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Raman Investigation of Proton Hydration and Structure in Concentrated Aqueous Hydrochloric Acid Solutions

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Proton Transfer in Hydrogen-Bonded Systems

Part of the book series: NATO ASI Series ((NSSB,volume 291))

Abstract

Polarized X(ZZ)Y, depolarized X(ZX)Y, and isotropic X(ZZ)Y - (4/3)X(ZX)Y Raman spectra, all Bose-Einstein corrected, were obtained between ≈3 and 350 cm-1 from concentrated aqueous HC1 solutions having compositions of 32.1, 34.6, and 36.9 wt. %. These spectra were compared to the corresponding spectra from pure water and concentrated aqueous NaCl. Marked Raman intensity enhancements were observed for bands between ≈50 to ≈200 cm-1 compared to the corresponding bands from liquid water, and these enhancements are thought to be related to proton tunnelling, which occurs because the hydrogen bonds of the concentrated HC1 solutions are short, ≈2.5 A, and nearly symmetric. Also, a very intense, broad, and asymmetric peak centered near 200 cm-1 dominates the istoropic spectra from the HC1 solutions, and a peak near 50 cm-1 dominates the X(ZX)Y spectra. These features are readily modelled by the H9O4 + ion, and intermolecular force constants for H9O4 + were obtained from normal mode calculations. An isotropic Raman component observed near 120–135 cm-1 is suggested to arise from C1-(H2O)n.

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References

  1. Composition (wt. %) and density data for aqueous HC1 solutions are presented in, “CRC Handbook of Physics and Chemistry”, R. C. Weast ed., 66th edition, CRC Press, Inc., Boca Raton, Florida, 1985–86, see pg. D-232. From these data we obtained the following least squares equation, applicable above 10 wt. % HC1: C = A0 + A1D + A2D2 + A3D3, where C = wt. %, and D = density in g-cm-3. A0 = -1474.18506, A1 = 3653.28272, A2 = -3113.59696, and A3 = 934.18982. This cubic polynomial was used to determine composition from densities measured in this work.

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Authors and Affiliations

  1. Chemistry Department, Howard University, Washington, D. C, 20059, USA

    G. E. Walrafen, Y. C. Chu & H. R. Carlon

Authors
  1. G. E. Walrafen
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  2. Y. C. Chu
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  3. H. R. Carlon
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Editor information

Editors and Affiliations

  1. University of Patras, Patras, Greece

    T. Bountis

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© 1992 Springer Science+Business Media New York

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Walrafen, G.E., Chu, Y.C., Carlon, H.R. (1992). Raman Investigation of Proton Hydration and Structure in Concentrated Aqueous Hydrochloric Acid Solutions. In: Bountis, T. (eds) Proton Transfer in Hydrogen-Bonded Systems. NATO ASI Series, vol 291. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3444-0_26

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  • DOI: https://doi.org/10.1007/978-1-4615-3444-0_26

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4613-6524-2

  • Online ISBN: 978-1-4615-3444-0

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