Chemical equilibrium examples

TABLE III. Single-Stage Simultaneous Phase and Chemical Equilibrium Example Problem... 

The changes, however, are both numerous and significant. First of all, there is a change in the organization of the subject matter. For example, material formerly contained in the section entitled Analytical Chemistry is now grouped by operational categories spectroscopy electrolytes, electromotive force, and chemical equilibrium and practical laboratory information. Polymers, rubbers, fats, oils, and waxes constitute a large independent section. 

An example of enhanced ion production. The chemical equilibrium exists in a solution of an amine (RNH2). With little or no acid present, the equilibrium lies well to the left, and there are few preformed protonated amine molecules (ions, RNH3+) the FAB mass spectrum (a) is typical. With more or stronger acid, the equilibrium shifts to the right, producing more protonated amine molecules. Thus, addition of acid to a solution of an amine subjected to FAB usually causes a large increase in the number of protonated amine species recorded (spectrum b). 

Steady state pi oblems. In such problems the configuration of the system is to be determined. This solution does not change with time but continues indefinitely in the same pattern, hence the name steady state. Typical chemical engineering examples include steady temperature distributions in heat conduction, equilibrium in chemical reactions, and steady diffusion problems. 

When chemical equilibrium is achieved qiiickly throughout the liquid phase (or can be assumed to exist), the problem becomes one of properly defining the physical and chemical equilibria for the system. It sometimes is possible to design a plate-type absorber by assuming chemical-equilibrium relationships in conjunction with a stage efficiency factor as is done in distillation calculations. Rivas and Prausnitz [Am. Tn.st. Chem. Eng. J., 25, 975 (1979)] have presented an excellent discussion and example of the correct procedures to be followed for systems involving chemical equihbria. 

The dissolving of limestone by ground water is another example of chemical equilibrium. The behavior of this system depends upon the chemical equilibrium between CaC03 and its dissolved ions and the equilibrium between carbonate ion and dissolved C02 in the water. When CaC03 dissolves in water it establishes the equilibrium... 

Our sun is, of course, a star. It is a relatively cool star and, as such, contains a number of diatomic molecules (see Figure 25-3). There are many stars, however, with still lower surface temperatures and these contain chemical species whose presence can be understood in terms of the temperatures and the usual chemical equilibrium principles. For example, as the star temperature drops, the spectral lines attributed to CN and CH become more prominent. At lower temperatures, TiO becomes an important species along with the hydrides MgH, SiH, and A1H, and oxides ZrO, ScO, YO, CrO, AlO, and BO. 

Guldberg and Waage (1867) clearly stated the Law of Mass Action (sometimes termed the Law of Chemical Equilibrium) in the form The velocity of a chemical reaction is proportional to the product of the active masses of the reacting substances . Active mass was interpreted as concentration and expressed in moles per litre. By applying the law to homogeneous systems, that is to systems in which all the reactants are present in one phase, for example in solution, we can arrive at a mathematical expression for the condition of equilibrium in a reversible reaction. 

We are now prepared to use thermodynamics to make chemical equilibrium calculations. The following examples demonstrate some of the possibilities. 

This is usually thought of as a phase equilibrium problem. Earlier, we indicated that a phase equilibrium is nothing more than a simple chemical equilibrium. This problem is one such example. 

Chapters 7 to 9 apply the thermodynamic relationships to mixtures, to phase equilibria, and to chemical equilibrium. In Chapter 7, both nonelectrolyte and electrolyte solutions are described, including the properties of ideal mixtures. The Debye-Hiickel theory is developed and applied to the electrolyte solutions. Thermal properties and osmotic pressure are also described. In Chapter 8, the principles of phase equilibria of pure substances and of mixtures are presented. The phase rule, Clapeyron equation, and phase diagrams are used extensively in the description of representative systems. Chapter 9 uses thermodynamics to describe chemical equilibrium. The equilibrium constant and its relationship to pressure, temperature, and activity is developed, as are the basic equations that apply to electrochemical cells. Examples are given that demonstrate the use of thermodynamics in predicting equilibrium conditions and cell voltages. 

Sub-micro representations are used extensively in teaching the mole concept, stoichiometiy, solubihty and chemical equilibrium at UCT. Having students draw and annotate chemical diagrams representing chemical phenomena at the sub-micro level can provide some insight into their understanding of chemistiy at the macro level. The following examples are typical of the questions used to probe links between the sub-micro and symbohc levels of representations as part of the assessment practice for this course. For example, students were asked to balance the equation shown in Fig. 8.7. 

An excellent overview of the problems that students experience in learning the notions underlying chemical equilibrium is available (van Driel Graber, 2002). Research shows that conceptual problems arose when students, who had been introduced to chemical reactions through examples that evidently go to completion , first met examples of incomplete reactions . In this situation, they... 

It is possible to carry out this type of kinetic analysis whether a mechanism is simple or elaborate. That is, we can always derive the equilibrium expression for a reaction by applying reversibility and setting forward and reverse rates equal to one another at equilibrium. It is unnecessary to go through this procedure for every chemical equilibrium. As our two examples suggest, inspection of the overall stoichiometry always gives the correct expression for the equilibrium constant. That is, a reaction of the form tjA + iBf ofD + eE has an... 

In some problems, concentrations at equilibrium are provided, hi other problems concentrations at equilibrium must be calculated, usually by using amounts tables (see Chapter In this example, we are told that a solution of LiF at chemical equilibrium has [F ]gg =6.16x 10 M. The stoichiometric ratio of LiF is 1 1, so an equal amount of Li dissolves [Li+]gg = 6.16 X 10 M. 

The chemical equilibrium is the same one that we identified in Example. ... 

C16-0036. List the types of chemical equilibrium introduced in this chapter and give a specific example of each. 

Even if a system is not in chemical equilibrium it is possible to calculate the rate at which it is approaching equilibrium if we have sufficiently detailed knowledge of the energies involved in the transition state (so that it is possible to calculate the partition functions - the crucial step). However, computational chemistry has advanced to a level that good estimates of reaction rates can almost be obtained routinely. We will discuss examples in Chapter 6. 

Intelligent engineering can drastically improve process selectivity (see Sharma, 1988, 1990) as illustrated in Chapter 4 of this book. A combination of reaction with an appropriate separation operation is the first option if the reaction is limited by chemical equilibrium. In such combinations one product is removed from the reaction zone continuously, allowing for a higher conversion of raw materials. Extractive reactions involve the addition of a second liquid phase, in which the product is better soluble than the reactants, to the reaction zone. Thus, the product is withdrawn from the reactive phase shifting the reaction mixture to product(s). The same principle can be realized if an additive is introduced into the reaction zone that causes precipitation of the desired product. A combination of reaction with distillation in a single column allows the removal of volatile products from the reaction zone that is then realized in the (fractional) distillation zone. Finally, reaction can be combined with filtration. A typical example of the latter system is the application of catalytic membranes. In all these cases, withdrawal of the product shifts the equilibrium mixture to the product. 

For example, if sphalerite is in equilibrium with aqueous solution, the chemical equilibrium for the following reaction can be derived. 

Here K is the thermodynamic chemical equilibrium constant. If AH is constant, direct integration yields an explicit expression. If AH is a function of temperature, as described in Sec. 1.3.3, then its dependancy on Cp can be easily included and integration is again straight forward. A calculation with varying AH and Cp being functions of temperature is given in the simulation example REVTEMP. 

In this example the exit gas stream composition from a converter will be determined for a given inlet gas composition and steam ratio by assuming that in the outlet stream the gases reach chemical equilibrium. In practice the reaction is carried out over a catalyst, and the assumption that the outlet composition approaches the equilibrium composition is valid. Equilibrium constants for the reaction are readily available in the literature. 

An ecosystem can be thought of as a representative segment or model of the environment in which one is interested. Three such model ecosystems will be discussed (Figures 1 and 2). A terrestrial model, a model pond, and a model ecosystem, which combines the first two models, are described in terms of equilibrium schemes and compartmental parameters. The selection of a particular model will depend on the questions asked regarding the chemical. For example, if one is interested in the partitioning behavior of a soil-applied pesticide the terrestrial model would be employed. The model pond would be selected for aquatic partitioning questions and the model ecosystem would be employed if overall environmental distribution is considered. 

Here the square brackets indicate the concentration of the chemical species within the bracket. That is, [A] means the concentration of A, and so forth. [A]" means the concentration of A raised to the a power, where a is the value of the coefficient of A in the balanced equation for the chemical equilibrium. The value of the ratio of concentration terms is symbolized by the letter K, called the equilibrium constant. For example, for the reaction of nitrogen and hydrogen referred to in Sec. 19.3,... 

Propagation problems. These problems are concerned with predicting the subsequent behavior of a system from a knowledge of the initial state. For this reason they are often called the transient (time-varying) or unsteady-state phenomena. Chemical engineering examples include the transient state of chemical reactions (kinetics), the propagation of pressure waves in a fluid, transient behavior of an adsorption column, and the rate of approach to equilibrium of a packed distillation column. 

The thermodynamic effects of electric fields and are well known. Application of an electric field to a solution can affect the chemical equilibrium. For example, in Eq. (18) where C has a large dipole moment and B has a small dipole moment the equilibrium is shifted toward C under the action of an electric field. 

Quantitative structure-chemical reactivity relationships (QSRR). Chemical reactivities involve the formation and/or cleavage of chemical bonds. Examples of chemical reactivity data are equilibrium constants, rate constants, polarographic half wave potentials and oxidation-reduction potentials. 

---