Solvation
44041
224455279
2008-07-08T22:29:51Z
Stan J Klimas
2562403
/* Rate of dissolution */ - mention inhibitors of dissolution
[[Image:Na%2BH2O.svg|thumb|right|A sodium ion solvated by water molecules]]
'''Solvation''', commonly called '''dissolution''', is the process of attraction and association of [[molecule]]s of a [[solvent]] with molecules or [[ion]]s 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==
By an [[IUPAC]] definition<ref>IUPAC Compendium of Chemical Terminology, Electronic version, http://goldbook.iupac.org/S05747.html</ref>, 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 [[Complex (chemistry)|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 [[Chemical kinetics|kinetic]] process and it is quantified by its [[Reaction rate|rate]]. [[Solubility]] quantifies the [[dynamic equilibrium]] state achieved when the rate of dissolution equals the rate of [[Precipitation (chemistry)|precipitation]].
The consideration of the units makes the distinction clearer. Complexation can be described by [[coordination number]] and the complex [[Equilibrium constant|stability constant]]s. The typical unit for dissolution rate is mol/s. The unit for solubility can be mol/kg.
==Solvents and intermolecular interactions==
[[Chemical polarity|Polar]] solvents are those with a molecular structure that contains [[Bond dipole moment|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 attraction]]s or [[van der Waals force]]s. 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 energy]] of the solution is decreased compared to the [[Gibbs energy]] of 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.
[[Conductivity]] of a solution depends on the solvation of their ions.
==Thermodynamic considerations==
For solvation to occur, [[energy]] is required to release individual ions from the [[crystal lattice]]s 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 [[Thermodynamic free energy|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]].
The [[enthalpy of solution]] is the solution enthalpy minus the enthalpy of the separate systems, while the [[entropy]] is the corresponding difference in entropy. Most gases have a negative [[enthalpy]] of 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 [[lanthanide]]s and [[actinide]]s, 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 and non-negative numbers|negative]] value for the enthalpy change of solution corresponds to an ion that is likely to dissolve, whereas a high [[negative and non-negative numbers|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 [[entropy]] that 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 number]]s.
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 [[ammonia]] to water, on the other hand, would create a [[Chemical reaction|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:
<math>\frac {dm} {dt} = A \frac {D} {d} (C_s-C_b)</math>
where:
:m - amount of dissolved material, kg
: t - time, seconds
: A - surface area of the interface between the dissolving substance and the solvent, m<sup>2</sup>
: D - [[diffusion coefficient]], m<sup>2</sup>/s
: d - thickness of the boundary boundary layer of the solvent at the surface of the dissolving substance, m
: C<sub>s</sub> - concentration of the substance on the surface, kg/m<sup>3</sup>
: C<sub>b</sub> - concentration of the substance in the bulk of the solvent, kg/m<sup>3</sup>
For dissolution limited by diffusion, C<sub>s</sub> 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.
== See also ==
{{Wiktionary}}
* [[Complex (chemistry)]]
* [[Saturation (chemistry)|Saturation]]
* [[Solubility]]
* [[Solubility equilibrium]]
* [[Solute]]
* [[Solution]]
* [[Solvent]]
* [[Supersaturation]]
==Further reading==
*{{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)}}
==References==
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