Hydration, freezing effects

Hydrate control is not included in this chapter, but is discussed in Chapter 13 because of the relative importance and difference in chemical mechanism. Many chemicals added to water will result in a depression of the freezing point. The practical application is restricted, however, because of some other unwanted effects, such as corrosion, destruction of rubber sealings in engine parts, or economic aspects. 

Similarly, concepts of solvation must be employed in the measurement of equilibrium quantities to explain some anomalies, primarily the salting-out effect. Addition of an electrolyte to an aqueous solution of a non-electrolyte results in transfer of part of the water to the hydration sheath of the ion, decreasing the amount of free solvent, and the solubility of the nonelectrolyte decreases. This effect depends, however, on the electrolyte selected. In addition, the activity coefficient values (obtained, for example, by measuring the freezing point) can indicate the magnitude of hydration numbers. Exchange of the open structure of pure water for the more compact structure of the hydration sheath is the cause of lower compressibility of the electrolyte solution compared to pure water and of lower apparent volumes of the ions in solution in comparison with their effective volumes in the crystals. Again, this method yields the overall hydration number. 

The main non-chloride, non-corrosive accelerating admixtures available on the market are of two types (1) accelerating admixtures which accelerate hydration but do not depress the freezing point of water and (2) accelerating admixtures for use in sub-freezing ambient temperatures which depress the freezing point of water. The former contain salts of formates, nitrates and nitrites and are effective for set acceleration and strength development. However, their effectiveness is dependent on the ambient temperature at the time of placement. 

Distillation processes have a degree of flexibility not available to freezing processes in the choice of an operating temperature. The almost vertical ice-water line in the temperature-pressure phase diagram for water indicates essentially a fixed operating temperature. Similarly this is true for the hydrate-water line in the hydrate systems. The effect on vapor volume resulting from the relationship between vapor pressure and... 

Mention has already been made of the numerous effects attendant upon chemical substitutions on the polysaccharide linear chain. Natural branches impart a dispersion stability to amylopectin that is not afforded amylose. One only has to compare cellulose ethers, deesterified chitin, and the lysis product of protopectin with the underivatized parent compound to appreciate the impact of chemical substituents on functionality. The loosening of compact, parallel structures with alkyl, hydroxyalkyl, and alkoxyl groups facilitates hydration and transforms insoluble, refractory polysaccharides to soluble, reactive polysaccharides. Not only do these substituents obstruct the crystallization tendency, they almost always confer secondary functionalities like q enhancement and foam, suspension, and freeze-thaw stabilization. 

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