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Ion-Pair and Solvent Relaxation Processes in Aqueous Na2SO4 Solutions
Abstract
The complex dielectric permittivity of aqueous sodium sulfate solutions (0.025 ≤ c /mol dm -3 ≤ 1.6) has been determined in the frequency range 0.2 ≤ ν/GHz ≤ 20 with a commercial dielectric measurement system based on a vector network analyzer. The spectra were supplemented with interpolated literature data at 12 ≤ ν/GHz ≤ 89. To fit the complex permittivity spectra, a superposition of three Debye relaxation processes was necessary. The slow and intermediate dispersion steps are assigned to the tumbling motion of doubly solvent-separated (2SIP) and solvent-shared (SSIP) NaSO 4 - ion pairs, respectively. The fast process, of amplitude S 3, is due to the collective relaxation of the solvent. Effective solvation numbers were deduced from the effect of Na 2 SO 4 concentration on S 3 . From the ion-pair dispersion amplitudes, S 1 and S 2, the concentrations c 2SIP and c SSIP, and thus the overall stoichiometric stability constant, β NaSO 4 −, were determined.
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Citations
Cited by
Marcus, Y., & Hefter, G. (2006) · Chemical Reviews · doi:10.1021/cr040087x · Cited by 1,134
Self-citationCooperativity in Ion Hydration
Tielrooij, K. J., Garcia-Araez, N., Bonn, M., & Bakker, H. J. (2010) · Science · doi:10.1126/science.1183512 · Cited by 685
Interactions and dynamics in electrolyte solutions by dielectric spectroscopy
Buchner, R., & Hefter, G. (2009) · Physical Chemistry Chemical Physics · doi:10.1039/b906555p · Cited by 318
Self-citationWater-Mediated Ion Pairing: Occurrence and Relevance
van der Vegt, N. F. A., Haldrup, K., Roke, S., Zheng, J., Lund, M., & Bakker, H. J. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00742 · Cited by 284
Wang, X., Chou, I.-M., Hu, W., Yuan, S., Liu, H., Wan, Y., & Wang, X. (2016) · Chemical Geology · doi:10.1016/j.chemgeo.2016.04.020 · Cited by 25
Metadata
- Authors
- Buchner, R., Capewell, S. G., Hefter, G., & May, P. M.
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 1999-01-29
- Volume
- 103
- Issue
- 7
- Pages
- 1185-1192
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W1516241922
- Cited by
- 183
- References
- 0
- FWCI
- 2.47
- Type
- journal article
- Language
- en
- Open access
- closed
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- Buchner, R., Capewell, S. G., Hefter, G., & May, P. M. (1999). Ion-Pair and Solvent Relaxation Processes in Aqueous Na2SO4 Solutions. The Journal of Physical Chemistry B. https://doi.org/10.1021/jp983706c
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