Electrochemical activity of various types of aqueous In(III) species at a mercury electrode

An interpretation framework is presented which provides a straightforward means to characterise the electrochemical reactivity of aqueous ions together with their various hydrolysed counterparts. Our novel approach bypasses the more laborious strategy of solving rigorously, for all relevant species, the complete set of Butler-Volmer equations coupled to diffusion differential equations. Specifically, we consider the spatial variable via a Koutecký-Koryta type of differentiation between nonlabile and labile zones adjacent to the electrode. The theory is illustrated by an assessment of the electrochemical reactivity of aqueous In(III) species based upon proper comparison between relevant time scales of the involved interfacial processes, i.e. diffusion, (de)protonation of inner-sphere water, dissociation/release of H₂O and OH⁻, and electron transfer. The analysis reveals that whilst all In(III) species are labile on the experimental timescale with respect to (de)protonation and (de)hydration, there are large differences in the rates of electron transfer between \( \mathrm{In}{\left({\mathrm{H}}_2\mathrm{O}\right)}_6^{3+} \) and the various hydroxy species. Specifically, in the case of \( \mathrm{In}{\left({\mathrm{H}}_2\mathrm{O}\right)}_6^{3+} \), the rate of electron transfer is so slow that it replaces the traditional Eigen rate-limiting water release step in the overall passage from hydrated In³⁺ to its reduced metallic form; in contrast, the In(III) hydroxy species display electrochemically reversible behaviour.

     

Accurate mass determination,quantification and determination of detection limits in liquid chromatography–high-resolution time-of-flight mass spectrometry: Challenges and practical solutions

Uniform guidelines for the data processing and validation of qualitative and quantitative multi-residue analysis using full-spectrum high-resolution mass spectrometry are scarce.     

On the use of AES data analysis to determine local enrichments of conversion coating elements at intermetallic particles on rolled Al

In this paper, the behaviour of the industrial applied Ti/Zr conversion coating (CC) pretreatment on rolled automotive aluminium samples (AA5182) is analysed. Due to its nanometre lateral and depth resolution, Auger electron spectroscopy (AES) is used to analyse the CC distribution at surface cathodic intermetallic particles. As a result of its high surface sensitivity, the AES technique is very susceptible to differences in the top contamination layer thickness. It is demonstrated that AES point measurements performed on aluminium model samples coated with 1.5 and 3 nm of Ti (oxide) layer cannot differentiate the two-layer thicknesses if a difference in the top contamination thickness is not taken into account. A data analysis methodology is introduced, based on the ratio of normalized peak areas (enrichment ratios), to eliminate the effect of the contamination layer thickness. The experimental validation of the methodology is performed on the model samples, demonstrating errors of 2% on the enrichment ratios on similar samples with different contamination layer thicknesses, while the conventional spectra quantification results in errors of 49%. The methodology is also theoretically substantiated within certain constraints. By the use of the AES methodology, an enriched Ti and Zr deposition is confirmed at the cathodic intermetallic particles at the surface of the industrial no-rinse CC sprayed automotive aluminium sheet samples.     

The far infrared spectrum of trans-formic acid: An extension up to 175 cm−1

The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm^?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm^?1, showing transitions from the trans-isomer.Ground state rotational transitions with K_a up to 30, were identified up to 175 cm^?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the I^r representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P.     

Selection of working fluids for electrohydrodynamic experiments in terrestrial conditions and microgravity

Electrohydrodyamic (EHD) heat transfer enhancement and flow control methods are becoming increasingly popular in engineering science and applications both in terrestrial and low gravity applications. The correct choice of the working fluid is essential for the design and performance of EHD hardware and can pose challenge because some working fluids with favorable EHD properties can be unstable or hazardous. In this paper key properties and criteria for the selection of working fluids for single-phase (liquid) as well as gas–liquid and vapor–liquid two-phase electrohydrodynamic experiments and applications are discussed. Key physical and electrical properties as well as environmental and safety issues are reviewed for the sample fluids PF-5052, FC-72, R141b, cyclohexane and pure water. Microgravity experiments impose additional demands on the selection of the working fluids. Some of these demands are addressed by contrasting bubble dimensions and shapes at detachment, estimated using a simple thermodynamic model, in terrestrial and microgravity conditions with and without electric fields. Data are obtained using a simplified analytical model and verified experimentally.     

Crown-Containing N-(Thio)Phosphoryl-(Thio)Ureas,their Ligand Properties and Analytical Application

Abstract

Crown-containing N-(thio)phosphoryl(thio)ureas are related to a class of NH-acids due to the presence of two acceptor-groups: (thio)phosphorylic and (thio)acylic. In agreement with structure of lariat ether, it was observed a stage corresponding to the step ejection of two H* ion on the potentiometric titration curve of ligand by alkaline. Calculated step ionization constants demonstrate that these compounds are weak acids with relative values of pK₁ and pK₂.     

Templating Irreversible Covalent Macrocyclization by Using Anions

Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields.