Solubility


In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.
The extent of the solubility of a substance in a specific solvent is generally measured as the concentration of the solute in a saturated solution, one in which no more solute can be dissolved. At this point, the two substances are said to be at the solubility equilibrium. For some solutes and solvents, there may be no such limit, in which case the two substances are said to be "miscible in all proportions".
The solute can be a solid, a liquid, or a gas, while the solvent is usually solid or liquid. Both may be pure substances, or may themselves be solutions. Gases are always miscible in all proportions, except in very extreme situations, and a solid or liquid can be "dissolved" in a gas only by passing into the gaseous state first.
The solubility mainly depends on the composition of solute and solvent as well as on temperature and pressure. The dependency can often be explained in terms of interactions between the particles of the two substances, and of thermodynamic concepts such as enthalpy and entropy.
Under certain conditions, the concentration of the solute can exceed its usual solubility limit. The result is a supersaturated solution, which is metastable and will rapidly exclude the excess solute if a suitable nucleation site appears.
The concept of solubility does not apply when there is an irreversible chemical reaction between the two substances, such as the reaction of calcium hydroxide with hydrochloric acid; even though one might say, informally, that one "dissolved" the other. The solubility is also not the same as the rate of solution, which is how fast a solid solute dissolves in a liquid solvent. This property depends on many other variables, such as the physical form of the two substances and the manner and intensity of mixing.
The concept and measure of solubility are extremely important in many sciences besides chemistry, such as geology, biology, physics, and oceanography, as well as in engineering, medicine, agriculture, and even in non-technical activities like painting, cleaning, cooking, and brewing. Most chemical reactions of scientific, industrial, or practical interest only happen after the reagents have been dissolved in a suitable solvent. Water is by far the most common such solvent.
The term "soluble" is sometimes used for materials that can form colloidal suspensions of very fine solid particles in a liquid. The quantitative solubility of such substances is generally not well-defined, however.

Quantification of solubility

The solubility of a specific solute in a specific solvent is generally expressed as the concentration of a saturated solution of the two. Any of the several ways of expressing concentration of solutions can be used, such as the mass, volume, or amount in moles of the solute for a specific mass, volume, or mole amount of the solvent or of the solution.

Per quantity of solvent

In particular, chemical handbooks often express the solubility as grams of solute per 100 millilitres of solvent, or as grams of solute per decilitre of solvent ; or, less commonly, as grams of solute per litre of solvent. The quantity of solvent can instead be expressed in mass, as grams of solute per 100 grams of solvent, or as grams of solute per kilogram of solvent. The number may be expressed as a percentage in this case, and the abbreviation "w/w" may be used to indicate "weight per weight".
Alternatively, the solubility of a solute can be expressed in moles instead of mass. For example, if the quantity of solvent is given in kilograms, the value is the molality of the solution.

Per quantity of solution

The solubility of a substance in a liquid may also be expressed as the quantity of solute per quantity of solution, rather than of solvent. For example, following the common practice in titration, it may be expressed as moles of solute per litre of solution, the molarity of the latter.
In more specialized contexts the solubility may be given by the mole fraction or by the mass fraction at equilibrium. Both are dimensionless numbers between 0 and 1 which may be expressed as percentages.

Liquid and gaseous solutes

For solutions of liquids or gases in liquids, the quantities of both substances may be given volume rather than mass or mole amount; such as litre of solute per litre of solvent, or litre of solute per litre of solution. The value may be given as a percentage, and the abbreviation "v/v" for "volume per volume" may be used to indicate this choice.

Conversion of solubility values

Conversion between these various ways of measuring solubility may not be trivial, since it may require knowing the density of the solution — which is often not measured, and cannot be predicted. While the total mass is conserved by dissolution, the final volume may be different from both the volume of the solvent and the sum of the two volumes.
Moreover, many solids will dissociate in non-trivial ways when dissolved; conversely, the solvent may form coordination complexes with the molecules or ions of the solute. In those cases, the sum of the moles of molecules of solute and solvent is not really the total moles of independent particles solution. To sidestep that problem, the solubility per mole of solution is usually computed and quoted as if the solute does not dissociate or form complexes—that is, by pretending that the mole amount of solution is the sum of the mole amounts of the two substances.

Qualifiers used to describe extent of solubility

The extent of solubility ranges widely, from infinitely soluble such as ethanol in water, to essentially insoluble, such as titanium dioxide in water. A number of other descriptive terms are also used to qualify the extent of solubility for a given application. For example, U.S. Pharmacopoeia gives the following terms, according to the mass msv of solvent required to dissolve one unit of mass msu of solute:
TermRange Exampleg/dLmsv/msu
Very soluble<1calcium nitrate158.70.63
Freely soluble1 to 10calcium chloride651.54
Soluble10 to 30sodium oxalate3.926
Sparingly soluble30 to 100
Slightly soluble100 to 1000calcium sulfate0.21490
Very slightly soluble1000 to 10,000dicalcium phosphate0.025000
Practically insoluble or insoluble≥ 10,000barium sulfate0.000245409000

The thresholds to describe something as insoluble, or similar terms, may depend on the application. For example, one source states that substances are described as "insoluble" when their solubility is less than 0.1 g per 100 mL of solvent.

Molecular view

Solubility occurs under dynamic equilibrium, which means that solubility results from the simultaneous and opposing processes of dissolution and phase joining. A stable state of the solubility equilibrium occurs when the rates of dissolution and re-joining are equal, meaning the relative amounts of dissolved and non-dissolved materials are equal. If the solvent is removed, all of the substance that had dissolved is recovered.
The term solubility is also used in some fields where the solute is altered by solvolysis. For example, many metals and their oxides are said to be "soluble in hydrochloric acid", although in fact the aqueous acid irreversibly degrades the solid to give soluble products. Most ionic solids dissociate when dissolved in polar solvents. In those cases where the solute is not recovered upon evaporation of the solvent, the process is referred to as solvolysis. The thermodynamic concept of solubility does not apply straightforwardly to solvolysis.
When a solute dissolves, it may form several species in the solution. For example, an aqueous solution of cobalt chloride can afford, each of which interconverts.

Factors affecting solubility

Solubility is defined for specific phases. For example, the solubility of aragonite and calcite in water are expected to differ, even though they are both polymorphs of calcium carbonate and have the same chemical formula.
The solubility of one substance in another is determined by the balance of intermolecular forces between the solvent and solute, and the entropy change that accompanies the solvation. Factors such as temperature and pressure will alter this balance, thus changing the solubility.
Solubility may also strongly depend on the presence of other species dissolved in the solvent, for example, complex-forming anions in liquids. Solubility will also depend on the excess or deficiency of a common ion in the solution, a phenomenon known as the common-ion effect. To a lesser extent, solubility will depend on the ionic strength of solutions. The last two effects can be quantified using the equation for solubility equilibrium.
For a solid that dissolves in a redox reaction, solubility is expected to depend on the potential. For example, solubility of gold in high-temperature water is observed to be almost an order of magnitude higher when the redox potential is controlled using a highly oxidizing Fe3O4-Fe2O3 redox buffer than with a moderately oxidizing Ni-NiO buffer.
Solubility also depends on the physical size of the crystal or droplet of solute. For quantification, see the equation in the article on solubility equilibrium. For highly defective crystals, solubility may increase with the increasing degree of disorder. Both of these effects occur because of the dependence of solubility constant on the Gibbs energy of the crystal. The last two effects, although often difficult to measure, are of practical importance. For example, they provide the driving force for precipitate aging.