6618.5852 / -73.357511 / 23.009493 / 8502.604451 / -35.7454 / 20.500935 / 6625.47 / -69.441 / 23.326895 / 8857.791746 / -31.2716205
Cycloheptanol / 16.619362 / 4619.42 / -66.218829 / 18.93352 / 5965.640834 / -37.1091 / 16.895365 / 4816.812 / -62.9443 / 19.244805 / 6267.326674 / -30.9955023
1,7-Heptanediol / 21.259399 / 7087.7669 / -71.736437 / 23.464004 / 8940.662995 / -34.7949 / 21.037755 / 7100.783 / -68.7976 / 23.592575 / 9192.975936 / -31.536775
Aldehydes and ketones
Butanal / 14.759245 / 3074.9712 / -29.48923 / 15.421801 / 3467.13464 / -18.0002 / 14.759245 / 3074.971 / -29.4892 / 15.421805 / 3467.13464 / -18.0001972
2-Methylpropanal / 14.646961 / 3010.8731 / -27.274242 / 15.360944 / 3400.495229 / -14.3209 / 14.646965 / 3010.873 / -27.2742 / 15.360945 / 3400.495229 / -14.3208786
Cyclopentanone / 14.742663 / 3834.403 / -21.827578 / 15.626887 / 4259.599873 / -15.2914 / 14.742665 / 3834.403 / -21.8276 / 15.626885 / 4259.599873 / -15.2914025
Cyclohexanone / 14.949946 / 4264.2204 / -20.482955 / 15.987791 / 4795.318164 / -10.4356 / 14.949945 / 4264.22 / -20.483 / 15.987795 / 4795.318164 / -10.4356315
3-Hexanone / 15.433177 / 3990.6345 / -25.773592 / 16.059642 / 4408.910201 / -14.6507 / 15.433175 / 3990.635 / -25.7736 / 16.059645 / 4408.910201 / -14.6507124
4-Hydroxy-4-methyl-2-pentanone / 15.046757 / 4492.6857 / -41.306342 / 16.265969 / 4980.101807 / -30.753 / 15.531065 / 4765.017 / -27.7939 / 15.834355 / 4755.221743 / -31.9172196
Heptanal / 15.888957 / 4366.2789 / -25.664027 / 16.533406 / 4879.42591 / -10.1825 / 15.888955 / 4366.279 / -25.664 / 16.533405 / 4879.42591 / -10.1825334
Hexanal / 15.473268 / 3935.8851 / -26.132847 / 16.154363 / 4407.036336 / -11.6297 / 15.473265 / 3935.885 / -26.1328 / 16.154365 / 4407.036336 / -11.6297112
2-Heptanone / 15.894217 / 4487.8779 / -26.138261 / 16.420678 / 4897.037984 / -15.0159 / 15.894215 / 4487.878 / -26.1383 / 16.420675 / 4897.037984 / -15.0159005
Octanal / 16.316943 / 4799.2274 / -25.214696 / 16.913864 / 5335.191027 / -9.14625 / 16.316945 / 4799.227 / -25.2147 / 16.913865 / 5335.191027 / -9.14624622
2-Octanone / 16.318983 / 4914.4183 / -25.752213 / 16.803495 / 5365.32699 / -12.9547 / 16.318985 / 4914.418 / -25.7522 / 16.803495 / 5365.32699 / -12.9547443
Carboxylic acids
Propanoic / 17.315567 / 4393.346 / -60.586866 / 18.004329 / 5038.368783 / -34.7608 / 17.156735 / 4212.521 / -63.6176 / 18.016065 / 4938.954672 / -36.6540871
2-Methylpropanoic / 17.557982 / 4422.3817 / -62.775156 / 18.736118 / 5185.835126 / -33.784 / 17.312295 / 4411.163 / -62.9703 / 18.105955 / 5063.986095 / -35.4651181
Butanoic / 17.901464 / 4541.8705 / -61.948918 / 18.649233 / 5188.894162 / -36.8561 / 17.313545 / 4450.482 / -63.3738 / 18.293675 / 5240.503547 / -36.0508834
3-Methylbutanoic / 17.467097 / 4617.253 / -64.398013 / 18.114704 / 5222.173778 / -38.0872 / 17.495795 / 4653.017 / -63.419 / 18.213045 / 5241.68174 / -37.866165
Pentanedioic / 19.830764 / 7664.7478 / -63.732495 / 20.746914 / 8873.799788 / -35.939 / 19.935535 / 7789.033 / -56.3174 / 21.087765 / 9154.960502 / -27.3413827
Ethanoic / 17.079474 / 4113.3285 / -63.294854 / 18.622151 / 4901.220761 / -36.5268 / 17.111195 / 4120.641 / -63.2969 / 17.746945 / 4762.344827 / -38.0705265
Pentanoic / 17.422055 / 4657.5769 / -63.664474 / 18.228636 / 5363.997108 / -37.5102 / 17.500675 / 4677.073 / -63.3388 / 18.397305 / 5395.228748 / -37.2125707
4-Oxo-pentanoic / 16.31157 / 5663.023 / -61.215583 / 18.072574 / 6842.58122 / -36.491 / 16.217775 / 6026.077 / -29.1771 / 16.529835 / 6069.787831 / -36.3972616
2-Ethyl-butanoic / 18.318982 / 4851.8775 / -63.532036 / 19.540782 / 5767.024467 / -32.9118 / 17.672015 / 4870.38 / -63.1422 / 18.961735 / 5817.751132 / -31.9093925
4-Methyl-pentanoic / 17.64426 / 4979.252 / -62.862043 / 18.40294 / 5662.516639 / -37.2238 / 17.743545 / 5009.362 / -62.3311 / 18.615255 / 5720.440299 / -36.3915977
Hexanoic / 17.763256 / 5045.8441 / -62.524731 / 18.656376 / 5875.505028 / -35.9163 / 17.833025 / 5064.717 / -62.2268 / 18.838355 / 5919.671243 / -35.395289
Heptanoic / 18.008255 / 5351.0947 / -62.618974 / 18.843689 / 6168.027569 / -35.7327 / 18.179745 / 5409.876 / -61.6193 / 19.098715 / 6255.285029 / -34.4031203
Octanoic / 18.350579 / 5706.9895 / -61.383762 / 19.121808 / 6568.84471 / -34.2491 / 18.495615 / 5751.032 / -60.7073 / 19.393515 / 6627.947563 / -33.7148465
Nonanoic / 18.891044 / 6127.1979 / -60.139888 / 19.677681 / 7045.372012 / -32.2746 / 18.892685 / 6130.012 / -60.0309 / 19.685695 / 7018.088608 / -32.9759204

SM6a. Predicted COSMO-RS vapor pressures vs. critical evaluated experimental vapor pressures, at the BP-TZVP level of theory, most stable conformers only (captions valid for all figures).

SM 6b. Predicted COSMO-RS vapor pressures vs. critical evaluated experimental vapor pressures, at the BP-TZVPD-FINE level of theory, most stable conformers only.

SM 6c. Logarithm of standard error of each estimate, at the BP-TZVP level of theory, most stable conformers only.

SM 6d. Logarithm of standard error of each estimate, at the BP-TZVPD-FINE level of theory, most stable conformers only.

SM 7. Results of the Donahue volatility binning principle

log Ci*
No. / Compound / experimental / BP-TZVPD-FINE
1 / Cyclohexane / 9 / 9
2 / 1,1-Dimethylcyclopentane / 9 / 9
3 / trans-1,3-Dimethylcyclopentane / 9 / 9
4 / 2,2-Dimethylpentane / 9 / 9
5 / 1,1-Dimethylcyclohexane / 8 / 8
6 / cis-1,2-Dimethylcyclohexane / 8 / 8
7 / 2,2,4-Trimethylpentane / 8 / 9
8 / 2,3,4-Trimethylpentane / 8 / 9
9 / 2,2,3,3-Tetramethylbutane / 8 / 9
10 / 1,2-Propanediol / 6 / 6
11 / 2-Butanol / 8 / 8
12 / 2-Methyl-1-propanol / 8 / 8
13 / 1-Butanol / 7 / 7
14 / 1,4-Butanediol / 4 / 5
15 / 2,3-Butanediol / 6 / 6
16 / 1,3-Butanediol / 5 / 5
17 / 1,2-Butanediol / 6 / 6
18 / 1,5-Pentanediol / 4 / 4
19 / 1-Pentanol / 7 / 7
20 / Cyclohexanol / 7 / 7
21 / 1-Hexanol / 7 / 7
22 / 2-Methyl-2-pentanol / 8 / 7
23 / 2,3-Dimethyl-2-butanol / 8 / 7
24 / 2-Methyl-2,4-pentanediol / 6 / 5
25 / 2-Methylciscyclohexanol / 7 / 7
26 / 1,2,3-Propanetriol / 3 / 5
27 / 2,2-Dimethyl-1-propanol / 8 / 8
28 / 2-Pentanol / 7 / 7
29 / 1,2-Pentanediol / 5 / 6
30 / 3-Hexanol / 7 / 7
31 / 1,6-Hexanediol / 3 / 4
32 / Cycloheptanol / 6 / 6
33 / 1,7-Heptanediol / 4 / 3
34 / Butanal / 9 / 9
35 / 2-Methylpropanal / 9 / 9
36 / Cyclopentanone / 8 / 8
37 / Cyclohexanone / 7 / 7
38 / 3-Hexanone / 8 / 8
39 / 4-Hydroxy-4-methyl-2-pentanone / 7 / 7
40 / Heptanal / 7 / 7
41 / hexanal / 8 / 8
42 / 2-Heptanone / 7 / 7
43 / Octanal / 7 / 7
44 / 2-Octanone / 7 / 7
45 / Propanoic / 7 / 7
46 / 2-Methylpropanoic / 7 / 7
47 / Butanoic / 7 / 7
48 / 3-Methylbutanoic / 6 / 7
49 / Pentanedioic / 2 / 2
50 / Ethanoic / 8 / 7
51 / Pentanoic / 6 / 7
52 / 4-Oxo-pentanoic / 4 / 4
53 / 2-Ethyl-butanoic / 6 / 7
54 / 4-Methyl-pentanoic / 6 / 6
55 / Hexanoic / 5 / 6
56 / Heptanoic / 5 / 6
57 / Octanoic / 5 / 5
58 / Nonanoic / 4 / 5

SM 8. Comparison of different prediction methods

All data taken unadjusted from Asher et al. (2002), except COSMO-RS data from this work.

1.