Role of H+ in Solvent Extraction of Am(III) and Eu(III) Using a Polydentate Bipyridine N-,O-Donor Ligand: Chemical Equilibrium States and Kinetic Aspects DOI
Ekaterina A. Konopkina, Elizaveta A. Pavlova, А. В. Гопин

et al.

The Journal of Physical Chemistry B, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

In this work, the influence of protonation on kinetics and thermodynamics extraction Am/Eu pair using N-heterocyclic dicarboxylic acid diamide N,N′-diethyl-N,N′-bis(4-ethylphenyl)-[2,2′-bipyridine]-6,6′-dicarboxamide (L) was investigated. The efficiency ligand did not decrease, even at a nitric concentration 4 times higher than that in organic phase. X-ray diffraction analysis established leads to preorganization due reversal bipyridyl rings into binding conformation when both nitrogen atoms are turned one side. Also, effect chemical shifts functional groups (bipyridyl amide) solution demonstrated by NMR spectroscopy. However, presaturation phase with lead significant changes surface activity ligand. For kinetics, mechanism proposed which limiting stage.

Language: Английский

Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption DOI
Pan Sun, Nabarupa Bhattacharjee, Jeffrey D. Einkauf

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 2128 - 2135

Published: Feb. 20, 2025

The competition between bulk and interfacial phenomena underlies many key processes in complex chemical transport. While competitive are often framed a thermodynamic context, opportunities to leverage transient species found away from equilibrium can provide kinetic handle achieve unconventional reaction outcomes. In this work, we outfit an iminoguanidinium headgroup capable of selective SO42- complexation with alkyl tails varying complexity probe pathways tune for separations. Using sum frequency generation (SFG) vibrational spectroscopy unexpectedly find that adsorption ligands the air-aqueous interface was dramatically slowed down increasingly hydrophobic tails. Underlying phenomenon, show formation colloidal differing propensities inhibited surface via bottleneck exchange molecular extractants aggregates. This effect could open up avenues access selectivity strongly coordinating phase, allowing more weakly transport mechanisms. work broadly probes nonequilibrium separations arise through unexpected events neglected traditional descriptions.

Language: Английский

Citations

0
Role of H+ in Solvent Extraction of Am(III) and Eu(III) Using a Polydentate Bipyridine N-,O-Donor Ligand: Chemical Equilibrium States and Kinetic Aspects DOI
Ekaterina A. Konopkina, Elizaveta A. Pavlova, А. В. Гопин

et al.

The Journal of Physical Chemistry B, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

In this work, the influence of protonation on kinetics and thermodynamics extraction Am/Eu pair using N-heterocyclic dicarboxylic acid diamide N,N′-diethyl-N,N′-bis(4-ethylphenyl)-[2,2′-bipyridine]-6,6′-dicarboxamide (L) was investigated. The efficiency ligand did not decrease, even at a nitric concentration 4 times higher than that in organic phase. X-ray diffraction analysis established leads to preorganization due reversal bipyridyl rings into binding conformation when both nitrogen atoms are turned one side. Also, effect chemical shifts functional groups (bipyridyl amide) solution demonstrated by NMR spectroscopy. However, presaturation phase with lead significant changes surface activity ligand. For kinetics, mechanism proposed which limiting stage.

Language: Английский

Citations

0