Thermodynamic anomalies in a lattice model of water: solvation properties

We investigate a lattice-fluid model of water, defined on a three-dimensional body-centered-cubic lattice. Model molecules possess a tetrahedral symmetry, with four equivalent bonding arms. The model is similar to the one proposed by Roberts and Debenedetti [J. Chem. Phys. 105, 658 (1996)], simplified by removing distinction between "donors" and "acceptors." We focus on the solvation properties, mainly as far as an ideally inert (hydrophobic) solute is concerned. As in our previous analysis, devoted to neat water [J. Chem. Phys. 121, 11856 (2004)], we make use of a generalized first-order approximation on a tetrahedral cluster. We show that the model exhibits quite a coherent picture of water thermodynamics, reproducing qualitatively several anomalous properties observed both in pure water and in solutions of hydrophobic solutes. As far as supercooled liquid water is concerned, the model is consistent with the second critical-point scenario.     

Thermodynamic anomalies in a lattice model of water

We investigate a lattice-fluid model of water, defined on a three-dimensional body centered cubic lattice. Model molecules possess a tetrahedral symmetry, with four equivalent bonding arms, aiming to mimic the formation of hydrogen bonds. The model is similar to the one proposed by Roberts and Debenedetti [J. Chem. Phys. 105, 658 (1996)], simplified in that no distinction between bond "donors" and "acceptors" is imposed. Bond formation depends both on orientation and local density. In the ground state, we show that two different ordered (ice) phases are allowed. At finite temperature, we analyze homogeneous phases only, working out phase diagram, response functions, the temperature of maximum density locus, and the Kauzmann line. We make use of a generalized first-order approximation on a tetrahedral cluster. In the liquid phase, the model exhibits several anomalous properties observed in real water. In the low temperature region (supercooled liquid), there are evidences of a second critical point and, for some range of parameter values, this scenario is compatible with the existence of a reentrant spinodal.     

Thermodynamic properties of lattice hard-sphere models

Thermodynamic properties of several lattice hard-sphere models were obtained from grand canonical histogram- reweighting Monte Carlo simulations. Sphere centers occupy positions on a simple cubic lattice of unit spacing and exclude neighboring sites up to a distance sigma. The nearestneighbor exclusion model, sigma = radical2, was previously found to have a second-order transition. Models with integer values of sigma = 1 or 2 do not have any transitions. Models with sigma = radical3 and sigma = 3 have weak first-order fluid-solid transitions while those with sigma = 2 radical2, 2 radical3, and 3 radical2 have strong fluid-solid transitions. Pressure, chemical potential, and density are reported for all models and compared to the results for the continuum, theoretical predictions, and prior simulations when available.     

A lattice Monte Carlo simulation of the FePt alloy using a first-principles renormalized four-body interaction

Although a lattice Monte Carlo method provides an effective, simple, and fast way to study thermodynamic properties of substitutional alloys, it cannot treat by itself the off-lattice effects, such as thermal vibrations and local distortions. Therefore, even if the interaction among atoms at lattice points is calculated accurately by means of first-principles calculations, the lattice Monte Carlo simulation overestimates the order-disorder phase transition temperature. In this paper, we treat this problem in the investigation of the FePt alloy, which has recently attracted considerable interest in its magnetic properties. We apply a simple version of the potential renormalization theory to determine the interaction among atoms, including partly the off-lattice effects by means of first-principles calculations. Then, we use the interaction to perform a lattice Monte Carlo simulation of the FePt alloy on a fcc lattice. From the results, we find that the transition temperature obtained after the present renormalization procedure becomes closer to the experimental value.     

Thermodynamic stability and kinetic foldability of a lattice protein model

By using serial mutations, i.e., a residue replaced by 19 kinds of naturally occurring residues, the stability of native conformation and folding behavior of mutated sequences are studied. The 3 x 3 x 3 lattice protein model with two kinds of interaction potentials between the residues, namely the original Miyazawa and Jernigan (MJ) potentials and the modified MJ potentials (MMJ), is used. Effects of various sites in the mutated sequences on the stability and foldability are characterized through the Z-score and the folding time. It is found that the sites can be divided into three types, namely the hydrophobic-type (H-type), the hydrophilic-type (P-type) and the neutral-type (N-type). These three types of sites relate to the hydrophobic core, the hydrophilic surface and the parts between them. The stability of the native conformation for the serial mutated sequences increases (or decreases) as the increasing in the hydrophobicity of the mutated residues for the H-type sites (or the P-type sites), while varies randomly for the N-type sites. However, the foldability of the mutated sequences is not always consistent with the thermodynamic stability, and their relationship depends on the site types. Since the hydrophobic tendency of the MJ potentials is strong, the ratio between the number of the H-type sites and the number of the P-type sites is found to be 1:2. Differently, for the MJJ potentials it is found that such a ratio is about 1:1 which is relevant to that of real proteins. This suggests that the modification of the MJ potentials is rational in the aspect of thermodynamic stability. The folding of model proteins with the MMJ potentials is fast. However, the relationship between the foldability and the thermodynamic stability of the mutated sequences is complex.     

Thermodynamic and structural properties of a fluid with a rectangular well potential

Thermodynamic and structural properties of a system with a rectangular well potential are investigated in the supercritical region using the approximate Martynov-Sarkisov (MS) integral equation for the binary distribution function. It is shown that, in contrast to other approximations, in particular the Percus-Yevick equation (PY) and hypernetted chain approximation (HNC), the MS equation describes the limits of existence of the homogeneous phase.Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences, Pushchino. State University of New York, Mt. Sinai Medical Center, USA. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 88–95, March–April, 1993.     

Thermodynamic and dynamic anomalies in a one-dimensional lattice model of liquid water

We investigate the occurrence of waterlike thermodynamic and dynamic anomalous behavior in a one dimensional lattice gas model. The system thermodynamics is obtained using the transfer matrix technique and anomalies on density and thermodynamic response functions are found. When the hydrogen bond (molecules separated by holes) is more attractive than the van der Waals interaction (molecules in contact) a transition between two fluid structures is found at null temperature and high pressure. This transition is analogous to a 'critical point' and intimately connects the anomalies in density and in thermodynamic response functions. Monte Carlo simulations were performed in the neighborhood of this transition and used to calculate the self diffusion constant, which increases with density as in liquid water.     

Thermodynamic properties of a shell molecule-gas particles system

A Lennard-Jones potential is used to derive formulaefor the potential of interaction between shell macromolecules and gas atoms. Calculations are carried as far as thespherical symmetry approximation. The potential of interaction determines the stability of a shell topological compound. When the distance R between a shell molecule and a gas atom is equal the radius 1 of the outer shell, the potential is the highest and determines a barrier, which must be lower than an energy of the trapped/by the shell molecule/atom to be released.     

Thermodynamic properties of the intermediate phases of a Ag-Te-AgBr system

Silver interaction in galvanic elements C|Ag|Ag₃GeS₃I|B|C with heterophase alloys of the system (C corresponds to current electrodes; B, to heterophase alloys of the Ag-Te-AgBr system; and Ag₃GeS₃I, to glassy alloy with pure ionic (Ag⁺) electroconductivity) was studied. Data on the EMF temperature dependence of galvanic elements are used to calculate the values of thermodynamic functions for α-Ag₅Te₃, β-Ag₂Te, and α-Ag₃TeBr phases in the standard state.     

Thermodynamic properties of Al-Y system melts

The thermochemical properties of Al-Y melts were determined by isoperibolic calorimetry. It was established that the minimal value of integral mixing enthalpies is equal to −40.8 + 0.4 kJ/mol at 1770 K and x _Y = 0.41. The thermodynamic properties of liquid alloys were modeled by the developed procedure using the coordinates of a liquidus line in the phase diagram of the Al-Y system, and by the theory of ideal associated solutions. The component activities exhibit high negative deviations from the Raoult law. The Gibbs energies of mixing of Al-Y melts have a minimum of −30.6 kJ/mol at x _Y = 0.48.     

The renormalized Jellium model of colloidal suspensions with multivalent counterions

An extension of the renormalized Jellium model which allows to study colloidal suspensions containing trivalent counterions is proposed. The theory is based on a modified Poisson-Boltzmann equation which incorporates the effects of counterion correlations near the colloidal surfaces using a new boundary condition. The renormalized charges, the counterion density profiles, and osmotic pressures can be easily calculated using the modified renormalized Jellium model. The results are compared with the ones obtained using the traditional Wigner-Seitz (WS) cell approximation also with a new boundary condition. We find that while the thermodynamic functions obtained within the renormalized Jellium model are in a good agreement with their WS counterpart, the effective charges predicted by the two theories can be significantly different.     

Structural properties of a model system with effective interparticle interaction potential applicable in modeling of complex fluids

We report grand canonical ensemble Monte Carlo (MC) simulation and theoretical studies of the structural properties of a model system described by an effective interparticle interaction potential, which incorporates basic interaction terms used in modeling of various complex fluids composed of mesoscopic particles dispersed in a solvent bath. The MC results for the bulk radial distribution function are employed to test the validity of the hard-sphere bridge function in combination with a modified hypernetted chain approximation (MHNC) in closing the Ornstein-Zernike (OZ) integral equation, while the MC data for the density profiles in different inhomogeneous environments are used to assess the validity of the third-order+second-order perturbation density functional theory (DFT). We found satisfactory agreement between the results predicted by the pure theories and simulation data, which classifies the proposed theoretical approaches as convenient tools for the investigation of complex fluids. The present investigation indicates that the bridge function approximation and density functional approximation, which are traditionally used for the study of neutral atomic fluids, also perform well for complex fluids only on condition that the underlying effective potentials include a highly repulsive core as an ingredient.     

Thermodynamic evaluation of a partial charge model assumptionfor the dissolved silica system

The Partial Charge Model was developed to predict the hydroxylation, polymerization, and precipitation of ions. The purpose of this study is to evaluate the Partial Charge Model for describing the polymerization of silica in aqueous solutions. The Partial Charge Model predicts the stability of ions and complexes based on the assumption that the stable species will have the same electronegativity as the mean electronegativity of the solution. The silica system was chosen for model validation because of the rare availability of self-consistent thermodynamic data on many dissolved but polymerized silicate anions, including both linear and cyclical species. The electronegativity of each species was calculated using the Partial Charge Model and the results were plotted against the stability constants for the ions. The silicate anions segregated into groups on the plot based on the number of charges per silicon atom in the polymer. Plots of the log of the stability constant versus the change in electronegativity produced a linear relationship for the silica polymers containing one negative charge per silicon atom, which resulted in an r ² of 0.9978. Thus, the Partial Charge Model successfully describes the thermodynamics of silica polymerization in aqueous solution for species that are sufficiently alike, but was not accurate for all silica species.     

Thermodynamic properties of complex oxides in the La-Ni-O system

Complex oxides La₂NiO_4+δ, La₃Ni₂O_7−δ, La₄Ni₃O_10−δ and LaNiO_3−δ, the members of Ruddlesden-Popper series La_n+1Ni_nO_3n+1, were prepared using citrate precursors. The stability range of LaNiO_3−δ in air as well as the oxygen nonstoichiometry of La₃Ni₂O_7−δ and La₄Ni₃O_10−δ as a function of temperature and oxygen partial pressure was determined by means of thermogravimetric technique. Decomposition temperatures of La₃Ni₂O_7−δ, La₄Ni₃O_10−δ and LaNiO_3−δ in air were determined by conductivity measurement method. The boundary of stability for La₄Ni₃O_10−δ was determined by EMF measurements of galvanic cell with oxygen conducting solid electrolyte. The isothermal (1400 K) projection of La-Ni-O system phase diagram to the plane “log(PO₂)-relative mole fraction of metal components” was suggested.     

Thermodynamic properties of melts based on the Al-Sm system

The equilibrium composition and thermodynamic characteristics of melts based on the Al-Sm system were studied by thermodynamic modeling using the ideal solution model of reaction products over the whole range of compositions 0 ?? x _Al ?? 1 in argon at a total pressure of 1 atm and temperatures from 1873 to 2100 K.     

Thermodynamic properties of the intermediate phases of the Ag-Sb-Se system

The emf (?) dependence of C|Ag|AgI|glass Ag₂GeS₃|D|C galvanic elements on temperature is studied in the range of 470 to 575 K (C represents current electrodes, D denotes equilibrium three-phase alloys of individual Ag-Sb-Se systems, and AgI|glass Ag₂GeS₃ is a bilayer membrane with purely ionic (Ag⁺) electroconductivity). Analytical equations ? = ?(T) are used to calculate the thermodynamic functions of saturated solid solutions of the AgSbSe₂, Sb₂Se₃, and Ag₂Se phases of the Ag-Sb-Se system in the standard state.     

Thermodynamic properties and phase equilibria of the lead-tellurium binary system

The liquidus curve of the Pb-Te binary was measured using two different DTA systems, one employing a small sample (0.2 g) and the second a large sample (5 g). An additional liquidus measurement method was employed for the Pb-rich region in which the liquid equilibrated with PbTe was analyzed chemically. The liquidus for the Pb-PbTe subsystem obtained is in agreement with several sets of data reported in the literature. The literature data for the PbTe-Te are in disagreement. Our measured values resolve this discrepancy and yield a eutectic temperature of 410.9±0.8°C at 89.1±0.3 at % Te. The system was thermochemically modelled using an associated solution model for the liquid phase and a defect model for PbTe. This model not only accounts for compositional and temperature dependences of the thermodynamic data but also for electron and hole concentrations within the homogeneous range of PbTe(c).On leave from India Institute of Technology-Kanpur, Kanpur, India.     

Thermodynamic properties of citric acid and the system citric acid-water

The binary system citric acid-water has been investigated with static vapour pressure measurements, adiabatic calorimetry, solution calorimetry, solubility measurements and powder X-ray measurements. The data are correlated by thermodynamics and a large part of the phase diagram is given. Molar heat capacities of citric acid are given from 90 to 330 K and for citric acid monohydrate from 120 to 300 K. The enthalpy of compound formation Δ_comH (298.15 K)=(?11.8±1) kJ mole^?1.