A perturbed hard-sphere equation of state extended to imidazolium-based ionic liquids

A perturbed hard-sphere equation of state (EOS) has been previously employed to predict pressure–volume–temperature properties of some ionic liquids (ILs) with phosphonium-, pyridinium-, and pyrrolidinium cations. In this work, we have extended the considered EOS to another class of ILs in compressed states. This class consists of 14 imidazolium-based ILs. The predicted densities were compared with those obtained from the experiment, over a broad pressure range from 0.1 to 200 MPa. From 1,122 data points examined for the aforementioned ILs, the total average absolute deviation was found to be 1.05%.     

LES study of diesel flame/wall interaction and mixing mechanisms at different wall distances

In this paper, the flame-wall interaction of reacting diesel spray under engine like conditions is investigated using large eddy simulations. The aim of this study is to understand the influence of the distance between the wall and the spray nozzle on the air entrainment rate, which is a key variable in formation/oxidation process of soot. Three experimental cases are investigated, a free jet case and two wall impingement cases with a distance from nozzle to wall of 30 mm and 50 mm, which are considered as characteristic wall impingement distances for light- and heavy-duty bores in diesel engines, respectively. The optical soot measurements imply a positive influence of wall on the rate of soot oxidation. Numerical simulations are employed to elucidate importance of different mechanisms for the air entrainment, i.e., air entrainment prior to flame lift-off position, enhanced mixing due to the wall impingement and enhanced mixing by the entrainment wave. The results show that oxidation process after the end of injection is driven by a different mixing mechanism depending on the distance to the wall. The 30 mm case resulted in a “mixing boost”, where the dominant mixing mechanism is the wall impingement vortex mixing, which gives rise to the fastest soot decay among the cases. The mixing in the 50 mm case is governed by a late wall impingement vortex mixing, giving rise to a low, but a constant air entrainment rate, i.e., a “mixing plateau”. The free jet case resulted in mixing governed by the entrainment wave mechanism. Both wall impingement cases have faster soot oxidation rate compared with the free jet case, but due to a different underlying mixing process. LES is shown to be able to replicate the line-of-sight measurements of natural OH* chemiluminescence and distribution of soot region from the optical soot diagnostics.     

Interactive effects of local smoothing window size and fundamental frequency on shimmer calculation

Slow amplitude modulation of human voice was approximated by a sinusoidal wave. The theoretical effects of smoothing window size, F₀, and modulation frequency on window amplitude average as well as calculated shimmer were mathematically derived. Subsequently, the theoretical predictions were tested using idealized and real voice signals from normal speakers. The theoretical and experimental results suggest that shimmer (when calculated using a smoothing window) is a function of window duration and modulation frequency. Window duration when defined as a constant number of pitch periods varies from speaker to speaker depending on their F₀. It may not be desirable to use local smoothing windows with a constant number of cycles for shimmer computation, especially if voices with known low-frequency amplitude modulations but notably different fundamental frequencies are compared.     

Light reflection from finite conductors with a Gaussian random roughness using Kirchhoff and geometric optics approximations

A comparison between exact solutions and two approximate models, Kirchhoff approximation (KA) and geometric optics approximation (GOA), for reflection from random Gaussian rough conductive metallic surfaces for three regimes of correlation length in both cases of polarization TM and TE has been reported. The phenomenon of excitation of surface plasmons (SPs) has been shown only at TM polarization for KA. The domains of validity of both approximate models have been quantified. It is shown that accuracy and efficiency of any approximate method depended of various parameters: surface roughness, polarization, SPs effects, wavelength, and surface materials. KA is efficient for weakly rough surfaces with correlation length greater than wavelength, but when rms height increases GOA is more suitable than KA. Excitation of SPs is observed only at TM-polarized light, only for weakly rough surfaces with correlation length less than wavelength using KA and not GOA.     

Electrocatalysis of oxygen reduction reaction on Nafion/platinum/gas diffusion layer electrode for PEM fuel cell

In this work a new membrane electrode based on Pt-coated Nafion membrane was fabricated. Chemical deposition process was used to coat platinum on Nafion 117 membrane and then Pt-coated Nafion membrane was hot pressed on gas diffusion layer (GDL) to make new membrane electrode. The electrochemical and chemical studies of the Pt-coated Nafions were investigated by electrochemical techniques, X-ray diffraction and scanning electron microscopy. The electrochemical results indicated that as the concentration of H₂PtCl₆ increased, the oxygen reduction reaction rate increased until the concentration was reached where the reduction reaction was limited by the problem of mass transport. The electrochemical results for oxygen reduction reaction showed that the new electrode which prepared by plating Nafion membrane with 0.06 M H₂PtCl₆ in electroless plating solution, has a higher performance than other electrodes. The XRD results showed that the average platinum particle size of the best sample was about 3 nm. The loading of platinum for this electrode was 0.153 mg cm⁻².     

Cooperative interaction between π-hole and single-electron σ-hole interactions in O2S···NCX···CH3 and O2Se···NCX···CH3 complexes (X = F,Cl, Br and I)

Ab initio calculations are performed to analyse the cooperative effects between π-hole and single-electron σ-hole interactions in O₂S···NCX···CH₃ and O₂Se···NCX···CH₃ complexes, where X = F, Cl, Br and I. These effects are investigated in terms of geometric and energetic features of the complexes, which are computed by UMP2/aug-cc-pVTZ(-PP) method. Our results indicate that the shortening of the each π-hole bond distance in the complexes is dependent on the strength of the σ-hole interaction. The maximum and minimum energetic cooperativity values correspond to the most and least stable complexes studied in the present work. The cooperativity between both types of interaction is chiefly caused by the electrostatic effects. The topological analysis, based on the quantum theory of atoms in molecules, is used to characterise the interactions and analyse their enhancement with varying electron density at bond critical points.     

Prediction and characterisation of a chalcogen···π interaction with acetylene as a potential electron donor in XHS···HCCH and XHSe···HCCH (X = F,Cl, Br,CN, OH,OCH3, NH2, CH3) σ-hole complexes

It is well-known that many covalently bonded atoms of group VI have specific positive regions of electrostatic potential (σ-holes) through which they can interact with Lewis bases. This interaction is called ‘chalcogen bond’ by analogy with halogen bond and hydrogen bond. In this study, ab initio calculations are performed to predict and characterise chalcogen···π interactions in XHS···HCCH and XHSe···HCCH complexes, where X = F, Cl, Br, CN, OH, OCH₃, NH₂, CH₃. For the complexes studied here, XHS(Se) and HCCH are treated as a Lewis acid and a Lewis base, respectively. The CCSD(T)/aug-cc-pVTZ interaction energies of this type of σ-hole bonding range from ?1.18 to ?4.83 kcal/mol. The calculated interaction energies tend to increase in magnitude with increasing positive electrostatic potential on the extension of X–S(Se) bond. The stability of chalcogen···π complexes is attributed mainly to electrostatic and correlation effects. The nature of chalcogen···π interactions is unveiled by means of the atoms in molecules, natural bond orbital, and electron localisation function analyses.