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Sustain. Chem. 2021, 2 302 Table 2. Summary of the recent investigations on the kinetic study of solketal synthesis. Author Pseudo-homogeneous (PH) Rossa, 2017 Dmitriev, 2018 Cornejo, 2019 Amri, 2019 Ji, 2020 Vannucci, 2020 Sulphonic Ion Sulistyo, 2020 EA (kJ·mol–1) 44.77 ± 1.2 87.1 39.78 ± 0.34 65.4 28.2 88.1 ± 8.9 13 69.0 ± 6.6 124.0 ± 12.9 15.7 Other Parameters 1,2,3,4,5 EA-1 = 41.40 ± 1.8 kJ·mol−1 Keq = 0.5159 (313 K) EA-1 = 101.67 kJ·mol−1 Keq = 0.77 (303 K) k = (4.800 ± 0.030). 10−3 L2 mol−1·gcat−1·min−1 (298 K) ∆H = − 6.605 ± 0.168 kJ·mol−1 EA-1 = 70.65 kJ·mol−1 Keq = 0.3931 (313 K) Keq = 0.4703 (298 K) k = 0.11516 ± 0.0093 mol·gcat−1·min−1 ∆H = −11.6 ± 1.1 kJ·mol−1 ∆G = 4.0 ± 0.1 kJ·mol−1 EA-1 = 64 k = 0.492 ± 0.093 mol·gcat–1·s–1 Kwater = 14.4 ± 3.1 Taddeo, 2021 Catalyst Zeolite H-Beta Sulfuric acid Purolite® CT275 HCl activated clay Ionic Liquid [P(C4H9) 3C14H29][TsO] Sulfated zirconium oxide Iron(III) Complex FeCl3(1–NO2) Ref. [76] [102] [71] [80] [85] [91] [103] [10] [70] [92] [78] [104] [70] in. Chem. 2021, 2, FOR PEER REVIEW Langmuir-Hinshelwood–Hougen–Watson (LHHW) 16 Moreira, 2019 Exchange Resin Amberlyst-35 ∆H = − 20.1 ± 1.1 kJ·mol−1 EA-1 = 127.3 ± 12.6 kJ·m−o1 l−1 Eley–Rideal (ER) Ion Exchange Esteban, 2015 Resin ∆G = 1.4 ± 0.3 kJ·mol Keq = 0.367879441 Metal Organic Keq = 6.345 (at 303 K) Framework Basolite F300 Kwater = 128.0 ± 21.4 ∆H = −29.7176 kJ·mol Ion Exchange Sulistyo, 2020 Resin ∆G =K−a4ce.t8on6e7=50k.J6·m2ol−1 EA-1 = 47.23 kJ·mol−1 Lewatit GF101 K = 1.029 water −1 21.2 1 EA-1: reverse reaction activation energy. 2 Keq: equilibrium constant. 3 ∆H: enthalpy 4 ∆G: reaction Cation Exchange Resin Ksolketal = 0.03 Keq = 0.9690 (323 K) Li, 2020 Eley–Rideal (ER) Gibbs free energy. 5 Ki: adsorption equilibrium constant of species i. NKC–9 Kwater = 0.7511 Indion 225 Na 44.3 Ion Exchange Resin EA-1 = 127.3 ± 12.6 kJ·mol−1 Esteban, 2015 124.0 ± 12.9 Being mLeinwdaftiutlGtFh1a0t1the PH model does not consider the aKdso=rp0.t3io67n8o79f4m41olecules onto the catalyst surface, it is intuitive to think that reactions withwhatoermogeneous catalysts are well described by this model. Dmitriev et al. proposed a mechanism (Figure 6) for the Sulistyo, 2020 Ion Exchange Resin 21.2 Kacetone = 0.62 reaction witIhndsiuolnfu2r2i5cNaacid (strong Brønsted acid) as a catalyst Kcompr=isi0n.0g3 a nucleophilic [78] EA-1: reverse reaction activation energy. Keq: equilibrium constant. ∆H: enthalpy ∆G: reaction Gibbs free energy. Ki: adsorption eq K = 128.0 ± 21.4 solketal addition of glycerol to2 the carbonyl group of3 acetone, for4ming a semiketal. Then, the5 ring closuretakesplace,formingacarbeniumion(limitingstep).Finally,theH ionisreleased and solketal is formed [102]. 1 equilibrium constant of species i. + FiguFriegu6.rePl6a.uPsliabulesimblecmhaencihsamniosfmreoafcrteioanctcioantaclyaztaeldyzbeydsbuylfusurilcfuarciicda(cbidas(ebdasoend[o1n02[]1)0.2]). It is important to notice, however, that the mechanism proposed by Dmitriev et al. is unlikely to occur since the protonation of the oxygen from the carbonyl group, promoted by the ions of the acidic medium, is what impels the nucleophilic attack, similar to what is proposed by Nanda et al., described in Figure 7 [48]. With ionic liquid as the catalyst, Ji et al. obtained activation energy of 28.2 kJ· mol−1. aPDF Image | Continuous Valorization of Glycerol into Solketal
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