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Effects of Ions on the OH Stretching Band of Water as Revealed by ATR-IR Spectroscopy

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Abstract

The effects of various cations (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, and Ni2+) and anions (Cl−, Br−, I−, \( {\text{NO}}_{3}^{ - } \), \( {\text{ClO}}_{4}^{ - } \), \( {\text{HCO}}_{3}^{ - } \), and \( {\text{CO}}_{3}^{2 - } \)) on the molar absorptivity of water in the OH stretching band region (2,600–3,800 cm−1) were ascertained from attenuated total reflection infrared spectra of aqueous electrolyte solutions (22 in all). The OH stretching band mainly changes linearly with ion concentrations up to 2 mol·L−1, but several specific combinations of cations and anions (Cs2SO4, Li2SO4, and MgSO4) present different trends. That deviation is attributed to ion pair formation and cooperativity in ion hydration, which indicates that the extent of the ion–water interaction reflected by the OH stretching band of water is beyond the first solvation shell of water molecules directly surrounding the ion. The obtained dataset was then correlated with several quantitative parameters representing structural and dynamic properties of water molecules around ions: ΔG HB, the structural entropy (S str), the viscosity B-coefficient (B η ), and the ionic B-coefficient of NMR relaxation (B NMR). Results show that modification of the OH stretching band of water caused by ions has quasi-linear relations with all of these parameters. Vibrational spectroscopy can be a useful means for evaluating ion–water interaction in aqueous solutions.

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Acknowledgments

We greatly appreciate Dr. Tadashi Yokoyama and Mr. Naoki Nishiyama of Osaka University for their help with sample preparations. We also thank two anonymous referees and associated editor Luigi Paduano for their careful reviews of this manuscript. This research was financially supported by a JSPS Research Fellowship for Young Scientists to Norio Kitadai.

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Authors and Affiliations

  1. Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1-IE-1, Ookayama, Megoro-ku, Tokyo, 152-8550, Japan

    Norio Kitadai

  2. Nakatsugawa Factory Manufacturing, Mitsubishi Electric Corporation, 1213 Matsuoshirota, Iida, Nagano, 395-0812, Japan

    Takashi Sawai

  3. Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan

    Ryota Tonoue, Satoru Nakashima & Makoto Katsura

  4. Institute of Nature and Environmental Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa, 920-1192, Japan

    Keisuke Fukushi

Authors
  1. Norio Kitadai
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  2. Takashi Sawai
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  3. Ryota Tonoue
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  4. Satoru Nakashima
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Corresponding author

Correspondence to Norio Kitadai.

Appendix

Appendix

Although it is not the main subject of this study, we show the effects of 1 mol·L−1 cations and 1 mol·L−1 anions on the molar absorptivity of water in the OH bending band region (1,200–2,000 cm−1) in Fig. 7. This presentation of the influences of various ions on the OH bending band of water is the first ever reported. We hope that these results can stimulate future theoretical and/or experimental studies in this area.

Fig. 7
figure 7

Effects of 1 mol·L−1 cations (a) and 1 mol·L−1 anions (b) on the molar absorptivity of water in the OH bending band region (1,200–2,000 cm−1). The effect of \( {\text{HCO}}_{3}^{ - } \) is not shown in this figure because of the strong overlap with a \( {\text{HCO}}_{3}^{ - } \) band [1]. The OH bending band of water is shown at the top of each figure for comparison

Full size image

We also present in Tables 2 and 3 a summary of the aqueous solutions measured in this study, and the numerical results on the areas of ∆MAL–H and ∆ATRL–H for each ion (at 1 mol·L−1 concentration), respectively.

Table 3 Left side: areas in the lower (2,600–3,420 cm−1) and the higher (3,420–3,800 cm−1) frequency regions of the bands portrayed in Fig. 4 (MAL and MAH, respectively) and their difference (∆MAL–H) calculated after drawing a linear baseline from 2,600 to 3,800 cm−1
Full size table

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Kitadai, N., Sawai, T., Tonoue, R. et al. Effects of Ions on the OH Stretching Band of Water as Revealed by ATR-IR Spectroscopy. J Solution Chem 43, 1055–1077 (2014). https://doi.org/10.1007/s10953-014-0193-0

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