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<p>This study investigates the molar conductivity, apparent molar volume, viscosity, and related physicochemical properties of potassium chloride (KCl) in methanol solutions containing two macrocyclic crown ethers, dicyclohexano-18-crown-6 (DC<sub>18</sub>C<sub>6</sub>) and dicyclohexano-24-crown-8 (DC<sub>24</sub>C<sub>8</sub>), at 298.15 ± 0.2&#xa0;K. Conductometric, densimetric, and viscometric measurements were employed to evaluate ion–solvent and ion–ligand interactions. The molar conductivity data were analyzed using the Fuoss–Kraus equation to obtain association constants (<i>K</i><sub>a</sub>, L·mol<sup>−1</sup>), limiting molar conductivities (<i>Λ</i><sub>°</sub>), and the limiting ionic conductivity of the K⁺– crown complex (<i>λ</i><sup>°</sup><sub>_(K–crown)</sub>). Apparent molar volumes (<i>ϕ</i><sub>V</sub>), limiting apparent molar volumes (<InlineEquation ID="IEq1"> <EquationSource Format="TEX">\({\phi }_{\text V}^{\text o}\)</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mi>ϕ</mi> <mrow> <mtext>V</mtext> </mrow> <mtext>o</mtext> </msubsup> </math></EquationSource> </InlineEquation>), and viscosity parameters (<i>A</i>, B, <i>D</i>) were derived to elucidate solvation and ion-pairing behavior. The results revealed that complexation between K⁺ ions and crown ethers notably affects ionic transport and solvation structure. DC<sub>24</sub>C<sub>8</sub> exhibited stronger complexation and greater solvent perturbation than DC<sub>18</sub>C<sub>6</sub>, consistent with its larger cavity size and higher flexibility. These findings provide new insights into ion–macrocycle interactions and the role of crown ether size and structure in modulating physicochemical properties of electrolytes in nonaqueous media, with broad relevance to analytical chemistry, material science, and biochemical applications.</p>

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Physicochemical Characterization of Potassium Chloride–Crown Ether Complexes (Dicyclohexano-18-crown-6 and Dicyclohexano-24-crown-8) in Methanol at 298.15 K

  • 期刊论文

  • 发表日期：

    2026年4月16日

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  • Ali Saad Alwesabi,
  • Badr Ismael Abdul-Razak,
  • M. G. Jalhoom,
  • Ammar Al-Dujaili,
  • Abdulmajeed A. A. Almaleki,
  • Yahya Alsayaad

摘要

This study investigates the molar conductivity, apparent molar volume, viscosity, and related physicochemical properties of potassium chloride (KCl) in methanol solutions containing two macrocyclic crown ethers, dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8), at 298.15 ± 0.2 K. Conductometric, densimetric, and viscometric measurements were employed to evaluate ion–solvent and ion–ligand interactions. The molar conductivity data were analyzed using the Fuoss–Kraus equation to obtain association constants (Ka, L·mol−1), limiting molar conductivities (Λ°), and the limiting ionic conductivity of the K⁺– crown complex (λ°_(K–crown)). Apparent molar volumes (ϕV), limiting apparent molar volumes ( \({\phi }_{\text V}^{\text o}\) ϕ V o ), and viscosity parameters (A, B, D) were derived to elucidate solvation and ion-pairing behavior. The results revealed that complexation between K⁺ ions and crown ethers notably affects ionic transport and solvation structure. DC24C8 exhibited stronger complexation and greater solvent perturbation than DC18C6, consistent with its larger cavity size and higher flexibility. These findings provide new insights into ion–macrocycle interactions and the role of crown ether size and structure in modulating physicochemical properties of electrolytes in nonaqueous media, with broad relevance to analytical chemistry, material science, and biochemical applications.