An extensive study on Raman spectra of water from 253 to 753 K at 30 MPa: A new insight into structure of water

Hu, Qingcheng; Lü, Xinbiao; Lü, Wanjun; Chen, Ying; Liu, Hong

doi:10.1016/j.jms.2013.09.006

Cited by 60 publications

(49 citation statements)

References 27 publications

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“…Careful observation on Raman spectra of H 2 O at wide range of temperature shows that (1) the shape of main peak (PK 2) above ~353 K broadens and then narrows around the top of spectral lines along with blue shifts of central wavenumber; and (2) the intensity of PK 2 remains almost the same at temperature range from 413 to 573 K. These phenomena indicate that (PK 2) H2O should compose several sub‐peaks among which some are intensified but some are weakened with increasing temperature. We roughly represented (PK 2) H2O by two different sub‐peaks with one falling and another rising in intensity with increasing temperature.…”

Section: Resultssupporting

confidence: 70%

“…As discussed previously, the first two Gaussian components in Raman spectra of H 2 O belong to two kinds of FHW with structures: ‘ideal’ tetrahedral water and deformed tetrahedral water. The former has linear O…H–O bond that is the dominant HB structure factor in normal H 2 O ice.…”

Section: Resultsmentioning

confidence: 91%

“…Previously, we investigated Raman spectra for neat H 2 O and analyzed the temperature dependence of OH stretch wavenumbers and line widths . We decomposed the OH stretch band into five components that were assigned to water molecules engaged in different HB environments.…”

Section: Introductionmentioning

confidence: 99%

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Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure

Ouyang

et al. 2017

J Raman Spectroscopy

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D2O and H2O structure are investigated by Raman spectroscopy from 303 to 573 K at saturated vapor pressures in a fused silica capillary tube. As temperature increases to 573 K, Raman peak of D2O is blue‐shifted by 93 cm−1, lower than that of H2O by 128 cm−1, but the two Raman shoulders of D2O/H2O nearly remain unchanged in wavenumber. By fitting the spectra into five Gaussian components assigned to water molecules with different hydrogen bonding (HB) environments, these spectral features are interpreted by a mechanism that D2O and H2O have equal types of water molecules with similar HB degrees – fully hydrogen‐bonded H2O/D2O (FHW/D) and partially hydrogen‐bonded H2O/D2O (PHW/D) but distinct HB configurations that O…D–O is more symmetric and stronger than O…H–O. Much smaller values but slightly weaker temperature dependence of full widths at half maxima for D2O spectra ((FWHM)D2O) than (FWHM)H2O are primarily due to much weaker but slightly less temperature‐dependent intermolecular couplings in D2O than in H2O. Enthalpy change (ΔH) and entropy change (ΔS) on transition from FHW/D to PHW/D are determined based on Gaussian fitting. At low temperatures, a higher ΔHD2O (8.62 ± 0.06 kJ mol−1) than ΔHH2O (7.19 ± 0.05 kJ mol−1) further indicates that O…D–O is about 20% stronger than O…H–O. However, difference between O…D–O strength and O…H–O strength tends to diminish above 434 K, suggested by the rather close ΔHD2O and ΔHH2O, and same value of ΔSD2O and ΔSH2O. Copyright © 2017 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 70%

Section: Resultsmentioning

confidence: 91%

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Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure

Ouyang

et al. 2017

J Raman Spectroscopy

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“…Dissolved NaCl reduces the width of the OH‐stretching band and causes the band position shift toward higher Raman shift wavenumbers. This change in the band shape is similar to the effect of increasing temperature on the Raman spectra of water . The raw data for Fig.…”

Section: Resultsmentioning

confidence: 99%

Temperature and salinity effects on the Raman scattering cross section of the water OH-stretching vibration band in NaCl aqueous solutions from 0 to 300 °C

Lü

et al. 2016

J. Raman Spectrosc.

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Water is often used as an internal standard in quantitative Raman spectroscopic measurements of dissolved species in aqueous solutions containing salts at varying temperatures. However, the effects of temperature and dissolved ions on the relative differential Raman scattering cross section (RSCS) of the OH‐stretching vibration band of water at elevated temperatures and salinities are not well defined quantitatively. In this study, the Raman spectra of NaCl solutions with different salinity (from 0 to 5 mol NaCl/kg · H2O) at 20 °C at atmospheric pressure and from 0 to 300 °C at 30 MPa were studied. The relative RSCS of the OH‐stretching vibration band of liquid water (σ(mNaCl, T, 30 MPa)/σ(Pure water, 20 °C, 30 MPa)) as a function of temperature (T, in °C) and salinity (mNaCl, in mol/kg · H2O) was established: σmNaCl,T,30MPatrue/σtrue(Pure water,0.25em20oC,0.25em300.25emMPatrue)=f()T,mNaCl0.25em=a()T−20+b where a = 0.000089 × mNaCl1/2 − 0.001164; b = 0.0355 × mNaCl + 1; The RSCS of the OH‐stretching vibration band of water in pseudo back‐scattering geometry decreases linearly with increasing temperature, but increases with the addition of dissolved NaCl within the whole temperature range. The enhancement factor of the RSCS by dissolved NaCl increases with temperature. Such effects of temperature and salinity should be considered in quantitative Raman spectroscopic study of species concentration in aqueous solution at high temperature when using water as internal standard. Copyright © 2016 John Wiley & Sons, Ltd.

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“…According to the phase diagram in Appendix (Figure 8), water under 30 MPa pressure remains its liquid states in the temperature range from 253 to 753 K. Figure 5a shows the Raman spectra of the H-O stretching vibration, ω L , of water under such conditions, as probed by Hu et al [35]. Initially, the spectra are dominated by both the 3200 cm -1 bulk mode and the 3450 cm -1 skin mode.…”

Section: Thermal Relaxation Of H-o Bond Under 300 Mpa Pressurementioning

confidence: 94%

Water's phase diagram: From the notion of thermodynamics to hydrogen-bond cooperativity

Zhang

Sun

Yan

et al. 2015

Progress in Solid State Chemistry

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An extensive study on Raman spectra of water from 253 to 753 K at 30 MPa: A new insight into structure of water

Cited by 60 publications

References 27 publications

Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure

Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure

Temperature and salinity effects on the Raman scattering cross section of the water OH-stretching vibration band in NaCl aqueous solutions from 0 to 300 °C

Water's phase diagram: From the notion of thermodynamics to hydrogen-bond cooperativity

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An extensive study on Raman spectra of water from 253 to 753 K at 30 MPa: A new insight into structure of water

Cited by 60 publications

References 27 publications

Raman spectroscopic investigation on pure D2O/H2O from 303 to 573 K: interpretation and implications for water structure

Raman spectroscopic investigation on pure D2O/H2O from 303 to 573 K: interpretation and implications for water structure

Temperature and salinity effects on the Raman scattering cross section of the water OH-stretching vibration band in NaCl aqueous solutions from 0 to 300 °C

Water's phase diagram: From the notion of thermodynamics to hydrogen-bond cooperativity

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Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure

Raman spectroscopic investigation on pure D₂O/H₂O from 303 to 573 K: interpretation and implications for water structure