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QSPR Flash Point Prediction of Solvents Using Topological Indices for Application in Computer Aided Molecular Design. Suhani J. Patel, Dedy Ng, and M. Sam Mannan* Volume 48, Issue 15 This revision corrects an unfortunate mistake in compiling data for experimental flash point values for hydrocarbons published in Table 4 (pages 7381-7384). The ensuing changes to the text of the publication are on the following pages: page 7378 in the Abstract “The neural network model showed higher accuracy (training set, r ) 0.939, R2 ) 0.883)”; page 7380 in the Methodology section “(range of flash points ) 513.15 K - 157.15 K ) 356 K, standard deviation ) 64.81 K)”; and page 7385 in the Results and Discussion “Upon using the entire data set for multiple linear regression analysis, poor accuracy was obtained (R2 ) 0.479, r ) 0.692)”, “The average absolute deviation is 20.819 K, the average absolute relative deviation is 6.57%, and the average bias is -0.21% for the data set using MLR”, “A 16:6:1 network (consisting of 16 input nodes as given in
Table 2, one output node, and one hidden layer with 6 nodes)”, “The average absolute relative deviation is 5.35%, the average absolute deviation is 16.08 K, and the average percent bias is -0.22% for the complete data set using ANN”. The ensuing changes for figures in the publication are Figures 3-5 (on page 7379), Figure 6 (on page 7380), and Figure 7 (on page 7385). The ensuing changes for tables in the publication are Tables 1 and 3 (on page 7380) and Table 4 (on pages 73817384). The authors gratefully acknowledge Mr. Max Bernhardt and Dr. Andreas Klamt (Universita¨t Regensburg, Germany), who found the issues with the reported flash point values and kindly brought these problems to our attention.
Figure 3. Distribution of flash point values in data set (n ) 236).
Figure 4. Box plots of test set and training set.
Figure 5. Distribution of flash point values for each class.
Ind. Eng. Chem. Res., Vol. 49, No. 17, 2010
Figure 6. Plot of calculated versus experimental values of flash point using MLR (graph depicts correlations from Table 1 for all classes).
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Figure 7. Plot of calculated versus experimental values of flash point using ANN.
Table 1. Results of Multiple Linear Regression on Different Classes of Solvents for Flash Point Predictiona training set
test set
class of solvents
equation
r
R2
R2(CV)
F
r
R2
monohydric alcohols polyhydric alcohols hydrocarbons amines ethers
Tf ) 9.248(SC:2) - 34.953(3χcluster) + 286.053 Tf ) 13.064(2κ) - 8.665(3κ) + 385.328 Tf ) 29.929(1χ) - 105.054 Tf ) 50.264(1χ) - 31.887(2χv) + 210.783 Tf ) 30.045(1χ) + 186.184
0.925 0.608 0.881 0.691 0.825
0.855 0.370 0.776 0.477 0.680
0.613
109.06 7.62 132.15 16.89 80.75
0.933 0.500 0.792 0.396 0.875
0.870 0.251 0.628 0.157 0.770
0.696 0.22 0.600
a 2 R ) coefficient of determination; r ) correlation coefficient; R2(CV) ) R2 for the cross validation set, F ) Fisher test statistic; SC:2 ) subgraph counts (second order): path; 3χcluster ) chi(3): cluster; nκ ) kappa-n; nχ ) chi(n); 2χv ) chi(2) (valence modified).
Table 3. Results of Neural Network Analysis for Flash Point Prediction (n ) 236, Network Configuration )16:6:1)
training set test set
r
R2
R2(CV)
0.940 0.878
0.883 0.772
0.638 0.664
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Table 4. Solvent Data Set with Experimental and Predicted (MLR and ANN) Flash Point Tf(predicted) (K) no.
iupac/cas name
Tf(exptl) (K)
MLR
ANN
283.706 286.483 298.15 295.372 303.15 284.261 313.706 294.261 347.039 331.483 358.15 353.15 377.594 373.706 325.372 356.483 393.15 324.15 386.15 332.15 346.15 314.15 306.15 354.15 386.15 313.15 341.15 302.15 333.15 314.15 293.15 302.15 330.15 350.15 333.15 327.15 418.15 327.15 377.15 389.15 284.817 309.817 330.372 324.817 340.928 363.706 295.372 347.039 383.15
286.053 295.302 304.55 308.776 308.776 271.635 318.024 296.24 332.294 334.407 345.769 360.038 369.287 362.152 309.714 352.904 396.931 308.776 331.452 336.521 341.542 327.272 318.024 350.79 392.489 322.204 349.948 296.24 351.918 322.251 296.24 305.488 334.407 352.904 331.32 336.342 406.279 349.106 364.265 397.031 293.617 313.798 323.046 318.024 349.948 350.79 304.55 352.904 361.058 349.948
285.091 281.885 274.462 301.044 291.057 258.303 308.542 288.576 321.632 325.531 347.779 357.757 371.028 354.812 348.755 350.476 378.539 307.247 385.71 333.879 332.95 321.81 333.533 346.454 472.342 305.993 367.998 306.357 330.423 316.174 288.576 311.749 325.531 347.905 325.312 307.242 416.163 332.281 369.771 404.323 278.532 297.732 308.322 317.046 311.449 346.454 326.194 352.845 378.618 408.592
392.594 411.483 435.928 477.594 377.594 397.039 416.483 433.15 382.039 394.261 402.594 372.15 352.15 366.15 358.15 401.15 425.15 420.15 374.15 380.15
389.86 411.722 423.681 438.116 380.062 420.52 409.9 401.138 380.919 404.435 411.722 380.062 402.925 401.138 388.364 404.435 404.435 414.388 374.379 419.21
375.36 407.13 445.617 478.926 373.765 422.148 412.671 424.783 392.755 394.196 406.614 369.324 382.459 385.339 366.991 383.484 377.609 417.903 395.676 383.197
Class: Monohydric Alcohols 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50
methanol ethanol propan-1-ol butan-2-ol 2-methylpropan-1-ol 2-methylpropan-2-ol pentan-2-ol 2-methylbutan-2-ol hexan-1-ol 2-ethylbutan-1-ol octan-2-ol nonan-1-ol decan-1-ol phenylmethanol 4-hydroxy-4-methylpentan-2-one 2-furylmethanol 2-methylpropanoic acid (3-hydroxy-2,2,4-trimethylpentyl) ester 1-chloropropan-2-ol 1,4-dibromobutan-2-ol heptan-2-ol heptan-1-ol hexan-2-ol 1-methoxypropan-2-ol octan-1-ol (2r)-2,4-dihydroxy-N-(3-hydroxypropyl)-3,3-dimethylbutanamide pentan-3-ol oct-1-en-3-ol 2,2,2-trifluoroethanol 2,3,4-trimethylpentan-1-ol 4-methylpentan-2-ol 2-methylbutan-2-ol 3,3-dimethylbutan-1-ol 2-ethylbutan-1-ol 2-ethylhexan-1-ol 2,2,4-trimethylpentan-1-ol 3-methylheptan-3-ol tetradecan-1-ol 5-methylheptan-3-ol 8-methylnonan-1-ol tridecan-1-ol propan-2-ola butan-1-ola pentan-1-ola 3-methylbutan-1-ola cyclohexanola octan-1-ola prop-2-en-1-ola 2-tetrahydrofuranylmethanola (1R)-1-(2-furyl)ethanola 5-methylheptan-1-ola
51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70
ethylene glycol 2-(2-hydroxyethoxy)ethanol 2-[2-(2-hydroxyethoxy)ethoxy]ethanol 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol propane-1,2-diol 3-(3-hydroxypropoxy)propan-1-ol 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol glycerol butane-1,3-diol butane-1,4-diol pentane-1,5-diol propane-1,1-diol propane-1,3-diol butane-1,2-diol butane-2,3-diol (E)-but-2-ene-1,4-diol but-2-yne-1,4-diol hexane-1,6-diol hexane-2,5-diol 2,2-diethylpropane-1,3-diol
Class: Polyhydric Alcohols
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Table 4. Continued Tf(predicted) (K) no.
iupac/cas name
Tf(exptl) (K)
MLR
ANN
71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
2,5-dimethylhex-3-yne-2,5-diol benzoic acid [4-[(oxo-phenylmethoxy)methyl]cyclohexyl]methyl ester [4-(hydroxymethyl)phenyl]methanol 2-butyl-2-ethylpropane-1,3-diol 3,6-dimethyloct-4-yne-3,6-diol 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 2,2-bis(hydroxymethyl)propane-1,3-diol (2R,3R,4R,5S)-hexane-1,2,3,4,5,6-hexol 2-(hydroxymethyl)-2-methylpropane-1,3-diol 2,2-dimethylpropane-1,3-diola 2-methylpentane-2,4-diola (2S)-butane-1,2,4-triola 2,3-dimethylbutane-2,3-diola 2-ethylhexane-1,3-diola 2-(2-hydroxyethylthio)ethanola hexane-1,2,6-triola
347.05 434.15 460.95 386.15 382.15 445.15 513.15 422.05 433.15 424.817 374.817 385.15 350.15 409.15 433.15 471.15
344.495 471.191 417.78 430.521 395.317 419.21 419.21 428.185 406.717 392.84 355.86 406.488 388.935 428.496 411.722 414.417
342.359 445.312 455.097 398.383 383.748 430 437.612 420.714 444.377 408.592 339.105 427.459 328.351 400.474 424.956 463.775
87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136
pentane hexane heptanes octane nonane decane dodecane cyclohexane cyclohexene benzene methylbenzene 1,2-dimethylbenzene 1,4-dimethylbenzene 1,3,5-trimethylbenzene isopropylbenzene tridecane tetradecane hexadecane heptadecane nonadecane isopentane isohexane 3-methylpentane 2,3-dimethylbutane buta-1,3-diene but-2-ene (z)-but-2-ene but-1-ene 2-methylprop-1-ene (Z)-pent-2-ene pent-1-ene dec-1-ene hept-1-ene cyclooctane cyclopenta-1,3-diene cyclopentane cyclopentene 2-methylheptane 4-vinylcyclohexene 4-methylpent-1-yne ethylbenzenea undecanea pentadecanea octadecanea tricosanea 2,2-dimethylbutanea 2-methylhexanea but-2-ynea 2,4,4-trimethylpent-1-enea 2,3,4-trimethylpent-2-enea
224.15 250.15 272.15 289.15 304.15 319.15 344.15 255.15 243.15 262.15 280.15 305.15 300.15 317.15 319.15 352.15 372.15 408.15 421.15 441.15 222.15 250.15 241.15 244.15 197.05 199.85 200.15 193.15 157.15 255.15 222.15 320.15 264.15 301.15 273.15 236.15 243.15 277.15 294.15 269.15 295.15 335.15 405.15 439.15 386.15 225.15 270.15 260.15 267.15 275.15
240.353 255.318 270.283 285.248 300.212 315.177 345.107 257.885 257.885 257.885 269.673 281.965 281.461 293.249 296.93 360.072 375.037 404.967 419.932 449.862 236.038 251.003 252.141 247.192 285.775 225.388 225.388 225.388 219.936 240.353 240.353 315.177 270.283 287.815 242.92 242.92 242.92 280.933 285.775 251.003 285.775 330.142 390.002 434.897 509.721 244.736 265.968 225.388 270.351 274.449
244.722 258.673 275.413 289.989 306.757 321.133 351.052 257.711 247.574 228.335 284.393 334.563 328.904 355.192 349.884 366.468 378.976 404.401 417.163 438.092 235.877 248.665 247.182 241.401 313.615 213.151 213.151 230.56 257.358 211.277 239.464 307.973 267.451 292.725 229.461 242.668 235.476 277.254 302.944 267.136 300.509 337.442 393.184 426.962 470.086 223.052 263.382 206.812 262.589 284.713
137 138 139 140
methoxymethane ethoxyethane 2-methoxy-2-methylpropane 2-isopropoxypropane
232.039 233.15 238.706 245.372
228.675 258.72 263.12 280.103
262.678 237.91 254.253 268.041
Class: Hydrocarbons
Class: Ether
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Table 4. Continued Tf(predicted) (K) no.
iupac/cas name
Tf(exptl) (K)
MLR
ANN
141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186
1-butoxybutane 1-pentoxypentane 1-ethenoxybutane 2-methyloxirane 2-ethyloxirane 1,4-dioxane (2,2-dimethyl-1,3-dioxolan-4-yl)methanol 2-methylfuran tetrahydrofuran tetrahydropyran methoxybenzene 1,2-bis(2-methoxyethoxy)ethane 2-(phenoxymethyl)oxirane 2-methoxy-2-methylbutane 2-(2-hydroxyethoxy)ethanol ethoxyethylene allyloxybenzene 2-methoxy-2-methylpropane phenylmethoxymethylbenzene 1-chloro-2-(2-chloroethoxy)ethane 1-chloro-2-methoxyethane 1-[2-(2-butoxyethoxy)ethoxy]butane 3-allyloxyprop-1-ene 1-chloro-4-(phenoxy)benzene 1-isopentyloxy-3-methylbutane 2-(allyloxymethyl)oxirane chloro-(chloromethoxy)methane 2-(butoxymethyl)oxirane 1-chloro-1-(1-chloroethoxy)ethane 1-butoxybutane 1,2-dimethoxybenzene 1,2-dimethoxyethane (3S,3aR,6R,6aR)-3,6-dimethoxy-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan phenoxybenzene 1,3,5-trioxane ethoxyethylene 1-hexoxyhexanea ethoxyethylenea 1-ethenoxy-2-methylpropanea furana phenoxybenzenea 4-(4-aminophenoxy)anilinea chloro-methoxymethanea 4,7,7-trimethyl-8-oxabicyclo[2.2.2]octanea 1-pentoxypentanea 1-ethenoxypropanea
304.261 330.372 263.706 235.928 260.928 291.483 267.039 243.15 247.594 253.15 324.817 386.15 388.15 262.15 416.15 228.15 335.15 245.15 408.15 328.15 288.15 374.15 266.15 386.15 319.15 321.15 292.15 314.15 328.15 298.15 345.15 271.15 376.15 388.15 318.15 227.15 349.817 227.594 263.706 237.594 388.15 491.15 289.15 322.15 330.15 247.15
318.811 348.856 288.765 243.085 259.25 276.32 310.541 273.131 261.298 276.32 304.318 363.879 349.916 279.965 288.765 258.72 334.363 263.12 410.007 288.765 258.72 408.947 288.765 391.794 340.193 304.318 258.72 319.341 280.103 318.811 332.822 273.743 362.361 379.961 276.32 258.72 378.901 258.72 284.434 261.297 379.961 403.628 243.697 336.993 348.856 273.743
291.177 327.25 274.498 242.002 258.008 298.632 320.874 280.25 266.445 280.536 321.482 364.855 379.468 278.489 407.13 259.356 336.911 254.253 422.252 328.89 278.95 373.549 295.111 415.391 318.73 298.392 300.365 330.12 305.909 291.177 363.198 292.028 355.042 391.754 314.384 259.356 363.131 259.356 285.693 238.432 391.754 464.648 268.983 322.116 327.25 253.605
187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212
acetamide 1-(2-pyridyl)ethanone 2-(bis(2-hydroxyethyl)amino)ethanol prop-2-en-1-amine 6-methyl-2-pyridinamine 2-(2-aminoethoxy)ethanol 2-pyridinamine aniline phenylmethanamine 3-bromopyridine butan-2-amine 2-methylpropan-2-amine 3-chloroaniline 2-chloroaniline 2-chloropyridine 2,4,6-trimethylpyridine 2-pyridinecarbonitrile 3-pyridinecarbonitrile 4-pyridinecarbonitrile 1-cyclohexyl-2-pyrrolidinone cyclohexanamine N-pentylpentan-1-amine 2,6-ditert-butylpyridine ethane-1,2-diamine N-cyclohexylcyclohexanamine N,N-diethylacetamide
315.15 349.15 452.15 245.15 376.15 400.15 236.15 343.15 345.15 324.15 254.15 235.15 391.15 371.15 337.15 330.15 362.15 357.15 361.15 418.15 300.15 277.15 345.15 330.35 376.15 343.15
278.371 370.67 390.196 290.279 346.839 346.534 341.367 336.39 354.535 314.827 280.705 235.866 337.668 340.514 332.276 343.568 366.108 365.256 365.441 379.197 304.905 382.028 334.552 288.59 380.74 343.773
310.272 389.519 436.342 300.604 351.516 385.27 318.273 310.158 337.317 298.997 283.293 257.271 352.07 365.247 306.731 358.223 341.904 344.993 347.087 404.158 295.267 329.366 331.44 327.026 376.24 326.557
Class: Amines
Ind. Eng. Chem. Res., Vol. 49, No. 17, 2010 Table 4. Continued Tf(predicted) (K)
a
no.
iupac/cas name
Tf(exptl) (K)
MLR
ANN
213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236
N-ethylethanamine 2-diethylaminoethanol diethylcyanamide N-(2-aminoethyl)ethane-1,2-diamine N,N-diethylformamide 1-(2-hydroxypropylamino)propan-2-ol n-isopropylpropan-2-amine N-methylmethanamine N,N-dimethylaniline 2-dimethylaminoethanol N,N-dimethylformamide 3,5-dimethylpiperidine heptan-2-amine heptan-1-amine 3-methyl-2-pyridinaminea propan-1-aminea 2-bromopyridinea butan-1-aminea 4-chloroanilinea N-allylprop-2-en-1-aminea N-butylbutan-1-aminea 2-(2-hydroxyethylamino)ethanola N,N-dimethylacetamidea 2-aminoethanola
245.15 324.65 342.15 363.15 333.15 399.15 266.15 255.15 336.15 313.15 330.15 294.65 327.15 317.15 384.15 243.15 327.15 261.15 461.15 280.15 312.15 411.15 336.15 358.15
301.613 348.285 338.401 340.071 336.669 343.034 288.95 265.924 356.04 301.33 290.798 302.183 321.424 337.285 347.631 281.851 318.717 295.71 337.778 342.997 354.311 344.221 298.548 290.664
237.992 336.194 316.907 358.463 316.305 405.999 263.146 244.246 353.182 323.81 293.096 303.333 316.324 316.826 371.888 259.021 303.486 279.44 356.749 286.198 294.626 405.273 328.412 351.183
The solvents belonging to the test set for MLR calculations.
IE101378H 10.1021/ie101378h Published on Web 08/05/2010
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