Solute physical properties, effect

Rocha, E. R. P. Nobrega, J. A. Effects of Solution Physical Properties on Copper and Chromium Signals in Plame Atomic Absorption Spectrometry, /. Chem. Educ. 1996, 73, 982-984. 

Greenfield ef. ai.l l) observed a reduction of signal intensity that correlates with sample intake effects from the modified solution viscosity and/or surface tension of mineral acids. This, coupled with peristaltic pumping of solutions into the nebulizer, considerably reduces physical interferences. Increased salt concentration also has an effect on solution physical properties. In the experience of these authors, the high levels of salt in the matrix also increases the noise from the nebulizer system. This degradation of nebulizer performance, which is not necessarily accompanied by a proportional reduction in sensitivity, is the cause of the observed deterioration of detection limits in real samples as opposed to ideal solutions. 

Physical Properties. Glycine is a colourless crystalline solid soluble in water. Owing to the almost equal opposing effects of the amino and the carboxylic groups. its aqueous solution is almost neutral (actually, slightly acidic to phenolphthalein) and glycine is therefore known as a neutral ampholyte. f It exhibits both acidic and basic properties. 

Sihcate solutions of equivalent composition may exhibit different physical properties and chemical reactivities because of differences in the distributions of polymer sihcate species. This effect is keenly observed in commercial alkah sihcate solutions with compositions that he in the metastable region near the solubihty limit of amorphous sihca. Experimental studies have shown that the precipitation boundaries of sodium sihcate solutions expand as a function of time, depending on the concentration of metal salts (29,58). Apparently, the high viscosity of concentrated alkah sihcate solutions contributes to the slow approach to equihbrium. 

The solvophobic model of Hquid-phase nonideaHty takes into account solute—solvent interactions on the molecular level. In this view, all dissolved molecules expose microsurface area to the surrounding solvent and are acted on by the so-called solvophobic forces (41). These forces, which involve both enthalpy and entropy effects, are described generally by a branch of solution thermodynamics known as solvophobic theory. This general solution interaction approach takes into account the effect of the solvent on partitioning by considering two hypothetical steps. Eirst, cavities in the solvent must be created to contain the partitioned species. Second, the partitioned species is placed in the cavities, where interactions can occur with the surrounding solvent. The idea of solvophobic forces has been used to estimate such diverse physical properties as absorbabiHty, Henry s constant, and aqueous solubiHty (41—44). A principal drawback is calculational complexity and difficulty of finding values for the model input parameters. 

Because the key operation in studying solvent effects on rates is to vary the solvent, evidently the nature of the solvation shell will vary as the solvent is changed. A distinction is often made between general and specific solvent effects, general effects being associated (by hypothesis) with some appropriate physical property such as dielectric constant, and specific effects with particular solute-solvent interactions in the solvation shell. In this context the idea of preferential solvation (or selective solvation) is often invoked. If a reaction is studied in a mixed solvent. 

This has been shown to correlate for a wide variety of tower packings, various operating conditions, and physical properties of the solute and inert gases. The k(j calculated must be used in conjunction with the effective interfacial areas determined by Shulman [65] Figure 9-47, to establish a reliable value for kGa. Figure 9-47 should be used with the abscissa as G/Vp/0.075 for inert gas other than air [67] ... 

While a metal or alloy may be selected largely on the basis of its mechanical or physical properties, the fact remains that there are very few applications where the effect of the interaction of a metal with its environment can be completely ignored, although the importance of this interaction will be of varying significance according to circumstances for example, the slow uniform wastage of steel of massive cross section (such as railway lines or sleepers) is of far less importance than the rapid perforation of a buried steel pipe or the sudden failure of a vital stressed steel component in sodium hydroxide solution. 

Thus, a velocity boundary layer and a thermal boundary layer may develop simultaneously. If the physical properties of the fluid do not change significantly over the temperature range to which the fluid is subjected, the velocity boundary layer will not be affected by die heat transfer process. If physical properties are altered, there will be an interactive effect between the momentum and heat transfer processes, leading to a comparatively complex situation in which numerical methods of solution will be necessary. 

The presence of a solute affects the physical properties of the solvent. For instance, when salt is spread on icy sidewalks, a mixture is created with a lower freezing point than that of pure water and the ice melts. In this part of the chapter we explore the molecular nature of these effects and see how to treat them quantitatively. 

Besides these special physical properties, hydrogen-bonded liquid water also has unique solvent and solution properties. One feature is high proton (H ) mobility due to the ability of individual hydrogen nuclei to jump from one water molecule to the next. Recalling that at temperatures of about 300 K, the molar concentration in pure water of H3O ions is ca. 10 M, the "extra" proton can come from either of two water molecules. This freedom of to transfer from one to an adjacent "parent" molecule allows relatively high electrical conductivity. A proton added at one point in an aqueous solution causes a domino effect, because the initiating proton has only a short distance to travel to cause one to pop out somewhere else. 

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