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Solubility
Solubility
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Example of a dissolved solid (left)
Formation of crystals in a 4.2 M ammonium sulfate solution. The solution was initially prepared at 20 °C and then stored for 2 days at 4 °C.

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.[1] 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" (or just "miscible").[2]

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,[3] 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 (including their pH and the presence of other dissolved substances) as well as on temperature and pressure. The dependency can often be explained in terms of interactions between the particles (atoms, molecules, or ions) 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.[4]

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.[5] The quantitative solubility of such substances is generally not well-defined, however.

Quantification of solubility

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The solubility of a specific solute in a specific solvent is generally expressed as the concentration of a saturated solution of the two.[1] 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

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In particular, chemical handbooks often express the solubility as grams of solute per 100 millilitres of solvent (g/(100 mL), often written as g/100 ml), or as grams of solute per decilitre of solvent (g/dL); or, less commonly, as grams of solute per litre of solvent (g/L). The quantity of solvent can instead be expressed in mass, as grams of solute per 100 grams of solvent (g/(100 g), often written as g/100 g), or as grams of solute per kilogram of solvent (g/kg). The number may be expressed as a percentage in this case, and the abbreviation "w/w" may be used to indicate "weight per weight".[6] (The values in g/L and g/kg are similar for water, but that may not be the case for other solvents.)

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 (mol/kg).

Per quantity of solution

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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 (mol/L), the molarity of the latter.

In more specialized contexts the solubility may be given by the mole fraction (moles of solute per total moles of solute plus solvent) or by the mass fraction at equilibrium (mass of solute per mass of solute plus solvent). Both are dimensionless numbers between 0 and 1 which may be expressed as percentages (%).

Liquid and gaseous solutes

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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

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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.[7]

Moreover, many solids (such as acids and salts) 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

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The extent of solubility ranges widely, from infinitely soluble (without limit, i.e. miscible[2]) 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:[8] (The solubilities of the examples are approximate, for water at 20–25 °C.)

Term Range (msv/msu) Example g/dL msv/msu
Very soluble <1 calcium nitrate 158.7 0.63
Freely soluble 1 to 10 calcium chloride 65 1.54
Soluble 10 to 30 sodium oxalate 3.9 26
Sparingly soluble 30 to 100
Slightly soluble 100 to 1000 calcium sulfate 0.21 490
Very slightly soluble 1000 to 10,000 dicalcium phosphate 0.02 5000
Practically insoluble or insoluble ≥ 10,000 barium sulfate 0.000245 409000

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.[9]

Molecular view

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Solubility occurs under dynamic equilibrium, which means that solubility results from the simultaneous and opposing processes of dissolution and phase joining (e.g. precipitation of solids). 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(II) chloride can afford [Co(H2O)6]2+, [CoCl(H2O)5]+, CoCl2(H2O)2, each of which interconverts.

Factors affecting solubility

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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.[clarification needed]

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 (ligands) in liquids. Solubility will also depend on the excess or deficiency of a common ion in the solution[clarification needed], 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 (within the range of potentials under which the solid remains the thermodynamically stable phase). For example, solubility of gold in high-temperature water is observed to be almost an order of magnitude higher (i.e. about ten times higher) when the redox potential is controlled using a highly oxidizing Fe3O4-Fe2O3 redox buffer than with a moderately oxidizing Ni-NiO buffer.[10]

Solubility (metastable, at concentrations approaching saturation) also depends on the physical size of the crystal or droplet of solute (or, strictly speaking, on the specific surface area or molar surface area of the solute).[11] 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.[citation needed] For example, they provide the driving force for precipitate aging (the crystal size spontaneously increasing with time).

Temperature

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The solubility of a given solute in a given solvent is function of temperature. Depending on the change in enthalpyH) of the dissolution reaction, i.e., on the endothermicH > 0) or exothermicH < 0) character of the dissolution reaction, the solubility of a given compound may increase or decrease with temperature. The van 't Hoff equation relates the change of solubility equilibrium constant (Ksp) to temperature change and to reaction enthalpy change.

  • For most solids and liquids, their solubility increases with temperature because their dissolution reaction is endothermic (ΔH > 0).[12] In liquid water at high temperatures, (e.g. that approaching the critical temperature), the solubility of ionic solutes tends to decrease due to the change of properties and structure of liquid water; the lower dielectric constant results in a less polar solvent and in a change of hydration energy affecting the ΔG of the dissolution reaction.
  • Gaseous solutes exhibit more complex behavior with temperature. As the temperature is raised, gases usually become less soluble in water (exothermic dissolution reaction related to their hydration) (to a minimum, which is below 120 °C for most permanent gases[13]), but more soluble in organic solvents (endothermic dissolution reaction related to their solvation).[12]

The chart shows solubility curves for some typical solid inorganic salts in liquid water (temperature is in degrees Celsius, i.e. kelvins minus 273.15).[14] Many salts behave like barium nitrate and disodium hydrogen arsenate, and show a large increase in solubility with temperature (ΔH > 0). Some solutes (e.g. sodium chloride in water) exhibit solubility that is fairly independent of temperature (ΔH ≈ 0). A few, such as calcium sulfate (gypsum) and cerium(III) sulfate, become less soluble in water as temperature increases (ΔH < 0).[15] This is also the case for calcium hydroxide (portlandite), whose solubility at 70 °C is about half of its value at 25 °C. The dissolution of calcium hydroxide in water is also an exothermic process (ΔH < 0). As dictated by the van 't Hoff equation and Le Chatelier's principle, low temperatures favor dissolution of Ca(OH)2. Portlandite solubility increases at low temperature. This temperature dependence is sometimes referred to as "retrograde" or "inverse" solubility.[citation needed] Occasionally, a more complex pattern is observed, as with sodium sulfate, where the less soluble decahydrate crystal (mirabilite) loses water of crystallization at 32 °C to form a more soluble anhydrous phase (thenardite) with a smaller change in Gibbs free energyG) in the dissolution reaction.[citation needed]

The solubility of organic compounds nearly always increases with temperature. The technique of recrystallization, used for purification of solids, depends on a solute's different solubilities in hot and cold solvent. A few exceptions exist, such as certain cyclodextrins.[16]

Pressure

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For condensed phases (solids and liquids), the pressure dependence of solubility is typically weak and usually neglected in practice. Assuming an ideal solution, the dependence can be quantified as:

where the index iterates the components, is the mole fraction of the -th component in the solution, is the pressure, the index refers to constant temperature, is the partial molar volume of the -th component in the solution, is the partial molar volume of the -th component in the dissolving solid, and is the universal gas constant.[17]

The pressure dependence of solubility does occasionally have practical significance. For example, precipitation fouling of oil fields and wells by calcium sulfate (which decreases its solubility with decreasing pressure) can result in decreased productivity with time.

Solubility of gases

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Henry's law is used to quantify the solubility of gases in solvents. The solubility of a gas in a solvent is directly proportional to the partial pressure of that gas above the solvent. This relationship is similar to Raoult's law and can be written as:

where is a temperature-dependent constant (for example, 769.2 L·atm/mol for dioxygen (O2) in water at 298 K), is the partial pressure (in atm), and is the concentration of the dissolved gas in the liquid (in mol/L).

The solubility of gases is sometimes also quantified using Bunsen solubility coefficient.

In the presence of small bubbles, the solubility of the gas does not depend on the bubble radius in any other way than through the effect of the radius on pressure (i.e. the solubility of gas in the liquid in contact with small bubbles is increased due to pressure increase by Δp = 2γ/r; see Young–Laplace equation).[18]

Henry's law is valid for gases that do not undergo change of chemical speciation on dissolution. Sieverts' law shows a case when this assumption does not hold.

The carbon dioxide solubility in seawater is also affected by temperature, pH of the solution, and by the carbonate buffer. The decrease of solubility of carbon dioxide in seawater when temperature increases is also an important retroaction factor (positive feedback) exacerbating past and future climate changes as observed in ice cores from the Vostok site in Antarctica. At the geological time scale, because of the Milankovich cycles, when the astronomical parameters of the Earth orbit and its rotation axis progressively change and modify the solar irradiance at the Earth surface, temperature starts to increase. When a deglaciation period is initiated, the progressive warming of the oceans releases CO2 into the atmosphere because of its lower solubility in warmer sea water. In turn, higher levels of CO2 in the atmosphere increase the greenhouse effect and carbon dioxide acts as an amplifier of the general warming.

Polarity

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A popular aphorism used for predicting solubility is "like dissolves like" also expressed in the Latin language as "Similia similibus solventur".[19] This statement indicates that a solute will dissolve best in a solvent that has a similar chemical structure to itself, based on favorable entropy of mixing. This view is simplistic, but it is a useful rule of thumb. The overall solvation capacity of a solvent depends primarily on its polarity.[a] For example, a very polar (hydrophilic) solute such as urea is very soluble in highly polar water, less soluble in fairly polar methanol, and practically insoluble in non-polar solvents such as benzene. In contrast, a non-polar or lipophilic solute such as naphthalene is insoluble in water, fairly soluble in methanol, and highly soluble in non-polar benzene.[20]

Dissolution of sodium chloride in water

In even more simple terms a simple ionic compound (with positive and negative ions) such as sodium chloride (common salt) is easily soluble in a highly polar solvent (with some separation of positive (δ+) and negative (δ-) charges in the covalent molecule) such as water, as thus the sea is salty as it accumulates dissolved salts since early geological ages.

The solubility is favored by entropy of mixingS) and depends on enthalpy of dissolutionH) and the hydrophobic effect. The free energy of dissolution (Gibbs energy) depends on temperature and is given by the relationship: ΔG = ΔH – TΔS. Smaller ΔG means greater solubility.

Chemists often exploit differences in solubilities to separate and purify compounds from reaction mixtures, using the technique of liquid-liquid extraction. This applies in vast areas of chemistry from drug synthesis to spent nuclear fuel reprocessing.

Rate of dissolution

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Dissolution is not an instantaneous process. The rate of solubilization (in kg/s) is related to the solubility product and the surface area of the material. The speed at which a solid dissolves may depend on its crystallinity or lack thereof in the case of amorphous solids and the surface area (crystallite size) and the presence of polymorphism. Many practical systems illustrate this effect, for example in designing methods for controlled drug delivery. In some cases, solubility equilibria can take a long time to establish (hours, days, months, or many years; depending on the nature of the solute and other factors).

The rate of dissolution can be often expressed by the Noyes–Whitney equation or the Nernst and Brunner equation[21] of the form:

where:

  • = mass of dissolved material
  • = time
  • = surface area of the interface between the dissolving substance and the solvent
  • = diffusion coefficient
  • = thickness of the boundary layer of the solvent at the surface of the dissolving substance
  • = mass concentration of the substance on the surface
  • = mass concentration of the substance in the bulk of the solvent

For dissolution limited by diffusion (or mass transfer if mixing is present), is equal to the solubility of the substance. When the dissolution rate of a pure substance is normalized to the surface area of the solid (which usually changes with time during the dissolution process), then it is expressed in kg/m2s and referred to as "intrinsic dissolution rate". The intrinsic dissolution rate is defined by the United States Pharmacopeia.

Dissolution rates vary by orders of magnitude between different systems. Typically, very low dissolution rates parallel low solubilities, and substances with high solubilities exhibit high dissolution rates, as suggested by the Noyes-Whitney equation.

Theories of solubility

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Solubility product

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Solubility constants are used to describe saturated solutions of ionic compounds of relatively low solubility (see solubility equilibrium). The solubility constant is a special case of an equilibrium constant. Since it is a product of ion concentrations in equilibrium, it is also known as the solubility product. It describes the balance between dissolved ions from the salt and undissolved salt. The solubility constant is also "applicable" (i.e. useful) to precipitation, the reverse of the dissolving reaction. As with other equilibrium constants, temperature can affect the numerical value of solubility constant. While the solubility constant is not as simple as solubility, the value of this constant is generally independent of the presence of other species in the solvent.

Other theories

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The Flory–Huggins solution theory is a theoretical model describing the solubility of polymers. The Hansen solubility parameters and the Hildebrand solubility parameters are empirical methods for the prediction of solubility. It is also possible to predict solubility from other physical constants such as the enthalpy of fusion.

The octanol-water partition coefficient, usually expressed as its logarithm (Log P), is a measure of differential solubility of a compound in a hydrophobic solvent (1-octanol) and a hydrophilic solvent (water). The logarithm of these two values enables compounds to be ranked in terms of hydrophilicity (or hydrophobicity).

The energy change associated with dissolving is usually given per mole of solute as the enthalpy of solution.

Applications

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Solubility is of fundamental importance in a large number of scientific disciplines and practical applications, ranging from ore processing and nuclear reprocessing to the use of medicines, and the transport of pollutants.

Solubility is often said to be one of the "characteristic properties of a substance", which means that solubility is commonly used to describe the substance, to indicate a substance's polarity, to help to distinguish it from other substances, and as a guide to applications of the substance. For example, indigo is described as "insoluble in water, alcohol, or ether but soluble in chloroform, nitrobenzene, or concentrated sulfuric acid".[22]

Solubility of a substance is useful when separating mixtures. For example, a mixture of salt (sodium chloride) and silica may be separated by dissolving the salt in water, and filtering off the undissolved silica. The synthesis of chemical compounds, by the milligram in a laboratory, or by the ton in industry, both make use of the relative solubilities of the desired product, as well as unreacted starting materials, byproducts, and side products to achieve separation.

Another example of this is the synthesis of benzoic acid from phenylmagnesium bromide and dry ice. Benzoic acid is more soluble in an organic solvent such as dichloromethane or diethyl ether, and when shaken with this organic solvent in a separatory funnel, will preferentially dissolve in the organic layer. The other reaction products, including the magnesium bromide, will remain in the aqueous layer, clearly showing that separation based on solubility is achieved. This process, known as liquid–liquid extraction, is an important technique in synthetic chemistry. Recycling is used to ensure maximum extraction.

Differential solubility

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In flowing systems, differences in solubility often determine the dissolution-precipitation driven transport of species. This happens when different parts of the system experience different conditions. Even slightly different conditions can result in significant effects, given sufficient time.

For example, relatively low solubility compounds are found to be soluble in more extreme environments, resulting in geochemical and geological effects of the activity of hydrothermal fluids in the Earth's crust. These are often the source of high quality economic mineral deposits and precious or semi-precious gems. In the same way, compounds with low solubility will dissolve over extended time (geological time), resulting in significant effects such as extensive cave systems or Karstic land surfaces.

Solubility of ionic compounds in water

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Some ionic compounds (salts) dissolve in water, which arises because of the attraction between positive and negative charges (see: solvation). For example, the salt's positive ions (e.g. Ag+) attract the partially negative oxygen atom in H2O. Likewise, the salt's negative ions (e.g. Cl) attract the partially positive hydrogens in H2O. Note: the oxygen atom is partially negative because it is more electronegative than hydrogen, and vice versa (see: chemical polarity).

AgCl(s) ⇌ Ag+(aq) + Cl(aq)

However, there is a limit to how much salt can be dissolved in a given volume of water. This concentration is the solubility and related to the solubility product, Ksp. This equilibrium constant depends on the type of salt (AgCl vs. NaCl, for example), temperature, and the common ion effect.

One can calculate the amount of AgCl that will dissolve in 1 liter of pure water as follows:

Ksp = [Ag+] × [Cl] / M2 (definition of solubility product; M = mol/L)
Ksp = 1.8 × 10−10 (from a table of solubility products)

[Ag+] = [Cl], in the absence of other silver or chloride salts, so

[Ag+]2 = 1.8 × 10−10 M2
[Ag+] = 1.34 × 10−5 mol/L

The result: 1 liter of water can dissolve 1.34 × 10−5 moles of AgCl at room temperature. Compared with other salts, AgCl is poorly soluble in water. For instance, table salt (NaCl) has a much higher Ksp = 36 and is, therefore, more soluble. The following table gives an overview of solubility rules for various ionic compounds.

Easily soluble Limited solubility or insoluble[23]
Group I and NH4+ compounds (except lithium phosphate) Carbonates (except Group I, NH4+ and uranyl compounds)
Nitrates Sulfites (except Group I and NH4+ compounds)
Acetates (ethanoates) (except Ag+ compounds) Phosphates (except Group I and NH4+ compounds (excluding Li+))
Chlorides (chlorates and perchlorates), bromides and iodides (except Ag+, Pb2+, Cu+ and Hg22+) Hydroxides and oxides (except Group I, NH4+, Ba2+, Sr2+ and Tl+)
Sulfates (except Ag+, Pb2+, Ba2+, Sr2+ and Ca2+) Sulfides (except Group I, Group II and NH4+ compounds)

Solubility of organic compounds

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The principle outlined above under polarity, that like dissolves like, is the usual guide to solubility with organic systems. For example, petroleum jelly will dissolve in gasoline because both petroleum jelly and gasoline are non-polar hydrocarbons. It will not, on the other hand, dissolve in ethyl alcohol or water, since the polarity of these solvents is too high. Sugar will not dissolve in gasoline, since sugar is too polar in comparison with gasoline. A mixture of gasoline and sugar can therefore be separated by filtration or extraction with water.

Solid solution

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This term is often used in the field of metallurgy to refer to the extent that an alloying element will dissolve into the base metal without forming a separate phase. The solvus or solubility line (or curve) is the line (or lines) on a phase diagram that give the limits of solute addition. That is, the lines show the maximum amount of a component that can be added to another component and still be in solid solution. In the solid's crystalline structure, the 'solute' element can either take the place of the matrix within the lattice (a substitutional position; for example, chromium in iron) or take a place in a space between the lattice points (an interstitial position; for example, carbon in iron).

In microelectronic fabrication, solid solubility refers to the maximum concentration of impurities one can place into the substrate.

In solid compounds (as opposed to elements), the solubility of a solute element can also depend on the phases separating out in equilibrium. For example, amount of Sn soluble in the ZnSb phase can depend significantly on whether the phases separating out in equilibrium are (Zn4Sb3+Sn(L)) or (ZnSnSb2+Sn(L)).[24] Besides these, the ZnSb compound with Sn as a solute can separate out into other combinations of phases after the solubility limit is reached depending on the initial chemical composition during synthesis. Each combination produces a different solubility of Sn in ZnSb. Hence solubility studies in compounds, concluded upon the first instance of observing secondary phases separating out might underestimate solubility.[25] While the maximum number of phases separating out at once in equilibrium can be determined by the Gibb's phase rule, for chemical compounds there is no limit on the number of such phase separating combinations itself. Hence, establishing the "maximum solubility" in solid compounds experimentally can be difficult, requiring equilibration of many samples. If the dominant crystallographic defect (mostly interstitial or substitutional point defects) involved in the solid-solution can be chemically intuited beforehand, then using some simple thermodynamic guidelines can considerably reduce the number of samples required to establish maximum solubility.[26]

Incongruent dissolution

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Many substances dissolve congruently (i.e. the composition of the solid and the dissolved solute stoichiometrically match). However, some substances may dissolve incongruently, whereby the composition of the solute in solution does not match that of the solid. This solubilization is accompanied by alteration of the "primary solid" and possibly formation of a secondary solid phase. However, in general, some primary solid also remains and a complex solubility equilibrium establishes. For example, dissolution of albite may result in formation of gibbsite.[27]

NaAlSi3O8(s) + H+ + 7H2O ⇌ Na+ + Al(OH)3(s) + 3H4SiO4.

In this case, the solubility of albite is expected to depend on the solid-to-solvent ratio. This kind of solubility is of great importance in geology, where it results in formation of metamorphic rocks.

In principle, both congruent and incongruent dissolution can lead to the formation of secondary solid phases in equilibrium. So, in the field of Materials Science, the solubility for both cases is described more generally on chemical composition phase diagrams.

Solubility prediction

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Solubility is a property of interest in many aspects of science, including but not limited to: environmental predictions, biochemistry, pharmacy, drug-design, agrochemical design, and protein ligand binding. Aqueous solubility is of fundamental interest owing to the vital biological and transportation functions played by water.[28][29][30] In addition, to this clear scientific interest in water solubility and solvent effects; accurate predictions of solubility are important industrially. The ability to accurately predict a molecule's solubility represents potentially large financial savings in many chemical product development processes, such as pharmaceuticals.[31] In the pharmaceutical industry, solubility predictions form part of the early stage lead optimisation process of drug candidates. Solubility remains a concern all the way to formulation.[31] A number of methods have been applied to such predictions including quantitative structure–activity relationships (QSAR), quantitative structure–property relationships (QSPR) and data mining. These models provide efficient predictions of solubility and represent the current standard. The draw back such models is that they can lack physical insight. A method founded in physical theory, capable of achieving similar levels of accuracy at an sensible cost, would be a powerful tool scientifically and industrially.[32][33][34][35]

Methods founded in physical theory tend to use thermodynamic cycles, a concept from classical thermodynamics. The two common thermodynamic cycles used involve either the calculation of the free energy of sublimation (solid to gas without going through a liquid state) and the free energy of solvating a gaseous molecule (gas to solution), or the free energy of fusion (solid to a molten phase) and the free energy of mixing (molten to solution). These two process are represented in the following diagrams.

Thermodynamic cycle for calculating solvation via sublimation
Thermodynamic cycle for calculating solvation via fusion

These cycles have been used for attempts at first principles predictions (solving using the fundamental physical equations) using physically motivated solvent models,[33] to create parametric equations and QSPR models[36][34] and combinations of the two.[34] The use of these cycles enables the calculation of the solvation free energy indirectly via either gas (in the sublimation cycle) or a melt (fusion cycle). This is helpful as calculating the free energy of solvation directly is extremely difficult. The free energy of solvation can be converted to a solubility value using various formulae, the most general case being shown below, where the numerator is the free energy of solvation, R is the gas constant and T is the temperature in kelvins.[33]

Well known fitted equations for solubility prediction are the general solubility equations. These equations stem from the work of Yalkowsky et al.[37][38] The original formula is given first, followed by a revised formula which takes a different assumption of complete miscibility in octanol.[38]

These equations are founded on the principles of the fusion cycle.

See also

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Notes

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References

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Solubility is the analytical composition of a saturated solution, expressed in terms of the proportion of a designated solute in a designated when the solvent is present in excess. This property quantifies the maximum amount of solute that can dissolve in a given quantity of solvent at equilibrium under specified conditions, such as and pressure, forming a homogeneous known as a solution. Solubility is typically expressed in units including grams of solute per 100 grams or milliliters of , molarity (moles per liter), (moles per kilogram of ), or , depending on the context and precision required. A key guiding principle for predicting solubility is "like dissolves like," meaning substances with similar intermolecular forces—such as polar solutes in polar s or nonpolar solutes in nonpolar s—tend to form solutions more readily due to favorable interactions between solute and particles. For ionic compounds, solubility often follows specific rules based on the ions involved, such as nitrates being generally soluble in . Several factors influence solubility, including , , and the chemical nature of the solute and . For most solutes in , solubility increases with rising as the enhances the disruption of solute lattice structures. In contrast, the solubility of gases in liquids generally decreases with increasing , as higher favors the escape of gas molecules from the solution. significantly affects gas solubility, with higher pressures increasing the amount of gas that dissolves according to , which states that the solubility of a gas is directly proportional to the of the gas above the solution. These factors are critical in applications ranging from pharmaceutical formulations, where controlled solubility ensures , to environmental processes like ocean carbon cycling influenced by gas solubility in .

Fundamentals of Solubility

Definition and Basic Principles

Solubility refers to the maximum amount of a solute that can dissolve in a given quantity of solvent under specified conditions of temperature, pressure, and composition, resulting in the formation of a saturated solution where the solution is in dynamic equilibrium with any undissolved solute. This property is fundamental to understanding solution formation and is expressed quantitatively as the analytical composition of the saturated solution, often in terms of concentration, mass per volume, or mole fraction. The process of dissolution represents a physical equilibrium, in which the rate of solute particles entering the solution equals the rate at which they crystallize out, maintaining a constant solute concentration once saturation is reached./Equilibria/Solubilty/Solubility_and_Factors_Affecting_Solubility) The concept of solubility has evolved through historical observations and formal definitions. Early insights into gas solubility were provided by English chemist William Henry in the early , who through systematic experiments demonstrated the proportional relationship between gas pressure and its solubility in liquids, laying groundwork for later quantitative studies. Over time, these empirical foundations led to modern standardization by the International Union of Pure and Applied Chemistry (IUPAC), which defines solubility precisely to account for diverse solute-solvent systems and conditions, ensuring consistency in scientific communication and application. To describe the extent of solubility, qualitative terms are commonly used based on approximate thresholds in grams of solute per 100 mL of solvent at standard conditions: substances are considered soluble if exceeding 1 g/100 mL, sparingly soluble if between 0.1 and 1 g/100 mL, and insoluble if less than 0.1 g/100 mL. For instance, (NaCl) exemplifies high solubility in , dissolving at about 36 g/100 mL at 25°C, enabling its widespread use in aqueous solutions. In contrast, (AgCl) is insoluble, with a solubility of only approximately 0.00019 g/100 mL at 25°C, which underlies its precipitation in qualitative analysis. These qualifiers help predict behavior in chemical processes without requiring exact measurements.

Molecular View of Dissolution

The dissolution of a solute in a occurs at the molecular level through the process of , where solute particles are surrounded and stabilized by molecules, forming new intermolecular interactions that replace the original solute-solute attractions. For ionic solutes in polar s like , this involves strong ion-dipole forces, in which the partial charges on the molecules align with the full charges on the ions, effectively pulling them apart from the solid lattice. In cases of non-ionic solutes, weaker van der Waals forces or dipole-dipole interactions may contribute to , facilitating the integration of the solute into the structure. A key aspect of dissolution is the energy balance between breaking solute-solute bonds and forming solute-solvent bonds; for ionic solids, this pits the —the energy required to separate ions in the crystal—against the released when ions interact with water molecules. If the sufficiently offsets the , the process becomes energetically favorable, though the overall spontaneity depends on the change, given by ΔG=ΔHTΔS\Delta G = \Delta H - T \Delta S where ΔH\Delta H represents the change (primarily from net energy shifts in bond breaking and forming), ΔS\Delta S is the change (reflecting increased disorder from dispersing solute particles), and TT is the absolute temperature. Negative ΔG\Delta G indicates a spontaneous dissolution, with often playing a crucial in overcoming any endothermic contributions. In the , or , molecules form a structured layer around the solute, dynamically orienting to maximize favorable interactions; for example, molecules arrange with their oxygen atoms facing Na+^+ ions and atoms toward Cl^- ions, creating a hydration sphere that stabilizes the ions in solution. This formation enhances solubility by isolating solute particles and preventing recombination, while the 's polarity is essential, as it enables the "like dissolves like" where solutes with similar intermolecular forces to the are more readily solvated.

Quantification of Solubility

Measures per Solvent or Solution

Solubility is often quantified relative to the amount of solvent used, providing a measure independent of the total solution volume. One common expression is grams of solute per 100 grams of solvent (g/100 g), which directly indicates the and is particularly useful for comparing solubilities across different solvents without considering variations. Another key unit is molality (m), defined as the number of moles of solute per of solvent, which normalizes concentrations based on solvent mass and remains constant despite changes in solution volume. For instance, the solubility of (KNO₃) in at 25°C is approximately 38 g per 100 g of , highlighting its high solubility in this metric. In contrast, measures expressed per quantity of solution account for the total mixture and are suited for volumetric analyses or reactions in fixed volumes. Grams of solute per 100 milliliters of solution (g/100 mL) is a practical unit for laboratory preparations, as it aligns with common measurement tools like pipettes and reflects the density of the solution implicitly. Molarity (M), or moles of solute per liter of solution, facilitates stoichiometric calculations in chemical reactions, while mole fraction (X), the ratio of moles of solute to total moles in the solution, offers a dimensionless scale ideal for thermodynamic discussions. The same KNO₃ solubility at 25°C corresponds to approximately 35 g/100 mL of solution, though exact values depend on whether expressed per solvent mass or solution volume. This approximation holds better for dilute systems where solution density ≈1 g/mL. Each unit has specific advantages depending on the context; for example, is preferred for like because it is unaffected by temperature-induced volume changes, unlike molarity, which varies with solution density. , meanwhile, simplifies applications by being independent of the solvent's mass or volume. For ionic compounds, saturation equilibrium is conceptually bounded by the (Ksp), an that equals the product of concentrations (in moles per liter) raised to their stoichiometric powers in a saturated solution. This value serves as a limit indicating the maximum solubility under ideal conditions, with lower Ksp values signifying poorer solubility, though it applies primarily to sparingly soluble salts and assumes no common effects or complex formations.

Handling Liquid and Gaseous Solutes

Liquid solutes are handled differently in solubility quantification due to their fluid nature, which allows for complete miscibility or partial mixing without the need to disrupt a rigid structure. Miscibility refers to the ability of two or more liquids to form a homogeneous solution in all proportions, as seen in the ethanol-water system where polar interactions enable full dissolution. In contrast, limited solubility occurs when liquids do not mix completely, such as oil and water, where nonpolar hydrocarbons separate into distinct layers due to unfavorable interactions. Common units for expressing the solubility of liquid solutes include volume percent (v/v), defined as the volume of solute per 100 volumes of solution, and mole fraction, which represents the ratio of moles of solute to total moles in the mixture. Gaseous solutes are quantified primarily through their equilibrium distribution between the gas phase and the liquid solvent, often expressed in volume/volume (V/V) terms or as a function of partial pressure. Henry's law provides the fundamental relationship, stating that at constant temperature, the solubility SS of a gas in a liquid is directly proportional to the partial pressure PP of the gas above the liquid: S=kHPS = k_H \cdot P where kHk_H is the Henry's law constant, which varies with temperature and the gas-solvent pair. This constant can be expressed in units such as atm/mol or mol/(L·atm), allowing conversion between concentration and pressure. A practical example is the dissolution of carbon dioxide (CO₂) in carbonated beverages, where high pressure during bottling increases kHPk_H \cdot P, dissolving CO₂ to create fizz upon opening as pressure drops and the gas escapes. Unlike solid solutes, which require energy to overcome for dissolution, liquid and gaseous solutes lack a crystalline lattice, so their solubility emphasizes equilibrium partitioning driven by intermolecular forces and phase distribution. This partitioning reflects a dynamic balance where the solute distributes between phases based on solubility parameters, without the enthalpic barrier of lattice disruption characteristic of solids.

Unit Conversions and Equivalents

Converting between different units of solubility is essential for comparing data across , applications, and regulatory standards, as solubility is often reported in context-specific formats such as per , moles per , or s. Common conversions involve transforming (moles of solute per of ) to molarity (moles of solute per liter of solution) or mass-based units like grams of solute per 100 grams of to . These transformations require knowledge of molar masses, solution densities, and sometimes approximations for dilute solutions. The conversion from molality to molarity accounts for the volume of the solution, which depends on the solvent's density and the solute's contribution to the total mass. For dilute aqueous solutions, an approximation is M ≈ m (since 1 kg water ≈ 1 L). For more accurate results, especially in concentrated solutions, the full calculation uses the actual solution density (ρ\rho): M=mρ1+mMsolute1000M = \frac{m \cdot \rho}{1 + m \cdot \frac{M_{\text{solute}}}{1000}} where MM is molarity in mol/L, mm is molality in mol/kg, ρ\rho is solution density in g/mL, and MsoluteM_{\text{solute}} is the molar mass of the solute in g/mol. This incorporates the total mass and volume of the solution. Similarly, converting from grams of solute per 100 grams of (g/100 g) to (XX) involves calculating the moles of each component. The of the solute is given by: X=nsolutensolute+nsolventX = \frac{n_{\text{solute}}}{n_{\text{solute}} + n_{\text{solvent}}} where nsoluten_{\text{solute}} and nsolventn_{\text{solvent}} are the moles of solute and , respectively, determined from their masses and molar masses. For example, if 36 g of solute is dissolved in 100 g of , divide each mass by the appropriate to find the moles, then apply the formula. A practical example is the solubility of sodium chloride (NaCl) in water at 25°C, reported as 36 g NaCl per 100 g water. First, convert to molality: moles of NaCl = 36 g / 58.44 g/mol ≈ 0.616 mol; molality mm = 0.616 mol / 0.100 kg = 6.16 m. To find molarity, note the total mass of solution = 136 g and density of the saturated solution ≈ 1.202 g/mL, so volume ≈ 136 g / 1.202 g/mL ≈ 0.113 L; thus, MM ≈ 0.616 mol / 0.113 L ≈ 5.4 M. This conversion highlights the need for solution density, which is often assumed as 1 g/mL for dilute cases but leads to errors in concentrated solutions like this one. In different systems, particularly for trace solubilities, parts per million (ppm) is widely used, defined as milligrams of solute per kilogram of solution (or equivalently, μ\mug/g for mass basis). This unit is common in environmental contexts, such as assessing pollutant solubility in water bodies, where concentrations below 1 mg/L (≈ 1 ppm assuming density ≈ 1 g/mL) indicate trace levels. For instance, the solubility of sparingly soluble salts like lead(II) sulfate in natural waters is often expressed in ppm to evaluate environmental risks. Errors in unit conversions can arise from variations in and solution density, which affect both the reported solubility and the conversion factors. Solubility itself often changes with (e.g., increasing for most in ), and decreases as rises, potentially introducing up to 5-10% error in molarity calculations if not adjusted. For precise work, use temperature-specific values and re-evaluate solubility data at the exact conditions.

Factors Influencing Solubility

Temperature Dependence

The solubility of solutes in solvents generally varies with , depending on whether the dissolution process is endothermic or exothermic. In endothermic dissolution, where the process absorbs , solubility increases as rises, shifting the equilibrium toward greater dissolution to absorb the added . For instance, the solubility of (KNO₃) in exemplifies this trend, increasing from about 13 g per 100 mL at 0°C to 247 g per 100 mL at 100°C. Conversely, exothermic dissolution releases , leading to decreased solubility with increasing as the system shifts to counteract the added by favoring the undissolved state. (Ca(OH)₂) in demonstrates this behavior, with solubility dropping from 0.173 g per 100 mL at 20°C to 0.066 g per 100 mL at 100°C. This temperature dependence can be understood through Le Chatelier's principle, which predicts that the equilibrium position will adjust to minimize changes in conditions. For dissolution, the process is treated as a reversible equilibrium: solute(s) ⇌ solute(aq) + heat (for exothermic) or solute(s) + heat ⇌ solute(aq) (for endothermic). Increasing temperature thus drives endothermic equilibria forward, enhancing solubility, while opposing exothermic ones, reducing it./Equilibria/Solubilty/Temperature_Effects_on_Solubility) Quantitatively, the relationship between temperature and solubility is described by the van't Hoff equation, derived from the temperature dependence of the equilibrium constant KK (here, related to the solubility product or saturation concentration). The equation is: d(lnK)dT=ΔHRT2\frac{d(\ln K)}{dT} = \frac{\Delta H}{RT^2} where ΔH\Delta H is the enthalpy change of dissolution, RR is the gas constant, and TT is the absolute temperature. Integrating this form allows prediction of how solubility varies with temperature, assuming ΔH\Delta H is constant; a positive ΔH\Delta H (endothermic) yields increasing KK with TT, while negative ΔH\Delta H (exothermic) yields decreasing KK./26%3A_Chemical_Equilibrium/26.07%3A_The_van_%27t_Hoff_Equation) Exceptions to these patterns occur, particularly with hydrated salts undergoing phase transitions. For example, decahydrate (Na₂SO₄·10H₂O) exhibits retrograde solubility above approximately 32°C, where its solubility peaks and then slightly decreases due to and transition to the form, altering the effective dissolution .

Pressure Effects

The solubility of gases in s is significantly influenced by , as described by , which states that at constant temperature, the solubility SS of a gas in a is directly proportional to the partial PP of the gas above the :
S=kPS = k \cdot P
where kk is the Henry's law constant, typically expressed in units such as mol/L/atm or mol/L/bar. This relationship arises from the increased frequency of gas collisions with the surface under higher , leading to greater dissolution until equilibrium is reached./Physical_Properties_of_Matter/Solutions_and_Mixtures/Ideal_Solutions/Dissolving_Gases_In_Liquids_Henrys_Law)
For instance, the solubility of oxygen in human , which follows , approximately doubles when the total pressure increases from 1 to 2 , assuming the partial pressure of oxygen also doubles in ; this enhances oxygen delivery but is limited by blood's low baseline solubility of about 0.003 mL O₂/100 mL blood/mm Hg at 37°C. constants for common gases vary widely; for oxygen in at 25°C, kk is approximately 0.0013 mol/L/, while for it is higher at 0.034 mol/L/, reflecting differences in gas-liquid interactions. In contrast, the solubility of liquids in liquids and solids in liquids exhibits minimal dependence on under normal conditions, due to the low of these phases, which results in negligible changes in during dissolution./13:_Solutions/13.04:_Effects_of_Temperature_and_Pressure_on_Solubility) However, under extreme pressures, such as those encountered in deep-sea environments (up to several hundred ) or industrial high-pressure processes, solubility of solids can increase slightly if the partial molar volume of the solute in solution is less than in the phase, as predicted by thermodynamic relations. A practical application of pressure effects on gas solubility is in , where increased ambient at depth raises the solubility of in blood and tissues according to ; upon rapid ascent and pressure reduction, dissolved forms bubbles, potentially causing if not managed through staged decompression stops.

Polarity and Intermolecular Forces

The solubility of a substance is fundamentally governed by the principle that "like dissolves like," where polar solutes tend to dissolve in polar solvents, and nonpolar solutes dissolve in nonpolar solvents, due to compatible intermolecular attractions. For instance, glucose, a polar with multiple hydroxyl groups, dissolves readily in through hydrogen bonding between its -OH groups and . In contrast, nonpolar dissolves in nonpolar primarily via dispersion forces between their structures. This compatibility arises because the solute-solvent interactions must overcome the solute-solute and solvent-solvent forces for dissolution to occur effectively. Intermolecular forces play a hierarchical role in determining solubility, ranked by strength as follows: ion-ion interactions are the strongest, followed by ion-, - (including hydrogen bonding as a specialized form), -induced , and the weakest dispersion forces. In polar solvents like , stronger forces such as ion- and hydrogen bonding stabilize ionic or polar solutes by surrounding them with oriented solvent molecules, enhancing solubility. Nonpolar solutes, lacking permanent s, rely on weaker dispersion forces, making them more soluble in nonpolar environments where similar weak attractions predominate. The dielectric constant (ε) of a quantifies its polarity and ability to screen charges, directly influencing solubility; high ε values, such as water's ε ≈ 80 at 25°C, promote the dissolution of ionic compounds by reducing electrostatic attractions between ions. Conversely, low ε like (ε ≈ 2) exhibit poor of ions but effectively dissolve nonpolar molecules through minimal charge separation. This property underscores why ionic salts are highly soluble in but insoluble in hydrocarbons. A classic example of polarity's impact is floating on : nonpolar molecules interact weakly via dispersion forces among themselves and cannot form favorable interactions with polar , leading to due to 's strong bonding network. address this incompatibility by featuring both polar (hydrophilic) heads and nonpolar (hydrophobic) tails, enabling them to bridge the two phases, stabilize emulsions, and enhance solubility of nonpolar substances in aqueous media. energy, derived from these molecular interactions, briefly quantifies the net stabilization achieved during dissolution.

Solubility in Specific Systems

Gases in Liquids

The solubility of gases in liquids is fundamentally described by Henry's law, which posits that at a constant temperature, the solubility of a gas in a liquid is directly proportional to the partial pressure of the gas in equilibrium with the liquid phase. This relationship is expressed as c=kHpc = k_H \cdot p, where cc is the concentration of the dissolved gas, pp is the partial pressure, and kHk_H is the Henry's law constant specific to the gas-solvent pair. The law assumes dilute solutions and ideal behavior, providing a foundational framework for predicting gas dissolution in processes ranging from industrial gas absorption to environmental equilibria. However, Henry's law has limitations, particularly at high pressures where non-ideal gas behavior and solute-solvent interactions cause deviations from linearity. For instance, at elevated pressures, the solubility of gases like CO₂ can exceed predictions due to enhanced molecular clustering or effects, complicating applications in high-pressure systems such as deep-sea environments or supercritical extractions. also profoundly influences gas solubility; unlike most , gases exhibit an inverse temperature dependence because dissolution is typically exothermic, favoring lower temperatures for higher solubility. The Henry's constant generally decreases with temperature for common gases in aqueous solvents, consistent with the overall decline in solubility. A representative example is oxygen in , where solubility drops from about 9.1 mg/L at 20°C to 6.4 mg/L at 40°C under , roughly a 30% reduction that impacts oxygen availability in warming aquatic systems. Additional factors modulate gas solubility in liquids. Electrolytes induce a salting-out effect by structuring molecules around ions, reducing the availability of sites for gas molecules and thereby decreasing solubility. This is evident in CO₂, which shows lower solubility in (salinity ~35 ppt) compared to at the same and , with reductions up to 10-20% attributed to ionic hydration competition. enhances solubility as per , but this section focuses on gas-specific behaviors beyond general effects. Practical examples illustrate these principles. In aquatic ecosystems, the oxygenation of water supports , with dissolved oxygen levels critically dependent on and ; warmer waters hold less oxygen, stressing and in climate-altered habitats. Similarly, carbonation of beverages relies on pressurizing CO₂ into liquids at low temperatures to achieve , releasing bubbles upon decompression for . In a modern environmental context, oceans absorb approximately 23-30% of anthropogenic CO₂ emissions, buffering atmospheric levels but driving . Since the 1980s, surface ocean has declined by about 0.1 units (a 30% acidity increase), with 2020s data indicating sustained uptake rates of ~9-10 billion metric tons of CO₂ annually despite warming trends that reduce solubility per . This has led to undersaturation of carbonate minerals, threatening calcifying organisms like corals and , as documented in recent global assessments.

Ionic Compounds in Water

The solubility of ionic compounds in arises from the balance between the energy required to disrupt the ionic lattice and the energy released through hydration. The represents the strong electrostatic attractions holding ions together in the solid crystal, which must be overcome for dissolution to occur. In contrast, is the exothermic process where molecules surround and stabilize the separated ions via ion-dipole interactions. Ionic compounds are generally highly soluble if the magnitude of the exceeds the , resulting in a net favorable change for dissolution. For example, (NaCl) exhibits high solubility of approximately 360 g/L at 25°C, as its sufficiently compensates for the . Empirical solubility rules provide guidelines for predicting the behavior of many ionic compounds in , based on observed patterns. All nitrates (NO₃⁻) are soluble, regardless of the cation, due to the weak lattice forces in these salts. Carbonates (CO₃²⁻), however, are typically insoluble except when paired with cations (e.g., Na⁺, K⁺) or (NH₄⁺), where the high hydration of these small, highly charged cations promotes dissolution. These rules stem from the interplay of sizes, charges, and hydration tendencies, allowing chemists to anticipate or solution formation without exhaustive experimentation. The further modulates solubility by introducing an ion already present in the equilibrium, shifting the dissolution process toward the solid phase per . For instance, the solubility of (AgCl), which is sparingly soluble in pure , decreases significantly in a solution containing chloride ions from (NaCl). The additional Cl⁻ ions suppress AgCl dissociation, reducing its molar solubility from about 1.3 × 10⁻⁵ M in pure to ≈1.8 × 10^{-9} M in 0.10 M NaCl. This effect is crucial in qualitative analysis and precipitation reactions. Certain ionic hydroxides display amphoteric behavior, dissolving in both acidic and basic conditions due to pH-dependent . Aluminum hydroxide (Al(OH)₃) exemplifies this, with minimal solubility near neutral (around 6–8), where it precipitates as the neutral hydroxide. In acidic media ( < 5), it dissolves by forming soluble aluminate ions or complexes like [Al(H₂O)₆]³⁺, while in basic media ( > 9), it forms tetrahydroxoaluminate ions ([Al(OH)₄]⁻). This pH-dependent solubility curve reflects the compound's ability to act as either an or base, enhancing its utility in buffering and extraction processes.

Organic Compounds in Solvents

The solubility of organic compounds in solvents is largely governed by the polarity of the solute and solvent, with polar functional groups facilitating dissolution in polar media like through bonding and interactions. Functional groups play a critical role in determining solubility patterns; for instance, the presence of a hydroxyl (-OH) group in alcohols enhances solubility by enabling bonding with molecules, as seen in short-chain alcohols like . In contrast, moieties, being nonpolar, reduce solubility in by limiting such interactions, making purely -based compounds like alkanes nearly insoluble. Other polar groups, such as amines or carboxylates, similarly promote solubility in aqueous solvents, while nonpolar groups like alkyl chains diminish it. A key quantitative measure of an organic compound's hydrophobicity is the logarithm of the (LogP), which indicates the distribution between a nonpolar (octanol) and polar () phase; values greater than 3 typically signify low solubility and high , aiding predictions for pharmaceutical and environmental applications. This metric correlates inversely with aqueous solubility, as higher LogP values reflect stronger partitioning into nonpolar environments. Solubility trends in homologous series, such as alcohols, show a decrease with increasing chain length due to the growing dominance of hydrophobic alkyl portions over the polar hydroxyl group; methanol and ethanol are fully miscible in water, but solubility drops sharply for longer chains, with hexanol exhibiting limited solubility of about 5.9 g/100 mL at 20°C. This pattern underscores the balance between polar and nonpolar contributions in molecular design. To enhance solubility of poorly water-soluble organics, particularly drugs, cosolvents like are commonly added to aqueous systems, reducing the overall polarity and improving dissolution through mechanisms such as weakened water structure and increased solute-solvent interactions; for example, mixtures can increase ibuprofen solubility by up to 10-fold in pharmaceutical formulations. This cosolvency approach is vital in , enabling higher without altering the active molecule. Recent advancements emphasize bio-based green solvents as sustainable alternatives for dissolving organic compounds, addressing environmental concerns with traditional solvents; post-2020 developments include the use of bio-derived systems like or cyrene for extracting lipophilic organics such as , offering comparable solubility enhancements while being biodegradable and low-toxicity. These solvents, often sourced from renewable feedstocks, support greener processes in industries like pharmaceuticals and fine chemicals.

Solid Solutions and Alloys

Solid solutions in alloys represent a form of solubility where one metal (the solute) dissolves into the crystal lattice of another metal (the ) to form a homogeneous crystalline phase without . This occurs at the atomic level, enhancing material properties such as strength and . Unlike liquid solutions, solid solubility is limited by thermodynamic factors and typically requires compatible atomic structures. There are two primary types: substitutional and solid solutions. In substitutional solid solutions, solute atoms replace solvent atoms in the lattice sites, requiring similar atomic sizes and crystal structures for stability. A classic example is the - (Cu-Ni) alloy, where atoms substitute for in the face-centered cubic lattice, forming a complete solid solution across all compositions at elevated temperatures. Interstitial solid solutions, by contrast, involve small solute atoms occupying the voids (interstices) between larger solvent atoms, without displacing them. Carbon in iron exemplifies this, where carbon atoms fit into the octahedral sites of the body-centered cubic iron lattice in low-carbon steels, enabling limited solubility up to about 0.02 wt% at . These mechanisms allow alloys to achieve uniform properties but are constrained by the solute's size relative to the host lattice. The extent of solid solubility is governed by the , empirical guidelines established in the 1930s that predict conditions for extensive substitutional solubility. These include: (1) a relative atomic size difference of less than 15% between solute and solvent; (2) similar crystal structures; (3) comparable electronegativities to ensure favorable bonding; and (4) the same count for electronic compatibility. For interstitial solubility, the solute must be significantly smaller (atomic radius ratio <0.59) to fit lattice gaps without excessive strain. These rules explain why elements like dissolve well in silver but not in magnesium, influencing alloy design for specific applications. Phase diagrams for binary alloys illustrate solubility limits through key features like the solvus line and eutectic points. The solvus line demarcates the boundary between a single solid solution phase and a two-phase region of solid solutions plus precipitates, showing how maximum solute solubility decreases with falling temperature in many systems. For instance, in the Cu-Ni diagram, the solvus is absent due to complete solubility, but in Al-Cu, it defines the α-phase solubility limit. Eutectic points mark the lowest melting temperature where a liquid decomposes into two solid phases, often bounding limited solid solubility regions; the lead-tin (Pb-Sn) eutectic at 183°C exemplifies this, with minimal mutual solubility in the solids. Temperature dependence thus plays a critical role, as cooling below the solvus can drive precipitation and alter properties. Applications of solid solutions leverage these principles for enhanced performance. In steel production, interstitial carbon forms solid solutions with iron, enabling where solute atoms distort the lattice and impede dislocation motion, increasing yield strength by up to 50% in low-alloy steels without brittleness. Substitutional alloys like (Fe-Cr-Ni) use Hume-Rothery-compliant elements for resistance via uniform lattice integration. In modern , solid solution perovskites—such as doped ABO₃ structures like La₀.₈Sr₀.₂MnO₃—have advanced battery technologies by improving ionic conductivity in solid-state electrolytes; recent lattice-matched antiperovskite-perovskite interfaces achieve near-theoretical lithium-ion transport rates, boosting in all-solid-state batteries toward commercialization by 2030. These developments highlight solid solutions' role in storage.

Dissolution Dynamics

Rate of Dissolution

The rate of dissolution describes the kinetics by which a solid solute disperses into a solvent, approaching the equilibrium solubility concentration over time. This dynamic process is governed by mass transfer mechanisms and is distinct from the equilibrium solubility, which represents the maximum solute concentration achievable; for instance, a sparingly soluble compound in fine powder form can exhibit a rapid initial dissolution rate, quickly saturating the solution despite its low ultimate solubility. Several key factors influence the dissolution rate. Increasing the surface area of the solute, such as by using powdered rather than crystalline forms, directly enhances the rate by providing more sites for interaction; for example, micronized aspirin tablets dissolve significantly faster across ranges of 1.2 to 6.8 compared to standard 500 mg tablets due to their greater surface area per unit mass. Agitation of the solution accelerates dissolution by thinning the hydrodynamic adjacent to the solute surface, thereby facilitating solute to the bulk . exerts a profound effect, as higher temperatures increase both the solute's saturation concentration and the molecular coefficient, with the temperature dependence of the rate constant following the k=AeEa/RTk = A e^{-E_a / RT}, where AA is the , EaE_a is the , RR is the , and TT is the absolute ; in dissolution studies of minerals like , activation energies around 89 kJ/mol have been reported, illustrating the exponential sensitivity to . The foundational mathematical model for dissolution kinetics is the Noyes-Whitney equation, originally derived from experiments on solids dissolving in their own solutions: dCdt=DAhV(CsC)\frac{dC}{dt} = \frac{D A}{h V} (C_s - C) Here, dCdt\frac{dC}{dt} is the rate of change of solute concentration in the bulk solution, DD is the diffusion coefficient of the solute, AA is the surface area of the exposed solid, hh is the thickness of the diffusion boundary layer, VV is the volume of the solvent, CsC_s is the saturation solubility, and CC is the current bulk concentration. This equation highlights that dissolution is often diffusion-controlled under typical conditions, with the driving force being the concentration gradient across the boundary layer. The dissolution process unfolds in sequential stages: first, detachment of solute molecules or ions from the solid lattice at the interface; second, of these detached through the unstirred to the bulk solution; and third, , where solvent molecules surround and stabilize the solute particles. In many pharmaceutical applications, such as the disintegration of aspirin tablets in aqueous media, the stage predominates as the rate-limiting step, particularly for poorly water-soluble drugs, emphasizing the importance of strategies to optimize dynamics and surface exposure.

Incongruent Dissolution Processes

Incongruent dissolution refers to the process in which a solid solute partially reacts or decomposes during dissolution, resulting in a saturated solution whose composition differs from that of the original solid, accompanied by the formation of a new solid phase that is typically more stable under the given conditions. Unlike congruent dissolution, where the solid fully dissolves into its constituent in stoichiometric proportions, incongruent dissolution involves selective dissolution of components, leading to secondary precipitates or altered solid residues. This phenomenon is common in multicomponent systems, such as hydrated salts or silicates, where environmental factors like , , or activity drive the reaction toward . This process is influenced by and temperature in systems like hydrated calcium sulfates, where a less soluble phase may form as a residue. in certain ionic compounds can also lead to of hydroxides due to local pH changes. in hydrated salts, where lose water to form less hydrated phases upon exposure to dry air, represents a related transformation without full dissolution. The Gibbs phase rule, F = C - P + 2, where F is the , C is the number of components, and P is the number of phases, governs these systems, particularly in condensed solid-liquid equilibria without vapor involvement (effectively F = C - P + 1). In incongruent dissolution, the presence of multiple solid phases (e.g., original solute and precipitate) alongside the liquid solution often results in invariant or univariant conditions, limiting the system's variability and dictating the equilibrium compositions. For instance, in a like a hydrated salt-water, the coexistence of multiple solid phases and saturated solution creates an invariant point. In industrial contexts, incongruent dissolution plays a critical role in cement hydration, where (C-S-H) gels, the primary binding phase in , dissolve non-stoichiometrically during leaching or degradation, preferentially releasing calcium while leaving a silica-enriched residue, which affects long-term durability and retention in waste repositories. In chemistry and , incongruent processes drive , such as the partial dissolution of feldspars to form secondary clays like , influencing nutrient cycling, , and ; studies on silicate highlight silica retention in soils, impacting global geochemical fluxes.

Theoretical Models of Solubility

Like Dissolves Like Principle

The "like dissolves like" principle is an empirical guideline in chemistry stating that substances with similar intermolecular forces tend to be mutually soluble, while those with dissimilar forces are typically immiscible. This rule arises from observations that polar solutes dissolve preferentially in polar solvents and nonpolar solutes in nonpolar solvents, due to comparable cohesive energies that minimize the energy change upon mixing. The principle originated as qualitative observations by early chemists studying solution behavior, but it was formalized quantitatively through the Hildebrand solubility parameter in the 1930s. Joel H. Hildebrand introduced this parameter, δ, defined as the square root of the cohesive energy density: δ=ΔHvRTVm\delta = \sqrt{\frac{\Delta H_v - RT}{V_m}}
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