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A strong acid is a compound that dissociates completely in an aqueous solution and produces a concentration of hydronium ions equal to the initial concentration of acid. For example, 0.20 M hydrobromic acid will dissociate completely in water and produces 0.20 M of hydronium ions and 0.20 M of bromide ions.
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Structural Evidence of Interanionic Hydrogen Bonding in Phosphoric Acid Solutions.

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Interanionic hydrogen bonding (IAHB) between like-charged phosphate ions was structurally confirmed in concentrated phosphoric acid solutions. This challenges electrostatic theories by showing solvent-mediated anion-anion association.

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Area of Science:

  • Physical Chemistry
  • Solution Chemistry
  • Spectroscopy

Background:

  • Interanionic hydrogen bonding (IAHB) involves interactions between like-charged ions, defying traditional electrostatic models.
  • Understanding IAHB is crucial for explaining chemical behavior in concentrated ionic solutions.

Purpose of the Study:

  • To provide direct structural evidence for IAHB in concentrated aqueous phosphoric acid (PA) solutions.
  • To elucidate the role of solvent in facilitating anion-anion association.

Main Methods:

  • Oxygen K-edge X-ray absorption fine structure (XAFS) spectroscopy.
  • Electron affinity time-dependent density functional theory (TD-DFT) calculations.
  • Extended X-ray absorption fine structure (EXAFS) and Near-edge X-ray absorption fine structure (NEXAFS) analyses.

Main Results:

  • Direct structural evidence of stable, cyclic phosphate-phosphate IAHB dimers formed at PA concentrations ≥7 M.
  • Long-range ordering consistent with dimer formation observed via EXAFS.
  • Concentration-dependent transition from monomeric to dimeric species confirmed by NEXAFS.
  • DFT calculations indicated energetically favorable IAHB formation driven by polarization and charge transfer, mediated by solvent.

Conclusions:

  • Solvent plays a critical role in facilitating anion-anion association through IAHB.
  • Findings offer crucial structural insights into hydrogen-bonded networks in concentrated PA solutions.
  • IAHB contributes significantly to the behavior of concentrated ionic systems.