Temperature dependence of ion association constants in nonaqueous solutions of metal perchlorates

Mishustin, A. I.

doi:10.1134/s0036023613060181

Cited by 4 publications

(7 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Let us denote the charge of cation A as z 1 , the charge of oxygen atom B nearest to the cation as z 2 , the charges of other oxygen atoms D, E, and F equidistant from the cation as z 3 , z 4 , and z 5 , respectively, and the charge of the sulfur atom as z 6 . The Coulomb contri bution to the potential is expressed as U e (r) = z 1 (z 2 /r + z 3 /r 1 + z 4 /r 1 + z 5 /r 1 + z 6 /(r + l), (6) where l is the distance between the sulfur atom and oxygen atoms (1.5 Å), and r 1 is the distance between the centers of the cation and three other oxygen atoms and determined as r 1 = {(r + l + f) 2 + g 2 } 0.5 ,…”

Section: Theorymentioning

confidence: 99%

“…The Coulomb contri bution to the potential is expressed as U e (r) = z 1 (z 2 /r + z 3 /r 1 + z 4 /r 1 + z 5 /r 1 + z 6 /(r + l), (6) where l is the distance between the sulfur atom and oxygen atoms (1.5 Å), and r 1 is the distance between the centers of the cation and three other oxygen atoms and determined as r 1 = {(r + l + f) 2 + g 2 } 0.5 ,…”

Section: Theorymentioning

confidence: 99%

“…The Lennard Jones potential will be taken into account only for the interaction of the cation with the nearest O atom as U LJ = 4ε{(σ/r) 12 -(σ/r) 6 }. (8) In calculations, we used the geometrical parameter of the Lennard Jones potential σ and also the cova lence parameter β, which were determined earlier [7] for each of the considered cations from the data for isolated monohydrates in the gas phase, and these val ues were used unchangeable in the calculations for the other O donating ligands [7].…”

Section: Mishustinmentioning

confidence: 99%

“…Close values of the radii of anions with the same charge must have led to close values of stability constants of their complexes (for example, from the viewpoint of Bjer rum's ion association theory, association constants must not differ by more than 10%). An "abnormally" high stability of carbonate complexes in comparison with that of sulfate complexes is also observed for the complexes of other metals [1].To clarify the reason for such a sharp difference between the stabilities of the carbonate and sulfate complexes of tervalent lanthanides and actinides, in this study we used an earlier developed method of the oretical calculations of stability constants [6,7]. The method is based on integrating the function of the ligand distribution density with respect to a cation, and the selection of integration limits allows either all types of ion pairs or only SSIPs to be taken into account in calculations.…”

mentioning

confidence: 99%

“…To clarify the reason for such a sharp difference between the stabilities of the carbonate and sulfate complexes of tervalent lanthanides and actinides, in this study we used an earlier developed method of the oretical calculations of stability constants [6,7]. The method is based on integrating the function of the ligand distribution density with respect to a cation, and the selection of integration limits allows either all types of ion pairs or only SSIPs to be taken into account in calculations.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

Mishustin

2012

Russ. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The determination of thermodynamic and struc tural characteristics of metal complexes in solutions is one of the most important problems of chemistry. Sul fate anions are incorporated into atmospheric aero sols, natural waters, and many minerals and ores. Metal sulfate complexes play an important part in nat ural and engineering processes. Despite the fact that the kinetics and equilibrium of formation of metal sul fate complexes have been studied for many years by different experimental and kinetic methods, their thermodynamic properties (stability constants, etc.) are known only for a restricted number of metals [1]. Owing to experimental difficulties in the operation with radioactive compounds, data for actinides are very scanty. There is no common view on the type of complex formed (inner sphere or outer sphere) in the literature. According to [2], the formation of cation complexes in a solution is considered as a multistage process: first, ions approach each other and form sol vent separated ion pairs (SSIP), some of which may form a contact ion pair (CIP) upon the removal of the water molecule that separates the cation and anion. Studies of sulfate complexes with the use of different techniques (conductometric, potentiometric, and spectroscopic methods, dielectric relaxation spectros copy, ultrasonic dispersion, etc.) bring the authors to contradictory conclusions on the dominant type of complex [3][4][5]. The coordination mode of an anion to a cation in solution (monodentate or bidentate) is also little studied. Different methods were noted to reveal a mixture of inner sphere and outer sphere complexes in aqueous lanthanide and actinide sulfate solutions [3], but there exist disagreements on the dominant type. On the basis of dielectric relaxation measure ments and other literature data, Wachter et al. [4] sup pose that only SSIPs are formed in lithium sulfate solutions, and CIPs are not formed at all even at a con centration of 2 mol/L. A critical view on the possibili ties of spectroscopic methods in the measurements of stability constants of complexes is given in [5] with the use of different metal sulfate complexes as an example.The clarification of a reason for a sharp discrep ancy between the stability constants of 1 : 1 carbonate and sulfate complexes of tervalent lanthanides and actinides in aqueous solutions (the stability constants of carbonate complexes are three to four orders of magnitude higher than those of sulfate complexes) remains to be one of the most intriguing unsolved problems. and anions have close values of crystal ionic radii. Both anions are classified as "hard" according to Pearson's terminology, and tervalent lan thanide and actinide cations are also "hard", so inte rionic interactions are dominantly electrostatic. Close values of the radii of anions with the same charge must have led to close values of stability constants of their complexes (for example, from the viewpoint of Bjer rum's ion association theory, association constants must not differ by more than 10%). An "abnorma...

show abstract

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Mishustinmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

Mishustin

2012

Russ. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Ion-Pairing Dynamics Revealed by Kinetically Resolved In Situ FTIR Spectroelectrochemistry during Lithium-Ion Storage

Cave

Olson

Schlenker

2021

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Understanding the kinetics of interfacial ion speciation could inform battery designs. However, this knowledge gap persists, largely due to the challenge of experimentally interrogating the evolution of ions near electrode interfaces in a sea of bulk signals. We report here the very first kinetically resolved correlation between interfacial ion speciation and lithium-ion storage in a model system, by applying global target analysis to in situ attenuated total reflectance (ATR) Fourier-Transform infrared (FTIR) spectroelectrochemical data. Our results suggest that it may be more kinetically viable for lithium to be extracted from contact ion pairs (CIPs) to contribute to faster electrode charging compared to fully solvated lithium. As the search for fast-charging lithium-ion batteries and supercapacitors wages on, this discovery suggests that manipulating the ion pairing within the electrolyte could be one effective strategy for promoting faster-charging kinetics.

show abstract

Selective complexation of divalent cations by a cyclic α,β-peptoid hexamer: a spectroscopic and computational study

et al. 2016

View full text Add to dashboard Cite

show abstract

Temperature dependence of ion association constants in nonaqueous solutions of metal perchlorates

Cited by 4 publications

References 15 publications

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

Stability constants of tervalent actinide and lanthanide sulfate complexes in aqueous solutions

Ion-Pairing Dynamics Revealed by Kinetically Resolved In Situ FTIR Spectroelectrochemistry during Lithium-Ion Storage

Selective complexation of divalent cations by a cyclic α,β-peptoid hexamer: a spectroscopic and computational study

Contact Info

Product

Resources

About