Copper chromite
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Copper chromite is an
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 ...
with the formula Cu2Cr2O5. It is a black solid that is used to catalyze reactions in
organic synthesis Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...
.


History

The material was first described in 1908. The catalyst was developed in North America by
Homer Burton Adkins Homer Burton Adkins (16 January 1892 – 10 August 1949) was an American chemist who studied the hydrogenation of organic compounds. Adkins was regarded as top in his field and a world authority on the hydrogenation of organic compounds. Adk ...
and Wilbur Arthur Lazier, partly based on interrogation of
German German(s) may refer to: * Germany (of or related to) **Germania (historical use) * Germans, citizens of Germany, people of German ancestry, or native speakers of the German language ** For citizens of Germany, see also German nationality law **Ge ...
chemists after
World War II World War II or the Second World War, often abbreviated as WWII or WW2, was a world war that lasted from 1939 to 1945. It involved the World War II by country, vast majority of the world's countries—including all of the great power ...
in relation to the Fischer–Tropsch process. For this reason it is sometimes referred to as the Adkins catalyst or the Lazier catalyst.


Chemical structure

The compound adopts a
spinel Spinel () is the magnesium/aluminium member of the larger spinel group of minerals. It has the formula in the cubic crystal system. Its name comes from the Latin word , which means ''spine'' in reference to its pointed crystals. Properties S ...
structure. The
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s for the constituent metals are Cu(II) and Cr(III). A variety of compositions are recognized for the substance, including Cu2CrO4·CuO·BaCrO4 ( CAS# 99328-50-4) and Cu2Cr2O5 (CAS# 12053-18-8). Commercial samples often contain barium oxide and other components.


Production

Copper chromite is produced by
thermal decomposition Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is re ...
of one of three substances. The traditional method is by the
ignition Ignition may refer to: Science and technology * Firelighting, the human act of creating a fire for warmth, cooking and other uses * Combustion, an exothermic chemical reaction between a fuel and an oxidant * Fusion ignition, the point at which a ...
of copper chromate: : 2 → 2 + Copper barium ammonium chromate is the most commonly used substance for production of copper chromite. The resulting copper chromite mixture produced by this method can only be used in procedures that contain materials inert to
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
, as barium is a product of the decomposition of copper barium ammonium chromate, and is thus present in the resulting mixture. The by-product copper oxide is removed using an
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 componen ...
extraction, consisting of washing with the acid,
decantation Decantation is a process for the separation of mixtures of immiscible liquids or of a liquid and a solid mixture such as a suspension. The layer closer to the top of the container—the less dense of the two liquids, or the liquid from which t ...
and then heat drying of the remaining solid to yield isolated copper chromite. Copper chromite is produced by the exposure of copper barium ammonium chromate to temperatures of 350-450 °C, generally by a muffle furnace: : → + CuO + 2 Ba + 4 + 4 Cr + + 6 Copper ammonium chromate is also used for production of copper chromite. It is generally utilized as an alternative to the route of barium ammonium chromate for usage in chemicals reactive with barium. This can also be washed with acetic acid and dried to remove impurities. Copper chromite is produced through the exposure of copper ammonium chromate to temperatures of 350-450 °C: : → + CrO + 4 + An active copper chromite catalyst which includes
barium Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element. Th ...
in its structure can be prepared from a solution containing barium nitrate,
copper(II) nitrate 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 ammonium chromate. When these compounds are mixed a resulting precipitate is formed. This solid product is then
calcine Calcination refers to thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), genera ...
d at 350–400 °C to yield the catalyst: : Cu(NO3)2 + Ba(NO3)2 + (NH4)2CrO4 → CuCr2O4·BaCr2O4


Illustrative reactions

* Hydrogenolysis 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 ...
compounds to the corresponding
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 carbon–carbon and carbon–oxygen double bonds to single bonds. For example, sebacoin, derived from the acyloin condensation of dimethyl sebacate, is hydrogenated to 1,2-cyclodecanediol by this catalyst.
Phenanthrene Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with formula C14H10, consisting of three fused benzene rings. It is a colorless, crystal-like solid, but can also appear yellow. Phenanthrene is used to make dyes, plastics and pesticides, ...
is also reduced, at the 9,10 position. * Hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol at 250–300 °C under 3300-6000 psi of H2. *
Decarboxylation Decarboxylation is a chemical reaction that removes a carboxyl group and releases carbon dioxide (CO2). Usually, decarboxylation refers to a reaction of carboxylic acids, removing a carbon atom from a carbon chain. The reverse process, which is ...
of α-phenylcinnamic acid to ''cis''- stilbene. Reactions involving hydrogen are conducted at relatively high gas pressure (135 atm) and high temperatures (150–300 °C) in a so-called hydrogenation bomb. More active catalysts, such as W-6 grade Raney nickel, also catalyze hydrogenations such as
ester reduction 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 are f ...
s. The latter catalyst benefits from requiring less vigorous conditions (i.e., it works at room temperature under similar hydrogenation pressures) but requires the chemist to use a higher ratio of catalyst to
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
s.


See also

* Amide reduction


References


External links

*
CAS registry A CAS Registry Number (also referred to as CAS RN or informally CAS Number) is a unique identification number assigned by the Chemical Abstracts Service (CAS), US to every chemical substance described in the open scientific literature. It inclu ...
440-47-3& 317-38-0 {{Organic reactions Reagents for organic chemistry Copper(II) compounds Hydrogenation catalysts Chromium(III) compounds Chromium–oxygen compounds Substances discovered in the 1900s