Solvation property

Supercritical Fluid Extraction. Supercritical fluid (SCF) extraction is a process in which elevated pressure and temperature conditions are used to make a substance exceed a critical point. Once above this critical point, the gas (CO2 is commonly used) exhibits unique solvating properties. The advantages of SCF extraction in foods are that there is no solvent residue in the extracted products, the process can be performed at low temperature, oxygen is excluded, and there is minimal protein degradation (49). One area in which SCF extraction of Hpids from meats maybe appHed is in the production of low fat dried meat ingredients for further processed items. Its apphcation in fresh meat is less successful because the fresh meat contains relatively high levels of moisture (50). 

A comparison of phenol acidity in DMSO versus the gas phase also shows an attenuation of substituent effects, but not nearly as much as in water. Whereas the effect of ubstituents on AG for deprotonation in aqueous solution is about one-sixth that in the gas phase, the ratio for DMSO is about one-third. This result points to hydrogen bonding of the phenolate anion by water as the major difference in the solvating properties of water and DMSO. ... 

Now, we should ask ourselves about the properties of water in this continuum of behavior mapped with temperature and pressure coordinates. First, let us look at temperature influence. The viscosity of the liquid water and its dielectric constant both drop when the temperature is raised (19). The balance between hydrogen bonding and other interactions changes. The diffusion rates increase with temperature. These dependencies on temperature provide uS with an opportunity to tune the solvation properties of the liquid and change the relative solubilities of dissolved solutes without invoking a chemical composition change on the water. 

In a series of papers published throughout the 1980s, Colin Poole and his co-workers investigated the solvation properties of a wide range of alkylammonium and, to a lesser extent, phosphonium salts. Parameters such as McReynolds phase constants were calculated by using the ionic liquids as stationary phases for gas chromatography and analysis of the retention of a variety of probe compounds. However, these analyses were found to be unsatisfactory and were abandoned in favour of an analysis that used Abraham s solvation parameter model [5]. 

It was noted that, on going from tetrabutylammonium to tetrabutylphosphoni-um, salts with a common anion displayed identical solvation properties. FLence, with these simple cations, the solvent properties are dominated by the choice of anion. It is possible that, had cations with acidic protons, such as triallcylammoni-um and trialkylphosphonium, been included in the study, these may then have also had an influence. 

One particular feature of ionic liquids lies in their solvation properties, not only for hydrophobic compounds but also for hydrophilic compounds such as carbohydrates. Park and Kazlauskas reported the regioselective acylation of glucose in 99 % yield and with 93 % selectivity in [MOEMIM][BF4] (MOE = CH3OCH2CH2), values much higher than those obtained in the organic solvents commonly used for this purpose (Entry 18) [22] (Scheme 8.3-4). 

A class of solvents which shows very marked solvating properties for inorganic compounds comprises the esters of phosphoric(V) (orthophosphoric) acid. The... 

PEO is found to be an ideal solvent for alkali-metal, alkaline-earth metal, transition-metal, lanthanide, and rare-earth metal cations. Its solvating properties parallel those of water, since water and ethers have very similar donicites and polarizabilities. Unlike water, ethers are unable to solvate the anion, which consequently plays an important role in polyether polymer-electrolyte formation. 

Surface ions are thus expected to substantially contribute to the polarization force at low frequencies. Also, one expects different ions to have different solvation properties and mobility. These phenomena can be explored by SPFM. They are important in surface reactions, ionic exchange processes between surface and bulk ions, rock weathering, ion sequestration, and other enviromnental problems. 

The solvation property of the cations of this very polar aprotic solvent can make some salts more stable. Therefore, aluminium, sodium, mercury or silver perchlorate solutions are explosive. The same goes for iron (III) nitrate solutions. 

Accelerated solvent extraction (ASE) is a technique which attempts to merge the beneficial solvation properties of SFE with traditional organic solvents. Specifically, the sample is placed in an extraction vessel which can withstand high pressures while being maintained at a constant temperature. Extraction is carried out by pumping the extraction solvent through the samples for a limited time. As an example of the use of ASE, Richter and Covino extracted PCBs from a 10-g fish tissue sample with hexane... 

Although SFC fills a niche in what can be considered as a continuum of separation eluents from gases to liquids, it cannot claim a unique status subcritical water extraction (SWE, cf. Section 3.4.3) and pressurised fluid extraction (PFE, cf. Section 3.4.6) are other examples of eluents where altering the conditions cause a useful change in the solvation properties. 

Considering that, roughly speaking, the electrostatic component of the solvation free energy varies as the cube of the molecular dipole moment, it becomes obvious that the corrective term (13.1) should be taken into account in the determination of differential solvation properties of very polar solutes. In the computation of transfer free energies across an interface, it has been suggested that equation (13.1) be expressed as a function of the number density of one of the two media, so that the correction is zero in solvent 1 and zl,l lsl lll in solvent 2 [115]. 

Water is a polar solvent so has different solvation properties that discriminate between polar and non-polar molecules. Chemical discrimination results in the formation of mixed phases, such as membranes, microenvironments and compartmentalisation. 

Nonequilibrium solvent effects can indeed by significant at the kcal level-maybe even at a greater level, but so far there is no evidence for that when the reaction coordinate involves protonic or heavier motions. Our goal in this section has been to emphasize just how powerful and general the equilibrium model is. In addition, in both the previous section and the present section, we have emphasized the use of models based on collective solvent coordinates for calculating both equilibrium and nonequilibrium solvation properties. 

The most abundant compound on our planet is water at the liquid state. Because of its diffusion and its solvating properties, a large number of chemical reactions, important in life and in industrial processes, take place in aqueous solution. 

Ludwig s (2001) review discusses water clusters and water cluster models. One of the water clusters discussed by Ludwig is the icosahedral cluster developed by Chaplin (1999). A fluctuating network of water molecules, with local icosahedral symmetry, was proposed by Chaplin (1999) it contains, when complete, 280 fully hydrogen-bonded water molecules. This structure allows explanation of a number of the anomalous properties of water, including its temperature-density and pressure-viscosity behaviors, the radial distribution pattern, the change in water properties on supercooling, and the solvation properties of ions, hydrophobic molecules, carbohydrates, and macromolecules (Chaplin, 1999, 2001, 2004). 

Solvation properties, of supercritical solvents, 14 80-81 Solvatochromic materials, 22 708t Solvatochromic probes, 26 853—855 Solvatochromic spectral shifts, 23 96 Solvatochromy, 20 517 Solvay, 7 641 Solvay process, 15 63... 

Supercritical regime, 11 756 Supercritical solvents, solvation properties of, 14 80-81... 

Table 9 compares ionic enthalpies of hydration from the Bernal and Fowler,164 Latimer et al.165 and Rashin and Honig88 procedures. Given the inherent uncertainty, the latter two sets of data are remarkably similar, considering that they were obtained 46 years apart. A number of tabulations of the thermodynamic solvation properties of ions in various solvents have now appeared. It is important to keep in mind, however, that there is a degree of arbitrariness associated with the experimental AHsoivation and AGSoiVation of individual ions. 

Cuprammonium hydroxide Cu(NH3)41(OH)2 Cuoxam Good solvating properties, extensive oxidative degradation1), rather unstable, clear, coloured (blue)... 

Tri-ethylene diamine Cobalt hydroxide [Co(en)3](OH)2 Cooxen Good solvating properties, extensive oxidative degradation, coloured (claret)... 

Iron tartaric acid -sodium complex solution KC4H306)3Fe]Na6 EWNN Good solvating properties, extremely high salt concentration, slight oxidative degradation, coloured (green)... 

Tri-ethylene diamine cadmium hydroxide [Cd(en)3](OH)2 Cadoxen and Cden3) Good solvating properties, slight oxidative degradation, clear, stable and colourless... 

The solvating properties of protonic solvents such as methanol, ethanol, or acetic acid, are intermediate between those of water and aprotic solvents. This factor accounts for many differences between water and the alcohols as solvents. For example, CoBr2 is ionized in water, while in methanol tetrahedral CoBr2 (CH3OH)2 is found23). 

The acceptor properties of Ni2 + are weaker than those of Co2 + and under analogous conditions the extent of complex formation is smaller. When sodium azide is added to a 10 3 molar nickel (II) perchlorate solution in excess, the only azide-complex is monoazidonickel (II). The monochloro complex is present only in strong hydrochloric acid 81L Due to the low solvating properties of DMA even tetrachloronickelate (II) is found in such solutions. 

Supercritical fluid chromatography is the name for all chromatographic methods in which the mobile phase is supercritical under the conditions of analysis and the solvating properties of the fluid have a measurable effect on the separation. SFC has some advantages over GC and HPLC it extends the molecular weight range of GC, thermally labile compounds can be separated at lower temperatures, compounds without chromophores can be sensitively detected, and the use of open-tubular and packed columns is feasible. SFC can be employed in both the analysis of natural pigments and synthetic dyes, however it has not been frequently applied in up-to-date analytical practice. 

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