Electrochemical ammonia gas sensing in nonaqueous systems: A comparison of propylene carbonate with room temperature ffonc liquids

First, the direct and indirect electrochemical oxidation of ammonia has been studied by cyclic voltammetry at glassy carbon electrodes in propylene carbonate. In the case of the indirect oxidation of ammonia, its analytical utility of indirect for ammonia sensing was examined in the range from 10 and 100 ppm by measuring the peak current of new wave resulting from reaction between ammonia and hydroquinone, as function of ammonia concentration, giving a sensitivity 1.29 x 10(-7) A ppm(-1) (r(2)=0.999) and limit-of-detection 5 ppm ammonia. Further, the direct oxidation of ammonia has been investigated in several room temperature ionic liquids (RTILs), namely 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim] [BF4]), 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim] [OTf]), 1-Ethyl -3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim] [NTf2]), 1-butyl-3-methylimidazolium bis(tritluoromethylsulfonyl)imide ([C4mim] [NTf2]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim] [PF6]) on a 10 put diameter Pt microdisk electrode. In four of the RTILs studied, the cyclic voltammetric analysis suggests that ammonia is initially oxidized to nitrogen, N-2, and protons, which are transferred to an ammonia molecule, forming NH4+ via the protonation of the anion(s) (A(-)). However, in [C4mim] [PF6], the protonated anion was formed first, followed by NH4+. In all five RTILs, both HA and NH4+ are reduced at the electrode surface, forming hydrogen gas, which is then oxidized. The analytical ability of this work has also been explored further, giving a limit-of-detection close to 50 ppm in [C(2)mim] [NTf2], [C(4)mim] [OTf], [C(4)mim] [BF4], with a sensitivity of ca. 6 x 10(-7) A ppm(-1) (r(2) = 0.999) for all three ionic liquids, showing that the limit of detection was ca. ten times larger than that in propylene carbonate since ammonia in propylene carbonate might be more soluble in comparison with RTILs when considering the higher viscosity of RTILs.

Improved fault diagnosis in multivariate systems using regression-based reconstruction

Subspace monitoring has recently been proposed as a condition monitoring tool that requires considerably fewer variables to be analysed compared to dynamic principal component analysis (PCA). This paper analyses subspace monitoring in identifying and isolating fault conditions, which reveals that the existing work suffers from inherent limitations if complex fault senarios arise. Based on the assumption that the fault signature is deterministic while the monitored variables are stochastic, the paper introduces a regression-based reconstruction technique to overcome these limitations. The utility of the proposed fault identification and isolation method is shown using a simulation example and the analysis of experimental data from an industrial reactive distillation unit.

Disturbance attenuation in linear systems via dynamical compensators: A parametric eigenstructure assignment approach

A simple approach is proposed for disturbance attenuation in multivariable linear systems via dynamical output compensators based on complete parametric eigenstructure assignment. The basic idea is to minimise the H-2 norm of the disturbance-output transfer function using the design freedom provided by eigenstructure assignment. For robustness, the closed-loop system is restricted to be nondefective. Besides the design parameters, the closed-loop eigenvalues are also optimised within desired regions on the left-half complex plane to ensure both closed-loop stability and dynamical performance. With the proposed approach, additional closed-loop specifications can be easily achieved. As a demonstration, robust pole assignment, in the sense that the closed-loop eigenvalues are as insensitive as possible to open-loop system parameter perturbations, is treated. Application of the proposed approach to robust control of a magnetic bearing with a pair of opposing electromagnets and a rigid rotor is discussed.

Correlated electron-ion dynamics in metallic systems

In this paper we briefly discuss the problem of simulating non-adiabatic processes in systems that are usefully modelled using molecular dynamics. In particular we address the problems associated with metals, and describe two methods that can be applied: the Ehrenfest approximation and correlated electron-ion dynamics (CEID). The Ehrenfest approximation is used to successfully describe the friction force experienced by an energetic particle passing through a crystal, but is unable to describe the heating of a wire by an electric current. CEID restores the proper heating.

Maternal effects on offspring size and packaging constraints in the whelk

Life-history theory predicts an optimal offspring size, irrespective of reproductive effort; however, in some species offspring size correlates positively with maternal size. We examine hypotheses for why this latter situation should occur in the whelk Buccinum undatum. The trade-offs between aspects of reproduction in whelks are complicated due to the provision of protective egg capsules. Many eggs are placed within each capsule but c. 99% of these eggs are consumed by the remaining developing young. Large maternal size results in more eggs, larger eggs, more eggs consumed per hatchling, more capsules, larger capsules, more eggs per capsule, a larger number of hatchlings per capsule and larger hatchlings. Increased intra-capsule and post-hatch sibling competition may decrease the marginal value for additional young and select for larger young, however, our data do not support this explanation. Instead, packaging constraints within each capsule limit the size of hatchlings but this constraint is relaxed for medium to large females because they produce large capsules. Small females appear to produce young below optimum size because of the space constraint thus explaining the correlation between maternal size and offspring size.

On the alignment of debris disks and their host stars' rotation axis -implications for spin-orbit misalignment in exoplanetary systems

It has been widely thought that measuring the misalignment angle between the orbital plane of a transiting exoplanet and the spin of its host star was a good discriminator between different migration processes for hot-Jupiters. Specifically, well-aligned hot-Jupiter systems (as measured by the Rossiter-McLaughlin effect) were thought to have formed via migration through interaction with a viscous disc, while misaligned systems were thought to have undergone a more violent dynamical history. These conclusions were based on the assumption that the planet-forming disc was well-aligned with the host star. Recent work by Lai et al. has challenged this assumption, and proposes that the star-disc interaction in the pre-main sequence phase can exert a torque on the star and change its rotation axis angle. We have estimated the stellar rotation axis of a sample of stars which host spatially resolved debris disks. Comparison of our derived stellar rotation axis inclination angles with the geometrically measured debris-disk inclinations shows no evidence for a misalignment between the two.

Scattering theory of cooling and heating in optomechanical systems

We present a one-dimensional scattering theory which enables us to describe a wealth of effects arising from the coupling of the motional degree of freedom of scatterers to the electromagnetic field. Multiple scattering to all orders is taken into account. The theory is applied to describe the scheme of a Fabry-Perot resonator with one of its mirrors moving. The friction force, as well as the diffusion, acting on the moving mirror is derived. In the limit of a small reflection coefficient, the same model provides for the description of the mechanical effect of light on an atom moving in front of a mirror.