Abstract
A comprehensive analysis of the transport properties of solutions of three pyridinium-based ionic liquids, 2-chloro-1-methylpyridinium iodide [o-mpy][I]; 3-chloro-1-methylpyridinium iodide [m-mpy][I], and 4-chloro-1-methylpyridinium iodide, [p-mpy][I], has been derived utilising conductometric data at temperatures ranging from 298.15 to 313.15 K (in steps of 5 K) in 10%, 30%, and 50% W/W mixtures of MeOH–H2O and DMF–H2O. On the basis of conductometric data, the limiting molar conductance and ion-pair association were evaluated and re-evaluated using a computer-programmed Fuoss-Edelson strategy, and the acquired results were evaluated in terms of the influence of temperature, the solvent's nature, ion-ion, ion–solvent interactions, and substituent positions on the transport characteristics. Using conductance-based data, the \(\Lambda_{ \circ } \eta_{ \circ }\),\({R}_{H}\), activation energy of the transport process and association's thermodynamic functions values of these ILs were computed and thoroughly analysed. Surprisingly, the "positioning" of the substituent (Cl) in the ortho, meta, or para-position had a minor impact on the ion pair association of three ILs in the chosen solvents, with the \({K}_{A}\) values for para-substituted [p-mpy][I] being about 1.07-fold lower than [m-mpy][I] and [o-mpy][I], respectively. This article's results supplied critical data about the transport properties of pyridinium-based ionic liquids, which is essential and beneficial for the diverse fields of such ionic liquids that are currently being utilised.
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Abbreviations
- [o-mpy][I]:
-
2-Chloro-1-methylpyridinium iodide (mg)
- [m-mpy][I]:
-
3-Chloro-1-methylpyridinium iodide (mg)
- [p-mpy][I]:
-
4-Chloro-1-methylpyridinium iodide (ml)
- MeOH:
-
Methanol (ml)
- DMF:
-
N,N-dimethylformamide (ml)
- \(\varepsilon\) :
-
The dielectric constants (Unitless)
- \(d\) :
-
The density (g cm− 3)
- \(\eta_{ \circ }\) :
-
The viscosity (\(cP\))
- \(Ks\) :
-
The specific conductances (S cm− 1)
- \(\Lambda\) :
-
The molar conductance (S mol− 1 cm2)
- \(\Lambda_{ \circ }\) :
-
The limiting molar conductance (S mol− 1 cm2)
- \({\uplambda }_{ \pm }^{ \circ }\) :
-
The limiting ionic conductance of cation/anion (S mol− 1 cm2)
- \(D_{o}\) :
-
The limiting diffusion coefficients (cm2 sec− 1)
- \({K}_{\mathrm{A}}\) :
-
The association constant (mol dm− 3)
- \(F\) :
-
The Faraday constant (C mol− 1)
- Δ:
-
The Onsager reciprocal relations (\(\mathrm{Slope},\) Unitless)
- \({\gamma }_{\pm }\) :
-
The mean ion activity coefficients (Unitless)
- A :
-
The ion size parameter of the closet approach (Å)
- μ :
-
The ionic strength (mol m3))
- Z :
-
The valence of cation (Unitless)
- A :
-
The empirical constant (Unitless)
- B :
-
The empirical constant (Unitless)
- \(\Lambda_{ \circ } \eta_{ \circ }\) :
-
The Walden product (S mol− 1 cm2 cP)
- \({R}_{\mathrm{H}}\) :
-
The hydrodynamic radii (\(\mathrm{nm}\))
- \(E\mathrm{a}\) :
-
The activation energy of the transfer process (KJ mol− 1)
- \({\Delta }G_{{\text{A}}}^{^\circ }\) :
-
The standard free energy of association (KJ mol− 1)
- \({\Delta }H_{{\text{A}}}^{^\circ }\) :
-
The standard enthalpy of association (KJ mol− 1)
- \({\Delta }S_{{\text{A}}}^{^\circ }\) :
-
The standard entropy of association (KJ mol− 1)
- R :
-
The gas constant (8.314) (J mol− 1 K− 1)
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Acknowledgements
For all the resources, programmes, and facilities required to accomplish this work, the authors are grateful to Tobruk University in Libya and the University of Leicester in the United Kingdom.
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The experimental component is made in part by NA, and in part by FD and TA. The discussion and analysis of the obtained results have been done by Dr. A and Dr. D. The main manuscript text was written by Dr. N. Abdolla, and the final manuscript draught was reviewed and approved by all authors.
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Abdolla, N.S.Y., Aeyad, T.Y.M. & El-Dossiki, F.I. An insight into the influence of chlorine position on the ion-solvation and ion-association behaviour of pyridinium-based ionic liquids in alcohol-water mixed media and temperatures. J IRAN CHEM SOC 20, 2217–2232 (2023). https://doi.org/10.1007/s13738-023-02820-y
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DOI: https://doi.org/10.1007/s13738-023-02820-y