Solubility measurement techniques

Subject areas for the Series include solutions of electrolytes, liquid mixtures, chemical equilibria in solution, acid-base equilibria, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, equilibria in analytical chemistry, dissolution of gases in liquids, dissolution and precipitation, solubility in cryogenic solvents, molten salt systems, solubility measurement techniques, solid solutions, reactions within the solid phase, ion transport reactions away from the interface (i.e. in homogeneous, bulk systems), liquid crystalline systems, solutions of macrocyclic compounds (including macrocyclic electrolytes), polymer systems, molecular dynamic simulations, structural chemistry of liquids and solutions, predictive techniques for properties of solutions, complex and multi-component solutions applications, of solution chemistry to materials and metallurgy (oxide solutions, alloys, mattes etc.), medical aspects of solubility, and environmental issues involving solution phenomena and homogeneous component phenomena. 

CO2 solubility is of particular importance due to its use in industrial mixtures and its significance for green engineering. CO2 has one of the highest solubilities in ILs and most solubility measurement techniques can quantify CO2 sorption. 

Discussion. Because of the specific nature of atomic absorption spectroscopy (AAS) as a measuring technique, non-selective reagents such as ammonium pyrollidine dithiocarbamate (APDC) may be used for the liquid-liquid extraction of metal ions. Complexes formed with APDC are soluble in a number of ketones such as methyl isobutyl ketone which is a recommended solvent for use in atomic absorption and allows a concentration factor of ten times. The experiment described illustrates the use of APDC as a general extracting reagent for heavy metal ions. 

In order to determine the stability constants for a series of complexes in solution, we must determine the concentrations of several species. Moreover, we must then solve a rather complex set of equations to evaluate the stability constants. There are several experimental techniques that are frequently employed for determining the concentrations of the complexes. For example, spectrophotometry, polarography, solubility measurements, or potentiometry may be used, but the choice of experimental method is based on the nature of the complexes being studied. Basically, however, we proceed as follows. A parameter is defined as the average number of bound ligands per metal ion, N, which is expressed as... 

Phase solubility analysis is a technique to determine the purity of a substance based on a careful study of its solubility behavior [38,39]. The method has its theoretical basis in the phase mle, developed by Gibbs, in which the equilibrium existing in a system is defined by the relation between the number of coexisting phases and components. The equilibrium solubility of a material in a particular solvent, although a function of temperature and pressure, is nevertheless an intrinsic property of that material. Any deviation from the solubility exhibited by a pure sample arises from the presence of impurities and/or crystal defects, and so accurate solubility measurements can be used to deduce the purity of the sample. 

It is recommended that concentration measurements for this type of modeling work are based on analytical standards of mole or mass fraction, to avoid the conversion error caused by density effects. The excess solid phase should always be characterized by a suitable analytical technique, before and after the equilibrium solubility measurements, to confirm that the polymorphic form is unchanged. It should be noted that the crystal shape (habit) does not always change significantly between different polymorphic forms, and visual assessments can be misleading. 

Various procedures have been reported in literature to investigate the sol-ubihty of compoimds in SCCO2 [34], They can be divided into static [34, 35] and dynamic [36,37] methods. Most recently, also parallel techniques have been developed for solubility measurements [38]. All methods, except for the static synthetic one (see below), require analytical measurements to quantify the amount of solute dissolved in SCCO2. Mainly spectroscopic, chromatographic, and gravimetric techniques are applied for the analytical measurements. 

Gas solubilities in ionic liquids and related measurement techniques... 

After reviewing the properties and structure of ionic liquids, leading specialists explore the role of these materials in optical, electrochemical, and biochemical sensor technology. The book then examines ionic liquids in gas, liquid, and countercurrent chromatography, along with their use as electrolyte additives in capillary electrophoresis. It also discusses gas solubilities and measurement techniques, liquid-liquid extraction, and the separation of metal ions. The final chapters cover molecular, Raman, nuclear magnetic resonance, and mass spectroscopies. 

The determination of the strength of the Lewis acids MF , has been carried out in various solvents using the conventional methods. Numerous techniques have been applied conductivity measurements, cryoscopy, aromatic hydrocarbon extraction,53,84 solubility measurements,85-87 kinetic parameters determinations,52,88,89 electroanalytical techniques (hydrogen electrode),90-93 quinones systems as pH indicators,94-97 or other electrochemical systems,98 99 IR,100,101 and acidity function (//,) determinations with UV-visible spectroscopy,8 9 14 19 102-105 or with NMR spectros-copy.20-22,44-46,106-108 Gas-phase measurements are also available.109-111 Comparison of the results obtained by different methods shows large discrepancies (Table 1.2). 

The apparatus used—the improved Othmer recirculation still modified for salt effect studies—was described previously (1,7), as were the analytical techniques, specifications on the purity and treatment of the solvents, and details of surface tension and solubility measurements (4). 

The more traditional approach is to use the chromatographic technique for the concentration determination necessary to derive physico-chemical properties for example, measuring the equilibrium concentration of compounds in a saturated solution for solubility measurements, or measuring the distribution concentration in two immiscible solvents for the determination of partition coefficients. Both approaches can be used for lipophilicity determinations and will be fully discussed in this chapter. 

Dissolved gases must be extracted from the aqueous system before analysis. This is usually accomplished by a simple gas-water partition into a vapour phase followed by standard headspace measurement techniques (McAuliffe, 1966). Alternatively a so-called stripper continuously partitions the dissolved gases into a carrier gas which is then sent to a gas chromatograph for analysis (Mousseau and Williams, 1979 Aldridge and Jones, 1987). These separations are aided by the very low solubility of the light hydrocarbon gases. 

Phase-solubility analysis17 (sometimes referred to as phase equilibrium purification) is the quantitative determination of the purity of a substance through the application of precise solubility measurements. At a given temperature, a definite amount of a pure substance is soluble in a definite quantity of solvent. The resulting solution is saturated with respect to the particular substance, but the solution remains unsaturated with respect to other substances even though such substances may be closely related in chemical structure and physical properties to the particular substance being tested. There are examples of the use of this technique in HPLC methods development18 and in the characterization of reference standards,19 but the... 

The shake-flask method is based on the phase solubility technique that was developed 40 years ago and is still the most reliable and widely used method for solubility measurement today (Higuchi and Connors, 1965). The method can be divided into hve steps sample preparation, equilibration, separation of phases, analysis of the saturated solution and residual solid, and data analysis and interpretation (Yalkowsky and Banerjee, 1992, Winnike, 2005). 

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