Mean activity coefficients of KCl in the KCl-K₂B₄O₇-H₂O ternary system at 308.15 K by EMF method

Abstract

The mean activity coefficients of KCl in a KCl-K₂B₄O₇-H₂O ternary system were experimentally determined at 308.15 K by the electromotive force measurement(EMF) via a battery cell without a liquid junction: K-ISE|KCl(m ₁), K₂B₄O₇(m ₂)|Cl-ISE(ISE=ion selective electrode) in a total ionic strength of from 0.01 mol/kg to 1.00 mol/kg at different ionic strength fractions of K₂B₄O₇ with y _B=0, 0.200, 0.400, 0.600 and 0.800. K-ISE and Cl-ISE presented a good Nernst effect, which implies that this method could be used to measure the activity coefficients of an electrolyte in the above system. The Harned rule was fitted to the experimental data, the Harned coefficients and the Pitzer single-salt ion parameters of KCl were evaluated, and the relationship diagrams between the mean activity coefficient of KCl and the ionic strength fraction(y _B) were drawn. The mean activity coefficients of KCl(γ _±KCl) decreased monotonically with the increase of I. The experimental results obeyed the Harned rule well.

Keywords

Activity coefficient / Electromotive force measurement / Ion selective electrode / Potassium chloride / Potassium borate

References

[1] Robinson R A, Stokes R H. Electrolyte Solut., 1959 2nd Ed. Boston, MA: Butterworth.

[2] Pitzer K S. Accounts of Chem. Res., 1977, 10: 371.

[3] Robinson R A, Stokes R H. Trans. Faraday Soc., 1949, 45: 612.

[4] Pitzer K S, Mayorga G. J. Phys. Chem., 1973, 77: 2300.

[5] Pitzer K S, Kim J J. J. Am. Chem. Soc., 1974, 96: 5701.

[6] Pitzer K S. Activity Coefficients in Electrolyte Solutions, 1991 Second Ed. Boca Raton, FL: CRC Press 75.

[7] Yan W D, Liu W D, Han S J. J. Chem. Eng. Chin. Univ., 1994, 8: 33.

[8] Yuan R Q, Cheng F Q. Chin. J. Salt. Lake. Res., 2008, 16: 67.

[9] Song P S, Li W, Sun B, Nie Z, Bu L Z, Wang Y S. Chin. J. Inorg. Chem., 2011, 27: 801.

[10] Song P S. J. Salt Lake Res., 2000, 8: 33.

[11] Huang Y, Zou F, Ni S J, Sang S H. Chem. Res. Chinese Universities, 2011, 27(3): 482.

[12] Huang X L, Wang X F, Chen L J. Chem. J. Chinese Universities, 2011, 32(6): 1378.

[13] Li Z G, Huang H J, Yan J. Chin. J. Chem. Phys., 2002, 15: 476.

[14] Tian H B, Yao Y, Song P S. Chem. Res. Appl., 2000, 12: 403.

[15] Galleguillos H R, Graber T A, Taboada M E, Hernández-Luis F. Fluid Phase Equilibria., 2009, 275: 39.

[16] Xie X M, Xie W H. Chem. Res. Chinese Universities, 1988, 4(3): 90.

[17] Dehghani M R, Modarress H, Monirifar M. J. Chem. Thermodynamics, 2005, 37: 1305.

[18] Daniela Ž P P, Jelena M, Milica D T, Milorad M Z, Joseph A R. J. Chem. Thermodynamics, 2012, 55: 172.

[19] Abderrahim D. J. Chem. Thermodynamics, 2007, 39: 96.

[20] Zhang X K, Zhuo K L, Ma J J, Liu H X, Wang J J. Chem. J. Chinese Universities, 2009, 30(9): 1844.

[21] Daniela Ž P P, Jelena M, Milica D T, Milorad M Z, Joseph A R. J. Chem. Thermodynamics., 2011, 43: 1877.

[22] Zhang J J, Sang S H, Zhong S Y. J. Chem. Eng. Data, 2012, 57: 2677.

[23] Zhang J J, Sang S H. J. Sichuan University: Engineering Science Edition, 2012, 44: 240.

[24] Harned H S, Owen B B. Phys. Chem. Electrolytic Solut., 1958, New York: Reinhold.

[25] Harned H S, Robinson R A. Multicomponent Electrolyte Solut., 1968, London: Pergamon Press.

[26] Pitzer K S. J. Phys. Chem., 1973, 77: 268.

[27] Greenberg J P, Møller N. Geochimica et Cosmochimica Acta, 1989, 53: 2503.

[28] Archer D G, Wang P. J. Phys. Chem. Ref. Data, 1990, 19: 371.