The Dielectric Constant of Water at High Temperatures and in Equilibrium with its Vapor

Åkerlöf, Gösta; Oshry, Howard I.

doi:10.1021/ja01163a006

Cited by 165 publications

(73 citation statements)

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“…͑12͔͒. They were deduced by fitting the theoretical results for dielectric constant ͑ o ͒ at low field strengths ͑where E Ӷ kT͒ to experimental data 41 over temperatures ranging from the freezing to the critical point of water. The quality of fit of results of the proposed theory, with u HB = −5.58 Kcal/ mole of H-bonds and s HB = −6.8 cal/ deg/ mole of H-bonds, vis a vis experimental data reported in the past is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Influence of electric field on the hydrogen bond network of water

Suresh

Satish

Choudhary

2006

The Journal of Chemical Physics

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Understanding the inherent response of water to an external electric ͑E͒-field is useful towards decoupling the role of E-field and surface in several practically encountered situations, such as that near an ion, near a charged surface, or within a biological nanopore. While this problem has been studied in some detail through simulations in the past, it has not been very amenable for theoretical analysis owing to the complexities presented by the hydrogen ͑H͒ bond interactions in water. It is also difficult to perform experiments with water in externally imposed, high E-fields owing to dielectric breakdown problems; it is hence all the more important that theoretical progress in this area complements the progress achieved through simulations. In an attempt to fill this lacuna, we develop a theory based on relatively simple concepts of reaction equilibria and Boltzmann distribution. The results are discussed in three parts: one pertaining to a comparison of the key features of the theory vis a vis published simulation/experimental results; second pertaining to insights into the H-bond stoichiometry and molecular orientations at different field strengths and temperatures; and the third relating to a surprising but explainable finding that H-bonds can stabilize molecules whose dipoles are oriented perpendicular to the direction of field ͑in addition to the E-field and H-bonds both stabilizing molecules with dipoles aligned in the direction of the field͒.

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Section: Resultsmentioning

confidence: 99%

Influence of electric field on the hydrogen bond network of water

Suresh

Satish

Choudhary

2006

The Journal of Chemical Physics

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“…The observed change in hydrogen bonding parallels with a change in the dielectric constant of water. For example, the dielectric constant of water is approximately 80 at 25 °C, compared with approximately 20 at 300 °C . With such a low dielectric constant, HCW behaves more as an organic solvent rather than ambient liquid water.…”

Section: Resultsmentioning

confidence: 99%

“…For example, the dielectric constant of water is approximately 80 at 25°C, compared with approximately 20 at 300°C. [45] With such a low dielectric constant, HCW behaves more as an organic solvent rather than ambient liquid water. The latest study demonstrated that the relative Raman scattering cross section of the O-H stretching vibration band of water decreases linearly with increasing temperature.…”

Section: Dissolution Mechanism Of 12-dichlorobenzene In Hot Compressmentioning

confidence: 99%

In situ Raman spectroscopy investigation of the solubility and dissolution mechanism of 1,2‐dichlorobenzene in hot compressed water in a fused silica capillary reactor

Bei

Chen

Wang

et al. 2017

J Raman Spectroscopy

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Hot compressed water (HCW), with its unique properties, is regarded as a promising solvent for industrial applications. A number of methods to measure the solubility of hydrophobic organic compounds (HOCs) in HCW have been reported. However, these methods were conducted in large‐scale stainless‐steel reactors, and few included an in situ study regarding the dissolution mechanism of HOCs in HCW during the solubility determination process. In this study, a fused silica capillary reactor in combination with Raman spectroscopy was applied to investigate phase changes, determine the solubility, and study the dissolution mechanism of 1,2‐dichlorobenzene in HCW. The total dissolution process of 1,2‐dichlorobenzene in HCW was observed under a microscope, and the images were recorded continuously using a digital camera. Raman spectroscopy was used to confirm the homogeneity of the 1,2‐dichlorobenzene solution during dissolution. The solubility of 1,2‐dichlorobenzene increased from 35.9 to 85.7 mg g−1 in water with increasing temperature from 256.7 to 294.1 °C. Furthermore, the dissolution mechanism of 1,2‐dichlorobenzene in HCW is proposed based on the Raman spectra of 1,2‐dichlorobenzene and water during the dissolution process in the fused silica capillary reactor. The breakage of the fully hydrogen‐bonded (tetrahedral) configuration and the consequent change in the static dielectric constant of water are deemed to be compelling reasons for the high solubility of 1,2‐dichlorobenzene in HCW. Our experimental method exhibits great potential for determining the solubility of HOCs in HCW and for investigating their dissolution behavior and dissolution mechanism at elevated pressure and temperature conditions. Copyright © 2017 John Wiley & Sons, Ltd.

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“…The dielectric constant of water is calculated to 100°C from the equation of Wyman and Ingalls as cited by Harned and Owen (1958, p. 159); it is calculated at higher temperatures from the function of Akerlof and Oshry (1950). ( The activity coefficients of all neutral species are assumed equal to the activity coefficients of dissolved CCU in NaCl solutions (Helgeson, 1967).…”

Section: Activity Coefficientsmentioning

confidence: 99%

Dewatering of the Clayton Formation during construction of the Walter F George Lock and Dam, Fort Gaines, Clay County, Georgia

1973

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The Dielectric Constant of Water at High Temperatures and in Equilibrium with its Vapor

Cited by 165 publications

References 0 publications

Influence of electric field on the hydrogen bond network of water

Influence of electric field on the hydrogen bond network of water

In situ Raman spectroscopy investigation of the solubility and dissolution mechanism of 1,2‐dichlorobenzene in hot compressed water in a fused silica capillary reactor

Dewatering of the Clayton Formation during construction of the Walter F George Lock and Dam, Fort Gaines, Clay County, Georgia

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