In nonaqueous solvents

Table 8.11 pK, Values for Proton-Transfer Reactions in Nonaqueous Solvents 8.81... 

FIGURE 8.1 Approximate potential ranges in nonaqueous solvents. 

Another important example of a redox titration for inorganic analytes, which is important in industrial labs, is the determination of water in nonaqueous solvents. The titrant for this analysis is known as the Karl Fischer reagent and consists of a mixture of iodine, sulfur dioxide, pyridine, and methanol. The concentration of pyridine is sufficiently large so that b and SO2 are complexed with the pyridine (py) as py b and py SO2. When added to a sample containing water, b is reduced to U, and SO2 is oxidized to SO3. 

Fritz, J. S. Acid-Base Titrations in Nonaqueous Solvents. Allyn and Bacon Boston, 1973. 

Other difficulties of measuring pH in nonaqueous solvents are the complications that result from dehydration of the glass pH membrane, increased sample resistance, and large Hquid-junction potentials. These effects are complex and highly dependent on the type of solvent or mixture used (1,5). 

Table 3. Solubilities of the Hydrox ybenzoic Acids in Nonaqueous Solvents, Wt % ...

Table 1. Solubility of Sodium Nitrite in Nonaqueous Solvents ...

Micellar properties are affected by changes in the environment, eg, temperature, solvents, electrolytes, and solubilized components. These changes include compHcated phase changes, viscosity effects, gel formation, and Hquefication of Hquid crystals. Of the simpler changes, high concentrations of water-soluble alcohols in aqueous solution often dissolve micelles and in nonaqueous solvents addition of water frequendy causes a sharp increase in micellar size. 

Regioselective Acylation of Hydroxy Compounds. AUphatic diols can be selectively acylated at the primary position by a number of Upases in nonaqueous solvents. For example, PPL suspended in solutions of various diols in ethyl carboxylates catalyzes transesterification in a highly regioselective manner, producing primary monoesters in up to 97% yield (93). Similarly, chloramphenicol [56-75-7] (72) (R = NO2) can be acylated by a number of Upases to produce optically pure, water-insoluble 3-0-palmitate in a highly selective manner (94). 

Work under this classification (76AHCS1, p. 31) continues to be sparse. Heat-of-solution data provide a useful method for estimating A// for tautomeric processes in nonaqueous solvents, as was illustrated in the case of 2-pyridone 15a/2-hydroxypyridine 15b equilibrium (76TL2685). Heats of dehydration of 4-hydroxypyrazolines into pyrazoles and 5-hydroxyisoxazolines... 

Active carbonyl compounds such as benzaldehyde attack the electron-rich double bond in DTDAFs to give a dipolar adduct, which immediately undergoes dissociation with formation of two molecules of 146 (64BSF2857 67LA155).Tlie existence of by-products such as benzoin led to the synthetic application of thiazolium salts in the acyloin condensation. For example, replacement of the classic cyanide ion by 3-benzyl-4-methyl-5(/3-hydroxyethyl) thiazolium salts allowed the benzoin-type condensation to take place in nonaqueous solvents (76AGE639) (Scheme 57). 

A recently discovered (2) oxidizing system promises to become very important for the oxidation of acid-sensitive compounds. The reagent is chromium trioxide-pyridine complex, which may be isolated after preparation and employed in nonaqueous solvents (usually methylene chloride). A remarkable feature of the reagent is that good yields of aldehydes are obtained by direct oxidation of primary alcohols. The preparation of the reagent and its use are given. 

Sulfur is known to be easily reducible in nonaqueous solvents and its reduction products exist at various levels of reduction of polysulfide radical anions (S . ) and dianions (Sm2 ) 173], Recently Be-senhard and co-workers [74] have examined the effect of the addition of polysulfide to LiC104-PC. Lithium is cycled on an Ni substrate with Qc=2.7 C cm 2 and cycling currents of 1 mA cm. The cycling efficiency in PC with polysulfide is higher than that without an additive. The lithium deposition morphology is compact and smooth in PC with added polysulfide, whereas it is dendritic in PC alone. 

The cost/performance factor of individual surfactants will always be considered in determining which surfactants are blended in a mixed active formulation. However, with the recent advent of compact powders and concentrated liquids, other factors, such as processing, density, powder flowability, water content, stabilization of additives, dispersibility in nonaqueous solvents, dispersion of builders, and liquid crystalline phase behavior, have become important in determining the selection of individual surfactants. 

The general picture emerging from the pzc in aqueous solutions is that the major variation of <7-0 between two metals is due to with a minor contribution from AX that is governed by metal-solvent interactions. If this is also the case in nonaqueous solvents, a similar picture should be obtained. This is confirmed by Fig. 20 in which the data in DMSO are reported. As in aqueous solution, all points lie to the left of the point of Hg. Bi, In(Ga), and Tl(Ga) lie with Hg on a common line deviating from the unit slope. As in aqueous solution, Ga is further apart. Au is in the same position, relatively close to the Hg line. Finally, the point of Pt is (tentatively) much farther than all the other metals. 

The increase of C as X increases appears to be a general occurrence.26 Since the Egm0 vs. plots in nonaqueous solvent reproduce the main... 

Almost all that is known about the crystal face specificity of double-layer parameters has been obtained from studies with metal single-crystal faces in aqueous solutions. Studies in nonaqueous solvents would be welcome to obtain a better understanding of the influence of the crystallographic structure of metal surfaces on the orientation of solvent molecules at the interface in relation to their molecular properties. 

Most 2,5-unsubstituted pyrroles and thiophenes, and most anilines can be polymerized by electrochemical oxidation. For pyrroles, acetonitrile,54 or aqueous55 electrolyte solutions are normally used, while the polymerization of thiophenes is performed almost exclusively in nonaqueous solvents such as acetonitrile, propylene carbonate, and benzonitrile. 0 Polyanilines are generally prepared from a solution of aniline in aqueous acid.21 Platinum or carbon electrodes have been used in most work, although indium-tin oxide is routinely used for spectroelectrochemical experiments, and many other electrode materials have also been employed.20,21... 

The Bronsted definitions of acids and bases are more general than the Arrhenius definitions they also apply to species in nonaqueous solvents and even to gas-phase reactions. For example, when pure acetic acid is added to liquid ammonia, proton transfer takes place and the following equilibrium is reached ... 

Intercalation from solutions in nonaqueous solvents (S21). This method may suffer from the drawback that final stoichiometries may not correspond to equilibrium conditions, because of partial leaching out of metal halide. For this reason, some chlorides can be intercalated only from solvents in which they have limited solubility iLS). It has often been the practice to wash intercalates with solvents to remove the excess of intercalant this may lead to stoichiometries lower than the original ones. The two-ampoule method may, therefore, be preferable (H24). 

Biocatalytic reduction has been performed in nonaqueous solvents to improve the efficiency of the reaction. This section explains the use of organic solvent, supercritical fluids, and ionic liquid. 

Autoxidation of ferrous chloride in nonaqueous solvents is much faster than in water. The rate law is ... 

The determination of the real energies of solvation from measurements of the voltaic cells (Section VI) makes it possible to find the absolute electrode potentials in nonaqueous solvents owing to the relation... 

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