Temperature effects upon aqueous micellar-assisted decarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its 5-methyl derivative.
An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobenzisoxazole-3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkylammonium bromide with alkyl = methyl (CTABr), ethyl (CTEABr), n-propyl (CTPABr), and n-butyl (CTBABr). The investigation shows that micelles speed up reactions by decreasing enthalpies of activation. Increase in head group bulk further speeds reactions still by a small decrease in the enthalpies, for both substrates. Values of DeltaH# and DeltaS# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier.
Effects of temperature on micellar-assisted bimolecular reaction of methylnaphtalene-2-sulphonate with bromide and chloride ions.
Reactivity of methyl naphthalene-2-sulphonate, MeONs, with H2O, Br(-) and Cl(-) in water and in cationic micelles of cetyltrialkylammonium surfactants, n-C16H33N(+)R3X(-), R=Me (CTA(+)), n-Pr (CTPA(+)), X=Br, Cl, CH3SO3, has been investigated in the temperature range 25-45°C. Micellar rate effects were analysed by using the pseudophase treatment, and the second-order rate constants in the micellar pseudophase were evaluated at the various temperatures. Values of these rate constants increase with temperature, and the effect is less important in micelles than in water and more important for chloride than for bromide ions. Micelles lead to an ion behaviour discrimination, whose extent depends on surfactant type and on temperature, with maximum effect in CTPA(+) at 25°C and with bromide being always more reactive than chloride. Quantitative analysis of the temperature effect by the Eyring equation showed that micelles speed up reaction of MeONs with halide ions by decreasing the activation enthalpies, which is partially offset by decreases in the activation entropies. The rate acceleration by increase in surfactant head group size has only enthalpic origin for bromide and only entropic origin for chloride: this different behaviour was rationalised taking into account both solvation of anions and the hydrophobic effect.
Research on velocity distribution in semi-dry flue gas desulfurization tower
As an accurate high-quality instantaneous measurement technology, particle image velocimetry (PIV in acronym) has applied widely in single-phase flow and multiphase flow. The velocity distribution in semi-dry FGD tower directly influences gas-solid mix and contact situation. In base of the tower, gas-solid two-phase flow field is more complex, and has the quite tremendous influence to the overall system desulphurization efficiency. This paper utilized PIV to study velocity distribution in Semi-dry flue gas desulfurization tower and obtained velocity distribution.