Possibility and reliability of conductometric determination of limiting ionic conductivities and complexation constants in solutions of 1-1 electrolytes in non-aqueous solvents with neutral ligands
Abstract
A method of determination of limiting ionic conductivities and complexation constants in solutions of 1-1 electrolytes in non-aqueous solvents with neutral ligands was proposed. The method is based on carrying out two conductometric experiments, with and without adding a ligand, followed by received conductometric data processing. The method was successfully tested on a sample of the system of LiClO4-crypt-[2.2.1] in acetonitrile at 25 °С. The modeling of the influence of random noise in the primary experimental data on an error in determination of the parameters of the model was carried out. It was found that when the level of random errors in the primary conductometric data is below 0.5%, the limiting molar conductivity of a simple cation can be determined with an accuracy of 0.1 S·cm2/mol and the complexation constant - with an accuracy of 0.03 log. units.
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Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries / K. Xu // Chem. Rev. — 2004. — Vol. 104, No. 10. — P. 4303–4417.
Xu K. Electrolytes and interphases in li-ion batteries and beyond / K. Xu // Chem. Rev. — 2014. — Vol. 114, No. 23. — P. 11503–11618.
Zugmann S. Measurement of transference numbers for lithium ion electrolytes via four differ-ent methods , a comparative study / S. Zugmann, M. Fleischmann, M. Amereller[et al.] // Electrochimica Acta. — 2011. — Vol. 56, No. 11. — P. 3926–3933.
MacInnes D. A. Trasference numbers by the method of moving boundaries / D. A. MacInnes, L. G. Longsworth // Chem. Rev. — 1932. — Vol. 11, No. 2. — P. 171–230.
P. Walden Conductivity measurements in acetone / P. Walden, H. Ulich, G. Busch// Z. Phys. Chem. – 1926. — Vol. 123. — P. 429–438.
Safonova L. Conductometry of electrolyte solutions / L. Safonova, A. Kolker //Russ. Chem. Rev. – 1992. – Vol. 61, No. 9. – P. 959–973.
Krumhaltz B. Separation of limiting equivalent conductances into ionic contributions in non-aqueous solutions by indirect methods / B. Krumhaltz // J. Chem. Soc., Faradey Trans. I. — 1983. — Vol. 79. — P. 571–587.
Apelblat A. Limiting conductances of electrolytes and the Walden product in mixed solvents in a phenomenological approach / A. Apelblat // J. Phys. Chem. B. — 2008. — Vol. 112, No. 23. — P. 7032–7044.
Afanas’ev V. N. Chemical modification of electrolytes for lithium batteries / V. N. Afanas’ev, A. G. Grechin // Russ. Chem. Rev. — 2002. — Vol. 71, No. 9. — P. 775–787.
D’Aprano A. Solvent effects on complexation of crown ethers with LiClO4, NaClO4 and KClO4 in methanol and acetonitrile / A. D’Aprano, M. Salomon, V. Mauro // J. Solution Chem. — 1995. — Vol. 24, No. 7. — P. 685–702.
D’Aprano A. Complexation of Li+, Na+ and K+ ions by [222], [222D], [221], [221D] cryptands in acetonitrile at 25ºC : conductometric determination of the true thermodynamic formation constants / A. D’Aprano, M. Salomon, V. Mauro // J. Inclusion Phenomena and Macrocyclic Chem. — 1999.—Vol 35. — P. 451–465.
Lee W.H. Conductance of symmetrical, unsymmetrical and mixed electrolytes. 1 Relaxation terms / W.H. Lee, R.J. Wheaton // J. Chem. Soc. Faraday Trans. II. — 1978. — Vol. 74, N 4. — P. 743-766.
Lee W.H. Conductance of symmetrical, unsymmetrical and mixed electrolytes. 2 Hydrody-namic terms and complete conductance equation / W.H. Lee, R.J. Wheaton // J. Chem. Soc. Faraday Trans. II. — 1978. — Vol. 74, N 8. — P. 1456-1482.
Himmel'blau D. Prikladnoe nelineynoe programmirovanie / D. Himmel'blau. — M.: Mir, 1975. — 534 s.
Kalugin O. N. Nekotory'e voprosy' obrabotki konduktometricheskih danny'h. II slojnoassocii-rovanny'e i nesimmetrichny'e e`lektrolity' / O. N. Kalugin, I. N. V'yunnik // Jurn. obsch'ey hi-mii. — 1989. — T. 59, No 7. — S. 1633-1637.
Platuhin V. F. Opredelenie predel'ny'h ionny'h e`lektricheskih provodimostey iz konduktome-tricheskih danny'h nesimmetrichny'h e`lektrolitov / V. F. Platuhin, O. N. Kalugin, I. N. V'yun-nik // Vest. Har'k. un-ta. Himiya. — 1997. — Him. nauki. No. 1. — S. 209-219.
Platuhin V. F. Transportny'e i ravnovesny'e svoystva CaCl2 v dimetilsul'fokside v intervale temperatur 25-125°S / V. F. Platuhin, O. N. Kalugin, A. V. Kramarenko, I. N. V'yunnik // Vestn. Har'k. un-ta. Himiya. —1998. — No. 2. — S. 165-170.
Springer C. H. Transference number measurements in acetonitrile as a solvent / C. H. Springer, J. F. Coetzee // J. Phys. Chem. — 1969. — Vol. 73, No. 3. — P. 471–476.
