Equilibrium and separation

Thermodynamic Properties of the Surface Consider two bulk phases I and II in equilibrium and separated by a surface of area As. For the thermodynamic variables Z = U, H, A or G, we define the surface quantity Zs as the excess over the amount for the bulk phases. That is... 

Excess iodine shifts chemical equilibrium and separates acids by liquid-liquid phase equilibrium... 

If point M in the previous example lies in the 1-phase region of the phase diagram, then we are done because we know the composition xc of the single phase leaving the mixer. If the point M lies in the two-phase region and the two phases are allowed to reach equilibrium and separate in the settler, we will have (not one, but) two product streams. 

Extraction involves the transfer of components between two liquid phases, much as absorption or stripping involves the transfer of components from liquid to vapor phase or vice versa. As in vapor-liquid multistage separation processes, the device employed to carry out liquid-liquid extraction is usually a counterflow column that performs the function of a number of equilibrium stages interconnected in counterflow configuration. In each stage, two inlet liquid streams mix, reach equilibrium, and separate into two outlet liquid streams. As in vapor-liquid columns, the lack of complete equilibrium in liquid-liquid extractors is accounted for by some form of tray efficiency. Liquid-liquid extraction may also be carried out in a cascade of mixing vessels connected in series in counterflow. 

Stagewise contact. In this category are included those arrangements of equipment where solvent and mixture to be separated are intimately contacted, allowed to approach equilibrium, and separated. The operation may then be repeated and with a variety of flowsheets. 

The calculation of single-stage equilibrium separations in multicomponent systems is implemented by a series of FORTRAN IV subroutines described in Chapter 7. These treat bubble and dewpoint calculations, isothermal and adiabatic equilibrium flash vaporizations, and liquid-liquid equilibrium "flash" separations. The treatment of multistage separation operations, which involves many additional considerations, is not considered in this monograph. 

In aqueous solution at 100° the change is reversible and equilibrium is reached when 95 per cent, of the ammonium cyanate has changed into urea. Urea is less soluble in water than is ammonium sulphate, hence if the solution is evaporated, urea commences to separate, the equilibrium is disturbed, more ammonium cyanate is converted into urea to maintain the equilibrium and evfflitually the change into urea becomes almost complete. The urea is isolated from the residue by extraction with boiling methyl or ethyl alcohol. The mechanism of the reaction which is generally accepted involves the dissociation of the ammonium cyanate into ammonia and cyanic acid, and the addition of ammonia to the latter ... 

E. J. Henley and. D. Seader, Equilibrium-Stage Separation Operations in ChemicalEngineering ]ohn. Wiley Sons, Inc., New York, 1981. 

In addition to constitution and configuration, there is a third important level of structure, that of conformation. Conformations are discrete molecular arrangements that differ in spatial arrangement as a result of facile rotations about single bonds. Usually, conformers are in thermal equilibrium and cannot be separated. The subject of conformational interconversion will be discussed in detail in Chapter 3. A special case of stereoisomerism arises when rotation about single bonds is sufficiently restricted by steric or other factors that- the different conformations can be separated. The term atropisomer is applied to stereoisomers that result fk m restricted bond rotation. ... 

Figure 9 is the VLE plot for a binary mixture that has essentially a uniform equilibrium, and therefore represents a relatively easy separation. However, there are many cases where non-ideal separations are encountered. These more difficult distillations are defined by the examples shown in Figure 10. 

Henley, E. J. and Seader, J. D. (1981). Equilibrium-Stage Separation Operations in Chemical Engineering. Wiley, New York. 

In systems such as the 2- and 6-hydroxypteridine series, rapid potentiometric or spectrophotometric pA determinations on neutral solutions usually give values near to the acidic pA of the hydrated series. (Exceptions include 2-hydroxy-4,6,7-trimethyl-, 6-hydroxy-7-methyl-, and 4,6-dihydroxy-pteridine, where the neutral solution contains comparable amounts of hydrated and anhydrous species. In such cases, rapid potentiometric titrations show two well-defined and separated curves, one for the hydrated, the other for the anhydrous, species.) Similarly, from solutions of the anion, an approximate pA value for the anhydrous species is obtained. For convenience, the anhydrous molecule is referred to as HX, its anion as X , the hydrated neutral molecule as HY, and its anion as Y, and the two equilibrium constants are defined as follows ... 

Henley, E. J. andj. D., Seader, Equilibrium Stage Separations in Chemical Engineering John Wiley and Sons (1981), p. 507. 

A low-pressure process has been developed by ICl operating at about 50 atm (700 psi) using a new active copper-based catalyst at 240°C. The synthesis reaction occurs over a bed of heterogeneous catalyst arranged in either sequential adiabatic beds or placed within heat transfer tubes. The reaction is limited by equilibrium, and methanol concentration at the converter s exit rarely exceeds 7%. The converter effluent is cooled to 40°C to condense product methanol, and the unreacted gases are recycled. Crude methanol from the separator contains water and low levels of by-products, which are removed using a two-column distillation system. Figure 5-5 shows the ICl methanol synthesis process. 

This distinction between the conditions in a chemical system at equilibrium and the rate at which these conditions are attained is very important in chemistry. By arguments that we shall consider a chemist can decide with confidence whether equilibrium favors reactants or products or neither. He cannot predict, however, how rapidly the system will approach the equilibrium conditions. That is a matter of reaction rates, and the chemist must perform separate experiments to learn whether a given rate is rapid or not. 

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