On overpotential and the photovoltaic process at polarized electrodes

1949 ◽  
Vol 199 (1058) ◽  
pp. 295-310 ◽  
Keyword(s):  
Incident Light ◽  
Wave Length ◽  
Electrode Reaction ◽  
Water Molecules ◽  
Adsorbed Hydrogen ◽  
Stationary Concentration ◽  
Rate Determining Step ◽  
Adsorbed Atoms ◽  
Complete Layer ◽  
Good Agreement

The acceleration of the electrodeposition of hydrogen and oxygen by light of wave-length from 4000 to 2000 A has been studied on different electrodes. The quantum efficiency of the photoreaction was determined as a function of the wave-length of the incident light and of the steady polarizing current. From these experiments it was concluded that the rate-determining step at these electrodes occurred after the discharge of the ions and that the overpotential corresponded to a stationary concentration of adsorbed atoms or radicals. It was further concluded that an electrode at which hydrogen is being evolved at a sensible rate is covered with a nearly complete layer of adsorbed hydrogen. The potential at which such evolution occurs is determined primarily by the negative potential necessary to displace adsorbed oxygen atoms or water molecules by hydrogen. Calculations of this potential, in the few cases where the necessary heats of adsorption are available, gave values in agreement with those observed experimentally. It was concluded that the rate-determining step on most cathodes, except platinum, was the electrochemical combination of an adsorbed atom with an ion in the double layer, and relations were obtained for the dependence of the overpotential on the current density and electrokinetic potential, which are in fairly good agreement with experiment. A similar mechanism is tentatively suggested for the electrode reaction at an anode at which oxygen is being evolved.

scholarly journals The molecular scattering of light in vapours and in liquids and its relation to the opalescence observed in the critical state

1922 ◽  
Vol 102 (715) ◽  
pp. 151-161 ◽  
Keyword(s):  
Critical Point ◽  
Critical State ◽  
Incident Light ◽  
Wave Length ◽  
Molecular Scattering ◽  
Avogadro’S Number ◽  
Quantitative Manner ◽  
The Mean ◽  
Good Agreement ◽  
Molecular Scattering Of Light

It has long been known that in the immediate vicinity of the critical state, many substances exhibit a strong and characteristic opalescence. In recent years, the phenomenon has been studied by Travers and Usher in the case of carefully purified CS 2 , SO 2 , and ether, by S. Young, by F. B. Young in the case of ether, and in a quantitative manner by Kammerlingh Onnes and Keesom in the case of ethylene. An explanation of the phenomenon on thermodynamic principles as due to the accidental deviations of density arising in the substance was put forward by Smoluchowski. He obtained an expression for the mean fluctuation of density in terms of the compressibility of the substance, and later, Einstein applied Maxwell’s equations of the electromagnetic field to obtain an expression for the intensity of the light scattered in consequence of such deviations of density. He showed that the fraction α of the incident energy scattered in the substance per unit volume is 8 π 3 /27 RT β ( μ 2 – 1) 2 ( μ 2 + 2) 2 /N λ 4 (1) In this, R and N are the gas constant and Avogadro’s number per grammolecule, β is the isothermal compressibility of the substance, μ is the refractive index and λ is the wave-length of the incident light. Keesom tested this formula over a range of 2·35° above the critical point of ethylene and found good agreement except very close to the critical point.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

Neutral 4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide and its salt forms with inorganic anions

2019 ◽  
Vol 75 (1) ◽  
pp. 1-7
Author(s):  
Vinicius Oliveira Araujo ◽  
Bárbara Tirloni ◽  
Lívia Streit ◽  
Vânia Denise Schwade
Keyword(s):  
Solid State ◽  
Spectroscopic Characterization ◽  
Water Molecules ◽  
Keto Form ◽  
Chloride Dihydrate ◽  
Ir And Nmr Spectroscopy ◽  
Tautomeric Forms ◽  
Counter Ions ◽  
Salt Forms ◽  
Good Agreement

Semicarbazones can exist in two tautomeric forms. In the solid state, they are found in the keto form. This work presents the synthesis, structures and spectroscopic characterization (IR and NMR spectroscopy) of four such compounds, namely the neutral molecule 4-phenyl-1-[phenyl(pyridin-2-yl)methylidene]semicarbazide, C19H16N4O, (I), abbreviated as HBzPyS, and three different hydrated salts, namely the chloride dihydrate, C19H17N4O+·Cl−·2H2O, (II), the nitrate dihydrate, C19H17N4O+·NO3 −·2H2O, (III), and the thiocyanate 2.5-hydrate, C19H17N4O+·SCN−·2.5H2O, (IV), of 2-[phenyl({[(phenylcarbamoyl)amino]imino})methyl]pyridinium, abbreviated as [H2BzPyS]+·X −·nH2O, with X = Cl− and n = 2 for (II), X = NO3 − and n = 2 for (III), and X = SCN− and n = 2.5 for (IV), showing the influence of the anionic form in the intermolecular interactions. Water molecules and counter-ions (chloride or nitrate) are involved in the formation of a two-dimensional arrangement by the establishment of hydrogen bonds with the N—H groups of the cation, stabilizing the E isomers in the solid state. The neutral HBzPyS molecule crystallized as the E isomer due to the existence of weak π–π interactions between pairs of molecules. The calculated IR spectrum of the hydrated [H2BzPyS]+ cation is in good agreement with the experimental results.

The continuous absorption of light in alkali-metal vapours

1953 ◽  
Vol 219 (1136) ◽  
pp. 89-101 ◽  
Keyword(s):  
Cross Section ◽  
Alkali Metals ◽  
Theoretical Calculations ◽  
Wave Length ◽  
Energy Difference ◽  
Continuous Absorption ◽  
Absorption Of Light ◽  
Sodium Vapour ◽  
Good Agreement ◽  
Dipole Length

The first section of this paper is an account of some experiments on the absorption of light in sodium vapour from the series limit at 2412 Å to about 1600 Å (an energy difference of 2·6 eV). The absorption cross-section at the limit is 11·6 ± 1·2 x 10 -20 cm 2 . The cross-section decreases giving a minimum of 1·3 ± 0·6 x 10 -20 cm 2 at 1900 Å and then increases to 1600 Å. A theoretical calculation by Seaton based on the dipole-length formula gives good agreement with the experiments at the series limit and also correctly predicts the wave-length for the minimum, but it predicts a significantly lower absorption at the minimum. The experiments described in the first section of the paper conclude a series on the absorption of light in the alkali metals. The second section consists of a general discussion of the results of these experiments and of their relation to theoretical calculations. There is good agreement between theory and experiment except in regard to the magnitude of the absorption at the minimum.

From the Understanding of the Reaction Mechanism Towards Optimizing the Deposition Rate and Optoelectronic Properties of a-Si:H

1989 ◽  
Vol 149 ◽  
Author(s):  
S. Veprek ◽  
M. Heintze ◽  
R. Bayer ◽  
N. Jurčik-Rajman
Keyword(s):  
Reaction Mechanism ◽  
Surface Coverage ◽  
Kinetic Studies ◽  
Reactive Intermediates ◽  
Sticking Coefficient ◽  
High Quality ◽  
Rate Determining Step ◽  
Homogeneous Good ◽  
Good Agreement

ABSTRACTWe present new results of kinetic studies of the deposition of high quality a-Si:H which strongly support the reaction mechanism suggested in our earlier papers: 1. SiH4 → SiH2; 2. SiH2 + SiS4 → Si2H6 (SiH2 + Si2H6 → Si3H6); 3. Si2H6 → 2a-Si:H (Si3H8 → 3a-Si:H). The “SiH3 mechanism”, as promoted by several workers, is in contradiction with these experimental facts.The di- and trisilane, which have a much higher reactive sticking coefficient than monosilane, play the role of reactive intermediates which facilitate the heterogeneous decomposition of silicon carrying species at the surface of the growing film. The values of the reactive sticking coefficient of Si2H6 and Si3H8 depend on the surface coverage by chemisorbed hydrogen; they increase with decreasing surface coverage. Under the conditions of the growth of high quality a-Si:H films the reactive sticking coefficient of disilane amounts to 10−4 to 10−2 which is in a good agreement with recent data of other authors.The rate determining step of the growth of high quality a-Si:H films is the desorption of hydrogen from the surface of the growing film. This can be strongly enhanced by ion bombardment at impact energy of <100 eV. In this way, homogeneous, good quality films were deposited at rates up to 1800 Angströms/min, and there is a well justified hope that this rate can be further increased.

scholarly journals Metalenses Based on Symmetric Slab Waveguide and c-TiO2: Efficient Polarization-Insensitive Focusing at Visible Wavelengths

Nanomaterials ◽  
2018 ◽  
Vol 8 (9) ◽  
pp. 699 ◽  
Author(s):  
Yaoyao Liang ◽  
Zhongchao Wei ◽  
Jianping Guo ◽  
Faqiang Wang ◽  
Hongyun Meng ◽  
...  
Keyword(s):  
Berry Phase ◽  
Incident Light ◽  
Visible Spectrum ◽  
Slab Waveguide ◽  
Optical Elements ◽  
Polarization Insensitive ◽  
Wavefront Shaping ◽  
Visible Wavelengths ◽  
532 Nm ◽  
Good Agreement

A key goal of metalens research is to achieve wavefront shaping of light using optical elements with thicknesses on the order of the wavelength. Here we demonstrate ultrathin highly efficient crystalline titanium dioxide metalenses at blue, green, and red wavelengths (λ0 = 453 nm, 532 nm, and 633 nm, respectively) based on symmetric slab waveguide theory. These metalenses are less than 488 nm-thick and capable of focusing incident light into very symmetric diffraction-limited spots with strehl ratio and efficiency as high as 0.96 and 83%, respectively. Further quantitative characterizations about metalenses’ peak focusing intensities and focal spot sizes show good agreement with theoretical calculation. Besides, the metalenses suffer only about 10% chromatic deviation from the ideal spots in visible spectrum. In contrast with Pancharatnam–Berry phase mechanism, which limit their incident light at circular polarization, the proposed method enables metalenses polarization-insensitive to incident light.

scholarly journals Molecular Dynamics Modellization and Simulation of Water Diffusion through Plant Cutin

1999 ◽  
Vol 54 (11) ◽  
pp. 896-902 ◽  
Author(s):  
Antonio Matas ◽  
Antonio Heredia
Keyword(s):  
Experimental Data ◽  
Molecular Dynamics ◽  
Structural Information ◽  
Md Simulations ◽  
Water Molecules ◽  
Plant Cuticle ◽  
X Ray Diffraction ◽  
Cross Link ◽  
X Ray ◽  
Good Agreement

Abstract A theoretical molecular modelling study has been conducted for cutin, the biopolyester that forms the main structural component of the plant cuticle. Molecular dynamics (MD) simulations, extended over several ten picoseconds, suggests that cutin is a moderately flexible netting with motional constraints mainly located at the cross-link sites of functional ester groups. This study also gives structural information essentially in accordance with previously reported experimental data, obtained from X -ray diffraction and nuclear magnetic resonance experiments. MD calculations were also performed to simulate the diffusion of water mole­cules through the cutin biopolymer. The theoretical analysis gives evidence that water perme­ation proceedes by a “hopping mechanism”. Coefficients for the diffusion of the water molecules in cutin were obtained from their mean-square displacements yielding values in good agreement with experimental data.

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

1982 ◽  
Vol 47 (7) ◽  
pp. 1773-1779 ◽  
Author(s):  
T. P. Radhakrishnan ◽  
A. K. Sundaram
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Outer Sphere ◽  
Electrode Reaction ◽  
Transfer Reactions ◽  
Cyclic Voltammetric ◽  
Edta Solution ◽  
Kinetics Of ◽  
Activated Complex ◽  
Good Agreement

The paper is a detailed study of the cyclic voltammetric behaviour of Eu3+ at HMDE in molar solutions of KCl, KBr, KI, KSCN and in 0.1M-EDTA solution with an indigenously built equipment. The computed values of the rate constants at various scan rates show good agreement with those reported by other electrochemical methods. In addition, the results indicate participation of a bridged activated complex in the electron-transfer step, the rate constants showing the trend SCN- > I- > Br- > Cl- usually observed for bridging order of these anions in homogeneous electron-transfer reactions. The results for Eu-EDTA system, however, indicate involvement of an outer sphere activated complex in the electrode reaction.

Complexation of the La(III) cation by p-sulfonatocalix[4]arene — A 139La NMR study

2002 ◽  
Vol 80 (2) ◽  
pp. 163-168 ◽  
Author(s):  
Yaël Israëli ◽  
Christine Bonal ◽  
Christian Detellier ◽  
Jean-Pierre Morel ◽  
Nicole Morel-Desrosiers
Keyword(s):  
Linear Relationship ◽  
Standard Enthalpy ◽  
Effective Radius ◽  
Water Soluble ◽  
Water Molecules ◽  
Standard Entropy ◽  
Nmr Data ◽  
Nmr Study ◽  
Good Agreement ◽  
Formation Of Complexes

The complexation of La(III) by the water-soluble p-sulfonatocalix[4]arene was thermodynamically characterized by 139La NMR. The 139La NMR data are consistent with the formation of a 1:1 complex resulting from electro static interactions between the sulfonato groups and La(III). The complexation is entropy-driven and is characterized by a positive standard enthalpy (ΔrH° = 11.0 ± 0.5 kJ mol–1) and a positive standard entropy (ΔrS° = 108 ± 2 J K–1 mol–1), which are in very good agreement with the ones determined previously by microcalorimetry. The linear relationship between the 139La NMR linewidth of the free and of the complexed cation, obtained at temperatures ranging from 290 to 340 K, excludes the formation of complexes or aggregates other than the 1:1 complex. It shows also that upon complexation, the effective radius of La(III) undergoes an increase of 50%, related to the replacement of water molecules of the hydrated cation by sulfonato groups of the ligand.Key words: complexation, water-soluble calixarene, p-sulfonatocalix[4]arene, 139La NMR, lanthanum.

scholarly journals Wave-lengths of the red lines of neon and their use as secondary standards

1933 ◽  
Vol 143 (848) ◽  
pp. 124-135 ◽  
Keyword(s):  
Wave Length ◽  
Great Intensity ◽  
International Astronomical Union ◽  
Interference Fringes ◽  
International Astronomical ◽  
Good Agreement ◽  
Strong Group

The spectrum of neon is dominated by a strong group of lines in the red. These are easily produced in an ordinary Geissler tube with very great intensity, and are sufficiently sharp to give measurable interference fringes with long path differences, of 120,000 waves or so. For these reasons the red lines of neon appear to be eminently suitable for use as secondary standards, and in view of the good agreement of the wave-length determinations of a number of observers (especially Burns, Meggers, and Merrill at the Bureau of Standards) they were adopted as secondary standards by the International Astronomical Union in 1922.

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