chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, structure, proper ...

, solvolysis is a type of

nucleophilic substitution In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). The ...

(S1/S2) or elimination where the

nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they ar ...

is a

solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...

molecule. Characteristic of S1 reactions, solvolysis of a

chiral Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from i ...

reactant affords the

racemate In chemistry, a racemic mixture, or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates. ...

. Sometimes however, the stereochemical course is complicated by intimate ion pairs, whereby the leaving

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...

remains close to the

carbocation A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encount ...

, effectively shielding it from an attack by the nucleophile. Particularly fast reactions can occur by neighbour group participation, with

nonclassical ion Nonclassical carbocations are stabilized by charge delocalization from contributions of neighbouring or bonds, which can form bridged intermediates or transition states. Nonclassical ions have been extensively studied with the 2-norbornyl sy ...

s as intermediates or transition states.

Examples

For certain nucleophiles, solvolysis reactions are classified. Solvolysis involving

water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...

is called

hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysi ...

. Related terms are

alcoholysis In chemistry, solvolysis is a type of nucleophilic substitution (S1/S2) or elimination where the nucleophile is a solvent molecule. Characteristic of S1 reactions, solvolysis of a chiral reactant affords the racemate. Sometimes however, the ste ...

(

alcohol Alcohol most commonly refers to: * Alcohol (chemistry), an organic compound in which a hydroxyl group is bound to a carbon atom * Alcohol (drug), an intoxicant found in alcoholic drinks Alcohol may also refer to: Chemicals * Ethanol, one of sev ...

s) and specifically methanolysis (

methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is ...

), acetolysis,

ammonolysis In chemistry, ammonolysis (/am·mo·nol·y·sis/) is the process of splitting ammonia into NH2- + H+. Ammonolysis reactions can be conducted with organic compounds to produce amines (molecules containing a nitrogen atom with a lone pair, :N), o ...

(

ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous ...

), and

aminolysis In chemistry, aminolysis (/am·i·nol·y·sis/) is any chemical reaction in which a molecule is Chemical decomposition, lysed (split into two parts) by reacting with ammonia () or an amine (any molecule containing a nitrogen atom with a lone pair, ...

(alkyl amines).

Glycolysis Glycolysis is the metabolic pathway that converts glucose () into pyruvate (). The free energy released in this process is used to form the high-energy molecules adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide (NADH ...

is however an older term for the multistep conversion of glucose to pyruvate.

Hydrolysis

While solvolysis often refers to an

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J ...

context, hydrolysis is common throughout

inorganic chemistry Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disci ...

, where aqua complexes of metal ions react with solvent molecules due to the

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...

ity of the metal center. For example, aqueous solutions of

aluminium chloride Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula . It forms hexahydrate with the formula , containing six water molecules of hydration. Both are colourless crystals, but samples are often contam ...

are acidic due to the aqua-aluminium complex losing protons to water molecules, giving hydronium ions which lowers the pH. In organic chemistry, hydrolysis reactions often give two fragments from an initial substrate. For example, the hydrolysis of

amide In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it i ...

s give

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxyli ...

s and

amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent ...

s; the hydrolysis of

ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...

s give alcohols and

Alcoholysis

An example of a solvolysis reaction is the reaction of a

triglyceride A triglyceride (TG, triacylglycerol, TAG, or triacylglyceride) is an ester derived from glycerol and three fatty acids (from ''tri-'' and ''glyceride''). Triglycerides are the main constituents of body fat in humans and other vertebrates, as ...

with a simple

such as

ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...

to give the methyl or ethyl

s of the fatty acid, as well as

glycerol Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...

. This reaction is more commonly known as a

transesterification In organic chemistry, transesterification is the process of exchanging the organic group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. The reaction ca ...

reaction due to the exchange of the alcohol fragments.

Ammonolysis

Ammonolysis refers to solvolysis by ammonia, but can also describe nucleophilic attack by ammonia more generally. Ammonia boils at −33 °C, and, as such, is rarely used as a solvent in its pure form. It is, however, readily

miscible Miscibility () is the property of two substances to mix in all proportions (that is, to fully dissolve in each other at any concentration), forming a homogeneous mixture (a solution). The term is most often applied to liquids but also applies ...

with water, and is commonly used in the form of a saturated aqueous solution. For this reason, ammonolysis may be considered as a special case of solvolysis, as the ammonia is itself dissolved in a solvent. Despite this, the reactions are usually highly selective, due to the greater nucleophilicity of ammonia compared to water.

References

{{Reflist Substitution reactions

Examples

Hydrolysis

Alcoholysis

Ammonolysis

See also

References