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Hydrogen Bonding in Supercritical Water

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Near-critical and Supercritical Water and Their Applications for Biorefineries

Part of the book series: Biofuels and Biorefineries ((BIOBIO,volume 2))

Abstract

Hydrogen bonding (HB) in supercritical water (SCW) is much less extensive than in water at ambient conditions. Still, it plays an important role in the structural and dynamic properties of SCW and its capacity as a solvent. In order to deal with the HB it is necessary to have definite criteria that specify when a hydrogen bond exists or not, and these are provided. The extent of HB in SCW is expressed by means of the mean number of hydrogen bonds per water molecule, the fractions of water molecules with 0, 1, 2… hydrogen bonds, and the percolation limit determining regions of continuous HB. The HB in SCW deduced from diffraction, spectroscopy, and computer simulations is described. The ionic dissociation of SCW itself is more extensive at low temperatures and high pressures than of ambient water. The solvent power of SCW regarding organic solutes is described by its solubility parameters, but solvatochromic probes have found little use in SCW. The solubility of salts in SCW and the hydration and pairing of their ions are discussed. HB as well as its related ion product and thermodynamic data of water plays an important role in biomass dissolution and reactions in SCW. The appendix contains tables of physical properties of SCW at temperatures and pressures relevant to biorefining.

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  1. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel

    Yizhak Marcus

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Correspondence to Yizhak Marcus .

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Editors and Affiliations

  1. Chinese Academy of Sciences, Xishuangbanna Tropical Botanical Garden, Kunming, China

    Zhen Fang

  2. Western University, London, Canada

    Chunbao (Charles) Xu

Appendix

Appendix

Some physicochemical properties of SCW at the temperatures and pressures applicable to bio-refining are required in order to benefit fully from the book. The values recorded here are adapted from Marcus [5], where references to the original publications are available. The critical temperature of water is T c = 647.096 K = 373.946 °C and its critical pressure is P c = 22.064 MPa = 217.8 atm. The critical density of water is ρ c = 322 kg·m–3 and its critical molar volume is V c = 56.0 × 10–6 m3·mol–1. Molar volumes, V, corresponding to the densities, ρ, are obtained by division of the molar mass of water, 0.01802 kg·mol–1 by the densities (and multiplication by 106 cm3·m–3 in order to obtain the volumes in cm3·mol–1).

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Marcus, Y. (2014). Hydrogen Bonding in Supercritical Water. In: Fang, Z., Xu, C. (eds) Near-critical and Supercritical Water and Their Applications for Biorefineries. Biofuels and Biorefineries, vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-8923-3_1

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