57 research outputs found
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Separation of Minor Actinides from Lanthanides by Dithiophosphinic Acid Extractants
The selective extraction of the minor actinides (Am(III) and Cm(III)) from the lanthanides is an important part of advanced reprocessing of spent nuclear fuel. This separation would allow the Am/Cm to be fabricated into targets and recycled to a reactor and the lanthanides to be dispositioned. This separation is difficult to accomplish due to the similarities in the chemical properties of the trivalent actinides and lanthanides. Research efforts at the Idaho National Laboratory have identified an innovative synthetic pathway yielding new regiospecific dithiophosphinic acid (DPAH) extractants. The synthesis provides DPAH derivatives that can address the issues concerning minor actinide separation and extractant stability. For this work, two new symmetric DPAH extractants have been prepared. The use of these extractants for the separation of minor actinides from lanthanides will be discussed
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Comparison of Aromatic Dithiophoshinic and Phosphinic Acid Derivatives for Minor Actinide Extraction
A new extractant for the separation of actinide(III) and lanthanide(III), bis(otrifluoromethylphenyl) phosphinic acid (O-PA) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(otrifluoromethylphenyl) dithiophosphinic acid (S-PA). Multinuclear NMR spectroscopy was used for elementary characterization of the new O-PA derivative. This new O-PA extractant was used to perform Am(III)/Eu(III) separations and the results were directly compared to those obtained in identical separation experiments using S-PA, an extractant that is known to exhibit separation factors of ~100,000 at low pH. The separations data are presented and discussed in terms comparing the nature of the oxygen atom as a donor to that of the sulfur atom in extractants that are otherwise identical
Constraint methods for determining pathways and free energy of activated processes
Activated processes from chemical reactions up to conformational transitions
of large biomolecules are hampered by barriers which are overcome only by the
input of some free energy of activation. Hence, the characteristic and
rate-determining barrier regions are not sufficiently sampled by usual
simulation techniques. Constraints on a reaction coordinate r have turned out
to be a suitable means to explore difficult pathways without changing potential
function, energy or temperature. For a dense sequence of values of r, the
corresponding sequence of simulations provides a pathway for the process. As
only one coordinate among thousands is fixed during each simulation, the
pathway essentially reflects the system's internal dynamics. From mean forces
the free energy profile can be calculated to obtain reaction rates and insight
in the reaction mechanism. In the last decade, theoretical tools and computing
capacity have been developed to a degree where simulations give impressive
qualitative insight in the processes at quantitative agreement with
experiments. Here, we give an introduction to reaction pathways and
coordinates, and develop the theory of free energy as the potential of mean
force. We clarify the connection between mean force and constraint force which
is the central quantity evaluated, and discuss the mass metric tensor
correction. Well-behaved coordinates without tensor correction are considered.
We discuss the theoretical background and practical implementation on the
example of the reaction coordinate of targeted molecular dynamics simulation.
Finally, we compare applications of constraint methods and other techniques
developed for the same purpose, and discuss the limits of the approach
Operational space weather service for GNSS precise positioning
The ionospheric plasma can significantly influence the propagation of radio waves and the ionospheric disturbances are capable of causing range errors, rapid phase and amplitude fluctuations (radio scintillations) of satellite signals that may lead to degradation of the system performance, its accuracy and reliability. The cause of such disturbances should be sought in the processes originating in the Sun. Numerous studies on these phenomena have been already carried out at a broad international level, in order to measure/estimate these space weather induced effects, to forecast them, and to understand and mitigate their impact on present-day technological systems. <P style="line-height: 20px;"> SWIPPA (Space Weather Impact on Precise Positioning Applications) is a pilot project jointly supported by the German Aerospace Centre (DLR) and the European Space Agency (ESA). The project aims at establishing, operating, and evaluating a specific space-weather monitoring service that can possibly lead to improving current positioning applications based on Global Navigation Satellite Systems (GNSS). This space weather service provides GNSS users with essential expert information delivered in the form of several products - maps of TEC values, TEC spatial and temporal gradients, alerts for ongoing/oncoming ionosphere disturbances, etc
On the definition and experimental use of ionospheric indices to evaluate space weather effects on GNSS positioning
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