Temperature, pressure, and isotope effects on the structure and properties of liquid water: A lattice approach

Abstract

We present a lattice model to describe the effect of isotopic replacement, temperature, and pressure changes on the formation of hydrogen bonds in liquid water. The approach builds upon a previously established generalized lattice theory for hydrogen bonded liquids [B. A. Veytsman, J. Phys. Chem. 94, 8499 (1990)], accounts for the binding order of 1/2 in water-water association complexes, and introduces the pressure dependence of the degree of hydrogen bonding (that arises due to differences between the molar volumes of bonded and free water) by considering the number of effective binding sites to be a function of pressure. The predictions are validated using experimental data on the temperature and pressure dependence of the static dielectric constant of liquid water. The model is found to correctly reproduce the experimentally observed decrease of the dielectric constant with increasing temperature without any adjustable parameters and by assuming values for the enthalpy and entropy of hydrogen bond formation as they are determined from the respective experiments. The pressure dependence of the dielectric constant of water is quantitatively predicted up to pressures of 2 kbars and exhibits qualitative agreement at higher pressures. Furthermore, the model suggests a--temperature dependent--decrease of hydrogen bond formation at high pressures. The sensitive dependence of the structure of water on temperature and pressure that is described by the model rationalizes the different solubilization characteristics that have been observed in aqueous systems upon change of temperature and pressure conditions. The simplicity of the presented lattice model might render the approach attractive for designing optimized processing conditions in water-based solutions or the simulation of more complex multicomponent systems.

Temperature effects on the hydrophobic interaction of parallel plates in the framework of the probabilistic approach to hydrogen bonding

“…The (solvent-mediated) hydrophobic interaction of solutes is affected by the solvent (water) temperature because the density of the solvent, strength of a hydrogen bonds, and number of hydrogen bonds per molecule are sensitive thereto [13,[25][26][27], -all these characteristics enter the PHB model [15][16][17][18]. They depend on the external pressure (whereto the solvent is subjected) [13,25,26] as well, but this effect was not be considered. The tetrahedral rigidity of the hydrogen bonding armes of a model water molecule was assumed to be unaffected by changing temperature.…”

Solution properties of a heteropolysaccharide extracted from pumpkin ( Cucurbita pepo , lady godiva)

“…On the other hand, the decrease in viscosity was a result of intramolecular hydrophobic associations and variation of M w led to simultaneous variation of electrostatic and hydrophobic interactions (Nichifor, Stanciu, Ghimici, & Simionescu, 2011). Studies on solvents also revealed that, in the case of water, the stability of the hydrogen bonds decreased with increasing temperature (at 300-400 • C, they have disappeared completely) due to the increasing influence of the entropy loss associated with the formation of bonds (Hakem, Boussaid, Benchouk-Taleb, & Bockstaller, 2007;Postorino, Tromp, Ricci, Soper, & Neilson, 1993). Besides, a temperature rise caused a restructuring of the hydrogen bonded network, since the stability of hydrogen bonds decreased, accompanied by a drop (of about 20%) in the number of OH groups that were closely associated (Hakem et al, 2007).…”

“…Studies on solvents also revealed that, in the case of water, the stability of the hydrogen bonds decreased with increasing temperature (at 300-400 • C, they have disappeared completely) due to the increasing influence of the entropy loss associated with the formation of bonds (Hakem, Boussaid, Benchouk-Taleb, & Bockstaller, 2007;Postorino, Tromp, Ricci, Soper, & Neilson, 1993). Besides, a temperature rise caused a restructuring of the hydrogen bonded network, since the stability of hydrogen bonds decreased, accompanied by a drop (of about 20%) in the number of OH groups that were closely associated (Hakem et al, 2007). Furthermore, the physicochemical properties of large biopolymers were also associated with pH of medium.…”

Polymer sequencing by molecular machines: a framework for predicting the resolving power of a sliding contact force spectroscopy sequencing method

“…. 29,30 In subsequent analyses presented below we use the free energy of sliding ΔG sl rather than equilibrium force f eq since the latter quantity is dependent on the spring constant of the particular cantilever used, 24 making direct comparison of values obtained with different cantilevers more difficult. ΔG sl is calculated from the value of f eq and the spring constant of the cantilever used and is therefore directly comparable across different experiments.…”