This paper explains the phenomena which occur in commercially available laboratory microwave equipment, and highlights several situations where experimental observations are often misinterpreted as a 'microwave effect'. Electromagnetic simulations and heating experiments were used to show the quantitative effects of solvent type, solvent volume, vessel material, vessel internals and stirring rate on the distribution of the electric field, the power density and the rate of heating. The simulations and experiments show how significant temperature gradients can exist within the heated materials, and that very different results can be obtained depending on the method used to measure temperature. The overall energy balance is shown for a number of different solvents, and the interpretation and implications of using the results from commercially available microwave equipment are discussed.
Running oil‐bath chemistry in a microwave! Using reaction vials made out of strongly microwave‐absorbing silicon carbide (SiC) in a microwave reactor simulates experiments conducted in an autoclave with conductive heating because of the efficient shielding of the electromagnetic field by the SiC vial. This technology makes it possible to study the significance of microwave effects.
The temperature profiles obtained from both an external infrared and internal fiber-optic sensor were compared for heating and synthesizing the ionic liquid 1-butyl-3-methylimidazolium bromide (bmimBr) under microwave conditions. Utilizing a single-mode microwave reactor that allows simultaneous infrared/fiber-optic temperature measurements, significant differences between the two methods of temperature monitoring were revealed. Due to the strong microwave absorptivity of ionic liquids and the delay experienced in monitoring temperature on the outer surface of a heavy-walled glass vial, external infrared temperature sensors can not be used to accurately control the temperature in the heating of ionic liquids under microwave conditions. The use of internal fiber-optic probes allows the monitoring and control of the heating behavior in a much better way. In order to prevent the strong exotherm in the synthesis of bmimBr under microwave conditions the use of a reaction vessel made out of silicon carbide is the method of choice. Because of the high thermal conductivity and effusivity of silicon carbide, the heat generated during the ionic liquid formation is efficiently exchanged with the comparatively cool air in the microwave cavity via the silicon carbide ceramic.
Silicon carbide (SiC) is a strongly microwave absorbing chemically inert ceramic material that can be utilized at extremely high temperatures due to its high melting point and very low thermal expansion coefficient. Microwave irradiation induces a flow of electrons in the semiconducting ceramic that heats the material very efficiently through resistance heating mechanisms. The use of SiC carbide reaction vessels in combination with a single-mode microwave reactor provides an almost complete shielding of the contents inside from the electromagnetic field. Therefore, such experiments do not involve electromagnetic field effects on the chemistry, since the semiconducting ceramic vial effectively prevents microwave irradiation from penetrating the reaction mixture. The involvement of electromagnetic field effects (specific/nonthermal microwave effects) on 21 selected chemical transformations was evaluated by comparing the results obtained in microwave-transparent Pyrex vials with experiments performed in SiC vials at the same reaction temperature. For most of the 21 reactions, the outcome in terms of conversion/purity/product yields using the two different vial types was virtually identical, indicating that the electromagnetic field had no direct influence on the reaction pathway. Due to the high chemical resistance of SiC, reactions involving corrosive reagents can be performed without degradation of the vessel material. Examples include high-temperature fluorine-chlorine exchange reactions using triethylamine trihydrofluoride, and the hydrolysis of nitriles with aqueous potassium hydroxide. The unique combination of high microwave absorptivity, thermal conductivity, and effusivity on the one hand, and excellent temperature, pressure and corrosion resistance on the other hand, makes this material ideal for the fabrication of reaction vessels for use in microwave reactors.
Investigations on heterogeneous iron catalysis in the selective aerobic oxidation of a primary alcohol are presented. Continuous flow technology was used in combination with an iron oxide nanoparticle catalyst stabilized in a mesoporous aluminosilicate support ("flow nanocatalysis") as a process intensification tool to maximize catalyst efficiency. Using 5 mol% 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a co-catalyst, up to 42% benzyl alcohol as a simple model substrate was selectively converted to benzaldehyde in a single pass of the reactor. Full conversion was achieved by continuous recirculation, simulating an extension of the catalyst bed. ICPMS analysis indicated that the catalyst is highly stable and does not leach under the investigated conditions, providing solid evidence for the participation of a heterogeneous iron species in the catalytic cycle.
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