METALS

Unit 3. The Chemistry of Engineering Materials

1.0 OCCURRENCE OF METALS

Mineral - where most metals come from, is a naturally occurring substance with a range

of chemical composition.

Ore - a mineral deposit concentrated enough to allow economical recovery of a desired

metal. Thus, an ore is a deposit in Earth’s crust of one or more valuable minerals.

Aluminum, iron, calcium, magnesium, sodium, potassium, titanium, and manganese

- most abundant metals which exist as minerals in the Earth’s crust.

Seawater - a rich source of some metal ions, such as Na+, Mg2+ and Ca2+.

Moreover, vast areas of the ocean floor are covered with manganese nodules which are

made up mostly of manganese, along with iron, nickel, copper, and cobalt in a

chemically combined state.

Manganese nodules - are combinations of rock on the sea bottom which is composed of

concentric layers of iron and manganese hydroxides around a core.

Principal Types of Minerals (Chang & Goldsby, 2017)

● Metals having low reactivity show little affinity for air, moisture, carbon dioxide or

other non-metals present in nature. Such metals may remain in elemental or native

(free) state in nature. Such metals are called "noble metals" as they show the least

chemical reactivity. For example gold, silver, mercury and platinum occur in free

state.

● On the other hand, most of the metals are active and combine with air, moisture,

carbon dioxide and non-metals like oxygen, sulfur, halogens, etc. to form their

compounds, like oxides, sulfides, carbonates, halides and silicates. i.e., they occur in

nature in a combined state.

● To convert an alkali metal ion into an alkali metal atom, it undergoes reduction.

Sodium and potassium - are isolated primarily from brines (solutions of NaCl and KCl).

Potassium - was the first alkali metal to be prepared by electrolysis.

Lithium - obtained mostly from the mineral spodumene, LiAl(SiO3)2.

Commercial production of tungsten: WO3 (s) + 3 H2 (g) à W (s) + 3 H 2O (g)

Metallic bond - a type of chemical bond formed between positively charged atoms in

which the free electrons are shared among a lattice of cations. Metallic bonds result from
the electrostatic attraction between metal cations and delocalized electrons. The nature

of metallic bonding accounts for many of the physical properties of metals, such as

conductivity and malleability.

Delocalized electron - an electron in an atom, ion, or molecule not associated with any

single atom or a single covalent bond. Delocalized electrons are also commonly seen in

solid metals, where they form a "sea" of electrons that are free to move throughout the

material. This is why metals are typically excellent electrical conductors.

2.0 METALLURGICAL PROCESS

Metallurgical process - the science and technology of separating metals from their ores

and of compounding alloys.

Alloy - a solid solution either of two or more metals, or of a metal or metals with one or

more nonmetals.

The three principal steps in the recovery of a metal from its ore are:

(1) preparation of the ore, (2) production of the metal, and (3) purification of the metal

(1) Preparation of the Ore

 In ore prior treatment, the desired mineral is separated from waste materials that

are usually clay and silicate minerals which are collectively called the gangue.

Methods used:

● Flotation

● Electromagnetism (ex.: magnetite and Cobalt)

● Amalgamation (ex. Gold and Silver)

Flotation - a very useful process for carrying out this separation. In this process, the ore

is finely ground and added to water containing oil and detergent.

Ferromagnetic metals - are strongly attracted to magnets.

Mineral magnetite (Fe3O4) - can be separated from the gangue by using a strong

electromagnet.

Cobalt - another ferromagnetic metal.

Mercury - forms amalgams with a number of metals. Mercury can therefore be used to

extract metal from ore.

Amalgam - an alloy of mercury with another metal or metals.

(2) Production of Metals

Reduction process - the production of a free metal because metals in their combined

forms always have positive oxidation numbers.

Preliminary operations - may be necessary to convert the ore to a chemical state more

suitable for reduction.

 For example, an ore may be roasted to drive off volatile impurities and at the

same time to convert the carbonates and sulfides to the corresponding oxides, which can

be reduced more conveniently to yield the pure metals:

This last equation points out the fact that the conversion of sulfides to oxides is a

major source of sulfur dioxide, a notorious air pollutant.

Types of reduction that can be used in the production of metals:

● Chemical Reduction

We can use a more electropositive metal as a reducing agent to separate a less

electropositive metal from its compound at high temperatures:

● Electrolytic Reduction

Electrolytic reduction is suitable for very electropositive metals, such as

sodium,

magnesium, and aluminum. The process is usually carried out on the anhydrous molten

oxide or halide of the metal:

The Metallurgy of Iron

Iron Ore - contain from 50% to around 70% iron, depending on grade (hematite is almost

70% iron).

Iron exists in Earth’s crust in many different minerals, such as iron pyrite

(FeS2), siderite (FeCO3), hematite (Fe2O3), and magnetite (Fe3O4, often represented as

FeO ∙ Fe2O3).

Hematite and magnetite - are predominantly suitable for the extraction of iron.

Coke - supplies heat for chemical reactions and produces carbon monoxide (CO) to

reduce iron ore.

Limestone - used as a flux to react with and remove impurities in molten iron.

Hot gases (CO, H2, CO2, H2O, N2, O2, and fuels) - used to burn coke.

Blast Furnace Process - a refractory-lined chamber with a diameter of about 9 to 11 m

(30 to 35 ft) at its widest and a height of 40 m (125 ft).

Slag - mixture of calcium silicate and calcium aluminate that remains molten at the

furnace temperature.

Pig iron - product of blast furnace. It contains over 4% C, plus other impurities: 0.3-1.3%

Si, 0.5-2.0% Mn, 0.1-1.0% P, and 0.02-0.08% S.

Steelmaking

Steel is an iron alloy that contains from 0.03 to 1.4 percent carbon plus various

amounts of other elements. The conversion of iron to steel is essentially an oxidation

process in which the unwanted impurities are removed from the iron by reaction with

oxygen gas. One of several methods used in steelmaking is the basic oxygen process.

Steels produced by BOF or electric furnaces are solidified for subsequent

processing either as cast ingots or by continuous casting.

● Casting of ingots – a discrete production process

● Continuous casting – a semi-continuous process

Four Categories of Steel

1. Plain carbon steels. Carbon is the principal alloying element, only small amounts of

other elements (.5% manganese is normal); strength increases with carbon content,

but ductility is reduced; high carbon steels can be heat treated to form martensite,

making the steel very hard and strong.

2. Low alloy steels. Iron-carbon alloys that contain additional alloying elements in

amounts totaling less than 5% wt. Heat treatment is often required to achieve these

improved properties.

3. Stainless steels. Highly alloyed steels (typically with Cr and/or Ni) designed for

corrosion resistance. In addition to corrosion resistance, stainless steels are noted for

their combination of strength and ductility.

4. Tool steels. A class of (usually) highly alloyed steels designed for use as industrial

cutting tools, dies, and molds. To perform in these applications, they must possess

high strength, hardness, hot hardness, wear resistance, and toughness under impact.

Tool steels are heat treated.

Tempering - heating the steel to some appropriate temperature for a short time and then

cooling it rapidly in order to give it the desired mechanical properties.

3.0 THE PURIFICATION OF METALS

Metals prepared by reduction usually need further treatment to remove impurities.

The extent of purification, of course, depends on how the metal will be used. Three

common purification procedures are distillation, electrolysis, and zone refining.

Distillation

Metals that have low boiling points, such as mercury, magnesium, and zinc, can

be separated from other metals by fractional distillation. One well-known method of

fractional distillation is the Mond process (named after Ludwig Mond, a British chemist

of German origin) for the purification of nickel.

Carbon monoxide gas is passed over the impure nickel metal at about 70°C to

form the volatile tetracarbonylnickel (b.p. 43C), a highly toxic substance, which is

separated from the less volatile impurities by distillation:

Pure metallic nickel is recovered from Ni(CO)4 by heating the gas at 200°C:

Electrolysis
 Another important purification technique is electrolysis. The copper metal

obtained by roasting copper sulfide usually contains impurities such as zinc, iron, silver,

and gold. The more electropositive metals are removed by an electrolysis process in

which the impure copper acts as the anode and pure copper acts as the cathode in a

sulfuric acid solution containing Cu2+ ions. The reactions are:

Zone Refining

In this process, a metal rod containing a few impurities is drawn through an

electrical heating coil that melts the metal. Most impurities dissolve in the molten metal.

As the metal rod emerges from the heating coil, it cools and the pure metal crystallizes,

leaving the impurities in the molten metal portion that is still in the heating coil. (This is

analogous to the freezing of seawater, in which the solid that separates is mostly pure

solvent—water.

In zone refining, the liquid metal acts as the solvent and the impurities as the

solutes.) When the molten zone carrying the impurities, now at increased concentration,

reaches the end of the rod, it is allowed to cool and is then cut off.

4.0 BAND THEORY OF ELECTRICAL CONDUCTIVITY

Band theory (a model used to study metallic bonding) states that delocalized

electrons move freely through “bands” formed by overlapping molecular orbitals. This

theory can also be applied to certain elements that are semiconductors.

Conductors

Metals are characterized by high electrical conductivity. In a metallic crystal, the

atoms are packed closely together, so the energy levels of each magnesium atom are

affected by the immediate neighbors of the atom as a result of orbital overlaps. The

interaction between two atomic orbitals leads to the formation of a bonding and an

antibonding molecular orbital. Because the number of atoms in even a small piece of

magnesium is enormously large (on the order of 1020 atoms), the number of molecular

orbitals they form is also very large.

Semiconductors

Semiconductors normally are not conductors, but will conduct electricity at

elevated temperatures or when combined with a small amount of certain other elements

(examples are silicon and germanium from Group 4A elements). The use of

semiconductors has changed the electronic industry in recent decades, leading to

increased miniaturization of electric component. Transistors and solar cells are two

examples of semiconductor’s applications.

Doping - enhancement of semiconductor’s ability to conduct electricity can be done, this

is by means of adding a small amount of certain impurities to the element. Impurities of

this type are known as donor impurities, because they provide conduction electrons.

Solids containing donor impurities are called n-type semiconductors, where n stands for

negative (the charge of the “extra” electron).

5.0 PERIODIC TRENDS IN METALLIC PROPERTIES

The Alkali Metals

The most electropositive or the least electronegative elements. These metals have

a body-centered crystal structure with low packing efficiency. They are also known

because of their low melting point and soft enough to be sliced with a knife.

Lithium - the lightest known metal and has great chemical reactivity. Lithium never

occurs naturally in elemental form and they are found with halide, sulfate, carbonate, and

silicate ions.

Sodium and Potassium

Electrolysis - the process where metallic sodium is ideally obtained from molten sodium

chloride.

Metallic potassium - soluble to molten KCl, that’s why it cannot be prepared easily by

the electrolysis process. Moreover, it vaporizes readily at the operating temperatures,

creating hazardous conditions.

Sodium and potassium - equally abundant in nature. They occur in silicate minerals

such as albite (NaAlSi3O8) and orthoclase (KAlSi3O8). These elements are also both
extremely reactive, but potassium is the more reactive of the two. Both react with water to

form the corresponding hydroxides. Sodium and potassium are essential elements of

living matter. Sodium ions and potassium ions are present in intracellular and

extracellular fluids, and they are essential for osmotic balance and enzyme functions.

Sodium Chloride

Sodium chloride (table salt) is a typical ionic compound, a brittle solid with a high

melting point (801°C) that conducts electricity in the molten state and in aqueous

solution. Sodium chloride also occurs in nature as the mineral halite.

Rock salt - one source of sodium chloride which can be found in subterranean deposits

where often hundreds of meters thick. It is also obtained from seawater or brine (a

concentrated NaCl solution) by solar evaporation.

Sodium Carbonate

Sodium carbonate (called soda ash) is used in all kinds of industrial processes,

including water treatment and the manufacture of soaps, detergents, medicines, and food

additives. For many years Na2CO3 was produced by the Solvay process (named after

Ernest Solvay, a Belgian chemist), in which ammonia is first dissolved in a saturated

solution of sodium chloride.

Sodium Hydroxide and Potassium Hydroxide

Sodium hydroxide and potassium hydroxide (has similar properties) are prepared

by the electrolysis of aqueous NaCl and KCl solutions; both hydroxides are strong bases

and very soluble in water.

Sodium hydroxide - used in the manufacture of soap and many organic and inorganic

compounds.

Potassium hydroxide - used as an electrolyte in some storage batteries.

Aqueous potassium hydroxide - used to remove carbon dioxide and sulfur dioxide from

air.

Sodium Nitrate and Potassium Nitrate

The Alkaline Earth Metals

The alkaline earth metals are considerably less electropositive and less reactive

than the alkali metals. Except for beryllium which resembles aluminum. The oxidation

number of alkaline earth metals in the combined form is almost always +2.

Properties of Alkaline Earth Metals

Magnesium

Magnesium is the sixth most plentiful element in Earth’s crust (about 2.5 percent

by mass). Among the principal magnesium ores are brucite, Mg(OH)2; dolomite, CaCO3

MgCo3; and epsomite, MgSO4 ∙ 7H2O.

Seawater - a good source of magnesium and there are about 1.3 g of magnesium in each

kilogram of seawater.

Metallic magnesium - obtained by electrolysis from molten chloride, MgCl2.

The chemistry of magnesium is intermediate between that of beryllium and the

heavier Group 2A elements. Magnesium does not react with cold water but does react

slowly with steam. It burns in air to produce magnesium oxide and magnesium nitride.

Magnesium oxide reacts very slowly with water to form magnesium hydroxide, a

white solid suspension called milk of magnesia, which is used to treat acid indigestion.

Calcium

Calcium is about 3.4% by mass in the Earth’s crust. Calcium can be found in

limestone, calcite, chalk, and marble as CaCO3; in dolomite as CaCO3 ∙ MgCO3; in

gypsum as CaSO4 ∙ 2H2O; and in fluorite as CaF2.

Metallic calcium - best prepared by the electrolysis of molten calcium chloride (CaCl2).

Calcium hydroxide [Ca(OH)2] - commonly known as slaked lime or hydrated lime.

Lime (CaO) - which is also referred to as quicklime, is one of the oldest materials known

to mankind.
Quicklime is produced by the thermal decomposition of calcium carbonate.

Slaked lime is produced by the reaction between quicklime and water.

Aluminum

Aluminum is the most abundant metal and the third most plentiful element in

Earth’s crust which is 7.5 percent by mass. The elemental form cannot be found in

nature; its principal ore is bauxite (Al2O3 ∙ 2H2O). Other minerals containing aluminum

are orthoclase (KAlSi3O8), beryl (Be3Al2Si6O18), cryolite (Na3AlF6), and corundum

(Al2O3).

Aluminum is usually prepared from bauxite with silica (SiO2), iron oxides, and

titanium(IV) oxide.

Anhydrous aluminum oxide, or corundum, is reduced to aluminum by the Hall

process (named after Charles Martin Hall, an American inventor). The cathode is also

made of carbon and constitutes the lining inside the cell. The key to the Hall process is

the use of cryolite, or Na3AlF6 (melting point is 1000 °C), as the solvent for aluminum

oxide (melting point is 2045 °C).

Transition Metals

Transition metals typically have incompletely filled d subshells or readily give

rise to ions with incompletely filled d subshells. (The Group 2B metals—Zn, Cd, and

Hg—do not have this characteristic electron configuration and so, although they are

sometimes called transition metals, they really do not belong in this category.) This

attribute is responsible for several notable properties, including distinctive coloring,

formation of paramagnetic compounds, catalytic activity, and especially a great tendency

to form complex ions. In this section we focus on the first-row elements from scandium

to copper, the most common transition metals.

As we read across any period from left to right, atomic numbers increase,

electrons are added to the outer shell, and the nuclear charge increases by the addition of

protons. In the third-period elements—sodium to argon—the outer electrons weakly

shield one another from the extra nuclear charge. Consequently, atomic radii decrease

rapidly from sodium to argon, and the electronegativities and ionization energies increase

steadily.

General Physical Properties

Most of the transition metals have a close-packed structure in which each atom

has a coordination number of 12. Furthermore, these elements have relatively small

atomic radii. The combined effect of closest packing and small atomic size results in

strong metallic bonds. Therefore, transition metals have higher densities, higher melting

points and boiling points, and higher heats of fusion and vaporization than the Group 1A,

2A, and 2B metals.

Chemistry of Iron

After aluminum, iron is the most abundant metal in Earth’s crust (6.2 percent by

mass). It is found in many ores; some of the important ones are hematite, Fe2O3; siderite,

FeCO3; and magnetite, Fe3O4.

Pure iron is a gray metal and is not particularly hard. It is an essential element in living

systems.

Iron reacts with hydrochloric acid to give hydrogen gas:

Fe(s) + 2H1(aq) → Fe2+(aq) + H2(g)

One of the best-known reactions of iron is rust formation. The two oxidation

states of iron are +2 and +3. Iron(II) compounds include FeO (black), FeSO4 ∙ 7H2O

(green), FeCl2 (yellow), and FeS (black). In the presence of oxygen, Fe2+ ions in solution

are readily oxidized to Fe3+ ions. Iron(III) oxide is reddish brown, and iron(III) chloride is

brownish black.

Chemistry of Copper

Copper, a rare element (6.8x10-3 percent of Earth’s crust by mass), is found in

nature in the uncombined state as well as in ores such as chalcopyrite, CuFeS2.

Impure copper can be purified by electrolysis. After silver, which is too

expensive for large-scale use, copper has the highest electrical conductivity. It is also a

good thermal conductor. Copper is used in alloys, electrical cables, plumbing (pipes),

and coins.
 Copper reacts only with hot concentrated sulfuric acid and nitric acid. Its two

important oxidation states are +1 and +2.

All compounds of Cu(I) are diamagnetic and colorless except for Cu2O, which is

red. The Cu(II) compounds are all paramagnetic and colored. The hydrated Cu2+ ion is

blue. Some important Cu(II) compounds are CuO (black), CuSO4 ∙ 5H2O (blue), and CuS

(black).