Copper(II) nitrate describes any member of the family of
inorganic compound
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 chemis ...
s with the formula
Cu(
NO3)
2(H
2O)
x. The hydrates are blue
solid
Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structur ...
s.
Anhydrous
A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achi ...
copper nitrate forms blue-green crystals and
sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.
Synthesis and reactions
Hydrated copper(II) nitrate
Hydrated copper nitrate is prepared by treating copper metal or its oxide with
nitric acid
Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
:
[
:Cu + 4HNO3 → Cu(NO3)2. + 2H2O + 2NO2
The same salts can be prepared treating copper metal with an ]aqueous solution
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, or sodium chloride (NaCl), in water would be r ...
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 causti ...
. That reaction illustrates the ability of copper metal to reduce silver ions.
In aqueous solution, the hydrates exist as the aqua complex 2O)6">u(H2O)6sup>2+. Such complexes are highly labile owing to the d9 electronic configuration of copper(II).
Attempted dehydration of any of the hydrated copper(II) nitrates by heating affords the oxides, not Cu(NO3)2. At 80 °C, the hydrates convert to "basic copper nitrate" (Cu2(NO3)(OH)3), which converts to CuO at 180 °C.[ Exploiting this reactivity, copper nitrate can be used to generate ]nitric acid
Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available ni ...
by heating it until decomposition and passing the fumes directly into water. This method is similar to the last step in the Ostwald process. The equations are as follows:
:2 Cu(NO3)2 → 2 CuO + 4 NO2 + O2
:3NO2 + H2O → 2HNO3 + NO
Treatment of copper(II) nitrate solutions with triphenylphosphine
Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to P Ph3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists ...
, triphenylarsine
Triphenylarsine is the chemical compound with the formula As(C6H5)3. This organoarsenic compound, often abbreviated As Ph3, is a colorless crystalline solid that is used as a ligand and a reagent in coordination chemistry and organic synthesis. Th ...
, and triphenylstibine
Triphenylstibine is the chemical compound with the formula Sb(C6H5)3. Abbreviated SbPh3, this colourless solid is often considered the prototypical organoantimony compound. It is used as a ligand in coordination chemistry and as a reagent in or ...
gives the corresponding copper(I) complexes 6H5)3)3">u(E(C6H5)3)3O3 (E = P, As, Sb). The group V ligand is oxidized to the oxide.
Anhydrous copper(II) nitrate
Two polymorphs of anhydrous Cu(NO3)2 are known. The so-called β-form is a covalent molecular complex, as evidenced by its tendency to sublime. It is one of the few anhydrous transition metal nitrates. It cannot be prepared by reactions containing or producing water. Instead, anhydrous Cu(NO3)2 forms when copper metal is treated with dinitrogen tetroxide
Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium ...
:
:Cu + 2 N2O4 → Cu(NO3)2 + 2 NO
The α-form of anhydrous copper(II) nitrate is a coordination polymer.
Structure
Anhydrous copper(II) nitrate
: left, Structure of anhydrous copper(II) nitrate.
Anhydrous copper(II) nitrate has been crystallized in two solvate
Solvation (or dissolution) describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the ...
-free polymorphs. α- and β-Cu(NO3)2 are fully 3D coordination polymer networks. The alpha form has only one Cu environment, with +1coordination, but the beta form has two different copper centers, one with +1and one that is square planar. The nitromethane solvate also features " + 1coordination", with four short Cu-O bonds of approximately 200 pm and one longer bond at 240 pm. They are coordination polymer
A coordination polymer is an inorganic or organometallic polymer structure containing metal cation centers linked by ligands. More formally a coordination polymer is a coordination compound with repeating coordination entities extending in 1, 2 ...
s, with infinite chains of copper(II) centers and nitrate groups. In the gas phase, copper(II) nitrate features two bidentate nitrate ligands (see image at upper right). Thus, evaporation of the solid entails " cracking" to give the copper(II) nitrate molecule.
Hydrated copper(II) nitrate
Five hydrates have been reported: the monohydrate (Cu(NO3)2·H2O),[ the sesquihydrate (Cu(NO3)2·1.5H2O), the hemipentahydrate (Cu(NO3)2·2.5H2O), a trihydrate (Cu(NO3)2·3H2O), and a hexahydrate ( 2O)6">u(H2O)6NO3)2). The hexahydrate is interesting because the Cu-O distances are all equal, not revealing the usual effect of Jahn-Teller distortion that is otherwise characteristic of octahedral Cu(II) complexes. This non-effect is attributed to the strong hydrogen bonding that limits the elasticity of the Cu-O bonds.
]
Applications
Copper(II) nitrate finds a variety of applications, the main one being its conversion to copper(II) oxide
Copper(II) oxide or cupric oxide is an inorganic compound with the formula CuO. A black solid, it is one of the two stable oxides of copper, the other being Cu2O or copper(I) oxide (cuprous oxide). As a mineral, it is known as tenorite. It ...
, which is used as catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
for a variety of processes in 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 ...
. Its solutions are used in textiles and polishing agents for other metals. Copper nitrates are found in some pyrotechnics.[H.Wayne Richardson "Copper Compounds" Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. .] It is often used in school laboratories to demonstrate chemical voltaic cell reactions. It is a component in some ceramic glazes and metal patinas.
Organic synthesis
Copper nitrate, in combination with acetic anhydride
Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula (CH3CO)2O. Commonly abbreviated Ac2O, it is the simplest isolable anhydride of a carboxylic acid and is widely used as a reagent in organic synthesis. It is a co ...
, is an effective reagent for nitration of aromatic
In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
compounds, known as the Menke nitration.
Hydrated copper nitrate adsorbed onto clay affords a reagent called "Claycop". The resulting blue-colored clay is used as a slurry, for example for the oxidation of thiol
In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...
s to disulfide
In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In ...
s. Claycop is also used to convert dithioacetals to carbonyls. A related reagent based on montmorillonite has proven useful for the nitration
In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols an ...
of aromatic compounds.
Naturally occurring copper nitrates
No mineral of the ideal Cu(NO3)2 formula, or the hydrate, are known. Likasite, Cu3(NO3)(OH)5.2H2O and buttgenbachite, Cu19(NO3)2(OH)32Cl4·2H2O are related minerals.[
Natural basic copper nitrates include the rare minerals ]gerhardtite
Copper(II) nitrate describes any member of the family of inorganic compounds with the formula Cu( NO3)2(H2O)x. The hydrates are blue solids. Anhydrous copper nitrate forms blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hy ...
and rouaite, both being polymorphs of Cu2(NO3)(OH)3 substance. A much more complex, basic, hydrated and chloride-bearing natural salt is buttgenbachite.[
]
References
External links
National Pollutant Inventory – Copper and compounds fact sheet
{{nitrates
Copper(II) compounds
Nitrates
Pyrotechnic oxidizers
Pyrotechnic colorants
Oxidizing agents