Bài 5 ĐỒNG VÀ HỢP CHẤT

5.1 Đặc điểm chung về tính chất của đồng và hợp chất:

Cấu hình electron: In the Periodic Table copper is placed in the first transition series
(period 4). It belongs to Group 1B and, together with silver and gold, forms the coinage
metals. Its electron configuration is [Ar] 3d10 4s1.

Bậc oxi hóa: Copper compounds are known in oxidation states ranging from +1 to +4,
although the +2 (cupric) and the +1 (cuprous) are by far the most common. In aqueous
solutions or below 800◦C, the +2 oxidation state is the most stable.

Standard electron potentials of copper are as follows:

Potentials in standard (acid) solution:

Cu+ + e → Cu E0 = 0,521V

Cu2+ + e → Cu+ E0 = 0,153V

Potentials with complexing ligands:

As the standard electron potentials show, copper metal is stable to nonoxidizing acids
like dilute sulfuric or hydrochloric acid, similar to the precious metals. Dissolution of
copper is possible in oxidizing acids such as nitric acid or hot concentrated sulfuric acid.
Also other redox systems such as iron(III) or copper(II) chloride solutions are suitable
reagents for leaching copper in practice.

Copper dissolves not only in oxidizing acids but also, for example, in ammonia or
cyanide solutions in the presence of oxygen because stable complexes are formed. Also
acetic acid together with oxygen or hydrogen peroxide attacks copper forming a green
pigment called verdigris.
Free Cu+ ions are not stable in aqueous solution although Cu + (3d10) has a filled d shell.
Spontaneous disproportion into Cu2+ and Cu takes place.

(Dựa vào thế khử cho ở bảng trên, tính thế và hằng số cân bằng của phản ứng sau:

2Cu+ (aq) = Cu2+(aq) + Cu)

[ The distorted octahedral coordination of six water molecules around the Cu 2+ ion (d9)
gives an additional stabilization energy (ligand-field effect). In aqueous solutions, Cu + is
only existent in form of very stable complexes like [Cu(CN) 2]− or in the presence of an
excess of copper metal. Also, insoluble Cu + compounds such as cuprous oxide do not
disproportionate in water.

By virtue of its large ionic radius and low electrical charge, the Cu + ion is a soft acid.
Therefore, the chemistry of copper in the oxidation state + 1 is predominated by
reactions with soft bases like iodine (CuI), sulfur (CuSCN), or unsaturated nitrogen
ligands. In contrast,the chemistry of Cu 2+, which is smaller and more highly charged, is
dominated by hard ligands like oxygen ([Cu(H2O)6]2+) or nitrogen] ([Cu(NH3)4]2+).

Behavior in Air. Copper in dry air at room temperature slowly develops a thin protective
film of opper(I) oxide. On heating to a high temperature in the presence of oxygen,
copper forms first copper(I) oxide, then copper(II) oxide, both of which cover the metal
as a loose scale.

In the atmosphere, the surface of copper oxidizes in the course of years to a mixture of
green basic salts, the patina, which consists chiefly of the basic sulfate, with some basic
carbonate.(In a marine atmosphere, there is also some basic chloride.) Such covering
layers protect the metal.

Behavior versus Diverse Substances.

While many substances scarcely react with copper under dry conditions, the rate of
attack increases considerably in the presence of moisture. Copper has a high affinity for
free halogens, molten sulfur or hydrogen sulfide.

Copper is very stable in fresh water and also in sea water or alkali metal hydroxide
solutions.Wastewater containing organic sulfur compounds can be corrosive to copper.

Corrosion M. J. N. Pourbaix has developed potential – pH equilibrium diagrams for

metals in dilute aqueous solutions. Such graphs give a rough indication of the feasibility
of electrochemical reactions. Figure 1 shows the behavior of copper at room
temperature and atmospheric pressure. The Cu –H2O

system contains three fields of different character:

1) Corrosion, in which the metal is attacked

2) Immunity, in which reaction is thermodynamically impossible

3) Passivity, in which there is no reaction because of kinetic phenomena

Gases and Copper An exact knowledge of the behavior of solid and liquid copper toward
gases is important for production and use of the metal. With the exception of hydrogen,
the solubility of gases in molten copper follows Henry’s law: the solubility is
proportional to the partial pressure.

Oxygen dissolves in molten copper as copper(I) oxide up to a concentration of 12.6wt %

Cu2O (corresponding to 1.4 wt % O) (also see Fig. 32). Copper(I) oxide in solid copper
forms a separate solid phase.

Sulfur dioxide dissolves in molten copper and reacts:

Hydrogen is considerably soluble in liquid copper,and after solidification some remains

dissolved in the solid metal, although copper does not form a hydride. The solubility
follows Sievert’s law, being proportional to the square root of the partial pressure
because the H2 molecules dissociate into H atoms on dissolution. Hydrogen has high
diffusibility because of its extremely small atomic volume.

Hydrogen dissolved in oxygen-bearing copper reacts with copper(I) oxide at high

temperatures to form steam:

Steam is not soluble in copper; therefore, it either escapes or forms micropores.

Nitrogen, carbon monoxide, and carbon dioxide are practically insoluble in liquid or solid
copper. Hydrocarbons generally do not react with copper. An exception is acetylene,
which reacts at room temperature to form the highly explosive copper acetylides Cu2C2
and CuC2;therefore, acetylene gas cylinders must not be equipped with copper fittings.

5.2. Occurrence
In the upper part of the earth’s crust (16km deep), the average copper content is ca. 50
ppm. It is thus about half as abundant as chromium, about twice as abundant as cobalt,
and 26th in order of abundance of the elements in the accessible sphere of the earth.
Table 5 shows average copper contents in natural materials.

Copper Minerals

More than 200 minerals contain copper in definable amounts, but only about 20 are of
importance
as copper ores (Table 6) or as semiprecious stones (turquoise and malachite). Copper is
a typical chalcophilic element; therefore, its principal minerals are sulfides, mostly
chalcopyrite, bornite, and chalcocite, often accompanied by pyrite, galena, or sphalerite.

Secondary minerals are formed in sulfide ore bodies near the earth’s surface in two
stages. In the oxidation zone, oxygen-containing water forms copper oxides, basic salts
(basic carbonates and basic sulfates), and silicates. In the deeper cementation zone,
copper-bearing solutions from these salts are transformed into secondary copper
sulfides (chalcocite and covellite) and even native copper of often high purity, e.g., in
the Michigan copper district (Keweenaw Peninsula).

Other metallic elements frequently found in copper ores are iron, lead, zinc, antimony,
and arsenic;

less common are selenium, tellurium, bismuth, silver, and gold. Substantial enrichments
sometimes occur in complex ores. For example, ores from Sudbury, Ontario, in Canada
contain nickel and copper in nearly the same concentrations,as well as considerable
amounts of platinum metals. The copper ores from Zaire and Zambia are useful sources
of cobalt. Many porphyry copper ores in America contain significant amounts of
molybdenum and are the most important single source of rhenium. The extraction of
precious metals and other rare elements can be decisive for the profitability of copper
mines, smelters, and refineries.

Compounds of primary industrial importance (mục 2 và 3 ) are distinguished from

compounds of minor importance (mục 4) in this article.

5.3. Basic Copper Compounds

5.3.1. Copper(I) Oxide

Cu2O , Mr 143.09, mp 1235◦C, d254 5.8 – 6.2, decomposes above 1800◦C. It occurs in
nature as the red or reddish brown mineral cuprite with a cubic or octahedral crystal
morphology. Depending on the method of preparation and particle size, the synthetic
material is yellow, orange, red, or purple. The yellow material has erroneously been
referred to as copper(I) hydroxide, but X-ray diffraction patterns indicate that there are
no differences in the crystal structures of the colored forms. Their thermodynamic data

are as follows: cp (298 K) 429.8 J kg−1 K−1,cp (290 – 814 K) 519.2 J kg−1 ・K−1, cp (290 –
1223 K) 565.2 J kg−1 K−1, ΔH◦ (25 ◦C) −166.6 kJ/mol. Copper(I) oxide is stable in dry air
but slowly oxidizes to copper(II) oxide [1317-38-0] in moist air. It is practically insoluble
in water but dissolves in aqueous ammonia.

In excess hydrochloric acid, soluble copper(I) chloride complexes are formed; however,
in dilute sulfuric or nitric acids, disproportionation to the soluble copper(II) salts and
copper powder results.

Production. Copper(I) oxide is produced easily by a variety of methods; its instability

with respect to oxidation requires careful consideration. Copper(I) oxide produced
pyrometallurgically is usually coated with isophthalic acid or pine oil to preserve its
integrity [12]. Hydrometallurgically produced material can be stabilized by mixing the
particle slurry with glue, gelatin,casein, or dextrin before drying [13–16].

Pyrometallurgical Processes. Copper(I) oxide is formed when copper powder is heated

above 1030◦C in air; to prevent further oxidation, it must be cooled quickly in an inert
atmosphere. To allow for lower temperature production of copper(I) oxide, carbon can
be blended with copper(II) oxide and heated to 750◦C in an inert atmosphere. The
material must be stabilized by coating the formed particles with isophthalic acid or pine
oil [12]. A more stable copper(I) oxide results when stoichiometric amounts of copper
powder and copper(II) oxide are blended, heated to 800 – 900◦C in an inert atmosphere,
and allowed to cool. The production can be effected at lower temperature if ammonia
or certain ammonium salts are added to the blend [17–19]. The autoclave oxidation of
copper metal at 120◦C and about 0.6MPa gauge pressure with air in the presence of
water and small amounts of sulfuric and hydrochloric acids produces a red, pigment-
grade product [20]. By varying the pressure and temperature, considerable differences
in particle size, coloring, apparent bulk density, and buoyancy have been found.

Hydrometallurgical Processes. Tetraamminedicopper(I) sulfate, Cu2(NH3)4SO4, prepared

by leaching an excess of copper with a solution of ammonia and ammonium sulfate,
with air as the oxidant, yields a red copper(I) oxide upon acidification to pH 3 – 5 [21].
The less corrosive ammonium carbonate leach system in which Cu2(NH3)4CO3 is
produced is more common (see page 5). Upon vacuum distillation, a very stable red
Cu2O product remains [21]. If sodium hydroxide is added to the leach liquor, a yellow
microcrystalline powder is precipitated [22]. When the yellow Cu 2O is heated in an
excess of sodium hydroxide, it is converted to an orange material of somewhat larger
particle size.

Steam stripping of the copper(I) ammine carbonate solution yields a brown, impure
product [23] which can be converted to a red material by washing it in an organic acid,
e.g., formic or acetic acid [24]. An impure, brown product can also be converted to a red
material by boiling it in 20 % sodium hydroxide solution [25]. If a saturated solution of
copper(I) ammine carbonate is agitated over copper metal, a layer of red copper(I) oxide
is continuously produced which can be broken loose and recovered [26]. When copper
salts are leached with chelating agents such as ethylenediaminetetraacetic acid [27] or
ammonia [28] under pressure of carbon monoxide or hydrogen, and sodium hydroxide
is subsequently added, a relatively stable, yellow copper(I) oxide is obtained; the
reaction is catalyzed by an alkali metal iodide [29].

The reduction of a boiling slurry of basic copper(II) sulfate with sulfur dioxide at a pH of
about 3 produces a reddish product [30]. Red copper(I) oxide has also been prepared by
mixing a slurry of basic copper(II) sulfate with neutral copper(II) sulfate and adding
sodium sulfite to a pH of 5.2. The mixture is then acidified to pH 3.5 – 5 and heated to
boiling. The intermediate copper(I) sulfite slurry is decomposed to copper(I) oxide and
sulfurous acid. Alkali is subsequently added to maintain a pH of 2.6– 2.8 [31].
When a solution of copper(I) chloride and sodium chloride is neutralized with sodium
hydroxide and then heated to 138 ◦C under pressure, a red copper(I) oxide is obtained
which has an average particle diameter of about 2.5 μm [32]; an orange product (about
1-μmparticles) is prepared by neutralizing the solution to pH 8.5 at 60 ◦C [33].
Simultaneous mixing of copper(I) chloride solutions with sodium chloride and sodium
hydroxide solution in the presence of copper(I) oxide seed crystals at a controlled pH of
10.0, 55 ◦C, and under nitrogen, gives a reddish purple material (average diameter 48
μm). At pH 7.0, a yellow material is obtained with an average particle size of 0.4 μm
[34].

The electrolytic production of copper(I) oxide between copper electrodes in brine yields
a yellow product at room temperature. At higher temperature, an orange or red
material is produced.

Uses. The largest commercial use of copper(I) oxide is in antifouling paints for boat and
ship bottoms; it is an effective control for barnacles and algae. The yellow or orange
copper(I) oxide is used as a seed and crop fungicide, and the red material is used as a
pigment in ceramic glazes and glass. Copper(I) oxide is also used in rectifiers and in
brazing. Numerous organic reactions are catalyzed by copper(I) oxide, and it is an
effective absorbent for carbon monoxid.

3.2. Copper(II) Oxide

CuO [1317-38-0], Mr 79.54, mp 1330◦C, d4 25 6.48, occurs in nature as the black minerals
tenorite (triclinic crystals) and paramelaconite (tetrahedral, cubic crystals).
Commercially produced copper(II) oxide is usually black, although a brown product
(particle size < 10−6 m) can also be produced. Thermodynamic data: cp (298 K) 531.1 J
kg−1 K−1, cp (290 – 1253 K) 682.4 J kg−1.K−1, ΔH◦(25 ◦C) −155.3 kJ/mol. Copper(II) oxide is
stable to air and moisture at room temperature. It is virtually insoluble in water or
alcohols. Copper(II) oxide dissolves slowly in ammonia solution but quickly in
ammonium carbonate solution; it is dissolved by alkali metal cyanides and by strong acid
solutions. Hot formic acid

and boiling acetic acid solutions readily dissolve the oxide. Copper(II) oxide is
decomposed to copper(I) oxide and oxygen at 1030 ◦C and atmospheric pressure; the
reduction can proceed at lower temperature in a vacuum. Hydrogen and carbon
monoxide reduce copper(II) oxide to the metal at 250 ◦C and to copper(I) oxide at about
150 ◦C. Ammonia gas reduces copper(II) oxide to copper metal and copper(I) oxide at
425 – 700 ◦C [17].

Production. Copper(II) oxide can be prepared pyrometallurgically by heating copper

metal above 300 ◦C in air; preferably, 800 ◦C is employed. Molten copper is oxidized to
copper(II) oxide when sprayed into an oxygen containing gas [37]. Ignition of copper(II)
nitrate trihydrate [10031-43-3] at about 100 – 200 ◦C produces a black oxide. Basic
copper(II) carbonate [12069-69-1], when heated above 250 ◦C, produces a black oxide if
a dense carbonate is employed; a brown material is produced when the light and fluffy
carbonate is used. An alkali - free oxide can be prepared by ignition of copper(II)
carbonate produced from ammonium carbonate and a copper(II) salt solution.
Copper(II) hydroxide [20427-59-2], when heated above 100 ◦C, is converted to the
oxide.

Hydrometallurgy is the most common method for the production of copper(II) oxide.A
solution of ammonia and ammonium carbonate in the presence of air effectively leaches
metallic copper; the process is represented by the following reactions:

2Cu+1/2O2 +2NH3 + (NH4)2CO3 −→ [Cu2(NH3)4]CO3 +H2O

2NH3 + (NH4)2CO3 + [Cu2(NH3)4]CO3 + 1/2O2 −→ 2 [Cu(NH3)4]CO3 +H2O

Cu + [Cu(NH3)4]CO3 −→ Cu2(NH3)4CO3

The second and third reactions proceed readily; the first is slow. Consequently, in batch
operations the leach is usually begun with a small charge of the copper solution, but
continuous operations offer significantly improved rates. The leach liquor is then filtered
to remove iron impurities and metallic copper, and is subsequently oxidized by air
sparging. If necessary, lead and tin are removed by treatment with strontium, barium, or
calcium salts [38–41]. The solution is filtered again and stripped of ammonia and carbon
dioxide by steam injection or pressurized boiling to produce a black copper(II) oxide
[38]. The ammonia and carbon dioxide are recycled for further use. The process is
illustrated in Figure 1. Alternatively, the leach liquor can be treated with strong alkali to
precipitate the intermediate copper(II) hydroxide, and then boiled to remove ammonia,
with subsequent decomposition of the hydroxide to the black oxide.

Figure 1. Process flow diagram for production of copper(II) oxide from ammonia –
ammonium carbonate leach

a) Leach vat; b) Filter; c) Treatment tank; d) Strip tank; e) Press; f) Bag house; g) Drying
kiln

The copper(II) ammine sulfate and chloride systems are treated similarly although they
are utilized much less frequently because of their highly corrosive nature. However, the
copper ammine chloride system, a byproduct of circuit board etching, is recycled out of
economic and environmental necessity to opper(II) oxide [42] (see Chap. 6).

Uses. Copper(II) oxide is used as a precursor to a number of copper(II) salts. One of the
largest commercial applications is in the production of compounds for wood
preservation. Copper(II) oxide is also used extensively as a feed additive and as a
pigment in glass, ceramic, and porcelain enamels [43]. In combination with manganese
dioxide, it is used as an oxidative catalyst for exhaust gas [44], in the removal of NOx,
CO, and O3 [45], [46], and in the purification of formaldehyde-containing waste gas [47].
Supported on aluminum phosphate, copper(II) oxide is active in reducing tar and
polycyclic hydrocarbons in smoke by absorption and catalytic conversion [48]. Copper(II)
oxide is used as a catalyst in the preparation of acrylates [49] and in the production of
magnetic storage devices [50]. It has limited application in the petroleum industry as a
gas sweetener and is used in welding fluxes for bronze.

Analysis and Specifications. Electrolytic deposition from a solution or iodometric

analysis with sodium thiosulfate is standard for copper determination [51]. The
technical specification is shown in Table 2.

3.3. Copper(II) Hydroxide

Cu(OH)2 [20427-59-2], Mr 97.54, d25 4 3.37, ΔH◦ (25 ◦C) 446.7 kJ/mol, decomposes over
100 ◦Cor over 50 ◦C in the presence of an excess of alkali. Copper(II) hydroxide is
virtually insoluble in water (0.003 mg/L), and decomposes in hot water to the more
stable copper(II) oxide and water:

Copper(II) hydroxide is readily soluble in mineral acids and ammonia solution. When
freshly precipitated, it is soluble in concentrated alkali, with the formation of
[Cu(OH)3]− or [Cu(OH)4]2−. Copper(II) hydroxide is inherently unstable but can be
kinetically stabilized by a suitable production method.

Production. There are two classes of copper(II) hydroxide. The first is stoichiometrically
rather precise, with a copper content as high as 64%; the theoretical copper content of
Cu(OH)2 is 65.14 %. This class is produced by the ammonia process [52–55], which yields
a pure product of relatively good stability and large particle size. The best product
results from the addition of strong alkali to the soluble copper(II) ammine complex [52],
[55]. A relatively large particlesize product, deep blue in color and high in copper
content, is precipitated below 35 ◦C. The resulting material is fairly stable or can be
coated with gelatin to enhance its stability [56].

In the copper(II) hydroxide made by the ammonia process, the solubility of the
copper(II) ammine complexes provides for crystallite growth. This affords a large particle
size, a limited surface area (point of dehydration), and hence a relatively stable product,
in contrast with the unstable product (variable assay) that results from the addition of
hydroxide solutions to copper(II) salt solutions at 20 ◦C or above. The reaction with
hydroxide is diffusion-controlled, allowing essentially no time for crystallite growth.
The product is obtained as a gelatinous, voluminous precipitate with a large surface
area, which is quite unstable and difficult to wash free of impurities. If the same
reaction, with the same order of addition, is allowed to occur at 0 – 10 ◦C, a product of
defined particle size and measurable surface area results, with greater stability but low
assay.
The second class of copper(II) hydroxide, which represents a “stable” product but has
lower assay and greater impurity, is produced from an insoluble precursor such as basic
copper(II) carbonate or copper(II) phosphate. The first stable copper(II) hydroxide of this
kind was made from copper(II) phosphate with alternate additions of copper(II) sulfate
and sodium hydroxide solutions [57]. The process is illustrated by the following series of
reactions:

3 CuSO4 +2Na3PO4 −→ Cu3(PO4)2 +3Na2SO4

Cu3(PO4)2 + 6NaOH −→ 3 Cu(OH)2 +2Na3PO4
The alternate copper(II) sulfate – sodium hydroxide addition is continued through 15 or
20 cycles and yields a stable product with 58 – 59% copper and 3 – 5 % phosphate. The
product has a small particle size and a high surface area, and is used as an agricultural
fungicide.
Other stable copper(II) hydroxides of high surface area and fine particle size have been
produced
more recently [58–60]; the processes include the use of a copper(II) oxychloride
precursor in the presence of an anionic surfactant [59] or a magnesium sulfate-
precipitated precursor [58]. An electrolytically produced material has also been made by
using trisodium phosphate as
the electrolyte [61].
The classic Bordeaux slurry of copper(II) sulfate and lime in water has been replaced by
a powdered stabilized product. This is obtained by mixing copper(II) nitrate solution and
lime, adding cellulose pitch liquor (a waste product of the paper industry), and drying to
yield a powder which is effective as a fungicide [62]. Sodium carbonate can be used as
the precipitating agent instead of lime [63].
Uses. Copper(II) hydroxide is used as an active precursor in the production of copper(II)
compounds. Ammonia-processed copper(II) hydroxide is used in the production of
copper(II) naphthenate, copper(II) 2-ethylhexanoate, and copper soaps. Ammonia-
processed copper(II) hydroxide is also used in the production of rayon (Schweitzer’s
reagent) and in the stabilization of nylon. Copper(II) hydroxides of the second class are
often used as fungicides because of their small particle size. Copper(II) hydroxide
is also used as a feed additive, a catalyst in the vulcanization of polysulfide rubber, and
an antifouling
pigment.
Analysis and Specifications. Copper is determined iodometrically with sodium
thiosulfate [51]. The analysis of typical ammonia-processed copper(II) hydroxide (mass
fractions in %) is copper 63.0, iron 0.05, zinc 0.05, lead 0.05, naphthenic acid-insoluble
material 2.0, sulfate 0.3.
3.4. Copper(II) Carbonate Hydroxide
Copper(II) carbonate hydroxide, also called basic copper(II) carbonate, occurs in nature
as the metastable mineral azurite [12070-39-2], also called chessylite, a blue, monoclinic
crystalline
or amorphous powder with a formula approximating 2 CuCO3 ・ Cu(OH)2, Mr 344.67,
d244 3.8, ΔH◦ (20 ◦C) −87.4 kJ/mol, and malachite [12069-69-1], green, monoclinic
crystals
with a formula approximating CuCO3 ・Cu(OH)2, Mr 221.12, d25 4 3.9 – 4.0, ΔH◦(20 ◦C)
−57.7 kJ/mol. The copper(II) carbonate of commerce, malachite, is also known as
Bremen green. Pure copper(II) carbonate, CuCO3, has not been isolated. Copper(II)
carbonate is virtually insoluble in water but dissolves readily in aqueous ammonia and
alkali metal cyanide solutions. Copper(II) carbonate
dissolves quickly in mineral acid solutions and warm acetic acid solution, with the
formation of
the corresponding copper(II) salt. Malachite is much more stable than copper(II)
hydroxide but
slowly decomposes to the oxide according to the following reaction:
CuCO3. Cu(OH)2 −→ 2CuO+H2O+CO2
Malachite is rapidly decomposed to the oxide
above 200 ◦C.
Production. Two grades of copper(II) carbonate are available commercially, the light and
the dense. The light grade is a fluffy product of high surface area. It is precipitated by
adding a copper(II) salt solution, usually copper(II) sulfate solution, to a concentrated
solution of sodium carbonate at 45 – 65 ◦C. Azurite
is formed initially, and complete conversion to malachite usually occurs within two
hours.
The conversion is accelerated by the addition of malachite nuclei to the reactor.
A dark green, dense product results when a copper(II) salt solution is added to a solution
of sodium hydrogen carbonate at 45 – 65 ◦C; conversion to malachite requires about
one hour in this case. The density is maximized if the reactor is washed with acid prior to
the precipitation to prevent premature nucleation on malachite nuclei. (A less dense
product would be produced if malachite nuclei are added to the slurry of azurite.)
Solutions of copper(II) salt and sodium carbonate can also be added simultaneously at a
pH of 6.5 – 7.0 and a temperature between 45 and 65 ◦C; conversion to malachite is
usually complete within one hour.
When a solution of copper(II) ammonium carbonate is boiled, ammonia and carbon
dioxide are expelled from the solution, and a deep green, dense copper(II) carbonate
precipitates [38].
Uses. Copper(II) carbonate is used as a precursor in the production of copper salts and
soaps. It is used in animal feeds as a source of copper, in the sweetening of petroleum,
and in electroplating for the control of pH. Copper(II) carbonate is used as a
hydrogenation catalyst and as an accelerator in polymerization reactions. The light
grade is somewhat effective as a fungicide and is used as a seed protectant.
Analysis and Specifications. Copper is analyzed by iodometric titration with sodium
thiosulfate
solution [51]. Table 3 gives typical analyses of light and dense technical-grade copper(II)
carbonates.

4. Salts and Basic Salts

4.1. Copper(I) Chloride
Copper(I) chloride [7758-89-6], CuCl, Mr 99.00, mp 422 ◦C, bp 1367 ◦C, d25 4 4.14, ΔH◦
(25 ◦C) −134.6kJ/mol, occurs in nature as the colorless or gray cubic-crystal nantokite.
The
commercially available product is white to gray to green and of variable purity.
Copper(I) chloride
is fairly stable in air or light if the relative humidity is less than about 50 %. In the
presence of moisture and air, the product is oxidized and hydrolyzed to a green product
that approaches copper(II) oxychloride, CuCl2 ・ 3 Cu(OH)2[12356-86-4]. In the
presence of light and moisture, a brown or blue product is obtained. Copper(I) chloride
is slightly soluble to insoluble in water, with values from 0.001 to
0.1 g/L being reported. It is readily hydrolyzed to copper(I) oxide by hot water. Copper(I)
chloride is insoluble in dilute sulfuric and nitric acids, ketones, alcohols, and ethers, but
it quickly dissolves
in hydrochloric acid, alkali halide, or ammonia solutions with the formation of complex
compounds that are readily oxidized by air. Copper(I) chloride is soluble in solutions of
alkali metal cyanides or thiosulfates and of coordinating amines, pyridines, and nitriles,
notably, acetonitrile [64]. The increase in solubility of copper(I) chloride with chloride
ion concentration illustrated in Figure 2 [65]. When the chloride concentration is
decreased by dilution with water, the pure white copper(I) chloride precipitates.

Figure 2. Solubility of copper(I) chloride in excess chloride

ion solution at different temperatures

Production. The direct combination of the elements is the most common method of
production.
The reaction of copper metal and chlorine is not spontaneous at ambient temperature.
Once the metal is heated to red heat in the presence of chlorine, the reaction is self-
sustaining and requires external cooling to prevent the metal from melting. A number of
similar patents exist [66–69] in which copper metal is reacted with chlorine gas to
produce a molten copper(I) chloride that is cast and pulverized. The primary difference
in conditions is the use of a shaft furnace [66] as opposed to the use of crucibles. The
recommended process temperature varies from 450 to 800 ◦C [66], [67] or 500 to 700 ◦C
[68], [69].The conditions required for the high-temperature production of a pure
copper(I) chloride can be illustrated by the following:

Cu + 1/2 Cl2 −→ CuCl ΔH =−134.6kJ/mol

Cu+Cl2 −→ CuCl2 ΔH =−247.2 kJ/mol
CuCl + 1/2 Cl2 −→ CuCl2 ΔH =−122.6kJ/mol
CuCl2 +Cu −→ 2CuCl ΔH =−22 kJ/mol
Higher temperature and excessive contact with copper metal favor the production of a
very pure copper(I) chloride. The lowest possible temperature is obviously 422 ◦C, the
melting point of copper(I) chloride. As the temperature approaches the decomposition
temperature for the reaction

CuCl2 −→ CuCl + 1/2 Cl2 (993 ◦C)

a product of higher purity is obtained. Operationally, a temperature between 750 and
900 ◦C
is ideal, and results in a product of>98%purity. The process of Degussa [67] illustrates a
commonly
used commercial process for the high temperature production of copper(I) chloride;
Figure 3 shows a suitable crucible for the production of technical-grade copper(I)
chloride. Once the reaction is initiated, chlorine and copper metal (shot, chopped wire,
or briquettes) are added continuously. As the molten product is formed on the surface
of the upper metal layer, it flows by gravity downthrough the porous copper bed to
effect further reduction of any copper(II) chloride, and out the exit port onto a rotating
table where the product is allowed to cool and solidify. The flakes that form are
packaged as is or ground to a powder and packaged. Because of the high temperature
during the reaction and the volatility of copper(I) chloride, the exit port must be vented
to a caustic scrubber. When the molten product is allowed to fall onto a highspeed,
horizontally rotating disk constructed of
quartz, graphite, or porcelain, small prills of uniform size are produced [70]. The product
is spun out onto a water cooled diaphragm and collected. If the copper is contaminated
with oxides, hydrogen
chloride gas should be added to the chlorine gas stream to prevent the production of
basic copper(II) chlorides that would contaminate the product [66].

Figure 3. Crucible used in the production of copper(I) chloride

If the product is packaged quickly and sealed properly, no extreme precautions are
required.
Otherwise, the product must be stored under nitrogen to preserve its integrity or
coated with
mineral oil as a barrier to moisture.
Copper(I) chloride is also produced hydrometallurgically by the reduction of
copper(II) in the presence of chloride ions [71]:

2 CuCl2 +Na2SO3 +H2O −→ 2CuCl+Na2SO4 + 2 HCl

Other reducing agents can be used, such as metallic copper, sulfurous acid,
hydroxylamine,
hydrazine, or phosphorous acid. The copper(I) chloride solution is produced, for
example,
by mixing a copper(II) chloride solution with metallic copper in the presence of
hydrochloric
acid or sodium chloride. The colorless to brown solution is stable only in the absence of
air. Continuous preparations of copper(I) chloride solutions have been developed [72],
[73]. When they are diluted with water, a white crystalline material precipitates which
can be vacuum dried or washed with sulfurous acid, then with alcohol and ether, and
carefully dried. Zinc has also been used as a reducing agent in a
more recent process [74].
Production of copper(I) chloride by treatment of ores with iron(III) chloride solutions
[75],
[76] and recovery of the product through chlorination in pit furnaces above 800 ◦C [77]
have
also been attempted.
Uses. Copper(I) chloride is used as a precursor in the production of copper(II)
oxychloride and copper(I) oxide, as well as fine copper powder [78]. The production of
silicone polymers,the vulcanization of ethylene – propene rubbers (EPDM) [79], and
acrylonitrile production are other applications. Copper(I) chloride is also used in the
purification of carbon monoxide gas [80–83] and the production of phthalocyanine
pigments [84], [85]. More recently, copper(I) chloride has been found to be an effective
catalyst in the production of dialkyl carbonates [86– 88].
Analysis and Specifications. Copper(I) chloride is analyzed according to [51]. Table 4 lists
specifications for technical- and reagent grade material.
4.2. Copper(II) Chloride
Copper(II) chloride [7447-39-4], CuCl2, Mr 134.45, mp (extrapolated) 630 ◦C, d254
3.39,begins to decompose to copper(I) chloride and chlorine at about 300 ◦C. The often
reported melting point of 498 ◦C is actually a melt of a mixture of copper(I) chloride and
copper(II) chloride. Decomposition
to copper(I) chloride and chlorine is complete at 993 ◦C. The deliquescent (dể hút
ẩm ?)monoclinic crystals are yellow to brown when pure; their thermodynamic data are
as follows:cp (298 K) −579.2 J kg−1 K−1, cp (288 –
473 K) −621.7 J kg−1 K−1, cp (288 – 773 K) −661.9 J kg−1 K−1, ΔH◦ (25 ◦C) −247.2 kJ/mol.
In moist air, the dihydrate is formed. Figure 4 shows the solubility of copper(II) chloride
in water and hydrochloric acid at two temperatures [89]. At higher concentrations of
hydrogen chloride, [CuCl3]− and [CuCl4]2− complexes are formed. Copper(II) chloride is
easily soluble in methanol and ethanol and moderately soluble in acetone.
Figure 4. Solubility of copper(II) chloride in hydrochloric acid solutions at different
temperatures

The more common commercial form of copper(II) chloride is the dihydrate [10125-13-
0], CuCl2 ・ 2H2O, Mr 170.45, mp around 100 ◦C (with decomposition to the anhydrous
form). This occurs in nature as blue-green orthorhombic, bipyramidal crystals of
eriochalcite, d25 4 2.51. Its solubility characteristics are proportionally similar to those
of the anhydrous form. In moist air the dihydrate deliquesces (chảy lỏng), and in dry air
it effloresces (mát nước / nở bông).
Production. Because of the relative stabilities of copper(I) chloride and copper(II)
chloride at high temperature, it is improbable that a pure anhydrous copper(II) chloride
can be prepared by excessive chlorination of copper in a melt, even though such
methods have been reported.
The most common method for the production of anhydrous copper(II) chloride is by
dehydration
of the dihydrate at 120 ◦C. The product must be packaged in air-tight or desiccated
containers.
The dihydrate can be prepared by the reaction of copper(II) oxide, copper(II) carbonate,
or
copper(II) hydroxide with hydrochloric acid and subsequent crystallization. Commercial
production
of copper(II) chloride dihydrate uses a tower packed with copper. An aqueous solution is
circulated
through the tower. Sufficient chlorine is passed into the bottom of the tower to oxidize
the
copper completely [72], [73]; to prevent hydrolysis [precipitation of copper(II)
oxychloride] of
concentrated copper(II) chloride solutions, they are kept acidic with hydrochloric acid.
The tower
can be operated batchwise or continuously; Figure 5 (see next page) shows the
continuous operation.
A hot, concentrated liquor is circulated continuously through the tower, and the
overflow from the tower is passed through a crystallizer where the liquor is cooled; the
product is then centrifuged, dried, and packaged. The addition of hydrogen chloride is
pH controlled; the addition of water is controlled by specific gravity. Copper is added
daily or twice daily, as needed.
Uses. Copper(II) chloride dihydrate is used in the preparation of copper(II) oxychloride
[90], [91]. It serves as a catalyst in numerous organic chlorination reactions such as the
production of vinyl chloride [92] or 1,2-dichloroethane [93]. Copper(II) chloride
dihydrate is used in the textile industry as a mordant and in the petroleum industry to
sweeten sulfidic crude oil. Copper(II) chloride solutions are used for plating copper on
aluminum, and in tinting baths for tin and germanium. Copper(II) chloride dihydrate
is used as a pigment in glass and ceramics, as a wood preservative, and in water
treatment.
Figure 5. Reactor for the production of copper(II) chloride
solutions
a) Copper metal; b) Porous plates; c) Raschig rings; d) Chlorine
inlet; e) Steam inlet; f) Solution recycle; g) Solution to
crystallizer; h) Drain
Analysis and Specifications. Copper is analyzed iodometrically with sodium thiosulfate
[51]. A typical analysis of technical-grade copper(II) chloride dihydrate (mass fractions in
%) is as follows:
copper(II) chloride dihydrate 99.0 (min.), iron 0.02, zinc 0.05, sulfate 0.05,
waterinsoluble
material 0.01, material not precipitated by hydrogen sulfide as sulfate 0.15.
4.3. Copper(II) Oxychloride
Copper(II) oxychloride,Cu2Cl(OH)3[1332-65-6], Mr 213.56, is usually written as CuCl 2.3
Cu(OH)2. The trade name is copper oxychloride or basic copper chloride; the
internationally accepted name (IUPAC) is dicopper chloride trihydroxide. Copper
oxychloride is found in nature as the minerals paratacamite,
green hexagonal crystals, and atacamite, green rhombic crystals, d25 4 3.72 – 3.76[94].
It is virtually
insoluble in water, dissolves readily in mineral acids or warm acetic acid, and is soluble
in ammonia and alkali-metal cyanide solutions.
The green oxychloride is converted into blue copper(II) hydroxide in cold sodium
hydroxide solution [59] and into the oxide in hot sodium hydroxide solution. With a lime
suspension, copper oxychloride is converted into the blue calcium tetracuproxychloride,
calcium tetracopper(II) chloride tetrahydroxide, CaCl2 ・ 4 Cu(OH)2 [95]. It is
decomposed to the oxide at 200 ◦C.
Production. Copper(II) oxychloride is most often prepared commercially by air oxidation
of copper(I) chloride solutions [90], [91], [96],[97]. For this purpose, a concentrated
sodium chloride solution containing about 50 g/L copper(II) is contacted with copper
metal to produce a solution containing about 100 g/L copper(I). The copper(I) chloride –
sodium chloride solution,with or without the copper metal, is then heated to 60 – 90 ◦C
and aerated to effect oxidation:
CuCl2 +Cu −→ 2 CuCl
6CuCl+3H2O+ 3/2O2 −→ CuCl2 ・ 3 Cu(OH)2 + 2 CuCl2

The mother liquor is separated from the precipitate and recycled into the process. The
particles
that are obtained by the above process are generally less than 4 μmin diameter and are
suitable
as crop fungicides. The particle size can be reduced further by increasing the agitation
during oxidation and by utilizing a lower temperature [96]. Also, spray-drying of the
product slurry gives a micronized product [98] as a result of deagglomeration of the
material. Copper(II) oxychloride can also be prepared by reaction of a copper(II) chloride
solution with sodium hydroxide [94]:
4 CuCl2 + 6NaOH −→ CuCl2 ・ 3 Cu(OH)2 + 6NaCl

or by reaction of a copper(II) chloride solution with freshly precipitated, hydrated

copper(II) oxide [99]:
CuCl2 + 2 NaOH −→ CuO ・H2O+ 2 NaCl
CuCl2 + 3 CuO ・H2O −→ CuCl2 ・ 3 Cu(OH)2

Copper oxychloride has also been produced as a byproduct in the electrolytic

production of copper(I) chloride [100].
Uses. Copper oxychloride is used primarily as a foliar fungicide [90], [101–105]; it is also
used as a pigment.
Analysis and Specifications. A typical analysis of technical-grade copper(II) oxychloride
(mass fractions in %) is as follows: copper 56.0, chloride 14.0 – 15.0, sulfate 2.0 – 2.5,
hydroxide
22.5 – 23.5, water 3.0 – 6.0. Copper is analyzed by iodometric titration with sodium
thiosulfate [51].

4.4. Copper(II) Sulfates

4.4.1. Copper(II) Sulfate Pentahydrate
CuSO4 ・ 5H2O [7758-99-8], Mr 249.61, d254 2.285, cp (273 – 291 K) 1126 J kg −1 K−1,
ΔH◦(25 ◦C) −850.8 kJ/mol, bluestone, blue vitriol, is found in nature as the mineral
chalcanthite,blue trichlinic crystals that can be ground to a light blue powder. Copper(II)
sulfate pentahydrate slowly effloresces in dry air or above 30.6 ◦C with the formation of
the trihydrate, CuSO4 ・ 3H2O. At 88 – 100 ◦C the trihydrateis produced more quickly.
Thermal analysis of the pentahydrate gives the following:
Above about 114 ◦C, the monohydrate is formed, and between about 245 and 340 ◦C,
the anhydrous product CuSO4, results. Figures 6A and 6B show solubility of CuSO4 in
water and density of the solution as a function of temperature and sulfuric acid
concentration [106], [107]. The pentahydrate can be crystallized from the solution
either by addition of sulfuric acid or by evaporation. Although the addition of sulfuric
acid appears to be more economical, the concentration of the solution by evaporation is
preferred because the crystals obtained from a “neutral” (pH 3.5 – 4.0) medium are less
prone to hard
cake formation than the acid crystals. As the particle size of the pentahydrate decreases,
the tendency
toward hard cake formation increases, and the necessity to increase the pH during
crystallization
is enforced. When a free-flowing, commercial product of fine particle size is required,
such alkaline additives as calcium oxide or calcium stearate must be incorporated into
the final product to assure flowability. The incorporation of excess acid into the product
accelerates the in situ dehydration of the pentahydrate and promotes hard cake
formation. Lower temperature and lower humidity slow the caking process.
Figure 6. Saturated solutions of copper(II) sulfate
A. Solubility of copper(II) sulfate (as copper) as a function of sulfuric acid concentration
and temperature; B. Density of copper(II) sulfate solutions as a function of sulfuric acid
concentration and temperature
Reprinted with permission [107]

Copper(II) sulfate pentahydrate is soluble in methanol (15.6g/100 mL solution) but

insoluble
in ethanol. It readily forms soluble alkaline complexes at sufficiently high concentrations
of amines or alkali cyanides (see Chap. 5), but basic sulfates are precipitated from
solution by ammonia at an intermediate pH (about 4.2 – 6.8).
Copper(II) sulfate pentahydrate is the most commonly used copper compound
because of
the economics and the availability of starting materials, the ease of production, and the
extent
of byproduct utilization (primarily copper electrowinning liquors).
Production. Copper(II) sulfate pentahydrate is prepared most easily by the reaction of a
basic
copper(II) compound with a sulfuric acid solution (100 – 200 g/L H2SO4), e.g.:
CuO+H2SO4 −→ CuSO4(aq) + H2O

Copper metal, sulfuric acid, and air are the most common starting materials for the
production
of copper sulfate pentahydrate:

Harike Process. The Harike process [108] is the best commercial example of the
preceding reaction (Fig. 7). Blister shot copper up to 25mm in diameter is added to the
reaction tower (2.9m2 cross – sectional area) to give a bed of copper metal 2.74-m high.
Two different reaction conditions are given in Table 5. Condition A allows for the
production of concentrated copper(II) sulfate solutions and subsequent crystallization
from acid media. Condition B gives a concentrated neutral solution of copper(II) sulfate
that can be crystallized or diluted with water and used for direct production of other
copper products.
Figure 7. Harike tower process for production of copper(II) sulfate solutions
a) Heat exchanger; b) Circulation pump; c) Air inlet; d) Copper input

The rate of oxygen consumption by the system is directly proportional to the mass of
copper metal
dissolved. Air flows of 46m 3h−1m−2 are used in order to fill with air the voids that are
created by the packing of the copper shot. The solution is circulated cocurrently with
the air flow to wet the particles continuously and enhance mixing of the solution with
the copper metal. If the air flow is decreased and the voids in the copper metal bed are
not filled sufficiently, the hot acid solution oxidizes the copper metal in the absence of
air with the formation of a copper sulfide film. This film renders the copper metal inert
to further oxidation and would lower the efficiency of the tower. On the other hand, an
increase in air flow above 46m3h−1m−2 decreases the fraction of oxygen consumed and
would also result
in a lowered efficiency of the tower. If an increased production (greater oxygen
consumption) with good tower efficiencies is required, the height of the tower must be
increased. This would also be necessary if a copper metal of lower surface area was
used such as scrap copper instead of the blister shot copper. The use of cement copper
and fine chopped wire creates insufficient voids for adequate air passage; such fine
copper must be leached in agitated vessels.
Table 5. Production of copper(II) sulfate by the Harike method

Two-Tower Process. Another commercial method for the preparation of copper(II)

sulfate pentahydrate utilizes two towers filled with copper shot. One of the towers is
filled with a sulfuric acid solution, whereas the other is sparged with air and steam to
oxidize the surface of the copper metal and form a layer of copper(II) oxide. The solution
is pumped alternately to the other tower to dissolve the layer of
oxide while the now drained tower is sparged with air and steam. This process is
continued until the desired copper(II) sulfate concentration is reached.
The Trickle method is also used commercially:a copper-filled tower is continuously
sprayed from the top with leach liquor from an adjacent reservoir. The liquor drains
through the tower and is pumped back to the reservoir. Steam and air are sparged
continuously into the tower from the bottom. The process is continued until the copper
sulfate solution has the desired concentration.
 Solvent Extraction. Copper(II) sulfate pentahydrate is produced from alkaline
ammoniacal copper(II) solutions by solvent extraction [107], [109]. The alkaline
copper(II) solution is first contacted with an organic extractant that is selective to
copper. One of the most common extractants can be represented by the following
general formula:

where R and R_ are preferably unsaturated alkyl groups and R__ is preferably hydrogen
[110].

[Cu(NH3)4]2+ (aq)+2RH −→ CuR2 +2NH3 (aq)+2NH+4 (aq)

The now copper-barren aqueous layer is continuously separated from the copper-
containing organic layer which is subsequently contacted with a sulfuric acid solution:

CuR2 +H2SO4 −→ CuSO4 +2RH

The saturated copper(II) sulfate liquor produced is cooled or concentrated by

evaporation to crystallize the pentahydrate. The copper barren ammonia – ammonium
salt solution is continuously returned to the copper leach tank. Figure 8 (see next page)
shows a flow diagram for a typical solvent extraction ammonia leach circuit utilizing
mixer – settlers.With the exception of small quantities ofwashwater and loss of
ammonia, the plant produces no effluent. Also, this process allows for lower overall
energy input
than acid dissolution, primarily as a result of the more facile oxidation of copper metal
in ammoniacal solutions. Ion-exchange resins are used to recover and concentrate
copper from the solution [111], [112]. Elution of the resins with sulfuric acid produces
copper(II) sulfate solutions.

Figure 8. Flow diagram for a solvent extraction plant

Byproduct Recovery. About 20 – 30 % of the total copper(II) sulfate pentahydrate

produced comes from the electrowinning industry as a byproduct. When the impurity
content of the electrowinning liquors is too high to make cathode copper, they are
concentrated and crystallized [113]. The product is suitable for most agricultural
applications. Acidic copper(II) sulfate etching wastes are neutralized with a copper
sludge, filtered, and concentrated to produce an agricultural-grade pentahydrate [114],
[115].
Uses. The major uses of copper(II) sulfate pentahydrate have been grouped as follows
[113]:
Agriculture (feed supplement,
soil nutrient, fungicide) 41 %
Industrial algicides 27 %
Mining (flotation activator) 10 %
Electroplating 5 %

In many instances, the copper(II) sulfate pentahydrate is used as an intermediate, e.g.,

to produce active foliar fungicides such as Bordeaux mixture, tribasic copper(II) sulfate,
or copper(II) hydroxide. A substantial amount of copper(II) sulfate pentahydrate is used
in combination with sodium dichromate and arsenic acid for the preservation of wood.
Copper(II) sulfate pentahydrate is an effective and economical algicide for lakes and
ponds. In the mining industry, it is used as a flotation activator for lead, zinc, and cobalt
ores. Copper(II) sulfate solutions are often used in the electroplating industry. The
compound is also used as a mordant in textile dyeing, in the preparation of azo and
formazan dyes, as a
pigment in paints and varnishes, for preserving hides and tanning leather, in pyrotechnic
compositions,
and in synthetic fire logs.
Analysis and Specifications. Typical analyses for various commercially available
crystal sizes are shown in Table 6. Table 7 (both see next page) lists specifications for an
electroless copper(II) sulfate pentahydrate. The analytical methods for copper(II)
sulfates are given in [51].

4.4.2. Anhydrous Copper Sulfate

CuSO4 [7758-98-7], Mr 159.61, occurs in nature as the mineral hydrocyanite [14567-54-
5]. It is gray to white and has a rhombic crystal morphology. It decomposes to the green
basic copper(II) sulfate at 340 ◦C, and at 600 – 650 ◦C it decomposes to copper(II) oxide.
Some of the properties of the anhydrous salt are as follows: d25 4 3.6, cp (273 – 291 K)
631.8 J kg−1 K−1, cp (273 – 373 K) 657.3 J kg−1 K−1, ΔH◦ (25 ◦C) −771.6kJ/mol. The
compound is soluble in water (Section 4.4.1), somewhat soluble in methanol
(1.1 g/100 mL), but insoluble in ethanol. It readily dissolves in aqueous ammonia and
excess alkali metal cyanides, with the formation of complexes. The material is
hygroscopic, with conversion to the pentahydrate in moist air below 30 ◦C.
The anhydrous salt is prepared by careful heating of the pentahydrate salt to 250 ◦C.
It can
also be prepared by the reaction of hot concentrated sulfuric acid with copper metal,
but purification
is rather difficult.
The compound has limited commercial use, but it can be used as a desiccant for
removing water from organic solvents and is a sensitive indicator of the presence of
moisture in such solvents.
4.4.3. Copper(II) Sulfate Monohydrate
CuSO4 ・ H2O [10257-54-2], Mr 175.63, d204 3.25, is a whitish powder. The solubility of
the monohydrate in water is identical to the pentahydrate on a copper basis. The
product is hygroscopic
and must be packaged in containers with moisture barriers. It is commercially produced
by dehydration of the pentahydrate at 120 –150 ◦C. A novel preparation is to triturate
stoichiometric ratios of copper(II) oxide and sulfuric acid:
CuO+H2SO4 −→ CuSO4 ・ H2O

The uses of the monohydrate are analogous to those of the pentahydrate. Although
there can be slight economic advantages (primarily freight costs) in using the
monohydrate, market acceptance has not been great. Presently, less than 5% (copper
basis) of copper(II) sulfate is marketed in the monohydrate form.
4.4.4. Basic Copper(II) Sulfates
Four distinct basic copper(II) sulfates can be identified by potentiometric titration of
a copper(II) sulfate solution with sodium carbonate or sodium hydroxide solution [115],
[116]: CuSO4.3Cu(OH)2.H2O (langite), CuSO4.2Cu(OH)2 (antlerite), CuSO4.3
Cu(OH)2(brochantite), and CuSO4.CuO.2 Cu(OH)2. x H2O. Their unique crystal
morphologies are confirmed by X-ray diffraction.
The most important commercial basic copper(II) sulfate, commonly referred to as
tribasic
copper sulfate [12068-81-4], is CuSO4.3 Cu(OH)2, Mr 452.27, mp ca. 380 ◦C
(decomp.),d254 3.78, occurs in nature as the green monoclinic mineral brochantite. It is
readily soluble in mineral acids, acetic acid solution, and ammonia solution; it is
insoluble inwater. Above 650 ◦C it decomposes to copper(II) oxide. If anhydrous
copper(II) sulfate is heated cautiously to 650 ◦C, another naturally occurring mineral is
obtained, dolerophane, CuSO4.CuO, which reacts readily with water at 20 ◦C to form
CuSO4.3 Cu(OH)2. H2O or at 100◦C to form CuSO4.2Cu(OH)2 [117].
Production. Tribasic copper(II) sulfate, the commercially available basic copper(II)
sulfate,
is most often prepared by the addition of sodium carbonate solution to hot solutions of
copper(II)
sulfate:
4 CuSO4 +3Na2CO3 +3H2O −→ CuSO4 ・ 3 Cu(OH)2 +3Na2SO4 +3CO2

Great variation of particle size can be achieved by control of the precipitation

temperature. As the temperature is increased, larger particles with greater bulk density
are formed. If a small particle size is desired, lower precipitation temperature should be
used. However, as the precipitation temperature is lowered, multiple hydrates and
larger amounts of sulfate are incorporated into the product; e.g., around 50 ◦C, the
dried product contains only about 50 % copper. A precipitation temperature around 90
◦C is
required to make a pure tribasic copper(II) sulfate.
The single largest use of the compound is as a crop fungicide, and small particles
are preferred
because they give a greater degree of coverage. These small particles can be obtained
by highenergy
attrition of the product or by carefully controlled precipitation conditions.
Another method of making tribasic copper(II) sulfate is the aeration of a
suspension of copper(I) oxide in the presence of stoichiometric quantities of sulfuric acid
or copper(II) sulfate [118]:
2Cu2O+H2SO4 +O2 +2H2O −→ CuSO4 ・ 3 Cu(OH)2
6Cu 2O+ 4 CuSO4 +3O2 +12H2O −→ 4 [CuSO4 ・ 3 Cu(OH)2]

A purified, concentrated solution of copper(II) sulfate containing ammonium sulfate can

be neutralized to pH 6.0 – 6.5 with ammonia to give a blue precipitate of approximate
stoichiometry 4CuSO4 . 2Cu(OH)2 . 5H2O. When this is dried, a green tribasic copper(II)
sulfate is formed with up to 1 mol of hydration water per mole of tribasic salt [119]; the
water content depends on the drying temperature.
A continuous process has been developed in which copper(II) sulfate solutions are
neutralized to pH 5.9 at 30 ◦C by addition of gaseous ammonia to an agitated vessel
[120]. A unique, germicidally active, basic copper(II) sulfate whose X-ray diffraction
pattern differs from langite and brochantite has been prepared
in this way [121].
Reaction of copper(II) sulfate with Na3PO4 ・ 12H2O and sodium hydroxide in
aqueous solution
gives a fine, blue, basic copper(II) sulfate powder (16% SO4, 2.6% PO4, and 54.9 % Cu)
that is formulated into a germicidal powder.
Tribasic copper(II) sulfate can also be prepared by cautiously heating copper(II)
sulfate to 340 ◦C or by the aeration of a hot copper(II) sulfate solution in contact with
copper metal.
Other basic copper(II) sulfates of commercial interest are the classic fungicial
mixtures, Bordeaux and Burgundy slurries, in which copper(II) sulfate solution is mixed
with lime and soda ash, respectively. They are of variable stoichiometry.More recently,
the aqueous Bordeaux suspension has been dried to yield a stable basic copper(II)
sulfate powder of variable composition [122].
Uses. As stated earlier, basic copper(II) sulfate is primarily used as a crop fungicide
[123],[124]. It has also been utilized as a precursor in the separation of copper from
metallic impurities [125].
5.2. Copper Complexes
Copper(I) and copper(II) ions form many stable complexes with halides, amines, azo
compounds,
cyanides, and other complexing media. This, in part, accounts for the fact that more
Xray crystal structures have been determined for copper complexes than for any other
first-row transition metal ion. Many of these complexes are of great commercial
significance. The dissociation constants for a number of copper complexes are given in
Table 8 (see next page).
Copper Ammine Complexes. Copper(II) salts form complexes of the type [Cu(NH 3)n]2+
where n =1–5. The pentaammine complex is favored only in concentrated ammonia
solution (Table 8). The hexaammine complex is formed only in anhydrous ammonia. The
tetraamine complex of copper(II) is favored at low ammonia concentrations. For the
copper(I) complexes of ammonia, the diammine complex is favored. Tetraammine
copper(II) hydroxide, [Cu(NH3)4](OH)2, Schweitzer’s reagent, is used in the dissolution of
cellulose and in the production of rayon (→Cellulose). Copper(I) diammine salt solutions
are used in the absorption of olefins and carbon monoxide. Many copper circuit boards
are etched with ammoniacal
ammonium salt solutions; copper ammine solutions, which can be used in the
production of copper compounds, are byproducts of this process.
Table 8. Dissociation constants of copper(I) and copper(II) complexes (pK=−log K)

Copper Chloride Complexes. Copper(I) and copper(II) ions form complexes with
hydrochloric acid or soluble metal chlorides. Dilute solutions of copper(II) chloride are
blue. As the chloride concentration increases, the color of the solution shifts toward
green, intensifying as the concentration of the distorted tetrahedral [CuCl 4]2− ion
increases. Copper(II) compounds have been isolated that contain either the [CuCl 4]2−
anion or the [CuCl3]− anion, e.g., CsCuCl4 and KCuCl3, respectively.
The insoluble copper(I) chloride can be solubilized by chloride-containing solutions,
with
the formation of the [CuCl2]− ion. The benzene insoluble copper(I) chloride dissolves
readily in the presence of anhydrous aluminum chloride, with formation of the Al[CuCl 4]
complex. In acetonitrile, copper(I) chloride is solubilized with the formation of the
isolable [Cu(CH3CN)4]Cl complex.
Copper(I) Cyanide Complexes. Alkali cyanides readily dissolve copper(I) cyanide, with
the formation of [Cu(CN) 2]− and [Cu(CN)3]2− complexes. Solutions of the complexes are of
great importance in the electroplating industry because of their versatility. From
saturated copper and sodium cyanide baths, crystals of the double salt Na 2Cu(CN)3 ・
2H2O can be obtained readily.
Other Copper Complexes of Industrial Significance. Solvent extraction of copper(II) ions
relies on the ability of copper to form complexes and to break those complexes as a
function of pH [110], [126], [127]. The most common reagents used commercially are
substituted salicylaldoximes, 1,8-hydroxyquinolines, and α-hydroxyoximes.
Copper(II) is solubilized in alkaline media by complex formation with tartrates for use as
Fehling’s solution, which is utilized in the analysis of reducing sugars. Copper(II) bis(1,8-
dihydroxyquinoline)
is used as a textile fungicide and as a pigment. Copper phthalocyanines [128], [129] are
exceptionally stable blue and green pigments, as are the azo dye complexes of copper
(→Azo Dyes; →Phthalocyanines).