Thermal conductivity, thermal effusivity, and specific heat capacity near the lower critical point of the binary liquid mixture n-butoxyethanol-water

Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry.     

Analysis of ion binding on humic substances and the determination of intrinsic affinity distributions

Humic substances are characterized by a variable electric potential and by a variety of binding sites leading to chemical heterogeneity. Binding of ions to these substances is influenced by both factors. A methodology based on acid—base titrations at several salt levels is presented that allows for the assessment of an appropriate electrostatic double-layer model and the intrinsic proton affinity distribution. The double-layer model is used for the conversion of pH to pH_S for each data point, where H_S is the proton concentration in the diffuse layer near the binding site. It is shown that with an appropriate double-layer model the proton binding curves at different salt levels converge into one “master curve” when plotted as a function of pH_S. The intrinsic proton affinity distribution can then be derived from the “master curve” using the LOGA method. A rigorous analysis of metal binding to humic substances is complex and in practice is not feasible. Under two different (simplifying) assumptions, namely fully coupled and uncoupled binding, it is shown how intrinsic metal ion affinity distributions can be obtained. Model calculations show that apparent metal ion affinity distributions do not resemble the intrinsic metal ion affinity distribution.     

Some aspects of the interactions of orthopositronium with perfect and defect surfaces of insulating materials

ETLA (Elastic Thermalisation Lifetime Analysis) is a new model function for the fitting of lifetime spectra of slowly thermalising orthopositronium in the free space between the grains of insulating oxide powders. From this model one can obtain three fundamental parameters; the mass of the cluster of atoms which scatters the o-Ps, the probability that the o-Ps is forced into two-quantum decay at each collision and the emission energyE(0) of the o-Ps from the powder surface. As a consequence of full thermalisation of the Ps it is shown that the o-Ps quenching constant _q () follows atT ^1/2 dependency for MgO, Al₂O₃ and SiO₂ and for temperatures between 77 and 500 K. In MgO powder at low temperatures the irradiation by the positrons induces surface paramagnetic defects which are identified as Mg⁺ sites. These surface defects do not affect the thermalisation, but they induce paramagnetic o-p conversion i.e., an increase in , and they are also responsible for an increase in the emission energyE(0) of the o-Ps.     

Study of a glassy carbon electrode in amperometric detection using d.c., normal and differential pulse techniques

The results of a comparative study on d.c., normal pulse and differential pulse techniques applied to anodic amperometric detection at a glassy carbon electrode in a voltammetric flow-through cell are presented. The important aspects examined are response time, linearity, limit of detection and selectivity. It is shown that the d.c. mode is the most favourable as long as no adsorption of oxidation products takes place. If strong adsorption occurs, normal pulse detection is recommended, although the limit of detection is somewhat larger.     

Low-temperature infrared and raman studies: XI. The vibrational behaviour of ammonium perchlorate- its phase changes and the rotational freedom of its ions

An infrared, Raman and X-ray diffraction study on NH₄CIO₄. was conducted in the temperature ranges 300 to 17 °K, 300 to 130 °K and 300 to 120 °K respectively. The infrared studies also included the deuterated salt. The spectra are discussed and vibrational assignments made. Changes in the infrared spectra, as well as intensity measurements of the vibrational bands indicate anomalous behaviour in the region 100–110 °K as well as 17–50 °K. Possible reasons for these changes are proposed. The rotational behaviour of the ammonium ion upon cooling and hydrogen bonding are discussed.     

Determination of limonin in grapefruit juice and other citrus juices by high-performance liquid chromatography

A method has been developed for the quantitation of the bitter component limonin in grapefruit juice and other citrus juices. The sample clean-up consisted of centrifugation, filtration and a selective, rapid and reproducible purification with a C2 solid-phase extraction column. The limonin concentration was determined by high-performance liquid chromatography on a C18 column with UV detection at 210 nm. A linear response was obtained from 0.0 to 45 ppm limonin. The minimum detectable amount was 2 ng. The minimum concentration which was detected without concentration with good precision was 0.1 ppm. The method was also used for the determination of limonin in different types of oranges, including navel oranges, mandarins, lemons, limes, pomelos and uglis.