Liquids, thermodynamic properties

Chapter 11 provides an analysis of ionic liquids thermodynamic properties. Here, only a representative example is provided. A modified Redlich-Kwong cubic equation of state was used to correlate VLE and predict the VLLE of (fluorocarbon + ionic liquid).Because the ionic liquids have no measurable vapour pressure, the equation of state pure-component parameters were fit to the liquid density data and critical constants.To correlate the experimental VLE data at temperature over the range (283 to 348) K, Shiflett and Yokozeki" used three binary interaction parameters. These parameters were used, without further adjustment, to predict the VLLE of these mixtures. In Eigure 4.8, experimental data and correlation are shown for (1,1,1,2-tetrafluoroethane+ 1-butyl-3-methylimidazolium hexafluorophosphate [bmim ][PF6 ]). 

Shimizu Y, Ohte Y, Yamamura Y, Tsuzuki S, Saito K (2012) Comparative study of imidazolium- and pyrrolidinium-based ionic liquids thermodynamic properties. J Phys ChemB 116 5406-5413... 

Properties of Liquids 4 3.1 Thermodynamic Properties of Liquids 43.1.1 Liquid Densities... 

Two simulation methods—Monte Carlo and molecular dynamics—allow calculation of the density profile and pressure difference of Eq. III-44 across the vapor-liquid interface [64, 65]. In the former method, the initial system consists of N molecules in assumed positions. An intermolecule potential function is chosen, such as the Lennard-Jones potential, and the positions are randomly varied until the energy of the system is at a minimum. The resulting configuration is taken to be the equilibrium one. In the molecular dynamics approach, the N molecules are given initial positions and velocities and the equations of motion are solved to follow the ensuing collisions until the set shows constant time-average thermodynamic properties. Both methods are computer intensive yet widely used. 

McDonald I R and Singer K 1967 Calculation of thermodynamic properties of liquid argon from Lennard-Jones parameters by a Monte Carlo method Discuss. Faraday Soc. 43 40-9... 

Lsc th e force fields th at have dern on strated accuracy for particu lar molecules or simulations. For example, CiPLS reproduces physical properties in liquid simulations extremely well. MM+ reproduces the structure and thermodynamic properties of small, nonpolar molecules better than AMBER, BIO+, and OPLS. 

Monte Carlo simulations are commonly used to compute the average thermodynamic properties of a molecule or a system of molecules, and have been employed extensively in the study of the structure and equilibrium properties of liquids and solutions. Monte Carlo methods have also been used to conduct conformational searches under non-equilibrium conditions. 

The values of the thermodynamic properties of the pure substances given in these tables are, for the substances in their standard states, defined as follows For a pure solid or liquid, the standard state is the substance in the condensed phase under a pressure of 1 atm (101 325 Pa). For a gas, the standard state is the hypothetical ideal gas at unit fugacity, in which state the enthalpy is that of the real gas at the same temperature and at zero pressure. 

Table 3. Physical and Thermodynamic Properties of Liquid Hydrogen...

Anhydrous Hydrogen Chloride. Anhydrous hydrogen chloride is a colorless gas that condenses to a colorless liquid and freezes to a white crystalline solid. The physical and thermodynamic properties of HCl are summarized in Table 2 for selected temperatures and pressures. Figure 1 shows the temperature dependence of some of these properties. 

Table 3. Thermodynamic Properties of Quartz, Cristobalite, and Liquid Si02...

Chlorine dioxide, CIO2, is a greenish yellow gas having a pungent odor that is distinctive from that of chlorine. Liquid chlorine dioxide has a deep red color and is explosive at temperatures above —40° C. Selected physical and thermodynamic properties of chlorine dioxide are given in Table 1. 

From Mercury—Density and Thermal Expansion at Atmospheric Pressure and Temperatures from 0 to. 350 C, Tables of Standard Handbook Data, Standartov, Moscow, 1978. The density values obtainable from those cited for the specific volume of the saturated liquid in the Thermodynamic Properties subsection show minor differences. No attempt was made to adjust either set. 

Extensive tables of the viscosity and thermal conductivity of air and of water or steam for various pressures and temperatures are given with the thermodynamic-property tables. The thermal conductivity and the viscosity for the saturated-liquid state are also tabulated for many fluids along with the thermodynamic-property tables earlier in this section. 

Vapor pressure is the most important of the basic thermodynamic properties affec ting liquids and vapors. The vapor pressure is the pressure exerted by a pure component at equilibrium at any temperature when both liquid and vapor phases exist and thus extends from a minimum at the triple point temperature to a maximum at the critical temperature, the critical pressure. This section briefly reviews methods for both correlating vapor pressure data and for predicting vapor pressure of pure compounds. Except at very high total pressures (above about 10 MPa), there is no effect of total pressure on vapor pressure. If such an effect is present, a correction, the Poynting correction, can be applied. The pressure exerted above a solid-vapor mixture may also be called vapor pressure but is normallv only available as experimental data for common compounds that sublime. 

Denotes excess thermodynamic property Denotes value for an ideal solution Denotes value for an ideal gas Denotes liquid phase... 

Denotes phase transition from liquid to vapor Denotes residual thermodynamic property Denotes a total value of a thermodynamic property V Denotes vapor phase... 

The residual Gibbs energy and the fugacity coefficient are useful where experimental PVT data can be adequately correlated by equations of state. Indeed, if convenient treatment or all fluids by means of equations of state were possible, the thermodynamic-property relations already presented would suffice. However, liquid solutions are often more easily dealt with through properties that measure their deviations from ideal solution behavior, not from ideal gas behavior. Thus, the mathematical formahsm of excess properties is analogous to that of the residual properties. 

Data on the gas-liquid or vapor-liquid equilibrium for the system at hand. If absorption, stripping, and distillation operations are considered equilibrium-limited processes, which is the usual approach, these data are critical for determining the maximum possible separation. In some cases, the operations are are considerea rate-based (see Sec. 13) but require knowledge of eqmlibrium at the phase interface. Other data required include physical properties such as viscosity and density and thermodynamic properties such as enthalpy. Section 2 deals with sources of such data. 

Essentially, the RISM and extended RISM theories can provide infonnation equivalent to that obtained from simulation techniques, namely, thermodynamic properties, microscopic liquid structure, and so on. But it is noteworthy that the computational cost is dramatically reduced by this analytical treatment, which can be combined with the computationally expensive ab initio MO theory. Another aspect of such treatment is the transparent logic that enables phenomena to be understood in terms of statistical mechanics. Many applications have been based on the RISM and extended RISM theories [10,11]. 

The theory of seaweed formation does not only apply to solidification processes but in fact to the completely different phenomenon of a wettingdewetting transition. To be precise, this applies to the so-called partial wetting scenario, where a thin liquid film may coexist with a dry surface on the same substrate. These equations are equivalent to the one-sided model of diffusional growth with an effective diffusion coefficient which depends on the viscosity and on the thermodynamical properties of the thin film. 

M. J. Vlot, S. Claassen, H. E. Huitema, J. P. v. d. Eerden. Monte Carlo simulation of racemic liquid mixtures thermodynamic properties and local structures. Mol Phys 97 19, 1997 M. J. Vlot, J. C. v. Miltenburg, H. A. Oonk, J. P. V. d. Eerden. Phase diagrams of scalemic mixtures. J Chem Phys 707 10102, 1997. 

The thermodynamic properties of thiophene,2-methylthiophene, ° and 3-methylthiophene have been computed from careful measurements of the heat capacity of the solid, liquid, and vapor states, the heat of fusion, the heat of vaporization, and the heat of combustion. From the heat of combustion of thiophene and from thermochemical bond energies, the resonance energy of thiophene has been re-estimated to be only 20 kcal/mole. 

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