Closed system equilibrium state

If such a reaction is isolated from its surroundings, so that A and B neither enter nor leave the system, creating a closed system, these reactants will eventually reach equilibrium, i.e. the forward and reverse rates are the same. For a closed system, equilibrium is the only state in which the concentrations of A and B do not vary with time. Since AG = 0, the reaction can do no useful work and has no direction. Hence a closed system is not a useful model of a living cell or, indeed, a living animal. 

The study of equilibrium polymerization is hindered by the difficulties of description of the destruction process. Since the processes of polymerization and destruction are of the same origin, they compete. For technological reasons, in most cases, it is desirable to carry out the polymerization far from equilibrium to avoid their competition. However, in numerous situations, close to equilibrium both processes may accelerate this allows us to find an optimum when the real brutto rate of the reaction is maximum. This is the reason to study theoretically the equilibrium and close to equilibrium states of polymeric systems independently of the exploration of destruction. 

Quasistatic process. One that involves passage through a large succession of very closely spaced equilibrium states. In this process the surroundings may be altered such that on the return path to the original system configuration the universe ends up in a different state. 

Reversible process. One whose path may be exactly reversed though a succession of very closely spaced equilibrium states, such that on reversal of the path both the system and its surroundings are restored to their original state. 

Comparison of equations 3 and 10 shows the essential difference between the stationary states of closed and continuous, open systems. For the closed system, equilibrium is the time-invariant condition. The total of each independently variable constituent and the equilibrium constant (a function of temperature, pressure, and composition) for each independent reaction (ATab in the example) are required to define the equilibrium composition Ca- For the continuous, open system, the steady state is the time-invariant condition. The mass transfer rate constant, the inflow mole number of each independently variable constituent, and the rate constants (functions of temperature, pressure, and composition) for each independent reaction are requir to define the steady-state composition Ca- It is clear that open-system models of natural waters require more information than closed-system models to define time-invariant compositions. An equilibrium model can be expected to describe a natural water system well when fluxes are small, that is, when flow time scales are long and chemical reaction time scales are short. 

For each of these idealized models there is a stationary state. For a continuous open system, this is the steady state. Rate laws and steady material flows arc required to define the steady state. For a closed system, equilibrium is the stationary state. Equilibrium may be viewed as simply the limiting case of the stationary state when the flows from the surroundings approach zero. The simplicity of closed-system models at equilibrium is in the rather small body of information required to describe the time-invariant composition. We now turn our attention to the principles of chemical thermodynamics and the development of tools for the description of equilibrium states and energetics of chemical change in closed systems. 

It must be emphasized that the results derived above, like those obtained in 20b, et seq, are applicable only to closed systems, as stated in 20g. Such systems may be homogeneous or heterogeneous, and may consist of solid, liquid or gas, but the total mass must remain unchanged. It will be seen later that in some cases a system consists of several phases, and although the mass of the whole system is constant, changes may take place among the phases. In these circumstances the equations apply to the system as a whole but not to the individual phases. Since it has been postulated that the work done in a change in state is only work of expansion, equal to PdV, the second condition stated in 20g, that the system is always in equilibrium with the external pressure, must also be operative. 

Given sufficient time, chemical substances in contact with each other tend to come to chemical equilibrium. Chemical equilibrium is the time-invariant, most stable state of a closed system (the. state of minimum Gibbs free energy). We study chemical equilibrium concepts so as to learn the direction of spontaneous change of chemical reactions in any system, especially for conditions of constant temperature and pressure. We want to be able to compute the hypothetical equilibrium stale of a system. We would like to predict the conditions for equilibrium in different systems and at different temperatures and pressures without having to measure them. 

By the use of this equation and the first law, the fundamental equations for closed systems in states of equilibrium may be easily obtained. Substitution of Eq. (6-17) into Eqs. (3-16) and (3-18) results in... 

A system in which the dependent variables are constant in time is said to be in a steady or stationary state. In a chemical system, the dependent variables are typically densities or concentrations of the component species. Two fundamentally different types of stationary states occur, depending on whether the system is open or closed. There is only one stationary state in a closed system, the state of thermodynamic equilibrium. Open systems often exhibit only one stationary state as well however, multistability may occur in systems with appropriate elements of feedback if they are sufficiently far from equilibrium. This phenomenon of multistability, that is, the existence of multiple steady states in which more than one such state may be simultaneously stable, is our first example of the universal phenomena that arise in dissipative nonlinear systems. 

For a system which is close to equilibrium, it is assumed that its state is described by a set of extensive themiodynamic variables, o jCO, where n is very much less than the total number of degrees of... 

The exponential fiinction of the matrix can be evaluated tln-ough the power series expansion of exp(). c is the coliinm vector whose elements are the concentrations c.. The matrix elements of the rate coefficient matrix K are the first-order rate constants W.. The system is called closed if all reactions and back reactions are included. Then K is of rank N- 1 with positive eigenvalues, of which exactly one is zero. It corresponds to the equilibrium state, witii concentrations r detennined by the principle of microscopic reversibility ... 

In practice, colloidal systems do not always reach tlie predicted equilibrium state, which is observed here for tlie case of narrow attractions. On increasing tlie polymer concentration, a fluid-crystal phase separation may be induced, but at higher concentration crystallization is arrested and amorjihous gels have been found to fonn instead [101, 102]. Close to the phase boundary, transient gels were observed, in which phase separation proceeded after a lag time. 

Most chemically reacting systems tliat we encounter are not tliennodynamically controlled since reactions are often carried out under non-equilibrium conditions where flows of matter or energy prevent tire system from relaxing to equilibrium. Almost all biochemical reactions in living systems are of tliis type as are industrial processes carried out in open chemical reactors. In addition, tire transient dynamics of closed systems may occur on long time scales and resemble tire sustained behaviour of systems in non-equilibrium conditions. A reacting system may behave in unusual ways tliere may be more tlian one stable steady state, tire system may oscillate, sometimes witli a complicated pattern of oscillations, or even show chaotic variations of chemical concentrations. 

The second law reqmres that the entropy of an isolated system either increase or, in the limit, where the system has reached an equilibrium state, remain constant. For a closed (but not isolated) system it requires that any entropy decrease in either the system or its surroundings be more than compensated by an entropy increase in the other part or that in the Emit, where the process is reversible, the total entropy of the system plus its surroundings be constant. 

Although derived for a reversible process, this equation relates properties only and is valid for any change between equilibrium states in a closed system. It may equally well be written... 

Since the phase rule treats only the intensive state of a system, it apphes to both closed and open systems. Duhem s theorem, on the other hand, is a nJe relating to closed systems only For any closed system formed initially from given masses of preseribed ehemieal speeies, the equilibrium state is completely determined by any two propeities of the system, provided only that the two propeities are independently variable at the equilibrium state The meaning of eom-pletely determined is that both the intensive and extensive states of the system are fixed not only are T, P, and the phase compositions established, but so also are the masses of the phases. 

It is known that polymers may exist in various stationary states, which are defined by the amount and distribution of intermolecular bonds in the sample at definite network structure. The latter is defined by the conditions of storage, exploitation, and production of the network. That is why T values may be different. The highest value is observed in the equilibrium state of the system. In this case it is necessary to point out, that the ph value becomes close to the ph one at n,. 

Now suppose that an actual change, in which the system is transferred from one equilibrium state to another infinitely close equilibrium state, occurs, and let us denote this real change by d to distinguish it frorii the virtual change 8. The temperature... 

The chemical reactivity of radicals is governed of course by the same chemical principles as the reactivity of systems having closed-shell ground states. Both equilibrium and rate processes are important here. The paucity of quantitative data on equilibrium and rate constants of radical reactions, suitable from the viewpoint of the present state of the theory, prevents a more rapid development in the MO applications this difficulty, however, is not specific for open-shell systems. 

As we all know from thermodynamics, closed systems in equilibrium have minimum free energy and maximum entropy. If such a system were brought out of equilibrium, i.e. to a state with lower entropy and higher free energy, it would automatically decay to the state of equilibrium, and it would lose all information about its previous states. A system s tendency to return to equilibrium is given by its free energy. An example is a batch reaction that is run to completion. 

A reaction at steady state is not in equilibrium. Nor is it a closed system, as it is continuously fed by fresh reactants, which keep the entropy lower than it would be at equilibrium. In this case the deviation from equilibrium is described by the rate of entropy increase, dS/dt, also referred to as entropy production. It can be shown that a reaction at steady state possesses a minimum rate of entropy production, and, when perturbed, it will return to this state, which is dictated by the rate at which reactants are fed to the system [R.A. van Santen and J.W. Niemantsverdriet, Chemical Kinetics and Catalysis (1995), Plenum, New York]. Hence, steady states settle for the smallest deviation from equilibrium possible under the given conditions. Steady state reactions in industry satisfy these conditions and are operated in a regime where linear non-equilibrium thermodynamics holds. Nonlinear non-equilibrium thermodynamics, however, represents a regime where explosions and uncontrolled oscillations may arise. Obviously, industry wants to avoid such situations ... 

In order to obtain a qualitative view of how the transition regime differs from the continuum flow or the slip flow regime, it is instructive to consider a system close to thermodynamic equilibrium. In such a system, small deviations from the equilibrium state, described by thermodynamic forces X, cause thermodynamic fluxes J- which are linear functions of the (see, e.g., [15]) ... 

Figure 4. Evolution of the (N2/N1) ratio in a reservoir in the two cases of closed system evolution (as a function of t/T2, where t is the time since fractionation), or in an open-system, steady-state reservoir (the steady-state (N2/N1) ratio is plotted as a function of x/ T2, where x is the residence time of the magma in the reservoir). Initial fractionation results in an arbitrarily chosen ratio of 2, which is kept constant for the iirfluent magma in the continuously replenished reservoir. The diagram shows that radioactive equilibrium is reached sooner in a closed system evolution. It also illustrates the fact that the radioactive parent-daughter pair should be chosen such as T2 is commensmate with the residence time of the magma in the reservoir (e.g., x/ T2 between 0.1 and 10). If T2 is much longer than the residence time x, then the (N2/N1) ratio will remain close to the initial value (here 2). If T2 is much shorter than x, equilibrium will be nearly established in the reservoir.

Here, the sign of equality (=) has been replaced by the double oppositely directed arrows (s=) called a sign of reversibility. Such a reaction is called a reversible reaction. The reversibility of reactions can be detected when both the forward and the reverse reactions occur to a noticeable extent. Generally, such reactions are described as reversible reactions. The most important criterion of a reaction of this type is that none of the reactants will become exhausted. When the reaction is allowed to take place in a closed system from where none of the substances involved in the reaction can escape, one obtains a mixture of the reactants and the products in the reaction vessel. Every reversible reaction, depending on its nature, will after some time reach a stage when the reactants and the products coexist in a state of balance, and their amounts will remain unaltered for unlimited time. Such a state of a chemical reaction is called chemical equilibrium, and the point of such an equilibrium varies only with temperature. 

Some of the terms used in classical thermodynamics which refer to equilibrium states and closed systems have become important outside the boundaries of physics one example is the term adapted state in Darwinian evolution theory, which represents a type of equilibrium state between the organism and its environment. 

In the simplest class of geochemical models, the equilibrium system exists as a closed system at a known temperature. Such equilibrium models predict the distribution of mass among species and minerals, as well as the species activities, the fluid s saturation state with respect to various minerals, and the fugacities of different gases that can exist in the chemical system. In this case, the initial equilibrium system constitutes the entire geochemical model. 

Closed-system models are those in which no mass transfer occurs. Equilibrium models, the simplest of this class, describe the equilibrium state of a system composed of a fluid, any coexisting minerals, and, optionally, a gas buffer. Such models... 

---