Presence of electrolytes

The swelling of gels is markedly affected by the presence of electrolytes, this effect being a minimum at the isoelectric point of the material. In general, sulphates, tartrates, etc. inhibit swelling, while iodides and thiocyanates promote the swelling. Thus gelatine disperses completely in iodide solution even at low temperatures. 

The main reason for the importance of aeration Hes in the limited solubiUty of oxygen in water, a value which decreases in the presence of electrolytes and other solutes and as temperature increases. A typical value for the solubiUty of oxygen (the equiUbrium saturation concentration) in water in the presence of air at atmospheric pressure at 25°C is about 0.008 kg 02/m (= Sparts per million = 0.25 mmol/L). Thus, for a yeast or bacterial bioreaction demanding oxygen at the rates given in Table 1, all oxygen is utilized in about 10 to 40 s (3,7). 

When values for the internal pH are calculated (6) it is found that the relationship between internal and external pH is strongly influenced by the presence of electrolyte. With no added electrolyte the internal pH is always lower than the external pH, and for pH values below 12 considerably lower. 

The polymers which have stimulated the greatest interest are the polyacetylenes, poly-p-phenylene, poly(p-phenylene sulphide), polypyrrole and poly-1,6-heptadiyne. The mechanisms by which they function are not fully understood, and the materials available to date are still inferior, in terms of conductivity, to most metal conductors. If, however, the differences in density are taken into account, the polymers become comparable with some of the moderately conductive metals. Unfortunately, most of these polymers also have other disadvantages such as improcessability, poor mechanical strength, instability of the doped materials, sensitivity to oxygen, poor storage stability leading to a loss in conductivity, and poor stability in the presence of electrolytes. Whilst many industrial companies have been active in their development (including Allied, BSASF, IBM and Rohm and Haas,) they have to date remained as developmental products. For a further discussion see Chapter 31. 

Whilst the conductivity of these polymers is generally somewhat inferior to that of metals (for example, the electrical conductivity of polyacetylenes has reached more than 400 000 S/cm compared to values for copper of about 600 000 S/cm), when comparisons are made on the basis of equal mass the situation may be reversed. Unfortunately, most of the polymers also display other disadvantages such as improcessability, poor mechanical strength, poor stability under exposure to common environmental conditions, particularly at elevated temperatures, poor storage stability leading to a loss in conductivity and poor stability in the presence of electrolytes. In spite of the involvement of a number of important companies (e.g. Allied, BASF, IBM and Rohm and Haas) commercial development has been slow however, some uses have begun to emerge. It is therefore instructive to review briefly the potential for these materials. 

Primers for protective coatings may be divided into three broad classes based on the mechanism of substrate protection barrier primers that function by preventing the ingress of moisture and electrolytes, primers that protect the substrate galvanically in the presence of electrolytes, and primers that contain electrochemical inhibitors to passivate the substrate. Each of these approaches requires a distinct primer film structure due to the different mechanisms of protection. 

The anodic oxidation of the iron is usually localized in surface pits and crevices which allow the formation of adherent rust over the remaining surface area. Eventually the lateral extension of the anodic area undermines the rust to produce loose flakes. Moreover, once an adherent film of rust has formed, simply painting over gives but poor protection. This is due to the presence of electrolytes such as iron(II) sulfate in the film so that painting merely seals in the ingredients for anodic oxidation. It then only requites the exposure of some other portion of the surface, where cathodic reduction can take place, for rusting beneath the paint to occur. 

In pure dry air at normal temperatures a thin protective oxide film forms on the surface of polished mild steel. Unlike that formed on stainless steels it is not protective in the presence of electrolytes and usually breaks down in air, water and soil. The anodic reaction is ... 

Gas holdup may be of the same magnitude in the various operations, although for bubble-columns, the presence of electrolytes or surface-active agents appears to be a condition for high gas holdup. The gas residence-time distribution resembles that of a perfect mixer in the stirred-slurry operation, and comes close to piston flow in the others. 

Aggregation numbers increase as the length of the hydrophobic chain increases. The presence of electrolytes also causes an increase in the aggregation... 

At a finite distance, where the surface does not come into molecular contact, equilibrium is reached between electrodynamic attractive and electrostatic repulsive forces (secondary minimum). At smaller distance there is a net energy barrier. Once overcome, the combination of strong short-range electrostatic repulsive forces and van der Waals attractive forces leads to a deep primary minimum. Both the height of the barrier and secondary minimum depend on the ionic strength and electrostatic charges. The energy barrier is decreased in the presence of electrolytes (monovalent < divalent [Pg.355]

Englezos, P. and S. Hull, Phase Equilibrium Data on Carbon Dioxide Hydrate in the Presence of Electrolytes, Water Soluble Polymers and Montmorillonite , CanJ. Chem. Eng, 72, 887-893 (1994). 

Many acrylic acid copolymers are water-soluble but unlike poly(vinyl alcohol) they are not degraded by alkali. In fact they need alkali for effective desizing as they are more soluble at alkaline pH than in neutral solutions. They are sensitive to acidic media, which should not be used. Solubilisation occurs by the formation of sodium carboxylate groups from the anionic polyacid. The polyelectrolyte formed in this way is readily soluble and shows a rapid rate of dissolution. However, the presence of electrolytes such as magnesium or calcium salts from hard water can inhibit removal [191]. 

Figure 12.4 Equilibrium absorption isotherms at 34 °C and rate of dyeing curves at 40 °C for Cl Direct Blue 1 on viscose in the presence of electrolytes singly and in binary mixtures [70]...

Surprisingly, other investigators were unable to confirm the adverse effect of nonionic surfactants of low cloud point in the high-temperature dyeing of polyester, even in the presence of electrolytes [111]. This was probably because of the rather low concentrations used. Adducts containing a C18-C2o hydrophobe and a decaoxyethylene hydrophile, as well... 

In the presence of electrolyte, montmorillonite will flocculate. If flocculation occurs macromolecules of lower molecular weight will exhibit greater adsorption due to the greater surface available to smaller hydrodynamic volumes. 

For most organic chemicals the solubility is reported at a defined temperature in distilled water. For substances which dissociate (e.g., phenols, carboxylic acids and amines) it is essential to report the pH of the determination because the extent of dissociation affects the solubility. It is common to maintain the desired pH by buffering with an appropriate electrolyte mixture. This raises the complication that the presence of electrolytes modifies the water structure and changes the solubility. The effect is usually salting-out. For example, many hydrocarbons have solubilities in seawater about 75% of their solubilities in distilled water. Care must thus be taken to interpret and use reported data properly when electrolytes are present. 

As with solubility, Kow is a function of the presence of electrolytes and for dissociating chemicals it is a function of pH. Accurate values can generally be measured up to about 107, but accurate measurement beyond this requires meticulous technique. A common problem is the presence of small quantities of emulsified octanol in the water phase. The high concentration of chemical in that emulsion causes an erroneously high apparent water phase concentration. 

It was mentioned previously that the narrow range of concentrations in which sudden changes are produced in the physicochemical properties in solutions of surfactants is known as critical micelle concentration. To determine the value of this parameter the change in one of these properties can be used so normally electrical conductivity, surface tension, or refraction index can be measured. Numerous cmc values have been published, most of them for surfactants that contain hydrocarbon chains of between 10 and 16 carbon atoms [1, 3, 7], The value of the cmc depends on several factors such as the length of the surfactant chain, the presence of electrolytes, temperature, and pressure [7, 14], Some of these values of cmc are shown in Table 2. 

Microwave heating is achieved with a pulse of microwave energy generated within a magnetron. The only requirement for the use of this heating method is that the solvent has a permanent dipole moment.24 This technique can be employed to study reactions in non-aqueous solvents since the presence of electrolytes is not necessary.30 However, the temperature changes attained were much lower than in the case of Joule or laser heating.24... 

In early research efforts, attention was concentrated on carbonaceous anodes because of the earlier experiences with metallic lithium. Dahn and coworkers studied the thermal response of carbonaceous materials in the presence of electrolytes in an adiabatic environment created in a thermal analysis technique known as accelerating rate calorimetry (ARC). By choosing an arbitrary threshold value for... 

The seminal work by Maleki et al. in 1999 seemed to provide a direct answer to the question about which of the five possible processes was responsible for the thermal runaway of a lithium ion cell. Using ARC, they first determined the thermal runaway onset temperature in a lithium ion cell based on LiCo02/graphite with LiPFe/EC/DMC/DEC to be 167 °C. The thermal reaction, however, was found to start at 123 °C and continued to self-heat the system to the above onset temperature. Using DSC and TGA, they further determined the heat evolution as well as the thermal profile for the individual components of the cell in the presence of electrolytes, which included cathode, anode, and anode binder (PVdF). 

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