| 1. |
- Lilja, J., et al.
(författare)
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Esterification of propanoic acid with ethanol, 1-propanol and butanol over a heterogeneous fiber catalyst
- 2005
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Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947 .- 1873-3212. ; 115:02-jan, s. 1-12
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Tidskriftsartikel (refereegranskat)abstract
- Esterification kinetics of propanoic acid with ethanol, 1-propanol and butanol over a fibrous polymer-supported sulphonic acid catalyst (Smopex-101) was studied. Experiments were carried out in a batch reactor operating isothermally at three different temperatures: 60, 70 and 75 degrees C (80 degrees C for butanol) and with different initial molar ratios of propanoic acid and alcohol (1:1, 1:2 and 2:1). The fiber catalyst was active and stable in all the experiments. The experimental results were modeled according to a Langmuir-Hinshelwood model and with an advanced adsorption-based model. The activity coefficients were calculated according to the UNIFAC model. The activation energy of esterification of propanoic acid with ethanol was found to be 52.6 kJ/mol, 49.9 kJ/mol with 1-propanol and 47.3 kJ/mol with butanol. The kinetic model, which includes the adsorption of carboxylic acid and water combined with the activities of the species, explained the experimentally recorded concentrations well.
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| 2. |
- Lofas, H., et al.
(författare)
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A computational study of potential molecular switches that exploit Baird's rule on excited-state aromaticity and antiaromaticity
- 2014
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Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 174, s. 105-124
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Tidskriftsartikel (refereegranskat)abstract
- A series of tentative single-molecule conductance switches which could be triggered by light were examined by computational means using density functional theory (DFT) with non-equilibrium Green's functions (NEGF). The switches exploit the reversal in electron counting rules for aromaticity and antiaromaticity upon excitation from the electronic ground state (S-0) to the lowest pi pi* excited singlet and triplet states (S-1 or T-1), as described by Wicket's and Baird's rules, respectively. Four different switches and one antifuse were designed which rely on various photoreactions that either lead from the OFF to the ON states (switches 1, 2 and 4, and antifuse 5) or from the ON to the OFF state (switch 3). The highest and lowest ideal calculated switching ratios are 1175 and 5, respectively, observed for switches 1 and 4. Increased thermal stability of the 1-ON isomer is achieved by benzannulation (switch 1B-OFF/ON). The effects of constrained electrode-electrode distances on activation energies for thermal hydrogen back-transfer from 1-ON to 1-OFF and the relative energies of 1-ON and 1-OFF at constrained geometries were also studied. The switching ratio is strongly distance-dependent as revealed for 1B-ON/OFF where it equals 711 and 148 when the ON and OFF isomers are calculated in electrode gaps with distances confined to either that of the OFF isomer or to that of the ON isomer, respectively.
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