In concentrated solutions

Timmermans, J. "The Physico-Chemical Constants of Binary Systems in Concentrated Solutions," Vol. 1-4, Interscience, New York, 1959-60. 

Equation XI-27 shows that F can be viewed as related to the difference between the individual adsorption isotherms of components 1 and 2. Figure XI-9 [140] shows the composite isotherms resulting from various combinations of individual ones. Note in particular Fig. XI-9a, which shows that even in the absence of adsorption of component 1, that of component 2 must go through a maximum (due to the N[ factor in Eq. XI-27), and that in all other cases the apparent adsorption of component 2 will be negative in concentrated solution. 

The weakly basic 2-aminothiazoles are most readily diazotized in concentrated solutions of oxygen containing acids such as sulfuric acid, 40 to 50% (322-326) fiuoroboric phosphoric acids (589) phosphoric acid (327, 328) and mixtures of phosphoric and nitric acid (74. 322, 323. 329-331). From strong acid solutions, solid diazonium salts can be isolated (34, 332. 333). 

Properties. Fluoroboric acid is stable in concentrated solutions, and hydroly2es slowly in aqueous solution to hydroxyduoroborates. For the stabihty of the duoroborate species, see Reference 3. The equiUbrium quotients (4,5) in 1 molal NaCl at 25°C show the strong affinity of boron for duo ride ... 

Hexafluorophosphoric Acid. Hexafluorophosphoric acid (3) is present under ambient conditions only as an aqueous solution because the anhydrous acid dissociates rapidly to HF and PF at 25°C (56). The commercially available HPF is approximately 60% HPF based on PF analysis with HF, HPO2F2, HPO F, and H PO ia equiUbrium equivalent to about 11% additional HPF. The acid is a colorless Hquid which fumes considerably owiag to formation of an HF aerosol. Frequently, the commercially available acid has a dark honey color which is thought to be reduced phosphate species. This color can be removed by oxidation with a small amount of nitric acid. When the hexafluorophosphoric acid is diluted, it slowly hydrolyzes to the other fluorophosphoric acids and finally phosphoric acid. In concentrated solutions, the hexafluorophosphoric acid estabUshes equiUbrium with its hydrolysis products ia relatively low concentration. Hexafluorophosphoric acid hexahydrate [40209-76-5] 6 P 31.5°C, also forms (66). This... 

Reference Electrodes and Liquid Junctions. The electrical cincuit of the pH ceU is completed through a salt bridge that usually consists of a concentrated solution of potassium chloride [7447-40-7]. The solution makes contact at one end with the test solution and at the other with a reference electrode of constant potential. The Hquid junction is formed at the area of contact between the salt bridge and the test solution. The mercury—mercurous chloride electrode, the calomel electrode, provides a highly reproducible potential in the potassium chloride bridge solution and is the most widely used reference electrode. However, mercurous chloride is converted readily into mercuric ion and mercury when in contact with concentrated potassium chloride solutions above 80°C. This disproportionation reaction causes an unstable potential with calomel electrodes. Therefore, the silver—silver chloride electrode and the thallium amalgam—thallous chloride electrode often are preferred for measurements above 80°C. However, because silver chloride is relatively soluble in concentrated solutions of potassium chloride, the solution in the electrode chamber must be saturated with silver chloride. 

Data on the solubihty of magnesium hydroxide in water are not all in agreement, but the solubihty is extremely low. The extent of Mg(OH)2 solubihty is 10 mg/L, which is about 1/100 the solubihty of Ca(OH)2. In concentrated solutions of NH Cl and NH CO, the solubihty of Mg(OH)2 is markedly increased, but in no instance does its solubihty equal that of MgCO in water heavily permeated with CO2. Dolomitic hydrates are slightly less soluble than high calcium hydrates, but much nearer the latter in value than Mg(OH)2, because the presence of MgO and Mg(OH)2 does not impede the dissolution of its Ca(OH)2 constituent. 

Chemical Properties and Reactivity. LLDPE is a saturated branched hydrocarbon. The most reactive parts of LLDPE molecules are the tertiary CH bonds in branches and the double bonds at chain ends. Although LLDPE is nonreactive with both inorganic and organic acids, it can form sulfo-compounds in concentrated solutions of H2SO4 (>70%) at elevated temperatures and can also be nitrated with concentrated HNO. LLDPE is also stable in alkaline and salt solutions. At room temperature, LLDPE resins are not soluble in any known solvent (except for those fractions with the highest branching contents) at temperatures above 80—100°C, however, the resins can be dissolved in various aromatic, aUphatic, and halogenated hydrocarbons such as xylenes, tetralin, decalin, and chlorobenzenes. 

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. 

The physical picture in concentrated electrolytes is more apdy described by the theory of ionic association (18,19). It was pointed out that as the solutions become more concentrated, the opportunity to form ion pairs held by electrostatic attraction increases (18). This tendency increases for ions with smaller ionic radius and in the lower dielectric constant solvents used for lithium batteries. A significant amount of ion-pairing and triple-ion formation exists in the high concentration electrolytes used in batteries. The ions are solvated, causing solvent molecules to be highly oriented and polarized. In concentrated solutions the ions are close together and the attraction between them increases ion-pairing of the electrolyte. Solvation can tie up a considerable amount of solvent and increase the viscosity of concentrated solutions. 

Bismuth Salts. Bismuth trioxide dissolves in concentrated solutions of strong oxyacids to yield bismuth salts. In more dilute solutions of strong acids or in solutions of weak acids, the oxide reacts to form bismuthyl or basic salts. The normal salts are very susceptible to hydrolysis. 

Choline is a strong base (pif = 5.06for0.0065-0.0403 Afsolutions ) (3). It crystallizes with difficulty and is usually known as a colorless deHquescent sympy hquid, which absorbs carbon dioxide from the atmosphere. Choline is very soluble in water and in absolute alcohol but insoluble in ether (4). It is stable in dilute solutions but in concentrated solutions tends to decompose at 100°C, giving ethylene glycol, poly(ethylene glycol), and trimetbylamine (5). 

Fig. 23.5. Corrosion takes place less easily in concentrated solution.

In NMR the magnetic-spin properties of atomic nuclei within a molecule are used to obtain a list of distance constraints between those atoms in the molecule, from which a three-dimensional structure of the protein molecule can be obtained. The method does not require protein crystals and can be used on protein molecules in concentrated solutions. It is, however, restricted in its use to small protein molecules. 

I ratio in dilute solution, increasing 1.5 in concentrated solution... 

Fig. 9. Activation parameters for resole methylolation in the presence of NaOH in concentrated solutions [80,90].

Crossflow Filters - These are usually membrane-type filters used for ultrafiltration. In the field of biotechnology these types of filters are used in ultrafiltration devices used in concentrating solutions, and performing buffer exchanges. 

The effect of the substrate concentration on the rate of the tautomeric equilibrium also depends on substitution. Thus, for compounds 56 with r or = H, the equilibrium rate is faster in concentrated solutions, while a change in concentration has a little effect for the 2,2-disubstituted derivatives. Tautomers 56a and 56b (Ar = Ph, r = R = Me) could be obtained in the pure tautomeric forms and do not equilibrate in the solid state. 

Lead is not generally attacked rapidly by salt solutions (especially the salts of the acids to which it is resistant). The action of nitrates and salts such as potassium and sodium chloride may be rapid. In potassium chloride the corrosion rate increases with concentration to a maximum in 0.05m solution, decreases with a higher concentration, and increases again in 2m solution. Only loosely adherent deposits are formed. In potassium bromide adherent deposits are formed, and the corrosion rate increases with concentration. The attack in potassium iodide is slow in concentrations up to 0.1m but in concentrated solutions rapid attack occurs, probably owing to the formation of soluble KPblj. In dilute potassium nitrate solutions (0.001 m and below) the corrosion product is yellow and is probably a mixture of Pb(OH)2 and PbO, which is poorly adherent. At higher concentrations the corrosion product is more adherent and corrosion is somewhat reduced Details of the corrosion behaviour of lead in various solutions of salts are given in Figure 4.16. 

There are, in fact, two reasons why we should prefer to discuss proton transfers of class I. In concentrated solutions the average electrostatic forces between the ions will be intense. Only in proton transfers of class I does the number of positive and negative charges in the solution remain unaltered when the proton is transferred only here do we find the possibility that the contribution from the interionic forces will remain almost unchanged in a proton transfer. At the same time, although the number... 

Goldschmidt s mechanism was widely used by Hinshelwood240,2411 and Smith242 2431 for dilute solutions this corresponds to the experimental conditions for which relation (48) has been established. More recently, Van der Zeeuw244 applied Goldschmidt mechanism to the reaction of phthalic anhydride with model alcohols in concentrated solutions. 

Usually, dilute polymer solutions are isotropic systems, i.e. macromolecular chains can exist in these solutions independently of each other with a random distribution of orientations of the long axes of coils. The solutions of flexible-chain polymers remain isotropic when the solution concentration increases whereas in concentrated solutions of macromolecules of limited flexibility the chains can no longer be oriented arbitrarily and some direction of preferential orientations of macromolecular axes appears, i.e. the mutual orientations of the axes of neighboring molecules are correlated. This means that... 

The Zimm model predicts correctly the experimental scaling exponent xx ss M3/2 determined in dilute solutions under 0-conditions. In concentrated solution and melts, the hydrodynamic interaction between the polymer segments of the same chain is screened by the host molecules (Eq. 28) and a flexible polymer coil behaves much like a free-draining chain with a Rouse spectrum in the relaxation times. 

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