Stationary nonequilibrium condition

Hence, under the assumption of stationary nonequilibrium conditions, the particle flux of A that is consumed by chemical reaction is equal to that transported through the phase boudary at x = 0. Under the boundary conditions ... 

Reaction-Induced Phase Separation of Polymeric Systems under Stationary Nonequilibrium Conditions... 

From the materials viewpoint, phase separation under stationary, nonequilibrium conditions may be used to design functional polymer materials having... 

The relaxation mode distribution hy toy) is a universal function only depending on the parameter p. Cell cultures typified by p = 3 should display the same relaxation mode pattern independent of the distance from stationary nonequilibrium conditions. In that way we recognise a mandatory correlation between stationary structure and dynamics. 

The assumptions inherent in the derivation of the Hertz-Knudsen equation are (1) the vapor phase does not have a net motion (2) the bulk liquid temperature and corresponding vapor pressure determine the absolute rate of vaporization (3) the bulk vapor phase temperature and pressure determine the absolute rate of condensation (4) the gas-liquid interface is stationary and (5) the vapor phase acts as an ideal gas. The first assumption is rigorously valid only at equilibrium. For nonequilibrium conditions there will be a net motion of the vapor phase due to mass transfer across the vapor-liquid interface. The derivation of the expression for the absolute rate of condensation has been modified by Schrage (S2) to account for net motion in the vapor phase. The modified expression is... 

Note that Eq. (6) includes thermodynamic equilibrium (v° = 0) as a special case. However, usually the steady-state condition refers to a stationary nonequilibrium state, with nonzero net flux and positive entropy production. We emphasize the distinction between network stoichiometry and reaction kinetics that is implicit in Eqs. (5) and (6). While kinetic rate functions and the associated parameter values are often not accessible, the stoichiometric matrix is usually (and excluding evolutionary time scales) an invariant property of metabolic reaction networks, that is, its entries are independent of temperature, pH values, and other physiological conditions. 

Consider the propagation of a one-dimensional normal shock wave in a gas medium heavily laden with particles. Select Cartesian coordinates attached to the shock front so that the shock front becomes stationary. The changes of velocities, temperatures, and pressures of gas and particle phases across the normal shock wave are schematically illustrated in Fig. 6.12, where the subscripts 1, 2, and oo represent the conditions in front of, immediately behind, and far away behind the shock wave front, respectively. As shown in Fig. 6.12, a nonequilibrium condition between particles and the gas exists immediately behind the shock front. Apparently, because of the finite rate of momentum transfer and heat transfer between the gas and the particles, a relaxation distance is required for the particles to gain a new equilibrium with the gas. 

Since 8S< 0 under both the equilibrium and nonequilibrium conditions, the stability of a stationary state is accomplished if... 

At point B, corresponding to the glass transition, penetration of the solute into the bulk of the polymer begins, causing an inaease of retention volume with temperature. Due to an initially slow rate of diffusion of the solute into and out of the stationary phase, nonequilibrium conditions prevail. As the temperature is increased in region BC the diffusion coefficient rises sharply, leading to equilibrium conditions at point C. 

The plate theory assumes that the solute is in equilibrium with the mobile and stationary phases. Due to the continuous exchange of solute between the two phases as it progresses down the column, equilibrium between the phases can never actually be achieved. To accommodate this nonequilibrium condition, a technique originally introduced in distillation theory is adopted, where the column is considered to be divided into a number of cells or plates. Each cell is allotted a finite length and, thus, the solute spends a finite time in each cell. The size of the cell is such that the solute is considered to have sufficient residence time to achieve equilibrium with the two phases. Thus, the smaller the plate, the more efficient the solute exchange between the two phases and, consequently, the more plates there are in the column. As a result, the number of theoretical plates contained by a column has been termed the column efficiency. The plate theory shows that the peak width (the dispersion or peak spreading) is inversely proportional to the square root of the efficiency and, thus, the higher the efficiency, the narrower the peak. Consider the equilibrium that is assumed to exist in each plate then... 

Finite speed of equilibration, inability of solute molecules to truly equilibrate in one theoretical plate, the C term, present in all chromatographic columns. This term is also called the resistance to mass transfer term and, in more contemporary versions, consists of two mass transfer coefficients Cs, where S refers to the stationary phase, and Cm, where M refers to the mobile phase. Equilibrium is established between M and S so slowly that a chromatographic column always operates under nonequilibrium conditions. Thus, analyte molecules at the front of a band are swept ahead before they have time to equilibrate with S and thus be retained. Similarly, equilibrium is not reached at the trailing edge of a band, and molecules are left behind in S by the fast-moving mobile phase (23). 

As an example of a chemical reaction in which one of the affinities is unconstrained by the nonequilibrium conditions, let us consider the synthesis of HBr from Hi and Bri. In this case we expect the velocity of the unconstrained reaction to equal zero at the stationary state. We assume that the affinity of the net reaction... 

The above derivation shows that Jarzynski s identity is an immediate consequence of the Feynman-Kac theorem. This connection has not only theoretical value, but is also useful in practice. First, it forms the basis for an equilibrium thermodynamic analysis of nonequilibrium pulling experiments [3, 15]. Second, it helps in deriving a Jarzynski identity for dynamics using thermostats. Moreover, this derivation clarifies an important aspect trajectories can be thought of as mapping initial conditions (I = 0) to trajectory endpoints, and the Boltzmann factor of the accumulated work reweights that map to give the desired Boltzmann distribution. Finally, it can be easily extended to transformations between steady states [17] in which non-Boltzmann distributions are stationary. 

I would like to comment on the theoretical analysis of two systems described by Professor Hess, in order to relate the phenomena discussed by Professor Prigogine to the nonequilibrium behavior of biochemical systems. The mechanism of instability in glycolysis is relatively simple, as it involves a limited number of variables. An allosteric model for the phosphofrucktokinase reaction (PFK) has been analyzed, based on the activation of the enzyme by a reaction product. There exists a parameter domain in which the stationary state of the system is unstable in these conditions, sustained oscillations of the limit cycle type arise. Theoretical... 

In 1977. Professor Ilya Prigogine of the Free University of Brussels. Belgium, was awarded Ihe Nobel Prize in chemistry for his central role in the advances made in irreversible thermodynamics over the last ihrec decades. Prigogine and his associates investigated Ihe properties of systems far from equilibrium where a variety of phenomena exist that are not possible near or al equilibrium. These include chemical systems with multiple stationary states, chemical hysteresis, nucleation processes which give rise to transitions between multiple stationary states, oscillatory systems, the formation of stable and oscillatory macroscopic spatial structures, chemical waves, and Lhe critical behavior of fluctuations. As pointed out by I. Procaccia and J. Ross (Science. 198, 716—717, 1977). the central question concerns Ihe conditions of instability of the thermodynamic branch. The theory of stability of ordinary differential equations is well established. The problem that confronted Prigogine and his collaborators was to develop a thermodynamic theory of stability that spans the whole range of equilibrium and nonequilibrium phenomena. 

Therefore, the total entropy produced within the system must be discharged across the boundary at stationary state. For a system at stationary state, boundary conditions do not change with time. Consequently, a nonequilibrium stationary state is not possible for an isolated system for which deS/dt = 0. Also, a steady state cannot be maintained in an adiabatic system in which irreversible processes are occurring, since the entropy produced cannot be discharged, as an adiabatic system cannot exchange heat with its surroundings. In equilibrium, all the terms in Eq. (3.48) vanish because of the absence of both entropy flow across the system boundaries and entropy production due to irreversible processes, and we have dJS/dt = d dt = dS/dt = 0. 

Example 4.8 Chemical reactions and reacting flows The extension of the theory of linear nonequilibrium thermodynamics to nonlinear systems can describe systems far from equilibrium, such as open chemical reactions. Some chemical reactions may include multiple stationary states, periodic and nonperiodic oscillations, chemical waves, and spatial patterns. The determination of entropy of stationary states in a continuously stirred tank reactor may provide insight into the thermodynamics of open nonlinear systems and the optimum operating conditions of multiphase combustion. These conditions may be achieved by minimizing entropy production and the lost available work, which may lead to the maximum net energy output per unit mass of the flow at the reactor exit. 

This equation describes the pressure difference because of the mass fraction difference when there is no temperature difference. This is called the osmotic pressure. This effect is reversible because AT - 0,, /2 = 0. and at stationary state J = 0. Therefore, Eq. (7.244) yields Jq = 0, and the rate of entropy production is zero. The stationary state under these conditions represents an equilibrium state. Equation (7.263) does not contain heats of transport, which is a characteristic quantity for describing nonequilibrium phenomena. 

Equations (12.27) and (12.64) show the stability of the nonequilibrium stationary states in light of the fluctuations Sev The linear regime requires P > 0 and dP/dt < 0, which are Lyapunov conditions, as the matrix (dAJdej) is negative definite at near equilibrium. 

Under constant external conditions, a nonequilibrium system may reach its stationary state. Specific features of such a state are the time constant values of internal thermodynamic parameters characterizing the system... 

Inequalities (3.2) and (3.3) are generalizations of the principle of the minimal entropy production rate in the course of spontaneous evolution of its system to the stationary state. They are independent of any assump tions on the nature of interrelations of fluxes and forces under the condi tions of the local equilibrium. Expression (3.2), due to its very general nature, is referred to as the Qlansdorf-Prigogine universal criterion of evolution. The criterion implies that in any nonequilibrium system with the fixed boundary conditions, the spontaneous processes lead to a decrease in the rate of changes of the entropy production rate induced by spontaneous variations in thermodynamic forces due to processes inside the system (i.e., due to the changes in internal variables). The equals sign in expres sion (3.2) refers to the stationary state. 

---