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Shannon Keith

Chem 201

2003 Jan 29

An exploration of the properties of copper

Introduction

Copper, like the elements directly below it in the periodic table, silver and gold, is found in

nature in elemental form. All three metals are comparatively malleable with a high sheen.

These qualities make copper, silver and gold some of the most commonly used metals in

utensils and jewelry. Its unusual electron configuration gives copper many of its properties.

Instead of having an electron configuration of [Ar] 4s2 3d9, one electron that is expected to be

in the 4s orbital is actually in the 3d orbital creating a configuration of [Ar] 4s1 3d10. This

aspect of copper also applies to silver and gold. Many of the aspects that these elements have

in common are a result of this similarity.

Several copper alloys, which are mixtures of copper and another metal, are commonly

used throughout history and today. Copper and its durable tin alloy, bronze, became used in

large amounts when a method of producing the pure copper metal by reducing copper ions

using carbon in the form of coal was discovered1. Reaction 1 shows this reduction reaction,

where C is charcoal and CuO is copper oxide from copper ore.

Reaction 1

Reduction half-reaction

Cu2+ + 2e-  Cu

Oxidation half reaction

C  C4+ + 4e-
2

Net reaction

2CuO + C  CO2(g) + 2Cu

Brass is another copper alloy that consists of copper and zinc. In ancient times, brass

was produced by mixing copper with zinc oxide (ZnO) and Carbon1. In this reaction, copper

reduces the zinc (shown in Reaction 2) and then was reduced itself by carbon as seen in

Reaction 1 (c).

Reaction 2

ZnO + Cu  Zn + Cu 2+ + O2-

Copper, like other metals, forms positive ions (as opposed to negative ions) because

the orbital with the electrons of the highest energy is filled, and because of its relatively low

electro-negativity. The ion it most commonly forms is Cu2+, but it also forms Cu+ and Cu3+

ions. In its ionic form, copper is generally blue in color, so certain compounds with these ions

make attractive pigments. One such pigment is Azurite. This pigment (2CuCO3, Cu(OH)2) is

formed when copper is oxidized to Cu2+ and added to a solution containing CO32- ions. When

heated in solution, the reaction, which forms azurite, is driven further to produce Malachite

(CuCO3, Cu(OH)2. This modification causes the compound to appear green so malachite is

also used as a pigment.

The bright surface of copper is quickly corroded by environmental factors causing the

metal to appear dull. One environmental factor that can corrode it is heat. Since copper is

frequently used in cooking utensils, this corrosion is commonly recognizable. The heat excites

the outer electrons of the element allowing the atom to be more easily oxidized by oxygen in

the air. First, copper loses one electron to oxygen forming Cu+ and O2-. These ions then bond

forming red Cu2O as seen in Reaction 3.


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Reaction 3

4Cu + O2  2Cu2O

If the heating continues, copper is further oxidized by oxygen forming Cu2+ and O2-. These

ions form black CuO as in Reaction 4.

Reaction 4

Cu + O2  4CuO

Both red Cu2O and black CuO form on the surface of the metal discoloring it. However, this

layer also forms a barrier between the metal and oxygen in the air preventing further

oxidation.

Corrosion and corrosive materials can be removed (or even reversed in some cases)

using electro-chemical reduction—a method frequently employed in cleaning and restoring

metal artifacts. In this process, caustic soda is dissolved in water as the electrolyte or salt

bridge. Then the object to be restored is buried in a pile of granulated zinc (or zinc powder for

fine materials). The system is then heated to stimulate a faster reaction and to disrupt the

formation of a copper metal crust on the object. The zinc oxidizes the copper ions forming

copper metal and zinc ions. The muddy copper particles are then cleared away (191-194)2.

Removal of corrosion materials is one example of a use for copper oxidation-

reactions. Another use is etching to make prints and to decorate jewelry. In etching, a pattern

is made by protecting areas of the copper with a substance insoluble in the etching solution

and leaving other areas exposed. When the copper is submerged in the etching solution, only

the exposed areas of copper are corroded. Therefore, the pattern remains in raised areas of the

metal. In jewelry-making these patterns are the final product.


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In printmaking, however, ink is applied the etched metal and then transferred onto a

base, such as paper, to form an indefinite number of final products. The application of ink can

be accomplished in two ways. First, the pattern made in the etching process consists of very

thin grooves where the copper has been reduced. Ink is forced into these grooves and the

paper is pressed onto the metal so that the ink is transferred onto the paper. Second, ink is

spread on the raised portion of the etching and then is transferred onto the paper.

The trick of a successful etching is using a solution that will spontaneously reduce

copper. The ions that will reduce a metal can be predicted through reduction potentials.

Reduction potential is a number found experimentally and assigned to reduction half-reactions

to describe the energy involved in those reactions. Since potential is the charged difference

between two cells, the potential of one electrode cannot be measured. However, the reduction

potential of the reduction of hydrogen ions to hydrogen atoms (shown in Reaction 5) has been

assigned as 0.00. This provides a standard on which to base the assigned values of reduction

potentials of all other reactions.

Reaction 5

2H+ + 2e_  H2

A voltmeter placed between two electrodes of an electrochemical cell records the potential of

the cell. Reaction 6 shows the relationship between cell potential, reduction potential and

oxidation potential.

Reaction 6

Potentialcell = Reduction potential + Oxidation potential

Since oxidation is the reverse of reduction, oxidation potential is the inverse of the reduction

potential of a half-reaction. Therefore, by finding experimentally the potential of a cell with


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one hydrogen electrode and subtracting the oxidation potential of a hydrogen electrode (0.00),

the reduction potential of the reduction half-reaction of the cell is found. Accordingly, the

potential of a cell can be found using the standard reduction and oxidation potentials of the

half-reactions of a cell. If a cell’s potential is positive the reaction is spontaneous and energy

is produced, not absorbed by the reaction. Therefore, whether an atom will be reduced by a

particular ion is predictable.

Through the method described above we can predict whether iron(III) ions, tin(II) ions

or nitrate ions will reduce copper. Table 1 below shows the reduction potentials3 of the ions

involved and the oxidation-reduction reactions of copper with these ions are shown in

Reaction 7.

Table 1

Reaction Reduction potential (volts)


Cu2+ + 2e-  Cu 0.34
NO3- + 4H+ 4e-  NO + H2O .96
Sn2+ + 2e-  Sn -0.14
Fe3+ + 3e- Fe+ 0.77

Reaction 7
a) Cu + 2NO3-  Cu2+ + NO3

b) Cu + Fe3+  Cu2+ + Fe+

c) Cu + Sn2+  Cu2+ + Sn

The calculated cell potential for Reaction 7 (a) is:

-0.34 V + 0.96 V = 0.62 V

The calculated cell potential for reaction 7 (b) is:

-0.34 V + 0.77V = 0.43V

The calculated cell potential for reaction 7 (c) is:


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-0.34 V + -0.14 V = -0.48 V

From the positive signs of their electron potentials we can see that reactions 7 (a) and (b) will

take place spontaneously while reaction 7 (c) with a negative reduction potential will not. The

experimental results support this prediction. Copper was etched by Nitric acid and ferric

chloride, but not by stannous chloride.

We can also use this method to look at the restoration topic described above in which

copper ions resulting from the corrosion of copper metal are reduced by zinc metal. The

reduction potential of zinc(II) ions to zinc metal is –0.76 V, therefore its oxidation potential is

0.76 V. As seen above the reduction potential of copper(II) ions to copper metal is 0.34 V.

Since the sum of these potentials is 1.1 V, the reaction is spontaneous3.

Conclusion

This paper has explored many qualities and reactions of copper. Much of what has been

discussed can be applied to elements besides copper. Like copper, other transition metals are

frequently used in pigments. Etching and reduction potentials too can be applied to chemical

reactions in general.
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References

1. Department of Chemistry [Internet]. Edmonton (Canada): University of Alberta;


c2003 [cited 2003 Jan 19]. Available from: http://www.chem.ualberta.ca

2. Plenderleith HJ. The Conservation of antiquities and works of art: Treatment, repair,
and restoration. London (England): Oxford University Press; 1956.

3. Zumdahl SS. Chemical Principles. 3rd ed. Boston (MA): Houghton Mifflin; 1998.

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