Michal Fulem

Heat capacities of alkanols: Part I. Selected 1-alkanols C2 to C10 at elevated temperatures and pressures

Measurements of isobaric heat capacities in the liquid phase were carried on the following 1-alkanols: 1-hexanol, 1-heptanol, 1-octanol, and 1-decanol in the temperature range from 325 to 570 K and at pressures of 2, 10 and 30 MPa using a commercial heat conduction SETARAM C-80 calorimeter. Additional measurements, which provided saturation heat capacities, were carried out in a slightly different experimental arrangement for ethanol, 1-propanol, 1-butanol, 1-hexanol, 1-heptanol, 1-octanol, and 1-decanol at a pressure considered within the expected pressure variation of heat capacity close to the saturation vapour pressure.

Vapor pressure of metal organic precursors

The vapour pressure of four metal organic precursors, diethylzinc, triethylantimony, trimethylgallium and trimethylaluminium, used in the metal organic vapor phase epitaxy processes was measured by a static method in the technologically important temperature range from 238 to 293 K. The experimental data were fitted by the Antoine equation and represent updated values of the present day high-purity materials providing comparison with the previously published data.

Thermodynamic Properties of Selected Homologous Series of Ionic Liquids Calculated Using Molecular Dynamics

This work presents a molecular dynamics simulation study concerning the thermodynamic data of ionic liquids (ILs) including phase change enthalpies, liquid phase densities, radial and spatial distribution functions, and diffusive properties. Three homologous series of ILs were selected for this study, namely, 1-alkyl-3-methylimidazolium tetrafluoroborates, hexafluorophosphates, and 1,1,2,2-tetrafluoroethanesulfonates, so that properties of 36 ILs are calculated in total. The trends of calculated properties are compared to available experimental data and thoroughly discussed in context of the homologous series. The calculated trends of the vaporization enthalpies within the series are supported by analyzing the structural properties of the ILs. An excellent agreement of calculated structural properties (liquid phase density) with the experimental counterparts is reached. The calculated enthalpic properties are overestimated considerably; thus, further development of the force fields for ILs is required.

Heat capacities of some phthalate esters

Isobaric heat capacities Cp in the liquid phase of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethylhexyl) phthalate, and benzyl butyl phthalate were measured by commercial SETARAM heat conduction calorimeters. Results obtained cover the following temperature range: dimethyl phthalate 283 to 323 K, diethyl phthalate 306 to 370 K, dibutyl phthalate 313 to 447 K, bis(2-ethylhexyl) phthalate from 313 to 462 K, benzyl butyl phthalate from 313 to 383 K. The heat capacity data obtained in this work were merged with available experimental data from literature, critically assessed and sets of recommended data were developed by correlating selected data as a function of temperature.

Thermodynamic Properties of Molecular Crystals Calculated within the Quasi-Harmonic Approximation.

A computational study of the possibilities of contemporary theoretical chemistry as regards calculated thermodynamic properties for molecular crystals from first-principles is presented. The study is performed for a testing set of 22 low-temperature crystalline phases whose properties such as densities of phonon states, isobaric heat capacities, and densities are computed as functions of temperature within the quasi-harmonic approximation. Electronic structure and lattice dynamics are treated by plane-wave based calculations with optPBE-vdW functional. Comparison of calculated results with reliable critically assessed experimental data is especially emphasized.

CCSD(T)/CBS fragment-based calculations of lattice energy of molecular crystals.

A comparative study of the lattice energy calculations for a data set of 25 molecular crystals is performed using an additive scheme based on the individual energies of up to four-body interactions calculated using the coupled clusters with iterative treatment of single and double excitations and perturbative triples correction (CCSD(T)) with an estimated complete basis set (CBS) description. The CCSD(T)/CBS values on lattice energies are used to estimate sublimation enthalpies which are compared with critically assessed and thermodynamically consistent experimental values. The average absolute percentage deviation of calculated sublimation enthalpies from experimental values amounts to 13% (corresponding to 4.8 kJ mol(-1) on absolute scale) with unbiased distribution of positive to negative deviations. As pair interaction energies present a dominant contribution to the lattice energy and CCSD(T)/CBS calculations still remain computationally costly, benchmark calculations of pair interaction energies defined by crystal parameters involving 17 levels of theory, including recently developed methods with local and explicit treatment of electronic correlation, such as LCC and LCC-F12, are also presented. Locally and explicitly correlated methods are found to be computationally effective and reliable methods enabling the application of fragment-based methods for larger systems.

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty

A computational methodology for calculation of sublimation enthalpies of molecular crystals from first principles is developed and validated by comparison to critically evaluated literature experimental data. Temperature-dependent sublimation enthalpies for a set of selected 22 molecular crystals in their low-temperature phases are calculated. The computational methodology consists of several building blocks based on high-level electronic structure methods of quantum chemistry and statistical thermodynamics. Ab initio methods up to the coupled clusters with iterative treatment of single and double excitations and perturbative triples correction with an estimated complete basis set description [CCSD(T)/CBS] are used to calculate the cohesive energies of crystalline phases within a fragment-based additive scheme. Density functional theory (DFT) calculations with periodic boundary conditions (PBC) coupled with the quasi-harmonic approximation are used to evaluate the thermal contributions to the enthalpy of the solid phase. The properties of the vapor phase are calculated within the ideal-gas model using the rigid-rotor harmonic-oscillator model with correction for internal rotation using a one-dimensional hindered rotor approximation and a proper treatment of the molecular rotational degrees of freedom in the vicinity of 0 K. All individual terms contributing to the sublimation enthalpy as a function of temperature are discussed and their uncertainties estimated by comparison to critically evaluated experimental data.

Single‐Crystal‐to‐Single‐Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene‐Like Compound

Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid-solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X-ray diffraction analysis were used to unravel the mechanistic details of this process. The single-crystal-to-single-crystal course enabled direct monitoring of the structural changes by in situ variable-temperature X-ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene-like compound.

CHAPTER 17:Calculation of Thermodynamic Functions from Volumetric Properties

Volumetric properties are key inputs in calculations of thermodynamic properties of real fluids as they give information about the variation of the thermodynamic properties with pressure or density at constant temperature. In this chapter, a rational way of calculating thermodynamic quantities, including partial molar quantities based on volumetric properties, is presented. Finally, empirical rules are discussed which enable one to use state-of-the-art equations of state for each component of a given mixture. Some of these rules have rarely been reported in the literature.