Solvation, commonly called dissolution, is the process of attraction and association of
molecules of a solventwith molecules or ions of a solute. As ions dissolve in a solvent they spread out and become surrounded by solvent molecules. The bigger the ion, the more solvent molecules are able to surround it and the more it becomes solvated.
Distinction between solvation, dissolution and solubility
IUPACdefinition [IUPAC Compendium of Chemical Terminology, Electronic version, http://goldbook.iupac.org/S05747.html] , solvation is an interaction of a solute with the solvent which leads to stabilization of the solute species in the solution. One may also refer to the solvated state, whereby an ion in a solution is complexed by solvent molecules. The concept of the solvation interaction can also be applied to an insoluble material, for example, solvation of functional groups on a surface of ion-exchange resin.
Solvation should be conceptually separated from dissolution and
solubility. Dissolution is a kinetic process and it is quantified by its rate. Solubilityquantifies the dynamic equilibriumstate achieved when the rate of dissolution equals the rate of precipitation.
The consideration of the units makes the distinction clearer. Complexation can be described by
coordination numberand the complex stability constants. The typical unit for dissolution rate is mol/s. The unit for solubility can be mol/kg.
olvents and intermolecular interactions
Polar solvents are those with a molecular structure that contains dipoles. Such compounds are often found to have a high
dielectric constant. The polar molecules of these solvents can solvate ions because they can orient the appropriate partially charged portion of the molecule towards the ion in response to electrostatic attraction. This stabilizes the system. Water is the most common and well-studied polar solvent, but others exist, such as acetonitrile, dimethyl sulfoxide, methanol, propylene carbonate, ammonia, ethanol, and acetone. These solvents can be used to dissolve inorganic compounds such as salts.
Solvation involves different types of intermolecular interactions:
hydrogen bonding, ion-dipole and dipole-dipole attractions or van der Waals forces. The hydrogen bonding, ion-dipole, and dipole-dipole interactions occur only in polar solvents. Ion-ion interactions occur only in ionic solvents. The solvation process will only be thermodynamically favored if the overall Gibbs energyof the solution is decreased compared to the Gibbs energyof the separated solvent and solid (or gas or liquid). This means that the change in enthalpy minus the change in entropy(multiplied by the absolute temperature) is a negative value, or that the Gibbs free energy of the system decreases. Conductivityof a solution depends on the solvation of their ions.
For solvation to occur,
energyis required to release individual ions from the crystal lattices in which they are present. This is necessary to break the attractions the ions have with each other and is equal to the solid's lattice free energy (the energy released at the formation of the lattice as the ions bonded with each other). The energy for this comes from the energy released when ions of the lattice associate with molecules of the solvent. Energy released in this form is called the free energy of solvation.
enthalpy of solutionis the solution enthalpy minus the enthalpy of the separate systems, while the entropyis the corresponding difference in entropy. Most gases have a negative enthalpyof solution. A negative enthalpy of solution means that the solute is less soluble at high temperatures.
Although early thinking was that a higher ratio of a cation's ion charge to the size, or the charge density, resulted in more solvation, this does not stand up to scrutiny for ions like Iron(III) or
lanthanides and actinides, which are readily hydrolyzed to form insoluble (hydrous)oxides. As solids, these are obviously not solvated.
Enthalpy of solvation can help explain why solvation occurs with some ionic lattices but not with others. The difference in energy between that which is necessary to release an ion from its lattice and the energy given off when it combines with a solvent molecule is called the
enthalpy change of solution. A negative value for the enthalpy change of solution corresponds to an ion that is likely to dissolve, whereas a high positive value means that solvation will not occur. It is possible that an ion will dissolve even if it has a positive enthalpy value. The extra energy required comes from the increase in entropythat results when the ion dissolves. The introduction of entropy makes it harder to determine by calculation alone whether a substance will dissolve or not. A quantitative measure for solvation power of solvents is given by donor numbers.
Note that solvation does not mean a reaction takes place. Adding NaCl(s) to water, for example, will only create a solution of sodium and chloride ions; you would only have solvation of the salt's ions. Adding the weak base
ammoniato water, on the other hand, would create a reaction in this example.
Rate of dissolution
The rate of dissolution depends on:
*nature of the solvent and solute
*temperature (and to a small degree pressure)
*degree of undersaturation
* presence of mixing
* interfacial surface area
* presence of inhibitors (e.g., a substance adsorbed on the surface).
The rate of dissolution can be often expressed by the equation of the form:
where::m - amount of dissolved material, kg: t - time, seconds: A - surface area of the interface between the dissolving substance and the solvent, m2: D -
diffusion coefficient, m2/s: d - thickness of the boundary boundary layer of the solvent at the surface of the dissolving substance, m: Cs - concentration of the substance on the surface, kg/m3: Cb - concentration of the substance in the bulk of the solvent, kg/m3
For dissolution limited by diffusion, Cs is equal to the solubility of the substance.
The dissolution rate vary by orders of magnitude between different systems. Usually, substances exhibiting low solubility exhibit also low dissolution rates.
*cite book | last = Dogonadze | first = Revaz R. | coauthors = et al. (eds.) | year = 1985-88 | title = The Chemical Physics of Solvation | edition = 3 vols. | publisher = Elsevier | location = Amsterdam | id = ISBN 0-444-42551-9 (part A), ISBN 0-444-42674-4 (part B), ISBN 0-444-42984-0 (part C)
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