Thermochemistry of Ionic Liquid-Catalyzed Reactions. Experimental and Theoretical Study of Chemical Equilibria of Isomerization and Transalkylation of tert-Butylbenzenes

The chemical equilibrium of mutual interconversions of tert-butylbenzenes was studied in the temperature range 286 to 423 K using chloroaluminate ionic liquids as a catalyst. Enthalpies of five reactions of isomerization and transalkylation of tert-butylbenzenes were obtained from temperature dependences of the corresponding equilibrium constants in the liquid phase. Molar enthalpies of vaporization of methyl-tert-butylbenzenes and 1,4-ditert-butylbenzene were obtained by the transpiration method and were used for a recalculation of enthalpies of reactions and equilibrium constants into the gaseous phase. Using these experimental results, ab initio methods (B3LYP and G3MP2) have been tested for prediction thermodynamic functions of the five reactions under study successfully. Thermochemical investigations of tert-butyl benzenes available in the literature combined with experimental results have helped to resolve contradictions in the available thermochemical data for tert-butylbenzene and to recommend consistent and reliable enthalpies of formation for this compound in the liquid and the gaseous state.

Vapour layer formation by electrical discharges through electrically conducting liquids-modelling and experiment

Experimental and finite element modelling methods are used to study the formation of vapour layers in electrical discharges through saline solutions. The experiments utilize shadowgraphic and photometric methods to observe the time dependence of thin vapour layers and plasma formation around electrodes driven by moderate voltage (<500 V) pulses, applied to an electrode immersed in a conducting saline solution. Finite element multiphysics software, coupling thermal and electrical effects, is employed to model the vapour layer formation. All relevant electrical and thermal properties of the saline are incorporated into the model, but hydrodynamic and surface tension effects are ignored. Experimental shadowgraph and modelling images are compared, as are current histories, and the agreement is very good. The comparison of experiment and modelling gives insight into both vapour layer production and subsequent plasma production. We show that, for example, superheating of the saline above its normal vaporization temperature may be playing a significant role in vapour formation. We also show that electric fields of approaching 10(7) V m(-1) can be achieved in the vapour layer.

Water Content Determinations for Peat and Other Organic Soils Using the Oven-Drying Method

There has been much debate in the literature over the past 60 years regarding an appropriate oven-drying temperature for water content determinations in peat and other organic soils. For inorganic soils, the water content is usually based on the equilibrium dry mass corresponding to drying temperatures in the range 100-110°C. However, for peat and other organic soils, several researchers have recommended lower drying temperatures in the range 60-90°C in an attempt to prevent possible charring, oxidation, and/or vaporization of substances other than pore water. However, all of the relevant water is not fully evaporated at too low a temperature, and because specimen dry mass is a function of drying temperature, the resulting water content values are lower than those determined for the temperature range 100-110°C. Experimental data reported in this article show that oven drying of peat and other organic soils at 100-110°C using either gravity-convection or forced-draft ovens is acceptable for routine water content determinations. Because a standardized oven temperature is desirable when correlating water content with other material properties, it is recommended that oven drying of peat and other organic soils be performed over temperature ranges of either 105-110°C or 105 ± 5°C, in line with standardized ranges for inorganic soils. © 2014 Copyright Taylor & Francis Group, LLC.