Precipitation (chemistry)

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Principle of chemical precipitation in aqueous solution Chemical precipitation diagram multilang.svg
Principle of chemical precipitation in aqueous solution

In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a supersaturated solution. [1] [2] The solid formed is called the precipitate. [3] In case of an inorganic chemical reaction leading to precipitation, the chemical reagent causing the solid to form is called the precipitant. [4]

Contents

The clear liquid remaining above the precipitated or the centrifuged solid phase is also called the supernate or supernatant.

The notion of precipitation can also be extended to other domains of chemistry (organic chemistry and biochemistry) and even be applied to the solid phases (e.g. metallurgy and alloys) when solid impurities segregate from a solid phase.

Supersaturation

The precipitation of a compound may occur when its concentration exceeds its solubility. This can be due to temperature changes, solvent evaporation, or by mixing solvents. Precipitation occurs more rapidly from a strongly supersaturated solution.

The formation of a precipitate can be caused by a chemical reaction. When a barium chloride solution reacts with sulphuric acid, a white precipitate of barium sulfate is formed. When a potassium iodide solution reacts with a lead(II) nitrate solution, a yellow precipitate of lead(II) iodide is formed.

Inorganic chemistry

Precipitate formation is useful in the detection of the type of cation in a salt. To do this, an alkali first reacts with the unknown salt to produce a precipitate that is the hydroxide of the unknown salt. To identify the cation, the color of the precipitate and its solubility in excess are noted. Similar processes are often used in sequence – for example, a barium nitrate solution will react with sulfate ions to form a solid barium sulfate precipitate, indicating that it is likely that sulfate ions are present.

A common example of precipitation from aqueous solution is that of silver chloride. When silver nitrate (AgNO3) is added to a solution of potassium chloride (KCl) the precipitation of a white solid (AgCl) is observed. [5] [6]

The ionic equation allows to write this reaction by detailing the dissociated ions present in aqueous solution.

Reductive precipitation

Illustration of the Walden reductor. Copper from a wire is displaced by silver from a silver nitrate solution it is dipped into, and metallic silver crystals precipitate onto the copper wire. Precipitation of Silver on Copper 1.jpg
Illustration of the Walden reductor. Copper from a wire is displaced by silver from a silver nitrate solution it is dipped into, and metallic silver crystals precipitate onto the copper wire.

The Walden reductor is an illustration of a reduction reaction directly accompanied by the precipitation of a less soluble compound because of its lower chemical valence:

The Walden reductor made of tiny silver crystals obtained by the immersion of a copper wire into a solution of silver nitrate is used to reduce to their lower valence any metallic ion located above the silver couple (Ag+ + 1 e– → Ag) in the redox potential scale.

Colloidal suspensions

Without sufficient attraction forces (e.g., Van der Waals force) to aggregate the solid particles together and to remove them from solution by gravity (settling), they remain in suspension and form colloids. Sedimentation can be accelerated by high speed centrifugation. The compact mass thus obtained is sometimes referred to as a 'pellet'.

Digestion and precipitates ageing

Digestion, or precipitate ageing, happens when a freshly formed precipitate is left, usually at a higher temperature, in the solution from which it precipitates. It results in purer and larger recrystallized particles. The physico-chemical process underlying digestion is called Ostwald ripening. [7] [8]

Organic chemistry

Crystals of meso-tetratolylporphyrin from a reflux of propionic acid precipitate on cooling. Photograph of the Buchner funnel on top of a Buchner flask. Tetratolylporphyrin.jpg
Crystals of meso-tetratolylporphyrin from a reflux of propionic acid precipitate on cooling. Photograph of the Büchner funnel on top of a Büchner flask.

While precipitation reactions can be used for making pigments, removing ions from solution in water treatment, and in classical qualitative inorganic analysis, precipitation is also commonly used to isolate the products of an organic reaction during workup and purification operations. Ideally, the product of the reaction is insoluble in the solvent used for the reaction. Thus, it precipitates as it is formed, preferably forming pure crystals. An example of this would be the synthesis of porphyrins in refluxing propionic acid. By cooling the reaction mixture to room temperature, crystals of the porphyrin precipitate, and are collected by filtration on a Büchner filter as illustrated by the photograph here beside: [9]

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Precipitation may also occur when an antisolvent (a solvent in which the product is insoluble) is added, drastically reducing the solubility of the desired product. Thereafter, the precipitate may be easily separated by decanting, filtration, or by centrifugation. An example would be the synthesis of Cr3+ tetraphenylporphyrin chloride: water is added to the dimethylformamide (DMF) solution in which the reaction occurred, and the product precipitates. [10] Precipitation is useful in purifying many other products: e.g., crude bmim-Cl is taken up in acetonitrile, and dropped into ethyl acetate, where it precipitates. [11]

Biochemistry

Proteins purification and separation can be performed by precipitation in changing the nature of the solvent or the value of its relative permittivity (e.g., by replacing water by ethanol), or by increasing the ionic strength of the solution. As proteins have complex tertiary and quaternary structures due to their specific folding and various weak intermolecular interactions (e.g., hydrogen bridges), these superstructures can be modified and proteins denaturated and precipitated. Another important application of an antisolvent is in ethanol precipitation of DNA.

Metallurgy and alloys

In solid phases, precipitation occurs if the concentration of one solid is above the solubility limit in the host solid, due to e.g. rapid quenching or ion implantation, and the temperature is high enough that diffusion can lead to segregation into precipitates. Precipitation in solids is routinely used to synthesize nanoclusters. [12]

In metallurgy, precipitation from a solid solution is also a way to strengthen alloys.

Precipitation of ceramic phases in metallic alloys such as zirconium hydrides in zircaloy cladding of nuclear fuel pins can also render metallic alloys brittle and lead to their mechanical failure. Correctly mastering the precise temperature and pressure conditions when cooling down spent nuclear fuels is therefore essential to avoid damaging their cladding and to preserve the integrity of the spent fuel elements on the long term in dry storage casks and in geological disposal conditions.

Industrial processes

Hydroxide precipitation is probably the most widely used industrial precipitation process in which metal hydroxides are formed by adding calcium hydroxide (slaked lime) or sodium hydroxide (causticsoda) as precipitant.

History

Powders derived from different precipitation processes have also historically been known as 'flowers'.

See also

Related Research Articles

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<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a solvent in a homogeneous way

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.

Solubility equilibrium is a type of dynamic equilibrium that exists when a chemical compound in the solid state is in chemical equilibrium with a solution of that compound. The solid may dissolve unchanged, with dissociation, or with chemical reaction with another constituent of the solution, such as acid or alkali. Each solubility equilibrium is characterized by a temperature-dependent solubility product which functions like an equilibrium constant. Solubility equilibria are important in pharmaceutical, environmental and many other scenarios.

The term chloride refers either to a chloride ion, which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond. Many inorganic chlorides are salts. Many organic compounds are chlorides. The pronunciation of the word "chloride" is.

<span class="mw-page-title-main">Aqueous solution</span> Solution in which the solvent is water

An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, also known as sodium chloride (NaCl), in water would be represented as Na+(aq) + Cl−(aq). The word aqueous means pertaining to, related to, similar to, or dissolved in, water. As water is an excellent solvent and is also naturally abundant, it is a ubiquitous solvent in chemistry. Since water is frequently used as the solvent in experiments, the word solution refers to an aqueous solution, unless the solvent is specified.

<span class="mw-page-title-main">Silver nitrate</span> Chemical compound

Silver nitrate is an inorganic compound with chemical formula AgNO
3. It is a versatile precursor to many other silver compounds, such as those used in photography. It is far less sensitive to light than the halides. It was once called lunar caustic because silver was called luna by ancient alchemists who associated silver with the moon. In solid silver nitrate, the silver ions are three-coordinated in a trigonal planar arrangement.

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<span class="mw-page-title-main">Gravimetric analysis</span> Quantitative determination of a chemical species based on its mass

Gravimetric analysis describes a set of methods used in analytical chemistry for the quantitative determination of an analyte based on its mass. The principle of this type of analysis is that once an ion's mass has been determined as a unique compound, that known measurement can then be used to determine the same analyte's mass in a mixture, as long as the relative quantities of the other constituents are known.

<span class="mw-page-title-main">Barium chloride</span> Chemical compound

Barium chloride is an inorganic compound with the formula BaCl2. It is one of the most common water-soluble salts of barium. Like most other water-soluble barium salts, it is a white powder, highly toxic, and imparts a yellow-green coloration to a flame. It is also hygroscopic, converting to the dihydrate BaCl2·2H2O, which are colourless crystals with a bitter salty taste. It has limited use in the laboratory and industry.

<span class="mw-page-title-main">Silver chloride</span> Chemical compound with the formula AgCl

Silver chloride is a chemical compound with the chemical formula AgCl. This white crystalline solid is well known for its low solubility in water and its sensitivity to light. Upon illumination or heating, silver chloride converts to silver, which is signaled by grey to black or purplish coloration in some samples. AgCl occurs naturally as a mineral chlorargyrite.

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<span class="mw-page-title-main">Lithium chloride</span> Chemical compound

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<span class="mw-page-title-main">Silver perchlorate</span> Chemical compound

Silver perchlorate is the chemical compound with the formula AgClO4. This white solid forms a monohydrate and is mildly deliquescent. It is a useful source of the Ag+ ion, although the presence of perchlorate presents risks. It is used as a catalyst in organic chemistry.

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<span class="mw-page-title-main">Aluminium nitrate</span> Chemical compound

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<span class="mw-page-title-main">Liesegang rings</span>

Liesegang rings are a phenomenon seen in many, if not most, chemical systems undergoing a precipitation reaction under certain conditions of concentration and in the absence of convection. Rings are formed when weakly soluble salts are produced from reaction of two soluble substances, one of which is dissolved in a gel medium. The phenomenon is most commonly seen as rings in a Petri dish or bands in a test tube; however, more complex patterns have been observed, such as dislocations of the ring structure in a Petri dish, helices, and "Saturn rings" in a test tube. Despite continuous investigation since rediscovery of the rings in 1896, the mechanism for the formation of Liesegang rings is still unclear.

<span class="mw-page-title-main">Silver chromate</span> Chemical compound

Silver chromate is an inorganic compound with formula Ag2CrO4 which appears as distinctively coloured brown-red crystals. The compound is insoluble and its precipitation is indicative of the reaction between soluble chromate and silver precursor salts (commonly potassium/sodium chromate with silver nitrate). This reaction is important for two uses in the laboratory: in analytical chemistry it constitutes the basis for the Mohr method of argentometry, whereas in neuroscience it is used in the Golgi method of staining neurons for microscopy.

Lithium nitrite is the lithium salt of nitrous acid, with formula LiNO2. This compound is hygroscopic and very soluble in water. It is used as a corrosion inhibitor in mortar. It is also used in the production of explosives, due to its ability to nitrosate ketones under certain conditions.

Radium compounds are compounds containing the element radium (Ra). Due to radium's radioactivity, not many compounds have been well characterized. Solid radium compounds are white as radium ions provide no specific coloring, but they gradually turn yellow and then dark over time due to self-radiolysis from radium's alpha decay. Insoluble radium compounds coprecipitate with all barium, most strontium, and most lead compounds.

References

  1. ↑ "Precipitation (Chemical) - an overview". ScienceDirect . Retrieved 2020-11-28.
  2. ↑ "Chemical precipitation". Encyclopedia Britannica . Retrieved 2020-11-28.
  3. ↑ "precipitate". Merriam-Webster.com Dictionary . Retrieved 2020-11-28.
  4. ↑ "precipitant". Merriam-Webster.com Dictionary . Retrieved 2020-11-28.
  5. ↑ Zumdahl, Steven S.; DeCoste, Donald J. (2012). Chemical Principles. Cengage Learning. ISBN   978-1-133-71013-4.
  6. ↑ Zumdahl, Steven S.; DeCoste, Donald J. (2018). Introductory Chemistry: A Foundation. Cengage Learning. ISBN   978-1-337-67132-3.
  7. ↑ Vengrenovitch, R.D. (1982). "On the Ostwald ripening theory". Acta Metallurgica. 30 (6): 1079–1086. doi:10.1016/0001-6160(82)90004-9. ISSN   0001-6160.
  8. ↑ Voorhees, P.W. (1985). "The theory of Ostwald ripening". Journal of Statistical Physics. 38 (1–2): 231–252. Bibcode:1985JSP....38..231V. doi:10.1007/BF01017860. ISSN   0022-4715. S2CID   14865117.
  9. ↑ A. D. Adler; F. R. Longo; J. D. Finarelli; J. Goldmacher; J. Assour; L. Korsakoff (1967). "A simplified synthesis for meso-tetraphenylporphine". J. Org. Chem. 32 (2): 476. doi:10.1021/jo01288a053.
  10. ↑ Alan D. Adler; Frederick R. Longo; Frank Kampas; Jean Kim (1970). "On the preparation of metalloporphyrins". Journal of Inorganic and Nuclear Chemistry. 32 (7): 2443. doi:10.1016/0022-1902(70)80535-8.
  11. ↑ Dupont, J., Consorti, C., Suarez, P., de Souza, R. (2004). "Preparation of 1-Butyl-3-methyl imidazolium-based room temperature ionic liquids". Organic Syntheses .{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, vol. 10, p. 184
  12. ↑ Dhara, S. (2007). "Formation, Dynamics, and Characterization of Nanostructures by Ion Beam Irradiation". Critical Reviews in Solid State and Materials Sciences. 32 (1): 1–50. Bibcode:2007CRSSM..32....1D. doi:10.1080/10408430601187624. S2CID   98639891.

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