Chemical reaction equilibrium sequential

In the case of two sequential chemical reactions, A B and B C, each reaction has its own equilibrium constant and each has its characteristic standard free-energy change, AG ° and AG2°. As the two reactions are sequential, B cancels out to give the overall reaction A C, which has its own equilibrium constant and thus... 

Systems of biochemical reactions like glycolysis, the citric acid cycle, and larger and smaller sequential and cyclic sets of enzyme-catalyzed reactions present challenges to make calculations and to obtain an overview. The calculations of equilibrium compositions for these systems of reactions are different from equilibrium calculations on chemical reactions because additional constraints, which arise from the enzyme mechanisms, must be taken into account. These additional constraints are taken into account when the stoichiometric number matrix is used in the equilibrium calculation via the program equcalcrx, but they must be explicitly written out when the conservation matrix is used with the program equcalcc. The stoichiometric number matrix for a system of reactions can also be used to calculate net reactions and pathways. 

To calculate thermodynamic equilibrium in multicomponent systems, the so-called optimization method and the non-linear equation method are used, both discussed in [69]. In practice, however, kinetic problems have also to be considered. A heterogeneous process consists of various occurrences such as diffusion of the starting materials to the surface, adsorption of these materials there, chemical reactions at the surface, desorption of the by-products from the surface and their diffusion away. These single occurrences are sequential and the slowest one determines the rate of the whole process. Temperature has to be considered. At lower substrate temperatures surface processes are often rate controlling. According to the Arrhenius equation, the rate is exponentially dependent on temperature ... 

Activities of electrons and protons capable of participating in chemical reactions are determined only by conditions under which the rest of water components interact between themselves on the way to equilibrium. Main forms of such interaction are association, i.e., attaching of one component to the other with the formation of more complex compounds, and dissociation, i.e., destruction of these complex compoxmds. A series of sequential associations with the formation of larger super-molecular compoxmds is called complexation. In this process participate mostly ions and dipoles of H O, much more seldom neutral molecxiles with the covalent bond. 

Thus, for ideal systems, both the constants of chemical equilibrium, thermodynamic and kinetic, have one and the same expression. Let us emphasize again that everything stated above is valid only for the elementary act of a chemical reaction. If reaction (2.1) is not an elementary act, but actually represents a scheme of sequential or parallel elementary acts, the kineti-cally and thermodynamically determined equilibrium constants may differ substantially. 

The holistic thermodynamic approach based on material (charge, concentration and electron) balances is a firm and valuable tool for a choice of the best a priori conditions of chemical analyses performed in electrolytic systems. Such an approach has been already presented in a series of papers issued in recent years, see [1-4] and references cited therein. In this communication, the approach will be exemplified with electrolytic systems, with special emphasis put on the complex systems where all particular types (acid-base, redox, complexation and precipitation) of chemical equilibria occur in parallel and/or sequentially. All attainable physicochemical knowledge can be involved in calculations and none simplifying assumptions are needed. All analytical prescriptions can be followed. The approach enables all possible (from thermodynamic viewpoint) reactions to be included and all effects resulting from activation barrier(s) and incomplete set of equilibrium data presumed can be tested. The problems involved are presented on some examples of analytical systems considered lately, concerning potentiometric titrations in complex titrand + titrant systems. All calculations were done with use of iterative computer programs MATLAB and DELPHI. 

As pointed out earlier, CVD is a steady-state, but rarely equilibrium, process. It can thus be rate-limited by either mass transport (steps 2, 4, and 7) or chemical kinetics (steps 1 and 5 also steps 3 and 6, which can be described with kinetic-like expressions). What we seek from this model is an expression for the deposition rate, or growth rate of the thin film, on the substrate. The ideal deposition expression would be derived via analysis of all possible sequential and competing reactions in the reaction mechanism. This is typically not possible, however, due to the lack of activation or adsorption energies and preexponential factors. The most practical approach is to obtain deposition rate data as a function of deposition conditions such as temperature, concentration, and flow rate and fit these to suspected rate-limiting reactions. 

Reactions in which all the substrates bind to the enzyme before the first product is formed are called sequential. Reactions in which one or more products are released before all the substrates are added are called ping-pong. Sequential mechanisms are called ordered if the substrates combine with the enzyme and the products dissociate in an obligatory order. A random mechanism implies no obligatory order of combination or release. The term rapid equilibrium is applied when the chemical steps are slower than those for the binding of reagents. Some examples follow. 

Flush The flush reaction path model is analogous to the perfectly mixed-flow reactor or the continuously stirred tank reactor in chemical engineering (Figure 2.5). Conceptually, the model tracks the chemical evolution of a solid mass through which fresh, unreacted fluid passes through incrementally. In a flush model, the initial conditions include a set of minerals and a fluid that is at equilibrium with the minerals. At each step of reaction progress, an increment of unreacted fluid is added into the system. An equal amount of water mass and the solutes it contains is displaced out of the system. Environmental applications of the flush model can be found in simulations of sequential batch tests. In the experiments, a volume of rock reacts each time with a packet of fresh, unreacted fluids. Additionally, this type of model can also be used to simulate mineral carbonation experiments. 

The Equilibrium reactor is a vessel which models equilibrium reactions. The outlet streams of the reactor are in a state of chemical and physical equilibrium. The reaction set which you attach to the Equilibrium reactor can contain an unlimited number of equilibrium reactions, which are simultaneously or sequentially solved. Neither the components nor the mixing process need be ideal, since HYSYS can compute the chemical activity of each component in the mixture based on mixture and pure component fugacities. 

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