Second-Sphere and Outer-Sphere Proton Relaxation of Paramagnetic Complexes:  From EPR to NMRD

1998 ◽  
Vol 102 (12) ◽  
pp. 2117-2130 ◽  
Author(s):  
J. W. Chen ◽  
R. L. Belford ◽  
R. B. Clarkson
Keyword(s):  
Outer Sphere ◽  
Proton Relaxation ◽  
Paramagnetic Complexes

Etude des complexes aqueux d'uranium(IV) en milieu acide par résonance magnétique nucléaire

1976 ◽  
Vol 54 (2) ◽  
pp. 303-312 ◽  
Author(s):  
C. Kiener ◽  
G. Folcher ◽  
P. Rigny ◽  
J. Virlet
Keyword(s):  
Exchange Rate ◽  
Chemical Shift ◽  
Exchange Process ◽  
Bound Water ◽  
Outer Sphere ◽  
Bulk Water ◽  
Proton Relaxation ◽  
Water Molecules ◽  
Relaxation Rates ◽  
The Exchange Rate

The hydration of tetravalent uranium in acid solutions has been studied by proton magnetic resonance. Longitudinal and transversal relaxation rates of water are reported as a function of temperature, acidity, and added ions. The relaxation rates observed in perchloric solutions at high temperature are governed by the exchange process of water molecules between the inner coordination sphere of uranium(IV) and the bulk water. The bound proton's lifetime τM lies between 10 ms and 1 s. At pH > 0, the exchange rate depends upon acidity according to the law 1/τM ≈ A + B/[H+]. At high concentrations of diamagnetic ions the exchange rate depends linearly upon water activity. At low temperature, the proton relaxation rates are dominated by an outer sphere effect and the electronic relaxation time of uranium(IV) is found to be about 10−13 s. No signal is observed from protons of the water molecules in the first sphere, firmly bound to uranium(IV), which undergo rapid relaxation. The chemical shift of the proton absorption signal in hydrochloric solutions arise from tightly bound water molecules in paramagnetic interaction with uranium(IV) in a second sphere, and in fast exchange with the bulk water. Above a chlorine concentration of 6 M, the monochloro complex of uranium(IV) contributes to the chemical shift.

Finite difference code for velocity and surface traction of a Fluid between Two Eccentric Spheres

2015 ◽  
Vol 11 (1) ◽  
pp. 2960-2971
Author(s):  
M.Abdel Wahab
Keyword(s):  
Velocity Field ◽  
Angular Velocity ◽  
Finite Difference ◽  
Numerical Study ◽  
Outer Sphere ◽  
Equation Of Motion ◽  
Annular Region ◽  
Surface Traction ◽  
Angular Velocities ◽  
Axis Passing

The Numerical study of the flow of a fluid in the annular region between two eccentric sphere susing PHP Code isinvestigated. This flow is created by considering the inner sphere to rotate with angular velocity 1  and the outer sphererotate with angular velocity 2  about the axis passing through their centers, the z-axis, using the three dimensionalBispherical coordinates (, ,) .The velocity field of fluid is determined by solving equation of motion using PHP Codeat different cases of angular velocities of inner and outer sphere. Also Finite difference code is used to calculate surfacetractions at outer sphere.

Kinetics and mechanism of redox reactions of U(III) ions with monochloroacetic and dichloroacetic acids

1979 ◽  
Vol 44 (2) ◽  
pp. 401-405 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Alcohol Concentration ◽  
Kinetics And Mechanism ◽  
Solvent Structure ◽  
Influence Of Ph ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reactions of U3+ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U3+ with CHCl2COO- ions and oxidation of U3+ with CHCl2.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.

Outer-sphere interaction of (S)-asparagine and (S)-glutamine with [Co(NH3)6]3+ ion and its possible role in ligand substitution

1987 ◽  
Vol 52 (10) ◽  
pp. 2457-2459
Author(s):  
František Jursík
Keyword(s):  
Amino Acids ◽  
Transition Region ◽  
Alkaline Medium ◽  
Optical Activity ◽  
Substitution Reaction ◽  
Outer Sphere ◽  
Ligand Substitution ◽  
Cotton Effect ◽  
Negative Cotton Effect

Optical activity of the achiral cation [Co(NH3)6]3+ is induced both by (S)-AsnONa and (S)-GlnONa, as shown by a negative Cotton effect in the 1A1g → 1T1g transition region. An outer-sphere interaction by three-point attachment of the amides can explain the fact that substitution reaction of [Co(NH3)6]3+ with the mentioned amides in an alkaline medium is unusually slow as compared with other amino acids.

Complexes of copper(II) and nickel(II) with a Schiff base bonded to a polymeric support

1983 ◽  
Vol 48 (7) ◽  
pp. 2021-2027 ◽  
Author(s):  
Eliška Kálalová ◽  
Olga Populová ◽  
Štěpánka Štokrová ◽  
Pavel Stopka
Keyword(s):  
Magnetic Properties ◽  
Schiff Base ◽  
Coordination Sphere ◽  
Polymer Matrix ◽  
Glycidyl Methacrylate ◽  
Epr Spectra ◽  
Polymeric Support ◽  
Tetrahedral Configuration ◽  
Paramagnetic Complexes

Copper(II) and nickel(II) ions were bonded in complexes of salicylideneimine type on a glycidyl methacrylate-ethylenedimethacrylate copolymer. The geometry of the complexes on the polymer was studied by measuring their magnetic properties, EPR spectra, and ultraviolet-visible spectra.Only paramagnetic complexes possessing a pseudo-tetrahedral configuration were found. The effect of the polymer matrix and of the immobility of the bonded Schiff base on the distortion of the coordination sphere of the central ion is discussed.

Protonation effects on dynamic flux properties of aqueous metal complexes

2009 ◽  
Vol 74 (10) ◽  
pp. 1543-1557 ◽  
Author(s):  
Herman P. Van Leeuwen ◽  
Raewyn M. Town
Keyword(s):  
Complex Formation ◽  
Metal Ion ◽  
Good Description ◽  
Minor Component ◽  
Outer Sphere ◽  
Metal Species ◽  
Central Metal ◽  
Inner Sphere ◽  
A Minor ◽  
Protonated Ligand

The degree of (de)protonation of aqueous metal species has significant consequences for the kinetics of complex formation/dissociation. All protonated forms of both the ligand and the hydrated central metal ion contribute to the rate of complex formation to an extent weighted by the pertaining outer-sphere stabilities. Likewise, the lifetime of the uncomplexed metal is determined by all the various protonated ligand species. Therefore, the interfacial reaction layer thickness, μ, and the ensuing kinetic flux, Jkin, are more involved than in the conventional case. All inner-sphere complexes contribute to the overall rate of dissociation, as weighted by their respective rate constants for dissociation, kd. The presence of inner-sphere deprotonated H2O, or of outer-sphere protonated ligand, generally has a great impact on kd of the inner-sphere complex. Consequently, the overall flux can be dominated by a species that is a minor component of the bulk speciation. The concepts are shown to provide a good description of experimental stripping chronopotentiometric data for several protonated metal–ligand systems.

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