Ion association and ionic reaction rates. An investigation of the bromoacetate-thiosulfate reaction

1971 ◽  
Vol 48 (9) ◽  
pp. 626 ◽  
Author(s):  
R. K. Cosgrove ◽  
P. W. King ◽  
A. C. Norris
Keyword(s):  
Ion Association ◽  
Reaction Rates ◽  
Ionic Reaction

SEM analysis of the change in the reaction rates with deposit structures in the copper-iron cementation system

1978 ◽  
Vol 36 (1) ◽  
pp. 456-457
Author(s):  
V. Annamalai ◽  
L.E. Murr
Keyword(s):  
Structural Characteristics ◽  
Secondary Electron Emission ◽  
Copper Deposit ◽  
Reaction Rates ◽  
Sem Analysis ◽  
Experimental Conditions ◽  
Major Drawback ◽  
Emission Mode ◽  
Scrap Iron ◽  
Image Position

Economical recovery of copper metal from leach liquors has been carried out by the simple process of cementing copper onto a suitable substrate metal, such as scrap-iron, since the 16th century. The process has, however, a major drawback of consuming more iron than stoichiometrically needed by the reaction.Therefore, many research groups started looking into the process more closely. Though it is accepted that the structural characteristics of the resultant copper deposit cause changes in reaction rates for various experimental conditions, not many systems have been systematically investigated. This paper examines the deposit structures and the kinetic data, and explains the correlations between them.A simple cementation cell along with rotating discs of pure iron (99.9%) were employed in this study to obtain the kinetic results The resultant copper deposits were studied in a Hitachi Perkin-Elmer HHS-2R scanning electron microscope operated at 25kV in the secondary electron emission mode.

The Effects of Nitrogen on Electrical and Structural Properties in TaSixNy/SiO2/p-Si MOS Capacitors

2002 ◽  
Vol 716 ◽  
Author(s):  
You-Seok Suh ◽  
Greg Heuss ◽  
Jae-Hoon Lee ◽  
Veena Misra
Keyword(s):  
Structural Properties ◽  
Electron Spectroscopy ◽  
Oxygen Diffusion ◽  
Gate Dielectric ◽  
Barrier Properties ◽  
Reaction Rates ◽  
Cross Sectional ◽  
Mos Capacitors ◽  
Transmission Electron ◽  
Thermal Stability Of

AbstractIn this work, we report the effects of nitrogen on electrical and structural properties in TaSixNy /SiO2/p-Si MOS capacitors. TaSixNy films with various compositions were deposited by reactive sputtering of TaSi2 or by co-sputtering of Ta and Si targets in argon and nitrogen ambient. TaSixNy films were characterized by Rutherford backscattering spectroscopy and Auger electron spectroscopy. It was found that the workfunction of TaSixNy (Si>Ta) with varying N contents ranges from 4.2 to 4.3 eV. Cross-sectional transmission electron microscopy shows no indication of interfacial reaction or crystallization in TaSixNy on SiO2, resulting in no significant increase of leakage current in the capacitor during annealing. It is believed that nitrogen retards reaction rates and improves the chemical-thermal stability of the gate-dielectric interface and oxygen diffusion barrier properties.

Hydrostibination of Alkynes: A Radical Mechanism

2020 ◽  
Author(s):  
Josh MacMillan ◽  
Katherine Marczenko ◽  
Erin Johnson ◽  
Saurabh Chitnis
Keyword(s):  
Density Functional ◽  
Activation Barrier ◽  
Closed Shell ◽  
Reaction Rates ◽  
Radical Mechanism ◽  
Neutral Radical ◽  
Kinetic Isotope ◽  
Rate Limiting Step ◽  
Ionic Mechanisms ◽  
Terminal Acetylenes

The addition of Sb-H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov <i>Z</i>-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring neutral radical Sb<sup>II</sup> and Sb<sup>III</sup> intermediates. Density Functional Theory (DFT) calculations are consistent this model, predicting an activation barrier that is within 1 kcal mol<sup>-1</sup> of the experimental value (Eyring analysis) and a rate limiting step that is congruent with experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb<sup>II</sup> and Sb<sup>III</sup> intermediates to yield the observed <i>Z</i>-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a methodology for accessing challenging products such as <i>E</i>-olefins.

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