Die elektrischen Kräfte zwischen den Ionen und ihre Wirkungen

Thermodynamic gE Models and Equations of State for Electrolytes in a Water-Poor Medium: A Review

“…However, this assumption is not valid at small ion separations, for which the contribution of higher-order terms on the Taylor expansion of the radial distribution function becomes non-negligible . In 1926, Danish chemist Niels Bjerrum proposed to modify the DH term by introducing a distinction between free ions and ion pairs. Free ions possess electrostatic interionic energy much lower than k B T , which prohibits the two free counterions from being bonded strongly by electrostatic forces.…”

On the Tendency of the Metal Ions toward Complex Formation.

“…It e.g., the chromic-thiocyanate system, the statistical correction accounts for a large part of the trend in the experimentally determined consecutive constants. Assuming for this system that any effects not accounted for on statistical grounds were due solely to electrostatic causes, N. Bjerrum (26) was able to calculate reasonable values for the dimensions of the complexes. On the other hand in, for example, the cadmium-iodide system, where log h is seen to have an abnormally low value, it is obvious that specific chemical influences must also play a part.…”

“…As N. Bjerrum (26) was among the first to point out, one should expect, on purely statistical grounds, that the first ligands to be taken up would be bound somewhat more strongly than the subsequent ones. If the ligand is an electrically charged anion, one must reckon in addition with an electrostatic effect, which has the effect of lowering still further the affinity for subsequent ligands.…”

Interfacial Dissociation of Contact-Ion-Pair on MXene Electrodes in Concentrated Aqueous Electrolytes

“…With increasing the salt concentration, E A for R s and σ increase significantly (e.g., 23.0 and 28.9 kJ/mol for the Ti 3 C 2 T x electrode with a hydrate-melt electrolyte). As Li + is coordinated by anions as well as H 2 O to form contact-ion-pair (CIP) in concentrated electrolytes, 9,40,41 large E A for R s and σ should be ascribed to the dissociation of CIP (Figure 7b). Indeed, a Raman peak at around 750 cm −1 corresponding to the S-N-S bending of TFSI − shows a blueshift with increasing the salt concentration (Figure S9), indicating the CIP formation in concentrated electrolytes.…”