Mid-Infrared Fiber-Optic Attenuated Total Reflection Spectroscopy of the Solid—Liquid Phase Transition of Water

Millo, Arnon; Raichlin, Yosef; Katzir, Abraham

doi:10.1366/0003702053641469

Cited by 53 publications

(35 citation statements)

References 34 publications

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“…35,36 Next to H 2 O and D 2 O, the used additives THF and SDS also provide specic vibrational absorption features in the MIR. The magnications of the obtained MIR-FEFS spectra represent the region of interest for the n asCH SDS (centered at 2920 cm 39,40 While in the present study these changes are qualitatively similar for both H 2 O and D 2 O, they appear more clearly evident during H 2 O experiments, due to the absence of HOD and other interferences (CO 2 and PTFE). While the n OH (n OD ) features are subject to a red-shi, the 3n L and n L features shi to the blue.…”

Section: In Situ Mir-fefs Monitoring Of Co 2 Gas Hydratessupporting

confidence: 57%

In situ monitoring of additives during CO₂gas hydrate formation

2016

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Research activities on the reduction of carbon dioxide emissions via effective carbon capture and storage (CCS) techniques are steadily increasing with the concept of storing CO 2 as hydrates among the most prominently discussed strategies. The present study utilizes mid-infrared (MIR) fiber-optic evanescent field sensing techniques as a promising in situ monitoring tool for investigation of molecular changes occurring during CO 2 hydrate formation. The identification and evaluation of characteristic IR absorption features associated with additive molecules (here, THF and SDS) and their changes during hydrate formation were pronounced via studies in D 2 O next to H 2 O as the hydrate-forming matrix. By correlating IR-spectroscopic data with continuously recorded pressure and temperature traces, hypotheses on the involvement and promoting effect of such additives during carbon dioxide gas hydrate formation were experimentally consolidated.

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Section: In Situ Mir-fefs Monitoring Of Co 2 Gas Hydratessupporting

confidence: 57%

In situ monitoring of additives during CO₂gas hydrate formation

2016

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“…It is unclear whether the number of hydrogen bonds are important, [29] or is it the type of hydrogen bond (single, bifurcated or trifurcated), [30] or is it the hydrogen-bending angle, [31] or perhaps the nature of the formed broken donor and acceptor hydrogen bonds. [32] However, the calculated spectrum for our (H 2 O) 17 structure looks as follows: The OÀH stretch region is mainly given by five vibrational bands (Figure 9 a). [33] Four of them (solid lines) refer to the symmetric and asymmetric stretch vibrations of water molecules which are tetrahedrally coordinated.…”

Section: Resultsmentioning

confidence: 97%

The Importance of Tetrahedrally Coordinated Molecules for the Explanation of Liquid Water Properties

Ludwig

2007

ChemPhysChem

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Ab initio calculations on molecular clusters and a quantum statistical model are used to probe the structure of liquid water and its anomalies. Characteristic temperature dependent mixtures of ring and three-dimensional, voluminous water clusters provide the famous density maximum. The mixture model also reproduces the shift of the density maximum as a function of pressure and isotopic substitution. This finding is consistent with femtosecond spectroscopy data suggesting that two distinct molecular species exist in liquid water. The given structures also reproduce the oxygen-oxygen pair correlation function and the vibrational IR spectrum of liquid water. The results underline the importance of three-dimensional, tetrahedrally coordinated structures for the understanding of water anomalies and the existence of two liquid phases in the supercooled region.

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“…The weak band at ∼2100 cm −1 is due to a combination vibration of H 2 O. 35 It is noteworthy that the contribution of the O-H · · · OH − oscillators to the absorption is significantly weaker than that of water molecules hydrating the proton (H 2 O · · · H + ), as observed in acidic solutions. 12 The linear absorption spectrum of an acidic solution (in absence of deuterium) shows an approximately two times higher total absorbance at ∼ 2500 cm −1 than an aqueous solution of NaOH of the same concentration.…”

Section: A Linear Infrared Spectramentioning

confidence: 92%

Vibrational and orientational dynamics of water in aqueous hydroxide solutions

Hunger

Liu

Tielrooij

et al. 2011

The Journal of Chemical Physics

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We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton.

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Mid-Infrared Fiber-Optic Attenuated Total Reflection Spectroscopy of the Solid—Liquid Phase Transition of Water

Cited by 53 publications

References 34 publications

In situ monitoring of additives during CO₂gas hydrate formation

In situ monitoring of additives during CO₂gas hydrate formation

The Importance of Tetrahedrally Coordinated Molecules for the Explanation of Liquid Water Properties

Vibrational and orientational dynamics of water in aqueous hydroxide solutions

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Mid-Infrared Fiber-Optic Attenuated Total Reflection Spectroscopy of the Solid—Liquid Phase Transition of Water

Cited by 53 publications

References 34 publications

In situ monitoring of additives during CO2gas hydrate formation

In situ monitoring of additives during CO2gas hydrate formation

The Importance of Tetrahedrally Coordinated Molecules for the Explanation of Liquid Water Properties

Vibrational and orientational dynamics of water in aqueous hydroxide solutions

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Product

Resources

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In situ monitoring of additives during CO₂gas hydrate formation

In situ monitoring of additives during CO₂gas hydrate formation