Thermodynamics of Na+ Cl− ion – pair association in acetonitrile–dimethyl sulfoxide mixtures

Patil, Ujwala N.; Keshri, Sonanki; Tembe, B. L.

doi:10.1016/j.cplett.2014.12.031

Cited by 14 publications

(9 citation statements)

References 34 publications

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“…For simple salts in water–dimethyl sulfoxide (DMSO) mixtures, it was observed that sodium ions are preferentially solvated by water molecules, whereas chloride ions favor a coordination by DMSO, which stands in sharp contrast to the corresponding donor numbers of the solvents in pure solution . Furthermore, it was observed that sodium chloride reveals a homoselective preferential solvation behavior by water molecules in water–methanol and DMSO–acetonitrile (AN) solutions, , as well as in water–AN mixtures . For more complex organic ions, recent simulations of DMSO–water mixtures also revealed a homoselective solvation mechanism, where water molecules form the first solvation shell around both ion species.…”

Section: Introductionmentioning

confidence: 99%

Influence of Cosolutes on Chemical Equilibrium: a Kirkwood–Buff Theory for Ion Pair Association–Dissociation Processes in Ternary Electrolyte Solutions

2018

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We present an application of the Kirkwood− Buff theory, which is introduced to describe the influence of cosolutes on the chemical equilibrium between dissociated and associated ion pairs in ternary electrolyte solutions. Our approach makes use of Kirkwood−Buff integrals and the introduction of a local/bulk partition model. The cosolute species can be either charged or uncharged, and our approach is applicable for ideal and weak nonideal solutions in combination with low ion concentrations. As the main result, the theory reveals that differences in the local cosolute accumulation behavior around the ions induce a shift of the chemical equilibrium either to the associated or the dissociated state. The findings of our analysis are useful for a deeper understanding of electrolyte solutions in modern electrochemical storage devices. All results are verified by atomistic molecular dynamics simulations in terms of sodium chloride pairs in dimethylacetamide−water mixtures.

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Section: Introductionmentioning

confidence: 99%

Influence of Cosolutes on Chemical Equilibrium: a Kirkwood–Buff Theory for Ion Pair Association–Dissociation Processes in Ternary Electrolyte Solutions

2018

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“…A number of sampling methods have been also developed to compute reaction free energies. For example, the constrained MD method has been validated in various systems to calculate dissociation free energy. ,,,− The FPMD-based vertical energy gap method has been extensively applied to estimate the acidity constants of both organic and inorganic systems covering main group and transition metal elements. − …”

Section: Introductionmentioning

confidence: 99%

Uranyl Arsenate Complexes in Aqueous Solution: Insights from First-Principles Molecular Dynamics Simulations

Liu

Cheng

et al. 2018

Inorg. Chem.

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In this study, the structures and acidity constants (p K's) of uranyl arsenate complexes in solutions have been revealed by using the first principle molecular dynamics technique. The results show that uranyl and arsenate form stable complexes with the U/As ratios of 1:1 and 1:2, and the bidentate complexation between U and As is highly favored. Speciation-pH distributions are derived based on free energy and p K calculations, which indicate that for the 1:1 species, UO(HAsO)(HO) is the major species at pH < 7, while UO(HAsO)(HO) and UO(AsO)(HO) dominate in acid-to-alkaline and extreme alkaline pH ranges. For the 1:2 species, UO(HAsO)(HO) is dominant under acid-to-neutral pH conditions, while UO(HAsO)(HAsO)(HO), UO(HAsO)(HAsO)(HO), and UO(AsO)(HAsO)(HO) become the major forms in the pH range of 7.2-10.7, 10.7-12.1, and >12.1, respectively.

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“…Furthermore, a significant inhibition of the Li + and Cl − ion‐association reaction in pure DMSO was shown compared to the ion‐aggregation in ACN . Similar noticeable inhibition of the Na + and Cl − association in DMSO was observed . These numerous simulation results, that implicitly contain the relationship between the ion size and solvation properties, should be analyzed and interpreted.…”

Section: Introductionmentioning

confidence: 79%

“…[22] Similar noticeable inhibition of the Na + and Cl À association in DMSO was observed. [26] These numerous simulation results, that implicitly contain the relationship between the ion size and solvation properties, should be analyzed and interpreted.…”

Section: Introductionmentioning

confidence: 99%

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

Smirnov

Kislenko

2019

ChemPhysChem

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Influence of cation size on solvation strength, diffusion, and kinetics of the association reaction with anions O2− in aprotic solvents, such as acetonitrile and dimethyl sulfoxide, has been investigated by means of molecular dynamics simulations. The work is motivated by the need to understand the molecular nature of the solvent‐induced changes in capacity of Li‐air batteries. We have shown that the dependence of the solvation shell stability on the cation size has a maximum at a particular ion radius that corresponds to a solvent coordination number of 4. The shell stability maximum coincides with the diffusion coefficient minimum. The variation of the cation shell stability has a crucial impact on the kinetics of the cation‐O2− association. We have demonstrated that profound inhibition of the association reaction for Li+ in dimethyl sulfoxide is a result of the lock‐and‐key effect that cannot be described in the framework of Hard Soft Acid Base theory.

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Thermodynamics of Na+ Cl− ion – pair association in acetonitrile–dimethyl sulfoxide mixtures

Cited by 14 publications

References 34 publications

Influence of Cosolutes on Chemical Equilibrium: a Kirkwood–Buff Theory for Ion Pair Association–Dissociation Processes in Ternary Electrolyte Solutions

Influence of Cosolutes on Chemical Equilibrium: a Kirkwood–Buff Theory for Ion Pair Association–Dissociation Processes in Ternary Electrolyte Solutions

Uranyl Arsenate Complexes in Aqueous Solution: Insights from First-Principles Molecular Dynamics Simulations

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

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