Chemical, quasi‐chemical and perturbation theories for associating fluids

Economou, Ioannis G.; Donohue, Marc D.

doi:10.1002/aic.690371212

Cited by 138 publications

(108 citation statements)

References 57 publications

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“…The degree of hydrogen bonding at supercritical condition was estimated and compared with the results of NPT molecular-dynamics calculations and with available experimental data. To accurately reproduce the thermodynamic behavior of associating fluids (hydrogen bonding sys-tems), Economou and Donohue [20] have developed chemical, quasichemical, and perturbation (physical) theories that explicitly take into account hydrogen-bonding interactions. It has been shown that all three approaches lead to expressions that are of the same functional form for pure components and for mixtures.…”

Section: Classical Analytical Modelsmentioning

confidence: 99%

“…However, because of the complexity of methanol, there are neither representative experimental data nor predictive thermodynamic models available that will offer sufficient insight for optimum process design. Existing semi-empirical and statistical-mechanics-based thermodynamic models [19][20][21][22][23][24][25][26][27] have not yet been developed to a degree that they can be used for an accurate prediction of the thermodynamic properties of methanol in the critical and supercritical regions. Therefore, development of a thermodynamically self-consistent theoretically based model for prediction of thermodynamic properties of methanol close to and far away from the critical point is an important goal.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

et al. 2005

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The isochoric heat capacity of pure methanol in the temperature range from 482 to 533 K, at near-critical densities between 274.87 and 331.59 kg · m −3 , has been measured by using a high-temperature and high-pressure nearly constant volume adiabatic calorimeter. The measurements were performed in the singleand two-phase regions including along the coexistence curve. Uncertainties of the isochoric heat capacity measurements are estimated to be within 2%. The single-and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. The critical temperature (T c = 512.78 ± 0.02 K) and the critical density (ρ c = 277.49 ± 2 kg · m −3 ) for pure methanol were derived from the isochoric heat-capacity measurements by using the well-established method of quasi-static thermograms. The results of the C V V T measurements together with recent new experimental PVT data for pure methanol were used to develop a thermodynamically self-consistent Helmholtz free-energy parametric crossover model, CREOS97-04. The accuracy of the crossover model was confirmed by a comprehensive comparison with available experimental data for pure methanol and values calculated with various multiparameter equations of state and correlations. In the critical and supercritical regions at 0.98T c T 1.5T c and in the density range 0.35ρ c ρ 1.65ρ c , CREOS97-04 represents all available experimental thermodynamic data for pure methanol to within their experimental uncertainties.

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Section: Classical Analytical Modelsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

et al. 2005

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“…Different approaches are used for complex liquids, and especially for those with H-bonds [4][5][6][7][8]12]. The first ones are physical statistical-mechanical models, e.g., SAFT (statistical associated fluid theory) [13], based on Wertheim's perturbation theory; secondly, the lattice models, founded on Guggenheim-Barker theory [14], and its further modifications, e.g., LFHB (lattice fluid hydrogen bond) [15], and finally the chemical ones, combining extensions of hard sphere approaches for anisotropic particles with equations for chemical equilibria [12].…”

Section: Description Of Liquid Structurementioning

confidence: 99%

Models of liquid mixtures: Structure, dynamics, and properties

Durov

2004

Pure and Applied Chemistry

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Models of the structure and properties of liquid mixtures are outlined. The main focus is on quasichemical models for the modeling of supramolecular ordering in mixtures, self-organized by H-bonds, leading to a unified description of their physicochemical properties. Models of polyvariable supramolecular species are discussed with respect to structure and composition of the mixtures, taking into account the cooperativity of H-bonding, and leading to a description of electric (dipole moment) and optic (polarizability) properties. We analyze the interrelations of thermodynamic functions (Gibbs energy, enthalpy, entropy), dielectric (permittivity) and optical properties (refractive index and its fluctuation derivatives, defining Rayleigh light scattering) of nonideal mixtures as well as the microscopic characteristics of the aggregates. Methods are developed in order to obtain both integral and differential parameters of aggregation. Models for the description of supramolecular reorganization, intramolecular transitions, and energy transfer during molecular thermal motion as well as fluctuation and relaxation phenomena are considered. Applications both to liquids and mixtures are outlined. The supramolecular assemblies in liquids with long-range molecular correlations are established. Macroscopic manifestations of the supramolecular organization in the properties of liquids are characterized.

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“…One aspect of the network view of liquid water is that models with defined short-ranged hydrogen bonding interactions that vanish precisely outside a finite range are designed specifically to study the network characteristics of that fluid. The work of Peery & Evans 1 gives a recent example that reviews and advances the forefront of statistical mechanical theory built explicitly on that network concept; this line of inquiry does indeed have an extended history, and the citations 2,3,4,5,6 give further examples. The finite range of interactions is a common feature of lattice-gas models of liquid water.…”

Section: Introductionmentioning

confidence: 99%

Balancing local order and long-ranged interactions in the molecular theory of liquid water

Shah

Asthagiri

Pratt

et al. 2007

The Journal of Chemical Physics

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A molecular theory of liquid water is identified and studied on the basis of computer simulation of the TIP3P model of liquid water. This theory would be exact for models of liquid water in which the intermolecular interactions vanish outside a finite spatial range, and therefore provides a precise analysis tool for investigating the effects of longer-ranged intermolecular interactions. We show how local order can be introduced through quasi-chemical theory. Long-ranged interactions are characterized generally by a conditional distribution of binding energies, and this formulation is interpreted as a regularization of the primitive statistical thermodynamic problem. These bindingenergy distributions for liquid water are observed to be unimodal. The gaussian approximation proposed is remarkably successful in predicting the Gibbs free energy and the molar entropy of liquid water, as judged by comparison with numerically exact results. The remaining discrepancies are subtle quantitative problems that do have significant consequences for the thermodynamic properties that distinguish water from many other liquids. The basic subtlety of liquid water is found then in the competition of several effects which must be quantitatively balanced for realistic results.

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Chemical, quasi‐chemical and perturbation theories for associating fluids

Cited by 138 publications

References 57 publications

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

Models of liquid mixtures: Structure, dynamics, and properties

Balancing local order and long-ranged interactions in the molecular theory of liquid water

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