Gibbs energies of transfer of the proton from water into mixtures of water with chain multiple ethers: Equilibria involving changes of solvation of the proton

Goldie, Rachel; Luck, Deborah; Wells, Cecil F.

doi:10.1039/b206085j

Cited by 2 publications

(1 citation statement)

References 45 publications

(162 reference statements)

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“…It was recently proposed that the protonation of diglyme and TRIG in water occurs at only one basic site, preferentially the terminal ether group, and that the equilibrium constant is much higher than for simple ethers. 21 Furthermore, it was also proposed that, at least in the gas phase, both the proton and the hydroxonium ion can be engaged in polydentate structures with the glymes. 22 This supports a much stronger complexation of the proton by the TRIG than by DOX.…”

Section: Resultsmentioning

confidence: 99%

Cationic Copolymerization of 1,3,5-Trioxane with 1,3-Dioxepane: A Comprehensive Approach to the Polyacetal Process

et al. 2009

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The bulk copolymerization of 1,3,5-trioxane (TOX) with 1,3-dioxepane (DXP) initiated by perchloric acid hydrate(s) is studied at 80 °C with DXP/TOX initial ratios from 20/80 to 3/97 w/w. As usually observed for the polyacetal synthesis, the polymerization takes place within seconds to tenths of seconds and proceeds in two steps, a homogeneous (“induction”) period, followed by a very rapid heterogeneous propagation−crystallization step. The influence of the reaction conditions was systematically examined (diluent of initiator, comonomer concentration, transfer to residual water), and the products formed during the short induction period were identified using NMR. The difference between the respective basicities of the comonomers is such that during the induction period the initiation takes place on the DXP, and for DXP initial concentrations above its equilibrium value [DXP]eq,ss the early formed soluble polymer is either the homopolymer or a DXP highly enriched copolymer. The precipitation step starts only after the concentration of DXP is lowered enough to allow the copolymerization with TOX to proceed significantly and the poly(oxymethylene) −[CH2−O] n − sequences to reach their critical crystallization length. This critical concentration was found constant whatever the initial DXP/TOX ratio. For initial concentrations lower than [DXP]eq,ss (i.e., DXP/TOX ≤ 5/95 w/w), the DXP cannot homopolymerize and should be consumed by single unit insertion during a copolymerization effective since the early beginning. Therefore, during the further heterogeneous propagation−crystallization step, the insertion of two successive DXP units in the copolymer chain becomes highly improbable. The copolymer formed by both propagation and transacetalization processes is either inserted into the crystal (or its immediate interface) if only isolated DXP units are present along the poly(oxymethylene) chain or rejected in the amorphous phase if preformed DXP sequences are present. The latter situation occurs for DXP/TOX initial ratios ≥10/90 w/w. This is in agreement with our previous measurements of the crystal partitioning coefficient, which confirmed that the tetramethyleneoxy −[(CH2)4−O]− units from DXP are progressively rejected into the increasing amorphous fraction for initial DXP richer compositions. Coherent chemical pathways are proposed for the overall process, which are in accordance with the experimental behaviors during both homogeneous and heterogeneous steps.

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Section: Resultsmentioning

confidence: 99%

Cationic Copolymerization of 1,3,5-Trioxane with 1,3-Dioxepane: A Comprehensive Approach to the Polyacetal Process

et al. 2009

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A Dual Salt/Dual Solvent Electrolyte Enables Ultrahigh Utilization of Zinc Metal Anode for Aqueous Batteries

Guan,

Chen,

Yang

et al. 2024

Advanced Materials

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Rechargeable aqueous zinc batteries are promising in next‐generation sustainable energy storage. However, the low zinc (Zn) metal anode reversibility and utilization in aqueous electrolytes due to Zn corrosion and poor Zn2+ deposition kinetics significantly hinder the development of Zn‐ion batteries. Here, a dual salt/dual solvent electrolyte composed of Zn(BF4)2/Zn(Ac)2 in water/TEGDME (tetraethylene glycol dimethyl ether) solvents to achieve reversible Zn anode at an ultrahigh depth of discharge (DOD) is developed. An “inner co‐salt and outer co‐solvent” synergistic effect in this unique dual salt/dual solvent system is revealed. Experimental results and theoretical calculations provide evidence that the ether co‐solvent inhibits water activity by forming hydrogen bonding with the water and coordination effects with the proton in the outer Zn2+ solvation structure. Meanwhile, the anion of zinc acetate co‐salt enters the inner Zn2+ solvation structure, thereby accelerating the desolvation kinetics. Strikingly, based on the electrolyte design, the zinc anode shows high reversibility at an ultrahigh utilization of 60% DOD with 99.80% Coulombic efficiency and 9.39 mAh cm−2 high capacity. The results far exceed the performance reported in electrolyte design work recently. The work provides fundamental insights into inner co‐salt and outer co‐solvent synergistic regulation in multifunctional electrolytes for reversible aqueous metal‐ion batteries.

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Gibbs energies of transfer of the proton from water into mixtures of water with chain multiple ethers: Equilibria involving changes of solvation of the proton

Cited by 2 publications

References 45 publications

Cationic Copolymerization of 1,3,5-Trioxane with 1,3-Dioxepane: A Comprehensive Approach to the Polyacetal Process

Cationic Copolymerization of 1,3,5-Trioxane with 1,3-Dioxepane: A Comprehensive Approach to the Polyacetal Process

A Dual Salt/Dual Solvent Electrolyte Enables Ultrahigh Utilization of Zinc Metal Anode for Aqueous Batteries

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