A salt metathesis reaction, sometimes called a double displacement reaction, is a chemical process involving the exchange of
bonds between two reacting
chemical species
A chemical species is a chemical substance or ensemble composed of chemically identical molecular entity, molecular entities that can explore the same set of molecular energy levels on a characteristic or delineated time scale. These energy levels ...
which results in the creation of products with similar or identical bonding affiliations. This reaction is represented by the general scheme:
:
AB + CD -> AD + CB
The bond between the reacting species can be either
ionic or
covalent
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
. Classically, these reactions result in the precipitation of one product.
In older literature, the term double decomposition is frequently encountered. The term double decomposition is more specifically used when at least one of the substances does not dissolve in the
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 ...
, as the ligand or ion exchange takes place in the solid state of the reactant. For example:
:AX(aq) + BY(s) → AY(aq) + BX(s).
Types of reactions
Counterion exchange
Salt metathesis is a common technique for exchanging
counterion
160px, Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion.">cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typical ...
s. The choice of reactants is guided by a
solubility chart A solubility chart is a chart with a list of ions and how, when mixed with other ions, they can become precipitates or remain aqueous.
The following chart shows the solubility of multiple independent and various compounds, in water, at a pressure o ...
or
lattice energy
In chemistry, the lattice energy is the energy change upon formation of one mole of a crystalline ionic compound from its constituent ions, which are assumed to initially be in the gaseous state. It is a measure of the cohesive forces that bind ...
.
HSAB theory
HSAB concept is a jargon for "hard and soft Lewis acids and bases, (Lewis) acids and bases". HSAB is widely used in chemistry for explaining stability of chemical compound, compounds, reaction mechanisms and pathways. It assigns the terms 'hard' o ...
can also be used to predict the products of a metathesis reaction.
Salt metathesis is often employed to obtain salts that are soluble in organic solvents. Illustrative is the conversion of
sodium perrhenate
Sodium perrhenate (also known as sodium rhenate(VII)) is the inorganic compound with the formula NaReO4. It is a white salt that is soluble in water. It is a common precursor to other rhenium compounds. Its structure resembles that of sodium per ...
to the
tetrabutylammonium
Tetrabutylammonium is a quaternary ammonium cation with the formula (C4H9)4sup>+. It is used in the research laboratory to prepare lipophilic salts of inorganic anions. Relative to tetraethylammonium derivatives, tetrabutylammonium salts are more ...
salt
Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quantitie ...
:
:NaReO
4 + N(C
4H
9)
4Cl → N(C
4H
9)
4 4">eO4 + NaCl
The tetrabutylammonium salt precipitates from the aqueous solution. It is soluble in
dichloromethane
Dichloromethane (DCM or methylene chloride, methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odour is widely used as a solvent. Although it is not miscible with ...
.
Salt metathesis can be conducted in nonaqueous solution, illustrated by the conversion of
ferrocenium tetrafluoroborate
Ferrocenium tetrafluoroborate is an organometallic compound with the formula e(C5H5)2F4. This salt is composed of the cation e(C5H5)2sup>+ and the tetrafluoroborate anion (). The related hexafluorophosphate is also a popular reagent with simil ...
to a more lipophilic salt containing the
tetrakis(pentafluorophenyl)borate anion:
:
5H5)2">e(C5H5)2F
4 + NaB(C
6F
5)
4 →
5H5)2">e(C5H5)2(C
6F
5)
4 + NaBF
4
When the reaction is conducted in
dichloromethane
Dichloromethane (DCM or methylene chloride, methylene bichloride) is an organochlorine compound with the formula . This colorless, volatile liquid with a chloroform-like, sweet odour is widely used as a solvent. Although it is not miscible with ...
, the salt NaBF
4 precipitates and the B(C
6F
5)
4- salt remains in solution.
Metathesis reactions can occur between two
inorganic
In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
salt
Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quantitie ...
s when one product is
insoluble
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 solubil ...
in water. For example, the
precipitation
In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls under gravitational pull from clouds. The main forms of precipitation include drizzle, rain, sleet, snow, ice pellets, graupel and hail. ...
of
silver chloride
Silver chloride is a chemical compound with the chemical formula Ag Cl. This white crystalline solid is well known for its low solubility in water (this behavior being reminiscent of the chlorides of Tl+ and Pb2+). Upon illumination or heating, ...
from a mixture of
silver nitrate
Silver nitrate is an inorganic compound with chemical formula . 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' ...
and
cobalt hexammine chloride delivers the
nitrate
Nitrate is a polyatomic ion
A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zer ...
salt of the cobalt complex:
:3 +
3)6">o(NH3)6l
3 → 3 AgCl +
3)6">o(NH3)6NO
3)
3
The reactants need not be highly soluble for metathesis reactions to take place. For example
barium thiocyanate forms when boiling a slurry of
copper(I) thiocyanate
Copper(I) thiocyanate (or cuprous thiocyanate) is a coordination polymer with formula CuSCN. It is an air-stable, white solid used as a precursor for the preparation of other thiocyanate salts.
Structure
At least two polymorphs have been charac ...
and
barium hydroxide
Barium hydroxide is a chemical compound with the chemical formula Ba(OH)2. The monohydrate (''x'' = 1), known as baryta or baryta-water, is one of the principal compounds of barium. This white granular monohydrate is the usual commercial form.
P ...
in water:
: + 2 → + 2CuOH
Alkylation
Metal complexes are
alkylated
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting al ...
via salt metathesis reactions. Illustrative is the
methylation
In the chemical sciences, methylation denotes the addition of a methyl group on a substrate, or the substitution of an atom (or group) by a methyl group. Methylation is a form of alkylation, with a methyl group replacing a hydrogen atom. These t ...
of
titanocene dichloride
Titanocene dichloride is the organotitanium compound with the formula ( ''η''5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. This metallocene is a common reagent in organometallic and organic synthesis. It exists as a bright red solid that slowl ...
to give the
Petasis reagent
The Petasis reagent, named after Nicos A. Petasis, is an organotitanium compound with the formula Cp2Ti(CH3)2. It is an orange-colored solid.
Preparation and use
The Petasis reagent is prepared by the salt metathesis reaction of methylmagnesium ...
:
:(C
5H
5)
2TiCl
2 + 2 ClMgCH
3 → (C
5H
5)
2Ti(CH
3)
2 + 2 MgCl
2
The salt product typically precipitates from the reaction solvent.
Neutralization reaction
A
neutralization reaction is a type of double replacement reaction. A neutralization reaction occurs when an
acid
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
reacts with an equal amount of a
base. This usually creates a solution of a salt and
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 a ...
. For example,
hydrochloric acid
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid
Acid strength is the tendency of an acid, symbol ...
reacts with
sodium hydroxide
Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions .
Sodium hydroxide is a highly caustic base and alkali ...
to produce
sodium chloride
Sodium chloride , commonly known as salt (although sea salt also contains other chemical salts), is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. With molar masses of 22.99 and 35.45 g ...
and water:
:HCl + NaOH → NaCl +
Reaction between an acid and a carbonate or bicarbonate always yields
carbonic acid as a product, which spontaneously decomposes into
carbon dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
and water. The release of carbon dioxide gas from the reaction mixture drives the reaction to completion. For example, a common, science-fair "volcano" reaction involves the reaction of
acetic acid
Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...
with
sodium bicarbonate
Sodium bicarbonate (IUPAC name: sodium hydrogencarbonate), commonly known as baking soda or bicarbonate of soda, is a chemical compound with the formula NaHCO3. It is a salt composed of a sodium cation ( Na+) and a bicarbonate anion ( HCO3−) ...
:
: + → + +
Salt-free metathesis reaction
In contrast to salt metathesis reactions, which are driven by the precipitation of solid salts, are
salt-free reduction In chemistry, salt-free reduction describes methodology for reduction of metal halides by electron-rich trimethylsilyl reagents. Traditional reductions of metal halides are accomplished with alkali metals, a process that cogenerates alkali metal s ...
s, which are deriven by formation of silyl halides, Salt-free metathesis reactions proceed homogeneously.
See also
*
Single displacement reaction
A single-displacement reaction, also known as single replacement reaction or exchange reaction, is a chemical reaction in which one element is replaced by another in a compound.
It can be represented generically as:
:A + BC -> AC + B
where eithe ...
References
{{Authority control
Chemical reactions