Search results for "Thermodynamic state"
showing 6 items of 6 documents
Residual Stresses in Glasses
2013
The history dependence of the glasses formed from flow-melted steady states by a sudden cessation of the shear rate $\dot\gamma$ is studied in colloidal suspensions, by molecular dynamics simulations, and mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of $\dot\gamma t$, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables, but differi…
Central role of the observable electric potential in transport equations.
2001
Nonequilibrium systems are usually studied in the framework of transport equations that involve the true electric potential (TEP), a nonobservable variable. Nevertheless another electric potential, the observable electric potential (OEP), may be defined to construct a useful set of transport equations. In this paper several basic characteristics of the OEP are deduced and emphasized: (i) the OEP distribution depends on thermodynamic state of the solution, (ii) the observable equations have a reference value for all other transport equations, (iii) the bridge that connects the OEP with a certain TEP is usually defined by the ion activity coefficient, (iv) the electric charge density is a non…
Relations frequency hypermatrices in mutual, conditional and joint entropy-based information indices.
2012
Graph-theoretic matrix representations constitute the most popular and significant source of topological molecular descriptors (MDs). Recently, we have introduced a novel matrix representation, named the duplex relations frequency matrix, F, derived from the generalization of an incidence matrix whose row entries are connected subgraphs of a given molecular graph G. Using this matrix, a series of information indices (IFIs) were proposed. In this report, an extension of F is presented, introducing for the first time the concept of a hypermatrix in graph-theoretic chemistry. The hypermatrix representation explores the n-tuple participation frequencies of vertices in a set of connected subgrap…
Finite-size effects of Kirkwood–Buff integrals from molecular simulations
2017
The modelling of thermodynamic properties of liquids from local density fluctuations is relevant to many chemical and biological processes. The Kirkwood–Buff (KB) theory connects the microscopic structure of isotropic liquids with macroscopic properties such as partial derivatives of activity coefficients, partial molar volumes and compressibilities. Originally, KB integrals were formulated for open and infinite systems which are difficult to access with standard Molecular Dynamics (MD) simulations. Recently, KB integrals for finite and open systems were formulated (J Phys Chem Lett. 2013;4:235). From the scaling of KB integrals for finite subvolumes, embedded in larger reservoirs, with the…
Gibbs equation in the nonlinear nonequilibrium thermodynamics of dilute nonviscous gases
2003
AbstractThis paper deals with the derivation of the Gibbs equation for a nonviscous gas in the presence of heat flux. The analysis aims to shed some light on the physical interpretation of thermodynamic potentials far from equilibrium. Two different definitions for the chemical potential and thermodynamic pressure far from equilibrium are introduced: nonequilibrium chemical potential and nonequilibrium thermodynamic pressure at constant heat flux q and nonequilibrium chemical potential and nonequilibrium thermodynamic pressure at constant J = Vq, where V is the specific volume.
Criteria for validity of thermodynamic equations from non-equilibrium molecular dynamics simulations
2008
Abstract The assumption of local equilibrium is validated in four different systems where heat and mass are transported. Mass fluxes up to 13 kmol / m 2 s and temperature gradients up to 10 12 K / m were used. A two-component mixture, two vapor–liquid interfaces, a chemical reaction in a temperature gradient and gas adsorbed in zeolite were studied using non-equilibrium molecular dynamics simulations. In all cases, we verified that thermodynamic variables obeyed normal thermodynamic relations, with an accuracy better than 5%. The heat and mass fluxes, and the reaction rate were linearly related to the driving forces. Onsager's reciprocal relations were validated for two systems. Equipartiti…