Are lattice models valid for fluids with hydrogen bonds?

Veytsman, Boris

doi:10.1021/j100386a002

Cited by 200 publications

(189 citation statements)

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“…20 Of particular relevance to the present paper is the work by Veytsman, 21 Wertheim,22,23 and Stell and Zhou. 24 Despite the approaches followed by each of them being different, the final equations describing the equilibrium properties of water were found to be similar in a͒ Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 85%

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: Introductionmentioning

confidence: 85%

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 hydrogen-bonding Helmholtz energy is found from a proposal of Veytsman (Veytsman, 1990;Panayiotou and Sanchez, 1991;Gupta et al, 1992) and further improvement by Gupta and Johnston (1994) using local-segment density. The derivation was based on the combinatorial expression for distributing hydrogen bonds between given donor and acceptor sites.…”

Section: Systems With Specific Interactions (Hydrogen Bonding)mentioning

confidence: 99%

Vapor−Liquid Equilibria for Solvent−Polymer Systems from a Perturbed Hard-Sphere-Chain Equation of State

Gupta

Prausnitz

1996

Ind. Eng. Chem. Res.

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Vapor−liquid equilibria (VLE) for solvent−polymer mixtures at modest pressures are obtained from a perturbed hard-sphere-chain equation of state. This equation of state is the sum of a hard-sphere-chain term as the reference system and a van der Waals attractive term as the perturbation. The reference equation follows from the Percus−Yevick integral theory coupled with chain connectivity as described by Chiew. The effect of specific interactions, such as hydrogen bonding, is introduced through the proposal of Veytsman based on the statistical distribution of hydrogen bonds between donor and acceptor sites suggested by molecular structure. Calculated and observed vapor−liquid equilibria are presented for nonpolar, polar, and hydrogen-bonding solvent + homopolymer systems. Pure-component parameters (number of segments per molecule, segment−segment energy, and segment diameter) are obtained from pure-component properties: liquid density and vapor pressure data for normal fluids and pressure−volume−temperature data for polymers. A binary energy interaction parameter must be obtained from limited VLE data for each binary system; this parameter appears to be independent of temperature and composition over a useful range. Theoretical correlations and predictions are in good agreement with experiment.

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“…Two observations are of special interest. One is their ability to predict the qualitative features of the phase diagram and fit experimentally observed phase boundaries [7,8,9,10,12,13,14,15]. The second concerns the stretching of PEO chains in atomic force microscopy experiments.…”

Section: Discussionmentioning

confidence: 99%

On the Adsorption of Two-State Polymers

2008

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Monte Carlo(MC) simulations produce evidence that annealed copolymers incorporating two interconverting monomers, P and H, adsorb as homopolymers with an effective adsorption energy per monomer, ǫ ef f , that depends on the PH equilibrium constants in the bulk and at the surface.The cross-over exponent, Φ, is unmodified. The MC results on the overall PH ratio, the PH ratio at the surface and in the bulk as well as the number of adsorbed monomers are in quantitative agreement with this hypothesis and the theoretically derived ǫ ef f . The evidence suggests that the form of surface potential does not affect Φ but does influence the PH equilibrium.

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Are lattice models valid for fluids with hydrogen bonds?

Abstract: A Flory-like approximation for a lattice model of fluid mixture with hydrogen bonds is proposed. The obtained excess free energy due to H bonds is consistent in the limiting cases with the asymptotics derived by Huyskens, but it is valid for the general case also.

Cited by 200 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

Vapor−Liquid Equilibria for Solvent−Polymer Systems from a Perturbed Hard-Sphere-Chain Equation of State

On the Adsorption of Two-State Polymers

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