In this work, a thermodynamic study of four important industrial solvents, ethylene carbonate (CAS RN: 96-49-1), propylene carbonate (CAS RN: 108-32-7), γ-valerolactone (CAS RN: 108-29-2), and γ-butyrolactone (CAS RN: 96-48-0), is presented. The vapor pressure measurements were performed by static method using two apparatuses in a combined temperature interval (238−363) K. Heat capacities of condensed phases were measured by Tian−Calvet calorimetry in the temperature interval (262−358) K. The phase behavior of ethylene carbonate and γ-valerolactone was investigated by a heat-flux DSC from 183−303 and 328 K, respectively. Ideal-gas thermodynamic properties were calculated using the methods of statistical thermodynamics based on calculated fundamental vibrational frequencies and molecular structure data. A consistent thermodynamic description of all involved properties (calculated ideal-gas heat capacities and experimental data on vapor pressures, condensed phase heat capacities, and vaporization enthalpies) was achieved by their simultaneous correlation.
We describe a modification of the Polaron sputter-coater unit series 11 HD enabling activation of carbon support films for electron microscopy of macromolecules and macromolecular assemblies. The modification is simple and the device can be used in two modes, for sputter-coating of SEM samples and for glow-discharge activation of carbon support films. Examples of protein-free spreading of DNA and negative staining of bacteriophage particles on activated carbon support films are presented.
This work is part of the effort on
establishing reliable thermodynamic data for amino acids and, in a
broader context, benchmarking first-principles calculations of thermodynamic
properties of molecular crystals against reliable experimental data.
In this work, crystal heat capacities of l-alanine (CAS RN:
56-41-7), l-valine (CAS RN: 72-18-4), l-isoleucine
(CAS RN: 73-32-5), and l-leucine (CAS RN: 61-90-5) were newly
measured in the temperature range 262–450 K by Tian–Calvet
calorimetry and power-compensation differential scanning calorimetry
(DSC) and combined with the critically assessed literature data to
obtain the reference data from near 0 to 450 K. The heat capacity
measurements were accompanied by thermogravimetric analysis to determine
the decomposition temperatures of the studied amino acids and phase
behavior studies by X-ray powder diffraction and heat-flux DSC to
identify the initial crystal structures and their possible transformations.
The crystal heat capacities calculated by combining the periodic density
functional theory and the quasi-harmonic approximation showed an agreement
with the developed reference experimental data within 10% which can
be considered as success of the employed computational methodology.
Quantum chemical calculations further helped interpret the differences
in thermodynamic and structural properties of the studied crystalline
amino acids.
were measured by a static method near ambient temperatures over an operating pressure range from 0.5 to 1270 Pa, thus complementing literature vapor pressure data obtained by ebulliometry at higher temperatures. Liquid heat capacities of 1-octanol, 1-nonanol, and 1decanol were determined by Tian−Calvet calorimetry. Ideal-gas thermodynamic properties of 1-alkanols up to 1-heptanol were obtained by a combination of quantum chemistry and statistical mechanics and validated against available experimental data. Ideal-gas heat capacities and entropies for longer homologues were obtained by deriving a methylene increment due to having a too complex conformational shape for analogical treatment. The thermodynamic consistency of available data was validated by simultaneous correlation of selected vapor pressures, literature enthalpies of vaporization, and heat capacity differences between the ideal gaseous and the liquid phase. The results are represented by the Cox equation and compared with available literature data. Moreover, the results were used to examine the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state for its performance in describing vapor pressures, enthalpies of vaporization, residual liquid heat capacities, and liquid densities of neat 1-alkanols from 1-hexanol to 1-decanol. A new PC-SAFT parameter set for each of them was also regressed that improves the PC-SAFT performance for the studied properties in comparison to existing parameters published in the literature.
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