Search results for "Free energy"
showing 10 items of 170 documents
Phase diagrams of the system tetrahydrofuran/γ-butyrolactone/poly(ether imide) and determination of interaction parameters
1998
Abstract The thermodynamic interactions in the ternary mixture tetrahydrofuran/γ-butyrolactone/poly(ether imide) (THF/γ-BL/PEI) are investigated from 30 to 50°C. This is a membrane-forming system with a high He-selectivity. Cloud point measurements show that the two binary polymer solutions THF/PEI and γ-BL/PEI exhibit miscibility gaps which close towards the centre of the ternary phase diagram where the mixtures become homogeneous (cosolvency). Vapour pressures were determined for the subsystem THF/γ-BL. For the theoretical calculations the Gibbs energy of mixing is formulated according to the Flory-Huggins theory and the interaction parameter χ THF γ-BL calculated from the vapour pressure…
Shear influence on the phase separation of oligomer blends
1994
Shear influences on the phase separation behaviour of four different blends of ethylene glycol/propylene glycol oligomers, exhibiting upper critical solution temperatures, were investigated. Cloud point curves at rest (turbidity measurements) are reported for all systems, spinodal conditions (light scattering) and tie-lines (analysis of the coexisting phases) are given for some examples. Phase diagrams under shear were obtained from rheological data. They demonstrate that the demixing temperatures of systems where both glycols bear OH end-groups are lowered up to ca. 1°C by shear rates of 1000s−1; the critical composition, generalized to the non-equilibrium conditions of flow, is markedly s…
The Dialectics of Free Energy Minimization
2019
Karl Friston’s free energy minimization has been received with great enthusiasm. With good reason: it not only makes the bold claim to a unifying theory of the brain, but it is presented as an a priori principle applicable to living systems in general. In this article, we set out to show how the breadth of scope of Friston’s framework converges with the dialectics of Georg Hegel. Through an appeal to the work of Catherine Malabou, we aim to demonstrate how Friston not only reinvigorates Hegelian dialectics from the perspective of neuroscience, but that the implicit alignment with Hegel necessitates a reading of free energy minimization from the perspective of Hegel’s speculative philosophy.…
An omics perspective to the molecular mechanisms of anticancer metallo-drugs in the computational microscope era
2017
Introduction: Metallo-drugs have attracted enormous interest for cancer treatment. The achievements of this drug-type are summarized by the success story of cisplatin. That being said, there have been many drawbacks with its clinical use, which prompted decades worth of research efforts to move towards safer and more effective agents, either containing platinum or different metals. Areas covered: In this review, the authors provide an atomistic picture of the molecular mechanisms involving selected metallo-drugs from structural and molecular simulation studies. They also provide an omics perspective, pointing out many unsettled aspects of the most relevant families of metallo-drugs at an ep…
Structure and Thermodynamics of Binary Mixtures (Solutions)
2014
The concepts of chapter 2 are generalized to binary liquid mixtures (solutions). With the help of the concept of number and concentration fluctuations contact to the thermodynamics of solutions and physical chemistry of solutions is made. The perturbative RPA is shown to be equivalent to Flory’s theory of regular solutions. The phase diagrams of regular solutions and metal-salt solutions are discussed and explained in terms of the theories.
A Comparative Ab Initio Thermodynamic Study of Oxygen Vacancies in ZnO and SrTiO3: Emphasis on Phonon Contribution
2013
Using a hybrid Hartree–Fock (HF)-DFT method combined with LCAO basis set and periodic supercell approach, the atomic, electronic structure and phonon properties of oxygen vacancies in ZnO and SrTiO3 were calculated and compared. The important role of a ghost basis function centered at the vacant site and defect spin state for SrTiO3 is discussed. It is shown that the use of hybrid functionals is vital for correct reproduction of defects basic properties. The Gibbs free energy of formation of oxygen vacancies and their considerable temperature dependence has been compared for the two oxides. These calculations were based on the polarizability model for the soft mode temperature behavior in S…
Integration of finite displacement interface element in reference and current configurations
2017
In the present paper the non-linear behaviour of a solid body with embedded cohesive interfaces is examined in a finite displacements context. The principal target is the formulation of a two dimensional interface finite element which is referred to a local reference frame, defined by normal and tangential unit vectors to the interface middle surface. All the geometric operators, such as the interface elongation and the reference frame, are computed as function of the actual nodal displacements. The constitutive cohesive law is defined in terms of Helmholtz free energy for unit undeformed interface surface and, in order to obtain the same nodal force vector and stiffness matrix by the two i…
Novel σ1 antagonists designed for tumor therapy: Structure – activity relationships of aminoethyl substituted cyclohexanes
2021
Abstract Depending on the substitution pattern and stereochemistry, 1,3-dioxanes 1 with an aminoethyl moiety in 4-position represent potent σ1 receptor antagonists. In order to increase the stability, a cyclohexane ring first replaced the acetalic 1, 3-dioxane ring of 1. A large set of aminoethyl substituted cyclohexane derivatives was prepared in a six-step synthesis. All enantiomers and diastereomers were separated by chiral HPLC at the stage of the primary alcohol 7, and their absolute configuration was determined by CD spectroscopy. Neither the relative nor the absolute configuration had a large impact on the σ1 affinity. The highest σ1 affinity was found for cis-configured benzylamines…
Phase equilibria and multiple azeotropy in the associating system methanol + diethylamine
1997
Vapor−liquid equilibrium has been measured for the binary system of methanol (1) + diethylamine (2) at 101.3 and 300 kPa. Both equilibrium isobars show strong deviations from ideal behavior and a single maximum boiling point azeotrope of practically constant composition x1 ≈ 0.76, corresponding to a temperature of 339.8 K at 101.3 kPa and 370.0 K at 300 kPa. The trend of the high-pressure isobar data is consistent with the formation of a second minimum boiling azeotrope, confirming the multiple azeotropic behavior found by others at a higher temperature (398.58 K). Furthermore, the excess Gibbs energy is negative and inflects markedly with composition with increased pressure. The equilibriu…
Damage and plasticity at the interfaces in composite materials and structures
2009
Abstract The structural behavior at the interface between two surfaces of ductile, brittle or quasi-brittle materials is studied by a new analytical elastoplastic damaging model. The model is developed in the framework of a thermodynamically consistent theory. The Helmholtz free energy is written to predict the materials’ hardening or softening. An isotropic damage is considered and the possible effects of dilatancy are taken into account including non-associative flow rules. The interface laws are presented both in a rate and a discrete incremental form. The analytical formulation is then implemented into a finite element code and two structural members are studied to validate the model. T…