Consider an equilibrium reaction aA+ bB ⇀↽ cC+ dD We do not specify any phases, as we will treat the reaction generally using activities. An equilibrium reaction is one that can proceed in both directions, as indicated by the ⇀↽ symbol replacing the usual −→ in the chemical equation. Recall that the molar free energy ∆Ḡj for compound j in the reaction in terms of its activity aj as ∆Ḡ = ∆Ḡ◦ +RT...

Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [J. Res. Natl. Bur. Stand. 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last ce...

The wish to determine thermodynamic data of electrochemical reactions and of the involved compounds is one of the most important motivations to perform electrochemical measurements. After calorimetry, electrochemistry is the second most important tool to determine thermodynamic data. Although ab initio quantum chemical calculations can be used for the calculation of thermodynamic data of small ...

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 ...

Strand displacement and tile assembly systems are designed to follow prescribed kinetic rules (i.e., exhibit a specific time-evolution). However, the expected behavior in the limit of infinite time—known as thermodynamic equilibrium—is often incompatible with the desired computation. Basic physical chemistry implicates this inconsistency as a source of unavoidable error. Can the thermodynamic e...

The promise of chemical computation lies in controlling systems incompatible with traditional electronic micro-controllers, with applications in synthetic biology and nano-scale manufacturing. Computation is typically embedded in kinetics—the specific time evolution of a chemical system. However, if the desired output is not thermodynamically stable, basic physical chemistry dictates that therm...

Given significant challenges with available measurements of aerosol acidity, proxy methods are frequently used to estimate the acidity of atmospheric particles. In this study, four of the most common aerosol acidity proxies are evaluated and compared: (1) the ion balance method, (2) the molar ratio method, (3) thermodynamic equilibrium models, and (4) the phase partitioning of ammonia. All meth...

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...

Abstract. We introduce a model of long-range interacting particles evolving under a stochastic Monte Carlo dynamics, in which possible increase or decrease in the values of the dynamical variables is accepted with preassigned probabilities. For symmetric increments, the system at long times settles to the Gibbs equilibrium state, while for asymmetric updates, the steady state is out of equilibr...

We introduce a lattice Boltzmann model for simulating an immiscible binary fluid mixture. Our collision rules are derived from a macroscopic thermodynamic description of the fluid in a way motivated by the Cahn-Hilliard approach to non-equilibrium dynamics and ensure that a thermodynamically consistent state is reached in equilibrium. The non-equilibrium dynamics is investigated numerically and...