Bromide hydration as a function of concentration and temperature
Letizia Scarabattoli, Lucia Comez and Paola Sassi

Abstract

In the fascinating world of the physico-chemical properties of water vibrational spectroscopy provides a powerful tool to unravel the complicated scenario of H-bonding structures. In this work, we used Raman spectroscopy to give an estimate of interactions and nearest-neighbour distances in water and KBr aqueous solutions. By H/D isotopic substitution and analysis of the OH/OD stretching regions, we followed the rearrangement of local structures in the proximity of bromide ions as a function of temperature, in the –30°C – 50°C temperature range, at different KBr concentrations. A more compact and interacting shell was recognized for the solution in the presence of ice, regardless of KBr concentration; however, both at high and low temperatures, a 20% lessening of H bonding enthalpy was estimated in water-bromide with respect to water-water interactions. This analysis of water properties in the bromide hydration shell below and above the melting range, gives a more comprehensive picture of the H bond network of water-electrolyte systems. ©Anita Publications. All rights reserved.
Keywords: Water, Electrolyte, Hydration, Raman spectroscopy.

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References

1. Shi R, Tanaka H, The anomalies and criticality of liquid water, PNAS, 117(2020)26591–26599.
2. Russo J, Tanaka H, Understanding water’s anomalies with locally favoured structures, Nat Commun, 5(2014)3556; doi.org/10.1038/ncomms4556.
3. Bagchi B., Approaches to understand water anomalies, Water in Biological and Chemical Processes. From Structure and Dynamics to Function, (Cambridge university Press), (2013), pp 323–344.
4. Orgel L, The hydrogen bond, Rev Mod Phys, 31(1959)100–102.
5. Huang Y, Zhang X, Ma Z, Li W, Zhou Y, Zhou J, Zheng W, Sun C Q, Size, separation, structural order, and mass density of molecules packing in water and ice, Sci Rep, 3(2013)3005; doi.org/10.1038/srep03005.
6. Freda M, Piluso A, Santucci A, Sassi P, Transmittance FTIR spectra of liquid water in the whole Mid-infrared region: temperature dependence and structural analysis, Appl Spectrosc, 59(2005)1155–1159.
7. Gallina M E, Sassi P, Paolantoni M, Morresi A, Cataliotti R S, Vibrational analysis of molecular interactions in the aqueous glucose solutions. Temperature and concentration effects, J Phys Chem B, 110(2006)8856–8864.
8. Paolantoni M, Gallina M E, Sassi P, Morresi A, Structural properties of α-D-glucose solutions in dimethylsulphoxide probed by Raman spectroscopy, J Chem Phys, 130(2009)164501; doi.org/10.1063/1.3116250.
9. Auer B M, Skinner J L, IR and Raman spectra of liquid water: Theory and interpretation, J Chem Phys, 128(2008) 224511; doi.org/10.1063/1.2925258.
10. Hribar B, Southall N T, Vlachy V, Dill K A, How ions affect the structure of water, J Am Chem Soc, 124(2002)12302–12311.
11. Comez L, Paolantoni M, Sassi P, Corezzi S, Morresi A, Fioretto D, Molecular properties of aqueous solutions: a focus on the collective dynamics of hydration water, Soft Matter, 12(2016)5501–5514.
12. Fox M F, Hayon E, The Far-ultraviolet solution spectroscopy of chloride ion, J Chem Soc, Faraday trans, 86(1990) 257–263.
13. Elton D C, Fernàndez-Serra M., The hydrogen-bond network of water supports propagating optical phonon-like modes, Nat Commun, 7(2006)10193; doi.org/10.1038/ncomms10193.
14. Ashihara S, Fujioka S, Shibuya K, Temperature dependence of vibrational relaxation of the OH bending excitation in liquid H₂O, Chem Phys Lett, 502(2011)57–62.
15. Kanno H, Yonehama K, Somraj A, Yoshimura Y, Structure-making ions become structure breakers in glassy aqueous electrolyte solutions, Chem Phys Lett, 427(2006)82–86.
16. Wernersson E,Jungwirth P, Effect of Water Polarizability on the Properties of Solutions of Polyvalent Ions: Simulations of Aqueous Sodium Sulfate with Different Force Fields,J Chem Theory Comput, 6(2010)3233–
17. Jungwirth P, Tobias D J,Specific Ion Effects at the Air/Water Interface, Chem Rev, 106(2006)1259–
18. Vazdar M, Uhlig F, Jungwirth P, Like-Charge Ion Pairing in Water: An ab Initio Molecular Dynamics Study of Aqueous Guanidinium Cations,J Phys Chem Lett, 3(2012)2021–
19. Tauber M J, Mathies R A,Structure of the Aqueous Solvated Electron from Resonance Raman Spectroscopy: Lessons from Isotopic Mixtures,J Am Chem Soc, 125(2003)1394–
20. Eftekhari-Bafrooei A, Borguet E,Effect of Hydrogen-Bond Strength on the Vibrational Relaxation of Interfacial Water,J Am Chem Soc, 132(2010)3756–
21. Heisler I A, Meech S R,Low-Frequency Modes of Aqueous Alkali Halide Solutions: Glimpsing the Hydrogen Bonding Vibration, Science, 327(2010)857–
22. Li R,Jiang Z, Guan Y, Yang H, Liu B,Effects of Metal Ion on the Water Structure Studied by the Raman O-H Stretching Spectrum,J Raman Spectrosc, 40(2009)1200–
23. Smith J D, Saykally R J, Geissler P L,The Effects of Dissolved Halide Anions on Hydrogen Bonding in Liquid Water,J Am Chem Soc, 129(2007)13847–
24. Bakker R J, Raman spectra of fluid and crystal mixtures in the systems H₂O, H₂O–NaCl and H₂O–MgCl₂ at low temperatures: applications to fluid-inclusion research, The Canadian Mineralogist, 42(2004)1283–1314.
25. Hanke F., Bottger U., Pavlov S. G., Hubers H. W., Raman Spectra of Frozen Salt Solutions Relevant for Planetary Surfaces, EPSC Abstracts, 9(2014)403-1.
26. Malley P P, Chakraborty S, Kahan T F, Physical characterization of frozen saltwater solutions using Raman microscopy, ACS Earth and Space Chemistry, 2(2018)702–710.
27. Nie G L, Sang S H, Cui R Z, Solid–Liquid Equilibrium Phase Diagram and Calculation in the Quaternary System (KBr+ NaBr+ MgBr₂+ H₂ O) at 298 K,J Sol Chem, 48(2019)862–874.
28. Perera P, Wyche M, Loethe Y, Ben-Amotz D, Solute-Induced Perturbations of Solvent-Shell Molecules Observed Using Multivariate Raman Curve Resolution, J Am Chem Soc, 130 (2008)4576–4577.
29. Wang S, Fang W, Li T, Li F, Sun C, Li Z, Men Z, An insight into liquid water networks through hydrogen bonding halide anion: Stimulated Raman scattering, J Appl Phys, 119(2016)163104; doi.org/10.1063/1.4947292.
30. Hu Q, Zhao H, Ouyang S, Interpreting the Raman OH/OD stretch band of ice from isotopic substitution and phase transition effects,PhysChemChemPhys, 20(2018)28600–28605.
31. Gallina M E, Sassi P, Paolantoni M, Morresi A, Cataliotti R S, Vibrational Analysis of Molecular Interactions in Aqueous Glucose Solutions. Temperature and Concentration Effects, J Phys Chem B, 110(2006)8856–8864.
32. Sun Q, Raman spectroscopic study of the effects of dissolved NaCl on water structure, Vib Spectrosc, 62(2012)110–114.
33. Busing W R, Hornig D F, The effect of dissolved KBr, KOH or HCl on the Raman spectrum of water, J Phys Chem, 65(1961)284–292.
34. Auer B M, Kumar R, Schmidt J R, Skinner J L, Hydrogen bonding and Raman, IR, and 2D-IR spectroscopy of dilute HOD in liquid D₂O, PNAS, 104(2007)14215–14220.
35. Hu Q, Zhao H, Ouyang S, Understanding water structure from Raman spectra of isotopic substitution H₂O/D₂O up to 573 K, Phys Chem Chem Phys, 19(2017)21540–21547.
36. Śmiechowski M, Janusz S, Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration, Pure and Appl Chem, 82(2010)1869–1887.
37. Bergmann U, Di Cicco A, Wernet P, Principi E, Glatzel P, Nilsson A, Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure, J Chem Phys, 127(2007) 174504; doi.org/10.1063/1.2784123.
38. Badger R M, Bauer S H, Spectroscopic studies of the hydrogen bond. II. The shift of the O–H vibrational frequency in the formation of the hydrogen bond, J Chem Phys, 5(1937)839–851.
39. Iogansen A V, Direct proportionality of the hydrogen bonding energy and the intensification of the stretching ν (XH) vibration in infrared spectra, Spectrochim Acta , 55A(1999)1585–1612.
40. Mikenda W, Steinböck S, Stretching frequency vs. bond distance correlation of hydrogen bonds in solid hydrates: A generalized correlation function, J Mol Struct, 384(1996)159–163.

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