Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions

Chorążewski, Mirosław; Troncoso, Jacobo; Jacquemin, Johan

doi:10.1021/ie5038903

Cited by 13 publications

(8 citation statements)

References 93 publications

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“…1 shows intervals, where the crossing occurs, for the series of α, ωdibromoalkanes. They are quite close to the ones found experimentally [17,18] although we use only the data measured at the normal conditions as referent ones.…”

Section: The Crossing Of Expansivity Isotherms and Molecular Packingsupporting

confidence: 86%

“…The present model was tested using experimental data concerning the density, the speed of sound and the thermal expansivity of α, ω-dibromoalkanes (1,3-dibromopropane to 1,6-dibromohexane [17], dibromomethane [18], and the results of recent new measurements for 1,2-dibromoethane [19], which complete this series), a polar non-associated liquid in which important electrostatic intermolecular interactions occur due to the permanent dipole moments of the molecules. In addition, these compounds are characterized by the socalled intramolecular proximity effect [20], according to which a change in the distance between two halogen atoms in the molecule causes a change in the molecular properties.…”

Section: The Crossing Of Expansivity Isotherms and Molecular Packingmentioning

confidence: 99%

“…Here Eqs. ( 2)-( 4) are used with the constants κ = 0.0035 m 3 /kg, b = −4.94, the referent sets ρ 0 , α 0 P are taken at the normal pressure from [18].…”

Section: The Crossing Of Expansivity Isotherms and Molecular Packingmentioning

confidence: 99%

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Transition in fluctuation behaviour of normal liquids under high pressures

Postnikov

Chorążewski

2016

Physica A: Statistical Mechanics and its Applications

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We explore the behaviour of the inverse reduced density fluctuations and the isobaric expansion coefficient using α, ω-dibromoalkanes as an example. Two different states are revealed far from the critical point: the region of exponentially decaying fluctuations near the coexistence curve and the state with longer correlations under sufficiently high pressures. The crossing of the isotherms of the isobaric expansion coefficient occurs within the PVT range of the mentioned transition. We discuss the interplay of this crossing with the changes in molecular packing structure connected with the analysed function of the density, which represents inverse reduced volume fluctuations.Highlights:• There are two regions with the different fluctuation behaviour• Fluctuation transition is determined by the random loose/close packing• The crossing of expansivity isotherms coincides with this transition

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Section: The Crossing Of Expansivity Isotherms and Molecular Packingsupporting

confidence: 86%

Section: The Crossing Of Expansivity Isotherms and Molecular Packingmentioning

confidence: 99%

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Transition in fluctuation behaviour of normal liquids under high pressures

Postnikov

Chorążewski

2016

Physica A: Statistical Mechanics and its Applications

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“…QM/MM simulations and calculations of Franck–Condon factors and electronic-interaction matrix elements were performed as described, − , using the restricted Hartree–Fock (RHF) programs ENZYQ and INDIP for photochemical charge separation in HPQ, and their unrestricted Hartree–Fock (UHF) versions (ENZYQ-uhf and INDIP-uhf) for the reactions of the BIP–BQO and BIP–NAP radicals. Each system included an all-atom bath of iso-octane, dichloromethane, or 2-methyltetrahydrofuran composed of the number of solvent molecules required to fill a sphere with a radius of 23.0 Å to the proper density at atmospheric pressure and 296 K. The volume of the sphere was adjusted as necessary to give the measured densities − of the solvents at other temperatures. The atomic charges, polarizabilities, dipole moments, and MM parameters for the solvents were the same as used previously. ,, The atomic charges of 2-methyltetrahydrofuran were from Tan et al Fields from the induced dipoles of solvent atoms were evaluated at each step, and interactions with these fields contributed to the energies of the subsystem that was treated quantum mechanically.…”

Section: Methodsmentioning

confidence: 99%

Temperature Dependence of the Rate of Intramolecular Electron Transfer

Parson

2018

J. Phys. Chem. B

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Quantum mechanical/molecular mechanical simulations are used to explore the temperature dependence of intramolecular electron-transfer rates in systems that represent both the "normal" and the "inverted" regions of the Marcus curve. The treatment uses an approach that includes effects of vibrational relaxations and dephasing and is largely free of adjustable parameters. Effects of temperature on the distribution of the energy gap between the reactant and product ( P( x)), the electronic-interaction matrix element, and the rates of dephasing and vibrational relaxations are considered. The simulations reproduce the measured rate constant and temperature dependence well for photochemical charge separation in a porphyrin-benzoquinone cyclophane and for a ground-state charge-shift reaction in a biphenylyl-androstane-naphthylyl radical. They overestimate the rate of the charge-shift reaction in a biphenylyl-androstane-benzoquinone adduct but are in accordance with the observation that this reaction is almost independent of temperature. Arrhenius plots of rate constants calculated with various P( x) distributions show that the apparent activation enthalpy depends on whether or not P( x) shifts with temperature.

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“…This study continues a series of investigations implementing an acoustic method for determining various thermodynamic properties of α,ω-dihaloalkanes in the temperature range from 293.15 to 313.15 K and at pressures up to 100 MPa. Previously, the data on 1,3-dibromopropane and 1,5-dibromopentane; 1,4-dibromobutane and 1,6-dibromohexane; and dichloromethane, bromochloromethane, and dibromomethane have been reported. Yet 1,2-dichloroethane and 1,2-dibromoethane are considered.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of 1,2-Dichloroethane and 1,2-Dibromoethane under Elevated Pressures: Experimental Results and Predictions of a Novel DIPPR-Based Version of FT-EoS, PC-SAFT, and CP-PC-SAFT

Chorążewski

Postnikov

Oster

et al. 2015

Ind. Eng. Chem. Res.

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This study reports the experimental measurements of speeds of sound from 293.15 to 313.15 K and pressures up to 100 MPa in 1,2-dichloroethane, and up to 45 MPa in 1,2-dibromoethane, approaching solidification of this compound. In addition, new atmospheric pressure data on densities of 1,2-dichloroethane from 278.15 to 348.15 K are presented. These experimental data have been implemented for calculating densities, isobaric heat capacities and coefficients of thermal expansion, isentropic and isothermal compressibilities, and internal pressures as functions of pressure and temperature by using an acoustic method of Davis–Gordon–Sun. Development of a new Design Institute for Physical Properties (DIPPR)-based version of the fluctuation theory-based Tait-like equation of state (FT-EoS) is presented. This model could become a simple and reliable tool implementing the DIPPR’s saturated state expressions for predicting the high-pressure densities and speeds of sound. It has also been demonstrated that both compounds under consideration can be included in the applicability range of the predictive critical point-based perturbed-chain statistical association fluid theory (CP-PC-SAFT) approach employing the DIPPR’s critical constants. In spite of its poor modeling of vapor pressures of these substances away from their critical points, CP-PC-SAFT appears as a robust estimator of various thermodynamic properties of both pure compounds and mixtures in the entire pressure range, and as well of the high-pressure phase equilibria. Unlike CP-PC-SAFT, parametrization of PC-SAFT comprises fitting large experimental databases, and it cannot be implemented for simultaneous modeling of the critical and the subcritical states. Although this model is the less successful estimator of sound velocities and compressibilities, it has a doubtless advantage in modeling the low-pressure phase equilibria.

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Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions

Cited by 13 publications

References 93 publications

Transition in fluctuation behaviour of normal liquids under high pressures

Transition in fluctuation behaviour of normal liquids under high pressures

Temperature Dependence of the Rate of Intramolecular Electron Transfer

Thermodynamic Properties of 1,2-Dichloroethane and 1,2-Dibromoethane under Elevated Pressures: Experimental Results and Predictions of a Novel DIPPR-Based Version of FT-EoS, PC-SAFT, and CP-PC-SAFT

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