Drying solvents

Having properly functioning solvents is an absolute necessity for fine home chemistry work, especially for those interested in organic chemistry. Removal of water and other impurities from these which is often required for store-bought or homemade solvents, can be accomplished by many means, depending on the solvent.

Drying with an anhydrous salt

Probably the most commonly used method for removing water from a solvent is by using the anhydrous form of a salt as desiccant. In this process, which is useful for both polar and nonpolar solvents, involves adding the salt (such as anhydrous magnesium sulfate, sodium sulfate, calcium sulfate, calcium chloride or compounds that react with water forming precipitates such as calcium oxide, calcium hydride) directly to the solvent, followed by one or more careful distillations to avoid drawing water out of the hydrated salt. If water is present, a finely powdered anhydrous salt tends to "clump up" upon absorbing the water. Desiccants used for this process typically need to be checked beforehand to ensure that they will not react with the solvent in any way. Though it isn't a salt, sodium metal is often used in the form of shavings in the same manner with nonpolar organic solvents due to its extreme reactivity towards water. Sodium should only be used in very clean solvents with a LOW water content, otherwise the risk is run of explosions and fire.

Salting out

Salting out is a technique that takes advantage of one solvent's reduced solubility in a solution of some compound relative to its solubility in pure water. This is mostly used for polar solvents that are miscible or highly soluble in water, especially when normal distillation produces an azeotrope. This technique is often used prior to distilling with a salt, as it cannot remove all of the water, but is a convenient way to remove most of it without having to use any anhydrous compounds, and it is one of the only ways to break an azeotrope outside of vacuum distillation. Examples of salting out include the separation of ethanol and water using potassium carbonate, the removal of isopropanol from water using sodium chloride, sodium hydroxide, or a mix of the two.

Molecular sieves

Molecular sieves are precise tools for the removal of water or other liquid components of a mixture. Using precisely sized pores in a material such as silica, clay, or alumina, they selectively trap molecules of a certain size by adsorption. While they may not be particularly cheap and can be difficult to re-dry after their use, molecular sieves have the advantage of being able to remove a significant amount of water from a solvent without introducing any of their own impurities. A disadvantage of molecular sieves, however, is the long amount of time they must be given to complete the water-removal process, often in excess of 24 hours.

Solvents and their principal method(s) of water removal

This section includes a commonly used method for drying a solvent that is sufficient enough for that solvent's typical use, either for solvation or as a reagent. This is not an exhaustive list by any means, and other methods can most likely be used.

Solvent	Method
Acetic acid	Anhydrous copper(II) sulfate Phosphorous pentoxide Fractionally distillation over 5% acetic anhydride and 2% CrO3.
Acetic anhydride	Drying with phosphorous pentoxide then fractionally distill over potassium carbonate Sodium wire (some sources)
Acetone	Salting out with sodium acetate, simple distillation to remove it from water followed by distillation over anhydrous calcium sulfate or magnesium sulfate. Drying with boron trioxide. Drying with anhydrous copper(II) sulfate
Acetonitrile	Drying with calcium chloride, followed by either distillation or decantation; Calcium chloride can also be used to keep the solvent dry Drying with anhydrous potassium carbonate, then 3A molecular sieves, followed by distillation Drying with phosphorous pentoxide (5% w/v), followed by distillation (tip: avoid this method if using in reactions with acid sensitive substrates)
Aniline	Distillation over potassium hydroxide Drying over calcium hydride, followed by distillation. Drying with barium oxide, decantation or filtration, followed by distillation over fresh barium oxide.
Anisole	Drying with calcium chloride/sulfate, another drying with sodium wire, followed by distillation over fresh sodium wire
Benzene	Drying with anhydrous sodium sulfate, followed by either decantation or distillation. Drying with phosphorous pentoxide, sodium, lithium aluminum hydride, calcium hydride, 4A molecular sieves, calcium sulfate, followed by decantation or filtration Drying with alumina, calcium hydride or 4A molecular sieves, followed by distillation. Store over molecular sieves or sodium wire.
Butanol	Drying with magnesium sulfate, calcium oxide or potassium carbonate, followed by distillation over magnesium/iodine, sodium or calcium metal Drying with 3A moloecular sieves (powder)
sec-Butanol	Drying over potassium carbonate or calcium sulfate, followed by fractional distillation. Distillation over calcium oxide, then over magnesium. Distillation over calcium hydride.
tert-Butanol	Drying with calcium hydride (5% w/v), followed by distillation. Drying with calcium oxide, potassium carbonate, calcium sulfate or magnesium sulfate, followed by fractional distillation. Distillation over magnesium/iodine or calcium, sodium, potassium metal. Storage over 3A molecular sieves.
Chloroform	Distillation over anhydrous magnesium sulfate Drying with phosphorus pentoxide followed by distillation.
Dichloromethane	Drying with anhydrous sodium sulfate or calcium hydride, followed by distillation Phosphorus pentoxide can also be used.
Diethyl ether	Dried using anhydrous calcium chloride, molecular sieves, followed by distillation For higher purity, sodium metal and benzophenone are used.
Dimethyl sulfoxide	Distillation in partial vacuum over molecular sieves Calcium hydride can also be used, though it's somewhat less effective.
Dimethylformamide	Drying with barium oxide or molecular sieves, followed by partial vacuum distillation.
Ethanol	Distillation of the 95% azeotrope followed by salting out with anhydrous potassium carbonate and a second distillation over anhydrous calcium or magnesium sulfate Direct drying can be done with magnesium metal, followed by distillation or filtration.
Ethyl acetate	Drying with anhydrous sodium sulfate, ethanol removal can be facilitated by salting out using potassium carbonate, followed by distillation of the ethyl acetate layer over anhydrous magnesium sulfate.
Isopropanol	Salting out to 91% using sodium chloride, followed by salting out to 100% using sodium hydroxide. Once sodium hydroxide has been added and the two layers separated, the entire mixture should be cooled as low as possible to precipitate/freeze sodium hydroxide, which will hurt glassware in a distillation. The isopropanol layer can be poured off the frozen sodium hydroxide solution and distilled over anhydrous magnesium sulfate, preferably with a small amount of sulfuric acid present to mitigate glassware damage from hot sodium hydroxide.
Methanol	Salting out with potassium carbonate or simple distillation to remove from water with or without a desiccant Direct drying can be done with magnesium metal turnings, followed by distillation or filtration.
Methyl ethyl ketone	Drying with calcium sulfate, magnesium sulfate, sodium sulfate or potassium carbonate. Drying over boron trioxide
Tetrahydrofuran	Distillation over molecular sieves Adding metallic potassium under inert conditions for complete removal of water, followed by distillation.
Toluene	Adding sodium metal with benzophenone, followed by distillation Azeotropic distillation with benzene, molecular sieves.
Xylene	Drying with molecular sieves followed by distillation or decantation Distillation over sodium metal.

Compatibility of desiccants with solvents

While most desiccants can be used safely to dry most common solvents, some cannot be used as they will either react with the said solvent or dissolve in it.

Desiccant	Compatible	Incompatible	Notes
Alkali metals	Alkanes, arenes, ethers	Acetone, alcohols, halogenated solvents, DMSO, nitromethane	Reacts violently with halogenated solvents, less so with alcohols and DMSO; air sensitive
Alkali metal hydroxide	Amines and pyridines	Acids, base-sensitive solvents, nitromethane	Reacts with acids releasing water
Alkaline earth metals	Alcohols, alkanes, arenes, ethers	Acetone, alcohols, halogenated solvents, DMSO	Reacts violently with halogenated solvents, less so with alcohols and DMSO; Reaction with alcohols give their respective alkoxides, that can be regenerated back to alcohol by adding water; air sensitive (except magnesium)
Alkaline earth metal oxides	Alcohols, alkanes, arenes, basic solvents, ethers, halogenated solvents	Acetone, esters, dipolar aprotic solvents	May react with alcohols in excess, will cause aldol condensation with ketones; not useful with dipolar aprotic solvents
Alumina	Alcohols, alkanes, arenes, esters, ethers, halogenated solvents	Acetone, acids	Reaction with acetone and acids
Boron trioxide	Acetone, acetonitrile, esters, ethers, halogenated solvents	Alcohols, basic solvents	Reacts with alcohols and basic solvents
Calcium chloride	Alkyl and aryl halides, esters, ethers, halogenated solvents	Acetone, acids, alcohols, aldehydes, amines, carbonyl compounds	Reaction of CaCl2 with acetone forms an addition compound
Calcium hydride	Alcohols, alkanes, amines, DMF, ethers, HMPA, pyridines	Esters	Reacts with esters; air sensitive
Calcium sulfate	Acetone, alcohols, aldehydes, halogenated solvents, ketones and pretty much all solvents	Inert	Drying may be strongly exothermic
Cement (Portland)	Alcohols, alkanes, arenes	Acids, esters	Reacts with acids, esters; after hydration results in a very hard mass
LiAlH4	Alkanes, arenes	Alcohols, esters, halogenated solvents	Reaction with alcohols, esters, halogenated solvents
LiBH4	Alkanes	Alcohols, halogenated solvents, esters	Reaction with alcohols, halogenated solvents, esters
Lithium chloride	Alkanes, arenes, halogenated solvents	Butanol, propanol, methylformamide, hydrazine	Dissolution in alcohols, methylformamide, hydrazine
Magnesium sulfate	Acetone, alcohols, aldehydes, alkanes, arenes, esters, ethers, halogenated solvents, ketones, pretty much all solvents	Inert	May cause small traces of aldol condensation with acetone
Molecular sieves	Alcohols, ethers	Acetone, acids	Will cause aldol condensation of acetone; reacts with acids
Phosphorus pentoxide	Halogenated solvents	Alcohols, amines, organic acids and carbonyl compounds; HMPA, DMSO, acetone	Reaction; decomposition
Potassium carbonate	Acetone, alcohols, aldehydes, halogenated solvents, various ketones, methyl ethyl ketone	Acids	Reaction with acids releases carbon dioxide and water
Silica gel	Alkanes, arenes, esters, ethers	Acetone	May cause self-condensation with acetone
Sodium sulfate	Acids, alcohols, esters, ethers, halogenated solvents	Acetone, ketones	Will cause some aldol condensation with ketones

References

• http://ccc.chem.pitt.edu/wipf/Web/Solvent_Drying.pdf
• http://www.chem.ucla.edu/~bacher/General/30BL/tips/dryingofsolvents.html
• http://chemwiki.ucdavis.edu/Reference/Lab_Techniques/Distillation/Drying_Solvents
• https://www.scripps.edu/shenvi/Education_files/Drying%20Solvents%20handout.pdf
• http://www.sas.upenn.edu/~marisa/documents/drying.pdf

Relevant Sciencemadness threads

• Drying with molecular seives - how fast?
• drying with sodium metal