Copper(II) chlorate

Copper(II) chlorate is a chemical compound of the transition metal copper and the chlorate anion with basic formula Cu(ClO₃)₂. Copper chlorate is an oxidiser.^[5] It commonly forms the tetrahydrate, Cu(ClO₃)₂·4H₂O.

Copper(II) chlorate

Names
IUPAC name Copper(2+) chlorate hydrate (1:2:4)
Other names Copper(II) chlorate; Cupric chlorate
Identifiers
CAS Number	14721-21-2 Y hexahydrate: 13478-36-9 Y
3D model (JSmol)	Interactive image
ChemSpider	2340508
ECHA InfoCard	100.035.228
EC Number	238-767-0
PubChem CID	3083246 3014850
UNII	242533NAM2 Y hexahydrate: TVV0TW380J Y
UN number	2721
CompTox Dashboard (EPA)	DTXSID20163621
InChI InChI=1S/2ClHO3.Cu.4H2O/c2*2-1(3)4;;;;;/h2*(H,2,3,4);;4*1H2/q;;+2;;;;/p-2 Key: VPXMBRBPUORXKO-UHFFFAOYSA-L InChI=1S/2ClHO3.Cu/c2*2-1(3)4;/h2*(H,2,3,4);/q;;+2/p-2 Key: IJCCOEGCVILSMZ-UHFFFAOYSA-L
SMILES O.O.O.O.[O-]Cl(=O)=O.[O-]Cl(=O)=O.[Cu+2]
Properties
Chemical formula	Cu(ClO3)2•4H2O
Molar mass	302.509
Appearance	Light blue
Density	2.26 g cm−3
Melting point	73 °C (anhydrous) 65 °C (hexahydrate) (decomposition)
Solubility in water	highly water-soluble tetrahydrate[1][2] 54.59 g/100 mL (-31 °C) 57.12 g/100 mL (-21 °C) 58.51 g/100 mL (0.8 °C) 62.17 g/100 mL (18 °C) 66.17 g/100 mL (45 °C) 69.42 g/100 mL (59.6 °C) 76.9 g/100 mL (71 °C) hexahydrate[3] 141 g/100 mL (0 °C) 164.4 g/100 mL (18 °C) 195.6 g/100 mL (45 °C) 332 g/100 mL (70 °C)
Solubility	soluble in acetone and ethanol (hexahydrate)
Structure[4]
Crystal structure	Orthorhombic
Space group	Pcab
Point group	mmm
Lattice constant	a = 12.924 Å, b = 9.502 Å, c = 7.233 Å
Lattice volume (V)	880.4 Å3
Formula units (Z)	4
Coordination geometry	distorted octahedral
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	oxidiser
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Production

Copper chlorate can be made by combining a hot one molar solution of copper sulfate, with barium chlorate, which results in the precipitation of barium sulfate. When the solution is filtered, cooled and evaporated under a vacuum blue crystals form.^[6]

CuSO₄ + Ba(ClO₃)₂ → Cu(ClO₃)₂ + BaSO₄(s)

Properties

In 1902, A. Meusser investigated solubility of copper chlorate and found that it melted and started decomposing above 73 °C, giving off chlorine.^[7]

Copper chlorate decomposes when heated, giving off a yellow gas, which contains chlorine, oxygen and chlorine dioxide.^[8] A green solid is left that is a basic copper salt.^[9]

2 Cu(ClO₃)₂ → 2 CuO + Cl₂ + 3 O₂ + 2 ClO₂

Sulfur is highly reactive with copper chlorate, and it is important not to cross contaminate these chemicals, for example in pyrotechnic making.^[10]

Structure

Copper(II) chlorate commonly crystallizes as a tetrahydrate, though a hexahydrate is also known. Tetraaquacopper(II) chlorate, Cu(ClO₃)₂·4H₂O, has an orthorhombic crystal structure.^[4] Each copper atom is octahedrally coordinated, surrounded by four oxygen atoms of water, and two oxygen atoms from chlorate groups, which are opposite each other. Water is closer to the copper than chlorate, 1.944 Å compared to 2.396 Å, exhibiting the Jahn-Teller effect. The chlorate groups take the shape of a distorted tetrahedron. At 298 K (25 °C), the chlorine-oxygen distances in each chlorate ion are 1.498, 1.488 and 1.468 Å, with the longest being the oxygen next to copper. The ∠O-Cu-O (angle subtended at copper by oxygen atoms) is 105.2°, 108.3°, and 106.8°. At lower temperatures (233 K, −40 °C), the water molecules and copper-chlorate distance shrink.^[4]

Use

François-Marie Chertier used tetraamminecopper(II) chlorate to colour flames blue in 1843. This material was abbreviated TACC with formula Cu(NH₃)₄(ClO₃)₂. TACC explodes on impact.^[11]

The substance became known as Chertier's copper for use in blue coloured pyrotechnics.^[12] However its deliquescence causes a problem.^[13] Mixtures with other metal salts can yield violet or lilac colours also.^[14]

It has also been used to colour copper brown.^[15]