Donor Numbers for Binary Mixtures of Dimethyl Sulfoxide with Dipolar Aprotic Solvents

Rzeszotarska, J.; Ranachowski, P.; Kalinowski, Marek K.

doi:10.1135/cccc19942201

Cited by 8 publications

(4 citation statements)

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“…The liquid alcohols and amines are hydrogen bonded liquids, which could impinge on their β values but, in principal, the DN* values are measured for individual molecules where hydrogen bonding shouldn't be a factor. In practice, this distinction between β and DN* is commonly lost and donor numbers are determined using proxy experiments where, for example, the NMR [22] or visible [23] spectra of a probe molecule are measured in different liquid solvents and the donor number is estimated from the variation of the measured property with donor numbers for other solvents. In these cases, the values determined are properties of the liquid solvent and need not coincide with the property of the isolated molecule.…”

Section: Discussionmentioning

confidence: 99%

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Waghorne

O’Farrell

2018

J Solution Chem

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Solvent basicity is recognized as playing a major role in solvation and is included, through empirical basicity parameters, in linear free energy relationships that account for the effects of changes in solvent on chemical reactions. It is reasonable to postulate that the basicity of a solvent molecule reflects some combination of its molecular properties. In the present study, density functional calculations using the B3LYP functional, and Hartree-Fock calculations have been used to calculate the partial atomic charges (using the Hirshfeld and CM5 models), orbital energies, polarizabilities, dipole moments and quadrupolar amplitudes for over one hundred molecules for which there are experimental values for two basicity parameters, Kamlet and Taft's hydrogen bond acceptor strength, β, and Gutmann's donor number, DN, a measure of Lewis basicity. Regression of the experimental β and DN values against molecular descriptors reflecting the above molecular properties yields a remarkably consistent picture. For both parameters the values for alcohols and amines lie systematically off of the regression lines through the remaining compounds, which include alkanes, aromatics, halogenated alkanes and aromatics, esters, carbonates, carboxylic acids, ketones, ethers, nitriles, phosphates, sulfides and sulfates. Independent of the calculation method or method of estimating the partial atomic charges, both experimental β and DN are essentially determined by two molecular properties: the charge on the most negative atom of the molecule and the molecular orbital from which charge donation would occur. The regression results using any of the fours sets of descriptors (reflecting the two calculation methods and two methods of charge estimation) are remarkably similar for β and DN supporting the view that these are measures of the same "basicity".

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Section: Discussionmentioning

confidence: 99%

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Waghorne

O’Farrell

2018

J Solution Chem

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“…Here, dγ/d c is obtained by fitting the PC concentration dependent change in surface tension with a third order polynomial least-squares fit and differentiating. Note that the physical properties including relative permittivity, density, viscosity, donor numbers, refractive index, and heat capacity of this binary mixture all exhibit monotonic changes with the solvent composition, − implying that the inhibition of bubble coalescence is not strongly influenced by these properties. Also, the investigation of heat of mixing for DMSO and PC indicates that there are no hydrogen bonds in this system and the decisive roles in the intermolecular interactions are those of orientation and induction interactions of the two polar molecules .…”

Section: Resultsmentioning

confidence: 94%

Inhibition of Bubble Coalescence by Electrolytes in Binary Mixtures of Dimethyl Sulfoxide and Propylene Carbonate

2009

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We have investigated the effect of solvent composition on inhibition of bubble coalescence by electrolytes in binary mixtures of dimethyl sulfoxide (DMSO) and propylene carbonate (PC). Unlike most mixtures, combinations of DMSO and PC exhibit minimal foaming over all compositions (with the strongest effect being at 25% PC by volume); thus, the influence of electrolytes can be investigated. Both LiBr and KSCN at moderate concentrations inhibit bubble coalescence at all solvent compositions. However, the concentration of electrolyte required to inhibit coalescence was in both cases a minimum at the PC(v/v) of 25%. The surface tension of electrolyte solutions in the mixed solvents indicates that the gradient in surface tension is not correlated with coalescence inhibition and therefore inhibition cannot be attributed to surface elasticity. We have also studied the inhibition of bubble coalescence by HCl at different solvent compositions. HCl is strongly inhibitory in DMSO but only weakly so in PC. We have found that HCl exhibits strong inhibition behavior at all mixtures studied. All electrolytes studied were most effective at inhibiting bubble coalescence at the PC(v/v) of 25%, indicating that the interactions between solvent molecules strongly determine the influence of electrolyte on coalescence inhibition. We propose that the formation of solvent complexes between DMSO and PC results in an increase in surface viscosity and the presence of electrolytes further amplifies this effect.

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“…Cyclic voltammograms on a polished disc GC electrode recorded at a sweep rate of 100 mV/s in 0.1 M LiClO 4 in (a) pyridine, (b) DMSO, (c) DMA, (d) DMF, (e) DME, (f) GBL, (g) TEGDME, (h) TMS, and (i) MeCN. Solvent donor numbers in kcal/mol from ref (except GBL and TEGDME) are listed in parentheses.…”

Section: Resultsmentioning

confidence: 99%

Positive Electrode Passivation by Side Discharge Products in Li–O₂ Batteries

et al. 2020

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The development of high specific energy Li−O 2 batteries faces a problem of poor cycling as a result of passivation of the positive electrode by both the discharge product (Li 2 O 2 ) and side products (Li 2 CO 3 , etc.). The latter are the result of oxidation of the electrode materials or electrolyte components primarily by discharge intermediate superoxide anions (O 2 − ) and, in less degree, by Li 2 O 2 . We report cyclic voltammetry studies of the electrode passivation in different relatively stable solvents. We found that slower passivation is observed for the electrolytes based on high donor number solvents or solvents with high viscosity. Moreover, such behavior is reproduced for three different electrode materials [glassy carbon (GC), TiC, and TiN] that pinpoints the primary role of different oxygen reduction reaction mechanisms (Li 2 O 2 surface deposition or solution growth) influenced by Li + solvation energy and solvent viscosity. The chemistry of interaction between LiO 2 /Li 2 O 2 and the electrode/solvent turns out to be less important. Additionally, we found that, for the electrode made of GC and TiN in all electrolyte solutions, the passivation by side products suppresses oxygen reduction after a certain number of cycles. In contrast, for TiC after several cycles, further passivation does not happen as a result of the formation of a thin and stable TiO 2 layer in high donor number solvents.

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Donor Numbers for Binary Mixtures of Dimethyl Sulfoxide with Dipolar Aprotic Solvents

Cited by 8 publications

References 0 publications

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Inhibition of Bubble Coalescence by Electrolytes in Binary Mixtures of Dimethyl Sulfoxide and Propylene Carbonate

Positive Electrode Passivation by Side Discharge Products in Li–O₂ Batteries

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Donor Numbers for Binary Mixtures of Dimethyl Sulfoxide with Dipolar Aprotic Solvents

Cited by 8 publications

References 0 publications

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Solvent Basicity, A Study of Kamlet–Taft β and Gutmann DN Values Using Computationally Derived Molecular Properties

Inhibition of Bubble Coalescence by Electrolytes in Binary Mixtures of Dimethyl Sulfoxide and Propylene Carbonate

Positive Electrode Passivation by Side Discharge Products in Li–O2 Batteries

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Product

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Positive Electrode Passivation by Side Discharge Products in Li–O₂ Batteries