Thermochemistry of ionic liquid-catalysed reactions. Isomerisation and transalkylation of tert-alkyl-benzenes. Are these systems ideal?

Theory and Practice of Alkyl Aromatic Hydrocarbon Synthesis. 1. Branched Alkylbenzenes

“…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 51 52 53 54 55 56 57 58 59 60 16 363 7 1 3.55±0.17 0.6231 5.70 a -n is the number of determination for isomers equilibrium concentration; b -m is the number of experiments sets; c -K x is the equilibrium constant in liquid phase; d -ܲ ௩ሺூሻ is saturated vapor pressure of an initial reagent, ܲ ௩ሺூூሻ is saturated vapor pressure of an isomerization product; e -K p is the equilibrium constant in gas phase; f -‫ܭ‬ х value involves the results from work; 14 g -data from work. 9 Verevkin et al 11,12 also obtained the experimental equilibrium data for reaction 6 over chloroaluminate ionic liquids and FeCl 3 . All experimental data for different catalysts is compared on figure 9, and it has a systematic drift relative to each other which includes catalytic system used in.…”

“…In recent paper 5 Verevkin et al 11,12 show that the transalkylation and the positional isomerization also proceed with an adequate selectivity (without carbon skeleton change of pentyl) up to the equilibrium attainment in the system of benzene + toluene + (1,1-diMP)benzene + meta-di (1,benzene + paradi(1,1-diMP)benzene + meta-(1,1-diMP)toluene + para- (1, Hence the catalysts variety that provides the selective production of tert-pentyl substituted hydrocarbons (and potentially not only hydrocarbons) should be wide enough. The question about the maximum selectivity in alkylaromatic hydrocarbon processes and possibly not only hydrocarbons is still unsolved.…”

“…All experimental data for different catalysts is compared on figure 9, and it has a systematic drift relative to each other which includes catalytic system used in. 11,12 The difference between the equilibrium constants is 30 % rel. 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 51 52 53 54 55 56 57 58 59 60 17 dimethylpropyl)toluenes + (1,2-dimethylpropyl)toluenes toluene rings is presented by two transalkylation reactions 8 and 9 (table 1).…”

“…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 51 52 53 54 55 56 57 58 59 60 17 dimethylpropyl)toluenes + (1,2-dimethylpropyl)toluenes toluene rings is presented by two transalkylation reactions 8 and 9 (table 1). The papers 11,12 also contain the data for reaction 9. The comparison of our data (over AlCl 3 ) and works' 11,12 results (over chloroaluminate ionic liquids and Neither quantity of methyl groups in an aromatic ring nor a structure of pentyl substituent affect the reaction enthalpies of isomerization and transalkylation, which are in range from -2.3 to 1.0 kJ•mol -1 .…”

“…The papers 11,12 also contain the data for reaction 9. The comparison of our data (over AlCl 3 ) and works' 11,12 results (over chloroaluminate ionic liquids and Neither quantity of methyl groups in an aromatic ring nor a structure of pentyl substituent affect the reaction enthalpies of isomerization and transalkylation, which are in range from -2.3 to 1.0 kJ•mol -1 . On the other hand, the reaction entropy essentially depends on methyl groups' quantity and substitution in an aromatic ring, as an example, ∆ ܵ ሺ݈ሻ values for pentylbenzenes, pentylortho-xylenes and pentyltoluenes (meta-and para-) change from 16.6±0.6 at 328 K to 5.6±3.3 at 323 K, 11.0±2.5 (at 333 K), and 9.3±3.8 (at 333 K) J•mol -1 •K -1 correspondingly.…”