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Supplementary Material forEnthalpies of Formation of Four Isoxazole Derivatives in the Solid and Gas Phases: Application to the Study of

Chemical Equilibria

Gastón Perdomoa, Henoc Flores*a, Rafael Notariob, E. Adriana Camarilloa, M. Patricia Amadora.aFacultad de Ciencias Químicas de la Benemérita Universidad Autónoma de Puebla, 14 sur y Av. San Claudio, C.P.

72570, Puebla Pue, México.

bInstituto de Química Física “Rocasolano”, CSIC, Serrano 119, 28006 Madrid, Spain.

TABLE S1. G3- and G4-calculated energies, at T = 0 K, E0, and enthalpies at T = 298 K, H298, in Hartrees.

G3 G4

E0 H 298 E0 H298

35dmi4c -512.924334 -513.018012 -512.913403 -513.007240

5mi3c -473.646749 -473.733927 -473.637661 -473.724890

3a5mi -340.484847 -340.547473 -340.477180 -340.539824

5a3mi -340.484897 -340.547373 -340.477195 -340.539732

35dmi -324.498677 -324.490724

TABLE S2. Values of the combustion experiments of benzoic acid to T = 298.15 K, p° = 0.1 MPa.1 2 3 4 5 6

m(ba)/g 0.99193 1.00270 0.99470 1.02705 1.00458 1.01196m(cotton)/g 0.00372 0.00340 0.00345 0.00336 0.00328 0.00315m(pt.)/g 11.51542 11.51562 11.52154 11.52819 11.52194 11.51846

∆T c=(T f−T i−∆T corr )/K 2.5866 2.6150 2.5945 2.6780 2.6188 2.6371

−ε (cont)(−∆T c)/kJ 0.0439 0.0444 0.0441 0.0457 0.0445 0.0449

∆U ign/kJ 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042

−∆U IBP/kJ 26.2835 26.5628 26.3521 27.2059 26.6105 26.8033

(−m Δcu°)(cotton)/kJ 0.0630 0.0576 0.0585 0.0569 0.0556 0.0534

(−m Δcu°)(ba) /kJ 26.2205 26.5052 26.2937 27.1490 26.5549 26.7499

ε (calor)/kJ ∙K−1 10.1461 10.1425 10.1415 10.1435 10.1460 10.1485

⟨ ε (calor)/kJ ∙ K−1 ⟩=10.1447±0.0011m(ba) is the mass of benzoic acid; m(cotton) is the mass of cotton thread; m(pt.) is the mass of platinum; ε (cont) energy equivalent of the bomb

contents ; ∆T c is the corrected temperature; ∆U ign is the ignition energy; ∆U IBP is the change of energy for the isothermal bomb process;

∆U Σ is the energy of standard state correction; −m Δc u° is the product of the mass of benzoic acid or cotton respectively, and standard

massic energy of combustion; ε (calor) is the energetic equivalent of calorimeter.The uncertainty associated with average result of specific combustion energy is the standard deviation of mean, which implies a Type A standard uncertainty. The benzoic acid is in solid phase.

TABLE S3. Values of the combustion experiments for 35dmi4c to T = 298.15 K, p° = 0.1 MPa.

1 2 3 4 5 6

m(cpd.)/g 0.99615 1.00532 0.99369 1.00060 0.99891 1.00220

m(poly.)/g 0.06941 0.07169 0.06694 0.07284 0.07226 0.06852

m(cotton)/g 0.00489 0.00454 0.00132 0.00322 0.00299 0.00332

m(pt.)/g 11.51519 11.52145 11.51533 11.51610 11.51712 11.51533

∆T c=(T f−T i−∆T corr )/K 2.3254 2.3506 2.3002 2.3487 2.3425 2.3312

∆T corr /K 0.0384 0.0464 0.0461 0.0437 0.0357 0.0381

ε i(cont)/kJ ∙ K−1 0.0174 0.0174 0.0174 0.0174 0.0174 0.0174

ε f (cont)/kJ ∙ K−1 0.0183 0.0183 0.0183 0.0183 0.0183 0.0183

∆U ign/kJ 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042

−∆U IBP/kJ 23.6263 23.8824 23.3701 23.8631 23.8000 23.6852

∆U dec(HNO3)/kJ 0.0057 0.0071 0.0056 0.0064 0.0063 0.0066

∆U Σ /kJ 0.0170 0.0172 0.0169 0.0171 0.0171 0.0171

(−m Δcu °)(poly .)/kJ 3.2187 3.3243 3.1041 3.3777 3.3508 3.1774

(−m Δcu °)(cotton)/kJ 0.0829 0.0769 0.0224 0.0546 0.0507 0.0563

(−Δcu° )(c pd .) /kJ ∙g−1 20.3805 20.3486 20.3495 20.3951 20.3973 20.3830

⟨ (−∆ cu° ) /kJ ∙ g−1 ⟩ = 20.3757±0.0088

m(cpd), mass of compound; m(poly), mass of polyethylene; m(cotton.), mass of cotton thread; m(pt), mass of platinum that includes the crucible and ignition wire; ∆Tc, corrected temperature rise; Ti, initial temperature; Tf, final temperature; Tcorr , correction term; εi (cont), initial energy equivalent of the bomb; εf (cont), final energy equivalent of the bomb; ∆Uign, ignition energy; ∆UIBP, energy of the isothermal bomb process; ∆Udec (HNO3) is energy of decomposition of nitric acid; ∆UΣ, correction to the standard states; m∆cu°(poly), mass energy of combustion of polyethylene; m∆cu°(catton), mass energy of combustion of cotton; and ∆cu°(cpd), mass energy of combustion calculated. The uncertainty associated with average result of specific combustion energy is the standard deviation of mean, which implies a Type A standard uncertainty. The 35dmi4c is in solid phase.

TABLE S4. Values of the combustion experiments for 5mi3c to T = 298.15 K, p° = 0.1 MPa.

1 2 3 4 5 6

m(cpd.)/g 1.00669 1.20370 1.19880 1.20293 1.20169 1.20321

m(cotton)/g 0.00403 0.00364 0.00405 0.00381 0.00408 0.00403

m(pt.)/g 11.51581 11.51590 11.51656 11.51529 11.51470 11.51994

∆T c=(T f−T i−∆T corr )/K 1.7708 2.1109 2.1059 2.1115 2.1104 2.1132

∆T corr /K 0.0470 0.0446 0.0430 0.0437 0.0464 0.0437

ε i(cont)/kJ ∙ K−1 0.00171 0.0173 0.0173 0.0173 0.0173 0.0173

ε f (cont)/kJ ∙ K−1 0.0176 0.0180 0.0180 0.0180 0.0180 0.0180

∆U ign/kJ 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042

−∆U IBP/kJ 17.9898 21.4463 21.3954 21.4523 21.4412 21.4696

∆U dec(HNO3)/kJ 0.0056 0.0065 0.0064 0.0065 0.0065 0.0065

∆U Σ /kJ 0.164 0.0200 0.0200 0.0200 0.0200 0.0200

(−m Δcu °)(cotton)/kJ 0.0683 0.0617 0.0686 0.0646 0.0691 0.0683

(−Δcu° )(c pd .) /kJ ∙g−1 17.7805 17.7437 17.7681 17.7576 17.7630 17.7648

⟨ (−∆ cu° ) /kJ ∙ g−1 ⟩ = 17.7630±0.0049

The symbols have the same meaning as in table S3.The uncertainty associated with average result of specific combustion energy is the standard deviation of mean, which implies a Type A standard uncertainty. The 5mi3c is in solid phase.

TABLE S5. Values of the combustion experiments for 5a3mi to T = 298.15 K, p° = 0.1 MPa.

1 2 3 4 5 6

m(cpd.)/g 1.00638 1.00947 1.00383 1.00522 1.00634 1.00164

m(cotton)/g 0.00393 0.00438 0.00346 0.00298 0.00377 0.00377

m(pt.)/g 11.51471 11.51671 11.51457 11.51519 11.51646 11.51804

∆T c=(T f−T i−∆T corr )/K 2.4189 2.4289 2.4113 2.4137 2.4200 2.4083

∆T corr /K 0.0348 0.0355 0.0403 0.0374 0.0404 0.0550

ε i(cont)/kJ ∙ K−1 0.0173 0.0173 0.0173 0.0173 0.0173 0.0172

ε f (cont)/kJ ∙ K−1 0.0182 0.0182 0.0182 0.0182 0.0182 0.0182

∆U ign/kJ 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042

−∆U IBP/kJ 24.5762 24.6779 24.4990 24.5234 24.5874 24.4683

∆U dec(HNO3)/kJ 0.0107 0.0109 0.0098 0.0101 0.0107 0.0097

∆U Σ /kJ 0.0149 0.0149 0.0148 0.0148 0.0149 0.0148

(−m Δcu °)(cotton)/kJ 0.0666 0.0742 0.0586 0.0505 0.0639 0.0639

(−Δcu° )(c pd .) /kJ ∙g−1 24.3288 24.3473 24.3226 24.3210 24.3436 24.3400

⟨ (−∆ cu° ) /kJ ∙ g−1 ⟩ = 24.3339±0.0046

The symbols have the same meaning as in table S3.The uncertainty associated with average result of specific combustion energy is the standard deviation of mean, which implies a Type A standard uncertainty. The 5a3mi is in solid phase.

TABLE S6. Values of the combustion experiments for 3a5mi to T = 298.15 K, p° = 0.1 MPa.

1 2 3 4 5 6

m(cpd.)/g 1.00820 1.00185 1.00488 1.00604 1.03105 1.00263

m(cotton)/g 0.00294 0.00404 0.00432 0.00422 0.00372 0.00431

m(pt.)/g 11.51623 11.51998 11.53430 11.51540 11.51541 11.51604

∆T c=(T f−T i−∆T corr )/K 2.4150 2.4015 2.4092 2.4117 2.4712 2.4051

∆T corr /K 0.0456 0.0340 0.0404 0.0407 0.0392 0.0388

ε i(cont)/kJ ∙ K−1 0.0175 0.0175 0.0175 0.0175 0.0175 0.0175

ε f (cont)/kJ ∙ K−1 0.0182 0.0182 0.0182 0.0182 0.0183 0.0182

∆U ign/kJ 0.0042 0.0042 0.0042 0.0042 0.0042 0.0042

−∆U IBP/kJ 24.5372 24.4000 24.4783 24.5037 25.1083 24.4366

∆U dec(HNO3)/kJ 0.0102 0.0088 0.0095 0.0097 0.0120 0.0089

∆U Σ /kJ 0.0148 0.0147 0.0148 0.0148 0.0152 0.0148

(−m Δcu °)(cotton)/kJ 0.0498 0.0685 0.0732 0.0715 0.0630 0.0730

(−Δcu° )(c pd .) /kJ ∙g−1 24.2634 24.2631 24.2624 24.2612 24.2647 24.2761

⟨ (−∆ cu° ) /kJ ∙ g−1 ⟩ = 24.2652±0.0022

The symbols have the same meaning as in table S3.The uncertainty associated with average result of specific combustion energy is the standard deviation of mean, which implies a Type A standard uncertainty. The 3a5mi is in solid phase.

TABLE S7. Effusion experimental results of 35dmi4c at T med=343.7K .

ts

TK

Δmg

(dm /d t )x 103

g ∙ s−1

ν=[( d md t )x 103∙√T ]g·s-1· K1/2

ln ( ν )

Δm1 Δm2 Δm3d m1

d td m2

d td m3

d t1 2 3 1 2 3

23400.0 333.15 0.02836 0.01853 0.01205 0.00121 0.00079 0.00051 0.02212 0.01445 0.00940 -3.8112 -4.2368 -4.6671

28800.0 336.15 0.04783 0.03250 0.02140 0.00166 0.00113 0.00074 0.03045 0.02069 0.01362 -3.4917 -3.8783 -4.2960

28800.0 339.15 0.05863 0.03856 0.02664 0.00204 0.00134 0.00093 0.03749 0.02465 0.01703 -3.2837 -3.7028 -4.0725

28830.0 342.15 0.08249 0.05297 0.04305 0.00286 0.00184 0.00149 0.05292 0.03398 0.02762 -2.9389 -3.3819 -3.5892

21674.0 345.15 0.08490 0.05840 - 0.00392 0.00269 - 0.07277 0.05006 - -2.6204 -2.9945 -

24560.0 345.15 - - 0.04540 - - 0.00185 - - 0.03434 - - -3.3713

18144.0 348.15 0.11499 0.06481 0.05059 0.00634 0.00357 0.00279 0.11825 0.06665 0.05202 -2.1350 -2.7083 -2.9561

7282.0 351.15 0.05998 - - 0.00824 - - 0.15435 - - -1.8686 - -

13720.0 351.15 - 0.07143 - - 0.00521 - - 0.09755 - - -2.3273 -

12646.0 351.15 - - 0.04810 - - 0.00380 - - 0.07127 - - -2.6413

7297.0 354.15 0.08094 0.05775 0.03953 0.01109 0.00791 0.00542 0.20873 0.14892 0.10195 -1.5667 -1.9043 -2.2833

1, 2, 3: cells with effusion orifices of different diameter.Standard uncertainties u are u(t)=0.1 s, u(T)=0.10 K, u(m)=0.01 mg, and the combined expanded uncertainty Uc is Uc(m/t)=8.63·10-10 g·s-1, Uc(ν)=4.0·10-4 g·s-1·K1/2.

a)b)

c)

Figure S1. Plots of Ln() versus 1/T of 3,5-dimethylisoxazole-4-carboxylic acid. a) Cell1, b) Cell2, c) Cell3.

TABLE S8. Experimental effusion results of 5mi3c at T med=343.7K .

ts

TK

Δmg

(d m /d t )x 103

g ∙ s−1

ν=[( d md t )x 103 ∙√T ]g·s-1· K1/2

ln ( ν )

Δm1 Δm2 Δm3 Δm4d m1

d td m2

d td m3

d td m4

d t1 2 3 4 1 2 3 4

18176.0 333.15 0.01333 - - - 0.00073 - - - 0.01339 - - - -4.3135 - - -

18176.0 333.15 - 0.00969 - - - 0.00053 - - - 0.00973 - - - -4.6321 - -

18160.0 333.15 - - 0.00621 - - - 0.00034 - - - 0.00624 - - - -5.0761 -

18085.0 333.15 - - - 0.00173 - - - 0.00010 - - - 0.00175 - - - -6.3504

18115.0 336.15 0.01794 - - - 0.00099 - - - 0.01816 - - - -4.0088 - - -

181040 336.15 - 0.01238 - - - 0.00068 - - - 0.01253 - - - -4.3794 - -

18147.0 336.15 - - 0.00876 - - - 0.00048 - - - 0.00885 - - - -4.7277 -

18115.0 336.15 - - - 0.00249 - - - 0.00014 - - - 0.00252 - - - -5.9834

18110.0 339.15 0.02424 0.01455 0.01135 0.00337 0.0013

4 0.00080 0.00063 0.00019 0.02465 0.0148

0 0.01154 0.00342 -3.7030 -4.2134 -4.4618 -5.6775

18293.0 342.15 0.03213 0.02149 0.01565 0.00484 0.0017

6 0.00117 0.00086 0.00026 0.03248 0.0217

3 0.01582 0.00489 -3.4270 -3.8291 -4.1465 -5.3208

18004.0 345.15 0.03840 - - - 0.00213 - - - 0.03962 - - - -3.2284 - - -

18042.0 345.15 - 0.02608 - - - 0.00145 - - - 0.02686 - - - -3.6173 - -

18029.0 345.15 - - 0.02035 - - - 0.00113 - - - 0.02097 - - - -3.8645

18080.0 345.15 - - - 0.00552 - - - 0.00031 - - - 0.00567 - - - -5.1722

18078.0 348.15 0.03641 0.02860 0.00813 0.00201 0.00158 0.0004

50.0375

8 0.02951 0.00839 - -3.2814 -3.5229 -4.7802

18098.0 348.15 0.05099 - - - 0.0028 - - - 0.05257 - - - -2.9457 - - -

2

18087.0 351.15 0.07170 0.04594 0.03628 0.01122 0.0039

6 0.00254 0.00201 0.00062 0.07428 0.0475

9 0.03758 0.01162 -2.5999 -3.0451 -3.2812 -4.4551

18014.0 354.15 0.09166 0.06444 0.04735 0.01508 0.0050

9 0.00358 0.00263 0.00084 0.09575 0.0673

2 0.04946 0.01575 -2.3460 -2.6983 -3.0066 -4.1510

1, 2, 3, 4: cells with effusion orifices of different diameter.Standard uncertainties u are u(t)=0.1 s, u(T)=0.10 K, u(m)=0.01 mg, and the combined expanded uncertainty Uc is Uc(m/t)=8.63·10-10 g·s-1, Uc(ν)=4.0·10-4 g·s-1·K1/2.

a)b)

c) d)

Figure S2. Plots of Ln() versus 1/T of 5-methylisoxazole-3-carboxylic acid. a) Cell1, b) Cell2, c) Cell3 d) Cell4

TABLE S9. Experimental effusion results of 3a5mi at T med=297.3K .

ts

TK

Δmg

(d m /d t )x 103

g ∙ s−1

ν=[( d md t )x 103 ∙√T ]g·s-1· K1/2

ln ( ν )

Δm1 Δm2 Δm3 Δm4dm1

d td m2

d td m3

d td m4

d t1 2 3 4 1 2 3 4

5092.0 287.15 0.00446 0.00291 0.00196 0.00056 0.00088 0.00057 0.00038 0.00011 0.0148

3 0.00968 0.00652 0.00185 -4.2110 -4.6373 -5.0325 -6.2912

7345.0 290.15 0.00929 0.00611 0.00429 0.00140 0.00126 0.00083 0.00058 0.00019 0.0215

3 0.01416 0.00995 0.00324 -3.8382 -4.2575 -4.6103 -5.7337

7306.0 293.15 0.01311 0.00865 0.00625 0.00178 0.00179 0.00118 0.00086 0.00024 0.0307

3 0.02026 0.01465 0.00417 -3.4827 -3.8991 -4.2235 -5.4794

7261.0 296.15 0.01669 0.01119 0.00764 0.00224 0.00230 0.00154 0.00105 0.00031 0.0395

5 0.02651 0.01810 0.00530 -3.2303 -3.6302 -4.0120 -5.2405

7255.0 299.15 0.02236 0.01511 0.01042 0.00307 0.00308 0.00208 0.00144 0.00042 0.0533

1 0.03602 0.02484 0.00732 -2.9317 -3.3236 -3.6952 -4.9173

7228.0 302.15 0.02979 0.02062 0.01443 0.00427 0.00412 0.00285 0.00200 0.00059 0.0716

4 0.04959 0.03469 0.01026 -2.6361 -3.0040 -3.3613 -4.5798

5419.0 304.15 0.02786 0.01919 0.01354 0.00400 0.00514 0.00354 0.00250 0.00074 0.0896

5 0.06176 0.04358 0.01287 -2.4118 -2.7844 -3.1332 -4.3525

4614.0 306.15 0.02892 - - 0.00439 0.00627 - - 0.00095 0.1096

8 - - 0.01663 -2.2102 - - -4.0965

4557.0 306.15 - 0.01951 0.01398 - - 0.00428 0.00307 - - 0.07492 0.05367 - - -2.5914 -2.9248 -


a)b)

c) d)

Figure S3. Plots of Ln() versus 1/T of 3-amino-5-methylisoxazole. a) Cell1, b) Cell2, c) Cell3 d) Cell4

TABLE S10. Experimental effusion results of 5a3mi at Tmed=313.7K .

ts

TK

Δmg

(d m /d t )x 103

g ∙ s−1

ν=[( d md t )x 103 ∙√T ]g·s-1· K1/2

ln ( ν )

Δm1 Δm2 Δm3 Δm4d m1

d td m2

d td m3

d td m4

d t1 2 3 4 1 2 3 4

10881.0 303.15 0.0165

3 0.01132 0.00749 0.00244 0.00152 0.00104 0.00069 0.0002

2 0.02645 0.01811 0.01199 0.00390 -3.6325 -4.0111 -4.4241 -5.5470

10868.0 306.15 0.0216

5 0.01528 0.01017 0.00314 0.00199 0.00141 0.00094 0.0002

9 0.03486 0.02461 0.01638 0.00506 -3.3565 -3.7047 -4.1117 -5.2873

10805.0 309.15 0.0291

4 0.02044 0.01317 0.00416 0.00270 0.00189 0.00122 0.0003

9 0.04741 0.03326 0.02142 0.00677 -3.0489 -3.4034 -3.8433 -4.9953

10812.0 312.15 0.0371

0 0.02595 0.01752 0.00558 0.00343 0.00240 0.00162 0.0005

2 0.06063 0.04240 0.02862 0.00912 -2.8030 -3.1606 -3.5536 -4.6974

10883.0 315.15 0.0469

5 0.03434 0.02287 0.00748 0.00431 0.00316 0.00210 0.0006

9 0.07659 0.05601 0.03730 0.01219 -2.5693 -2.8822 -3.2888 -4.4068

11083.0 318.15 0.0643

8 0.04630 0.03090 0.01037 0.00581 0.00418 0.00279 0.0009

4 0.10360 0.07451 0.04972 0.01668 -2.2672 -2.5969 -3.0013 -4.0935

10820.0 321.15 0.0784

2 0.05829 0.03935 0.01322 0.00725 0.00539 0.00364 0.0012

2 0.12988 0.09654 0.06517 0.02189 -2.0411 -2.3378 -2.7307 -3.8218

10851.0 324.15 0.0950

9 0.07618 0.05223 0.01724 0.00876 0.00702 0.00481 0.0015

9 0.15778 0.12640 0.08666 0.02861 -1.8465 -2.0683 -2.4458 -3.5541


a)b)

c) d)Figure S4. Plots of Ln() versus 1/T of 5-amino-3-methylisoxazole. a) Cell1, b) Cell2, c) Cell3 d) Cell4

TABLE S11. Experimental values of temperature, intercept, slope and enthalpy of sublimation at T med for compounds studied.

CellTmedK

Ba MK

a ∆ sgH (Tmed)kJ ∙mol−1

c

35dmi4c

1

343.7

28.2 1.2 -13004.9 405.2 108.1 3.4

2 27.6 1.4 -12934.1 464.8 107.5 3.9

3 28.8 0.6 -13457.5 195.3 111.9 1.6

Average 28.2 1.0b -13132.1 355.1b 109.2 4.1b

5mi3c

1

343.7

21.7 0.8 -10966.1 279.7 91.2 2.3

2 21.3 0.7 -10951.4 244.7 91.1 2.0

3 23.1 0.5 -11694.9 183.4 97.2 1.5

4 23.4 0.8 -12202.5 261.9 101.5 2.2

Average 22.4 0.7b -11453.8 242.4b 95.3 3.2b

3a5mi

1

297.3

20.5 ± 0.5 -9059.7 139.6 75.3 1.2

2 21.0 ± 0.4 -9330.2 119.4 77.6 1.0

3 21.1 ± 0.8 -9462.3 229.2 78.7 1.9

4 20.1 ± 1.2 -9541.4 360.2 79.3 3.00

Average 20.7 0.7b -9348.4 212.1b 77.7 2.8b

5a3mi

1

313.7

24.3 ± 0.4 -8451.3 132.4 70.3 1.1

2 25.8 ± 0.2 -9022.4 67.1 75.0 0.6

3 25.9 ± 0.2 -9181.3 62.7 76.3 0.5

4 25.6 ± 0.3 -9464.6 104.2 78.7 0.9

Average 25.4 0.3b -9029.9 91.6b 75.1 1.3b

1, 2, 3, 4: cells with effusion orifices of different diameter.Standard uncertainty u is u(Tmed)=0.1 K.aUncertainty is to the standard deviation of the fit.bThis is the average value.cEach sublimation enthalpy value and the associated uncertainty is computed as -M·R·10‒3 and σ·R·10‒3 where M is the slope and σ is the uncertainty associated.

TABLE S12. Experimental values of vapor pressure for the compounds studied.

TK

pPa

35dmi4c 5mi3c 5a3mi 3a5mi1 2 3 1 2 3 4 1 2 3 4 1 2 3 4

287.15 0.430 0.406 0.443 0.317290.15 0.625 0.594 0.675 0.553293.15 0.891 0.850 0.994 0.713296.15 1.147 1.113 1.228 0.905299.15 1.546 1.512 1.686 1.251302.15 2.078 2.081 2.354 1.753303.15 0.767 0.760 0.813 0.666304.15 2.600 2.592 2.957 2.200306.15 1.011 1.033 1.112 0.864 3.181 3.145 3.643 2.842309.15 1.375 1.396 1.454 1.157312.15 1.759 1.779 1.943 1.559315.15 2.222 2.351 2.531 2.084318.15 3.005 3.127 3.375 2.851321.15 3.768 4.052 4.423 3.741324.15 4.577 5.305 5.881 4.889333.15 0.535 0.506 0.532 0.341 0.359 0.372 0.262336.15 0.736 0.724 0.771 0.463 0.462 0.528 0.378339.15 0.907 0.863 0.964 0.628 0.546 0.688 0.514342.15 1.280 1.189 1.563 0.828 0.801 0.943 0.734345.15 1.760 1.752 1.943 1.010 0.990 1.251 0.852348.15 2.860 2.332 2.944 1.340 1.386 1.760 1.261351.15 3.733 3.414 4.033 1.893 1.755 2.241 1.745354.15 5.049 5.212 5.769 2.440 2.482 2.949 2.365

Standard uncertainty u is u(T)=0.10 K.Combined expanded uncertainty Uc is Uc(p)=0.174 Pa (level of confidence 0.9545)

TABLE S13. Areas and Clausing factors of the cell effusion holes.Hole number

1 2 3 4Area (mm2) 0.88 0.64 0.41 0.17

W0 0.90 0.89 0.86 0.80Combined expanded uncertainty Uc is Uc(Area)=0.01 mm2, Uc(W0)=0.01. (Level of confidence 0.9545)

TABLE S14. G3- and G4-calculated enthalpies at T = 298 K, and experimental enthalpies of formation in the gas phase for the molecules used as references in isodesmic reactions.

H 298(G 3)Hartrees

H 298(G 4 )Hartrees

Experimental∆ fH ° (g )kJ ∙mol−1 Reference

Methane -40.453847 -40.461486 -(74.4 ± 0.4) S1

Isoxazole -245.872843 -245.918983 82.0 ± 0.6 S2

5-methylisoxazole -285.152773 -285.205539 34.1 ± 0.8 S3

3-methylisoxazole -285.151102 -285.204117 35.6 ± 0.7 S3

Ethanoic acid -228.926254 -228.969310 -(432.8 ± 2.5) S1

Benzoic acid -420.537509 -420.613839 -(295.4 ± 0.2) S4

2-methylbenzoic acid -459.801603 -459.885108 -(320.6 ± 1.5) S5

Methylamine -95.755743 -95.773915 -(23.4 ± 1.0) S1

Ethylamine -135.028173 -135.053519 -(47.5 ± 0.6) S1

Ethane -79.718938 -79.733661 -(83.8 ± 0.3) S1

Benzene -232.046754 -232.088588 82.9 ± 0.9 S6

Toluene -271.321052 -271.370156 50.1 ± 1.1 S6

Aniline -287.368542 -287.420473 87.1 ± 1.1 S1

Ethene -78.503407 -78.517878 52.4 ± 05 S7

Methanal -114.427247 -114.449385 -(108.6 ± 0.5) S7

Methanol -115.624924 -115.647492 -(201.5 ± 0.2) S7

Hydroxylamine -131.625490 -131.651186 -41.8 S8

Methylenimine -94.550990 -94.568953 88.3 ± 2.1 S9

Ammonia -56.503203 -56.513792 -(45.9 ± 0.4) S10

Water -76.378260 -76.393472 -(241.83 ± 0.04) S10

[S1] J. B. Pedley, Thermochemical Data and Structure of Organic Compounds, Vol. 1, TRC Data Series, TX, 1994 [S2] W.V. Steele, R.D. Chirico, S.E. Knipmeyer, A. Nguyen, N.K. Smith, I.R. Tasker, Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Cyclohexene, Phthalan(2,5-Dihydrobenzo-3,4-furan), Isoxazole, Octylamine, Dioctylamine, Trioctylamine, Phenyl Isocyanate, and 1,4,5,6-Tetrahydropyrimidine, J. Chem. Eng. Data 41 (1996) 1269 – 1284 [S3] W.S. Hamilton, S. Benton, J. French, D. McCormick, S. Pustejovsky, P. Thompson, Enthalpies of Combustion and Formation of 3-Methylisoxazole and 5-Methylisoxazole, J. Chem. Eng. Data 23 (1978) 201 – 203 [S4] G. Pilcher, The Chemistry of Functional Groups, Supplement B: The Chemistry of Acid derivatives, Vol. 2, Ed. Patai, S. John Wiley and Sons, NYC 1992 [S5] M. Colomina, P. Jiménez, M.V. Roux, C. Turrión, Propiedades Termoquímicas de Derivados del Ácido Benzoico. XIII. Presiones de Vapor y Entalpías de Sublimación de los Ácidos Toluicos, An. Quim. 82 (1986) 126 – 130 [S6] M.V. Roux, M. Temprado, J. S. Chickos, Y. Nagano, Critically Evaluated Thermochemical Properties of Polycyclic Aromatic Hydrocarbons, J. Phys. Chem. Ref. Data 37 (2008) 1855 – 1996 [S7] J.A. Manion, Evaluated Enthalpies of Formation of the Stable Closed Shell C1 and C2 Chlorinated Hydrocarbons, J. Phys. Chem. Ref. Data 31 (2002) 123 – 172 [S8] D.S. Shaikhlislamov, M.R. Talipov, S.L. Khursan, Quantum-Chemical and Group-Additive Calculations of the Enthalpies of Formation of Hydroxylamines and Oximes, Russ. J. Phys. Chem. A 81 (2007) 235 – 240 [S9] G. De Oliveira, J.M.L. Martin, I.K.C. Silwal, J.F. Liebman, Definitive Heat of Formation of Methylenimine, CH2=NH, and of Methylenimmonium ion, CH2NH2

+, by Means of W2 Theory, J. Comput. Chem. 13 (2001) 1297 – 1305 [S10] M.W. Chase Jr., NIST-JANAF Thermochemical Tables, J. Phys. Chem. Ref. Data Monograph 9 (1998) 1 – 1951

TABLE S15. Formation enthalpies in gas phase at T = 298 K of each isodesmic reaction for each compound studied. The values were obtained using Gaussian–n theories at G3 and G4 levels.

Isodesmic Reactions

∆f H ° (g )kJ ∙mol−1

G3 G4

3,5-dimethylisoxazole-4-carboxilyc acid

-384.6 -383.0

-371.5 -362.2

5-methylisoxazole-3-carboxilyc acid

N

OCH3

+N

OCH3

+

O

HO

HO

O

-328.8 -328.8

-334.1 -326.1

3-amino-5-methylisoxazole

25.6 28.5

26.0 27.7

26.2 30.6


30.1 33.5

N

O

H3C

NH2

+N

O

+

H3C

NH2

28.5 30.0

26.2 30.9

TABLE S16. The absolute entropies of each element used to calculate the variation of entropy of each compound.

ElementS f °

J ∙mol−1 ∙ K−1 Reference

C(s) 5.74 ± 0.21

S10H2(g) 130.68 ± 0.03

O2(g) 205.15 ± 0.04

N2(g) 191.61 ± 0.02

[S10] M.W. Chase Jr., NIST-JANAF Thermochemical Tables, J. Phys. Chem. Ref. Data Monograph 9 (1998) 1 – 1951

Cartesian coordinates of the compounds studied.

1) MP2(Full)/6-31G(d)


Atomic Coordinates (Angstroms) Number X Y Z 6 1.132779 -0.748539 0.000000 6 -0.004536 0.111686 0.000000 7 0.764370 -2.021134 0.000000 8 -0.627701 -2.013228 0.000000 6 -1.078694 -0.741506 0.000000 6 -2.548370 -0.542765 0.000000 6 2.594140 -0.434649 0.000000 6 -0.151204 1.579715 0.000000 8 0.991391 2.318585 0.000000 8 -1.234324 2.132745 0.000000 1 1.772328 1.738556 0.000000 1 2.886752 0.129759 -0.891845 1 2.886752 0.129759 0.891845 1 3.156435 -1.370490 0.000000 1 -3.046999 -1.513625 0.000000 1 -2.854560 0.030065 -0.877831 1 -2.854560 0.030065 0.877831


Atomic Coordinates (Angstroms) Number X Y Z 6 0.433420 0.019062 0.000000 6 -0.627047 0.946664 0.000000 6 -1.748720 0.167237 0.000000 8 -1.379756 -1.146791 0.000000 7 -0.004612 -1.238441 0.000000 1 -0.555339 2.024003 0.000000 6 -3.208816 0.434332 0.000000 1 -3.381989 1.511656 0.000000 1 -3.682783 0.002620 0.885222 1 -3.682783 0.002620 -0.885222 6 1.893747 0.283860 0.000000 8 2.671858 -0.820732 0.000000 8 2.353728 1.408457 0.000000 1 2.093092 -1.612547 0.000000


Atomic Coordinates (Angstroms) Number X Y Z 6 -1.114499 0.252757 -0.058705 6 0.042022 1.058893 -0.230320 7 -0.803661 -0.995005 0.261293

6 1.078446 0.207228 0.003549 8 0.593306 -1.027829 0.289810 7 -2.442132 0.623992 -0.275384 1 -2.680726 1.502981 0.172736 1 -3.077299 -0.107622 0.033504 1 0.091799 2.102957 -0.503729 6 2.557354 0.346448 -0.003281 1 2.976623 0.096384 0.974932 1 3.006817 -0.320527 -0.743683 1 2.830138 1.374570 -0.248024


Atomic Coordinates (Angstroms) Number X Y Z 6 1.083390 0.082565 0.000293 6 -0.002694 0.994782 0.018154 7 0.676272 -1.177115 -0.007313 8 -0.728345 -1.110342 0.005677 6 -1.103731 0.187992 0.019788 7 -2.466438 0.411186 0.113549 6 2.545948 0.378159 -0.010544 1 2.820548 0.963751 -0.892253 1 2.835829 0.948602 0.876124 1 3.107374 -0.558031 -0.023313 1 0.030650 2.074095 0.034675 1 -3.012799 -0.363994 -0.248779 1 -2.756003 1.290349 -0.300056

2) B3LYP/6-31G(2df, p)


Atomic Coordinates (Angstroms) Number X Y Z 6 -1.061900 -0.828181 0.005644 6 0.012537 0.126851 -0.004465 7 -0.609186 -2.055140 0.017303 8 0.786051 -1.946360 0.015229 6 1.140454 -0.660165 0.002401 6 2.594450 -0.361347 -0.001561 6 -2.544400 -0.614885 0.004607 6 0.013987 1.604284 -0.018902 8 -1.194398 2.220288 -0.023708 8 1.014185 2.275838 -0.026471 1 -1.915790 1.582210 -0.016608 1 -2.871806 -0.057101 0.890253 1 -2.872996 -0.074059 -0.891056 1 -3.050701 -1.581594 0.014165 1 3.071513 -0.791748 0.885016 1 2.739555 0.717385 -0.012199 1 3.070240 -0.808917 -0.880288


Atomic Coordinates (Angstroms) Number X Y Z 6 0.432370 0.011440 0.000000 6 -0.634860 0.944922 0.000000 6 -1.746732 0.160990 0.000000 8 -1.377233 -1.142903 0.000000 7 -0.002748 -1.227783 0.000000 1 -0.564986 2.018715 0.000000 6 -3.206678 0.437947 0.000000 1 -3.381614 1.514946 0.000000 1 -3.686661 0.005061 0.883445 1 -3.686661 0.005061 -0.883445 6 1.899419 0.281771 0.000000 8 2.673053 -0.817405 0.000000 8 2.353933 1.392970 0.000000 1 2.103399 -1.603732 0.000000


Atomic Coordinates (Angstroms) Number X Y Z 6 -1.108658 0.128103 0.068271 6 0.028443 0.991327 0.031948 7 -0.760901 -1.140501 0.086925 6 1.082380 0.134002 0.018158 8 0.643257 -1.134425 0.043210 1 0.048462 2.068191 0.003216 6 2.556393 0.332561 -0.024441 1 3.037198 -0.117750 0.850169 1 2.987750 -0.137372 -0.914318 1 2.794861 1.397554 -0.043177 7 -2.441768 0.502705 0.019337 1 -3.067169 -0.256785 0.254997 1 -2.655629 1.335964 0.548513


Atomic Coordinates (Angstroms) Number X Y Z 6 1.081925 0.072254 -0.000343 6 -0.006020 0.989450 0.011456 7 0.681453 -1.177659 -0.004659 8 -0.733058 -1.110304 0.005407 6 -1.103481 0.175023 0.016695 7 -2.455704 0.410623 0.091311 6 2.546179 0.376232 -0.008463 1 2.817751 0.969604 -0.887745 1 2.830309 0.953590 0.877454 1 3.120889 -0.551756 -0.020786 1 0.024198 2.065749 0.022555 1 -3.024719 -0.354454 -0.242902 1 -2.749722 1.303649 -0.273980

3,5-dimethylisoxazole

Atomic Coordinates (Angstroms) Number X Y Z 6 1.115331 0.086860 0.059886 6 0.005293 0.962162 -0.130199 7 0.717178 -1.138890 0.307400 8 -0.678575 -1.096262 0.285315 6 -1.081570 0.160468 0.023800 6 2.575211 0.405298 0.008505 6 -2.549210 0.396151 -0.038372 1 3.161865 -0.495310 0.199001 1 2.854925 0.805043 -0.971778 1 2.838368 1.159934 0.757008 1 0.019630 2.017808 -0.346536 1 -2.754091 1.445606 -0.257712 1 -3.028058 0.138706 0.912081 1 -3.012296 -0.219575 -0.816400

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