Classical theory of collisional entropy production

A classical dynamical theory of elementary collision processes is formulated in analogy to the quantum theory of the dynamical scattering matrix, which can be defined for a pure quantum stationary scattering state. The elements of this matrix are probability amplitudes for transitions between internal states defined for given values of a reaction coordinate. The squared magnitudes of these amplitudes, modeled in the proposed classical theory, define normalized internal state population distributions suitable for information theoretical analysis. Statistical entropy and surprisal are defined as dynamical functions of a reaction coordinate. This formalism differs fundamentally from concepts based on the classical Liouville equation.     

Chiral polymerization: symmetry breaking and entropy production in closed systems

We solve numerically a kinetic model of chiral polymerization in systems closed to matter and energy flow, paying special attention to its ability to amplify the small initial enantiomeric excesses due to the internal and unavoidable statistical fluctuations. The reaction steps are assumed to be reversible, implying a thermodynamic constraint among some of the rate constants. Absolute asymmetric synthesis is achieved in this scheme. The system can persist for long times in quasi-stationary chiral asymmetric states before racemizing. Strong inhibition leads to long-period chiral oscillations in the enantiomeric excesses of the longest homopolymer chains. We also calculate the entropy production σ per unit volume and show that σ increases to a peak value either before or in the vicinity of the chiral symmetry breaking transition.     

Fluctuation theorem for entropy production in a chemical reaction channel

Fluctuation theorem for entropy production in a mesoscopic chemical reaction network is discussed. When the system size is sufficiently large, it is found that, by defining a kind of coarse-grained dissipation function, the entropy production in a reversible reaction channel can be approximately described by a type of detailed fluctuation theorem. Such a fluctuation relation has been successfully tested by direct simulations in a linear reaction model consisting of two reversible channels and in an oscillat...     

Freezing-in of molecular mobility of small molecules (probes) in glassy polymers and secondary relaxation transitions

The behavior of probe molecules of different sizes (1,2-bromofluoroethane, 1,2-dichloroethane, dichloromethoxyphosphine oxide, 1,2-di-p-bromophenylethane) in PMMA and PVAC was considered. There is a linear correlation between the freezing temperature of conformational transitions of probe molecules and the size of the rotating groups of the probe. Processes that lead to the freezing-in of conformational equilibria of probes in polymers with a decrease in temperature are discussed on the basis of these results. The free-volume distribution and the nature of secondary relaxation processes in glassy polyvinyltrimethylsilane and polytrimethylsilylpropyne were studied by means of the conformation-probe technique.     

Photosynthetic models with maximum entropy production in irreversible charge transfer steps

Steady-state bacterial photosynthesis is modelled as cyclic chemical reaction and is examined with respect to overall efficiency, power transfer efficiency, and entropy production. A nonlinear flux–force relationship is assumed. The simplest two-state kinetic model bears complete analogy with the performance of an ideal (zero ohmic resistance of the P–N junction) solar cell. In both cases power transfer to external load is much higher than the 50% allowed by the impedance matching theorem for the linear flux–force relationship. When maximum entropy production is required in the transition with a load, one obtains high optimal photochemical yield of 97% and power transfer efficiency of 91%. In more complex photosynthetic models, entropy production is maximized in all irreversible electron/proton (non-slip) transitions in an iterative procedure. The resulting steady-state is stable with respect to an extremely wide range of initial values for forward rate constants. Optimal proton current increases proportionally to light intensity and decreases with an increase in the proton-motive force (the backpressure effect). Optimal affinity transfer efficiency is very high and nearly perfectly constant for different light absorption rates and for different electrochemical proton gradients. Optimal overall efficiency (of solar into proton-motive power) ranges from 10% (bacteriorhodopsin) to 19% (chlorophyll-based bacterial photosynthesis). Optimal time constants in a photocycle span a wide range from nanoseconds to milliseconds, just as corresponding experimental constants do. We conclude that photosynthetic proton pumps operate close to the maximum entropy production mode, connecting biological to thermodynamic evolution in a coupled self-amplifying process.     

On local entropy production in gases and gaseous mixtures flowing though nanosized channels

The problem of local entropy production in gases flowing through nanosized channels has been discussed. The main attention has been focused on the role of adsorbed layers. It has been shown that the local entropy production differs from that obtained in terms of the classical approach. For example, the transfer in the adsorbed layer influences both the entropy production and the form of phenomenological equations. An additional difference results from the mass and energy exchange between the bulk phase and the adsorbed layer, this exchange being related to nonlinear adsorption isotherms. This exchange is described by independent local phenomenological equations.     

Mixed convection and entropy production in a nanofluid-filled closed space with inclined magnetic field

Journal of Thermal Analysis and Calorimetry - A computational analysis has been performed to study the impact of magnetic field on entropy generation due to mixed convective nanofluid flow with top...     

Melting and vitrification of Lennard-Jones spheres

Melting and vitrification processes of different types of mixtures of Lennard-Jones spheres are considered; mechanisms and geometrical models of transition from the solid to liquid state are defined and established.     

Exact solutions for the entropy production rate of several irreversible processes

We investigate thermal conduction described by Newton's law of cooling and by Fourier's transport equation and chemical reactions based on mass action kinetics where we detail a simple example of a reaction mechanism with one intermediate. In these cases we derive exact expressions for the entropy production rate and its differential. We show that at a stationary state the entropy production rate is an extremum if and only if the stationary state is a state of thermodynamic equilibrium. These results are exact and independent of any expansions of the entropy production rate. In the case of thermal conduction we compare our exact approach with the conventional approach based on the expansion of the entropy production rate near equilibrium. If we expand the entropy production rate in a series and keep terms up to the third order in the deviation variables and then differentiate, we find out that the entropy production rate is not an extremum at a nonequilibrium steady state. If there is a strict proportionality between fluxes and forces, then the entropy production rate is an extremum at the stationary state even if the stationary state is far away from equilibrium.     

A lattice model of vitrification and gelation

In this work we introduce a simple lattice model with T-shaped molecules in two dimensions that exhibits a rich range of morphological behaviors. Depending on the volume fraction and quench path, this system can adopt uniform liquid, solution, and phase-separated states, as well as inhomogeneous glass or gel-like states, as revealed by dynamic mean-field simulations. An important characteristic of this system is the existence of a large number of degenerate low-energy states with small barriers that leads to a broad, kinetically explored landscape. The mean-field stability and phase diagram of this model is constructed and provides a useful guide for understanding the complex behaviors of the system. One striking feature is that there is a cascade of instabilities that converge to mark the onset of what we identify as the glass transition. Both dynamic mean-field and Monte Carlo simulations reveal glass-like relaxation dynamics. Our results lead to a picture of gelation as a continuation of the glass transition into the two-phase region, or equivalently, as an incomplete phase separation arrested by the onset of the glass transition.     

Cell encapsulating droplet vitrification

The capability to encapsulate single cells in droplets while retaining high cell viability (>90%) has great impact on tissue engineering, high-throughput screening, as well as clinical diagnostics and therapeutics. We demonstrate a novel method to vitrify a small number of cells using cell-encapsulating droplets. The method allows vitrification at low cryoprotectant concentration (1.5 M propanediol and 0.5 M trehalose), similar to that used in slow freezing protocols. The method was successfully applied to five different mammalian cell types: AML-12 hepatocytes, NIH-3T3 fibroblasts, HL-1 cardiomyocytes, mouse embryonic stem cells, and RAJI cells.     

Pattern formation in nonextensive thermodynamics: selection criterion based on the Renyi entropy production

We analyze a system of two different types of Brownian particles confined in a cubic box with periodic boundary conditions. Particles of different types annihilate when they come into close contact. The annihilation rate is matched by the birth rate, thus the total number of each kind of particles is conserved. When in a stationary state, the system is divided by an interface into two subregions, each occupied by one type of particles. All possible stationary states correspond to the Laplacian eigenfunctions. We show that the system evolves towards those stationary distributions of particles which minimize the Renyi entropy production. In all cases, the Renyi entropy production decreases monotonically during the evolution despite the fact that the topology and geometry of the interface exhibit abrupt and violent changes.     

Computing minimal entropy production trajectories: an approach to model reduction in chemical kinetics

Advanced experimental techniques in chemistry and physics provide increasing access to detailed deterministic mass action models for chemical reaction kinetics. Especially in complex technical or biochemical systems the huge amount of species and reaction pathways involved in a detailed modeling approach call for efficient methods of model reduction. These should be automatic and based on a firm mathematical analysis of the ordinary differential equations underlying the chemical kinetics in deterministic models. A main purpose of model reduction is to enable accurate numerical simulations of even high dimensional and spatially extended reaction systems. The latter include physical transport mechanisms and are modeled by partial differential equations. Their numerical solution for hundreds or thousands of species within a reasonable time will exceed computer capacities available now and in a foreseeable future. The central idea of model reduction is to replace the high dimensional dynamics by a low dimensional approximation with an appropriate degree of accuracy. Here I present a global approach to model reduction based on the concept of minimal entropy production and its numerical implementation. For given values of a single species concentration in a chemical system all other species concentrations are computed under the assumption that the system is as close as possible to its attractor, the thermodynamic equilibrium, in the sense that all modes of thermodynamic forces are maximally relaxed except the one, which drives the remaining system dynamics. This relaxation is expressed in terms of minimal entropy production for single reaction steps along phase space trajectories.     

Isothermal desiccation and vitrification kinetics of trehalose-dextran solutions

The promise of dried state preservation is based on the hypothesis that lowering molecular mobility to halt chemical reaction and deterioration rates is the primary factor for the long-term stability of the dried specimen. In this research, the feasibility of utilizing isothermal, isobaric vitrification as an economical alternative to the preservation technologies currently in use (mainly, cryopreservation and lyophilization) is explored. Desiccation and vitrification kinetics of model trehalose and trehalose-dextran systems were examined using gravimetric analysis, modulated differential scanning calorimetry, and X-ray crystallography. It was shown that vitrification can be achieved isothermally without crystallization and that vitrification of trehalose solutions can be significantly accelerated by incorporating high-molecular-weight dextrans. Additionally, it was shown that, for the same water content, the glass transition temperature of the trehalose-dextran solution is significantly higher than that of the binary trehalose solution, making the glassy state achievable and storage feasible.     

An entropy production analysis for electroosmotic flow and convective heat transfer: a numerical investigation

Journal of Thermal Analysis and Calorimetry - In the current numerical study, an entropy production analysis is conducted for the electroosmotic flow and convective heat transfer in the microduct....     

The vitrification of alkali borate and alkali silicate melts

Glasses and crystals of compositions corresponding to the congruently melting compounds M₂O·2SiO₂ (M = Na. Rb, and Cs) and M₂O·4SiO₂ (M = K, Rb, and Cs) were studied by differential scanning calorimetry. The structure temperatures (T _f) and excess entropies at T _f of glasses were measured depending on the rate of cooling of the corresponding melts. The activation energies of glass formation (ΔE) and scale of cooperative motion in the transition region (ξ_a) were estimated. The totality of the data obtained were used to compare the thermodynamic (the ratio between the excess (with respect to the corresponding crystals) entropy of glass at T _f and the entropy of crystal melting), kinetic (fragility m = f(ΔE, T _f)), and microscopic (ξ_a) parameters of the vitrification of alkali silicate melts. The behaviors of alkali silicate and alkali borate melts were shown to be similar.     

A vitrification and curing study by simultaneous TMDSC-photocalorimetry

The development of photopolymers was helped by the development of photocalorimetry, which is now a basic technique for the study of these materials. This work shows how to obtain vitrification times in single isothermal curing experiments by monitoring the reversing heat capacity along time in modulated temperature DSC–photocuring systems, overcoming the time-consuming problem of standard DSC. The effects of the light intensity and the isothermal curing temperature on the vitrification time of a photocurable system were evaluated. The results obtained at a given curing temperature with different light intensities indicate that the UV-light affects the molecular mobility hindering the vitrification process. The effects of the curing temperature on the vitrification time, the conversion at the vitrification time and the maximum conversion were also evaluated.     

Ab initio study of the role of entropy in the kinetics of acetylene production in filament-assisted diamond growth environments

We present a new theoretical strategy, ab initio rate constants plus integration of rate equations, that is used to characterize the role of entropy in driving high-temperature/low-pressure hydrocarbon chemical kinetics typical of filament-assisted diamond growth environments. Twelve elementary processes were analyzed that produce a viable pathway for converting methane in a feed gas to acetylene. These calculations clearly relate the kinetics of this conversion to the properties of individual species, demonstrating that (1) loss of translational entropy restricts addition of hydrogen (and other radical species) to unsaturated carbon-carbon bonds, (2) rotational entropy determines the direction of the rate-limiting abstraction reactions, and (3) the overall pathway is enhanced by high beta-scission reaction rates driven by translational entropy. These results suggest that the proposed strategy is likely applicable to understand gas-phase chemistry occurring in the systems of combustion and other chemical vapor depositions.