Measurements solvates

Three types of methods are used to study solvation in molecular solvents. These are primarily the methods commonly used in studying the structures of molecules. However, optical spectroscopy (IR and Raman) yields results that are difficult to interpret from the point of view of solvation and are thus not often used to measure solvation numbers. NMR is more successful, as the chemical shifts are chiefly affected by solvation. Measurement of solvation-dependent kinetic quantities is often used (<electrolytic mobility, diffusion coefficients, etc). These methods supply data on the region in the immediate vicinity of the ion, i.e. the primary solvation sphere, closely connected to the ion and moving together with it. By means of the third type of methods some static quantities entropy and compressibility as well as some non-thermodynamic quantities such as the dielectric constant) are measured. These methods also pertain to the secondary solvation-sphere, in which the solvent structure is affected by the presence of ions, but the... 

An additional group of molecules that have been used as transient solvation probes actually rely on charge transfer to produce the necessary dipole moment charge for solvation measurements. Examples here are 4-(9-anthryl)-/V,/V-dimethylaniline (ADMA) [23,75] and bis(4-... 

Figure 3. Molecular structures for many of the probes that have been used in excited state solvation measurements.

McElroy R, Wynne K. Ultrafast dipole solvation measured in the par-infrared. Phys Rev Lett 1997 79 3078-3081. 

It can be seen for the [N(Tf)2] ionic liquids, that the hydrogen-bond acidity does indeed vary with cation with [BMIM]+ being the most acidic followed by [BMPYJ+ and finally [BMMIMJ+ in both studies. However, changing to more basic anions leads to a dramatic drop in the acidity measurements in the solvation study, whereas it has only a limited effect in the Kamlet-Taft experiment. That is, the solvation measurement is anion dominated, whereas the Kamlet-Taft measurement is cation dominated. 

Force constant and potential energy (C7) calculations indicate that the experimentally measured U does not vary with dielectric constant in a manner predicted by ion-pair potentials both electrostatic and repulsion forces in the solution are important. Solvation measurements provide information about the former vibration studies about the latter. 

A quantitative value of interaction between template and monomer in solution can be preferential solvation. If the interaction between monomer and template is stronger than that between template and solvent, monomer molecules are associated with macromolecules of the template. Preferential solvation measured by interferometric and dialysis experiments was defined as an enrichment of monomer around the template. For instance, for MAA in dimethylformamide (DMF) in the presence of poly(2-vinylpyridine) (P2VP), it was found that the preferential solvation is 0.4. Not only synthetic but also natural polymers can be applied as templates. 

A major advance in force measurement was the development by Tabor, Win-terton and Israelachvili of a surface force apparatus (SFA) involving crossed cylinders coated with molecularly smooth cleaved mica sheets [11, 28]. A current version of an apparatus is shown in Fig. VI-4 from Ref. 29. The separation between surfaces is measured interferometrically to a precision of 0.1 nm the surfaces are driven together with piezoelectric transducers. The combination of a stiff double-cantilever spring with one of a number of measuring leaf springs provides force resolution down to 10 dyn (10 N). Since its development, several groups have used the SFA to measure the retarded and unretarded dispersion forces, electrostatic repulsions in a variety of electrolytes, structural and solvation forces (see below), and numerous studies of polymeric and biological systems. 

The solute-solvent interaction in equation A2.4.19 is a measure of the solvation energy of the solute species at infinite dilution. The basic model for ionic hydration is shown in figure A2.4.3 [5] there is an iimer hydration sheath of water molecules whose orientation is essentially detemiined entirely by the field due to the central ion. The number of water molecules in this iimer sheath depends on the size and chemistry of the central ion ... 

Hydration and solvation have also been studied by conductivity measurements these measurements give rise to an effective radius for the ion, from which a hydration number can be calculated. These effective radii are reviewed in the next section. 

This fomuila does not include the charge-dipole interaction between reactants A and B. The correlation between measured rate constants in different solvents and their dielectric parameters in general is of a similar quality as illustrated for neutral reactants. This is not, however, due to the approximate nature of the Bom model itself which, in spite of its simplicity, leads to remarkably accurate values of ion solvation energies, if the ionic radii can be reliably estimated [15],... 

The analysis of recent measurements of the density dependence of has shown, however, that considering only the variation of solvent structure in the vicinity of the atom pair as a fiinction of density is entirely sufficient to understand tire observed changes in with pressure and also with size of the solvent molecules [38]. Assuming that iodine atoms colliding with a solvent molecule of the first solvation shell under an angle a less than (the value of is solvent dependent and has to be found by simulations) are reflected back onto each other in the solvent cage, is given by... 

It is possible to detemiine the equilibrium constant, K, for the bimolecular reaction involving gas-phase ions and neutral molecules in the ion source of a mass spectrometer [18]. These measurements have generally focused on tln-ee properties, proton affinity (or gas-phase basicity) [19, 20], gas-phase acidity [H] and solvation enthalpies (and free energies) [22, 23] ... 

B1.20.3.1 MEASURING SHORT-RANGE SOLVATION AND HYDRATION FORCES... 

The well defined contact geometry and the ionic structure of the mica surface favours observation of structural and solvation forces. Besides a monotonic entropic repulsion one may observe superimposed periodic force modulations. It is commonly believed that these modulations are due to a metastable layering at surface separations below some 3-10 molecular diameters. These diflftise layers are very difficult to observe with other teclmiques [92]. The periodicity of these oscillatory forces is regularly found to correspond to the characteristic molecular diameter. Figure Bl.20.7 shows a typical measurement of solvation forces in the case of ethanol between mica. 

Figure Bl.20.8. DLVO-type forces measured between two silica glass surfaces in aqueous solutions of NaCl at various concentrations. The inset shows the same data in the short-range regime up to D = 10 mn. The repulsive deviation at short range (<2 nm) is due to a monotonic solvation force, which seems not to depend on the salt concentration. Oscillatory surface forces are not observed. With pemiission from [73].

Kang T J, Yu J and Berg M 1990 Rapid solvation of a nonpolar solute measured by ultrafast transient hole burning Chem. Phys. Lett. 174 476-80... 

Rate increases with increasing po larity of solvent as measured by its dielectric constant e (Section 8 12) Polar aprotic solvents give fastest rates of substitution solvation of Nu IS minimal and nucleophilicity IS greatest (Section 8 12)... 

Since f is a measurable quantity for, say, a protein, and since the latter can be considered to fail into category (3) in general, the friction factor provides some information regarding the eilipticity and/or solvation of the molecule. In the following discussion we attach the subscript 0 to both the friction factor and the associated radius of a nonsolvated spherical particle and use f and R without subscripts to signify these quantities in the general case. Because of Stokes law, we write... 

Interaction Parameters. Early attempts to describe PVC—plasticizer compatibiHty were based on the same principles as used to describe solvation, ie, like dissolves like (2). To obtain a quantitative measure of PVC—plasticizer compatibihty a number of different parameters have been used. More recently these methods have been assessed and extended by many workers (7—9). In all cases it is not possible to adequately predict the behavior of polymeric plasticizers. 

This equation is a reasonable model of electrokinetic behavior, although for theoretical studies many possible corrections must be considered. Correction must always be made for electrokinetic effects at the wall of the cell, since this wall also carries a double layer. There are corrections for the motion of solvated ions through the medium, surface and bulk conductivity of the particles, nonspherical shape of the particles, etc. The parameter zeta, determined by measuring the particle velocity and substituting in the above equation, is a measure of the potential at the so-called surface of shear, ie, the surface dividing the moving particle and its adherent layer of solution from the stationary bulk of the solution. This surface of shear ties at an indeterrninate distance from the tme particle surface. Thus, the measured zeta potential can be related only semiquantitatively to the curves of Figure 3. 

In Raman spectroscopy the intensity of scattered radiation depends not only on the polarizability and concentration of the analyte molecules, but also on the optical properties of the sample and the adjustment of the instrument. Absolute Raman intensities are not, therefore, inherently a very accurate measure of concentration. These intensities are, of course, useful for quantification under well-defined experimental conditions and for well characterized samples otherwise relative intensities should be used instead. Raman bands of the major component, the solvent, or another component of known concentration can be used as internal standards. For isotropic phases, intensity ratios of Raman bands of the analyte and the reference compound depend linearly on the concentration ratio over a wide concentration range and are, therefore, very well-suited for quantification. Changes of temperature and the refractive index of the sample can, however, influence Raman intensities, and the band positions can be shifted by different solvation at higher concentrations or... 

Many organic reactions involve acid concentrations considerably higher than can be accurately measured on the pH scale, which applies to relatively dilute aqueous solutions. It is not difficult to prepare solutions in which the formal proton concentration is 10 M or more, but these formal concentrations are not a suitable measure of the activity of protons in such solutions. For this reason, it has been necessaiy to develop acidity functions to measure the proton-donating strength of concentrated acidic solutions. The activity of the hydrogen ion (solvated proton) can be related to the extent of protonation of a series of bases by the equilibrium expression for the protonation reaction. 

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