Table 2.
Gas phase thermochemical properties for reactants, products and all the intermediates MDA synthesis as well as MDA and MDAH+ isomers. Standard enthalpy of formation (Δf,298.15KH°(g)) is calculated from G3MP2B3 and CBS-QB3 enthalpies by means of atomization scheme (AS) at 1 atm pressure at 298.15 K. Absolute deviation is given in parenthesis.
| Species | Δf,298.15KH0 (g) | Method | Ref. | S0(g) | Cv(g) | Ref. |
|---|---|---|---|---|---|---|
| kJ/mol | J/molK | J/molK | ||||
| aniline (A) | 86.5 (0.5) | AS(G3MP2B3) | 1 | 319.0 | 96.6 | 1 |
| 96.0 (9.0) | AS(CBS-QB3) | 1 | 317.3 | 97.4 | ||
| 87.0 ± 0.88 | Burcat | [34] | 311.6 | 104.5 | [34] | |
| non-covalent aniline dimer (A2) | 156.2 | AS(G3MP2B3) | 311.7 | 529.6 | 214.3 | 1 |
| formaldehyde (F) | −111.5 (2.3) | AS(G3MP2B3) | 1 | 224.4 | 26.8 | 1 |
| −113.3 (4.1) | AS(CBS-QB3) | 1 | 224.3 | 26.8 | ||
| −109.2 ± 0.11 | Ruscic ATcT | [28] | 218.8 | 35.4 | [35] | |
| 4,4′-methylene diphenyl diamine (4,4′-MDA) | 171.2 | AS(G3MP2B3) | [19] | 500.1 | 221.4 | 1 |
| 191.5 | AS(CBS-QB3) | 503.6 | 223.3 | |||
| 165.6 | additivity rule | [18] | 522.7 | n.a. | [18] | |
| 172 | additivity rule [36,37] | NIST [37,38] | 511.6 | 234.7 | [38] | |
| 2,4-MDA | 159.4 | AS(G3MP2B3) | 1 | 490.4 | 220.6 | 1 |
| 2′,4-MDA | 168 | AS(G3MP2B3) | 1 | 484.0 | 219.8 | 1 |
| 3,4-MDA | 168.3 | AS(G3MP2B3) | 1 | 499.4 | 221.3 | 1 |
| N-(p-aminobenzyl)aniline (PABA) | 202.4 | AS(G3MP2B3) | 1 | 496.3 | 216.5 | 1 |
| 201.3 | additivity rule | [18] | 514.4 | n.a. | [18] | |
| N-hydroxymethylaniline | −71.8 | AS(G3MP2B3) | 1 | 379.3 | 129.3 | 1 |
| protonated aniline (AH+) | 739.4 | AS(G3MP2B3) | 1 | 339.9 | 97.2 | 1 |
| N-methylenebenzeneaminium | 828.6 | AS(G3MP2B3) | 1 | 346.2 | 107.9 | 1 |
| 4-(anilinomethyl)cyclo-hexa-2,5-dien-1-iminium | 858.5 | AS(G3MP2B3) | 1 | 491.2 | 220.0 | 1 |
| p-aminobenzylaniline (PABAH+) | 785.1 | AS(G3MP2B3) | 1 | 501.2 | 219.4 | 1 |
| 4-methylidenecyclohexa-2,5-diene-1-iminium (MCH+) | 802.8 | AS(G3MP2B3) | 1 | 340.9 | 113.7 | 1 |
| 4,4′-MDAH+ | 814.3 | AS(G3MP2B3) | 1 | 494.8 | 225.1 | 1 |
| 2,4-MDAH+ | 812.2 | AS(G3MP2B3) | 1 | 494.7 | 226.4 | 1 |
| 2′,4-MDAH+ | 830.9 | AS(G3MP2B3) | 1 | 487.1 | 224.4 | 1 |
| 3,4-MDAH+ | 858.6 | AS(G3MP2B3) | 1 | 534.2 | 236.5 | 1 |
1 this work.