Simulation schemes for liquids or strongly fluctuating systems that allow to change the molecular representation in a subvolume of the simulation box while preserving the equilibrium with the surroundings introduce conceptual problems of thermodynamic consistency. In this work we present a general scheme based on thermodynamic arguments which ensures a thermodynamic equilibrium among molecules ...

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization be...

Thermodynamics has established in chemistry principally as a science determining possibility and direction of chemical transformations and giving conditions for their final, equilibrium state. Thermodynamics is usually thought to tell nothing about rates of these processes, their velocity of approaching equilibrium. Rates of chemical reactions belong to the domain of chemical kinetics. However,...

The knowledge of sorption processes of nonelectrolytes in solution by solid adsorbents implies the study of kinetics, equilibrium, and thermodynamic functions. However, quite frequently the equilibrium isotherms are studied by comparing them with those corresponding to the Giles et al. classification (1); these isotherms are also analyzed by fitting them to equations based on thermodynamic or k...

The general mathematical formulation of the equilibrium statistical mechanics based on the generalized statistical entropy for the first and second thermodynamic potentials was given. The Tsallis and Boltzmann-Gibbs statistical entropies in the canonical and microcanonical ensembles were investigated as an example. It was shown that the statistical mechanics based on the Tsallis statistical ent...

In this paper we used a previously reported model for examining the adsorption of nonelectrolytes in solution by solid adsorbents to study the adsorption of lithium(I) cations by acid and sodium amberlites, which is an ion-exchange process. Based on the results, both are equilibrium processes and obey a kinetic law with a unity partial order in the Li+ concentration. The kinetic results were us...

A rigorous statistical-mechanical approach is adopted to derive general quantitative expressions that allow for the effects of thermodynamic nonideality in equilibrium measurements reflecting interaction between dissimilar macromolecular reactants. An analytical procedure based on these expressions is then formulated for obtaining global estimates of equilibrium constants and the corresponding ...

It has recently become possible to calculate the free energy and other thermodynamic functions of solids and liquids using density functional theory to treat the quantum mechanics of the electrons. We present the main ideas that have made this possible, emphasizing the key role of thermodynamic integration and the importance of well-adapted reference systems in the computation of the free energ...

A new model for equilibria at the interface of a sparingly soluble crystal is reviewed. It provides that several kinds of equilibria are present and each type is characterized by (i) a set of species that are transported across the phase boundary, (ii) a set · of chemical reactions which describe this transport process, and (iii) a set of thermodynamic expressions which define equilibrium. Thre...