Solution equilibrium processes

The Nemst equation above for the dependence of the equilibrium potential of redox electrodes on the activity of solution species is also valid for uncharged species in the gas phase that take part in electron exchange reactions at the electrode-electrolyte interface. For the specific equilibrium process involved in the reduction of chlorine ... 

Process Description Reverse osmosis (RO) and nanofiltration (NF) processes utilize a membrane that selectively restricts flow of solutes while permitting flow of the solvent. The processes are closely related, and NF is sometimes called loose RO. They are kinetic processes, not equilibrium processes. The solvent is almost always water. 

In this solvent the reaction is catalyzed by small amounts of trimethyl-amine and especially pyridine (cf. 9). The same effect occurs in the reaction of iV -methylaniline with 2-iV -methylanilino-4,6-dichloro-s-triazine. In benzene solution, the amine hydrochloride is so insoluble that the reaction could be followed by recovery. of the salt. However, this precluded study mider Bitter and Zollinger s conditions of catalysis by strong mineral acids in the sense of Banks (acid-base pre-equilibrium in solution). Instead, a new catalytic effect was revealed when the influence of organic acids was tested. This was assumed to depend on the bifunctional character of these catalysts, which act as both a proton donor and an acceptor in the transition state. In striking agreement with this conclusion, a-pyridone is very reactive and o-nitrophenol is not. Furthermore, since neither y-pyridone nor -nitrophenol are active, the structure of the catalyst must meet the conformational requirements for a cyclic transition state. Probably a concerted process involving structure 10 in the rate-determining step... 

Ketal 73 can be formed in a yield of about 60 % by refluxing a solution of tetronic acid (36), ethylene glycol, and a catalytic amount of para-toluenesulfonic acid in benzene for approximately 12 hours. With only one electrophilic site, 73 reacts smoothly with Dibal-H to give lactol 35 in 84% yield. Compound 35, a participant in a ring-chain tautomeric equilibrium process,18 should be regarded as a latent aldehyde. This substance can, in fact, serve as... 

Other measurements of AfG involve measuring AG for equilibrium processes, such as the measurement of equilibrium constants, reversible voltages of electrochemical cells, and phase equilibrium measurements. These methods especially come into play in the measurement of Afand AfG for ions in solution, which are processes that we will now consider. 

The electron transfer between an electrode (e.g. a metal) and a corresponding speeies in solution (e.g. the metal ion) is a dynamic equilibrium process st E = Eo with 7a= 7c =7o This implies a eontinuous ex-... 

Halide exchange, sometimes call the Finkelstein reaction, is an equilibrium process, but it is often possible to shift the equilibrium." The reaction is most often applied to the preparation of iodides and fluorides. Iodides can be prepared from chlorides or bromides by taking advantage of the fact that sodium iodide, but not the bromide or chloride, is soluble in acetone. When an alkyl chloride or bromide is treated with a solution of sodium iodide in acetone, the equilibrium is shifted by the precipitation of sodium chloride or bromide. Since the mechanism is Sn2, the reaction is much more successful for primary halides than for secondary or tertiary halides sodium iodide in acetone can be used as a test for primary bromides or chlorides. Tertiary chlorides can be converted to iodides by treatment with excess Nal in CS2, with ZnCl2 as catalyst. " Vinylic bromides give vinylic iodides with retention of configuration when treated with KI and a nickel bromide-zinc catalyst," or with KI and Cul in hot HMPA." ... 

The present state of the theory of equilibrium processes is satisfactory. This holds, of course, only for gas-phase reactions between components of ideal or nearly ideal behavior. For actual equilibrium reactions of interest in solutions, the situation becomes more complex. Here a difficulty emerges because of a rather disappointing state of the theory of solvation phenomena. In reactions of... 

Figure 5.3. A cellular automata model of the interface between two immiscible bquids, after the demixing process has reached an equilibrium. A solute (encircled cells) has partitioned into the two phases according to its partition coefficient...

Equilibrium processes of intermolecular proton transfer between the thiolate center and SH group are observed in a solution along with the isomerization of betaine 201 to 701. These processes result in salts 71 (Scheme 32) similar to salts 69 in the carbon series, which was proved by 29Si NMR spectroscopy. 

In solution, organocopper compounds may exist as an equilibrium of several species, and a loss of enantioselectivity may be inevitable if this equilibrium process produces some achiral but more reactive cuprate species. The way to overcome this problem is to develop a highly reactive chiral reagent to suppress the undesired, nonchiral species-mediated reactions. 

Extraction is an equilibrium process, and therefore a finite amount of solute might be in both phases, necessitating other processing steps or manipulation of the chemical equilibria. 

The process of a solute dissolved in one solvent being pulled out, or extracted into a new solvent actually involves an equilibrium process. At the time of initial contact, the solute will move from the original solvent to the extracting solvent at a particular rate, but, after a time, it will begin to move back to the original solvent at a particular rate. When the two rates are equal, we have equilibrium. We can thus... 

The kinetics of sorption can be considered as the sum of two processes 1) rapid sorption by labile sites which are in equilibrium with solutes dissolved in bulk solution, and 2) hindered sorption by sites which are accessible only by slow diffusion. Alternatively, sorption kinetics can be modeled by a radial diffu-sional process into spherical sorbents. The slow sorption process prevents complete equilibration within one day, the time used in typical batch experiments. Because the apparent rate of diffusion decreases with increasing hydrophobicity, time to equilibrium is longer for highly hydrophobic compounds. 

The high precision with which Mg isotope ratios can be measured using MC-ICPMS opens up new opportunities for using Mg as a tracer in both terrestrial and extraterrestrial materials. A key advance is the ability to resolve kinetic from equilibrium mass-dependent fractionation processes. From these new data it appears that Mg in waters is related to mantle and crustal reservoirs of Mg by kinetic fractionation while Mg in carbonates is related in turn to the waters by equilibrium processes. Resolution of different fractionation laws is only possible for measurements of Mg in solution at present laser ablation combined with MC-ICPMS (LA-MC-ICPMS) is not yet sufficiently precise to measure different fractionation laws. 

The main transport processes involved are shown in Figure 6.7. In essence these are the same as in a non-flooded soil there is a dynamic equilibrium between solutes in the soil solution and those sorbed on the immediately adjacent... 

Lactonization, like esterification, is an equilibrium process. y-Lactones and 8-lactones are so readily formed that the carboxylic acid itself can provide the required acidic catalyst, and substantial amounts of the lactone are typically present in solutions of 4- or 5-hydroxy acids respectively (Table 7.3). Interestingly, the proportion of lactone is usually higher for five-membered rings than for six-membered rings. 

Solution condensations are also equilibrium processes, with the reaction often driven by removal of the by-product through distillation, salt formation, or precipitation. Many solution condensations are carried out near room temperature. Solvent entrapment is a problem, but since a reaction may occur under considerably reduced temperatures, compared to the melt process, thermally induced side reactions are minimized. Side reactions with the... 

A number of different equilibria may be present in the solution of a chiral substrate and the added chiral auxiliary compound. When all equilibrium processes are fast on the NMR timescale at ambient temperature, an averaged spectrum of shifts is observed. This is also the reason why peak coalescence of the anisochronous nuclei is observed when a racemic auxiliary compound is used5,81. The observed anisochrony of the enantiomers AR sS is highest when the chiral auxiliary compound is enantiomerically pure. AR sS decreases as the enantiomeric purity of the chiral auxiliary compound is reduced. AR sS changes its sign when the chirality of the chiral auxiliary compound is inverted (peak reversal). 

A linear solvation energy relationship (LSER) has been developed to predict the water-supercritical CO2 partition coefficients for a published collection of data. The independent variables in the model are empirically determined descriptors of the solute and solvent molecules. The LSER approach provides an average absolute relative deviation of 22% in the prediction of the water-supercritical CO2 partition coefficients for the six solutes considered. Results suggest that other types of equilibrium processes in supercritical fluids may be modeled using a LSER approach (Lagalante and Bruno, 1998). 

Note that A is called the conjugate base of HA and BH+ the conjugate acid of B. Proton transfer reactions as described by Eq. 8-1 are usually very fast and reversible. It makes sense then that we treat such reactions as equilibrium processes, and that we are interested in the equilibrium distribution of the species involved in the reaction. In this chapter we confine our discussion to proton transfer reactions in aqueous solution, although in some cases, such reactions may also be important in nonaqueous media. Our major concern will be the speciation of an organic acid or base (neutral versus ionic species) in water under given conditions. Before we get to that, however, we have to recall some basic thermodynamic aspects that we need to describe acid-base reactions in aqueous solution. 

The coefficient C, related to the resistance to mass transfer between the two phases, becomes important when the flow rate is too high for equilibrium to be obtained. Local turbulence within the mobile phase and concentration gradients slow down the equilibrium process (Cs <=> Cm). The diffusion of solute between the phases is not instantaneous, hence the solute will be in a non-equilibrium process. 

The symbol (s) designates a solid. At the surface of the precipitate, Ag+ anc Cl ions are constantly going into solution and redepositing from the solution. Because this is an equilibrium process, we can apply the mathematical relation... 

Some carbohydrates actively inhibit the crystallization of lactose, whereas others do not. Carbohydrates that are active possess either the /3-galactosyl or the 4-substituted-glucose group in common with lactose, so that adsorption can occur specifically at certain crystal faces (Van Krevald 1969). (3-Lactose, which is present in all lactose solutions [see Equilibrium in Solution (Mutarotation )], has been postulated to be principally responsible for the much slower crystallization of lactose compared with that of sucrose, which does not have an isomeric form to interfere with the crystallization process (Van Krevald 1969). Lactose solubility can be decreased substantially by the pres-... 

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