Equilibrium controls

Hydrolysis (Sections 20 10 and 20 11) Ester hydrolysis may be catalyzed either by acids or by bases Acid catalyzed hydrolysis is an equilibrium controlled process the reverse of the Fischer esterification Hydrolysis in base IS irreversible and is the method usual ly chosen for preparative purposes... 

Now let s carry out the same reaction at some higher temperature so that both processes are readily reversible and an equilibrium is reached. Since C is more stable than B, C is the major product obtained. It doesn t matter that C forms more slowly than B, because the two are in equilibrium. The product of a readily reversible reaction depends only on stability, not on relative rates. Such reactions are said to be under equilibrium control, or thermodynamic control. 

Figure 12. Schematic flow sheet for methanation system using equilibrium-controlled adiabatic reactors...

Rainwater and snowmelt water are primary factors determining the very nature of the terrestrial carbon cycle, with photosynthesis acting as the primary exchange mechanism from the atmosphere. Bicarbonate is the most prevalent ion in natural surface waters (rivers and lakes), which are extremely important in the carbon cycle, accoxmting for 90% of the carbon flux between the land surface and oceans (Holmen, Chapter 11). In addition, bicarbonate is a major component of soil water and a contributor to its natural acid-base balance. The carbonate equilibrium controls the pH of most natural waters, and high concentrations of bicarbonate provide a pH buffer in many systems. Other acid-base reactions (discussed in Chapter 16), particularly in the atmosphere, also influence pH (in both natural and polluted systems) but are generally less important than the carbonate system on a global basis. 

SYNTHESIS OF P-D-GLUCOPYRANOSIDE UNDER EQUILIBRIUM-CONTROLLED CONDITION... 

It is believed that the regiospecifidty of the dioxabicyclization and the concurrent formation of bicyclic ethers 48 and 49 both result from equilibrium control of reversible (per)oxymercuration — de(per)oxymercuration. Thus to optimise the yield of 47 it is important to minimize the amount of water present in the reaction mixture and use of concentrated hydrogen peroxide (>80%) with anhydrous mercury(II) trifluoroacetate is recommended. 

Controlling the water concentration (thermodynamic equilibrium control). 

Equilibrium control the outcome of an acid-base reaction is determined by the position of an equilibrium. 

If the step is only equilibrium controlled, a lumped analysis of both fluid and solid phase is possible and the corresponding nonlinear wavefront analysis is straight forward too. Analysis of propagation speed data yield information about the relevant equilibrium sorption mechanism (7). The different form of the transients when a reaction step has been stimulated, is discussed in the Appendix. 

At 25°C and p = 0.1 M, the values of are 10 -10 M and those of k are 10 -10 s depending on the identity of L. The internal electron transfer rate in an outer-sphere complex can thus be analyzedwithout considering work terms or, what is equivalent, the equilibrium controlling the formation of precursor complex. This favorable situation is even improved when the metal centers are directly bridged. The relative orientation of the two metal centers in a well-established geometry can be better treated than in the outer-sphere complex (Sec. 5.8). 

Processes such as UOP s Isomar process are used to carry out isomerization of C8 aromatic species so that p-xylene can be removed selectively from the mixture of xylenes. The reaction is equilibrium controlled, so a continuous isomerization process is used. As is seen below, both aluminophosphate and aluminosilicate zeotypes are capable of catalyzing the reaction (Table 12.13). 

As discussed above, proteases are peptide bond hydrolases and act as catalysts in this reaction. Consequently, as catalysts they also have the potential to catalyze the reverse reaction, the formation of a peptide bond. Peptide synthesis with proteases can occur via one of two routes either in an equilibrium controlled or a kinetically controlled manner 60). In the kinetically controlled process, the enzyme acts as a transferase. The protease catalyzes the transfer of an acyl group to a nucleophile. This requires an activated substrate preferably in the form of an ester and a protected P carboxyl group. This process occurs through an acyl covalent intermediate. Hence, for kineticmly controlled reactions the eii me must go through an acyl intermediate in its mechanism and thus only serine and cysteine proteases are of use. In equilibrium controlled synthesis, the enzyme serves omy to expedite the rate at which the equilibrium is reached, however, the position of the equilibrium is unaffected by the protease. 

If a particular molecular entity(ies) participates in two or more parallel reactions and the proportion of the resulting products is determined by the relative equilibrium constants for the interconversion of reaction intermediates on or after the rate-determining step(s), then the more prevalent product is said to be thermodynamically controlled (i.e., the more stable product will be the one formed in highest amounts). If the reactions are reversible and the system is allowed to go to equilibrium, the favored product is the thermodynamically controlled species. A synonymous term is equilibrium control. See also Kinetic Control... 

The extent to which cyclization occurs during polymerization depends on whether the polymerization proceeds under equilibrium control or kinetic control, the ring sizes of the possible cyclic products, and the specific reaction conditions. 

When H2O deacetylates the acyl-enzyme, phenylacetic acid is formed. When nucleophiles other than H2O deacylate the acyl-enzyme, a new condensation product, in this case phenylacetyl-O-R or phenylacetyl-NH-R is formed. By definition the hydrolysis of these condensation products can be catalyzed by the same enzyme that catalyzes their formation in equation 10.1. Thus, when the acyl-enzyme is formed from phenylacetyl-glycine or phenylacetyl-O-Me, this gives rise to an alternative process to produce Penicillin G, in addition to the thermodynamically controlled (= equilibrium controlled) condensation of phenylacetic acid and 6-aminopenicillanic acid (6-APA). This reaction that involves an activated side chain is a kinetically controlled (= rate controlled) process where the hydrolase acts as a transferase (Kasche, 1986 1989). 

The stereo- and regioselectivity of deprotonation can be kinetically or thermodynamically (equilibrium) controlled. Equilibrium between enolates occurs when a proton donor is present. The proton donor can be the solvent or an excess of the ketone in relation to the strong base present for generation of the enolate. Ketone enolate equilibration can also proceed via an aldol-rever-... 

It is further stated by Kistiakowsky (Ref 24, PP 954-55) that a restatement of above reasoning from a slightly different point of view may be helpful for a correct perspective on the situation existing in a detonation wave. Such wave, from a chem standpoint, starts in the intact explosive certain fast reactions take place in it. which may eventually progress to a state of complete hydro-dynamic equilibrium, controlled by the local pressure and temp in the wave. 

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