Precipitation (chemistry)

Precipitation is the process of conversion of a chemical substance into a solid from a solution by converting the substance into an insoluble form or a super-saturated solution.[1][2] When the reaction occurs in a liquid solution, the solid formed is called the precipitate.[3] The chemical agent that causes the solid to form is called the precipitant.[4]

Chemical Precipitation

Without sufficient force of gravity (settling) to bring the solid particles together, the precipitate remains in suspension. After sedimentation, especially when using a centrifuge to press it into a compact mass, the precipitate may be referred to as a 'pellet'. Precipitation can be used as a medium. The precipitate-free liquid remaining above the solid is called the 'supernate' or 'supernatant'. Powders derived from precipitation have also historically been known as 'flowers'. When the solid appears in the form of cellulose fibers which have been through chemical processing, the process is often referred to as regeneration.

Sometimes the formation of a precipitate indicates the occurrence of a chemical reaction. When barium chloride solution reacts with sulphuric acid, a white precipitate of barium sulphate is formed. When potassium iodide solution reacts with lead(II) nitrate solution, a yellow precipitate of lead(II) iodide is formed.

The precipitation may occur if concentration of a compound exceeds its solubility (such as when mixing solvents or changing their temperature). Precipitation may also occur rapidly from a supersaturated solution.

In solids, 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.[5]

An important stage of the precipitation process is the onset of nucleation. The creation of a hypothetical solid particle includes the formation of an interface, which requires some energy based on the relative surface energy of the solid and the solution. If this energy is not available, and no suitable nucleation surface is available, supersaturation occurs.

The hydroxide precipitation is the most widely used industrial precipitation in which metal hydroxides are formed by using calcium hydroxide (slaked lime) or sodium hydroxide (caustic soda) as the precipitant.

Applications

Crystals of meso-tetratolylporphyrin from a reflux of propionic acid precipitate on cooling
Copper from a wire is displaced by silver in a silver nitrate solution it is dipped into, and solid silver precipitates out.

Precipitation reactions can be used for making pigments, removing salts from water in water treatment, and in classical qualitative inorganic analysis.

Precipitation is also useful to isolate the products of a reaction during workup. Ideally, the product of the reaction is insoluble in the reaction solvent. 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:[6]

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 easily be separated by filtration, decanting, or centrifugation. An example would be the synthesis of chromic tetraphenylporphyrin chloride: water is added to the DMF reaction solution, and the product precipitates.[7] Precipitation is also useful in purifying products: crude bmim-Cl is taken up in acetonitrile, and dropped into ethyl acetate, where it precipitates.[8] Another important application of an antisolvent is in ethanol precipitation of DNA.

In metallurgy, precipitation from a solid solution is also a useful way to strengthen alloys. This process is known as solid solution strengthening.

Representation using chemical equations

An example of a precipitation reaction: Aqueous silver nitrate (AgNO3) is added to a solution containing potassium chloride (KCl), the precipitation of a white solid, silver chloride (AgCl), is observed. (Zumdahl, 2005)

The silver chloride (AgCl) has formed a solid, which is observed as a precipitate.

This reaction can be written emphasizing the dissociated ions in a combined solution. This is known as the ionic equation.

A final way to represent a precipitate reaction is known as a net ionic reaction.

Precipitate colors

Green and reddish brown stains on a limestone core sample, respectively corresponding to precipitates of oxides/hydroxides of Fe2+
and Fe3+
.

Many compounds containing metal ions produce precipitates with distinctive colors. The following are typical colors for various metals. However, many of these compounds can produce colors very different from those listed.

Goldblack
ChromiumDeep green, murky green, orange, purple, yellow, brown
CobaltPink
CopperBlue
Iron(II)Green
Iron(III)Reddish brown
ManganesePale pink
NickelGreen
LeadYellow

Other compounds generally form white precipitates.

Anion/cation analysis

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.

Digestion

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 cleaner and bigger particles. The physico-chemical process underlying digestion is called Ostwald ripening.

See also

References

  1. "Precipitation (Chemical) - an overview | ScienceDirect Topics". ScienceDirect. Retrieved 2020-11-28.
  2. "Chemical precipitation". Encyclopedia Britannica. Retrieved 2020-11-28.
  3. "Definition of Precipitate". Merriam-Webster. Retrieved 2020-11-28.
  4. "Definition of Precipitant". Merriam-Webster. Retrieved 2020-11-28.
  5. 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.
  6. 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.
  7. 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.
  8. Dupont, J., Consorti, C., Suarez, P., de Souza, R. (2004). "Preparation of 1-Butyl-3-methyl imidazolium-based Room Temperature Ionic Liquids". Organic Syntheses.CS1 maint: multiple names: authors list (link); Collective Volume, 10, p. 184

Additional reading

This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.