Comparative Proton Transfer Efficiencies of Hydronium and Hydroxide in Aqueous Solution: Proton Transfer vs Brownian Motion

Uddin, Nizam; Kim, Jeongmin; Sung, Bong June; Choi, Tae Hoon; Choi, Cheol Ho; Kang, Heon

doi:10.1021/jp5093114

Cited by 18 publications

(36 citation statements)

References 60 publications

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“…8 However, the existence of the master plot collapse implies an energy of activation for t 0 consistent with the breaking of the H-bond and strongly links to the main Debye relaxation time, which is not consistent with the current view of liberations. 36,37 The value of t 0 is close to the predicted proton hopping lifetimes 38,39 in H-bonded structures and that measured in 1 h ice 40 and by femtosecond pump probe experiments. 41 While excess protons in pure water from auto-disassociation are necessarily in very low concentrations, the hopping process conceals many rearrangements between different types of protonated water 42 that do not result in a free proton.…”

Section: The Implication Of a And Qsupporting

confidence: 84%

What is the primary mover of water dynamics?

Ishai

Tripathi

Kawase

et al. 2015

Phys. Chem. Chem. Phys.

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Even today, the H-bonded cluster structure of water still stands as a major point of debate in the science of liquids. Much of this discussion is devoted to understand its dynamic nature. This has a direct impact on deciphering the many anomalies of water such as its exceptional heat capacity. Of these properties, dielectric permittivity and relaxation are of particular interest. The argument rages over whether the almost Debye-like character of the dispersion is the result of the reorientation of an apparent dipole moment of the water cluster or simply the cumulative effect of single water molecule reorientation. Furthermore, like many glass formers, it has a high frequency excess wing that does not fit into the accepted models of a single relaxation time of the main peak. Herein, we present evidence that the microscopic origins of both the excess wing and the main relaxation process of pure water are the same. The origin of these two features is explored and we suggest a new paradigm for water relaxation based on the concept of a proton cascade leading to a cluster reorientation.

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Section: The Implication Of a And Qsupporting

confidence: 84%

What is the primary mover of water dynamics?

Ishai

Tripathi

Kawase

et al. 2015

Phys. Chem. Chem. Phys.

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“…An asymmetry of like-charge ion parings was also found in the comparative study of Na + -Na + and Cl À -Cl À pairs in aqueous solution, 21 where the positive like-charge ions of Na + -Na + have a stronger tendency of pairings than Cl À -Cl À . In another dynamics study on hydronium and hydroxide, 27,28 the efficiency of proton transfer for hydronium was found to be significantly higher than that for hydroxide. Therefore it is not obvious that they behave similarly in aqueous solution.…”

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confidence: 94%

Like-charge ion pairs of hydronium and hydroxide in aqueous solution?

Ghosh

Choi

2015

Phys. Chem. Chem. Phys.

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The like-charge ion pairings of hydronium and hydroxide were investigated using both ab initio cluster calculations and QM/MM-MD aqueous simulations. While only a two-water-bridged H3O(+)(H2O)2H3O(+) is found in hydronium cluster calculations, three clusters of HO(-)(H2O)2HO(-), HO(-)(H2O)3HO(-) and HO(-)(H2O)4HO(-) are stable dihydroxide aggregates. In addition, an interesting yet very stable parallelogram structure of [O-H···H-O](2-) without any bridging water was also discovered using QM/MM-MD simulations. According to our analysis, its unique structure reduces the electrostatic repulsion and allows stable coordination with solvents at the same time. In conclusion, hydroxide can form stronger like-ion pairs than hydronium in aqueous solution mostly due to its versatile coordination ability with solvents.

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“…When a single electrode is in contact with the glass slide under high humidity, its surface acquires the same potential as the electrode. This is analogous to what happens when bulk water acquires excess charge, which was examined in great detail in a previous paper from this group and in related works …”

Section: Results and Discussionmentioning

confidence: 55%

“…This is analogous to what happens when bulk water acquires excess charge, which was examined in great detail in a previous paper from this group 50 and in related works. 55 When the two electrodes contact the glass surface and a potential difference is applied, mobile surface ions (H + from silanol dissociation and water self-ionization, which also produces OH − ) migrate to the electrodes of opposite sign. Ionization and ion migration depend on the water film adsorbed on the surface and do not take place on a dry glass surface.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Conduction and Excess Charge in Silicate Glass/Air Interfaces

et al. 2019

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The glass/air interface shows electrical properties that are unexpected for a widely used electrical insulator. The mobility of interfacial charge carriers under 80% relative humidity (RH) is 4.81 × 10 −5 m 2 s −1 V −1 , 3 orders of magnitude higher than the electrophoretic mobility of simple ions in water and less than 2 orders of magnitude lower than the electron mobility in copper metal. This allows the glass/air interface to reach the same potential as a biased contacting metal quickly. The interfacial surface resistance R increases by more than 5 orders of magnitude when the RH decreases from 80 to 2%, following an S-shaped curve with small hysteresis. Moreover, the biased surfaces store charge, as shown by Kelvin potential measurements. Applying an electric field parallel to the surface produces RH-dependent results: under low humidity, the interface behaves as expected for an ideal two-dimensional parallel-plate capacitor, while under high RH, it acquires and maintains excess negative charge, which is lost under low RH. The glass surface morphology and potential distribution change on the glass/air interface under high RH and applied potential, including the extensive elimination of nonglass contaminating particles and potential levelling. All these surprising results are explained by using a protonic-charge-transfer mechanism: mobile protons dissociated from silanol groups migrate rapidly along a field-oriented adsorbed water layer, while the matrix-bound silicate anions remain immobile. Glass may thus be classified as the ionic analogue of a topological insulator but based on structural features and charge-transfer mechanisms different from the chalcogenides that have been receiving great attention in the literature.

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Comparative Proton Transfer Efficiencies of Hydronium and Hydroxide in Aqueous Solution: Proton Transfer vs Brownian Motion

Cited by 18 publications

References 60 publications

What is the primary mover of water dynamics?

What is the primary mover of water dynamics?

Like-charge ion pairs of hydronium and hydroxide in aqueous solution?

Conduction and Excess Charge in Silicate Glass/Air Interfaces

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