A generalized approach for the calculation and automation of potentiometric titrations Part 1. Acid-Base Titrations

Fast and accurate calculation procedures for pH and redox potentials are required for optimum control of automatic titrations. The procedure suggested is based on a three-dimensional titration curve V = f(pH, redox potential). All possible interactions between species in the solution, e.g., changes in activity coefficients and influences of redox potential on pH variations, are taken into account. The number of titrant additions can be reduced considerably without loss of precision, by using the fact that the pH of a protolyte or mixture of protolytes at some fraction titrated does not depend strongly on the actual concentration

A generalized approach for the calculation and automation of potentiometric titrations Part 2. Redox Titrations

The very fast calculation procedure described earlier is applied to calculate the titration curves of complicated redox systems. The theory is extended slightly to cover inhomogeneous redox systems. Titrations of iodine or 2,6-dichloroindophenol with ascorbic acid are described. It is shown that correspondence between theory and practice is good as long as the relevant stability constants and redox potentials are known with sufficient accuracy

Irrigation and drainage performance assessment: practical guidelines

Irrigation management / Drainage / Performance evaluation / Performance indexes / Evapotranspiration / Precipitation / Water balance / Participatory rural appraisal / Databases / Simulation

Persistence of the valence bond glass state in the double perovskites Ba2-xSrxYMoO6

Peer reviewedPublisher PD

Rebel diplomacy and digital communication: public diplomacy in the Sahel

Most research on social media as a tool for public diplomacy focuses on its use by recognized international actors to advance their national interest and reputation, deliver foreign policy objectives or promote their global interests. This article highlights the need for paying more attention to non-state diplomacy in conflict situations outside the western world. We examine how rebel groups use new media to enhance their communications, and what the motivations behind this are. Our public diplomacy perspective helps convey the scope of rebel communications with external actors and provides insights for policy-makers seeking to ascertain the nature, intentions and capacities of myriad rebel groups. Our focus is on the Sahel region, where numerous such groups vying for international attention and support make use of multiple social media channels. We analyse two groups in Mali: the MNLA, a Tuareg secessionist group; and Ansar Dine, a Salafist insurgency with ties to Al-Qaeda in the Islamic Maghreb. Our qualitative analysis of Ansar Dine and MNLA communications on several digital platforms helps identify these African rebel groups' international and local framing activities. Rebel groups use public diplomacy nimbly and pragmatically. The digital age has fundamentally changed which stakeholders such groups can reach, and we suggest that social media increase the power they are able to carve out for themselves on the international stage

Determination of buffer capacity by means of an ISFET-based coulometric sensor-actuator system with a gate-covering porous actuator

In this paper we propose a dynamic way to measure the buffer capacity of an electrolyte by means of an ISFET-based coulometric sensor-actuator system whose gate is covered with a porous actuator. A theoterical model for this measurement is presented. Experiments are carried out in nitric and acetic acid as well as in phosphoric acid solutions. A fairly good agreement has been found between the theoretical calculations and the experimental results

Evidence for hard and soft substructures in thermoelectric SnSe

SnSe is a topical thermoelectric material with a low thermal conductivity which is linked to its unique crystal structure. We use low-temperature heat capacity measurements to demonstrate the presence of two characteristic vibrational energy scales in SnSe with Debye temperatures thetaD1 = 345(9) K and thetaD2 = 154(2) K. These hard and soft substructures are quantitatively linked to the strong and weak Sn-Se bonds in the crystal structure. The heat capacity model predicts the temperature evolution of the unit cell volume, confirming that this two-substructure model captures the basic thermal properties. Comparison with phonon calculations reveals that the soft substructure is associated with the low energy phonon modes that are responsible for the thermal transport. This suggests that searching for materials containing highly divergent bond distances should be a fruitful route for discovering low thermal conductivity materials.Comment: Accepted by Applied Physics Letter

Spectral imbalance and the normalized dissipation rate of turbulence

The normalized turbulent dissipation rate $C_\epsilon$ is studied in decaying and forced turbulence by direct numerical simulations, large-eddy simulations, and closure calculations. A large difference in the values of $C_\epsilon$ is observed for the two types of turbulence. This difference is found at moderate Reynolds number, and it is shown that it persists at high Reynolds number, where the value of $C_\epsilon$ becomes independent of the Reynolds number, but is still not unique. This difference can be explained by the influence of the nonlinear cascade time that introduces a spectral disequilibrium for statistically nonstationary turbulence. Phenomenological analysis yields simple analytical models that satisfactorily reproduce the numerical results. These simple spectral models also reproduce and explain the increase of $C_\epsilon$ at low Reynolds number that is observed in the simulations

Voltammetric investigation of the complexation equilibria in the presence of a low level of supporting electrolyte Part 1: Steady-state current-potential curves for inert complexes

The use of microelectrodes for voltammetric investigations of the complexation equilibria at very low concentrations of supporting electrolyte allows the risk of competitive complexation or contamination to be avoided, makes the activities of the species involved closer to their concentrations (which facilitates comparisons with the spectroscopic results) and finally, allows the concentrations of the species to be varied over a broader range. This paper presents the calculations of the steady-state currents for a wide range of complexes that are inert on the experimental time scale, and reports the influence of the concentration of the electroinactive ionic species on the limiting currents. Also, for a number of cases the variation of halfwave potential with the ligand concentration, resulting from changes in the ohmic drop, is given. It is assumed that only one species (the complex or the uncomplexed form) is electroactive; if this is the complex, it may or may not change the number of ligands. The theoretical results were obtained either employing the Myland-Oldham theory extended in this paper or by digital simulation. The results of calculations show that the magnitude of the changes in the steady-state limiting current on complexation depends on the type of complexation equilibrium, the type of the change in the reactant charge number in the electrode process, and the complex formation constant. In a number of situations migrational effects are negligibly small and no special treatment is necessary, despite the lack of supporting electrolyte. In other cases, where migration is significant, the relations between the measured steady-state limiting current and the complex formation constant ß are given in the form of fitted equations that can be used to obtain ß from appropriate experimental data