Bis-phosphonio-isophosphindolide Copper Complexes

1999 ◽  
Vol 54 (10) ◽  
pp. 1244-1252 ◽  
Author(s):  
Dietrich Gudat ◽  
Andreas W. Holderberg ◽  
Nikolaus Korber ◽  
Martin Nieger ◽  
Martin Schrott
Keyword(s):  
Copper Complexes ◽  
Dynamic Equilibrium ◽  
Solid Phase ◽  
Lone Pair ◽  
Binuclear Complexes ◽  
Exchange Reactions ◽  
Nmr Studies ◽  
Bonding Parameters ◽  
Stability Of Complexes ◽  
The Stability

Bis-triphenylphosphonio-isophosphindolide salts 1[X] react with Cu(I)-halides CuX to give isolable products of composition [(1)Cu2X3 ]. X-ray crystal structure analyses confirmed that for X = Br, Cl dinuclear complexes [(μ-1 )(μ-X)Cu2X2] with μ2, η1(P)-bridging cations 1 are formed, while for X = I a solid phase containing a salt (1)2[Cu4I6] and a complex [(1)2Cu4I6] with a terminal η1(P)-coordinated ligand 1 was obtained. The bonding parameters in the two types of complexes suggest that l i s a hybrid between a phosphenium cation and a phospholide anion whose π-system is less nucleophilic than the phosphorus lone-pair.31P NMR studies revealed that in solution in all cases binuclear complexes [(1)Cu2X3] are in dynamic equilibrium with small amounts of mononuclear species and free 1. The same equilibria were detected in the system 1[OTf]/CuOTf. NMR studies of ligand exchange reactions indicated that the stability of complexes [(1)Cu2X3 ] increases in the order X = OTf < I < Br, Cl, and titration of [(1)Cu2Br3] with Et4NBr allowed to determine the equilibrium constant of the complex formation reaction.

TEM characterization of Au/Polysilicon interactions

1990 ◽  
Vol 48 (4) ◽  
pp. 650-651
Author(s):  
N. David Theodore ◽  
Leslie H. Allen ◽  
C. Barry Carter ◽  
James W. Mayer
Keyword(s):  
Solid Phase ◽  
Single Crystal Silicon ◽  
Chemical Vapor ◽  
Electrical Contacts ◽  
Silicon Substrates ◽  
Crystal Silicon ◽  
Transmission Electron ◽  
Polysilicon Films ◽  
The Stability

Metal/polysilicon investigations contribute to an understanding of issues relevant to the stability of electrical contacts in semiconductor devices. These investigations also contribute to an understanding of Si lateral solid-phase epitactic growth. Metals such as Au, Al and Ag form eutectics with Si. reactions in these metal/polysilicon systems lead to the formation of large-grain silicon. Of these systems, the Al/polysilicon system has been most extensively studied. In this study, the behavior upon thermal annealing of Au/polysilicon bilayers is investigated using cross-section transmission electron microscopy (XTEM). The unique feature of this system is that silicon grain-growth occurs at particularly low temperatures ∽300°C).Gold/polysilicon bilayers were fabricated on thermally oxidized single-crystal silicon substrates. Lowpressure chemical vapor deposition (LPCVD) at 620°C was used to obtain 100 to 400 nm polysilicon films. The surface of the polysilicon was cleaned with a buffered hydrofluoric acid solution. Gold was then thermally evaporated onto the samples.

The influence of the Stokes and Archimedes forces on the stability of a two-phase flow

2003 ◽  
Vol 3 ◽  
pp. 266-270
Author(s):  
B.H. Khudjuyerov ◽  
I.A. Chuliev
Keyword(s):  
Spectral Method ◽  
Stability Region ◽  
Gas Flow ◽  
Two Phase Flow ◽  
Solid Phase ◽  
Stability Characteristic ◽  
Phase Flow ◽  
Two Phase ◽  
The Stability

The problem of the stability of a two-phase flow is considered. The solution of the stability equations is performed by the spectral method using polynomials of Chebyshev. A decrease in the stability region gas flow with the addition of particles of the solid phase. The analysis influence on the stability characteristic of Stokes and Archimedes forces.

Effect of delocalization of nonbonding electron density on the stability of the M–Ccarbene bond in main group metal-imidazol-2-ylidene complexes: a computational and structural database study

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Samuel Tetteh ◽  
Albert Ofori
Keyword(s):  
Electron Density ◽  
Lone Pair ◽  
Main Group ◽  
Binding Energies ◽  
Electrostatic Model ◽  
Group Metal ◽  
Main Group Metal ◽  
Structural Database ◽  
The Stability ◽  
Lone Pair Electrons

Abstract The M–Ccarbene bond in metal (M) complexes involving the imidazol-2-ylidene (Im) ligand has largely been described using the σ-donor only model with donation of σ electrons from the sp-hybridized orbital of the carbene carbon into vacant orbitals on the metal centre. Analyses of the M–Ccarbene bond in a series of group IA, IIA and IIIA main group metal complexes show that the M-Im interactions are mostly electrostatic with the M–Ccarbene bond distances greater than the sum of the respective covalent radii. Estimation of the binding energies of a series of metal hydride/fluoride/chloride imidazol-2-ylidene complexes revealed that the stability of the M–Ccarbene bond in these complexes is not always commensurate with the σ-only electrostatic model. Further natural bond orbital (NBO) analyses at the DFT/B3LYP level of theory revealed substantial covalency in the M–Ccarbene bond with minor delocalization of electron density from the lone pair electrons on the halide ligands into antibonding molecular orbitals on the Im ligand. Calculation of the thermodynamic stability of the M–Ccarbene bond showed that these interactions are mostly endothermic in the gas phase with reduced entropies giving an overall ΔG > 0.

scholarly journals A Two-Scale Computational Model of pH-Sensitive Expansive Porous Media

2013 ◽  
Vol 80 (2) ◽  
Author(s):  
Ranena V. Ponce F. ◽  
Márcio A. Murad ◽  
Sidarta A. Lima
Keyword(s):  
Electrolyte Solution ◽  
Solid Phase ◽  
Scale Model ◽  
Bulk Solution ◽  
Neumann Condition ◽  
Pore Scale ◽  
Exchange Reactions ◽  
Layer Potential ◽  
Bulk Fluid ◽  
Monovalent Ions

We propose a new two-scale model to compute the swelling pressure in colloidal systems with microstructure sensitive to pH changes from an outer bulk fluid in thermodynamic equilibrium with the electrolyte solution in the nanopores. The model is based on establishing the microscopic pore scale governing equations for a biphasic porous medium composed of surface charged macromolecules saturated by the aqueous electrolyte solution containing four monovalent ions (Na+,Cl-,H+,OH-). Ion exchange reactions occur at the surface of the particles leading to a pH-dependent surface charge density, giving rise to a nonlinear Neumann condition for the Poisson–Boltzmann problem for the electric double layer potential. The homogenization procedure, based on formal matched asymptotic expansions, is applied to up-scale the pore-scale model to the macroscale. Modified forms of Terzaghi's effective stress principle and mass balance of the solid phase, including a disjoining stress tensor and electrochemical compressibility, are rigorously derived from the upscaling procedure. New constitutive laws are constructed for these quantities incorporating the pH-dependency. The two-scale model is discretized by the finite element method and applied to numerically simulate a free swelling experiment induced by chemical stimulation of the external bulk solution.

Occurrence and persistence of bacterial and viral faecal indicators in wastewater biofilms

2007 ◽  
Vol 55 (8-9) ◽  
pp. 377-385 ◽  
Author(s):  
S. Skraber ◽  
K. Helmi ◽  
R. Willame ◽  
M. Ferréol ◽  
C. Gantzer ◽  
...  
Keyword(s):  
Dynamic Equilibrium ◽  
Wastewater Treatment Plants ◽  
Plate Count ◽  
Cryptosporidium Oocysts ◽  
The Matrix ◽  
Thermotolerant Coliforms ◽  
Viral Indicators ◽  
The Stability ◽  
Faecal Indicators ◽  
Giardia Cysts

Biofilms within wastewater treatment plants can capture enteric microorganisms initially present in the water phase immobilising them either definitively or temporarily. Consequently, fates of microorganisms may totally change depending on whether they interact or not with biofilms. In this study, we assessed the stability of wastewater biofilms comparing the evolution of the concentrations of bacteria (heterotrophic plate count [HPC], thermotolerant coliforms [TC]) and viral (somatic coliphages [SC] and F-specific phages [F+]) indicators in the biofilms and in the corresponding wastewaters at 4 and 20 °C. Additionally, we assessed the monthly occurrence of these bacterial and viral indicators as well as of pathogenic protozoa (Cryptosporidium oocysts and Giardia cysts) in three native wastewater biofilms for four months. Our results show that viral indicators (SC and F+) persist longer in biofilms than in the corresponding wastewaters at 4 °C as well as at 20 °C. In contrast, persistence of bacterial indicators (TC and HPC) depends on both the temperature and the matrix. Differences between viral and bacterial persistence are discussed. Monthly analysis of native wastewater biofilms shows that bacterial and viral indicators, as well as Cryptosporidium oocysts and Giardia cysts, attach to wastewater biofilms to a concentration that remains stable in time, probably as a result of a dynamic equilibrium between attachment and detachment processes.

scholarly journals The influence of the nature and textural properties of different supports on the thermal behavior of Keggin type heteropolyacids

2006 ◽  
Vol 71 (3) ◽  
pp. 235-249 ◽  
Author(s):  
Alexandru Popa ◽  
Viorel Sasca ◽  
Mircea Stefanescu ◽  
Erne Kis ◽  
Radmila Marinkovic-Neducin
Keyword(s):  
Thermal Stability ◽  
Thermal Decomposition ◽  
Thermal Behavior ◽  
Solid Phase ◽  
Textural Properties ◽  
Nitrogen Adsorption ◽  
Active Phase ◽  
Support Surface ◽  
Sem Images ◽  
The Stability

In order to obtain highly dispersed heteropolyacids (HPAs) species, H3PMo12O40 and H4PVMo11O40 were supported on various supports: silica (Aerosil - Degussa and Romsil types) and TiO2. The structure and thermal decomposition of supported and unsupported HPAs were followed by different techniques (TGA-DTA, FTIR, XRD, low temperature nitrogen adsorption, scanning electron microscopy). All the supported HPAs were prepared by impregnation using the incipient wetness technique with a 1:1 mixture of water-ethanol. Samples were prepared with different concentrations to examine the effect of loading on the thermal behavior of the supported acid catalysts. The thermal stability was evaluated with reference to the bulk solid acids and mechanical mixtures. After deposition on silica types supports, an important decrease in thermal stability was observed on the Romsil types and a small decrease on the Aerosil type. The stability of the heteropolyacids supported on titania increased due to an anion-support interaction, as the thermal decomposition proceeded in two steps. The structure of the HPAs was not totally destroyed at 450 ?C as some IR bands were still preserved. A relatively uniform distribution of HPAs on the support surface was observed for all compositions of the active phase. No separate crystallites of solid phase HPAs were found in the SEM images.

scholarly journals Phase Transformation of Cr(VI)-Adsorbed Ferrihydrite at Different pH in The Presence of Mn(II): Fate of Mn(II) and Cr(VI)

2021 ◽  
Author(s):  
Zecong Ding ◽  
Fenglian Fu ◽  
Guangzhao Sun ◽  
Chujia Ye
Keyword(s):  
Phase Transformation ◽  
Heavy Metal Ions ◽  
Solid Phase ◽  
Transformation Products ◽  
Transformation Process ◽  
Toxic Heavy Metal ◽  
Chromium Vi ◽  
Initial Ph ◽  
The Stability ◽  
Mn Concentration

Abstract Ferrihydrite is an important sink for the toxic heavy metal ions, such as chromium(VI). As ferrihydrite is thermodynamically unstable and gradually transforms into hematite and goethite, the stability of Cr(VI)-adsorbed ferrihydrite is environmentally significant. This study investigated the phase transformation of Cr(VI)-adsorbed ferrihydrite at different pH in the presence of aqueous Mn(II), as well as the fate of Mn(II) and Cr(VI) in the transformation process of ferrihydrite. Among the ferrihydrite transformation products, hematite was dominant, and goethite was minor. The pre-adsorbed Cr(VI) inhibited the conversion of ferrihydrite to goethite at initial pH 3.0, whereas little amount of adsorbed Mn(II) favored the formation of goethite at initial pH 7.0. After the aging process, Cr species in solid phase existed primarily as Cr(III) in the presence of Mn(II) at initial pH 7.0 and 11.0. The aqueous Mn concentration was predominantly unchanged at initial pH 3.0, whereas the aqueous Mn(II) was adsorbed onto ferrihydrite or form Mn(OH)2 precipitates at initial pH 7.0 and 11.0, promoting the immobilization of Cr(VI). Moreover, the oxidation of Mn(II) occurred at initial pH 7.0 and 11.0, forming Mn(III/IV) (hydr)oxides.

A New Electrically Reversible Depassivation/Passivation Mechanism in Polycrystalline Silicon

1996 ◽  
Vol 424 ◽  
Author(s):  
Vyshnavi Suntharalingam ◽  
Stephen J. Fonash
Keyword(s):  
Electric Fields ◽  
Polycrystalline Silicon ◽  
Solid Phase ◽  
Hydrogen Release ◽  
Temperature Bias ◽  
Polysilicon Films ◽  
The Stability ◽  
Quartz Substrates ◽  
Hydrogenated Amorphous ◽  
Positively Charged

AbstractAn electrically reversible depassivation/passivation phenomenon, recently found for hydrogen passivated polysilicon [1] is further explored in this report. This reversible effect is seen in both ECR and RE hydrogen passivated n-channel thin film transistors (TFTs) but is not seen in the corresponding hydrogen passivated pchannel TFrs, nor is it seen in either n- or p-channel TETs before hydrogenation. This phenomenon has been observed when room temperature bias stressing TFTs fabricated on solid phase or laser crystallized polysilicon films on quartz substrates [1]. A model involving hydrogen release or capture at defects, positively charged hydrogen motion in device electric fields, and subsequent hydrogen capture at other defects has been proposed. This phenomenon has significant implications for polycrystalline silicon TFT’ design and operation. By extension, it also offers significant insight into the stability problems of hydrogenated amorphous silicon.

scholarly journals Potentiometric Response of Ag/AgCl Chloride Sensors in Model Alkaline Medium

2018 ◽  
Vol 2018 ◽  
pp. 1-12 ◽  
Author(s):  
Farhad Pargar ◽  
Hristo Kolev ◽  
Dessi A. Koleva ◽  
Klaas van Breugel
Keyword(s):  
Alkaline Medium ◽  
Open Circuit Potential ◽  
Dynamic Equilibrium ◽  
Chloride Concentration ◽  
Chloride Content ◽  
Cementitious Materials ◽  
Open Circuit ◽  
Potentiometric Response ◽  
Before And After ◽  
The Stability

The stability and reproducibility of an Ag/AgCl sensors’ response in an alkaline medium are important for the application of these sensors in cementitious materials. The sensors’ response, or their open circuit potential (OCP), reflects a dynamic equilibrium at the sensor/environment interface. The OCP response in an alkaline medium is affected by the presence of hydroxide ions. The interference of hydroxide ions leads to inaccuracies or a delay in the sensors’ response to a certain chloride content. In this article, the potentiometric response (or OCP evolution) of the chloride sensors is measured in model solutions, resembling the concrete pore water. The scatter of the sensors’ OCP is discussed with respect to the interference of hydroxide ions at varying chloride concentration in the medium. The deviation of the sensor’s response from its ideal performance (determined by the Nernst law) is attributed to dechlorination of the AgCl layer and the formation of Ag2O on the sensor’s surface. Results from the surface XPS analysis of the AgCl layer before and after treatment in alkaline medium confirm these observations in view of chemical transformation of AgCl to Ag2O.

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