Salting-in ions

Typical ion-pairing reagents are, for cations, alkyl sulphonic acids, eg pentane, hexane, heptane or octane sulphonic acid, and for anions, tetrabutylammonium or dibutylamine ammonium salts. In ion-pair chromatography the retention of solutes can be controlled in a number of ways ... 

V.V. Egorov, E.M. Rakhman ko, E.B. Okaev, E.V. Pomelenok, and V.A. Nazarov, Effects of ion association of lipophilic quaternary ammonium salts in ion-exchange and potentiometric selectivity. Talanta 63,119-130 (2004). 

The lyotropic series was discovered by Hofmeister (1888) who found that certain ions would precipitate proteins and others would keep them in solution. He produced this series of ionic effects and speculated that it originates from the different affinities that ions have for water. Since then we have rediscovered the lyotropic series about every five years but we still do not understand its origin. An example of the series is the contribution of the various ions to the destabilisation energy of proteins (Franks and Eagland, 1975). So-called salting-in ions (I, CNS ) promote instability ... 

The subtleties concerning the balance between different effects emerge from the papers by Arakawa, Timasheff, and co-workers.In most systems, proteins are indeed stabilised by salting-out ions and destabilised by salting-in ions, but sometimes preferential hydration does not stabilise the native structure of proteins, as would be supposed according to the Hofrneister series. Moreover, these effects seem to crucially depend on the salt concentration, the nature of the proteins (basic or acidic), the pH values, and so forth. It should be noted that these authors used techniques such as densitometry and inferred interaction parameters... 

Because of ammine formation, when ammonia solution is added slowly to a metal ion in solution, the hydroxide may first be precipitated and then redissolve when excess ammonia solution is added this is due to the formation of a complex ammine ion, for example with copper(II) and nickel(II) salts in aqueous solution. 

The thiocyanate ion SCN forms an intensely red-coloured complex (most simply represented as [Fe(SCN)(H20)5] ) which is a test for iron(III). However, unlike cobalt(III), iron(lll) does not form stable hexammines in aqueous solution, although salts containing the ion [FefNHj) ] can be obtained by dissolving anhydrous iron(III) salts in liquid ammonia. 

Cobalt(II) is also easily oxidised in the presence of the nitrite ion NO2 as ligand. Thus, if excess sodium nitrite is added to a cobalt(II) salt in presence of ethanoic acid (a strong acid would decompose the nitrite, p. 244), the following reaction occurs ... 

Cobalt U) sulphide is precipitated as a black solid by addition of sulphide ion to a solution of a cobalt(II) salt, in alkaline solution. 

It has already been noted that, as well as alkylbenzenes, a wide range of other aromatic compounds has been nitrated with nitronium salts. In particular the case of nitrobenzene has been examined kinetically. Results are collected in table 4.4. The reaction was kinetically of the first order in the concentration of the aromatic and of the nitronium salt. There is agreement between the results for those cases in which the solvent induces the ionization of nitric acid to nitronium ion, and the corresponding results for solutions of preformed nitronium salts in the same solvent. 

The nitronium ion is the electrophile in nitrations with nitronium salts in organic solvents. 

The solubility of an insoluble salt decreases when it is placed in a solution already containing one of the salt s ions. 

Reaction of free-base porphyrin compounds with iton(II) salts in an appropriate solvent results in loss of the two N—H protons and insertion of iron into the tetradentate porphyrin dianion ligand. Five-coordinate iton(III) porphyrin complexes (hemins), which usually have the anion of the iton(II) salt for the fifth or axial ligand, ate isolated if the reaction is carried out in the presence of air. Iron(II) porphyrin complexes (hemes) can be isolated if the reaction and workup is conducted under rigorously anaerobic conditions. Typically, however, iton(II) complexes are obtained from iton(III) porphyrin complexes by reduction with dithionite, thiolate, borohydtide, chromous ion, or other reducing agents. 

In seawater—dolime and hrine—dolime processes, calcined dolomite or dolime, CaO MgO, is used as a raw material (Table 9). Dolime typically contains 58% CaO, 41% MgO, and less than 1% combined Si02, P O, and CO2 where R is a trivalent metal ion, eg, Al " or Fe " ( 4). Roughly one-half of the magnesia is provided by the magnesium salts in the seawater or brine and the other half is from dolime (75). Plant size is thus reduced using dolime and production cost is probably lower. 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

Poly(ethylene oxide) associates in solution with certain electrolytes (48—52). For example, high molecular weight species of poly(ethylene oxide) readily dissolve in methanol that contains 0.5 wt % KI, although the resin does not remain in methanol solution at room temperature. This salting-in effect has been attributed to ion binding, which prevents coagulation in the nonsolvent. Complexes with electrolytes, in particular lithium salts, have received widespread attention on account of the potential for using these materials in a polymeric battery. The performance of soHd electrolytes based on poly(ethylene oxide) in terms of ion transport and conductivity has been discussed (53—58). The use of complexes of poly(ethylene oxide) in analytical chemistry has also been reviewed (59). 

Direct. Some radionucHdes are packaged in solution for direct sampling (qv) via a septum and injection into the patient. GalHum-67 is a marker of inflammation, infection, and various tumor types. Its half-life is 78.3 h and it is suppHed as the gallium citrate salt. Indium-111 chloride is suppHed for the labeling of white blood ceUs. The In chloride is mixed with oxine (9-hydroxyquinoline) to form a lipophilic, cationic In oxine complex, which enters the white blood ceU. The complex dissociates within the ceU, and the cationic In " ion is trapped within the ceU, owing to its charge. 

The increased acidity of the larger polymers most likely leads to this reduction in metal ion activity through easier development of active bonding sites in siUcate polymers. Thus, it could be expected that interaction constants between metal ions and polymer sdanol sites vary as a function of time and the sihcate polymer size. The interaction of cations with a siUcate anion leads to a reduction in pH. This produces larger siUcate anions, which in turn increases the complexation of metal ions. Therefore, the metal ion distribution in an amorphous metal sihcate particle is expected to be nonhomogeneous. It is not known whether this occurs, but it is clear that metal ions and siUcates react in a complex process that is comparable to metal ion hydrolysis. The products of the reactions of soluble siUcates with metal salts in concentrated solutions at ambient temperature are considered to be complex mixtures of metal ions and/or metal hydroxides, coagulated coUoidal size siUca species, and siUca gels. 

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