Copper II

Copper(II) salts (blue in aqueous solution) are typical M(II) salts but generally have a distorted co-ordination (Jahn-Teller distortion, 4 near plus 2 far neighbours). Extensive ranges of complexes are known, particularly with /V-ligands. 

Copper(II) oxide, CuO. Black solid formed by heating Cu(OH)2, Cu(N03)2, etc. Dissolves in acid to Cu(II) salts, decomposes to CU2O at 800 C. Forms cuprates in solid state reactions. A cuprate(III), KCUO2, is also known. 

Copper(II) perchlorate, Cu(CI04)2,6H20. Formed from CuO and HCIO4. 

Copper Il) sulphide, CuS. Black solid, Cu plus excess S or copper(II) salt plus H2S. Decomposes to copper(l) sulphide, CU2S, on heating. 

When naming complex ions the number and type of ligands is written first, followed by the name of the central metal ion. If the complex as a whole has a positive charge, i.e. a cation, the name of the central metal is written unchanged and followed by the oxidation state of the metal in brackets, for example [Cu(N 113)4] becomes tetra-ammine copper(II). A similar procedure is followed for anions but the suffix -ate is added to the central metal ion some examples are ... 

When the reaction between zinc and copper(II) sulphate was carried out in the form of an electrochemical cell (p. 94), a potential difference between the copper and zinc electrodes was noted. This potential resulted from the differing tendencies of the two metals to form ions. An equilibrium is established when any metal is placed in a solution of its ions. 

Because of ammine formation, when ammonia solution is added slowly to a metal ion in solution, the hydroxide may first be precipitated and then redissolve when excess ammonia solution is added this is due to the formation of a complex ammine ion, for example with copper(II) and nickel(II) salts in aqueous solution. 

Ammonia will reduce metallic oxides which are reduced by hydrogen (for example copper(II) oxide, CuO, lead(II) oxide, PbO), being itself oxidised to nitrogen ... 

These are practically insoluble in water, are not hydrolysed and so may be prepared by addition of a sufficient concentration of sulphide ion to exceed the solubility product of the particular sulphide. Some sulphides, for example those of lead(II), copper(II) and silver(I), have low solubility products and are precipitated by the small concentration of sulphide ions produced by passing hydrogen sulphide through an acid solution of the metal salts others for example those of zincfll), iron(II), nickel(II) and cobalt(II) are only precipitated when sulphide ions are available in reasonable concentrations, as they are when hydrogen sulphide is passed into an alkaline solution. 

The equation is not strictly representative of the reaction for the acid is reduced further and a black deposit consisting of copper(I) and copper(II) sulphides is also produced. 

The reaction provides a valuable method of preparing anhydrous chlorides of metals. It has been used to prepare the anhydrous chlorides of copper(II), zinc, cadmium, chromium(III), iron(III). cobalt(Il) and nickel. 

By the oxidation of hydrogen chloride. A mixture of hydrogen chloride with air or oxygen is passed over a catalyst of copper(II)... 

Alternatively, the iodide is precipitated as copper(I) iodide by addition of copper(II) sulphate, in presence of sulphite, thus ... 

The copper(II) sulphate is recovered and used to precipitate more copper(I) iodide. 

Sulphur dichloride oxide (thionyl chloride) on the hydrated chloride can also be used to produce the anhydrous chloride in certain cases, for example copper(II) chloride and chromium(III) chloride ... 

The anhydrous chloride is prepared by standard methods. It is readily soluble in water to give a blue-green solution from which the blue hydrated salt CuClj. 2H2O can be crystallised here, two water molecules replace two of the planar chlorine ligands in the structure given above. Addition of dilute hydrochloric acid to copper(II) hydroxide or carbonate also gives a blue-green solution of the chloride CuClj but addition of concentrated hydrochloric acid (or any source of chloride ion) produces a yellow solution due to formation of chloro-copper(ll) complexes (see below). 

In the presence of excess iodide ions, copper(II) salts produce the white insoluble copper(I) iodide and free iodine, because copper(II) oxidises iodide under these conditions. The redox potential for the half-reaction ... 

Hydrated copper(ll) hydroxide, Cu(OH)2, is precipitated as a pale blue solid when alkali is added to an aqueous solution of a copper(II) salt ... 

The normal carbonate CuCOj is not known two naturalls occurring basic carbonates have already been mentioned. If a solution of, for example, sodium carbonate is added to a solution of a copper(II) salt, a green basic carbonate is precipitated the reactions are ... 

On heating, the basic carbonate readily yields the black copper(II) oxide. 

When a copper(II) salt dissolves in water, the complex aquo-ion [Cu(H2p)6P is formed this has a distorted octahedral (tetragonal) structure, with four near water molecules in a square plane around the copper and two far water molecules, one above and one below this plane. Addition of excess ammonia replaces only the four planar water molecules, to give the deep blue complex [Cu(NH3)4(H20)2] (often written as [Cu(NHj)4] for simplicity). TTo obtain [Cu(NH3)6], water must be absent, and an anhydrous copper(II) salt must be treated with liquid ammonia. 

Addition of halide ions to aqueous copper(II) solutions can give a variety of halo-complexes for example [CuCl4] (yellow square-planar, but in crystals with large cations becomes a flattened tetrahedron) [CuClj] (red, units linked together in crystals to give tetrahedral or distorted octahedral coordination around each copper). 

Addition of aqueous cyanide ion to a copper(II) solution gives a brown precipitate of copper(II) cyanide, soluble in excess cyanide to give the tetracyanocuprate(II) complex [Cu(CN)4] . However, copper(II) cyanide rapidly decomposes at room temperature, to give copper(I) cyanide and cyanogen(CN)2 (cf. the similar decomposition of copper(II) iodide, below) excess cyanide then gives the tetracyanocuprate(I) [Cu(CN)4] . 

In contrast to the + 2 state, copper(I) compounds are less frequently coloured and are diamagnetic, as expected since the 3d level is full. However, the copper(I) ion, unlike copper(II), is unstable in aqueous solution where it disproportionates into copper(II) and copper(O) (i.e. copper metal). 

Copperil) oxide, CujO, occurs naturally as the red cuprite. It is obtained as an orange-yellow precipitate by the reduction of a copper(II) salt in alkaline solution by a mild reducing agent, for example glucose, hydroxylamine or sodium sulphite ... 

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