Equilibrium chemical process

Vlachos, D.G., Molecular modeling for non-equilibrium chemical processes, in (S. Lee, Ed.), Encyclopedia of Chemical Processing , Marcel Dekker, Inc., New York (2004). 

Although equilibrium chemical processes have been widely used to model the early evolution of the Solar System, there is growing evidence, particularly in isotopic abundances, that non-equilibrium chemistry was also important. The specific process of isotopic self-shielding in the photolysis of carbon monoxide may have played a major role. A key test of this hypothesis will be provided by laboratory-based isotopic analysis of the solar wind sampled in the NASA Genesis mission. 

Substituting [9.49] in [9.48], we come to an equation that in general describes the mixed solvent effect on the equilibrium chemical process ... 

Many reactions involving ions, such as ion association, electron and proton transfer, and ligand exchange, occur very promptly, and the equilibrium state is established in the system. Several special methods were developed for the kinetic study of such systems. They can be classified as three types methods with fast single distortion of the equilibrium state of the system, methods of periodical physical action on a solution in which the equilibrium chemical process occurs, and electrochemical methods for studying ion reactions. 

The most frequent application of phase-equilibrium calculations in chemical process design and analysis is probably in treatment of equilibrium separations. In these operations, often called flash processes, a feed stream (or several feed streams) enters a separation stage where it is split into two streams of different composition that are in equilibrium with each other. 

A brief description of a low-density non-equilibrium plasma is given followed by a review of its characteristic features and of tire relevant collisionprocesses in tire plasma. Principles for tire generation of plasmas in teclmical devices are discussed and examples of important plasma chemical processes and tlieir technical applications are presented. 

P. A. Gupte, M. Nagvekar, R. P. Danner, and T. E. Daubert, Documentation of the Basis for Selection of the Contents of Chapters Phase Equilibrium in Manualfor Predicting Chemical Process Design Data, Design Institute for Physical Property Data (AIChE), (1987). 

For a symmetrical separation of component h from c, Brian Staged Cascades in Chemical Processing, Prentice-Hall, Englewood Cliffs, N.J., 1972) reported that the ratio of wash solvent to extraction solvent W /S should be set equal to the geometric mean of the two slopes of the equilibrium lines [Eq. (15-35)]. 

The second classification is the physical model. Examples are the rigorous modiiles found in chemical-process simulators. In sequential modular simulators, distillation and kinetic reactors are two important examples. Compared to relational models, physical models purport to represent the ac tual material, energy, equilibrium, and rate processes present in the unit. They rarely, however, include any equipment constraints as part of the model. Despite their complexity, adjustable parameters oearing some relation to theoiy (e.g., tray efficiency) are required such that the output is properly related to the input and specifications. These modds provide more accurate predictions of output based on input and specifications. However, the interactions between the model parameters and database parameters compromise the relationships between input and output. The nonlinearities of equipment performance are not included and, consequently, significant extrapolations result in large errors. Despite their greater complexity, they should be considered to be approximate as well. 

Stratospheric ozone is in a dynamic equilibrium with a balance between the chemical processes of formation and destruchon. The primary components in this balance are ultraviolet (UV) solar radiation, oxygen molecules (O2), and oxygen atoms (O) and may be represented by the following reactions ... 

Estimation of the free-energy change associated with a reaction permits the calcula-aon of the equilibrium position for a reaction and indicates the feasibility of a given chemical process. A positive AG° imposes a limit on the extent to which a reaction can x cur. For example, as can be calculated using Eq. (4.2), a AG° of 1.0 kcal/mol limits conversion to product at equilibrium to 15%. An appreciably negative AG° indicates that e reaction is thermodynamically favorable. 

For chemical reactions, just as for phase changes, at equilibrium, microscopic processes continue but in a balance which gives no macroscopic changes. 

In chemical processing the most fundamental constraint is that of the thermodynamics of the system. This constraint defines both the heat balance of the process and whether or not the processes in the reactor will be equilibrium limited. These constraints will limit the range of chemical engineering solutions to the problems of designing an economically viable process that can be found. 

In Chapter 1 we described the fundamental thermodynamic properties internal energy U and entropy S. They are the subjects of the First and Second Laws of Thermodynamics. These laws not only provide the mathematical relationships we need to calculate changes in U, S, H,A, and G, but also allow us to predict spontaneity and the point of equilibrium in a chemical process. The mathematical relationships provided by the laws are numerous, and we want to move ahead now to develop these equations.1... 

To derive the condition for thermodynamic equilibrium, we start with an isolated system consisting of two subsystems as shown in Figure 5.6. Subsystem A is the one of primary interest in that it is the one in which the chemical process is occurring. Subsystem B is a reservoir in contact with subsystem A in such a way that energy in the form of heat or work can flow between the two subsystems. If left alone, the system will come to equilibrium. Energy will be transferred between the subsystems so that the temperature and pressure will be... 

In summary, we now have the tools for describing phase equilibrium for both pure materials and for mixtures, and for understanding chemical processes at equilibrium. We will rely upon the foundation developed in this chapter as we... 

In Chapter 5, we considered systems in which composition becomes a variable, and defined and described the chemical potential. We showed that the chemical potential provides the condition for spontaneity or equilibrium. It is the potential that drives the flow of mass in a chemical process, A useful quantity related to the chemical potential is the fugacity. It can also be thought of as a measure of the flow of mass in a chemical process, and can be used to determine the point of equilibrium. It is often known as the escaping tendency since it can be used to describe the ease with which mass flows from one phase to another, particularly the flow from a solid or liquid phase to a gas phase. 

We now have the foundation for applying thermodynamics to chemical processes. We have defined the potential that moves mass in a chemical process and have developed the criteria for spontaneity and for equilibrium in terms of this chemical potential. We have defined fugacity and activity in terms of the chemical potential and have derived the equations for determining the effect of pressure and temperature on the fugacity and activity. Finally, we have introduced the concept of a standard state, have described the usual choices of standard states for pure substances (solids, liquids, or gases) and for components in solution, and have seen how these choices of standard states reduce the activity to pressure in gaseous systems in the limits of low pressure, to concentration (mole fraction or molality) in solutions in the limit of low concentration of solute, and to a value near unity for pure solids or pure liquids at pressures near ambient. 

Chemical processes are central to the study of chemistry. The thermodynamic principles and relationships we have developed provide powerful tools for describing these processes, especially in predicting the spontaneity of the process and the equilibrium conditions that apply. 

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