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Journal articles on the topic 'Ion-solvent'

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Published: 18 May 2024

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1

SAKAMOTO, Ikko, Kunishisa SOGABE, and Satoshi OKAZAKI. "Ion-Solvent Complexing and Ionic Solvent Transfer." Denki Kagaku oyobi Kogyo Butsuri Kagaku 61, no. 7 (July 5, 1993): 934–35. http://dx.doi.org/10.5796/electrochemistry.61.934.

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2

Krishtalik, L. I., N. M. Alpatova, and E. V. Ovsyannikova. "Electrostatic ion—solvent interaction." Electrochimica Acta 36, no. 3-4 (January 1991): 435–45. http://dx.doi.org/10.1016/0013-4686(91)85126-r.

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3

SAKAMOTO, Ikko, and Satoshi OKAZAKI. "(Ion-solvent interactions in acetylacetone. VIII). Sodium ion-solvent complexing and ion transfer between solvents." Bunseki kagaku 39, no. 6 (1990): 333–40. http://dx.doi.org/10.2116/bunsekikagaku.39.6_333.

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4

Kyselka, Petr, and Ivo Sláma. "Ion solvation. Application of combined discrete and continuum models." Collection of Czechoslovak Chemical Communications 50, no. 11 (1985): 2331–37. http://dx.doi.org/10.1135/cccc19852331.

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Thermodynamic functions for the solvation systems ion-solvent (ion = Li+, Be2+, Na+, Mg2+, and Al3+; solvent = H2O, CH3CN, DMSO, and DMF) are calculated on the basis of combined continuum and discrete models. For the mixed systems water-ion-solvent, the mole fraction of solvent is included in the calculation.

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5

Rathi, Meenakshi Virendra. "Comparative Study of Solvation Behaviour of Oxidising Agents Like Kclo3, Kbro3 and KIO3 in Aqueous Solvent Systems at Different Temperatures." Oriental Journal Of Chemistry 37, no. 1 (February 28, 2021): 151–56. http://dx.doi.org/10.13005/ojc/370120.

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The investigation of the solvationtrend of oxidizing agents like KClO3, KBrO3 and KIO3as electrolytes in aqueous salt solution rendersthe datasuited to interpret ion–ion, solute–solvent, ion-solvent and solvent–solvent interactions and synergy. Apparent molar volumes (∅_V) and viscosity B-coefficients for KClO3, KBrO3 and KIO3solutions in aqueous 0.5 % KCl ,system have been calculated from density (ρ) and viscosity (η) measurements at 298.15 to 313.15 K using a calibrated bicapillary pycnometer and the simple, yet accurate apparatus known as Ubbelohde viscometer respectively. Jones-Dole equation,Masson’s equation, Roots equation and Moulik’s equations are implemented to analyse various interactions inter and intra ionic attractions among the ion–ion, ion–solvent, and solute–solvent. Additionallythe apparent molar volumes of transfer Δ ∅(tr) and Rate constant diffusion controlled reaction (kd)are valuated.

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6

Paren, Benjamin, Graham Leverick, Benjamin Burke, Jeffrey Lopez, and Yang Shao-Horn. "Revealing Local Structure and Dynamics in Li-Salt Electrolytes Using Dielectric Relaxation Spectroscopy." ECS Meeting Abstracts MA2023-01, no. 1 (August 28, 2023): 394. http://dx.doi.org/10.1149/ma2023-011394mtgabs.

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Understanding the interplay between local structure and dynamics is critical for establishing design rules for advanced ion-conducting electrolytes. In this work, a set of Li-salt in liquid electrolytes is studied using dielectric relaxation spectroscopy (DRS) to examine correlations between several electrolyte properties, including conductivity, dielectric relaxation time and strength, ionicity, and viscosity. These properties were evaluated by changing ion concentration, solvent type, and anion type. DRS was used to identify relaxation processes associated with the solvent and different ion-solvent coordinating structures, and the dielectric properties are reported for the first time for a majority of these systems. The behavior of viscosity and conductivity were shown to change similarly with concentration when accounting for the local coordinating environment, regardless of the salt or solvent type. τα, the dielectric relaxation time of the solvent-ion complexes, is shown to be independent of ion content at low salt concentrations, when solvent separated ion pairs are the dominant ion-solvent complex. However, at high ion concentrations, a new relationship, a power-law dependence, was identified between molar conductivity and τα, as well as viscosity and τα, demonstrating that the dependence of molar conductivity or viscosity on τα is controlled in part by the solvent type, due to variation in shielding between contact ion pairs and aggregates. In contrast, there was not a clear change in the dependence of molar conductivity or viscosity on τα with changing anion. Furthermore, the effective dipole moments of the ion-solvent complexes were determined, and found to decrease with increasing ion concentration, as contact ion pairs and aggregates form. This systematic analysis of the wide range of Li-salts and solvents, and discussion of relations between different local structures and dynamic processes that contribute to conductivity, helps lay a foundation for the design of new liquid electrolytes.

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7

Away, Kenneth Charles West, and Zhu-Gen Lai. "Solvent effects on SN2 transition state structure. II: The effect of ion pairing on the solvent effect on transition state structure." Canadian Journal of Chemistry 67, no. 2 (February 1, 1989): 345–49. http://dx.doi.org/10.1139/v89-056.

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Identical secondary α-deuterium kinetic isotope effects (transition state structures) in the SN2 reaction between n-butyl chloride and a free thiophenoxide ion in aprotic and protic solvents confirm the validity of the Solvation Rule for SN2 Reactions. These isotope effects also suggest that hydrogen bonding from the solvent to the developing chloride ion in the SN2 transition state does not have a marked effect on the magnitude of the chlorine (leaving group) kinetic isotope effects. Unlike the free ion reactions, the secondary α-deuterium kinetic isotope effect (transition state structure) for the SN2 reaction between n-butyl chloride and the solvent-separated sodium thiophenoxide ion pair complex is strongly solvent dependent. These completely different responses to a change in solvent are rationalized by an extension to the Solvation Rule for SN2 Reactions. Finally, the loosest transition state in the reactions with the solvent-separated ion pair complex is found in the solvent with the smallest dielectric constant. Keywords: ion pairs, transition state, solvent effects, nucleophilic substitution, isotope effects.

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8

Pegado, Luís, Bo Jönsson, and Håkan Wennerström. "Ion-ion correlation attraction in a molecular solvent." Journal of Chemical Physics 129, no. 18 (November 14, 2008): 184503. http://dx.doi.org/10.1063/1.2985609.

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9

Hatzell, Kelsey B. "Make ion–solvent interactions weaker." Nature Energy 6, no. 3 (March 2021): 223–24. http://dx.doi.org/10.1038/s41560-021-00798-6.

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10

Hughes, M. A. "Ion exchange and solvent extraction." Endeavour 12, no. 4 (January 1988): 196. http://dx.doi.org/10.1016/0160-9327(88)90183-4.

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11

Sakamoto, Ikko, Ikuro Moriwaki, Mayumi Munechika, and Satoshi Okazaki. "Ion-solvent interactions in acetylacetone." Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 246, no. 1 (May 1988): 207–15. http://dx.doi.org/10.1016/0022-0728(88)85061-7.

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12

Schiffrin, DavidJ. "Ion exchange and solvent extraction." Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 241, no. 1-2 (February 1988): 391. http://dx.doi.org/10.1016/0022-0728(88)85143-x.

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13

Burns, D. Thorburn. "Ion Exchange and Solvent Extraction." Analytica Chimica Acta 281, no. 1 (September 1993): 226. http://dx.doi.org/10.1016/0003-2670(93)85366-r.

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14

Lee, Yu Jin, Yun Kyung Jo, Hyun Park, Ho Hwan Chun, and Nam Ju Jo. "Solvent Effect on Ion Hopping of Solid Polymer Electrolyte." Materials Science Forum 544-545 (May 2007): 1049–52. http://dx.doi.org/10.4028/www.scientific.net/msf.544-545.1049.

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Solid polymer electrolytes (SPEs) based on poly (vinyl alcohol) were prepared with dimethyl sulfoxide as a solvent. Prepared SPEs form the 'fast cationic transport process' and lithium ion hopping through 'fast cationic transport process' is occurred. In this study, we observed the dependence of ionic conductivity on the drying time of solvent and there was particular relationship between ionic conductivity and the amount of residual solvent. Especially, we investigated the influence of solvent on cation mobility in the ‘fast cationic transport process’ and we found that the solvent acted as a bridge to connect neighboring ion aggregates and made the ion hopping easy.

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15

Fang, Yao-Ren, and Kenneth Charles Westaway. "Isotope effects in nucleophilic substitution reactions. VIII. The effect of the form of the reacting nucleophile on the transition state structure of an SN2 reaction." Canadian Journal of Chemistry 69, no. 6 (June 1, 1991): 1017–21. http://dx.doi.org/10.1139/v91-149.

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A spectroscopic investigation indicated that lithium thiophenoxide exists as a contact ion pair complex in dry diglyme whereas the other alkali metal thiophenoxides exist as a solvent-separated ion pair complex in diglyme. The addition of small amounts of water converts the lithium thiophenoxide contact ion pair complex into a solvent-separated ion pair complex. A smaller secondary α-deuterium kinetic isotope effect and a larger Hammett p value are observed when the nucleophile is the contact ion pair complex in the SN2 reaction between n-butyl chloride and thiophenoxide ion in diglyme. This indicates that the transition state for the contact ion pair complex reaction is tighter with a shorter nucleophile–α-carbon bond than the transition state for the solvent-separated ion pair complex reaction. The secondary α-deuterium kinetic isotope effects for the free ion and the solvent-separated ion pair complex reactions between sodium thiophenoxide and n-butyl chloride in DMF suggest that the loosest transition state is found when the nucleophile is the free ion. Key words: transition state, SN2, isotope, deuterium, Hammett ρ.

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16

Bulavin, Viktor, Ivan Vyunnik, Alexander Rusinov, and Andrii Kramarenko. "ION-PAIR CONVERSION THERMODYNAMICS IN ALCOHOL SOLUTIONS OF HYDROGEN HALIDES." Bulletin of the National Technical University "KhPI". Series: Chemistry, Chemical Technology and Ecology, no. 2(10) (April 27, 2024): 9–14. http://dx.doi.org/10.20998/2079-0821.2023.02.10.

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The calculation of thermodynamic characteristics of dissociation of contact and solvent-separated ion pairs into ions, conversion of contact ion pairs into solvent-separated ion pairs of ionogens HCl, HBr and HI in n-alcohols from methyl alcohol to n-octyl alcohol by the method described earlier for the systems HCl – n-alcohol in the same solvents at the same temperatures was carried out. The following regularities were established in this work: a) positive values of the change in the Gibbs energy of dissociation (ΔdisG°) of contact and solvent-separated ion pairs increase in the case of increasing temperature and the number of carbon atoms in the n-alcohol molecule and decreasing radius of the halide ion, and their sign and magnitude are determined by the entropic component (–TΔdisS°). In this case, the values of ΔdisG° of contact ion pairs exceed the same values for ion pairs separated by solvent; b) the values of the Gibbs energy change (ΔconvG°) for the studied ionogens HCl, HBr, and HI are also positive, except for the values of ΔconvG° of ionogens in methanol and HBr solutions in ethanol. In these cases, the ΔdisG° values for solvent-separated ion pairs exceed the same values for contact ion pairs, and the ΔconvG° values are negative. With increasing temperature and radius of the halide ion, ΔconvG° become more negative, and vice versa with increasing hydrocarbon radical; c) the concentration of contact ion pairs increases in the methanol – n-octanol series for all ionogens, decreases slightly with increasing temperature and radius of the anion, and varies from ~30% (methanol) to ~95% (n-octanol). In methanol, solvent-separated ion pairs predominate; in alcohols from n-propyl to n-octyl, contact ion pairs predominate, i.e., deconversion of ion pairs occurs.

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17

Wahab, Abdul, and Sekh Mahiuddin. "Electrical conductivity, speeds of sound, and viscosity of aqueous ammonium nitrate solutions." Canadian Journal of Chemistry 79, no. 8 (August 1, 2001): 1207–12. http://dx.doi.org/10.1139/v01-104.

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Density, electrical conductivity, speeds of sound, and viscosity of aqueous ammonium nitrate solutions were measured as functions of concentration (m, mol kg1) (0.1599 [Formula: see text] m [Formula: see text] 20.42) and temperature (T, K) (273.15 [Formula: see text] T [Formula: see text] 323.15). Experimental values are consistent with the reported data. Variation of isotherms of electrical conductivity, isentropic compressibility, and structural relaxation time with concentration evoke structural information on the ion solvation in aqueous ammonium nitrate solution at different concentration regions. The primary hydration numbers of ammonium nitrate were estimated at a particular concentration at which the isentropic compressibility isotherms converge. The existence of free hydrated ions, resulting from strong ion solvent interactions in dilute to 9.1 mol kg1, the solvent-separated ion-pairs resulting from the relative competition between the ionsolvent and the ionion interactions in 9.1 to 12.0 mol kg1, and the solvent-shared ion-pairs beyond 12.0 mol kg1 resulting from a decrease in the number of solvent molecules, govern the transport process.Key words: electrical conductivity, speeds of sound, viscosity, ammonium nitrate, hydration number.

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18

Ishiguro, Shin-ichi, Yasuhiro Umebayashi, Kenta Fujii, and Ryo Kanzaki. "Solvent conformation and ion solvation: From molecular to ionic liquids." Pure and Applied Chemistry 78, no. 8 (January 1, 2006): 1595–609. http://dx.doi.org/10.1351/pac200678081595.

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Metal ions are solvated in solution, and, in a sterically congested organic solvent, those solvent molecules that are simultaneously bound to the metal ion will be subject to consequential steric interactions through space. The molecular structure of a solvent, particularly that of any functional groups in the vicinity of the coordinating atom to the metal ion, plays a key role in the solvation steric effect. Weak solvation steric effects lead to a distorted octahedral structure for six-coordinate transition-metal(II) ions, whereas strong steric effects lead to a decreased solvation number. In particular cases, the conformation of a solvent may undergo a change in response to coordination to the metal ion. Solvation steric effects play a decisive role in reaction thermodynamics and kinetics of the metal ion. Here, we show our recent results on solvation steric effects in terms of structure and thermodynamics, particularly, the conformational change of solvent and its effect on the metal-ion complexation.

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19

Hodges, Alastair M., Jilska M. Perera, and Peter T. McTigue. "Ion-coupled transport of solvent in a binary solvent mixture." Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 306, no. 1-2 (May 1991): 41–54. http://dx.doi.org/10.1016/0022-0728(91)85221-a.

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20

Marcus, Yizhak. "Electrostriction, Ion Solvation, and Solvent Release on Ion Pairing." Journal of Physical Chemistry B 109, no. 39 (October 2005): 18541–49. http://dx.doi.org/10.1021/jp051505k.

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21

Bulavin, Viktor Ivanovich, Ivan Nikolaevich Vyunnik, Alexander Ivanovich Rusinov, and Andrii Viktorovich Kramarenko. "ION PAIR CONVERSION THERMODYNAMICS IN HYDROGEN BROMIDE ALCOHOL SOLUTIONS." Bulletin of the National Technical University "KhPI". Series: Chemistry, Chemical Technology and Ecology, no. 1 (May 30, 2023): 49–55. http://dx.doi.org/10.20998/2079-0821.2023.01.07.

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The thermodynamic quantities of dissociation of contact and solvent-separated ion pairs into ions, conversion of contact ion pairs into solvent-separated ion pairs of HBr ionogen in n-alcohols from methyl to n-octyl have been calculated by the procedure we set forth earlier for the HCl – n-alcohol systems in the same solvents at 278.15–328.15 K. The following regularities were established in this work: a) positive values of ΔdisGº of contact and solvent-separated ion pairs increase with increasing temperature, the number of carbon atoms in the n-alcohol molecule, and decreasing radius of halide ion, and their sign and magnitude are determined by the entropic component (–TΔdis Sº). In this case, the values of ΔdisGº of contact ion pairs exceed the same values for solvent-separated ion pairs; b) ΔconvGº values for HCl and HBr are also positive, except for ΔconvGº values in methanol at 278.15–328.15 K and HBr solutions at the same temperatures in ethanol. For these cases, by contrast, ΔdisGº(RIP) > ΔdisGº(CIP) and ΔconvGº are negative. As the temperature and radius of the halide ion increase, ΔconvGº become more negative, and vice versa as the hydrocarbon radical increases; c) the concentration of contact ion pairs increases in the methanol-n-octanol series, decreases slightly with increasing temperature and anion radius, and changes within ~30 % (methanol) to 95 % (n-octanol) at 278.15 K. In methanol, solvent-separated ion pairs predominate; in ethanol, the concentration of both types of ion pairs is approximately the same; in other n-octanols, contact ion pairs predominate.

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22

Smiatek, Jens, Andreas Heuer, and Martin Winter. "Properties of Ion Complexes and Their Impact on Charge Transport in Organic Solvent-Based Electrolyte Solutions for Lithium Batteries: Insights from a Theoretical Perspective." Batteries 4, no. 4 (December 3, 2018): 62. http://dx.doi.org/10.3390/batteries4040062.

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Electrolyte formulations in standard lithium ion and lithium metal batteries are complex mixtures of various components. In this article, we review molecular key principles of ion complexes in multicomponent electrolyte solutions in regards of their influence on charge transport mechanisms. We outline basic concepts for the description of ion–solvent and ion–ion interactions, which can be used to rationalize recent experimental and numerical findings concerning modern electrolyte formulations. Furthermore, we discuss benefits and drawbacks of empirical concepts in comparison to molecular theories of solution for a more refined understanding of ion behavior in organic solvents. The outcomes of our discussion provide a rational for beneficial properties of ions, solvent, co-solvent and additive molecules, and highlight possible routes for further improvement of novel electrolyte solutions.

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23

Duignan, Timothy T., Drew F. Parsons, and Barry W. Ninham. "A continuum solvent model of ion–ion interactions in water." Phys. Chem. Chem. Phys. 16, no. 40 (2014): 22014–27. http://dx.doi.org/10.1039/c4cp02822h.

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24

Chen, Xiang, Nan Yao, Bo-Shen Zeng, and Qiang Zhang. "Ion–solvent chemistry in lithium battery electrolytes: From mono-solvent to multi-solvent complexes." Fundamental Research 1, no. 4 (July 2021): 393–98. http://dx.doi.org/10.1016/j.fmre.2021.06.011.

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25

Ratner, Mark A., and Duward F. Shriver. "Ion transport in solvent-free polymers." Chemical Reviews 88, no. 1 (January 1988): 109–24. http://dx.doi.org/10.1021/cr00083a006.

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26

Thomas, J. D. R. "Solvent polymeric membrane ion-selective electrodes." Analytica Chimica Acta 180 (1986): 289–97. http://dx.doi.org/10.1016/0003-2670(86)80011-3.

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27

Hefter, Glenn. "Ion solvation in aqueous–organic mixtures." Pure and Applied Chemistry 77, no. 3 (January 1, 2005): 605–17. http://dx.doi.org/10.1351/pac200577030605.

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The importance of ion solvation in determining the properties of electrolyte solutions in aqueous–organic solvent mixtures is discussed. Solubility measurements are shown to be particularly useful for determining the Gibbs energies of transfer of ions between solvents, which reflect differences in the overall solvation of the ions in different solvent mixtures. Solubility measurements can also be used to determine the other thermodynamic parameters of transfer, but such quantities are usually better obtained by more direct methods. The inadequacy of current theories of ion solvation to quantitatively account for the thermodynamics of ion transfer is discussed by reference to measurements on some simple model systems. Although donor/acceptor interactions can explain many of the observed effects between pure solvents, the situation is more complex in aqueous–organic mixtures because selective solvation and even solvent–solvent interactions may become significant. This is illustrated by consideration of ion transfer from water to water + t-butanol solutions, where spectacular effects are observed in the enthalpies and entropies and especially in the heat capacities and volumes.

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28

Vila Verde, Ana, Mark Santer, and Reinhard Lipowsky. "Solvent-shared pairs of densely charged ions induce intense but short-range supra-additive slowdown of water rotation." Physical Chemistry Chemical Physics 18, no. 3 (2016): 1918–30. http://dx.doi.org/10.1039/c5cp05726d.

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Magnesium and sulfate ions in solvent-shared (SIP) ion pair configuration supra-additively slowdown the rotation of water molecules between them; water molecules around solvent-separated (2SIP) ion pairs show only additive slowdown.

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29

Pathak, R. N., Indu Saxena, Archna, and Anoop Kumar Mishra. "Study of the Influence of Alkyl Chain Cation-Solvent Interactions on Water Structure in 1,3-Butanediol-Water Mixture by Apparent Molar Volume Data." E-Journal of Chemistry 8, no. 3 (2011): 1323–29. http://dx.doi.org/10.1155/2011/394108.

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The densities of 1,3-butanediol-water mixtures and some tetraalkylammonium iodide salt solutions in these solvent mixtures at different concentrations (0.02 M-0.14 M) have been determined at 298.15 K using magnetic float densitometer technique. Then apparent molar volumes ΦVof the electrolytes in above solvent mixtures were calculated. The apparent molar volumes of transfer ∆ΦV° (tr) were also calculated and the ion-ion / ion- solvent interactions are then discussed on the basis of changes in the Masson's slope and apparent molar volumes of transfer data.

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30

Delgado, Alexis Antoinette Ann, Daniel Sethio, and Elfi Kraka. "Assessing the Intrinsic Strengths of Ion–Solvent and Solvent–Solvent Interactions for Hydrated Mg2+ Clusters." Inorganics 9, no. 5 (April 22, 2021): 31. http://dx.doi.org/10.3390/inorganics9050031.

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Information resulting from a comprehensive investigation into the intrinsic strengths of hydrated divalent magnesium clusters is useful for elucidating the role of aqueous solvents on the Mg2+ ion, which can be related to those in bulk aqueous solution. However, the intrinsic Mg–O and intermolecular hydrogen bond interactions of hydrated magnesium ion clusters have yet to be quantitatively measured. In this work, we investigated a set of 17 hydrated divalent magnesium clusters by means of local vibrational mode force constants calculated at the ωB97X-D/6-311++G(d,p) level of theory, where the nature of the ion–solvent and solvent–solvent interactions were interpreted from topological electron density analysis and natural population analysis. We found the intrinsic strength of inner shell Mg–O interactions for [Mg(H2O)n]2+ (n = 1–6) clusters to relate to the electron density at the bond critical point in Mg–O bonds. From the application of a secondary hydration shell to [Mg(H2O)n]2+ (n = 5–6) clusters, stronger Mg–O interactions were observed to correspond to larger instances of charge transfer between the lp(O) orbitals of the inner hydration shell and the unfilled valence shell of Mg. As the charge transfer between water molecules of the first and second solvent shell increased, so did the strength of their intermolecular hydrogen bonds (HBs). Cumulative local vibrational mode force constants of explicitly solvated Mg2+, having an outer hydration shell, reveal a CN of 5, rather than a CN of 6, to yield slightly more stable configurations in some instances. However, the cumulative local mode stretching force constants of implicitly solvated Mg2+ show the six-coordinated cluster to be the most stable. These results show that such intrinsic bond strength measures for Mg–O and HBs offer an effective way for determining the coordination number of hydrated magnesium ion clusters.

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31

James, DW, and PG Cutler. "Ion Ion Solvent Interactions in Solution .XI. Spectroscopic Studies of Group-2 Perchlorates in Acetone." Australian Journal of Chemistry 39, no. 1 (1986): 149. http://dx.doi.org/10.1071/ch9860149.

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Solutions of Mg(ClO4)2 and Sr (ClO4)2 in acetone have been studied at various concentrations up to saturation by using infrared absorption, Raman scattering and multinuclear n.m.r (1H, 13C, 17O, 25Mg, 35Cl). Solvation numbers of c. 4.5 (Mg2+) and c. 5.5 (Sr2+) were determined from component band analysis of the c. 800 cm-1 acetone band in the Raman spectra. The solvent shell about the Mg2+ had a high level of steric crowding. There was a small amount of solvent-shared ion-pair formation at all oncentrations in solutions of Mg(ClO4)2 which showed little concentration dependence. In solutions of Sr (ClO4)2 there was evidence for the formation of both solvent-shared associated-ion species and ion-contact species. The solvent-shared species appeared to have two alternative configurations in one of which the anion was both polarized and highly hindered. There was a salt-promoted reaction in which the perchlorate was reduced to chloride and the solution darkened. This reaction prevented the use of Raman spectra to quantify the association equilibria.

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32

Gumtya, S. K., G. Bandyopadhyay, and S. C. Lahiri. "ΔS°t – as a Structural Probe – a Critical Analysis of the Method and Determination of Structure of Aquo-Alcoholic Mixtures." Zeitschrift für Physikalische Chemie 217, no. 6 (June 1, 2003): 615–36. http://dx.doi.org/10.1524/zpch.217.6.615.20443.

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AbstractAttempts were made for a critical examination of the use of ΔS°t as a structural probe to study the ion induced perturbations on aquo-alcoholic solvent mixtures. The division of the thermodynamic properties of TATB (tetraphenyl arsonium tetraphenyl borate) in solution into equal parts is not free from defects. Naturally, the calculation of single ion values based on TATB is also problematic. Dissection of the single ion values like TΔS°t(ion) as suggested by Kundu is full of errors. Analysis shows TΔS°t(ion) to be an insensitive parameter to determine the structural characteristics of aquo-alcoholic mixtures. Structure of aquo-alcoholic mixtures should be determined from the excess thermodynamic properties of mixing, excess dielectric properties of mixing, excess polarizabilities, the correlation parameter “g” etc. Other properties like ultrasonic sound absorption, excess volume and viscosity of mixing were found to be useful. Ion induced perturbations of any solvent system will be dictated by the structure of the particular solvent system. A knowledge of the structure of the aquo-alcoholic mixtures is imperative to develop an idea regarding ion induced perturbations as mirror image relations because of compensation of ΔH° and TΔS° (and of ΔH°t and TΔS°t) will be observed in any solvent system. The thermodynamic measurements provide a summary of all interaction energies over a long time. To comprehend the rational structural details of the solvent systems, accurate thermodynamic measurements alongwith relaxation experiments providing high time and good structural resolutions are necessary.

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33

Goswami, Prakash, Jayabrata Dhar, Uddipta Ghosh, and Suman Chakraborty. "Solvent-mediated nonelectrostatic ion-ion interactions predicting anomalies in electrophoresis." ELECTROPHORESIS 38, no. 5 (January 19, 2017): 712–19. http://dx.doi.org/10.1002/elps.201600394.

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34

Delgado, Alexis A. A., Daniel Sethio, Ipek Munar, Viktorya Aviyente, and Elfi Kraka. "Local vibrational mode analysis of ion–solvent and solvent–solvent interactions for hydrated Ca2+ clusters." Journal of Chemical Physics 153, no. 22 (December 14, 2020): 224303. http://dx.doi.org/10.1063/5.0034765.

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35

Lalrosanga and N. Mohondas Singh. "Thermodynamic Studies on Ion Association of Lithium Chloride and Lithium Nitrate in Acetonitrile + Water Mixed Solvents at Different Temperatures." Asian Journal of Chemistry 34, no. 1 (2021): 230–34. http://dx.doi.org/10.14233/ajchem.2022.23557.

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The present study reports the ion association of lithium chloride (LiCl) and lithium nitrate (LiNO3) electrolytes in acetonitrile + water (AN+W) mixtures at 283.15 K to 311.15 K. Their limiting molar conductance (Λo), the association constant values (KA) for their different mole fractions, i.e. 0.0000, 0.0588, 0.1233, 0.1942, 0.2727, 0.3600, 0.4576, 0.5676, 0.6923, 0.8351 and 1.0000 have been evaluated using Shedlovsky technique. The KA and Walden products (Λoηo) for LiCl and LiNO3 salts have been calculated in the acetonitrile-water solvent at experimental temperatures. The calculated values qualitatively examined the possible nature of the solvent-solvent, their ion-ion, and ion-solvent and interactions of the two selected compounds mixed solvents of (acetonitrile + water). Then dependence of KA temperature has also been investigated to obtain the thermodynamic functions of different parameters, such as ΔGº, ΔSº, ΔHº and Ea, as a function of the mixed composition of the composition solvents AN+W (acetonitrile + water).

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Li, Ruihe, Simon E. J. O'Kane, Andrew Wang, Taeho Jung, Monica Marinescu, Charles W. Monroe, and Gregory James Offer. "Effect of Solvent Segregation on the Performance of Lithium-Ion Batteries." ECS Meeting Abstracts MA2023-02, no. 7 (December 22, 2023): 975. http://dx.doi.org/10.1149/ma2023-027975mtgabs.

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The pseudo two-dimensional (P2D) model is one of the most powerful tools in modelling lithium-ion batteries (LIBs) 1, in that it can describe the complex electrochemical and thermal behaviours of LIBs with high fidelity yet maintain relatively high computing efficiency. To achieve that, many assumptions have been made, one of which is the single solvent assumption. However, most electrolytes used in LIBs uses multiple solvents to balance the requirements of conductivity, diffusivity and viscosity 2. Therefore, the single solvent assumption indicates that all solvents move as a single entity. However, previous experimental studies have shown that Li+ preferentially attracts cyclic carbonates (like ethylene carbonate, EC) rather than linear carbonates (such as ethyl-methyl carbonate, EMC) to form ion-solvent clusters 3. During charge/discharge, ion-solvent clusters move between the positive and negative electrodes to constitute ionic current. At the electrolyte-electrolyte interface, Li+ de-solvates from the clusters and intercalates into the electrode, or vice versa. Such process will induce concentration gradients of both solvents and lithium ions; the solvent concentration has been ignored in the P2D model. The simplification means the current P2D model fails to capture two important phenomena: (1) many electrolyte properties - including conductivity, diffusivity, and thermodynamic factors - are sensitive to the solvent concentration 4; (2) the solvent components in the ion-solvent clusters are preferentially consumed by interfacial side reactions such as the growth of solid-electrolyte interface (SEI) 3. To fill this gap, we add an extra governing equation for the solvent concentration (in our case, EC) which allows us to describe an electrolyte with two solvents and one salt. We also include a cross diffusion term to consider the dragging effect between the working solvent (EC) and lithium ions. For the charge conservation equation, we directly use measured liquid junction potential as a function of both solvent and lithium-ion concentration, which avoids possible errors brought by identifying the thermodynamic factors. To elucidate the effect of solvent segregation, we compare the overpotential and concentration profile of Li ion and EC at the end of 3C discharge of the normal DFN (single case) and our revised model (double case). The revised model predicts opposite EC concentration compared with Li+, which has been observed by Wang et al. 5 For a high value of , the dragging effect between Li+ and EC is more significant, inducing high concentration gradients of both species. The EC overpotential can be as high as 10 mV and further affects the rate performance of LIBs. This revised model captures more complicated transport mechanisms in the electrolyte and opens the chance of linking the microscopic understanding on solvation structure to a continuum level model. Reference: (1) Newman, J.; Thomas-Alyea, K. E. Electrochemical Systems; 2004. (2) Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem Rev 2014, 114 (23), 11503-11618. DOI: 10.1021/cr500003w. (3) Xu, K. Solvation Sheath of Li+ in Nonaqueous Electrolytes and Its Implication of Graphite/ Electrolyte Interface Chemistry. J. Phys. Chem. C 2007. (4) Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R. Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF6 in Ethylene Carbonate-Ethyl Methyl Carbonate. Journal of The Electrochemical Society 2001, 148 (10). DOI: 10.1149/1.1403730. (5) Wang, A. A.; Greenbank, S.; Li, G.; Howey, D. A.; Monroe, C. W. Current-driven solvent segregation in lithium-ion electrolytes. Cell Reports Physical Science 2022, 3 (9). DOI: 10.1016/j.xcrp.2022.101047. Figure 1

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37

Zeitouni, Farah Samih, Mohammad Fawzi Amira, Gehan Moustafa El-Subruiti, and Ghassan Omar Younes. "Comparison of the leaving groups during the study of the aquation of halopentaammine cobalt(III) complex in tartarate at different percentage of tert-butanol." European Journal of Chemistry 9, no. 3 (September 30, 2018): 228–35. http://dx.doi.org/10.5155/eurjchem.9.3.228-235.1728.

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The experimental kinetic study of aquation for both complexes bromopentaammine cobalt(III) and chloropentaammine cobalt(III) ions in the presence of tartarate solution in mixed solvent media of water with tert-butanol (10-50%, v:v) was examined spectrophotometrically at different temperatures (30-60 °C) by comparing the special effects of the leaving group of chloro and bromo on the rate constant of aquation. Comparison of kip (rate constant of ion-pairing) for both complexes and show the non-linear plots of log (kip) ion-pair rate constants against the reciprocal of the dielectric constant D. The thermodynamic analyses of the kinetic data for both complexes have been discussed in terms of solvent effect on the ion-pair aquation reactions. The obtained isokinetic temperatures of these systems indicate the existence of compensation effect arising from solute-solvent interaction. The excessive change of ΔHip* and ΔSip* with the mole fraction of the co-solvent can be recognized to the change of the physical properties of the solvent-water mixture with the solvent structure. Undersized changes in ΔGip* with the mole fraction of the co-solvent was found, representing a compensating effects between ΔHip* and ΔSip*.

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38

Hata, Noriko, Akane Igarashi, Rie Yasui, Maho Matsushita, Nozomi Kohama, Tomoka Komiyama, Kazuto Sazawa, Hideki Kuramitz, and Shigeru Taguchi. "Evaluation of an Ion-Associate Phase Formed In Situ from the Aqueous Phase by Adding Benzethonium Chloride and Sodium Ethylbenzenesulfonate for Microextraction." AppliedChem 3, no. 1 (January 9, 2023): 32–44. http://dx.doi.org/10.3390/appliedchem3010003.

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The concentration region at which the solvent is formed during in situ solvent formation microextraction is determined by varying the concentrations of the two components required to form a solvent. In particular, a solvent is formed in situ during ion-associate phase (IAP) microextraction by mixing an aqueous solution with an organic cation and an organic anion. In this study, benzethonium chloride (BenCl) and sodium ethylbenzenesulfonate (NaEBS) were employed as the organic cation and anion sources of model IAPs to thoroughly investigate the in situ solvent formation. Additionally, the formation of the IAPs and the solvent via centrifugation of the formed ion associates was examined. We demonstrated that ion associates are formed when the product of [EBS] and [Ben] is greater than the solubility product and [EBS] is greater than [Ben]. The highest extraction of polycyclic aromatic hydrocarbons (PAHs) was achieved with an amount of NaEBS 40 times greater than that of BenCl. A higher hydrophobicity in the IAP extraction of PAHs, estrogens, and pesticides facilitated extraction into the IAP.

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39

Ma, Peiyuan, Priyadarshini Mirmira, and Chibueze Amanchukwu. "Co-Intercalation-Free Fluorinated Ether Electrolytes for Lithium-Ion Batteries." ECS Meeting Abstracts MA2023-01, no. 2 (August 28, 2023): 550. http://dx.doi.org/10.1149/ma2023-012550mtgabs.

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Lithium-ion batteries are widely used to power portable electronics because of their high energy densities and have shown great promise in enabling the electrification of transport. However, the commercially used carbonate-based electrolytes are limited by a narrow operating temperature window and suffer against next generation lithium-ion battery chemistries such as silicon-containing anodes. The lack of non-carbonate electrolyte alternatives such as ether-based electrolytes is due to undesired solvent co-intercalation that occurs with graphitic anodes. Recently, fluorinated ether solvents have become promising electrolyte solvent candidates for lithium metal batteries but their applications in other battery chemistries have not been studied. In this work, we synthesize a group of novel fluorinated ether solvents and study them as electrolyte solvents for lithium-ion batteries. Using X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (ssNMR), we show that fluorinated ether electrolytes support reversible lithium-ion intercalation into graphite without solvent co-intercalation at conventional salt concentrations. To the best of our knowledge, they are the first class of ether solvents that intrinsically suppress solvent co-intercalation without the need for high or locally high salt concentration. In full cells using graphite anode, fluorinated ether electrolytes enable much higher energy densities compared to conventional glyme ethers, and better thermal stability over carbonate electrolytes (operation up to 60°C). As single-solvent-single-salt electrolytes, they remarkably outperform carbonate electrolytes with fluoroethylene carbonate (FEC) and vinylene carbonate (VC) additives when cycled with graphite-silicon composite anodes. Using X-ray photoelectron spectroscopy (XPS), NMR and density functional theory (DFT) calculations, we show that fluorinated ethers produce a solvent-derived solid electrolyte interphase, which is likely the key to suppressing solvent co-intercalation. Rational molecular design of fluorinated ether solvents will produce novel electrolytes that enable next generation lithium-ion batteries with higher energy density and wider working temperature window.

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P. Kakade, K. "The Use of Acoustic Parameters of Halo Substituted Chalconeimine for Determination of Ion Solvent Interaction." International Journal of Science and Research (IJSR) 12, no. 12 (December 5, 2023): 480–81. http://dx.doi.org/10.21275/sr231130180333.

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Shigenobu, Keisuke, Kaoru Dokko, Masayoshi Watanabe, and Kazuhide Ueno. "Solvent effects on Li ion transference number and dynamic ion correlations in glyme- and sulfolane-based molten Li salt solvates." Physical Chemistry Chemical Physics 22, no. 27 (2020): 15214–21. http://dx.doi.org/10.1039/d0cp02181d.

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Friesen, Sergej, Sebastian Krickl, Magdalena Luger, Andreas Nazet, Glenn Hefter, and Richard Buchner. "Hydration and ion association of La3+ and Eu3+ salts in aqueous solution." Physical Chemistry Chemical Physics 20, no. 13 (2018): 8812–21. http://dx.doi.org/10.1039/c8cp00248g.

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43

Haines, Robert I., and Sandra J. Northcott. "Kinetics and mechanism of oxidation of nickel(II) tetraazamacrocycles by the peroxydisulphate anion in aqueous and binary aqueous mixtures." Canadian Journal of Chemistry 70, no. 11 (November 1, 1992): 2785–91. http://dx.doi.org/10.1139/v92-354.

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The kinetics of oxidation of several nickel(II) tetraazamacrocycles by the peroxydisulphate anion have been studied in water and in binary aqueous mixtures. The reactions proceed via an ion-pairing pre-equilibrium, followed by metal ion-assisted peroxy-bond fissure within the ion-pair solvent shell. The derived rate law is[Formula: see text]Ion-pairing constants have been determined and have been found to be little influenced by steric factors, but do depend on solvent composition. Rate constants have been extracted using the rate expression and activation energies have been estimated from temperature dependences.

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Azeez, Fadhel, and Abdelrahman Refaie. "Integration of Semi-Empirical and Artificial Neural Network (ANN) for Modeling Lithium-Ion Electrolyte Systems Dynamic Viscosity." Journal of The Electrochemical Society 169, no. 2 (February 1, 2022): 020527. http://dx.doi.org/10.1149/1945-7111/ac4840.

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The dynamic viscosity is a key characteristic of electrolyte performance in a Lithium-ion (Li-ion) battery. This study introduces a one-parameter semi-empirical model and artificial neural network (ANN) to predict the viscosity of salt-free solvent mixtures and relative viscosity of Li-ion electrolyte solutions (lithium salt + solvent mixture), respectively. Data used in this study were obtained experimentally, in addition to data extracted from literature. The ANN model has seven inputs: salt concentration, electrolyte temperature, salt-anion size, solvent melting, boiling temperatures, solvent dielectric constant, and solvent dipole moment. Different configurations of the ANN model were tested, and the configuration with the least error was chosen. The results show the capability of the semi-empirical model in predicting the viscosity with an overall mean absolute percentage error (MAPE) of 2.05% and 3.17% for binary and tertiary mixtures, respectively. The ANN model predicted the relative viscosity of electrolyte solutions with MAPE of 4.86%. The application of both models in series predicted the viscosity with MAPE of 2.3%; however, the ANN MAPE alone is higher than this value. Thus, this study highlights the promise of using predictive models to complement physical approaches and effectively perform initial screening on Li-ion electrolytes.

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Suarez, Sophia, Domenec Paterno, Tawhid Pranto, and Fariha Ahmed. "Dynamics of Novel Zinc Ion Electrolytes." ECS Meeting Abstracts MA2023-02, no. 56 (December 22, 2023): 2720. http://dx.doi.org/10.1149/ma2023-02562720mtgabs.

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Zinc ion batteries are a niche alternative for battery applications. Their implementation is however afflicted by several factors, one of which is the need for more efficient electrolytes. Deep eutectic solvent (DES) electrolytes based on ZnCl2salt offer many attributes including, including improved stability and reduced dendrite formation. In this work we will present a molecular level understanding of the ion dynamics in electrolyte mixtures based on ZnCl2 and various co-solvents including organic carbonates and water. Focus is on the ion dynamics as interrogated by 1H NMR spin-lattice relaxation times (T1 ) combined with ionic conductivity, viscosity and density measurements. As shown in Figure 1, preliminary T1 results infers multiple ionic coordinated species with varying rates of mobilities that are co-solvent dependent. Additionally, data shows selective interaction sites between the hydrogen bond donors and acceptors, as well as the co-solvents. Figure 1. 1H T1 for the null and AcN co-solvent mixtures of (a) 1ZnCl2:4EtG and (b) 1ChCl:1ZnCl2:6EtG. Figure 1

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Lai, Zhu-Gen, and Kenneth Charles Westaway. "Isotope effects in nucleophilic substitution reactions. VII. The effect of ion pairing on the substituent effects on SN2 transition state structure." Canadian Journal of Chemistry 67, no. 1 (January 1, 1989): 21–26. http://dx.doi.org/10.1139/v89-004.

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The secondary α-deuterium kinetic isotope effects and substituent effect found in the SN2 reactions between a series of para-substituted sodium thiophenoxides and benzyldimethylphenylammonium ion are significantly larger when the reacting nucleophile is a free ion than when it is a solvent-separated ion pair complex. Tighter transition states are found when a poorer nucleophile is used in both the free ion and ion pair reactions. Also, the transition states for all but one substituent are tighter for the reactions with the solvent-separated ion pair complex than with the free ion. Hammett ρ values found by changing the substituent on the nucleophile do not appear to be useful for determining the length of the sulphur–α-carbon bond in the ion pair and free ion transition states. Keywords: Isotope effects, ion pairing, nucleophilic substitution, SN2 reactions, transition states.

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Kondou, Shinji, Morgan L. Thomas, Toshihiko Mandai, Kazuhide Ueno, Kaoru Dokko, and Masayoshi Watanabe. "Ionic transport in highly concentrated lithium bis(fluorosulfonyl)amide electrolytes with keto ester solvents: structural implications for ion hopping conduction in liquid electrolytes." Physical Chemistry Chemical Physics 21, no. 9 (2019): 5097–105. http://dx.doi.org/10.1039/c9cp00425d.

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Tang, Xiaowei, and Kunyu Ju. "Exploring Strategies for Copper Removal from Nickel Anolytes: A Review." ChemEngineering 7, no. 6 (December 5, 2023): 116. http://dx.doi.org/10.3390/chemengineering7060116.

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Various methods, such as electrochemical purification, chemical precipitation, solvent extraction, and ion-exchange resins, have been extensively employed for the removal of copper from nickel anolytes. However, these methods exhibit several significant drawbacks when applied in industrial settings. For instance, electrochemical purification fails to efficiently manage nickel anolyte solutions with low copper content. Chemical precipitation presents challenges in residue management and incurs high production costs for precipitants. Solvent extraction raises concerns related to toxicity, while the use of ion-exchange resins demands meticulous selection of suitable materials. In this review, we present a comprehensive review of the nickel removal methods used for nickel anolyte purification, electrochemical purification, chemical precipitation, solvent extraction, and ion-exchange resins. We also examine the suitability and benefits of each technique in industrial settings. The ion-exchange method has drawn significant attention due to its strong selectivity and small adsorption quantity. The ion-exchange separation process does not generate any slag, and the ion-exchange resin can be recycled and reused; this method has great potential in a wide range of applications.

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Stephen, L. Devaraj, S. G. Gunasekaran, and M. Soundarrajan. "Ion-Pair Formation of [CoIII(pn)2(Cl)(L)2+····· I−] by Aqueous-Organic Solvent Medium Enhanced Photoreduction: A Perspective Regression Analysis." Asian Journal of Chemistry 32, no. 6 (2020): 1379–83. http://dx.doi.org/10.14233/ajchem.2020.22598.

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Reduction of CoIII centre in CoIII(pn)2(Cl)(L)2+ with reference to solvent medium and structure of the complex via ion pair charge transfer (IPCT) paves way for the novel reaction mechanism route. In this work, we prepared, characterized and photoinduced the complexes CoIII(pn)2(Cl)(L)2+ (where L = RC6H4NH2, R = m-OMe, p-F and H) in the presence of iodide ion. Quantum yield for 254 nm excitation of CoIII(pn)2(Cl)(L)2+(where L = RC6H4NH2, R = m-OMe, p-F and H) in water-1,4-dioxane mixtures (Diox = 0, 5, 10, 15, 20, 25, and 30% (v/v)) were also derived for all the complexes in presence of added iodide ion, in which CoIII was reduced via [CoIII(pn)2(Cl)(L)2+….. I-] ion-pair formation. The photoinduced state is ion-pair charge transfer transition state and the quantum efficiency is solvent reliant and they are non-reactive. That is, change in ΦCo(II) is dependable with observed increase in xDiox of the mixed solvent medium. Correlation analysis using empirical parameters εr, Y, ET N and DNN provides a model to understand the solvent medium participation and interaction. This work gains an insight into the role of aqueous-organic solvent medium in CoIII(pn)2(Cl)(L)2+ photoreduction, which may be of great significance in developing novel approaches in the field of high performance catalysis

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Akhtar, Yasmin. "Ultrasonic and Density Studies of D(+) Mannose with Aqueous Electrolytes at 303K." Advanced Materials Research 1051 (October 2014): 215–20. http://dx.doi.org/10.4028/www.scientific.net/amr.1051.215.

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The present experimental investigation was carried out in order to explore the possible molecular interactions of D(+) mannose with mixed solvent of aqueous NaCl, KCl , MgCl2and CaCl2at 303 K. Experimental values of densities and ultrasonic velocities were carried out of the ternary mixture solution D(+) mannose with aqueous NaCl ,KCl, MgCl2and CaCl2. Aqueous alkali metal halides (NaCl ,KCl , MgCl2and CaCl2) were added under different molalities with D(+) mannose. The related and relevant parameters correlated to the present study such as adiabatic compressibility Ks, acoustic impedance Z, apparent molal volume фv, apparent molal adiabatic compressibility, фKs, and partial molal volume ф0vand partial molal adiabatic compressibility, фoKsat infinite dilution. The present investigation has exploited the possible molecular associations such as ion-ion, ion-solvent, solute-solute and solute-solvent interactions in these systems. It has been observed that there exist strong solute-solvent interaction and complex formation between in these ternary systems.

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