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Unit 3 – The Chemistry of Engineering

Materials

Metals




LEARNING OBJECTIVES


• Describe the occurrence and abundance of metals in the Earth’s crust.

• Explain the processes involve
in the metallurgy of iron and steel
making.

• Explain the concept of the Band Theory of Electrical Conductivity

• Discuss the periodic trends of some metals and their reactivity.

1.0 OCCURRENCE OF METALS

A mineral where most metals come from, is a naturally occurring substance with a
range of chemical composition. A mineral deposit concentrated enough to allow economical
recovery of a desired metal is known as ore. Thus, an ore is a deposit in Earth’s crust of one
or more valuable minerals. Table 1 has the lists of principal types of minerals.
Aluminum, iron, calcium, magnesium, sodium, potassium, titanium and manganese
are the most abundant metals which exists as minerals in the Earth’s crust. Seawater is a rich
source of some metal ions, such as 𝑁𝑎N , 𝑀𝑔!N , 𝑎𝑛𝑑 𝐶𝑎!N . 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 combine 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.

Table 1. Principal Types of Minerals (Chang & Goldsby, 2017)

Type Minerals
Uncombined 𝐴𝑔, 𝐴𝑢, 𝐵𝑖, 𝐶𝑢, 𝑃𝑑, 𝑃𝑡
metals
Carbonates 𝐵𝑎𝐶𝑂+ (witherite), 𝐶𝑎𝐶𝑂+ (calcite, limestone), 𝑀𝑔𝐶𝑂3

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(magnesite), 𝐶𝑎𝐶𝑂+ ∙ 𝑀𝑔𝐶𝑂+ (dolomite), 𝑃𝑏𝐶𝑂+ (cerussite), 𝑍𝑛𝐶𝑂+

(smithsonite)
Halides 𝐶𝑎𝐹! (fluorite), 𝑁𝑎𝐶𝑙 (halite), 𝐾𝐶𝑙 (sylvite), 𝑁𝑎+ 𝐴𝑙𝐹5 (cryolite)
Oxides 𝐴𝑙! 𝑂+ ∙ 2𝐻! 𝑂 (bauxite), 𝐴𝑙! 𝑂+ (corundum), 𝐹𝑒! 𝑂+ (hematite),
𝐹𝑒+ 𝑂$ (magnetite), 𝐶𝑢! 𝑂 (cuprite),
𝑀𝑛𝑂! (pyrolusite), 𝑆𝑛𝑂! (cassiterite), 𝑇𝑖𝑂! (rutile), 𝑍𝑛𝑂 (zincite)
Phosphates 𝐶𝑎+ (𝑃𝑂$ )! (phosphate rock), 𝐶𝑎# (𝑃𝑂$ )+ 𝑂𝐻 (hydroxyapatite)
Silicates 𝐵𝑒+ 𝐴𝑙! 𝑆𝑖5 𝑂(8 (beryl), 𝑍𝑟𝑆𝑖𝑂$ (zircon), 𝑁𝑎𝐴𝑙𝑆𝑖+ 𝑂8 (albite),
𝑀𝑔+ (𝑆𝑖$ 𝑂(0 )(𝑂𝐻)! (talc)
Sulfides 𝐴𝑔! 𝑆 (argentite), 𝐶𝑑𝑆 (greenockite), 𝐶𝑢! 𝑆 (chalcocite), 𝐹𝑒𝑆! (pyrite),
𝐻𝑔𝑆 (cinnabar), 𝑃𝑏𝑆 (galena), 𝑍𝑛𝑆 (sphalerite)
Sulfates 𝐵𝑎𝑆𝑂$ (barite), 𝐶𝑎𝑆𝑂$ (anhydrite), 𝑃𝑏𝑆𝑂$ (anglesite),
𝑆𝑟𝑆𝑂$ (celestite), 𝑀𝑔𝑆𝑂$ ∙ 7𝐻! 𝑂 (epsomite)

2.0 METALLURGICAL PROCESSES
The science and technology of separating metals from their ores and of compounding
alloys is called metallurgical process. An alloy is 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.

Preparation of the Ore
In ore prior treatment, the desired mineral is separated from waste materials that is
usually clay and silicate minerals which are collectively called the gangue. Flotation is 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. The liquid mixture is then beaten or blown to
form a froth. The oil preferentially wets the mineral particles, which are then carried to the
top in the froth, while the gangue settles to the bottom. The froth is skimmed off, allowed to
collapse, and dried to recover the mineral particles.
Another physical separation process makes use of the magnetic properties of certain
minerals. Ferromagnetic metals are strongly attracted to magnets. The mineral magnetite
(𝐹𝑒3𝑂4), in particular, can be separated from the gangue by using a strong electromagnet.
Cobalt is another ferromagnetic metal.
Mercury forms amalgams with a number of metals. An amalgam is an alloy of
mercury with another metal or metals. Mercury can therefore be used to extract metal from
ore. Mercury dissolves the silver and gold in an ore to form a liquid amalgam, which is easily
separated from the remaining ore. The gold or silver is recovered by distilling off mercury.

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Production of Metals
Because metals in their combined forms always have positive oxidation numbers, the
production of a free metal is a reduction process. 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:
𝐶𝑎𝐶𝑂+ (𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂! (𝑔)
2𝑃𝑏𝑆(𝑠) + 3𝑂! (𝑔) → 2𝑃𝑏𝑂(𝑠) + 2𝑆𝑂! (𝑔)

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. Most major metallurgical processes
now in use involve pyrometallurgy, procedures carried out at high temperatures.

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:
𝑉! 𝑂# (𝑠) + 5𝐶𝑎(𝑙) → 2𝑉(𝑙) + 5𝐶𝑎𝑂(𝑠)
𝑇𝑖𝐶𝑙$ (𝑔) + 2𝑀𝑔(𝑙) → 𝑇𝑖(𝑠) + 2𝑀𝑔𝐶𝑙! (𝑙)
𝐶𝑟2𝑂3(𝑠) + 2𝐴𝑙(𝑠) → 2𝐶𝑟(𝑙) + 𝐴𝑙2𝑂3(𝑠)
3𝑀𝑛+ 𝑂$ (𝑠) + 8𝐴𝑙(𝑠) → 9𝑀𝑛(𝑙) + 4𝐴𝑙2𝑂3(𝑠)

In some cases, even molecular hydrogen can be used as a reducing agent, as in the
preparation of tungsten (used as filaments in lightbulbs) from tungsten(VI) oxide:
𝑊𝑂3(𝑠) + 3𝐻2(𝑔) → 𝑊(𝑠) + 3𝐻2𝑂(𝑔)

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:
2𝑀𝑂(𝑙) → 2𝑀 (𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒) + 𝑂2 (𝑎𝑡 𝑎𝑛𝑜𝑑𝑒)
2𝑀𝐶𝑙(𝑙) → 2𝑀 (𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒) + 𝐶𝑙2 (𝑎𝑡 𝑎𝑛𝑜𝑑𝑒)

The Metallurgy of 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. The
metallurgical processing of iron involves the chemical reduction of the minerals by carbon
(in the form of coke) in a blast furnace (Figure 1). The concentrated iron ore, limestone
(𝐶𝑎𝐶𝑂3), and coke are feed into the furnace from the top. A blast of hot air is forced up the

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furnace from the bottom, that’s why it is called a blast furnace. The oxygen gas reacts with
the carbon in the coke to form mostly carbon monoxide and some carbon dioxide. These
reactions are highly exothermic, and as the hot 𝐶𝑂 𝑎𝑛𝑑 𝐶𝑂2 gases rise, they react with the
iron oxides in different temperature zones, as shown in Figure 1. The key steps in the
extraction of iron are:
3𝐹𝑒2𝑂3(𝑠) + 𝐶𝑂(𝑔) → 2𝐹𝑒3𝑂4(𝑠) + 𝐶𝑂2(𝑔)
𝐹𝑒3𝑂4(𝑠) + 𝐶𝑂(𝑔) → 3𝐹𝑒𝑂(𝑠) + 𝐶𝑂2(𝑔)
𝐹𝑒𝑂(𝑠) + 𝐶𝑂(𝑔) → 𝐹𝑒(𝑙) + 𝐶𝑂2(𝑔)

The decomposition of limestone in the furnace is shown the equation below:
𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

The calcium oxide then reacts with the impurities in the iron, which are mostly sand
(𝑆𝑖𝑂2) and aluminum oxide (𝐴𝑙2𝑂3):
𝐶𝑎𝑂(𝑠) + 𝑆𝑖𝑂2(𝑠) → 𝐶𝑎𝑆𝑖𝑂3(𝑙)
𝐶𝑎𝑂(𝑠) + 𝐴𝑙2𝑂3(𝑠) → 𝐶𝑎(𝐴𝑙𝑂2)2(𝑙)

A mixture of calcium silicate and calcium aluminate that remains molten at the
furnace temperature is known as slag.
By the time the ore works its way down to the bottom of the furnace, most of it has
already been reduced to iron.







Figure 1. A blast furnace. Iron ore, limestone,
and coke are introduced at the top of the
furnace. Iron is obtained from the ore by
reduction with carbon (Chang & Goldsby,
2017).

Iron extracted in this way contains many impurities and is called pig iron; it may
contain up to 5 percent carbon and some silicon, phosphorus, manganese, and sulfur. Some

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of the impurities stem from the silicate and phosphate minerals, while carbon and sulfur
come from coke. Pig iron is granular and brittle. It has a relatively low melting point (about
1180°𝐶), so it can be cast in various forms; for this reason it is also called cast iron.
Steelmaking
Steel is an iron alloy that contains from 0.03 to 1.4 percent carbon plus various
amounts of other elements. The wide range of useful mechanical properties associated with
steel is primarily a function of chemical composition and heat treatment of a particular type
of steel.
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.
Figure 2 shows the basic oxygen process. Molten iron from the blast furnace is poured
into an upright cylindrical vessel. Pressurized oxygen gas is introduced via a water-cooled
tube above the molten metal. Under these conditions, manganese, phosphorus, and silicon,
as well as excess carbon, react with oxygen to form oxides. These oxides are then reacted
with the appropriate fluxes (for example, CaO or SiO2) to form slag. If the main impurities
are silicon and phosphorus, a basic flux such as CaO is added to the iron:
𝑆𝑖𝑂2(𝑠) + 𝐶𝑎𝑂(𝑠) → 𝐶𝑎𝑆𝑖𝑂3(𝑙)
𝑃4𝑂10(𝑙) + 6𝐶𝑎𝑂(𝑠) → 2𝐶𝑎3(𝑃𝑂4)2(𝑙)

Figure 2. The basic oxygen process of

steelmaking. The capacity of a typical
vessel is 100 tons of cast iron (Chang
& Goldsby, 2017).

On the other hand, if manganese is the main impurity, then an acidic flux such as
𝑆𝑖𝑂2 is needed to form the slag:
𝑀𝑛𝑂(𝑠) + 𝑆𝑖𝑂2(𝑠) → 𝑀𝑛𝑆𝑖𝑂3(𝑙)

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The properties of steel depend not only on its chemical composition but also on the
heat treatment. At high temperatures, iron and carbon in steel combine to form iron carbide,
𝐹𝑒3𝐶, called cementite:
3𝐹𝑒(𝑠) + 𝐶(𝑠) ⟺ 𝐹𝑒3𝐶(𝑠)

The forward reaction is endothermic, so that the formation of cementite is favored at
high temperatures. When steel containing cementite is cooled slowly, the preceding
equilibrium shifts to the left, and the carbon separates as small particles of graphite, which
give the steel a gray color. (Very slow decomposition of cementite also takes place at room
temperature). If the steel is cooled rapidly, equilibrium is not attained and the carbon
remains largely in the form of cementite, 𝐹𝑒3𝐶. Steel containing cementite is light in color,
and it is harder and more brittle than that containing graphite.
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 is known as “tempering.” In
this way, the ratio of carbon present as graphite and as cementite can be varied within rather
wide limits. Table 2 shows the properties, composition and uses of various types of steels

Table 2. The properties and uses of various types of steel.

Composition (Percent by Mass)
Type C Mn P S Si Ni Cr Others Uses
Plain 1.35 1.65 0.04 0.05 0.06 - - Cu(0.2- Sheet products,
0.6) tools
High- 0.25 1.65 0.04 0.05 0.15- 0.4- 0.3- Cu(0.01- Construction, steam
strength 0.9 1.0 1.3 0.08 turbines
Stainless 0.03- 1.0- 0.04- 0.03 1-3 1- 4.0- - Kitchen utensils,
1.2 10 0.06 22 27 razor blades

3.0 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

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metal at about 70°𝐶 to form the volatile tetracarbonylnickel (𝑏. 𝑝. 43°𝐶), a highly toxic
substance, which is separated from the less volatile impurities by distillation:
𝑁𝑖(𝑠) + 4𝐶𝑂(𝑔) → 𝑁𝑖(𝐶𝑂)$ (𝑔)

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

The carbon monoxide that is released is recycled back into the process.

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 𝐶𝑢!N ions (Figure 3). The reactions are:
𝐴𝑛𝑜𝑑𝑒(𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 𝐶𝑢(𝑠) → 𝐶𝑢!N (𝑎𝑞) + 2𝑒 3
𝐶𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 𝐶𝑢!N (𝑎𝑞) + 2𝑒 3 → 𝐶𝑢(𝑠)

Reactive metals in the copper anode, such as iron and zinc, are also oxidized at the
anode and enter the solution as 𝐹𝑒 !N and 𝑍𝑛!N ions. They are not reduced at the cathode,
however. The less electropositive metals, such as gold and silver, are not oxidized at the
anode. Eventually, as the copper anode dissolves, these metals fall to the bottom of the cell.
Thus, the net result of this electrolysis process is the transfer of copper from the anode to
the cathode.






Figure 3. Electrolytic purification of copper (Chang &
Goldsby, 2017).

Zone Refining
In this process, a metal rod containing a few impurities is drawn through an electrical
heating coil that melts the metal (Figure 4). Most impurities dissolve in the molten metal. As
the metal rod emerges from the heating coil, it cools and the pure metal crystallizes, leaving

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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.












Figure 4. Zone-refining technique for purifying metals. Top to bottom: An impure metal rod
is moved slowly through a heating coil. As the metal rod moves forward, the impurities
dissolve in the molten portion of the metal while pure metal crystallizes out in front of the
molten zone (Chang & Goldsby, 2017).

4.0 BAND THEORY OF ELECTRICAL CONDUCTIVITY

Band theory (a model use 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. For example, magnesium has
an electron configuration of [𝑁𝑒]3𝑠2, so each atom has two valence electrons in the 3s
orbital. 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. These molecular orbitals are so closely spaced
on the energy scale that they are more appropriately described as a “band” (Figure 5). The
closely spaced filled energy levels make up the valence band. The upper half of the energy
levels corresponds to the empty, delocalized molecular orbitals formed by the overlap of the
3p orbitals. This set of closely spaced empty levels is called the conduction band.

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Figure 5. Formation of conduction bands in magnesium (Chang & Goldsby, 2017).

The electrons in the 1s, 2s, and 2p orbitals are localized on each Mg atom. However,
the 3s and 3p orbitals overlap to form delocalized molecular orbitals. Electrons in these
orbitals can travel throughout the metal, and this accounts for the electrical conductivity of
the metal.
The great cohesive force resulting from the delocalization is partly responsible for the
strength noted in most metals. Because the valence band and the conduction band are
adjacent to each other, the amount of energy needed to promote a valence electron to the
conduction band is negligible. There, the electron can travel freely through the metal,
because the conduction band is void of electrons. This freedom of movement accounts for
the fact that metals are good conductors, that is, they are capable of conducting electric
current.

Why don’t substances like wood and glass conduct electricity as metals do?
Basically, the electrical conductivity of a solid depends on the spacing and the state of
occupancy of the energy bands. In wood and glass, there is a gap between the valence band
and the conduction band is considerably greater than that in a metal. Consequently, much
more energy is needed to excite an electron into the conduction band. Lacking this energy,
electrons cannot move freely. Therefore, glass and wood are insulators, ineffective
conductors of electricity.

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.

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If the energy needed to excite electrons from the valence band into the conduction
band is provided, the solid becomes a conductor. Note that this behavior is opposite that of
the metals. A metal’s ability to conduct electricity decreases with increasing temperature
because the enhanced vibration of atoms at higher temperatures tends to disrupt the flow of
electrons.
Enhancement of semiconductor’s ability to conduct electricity can be done, this is by
means of adding small amount of certain impurities to the element, this process is called
doping. 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
Figure 6 shows the positions of the representative metals and the Group 2B metals in
the periodic table. There is an increase of electronegativity of these metals from left to right
across a period and from bottom to top in a group. The metallic character of metals increases
in just the opposite directions, that is, from right to left across a period and from top to
bottom in a group. Low electronegativities of metals results to the formation of cations and
almost have positive oxidation numbers in their compounds. However, beryllium and
magnesium in Group 2A and metals in Group 3A and beyond also form covalent compounds.











Figure 6. Representative metals and Group 2B metals according to their positions in the
periodic table (Chang & Goldsby, 2017).

The Alkali Metals
The most electropositive or the least electronegative elements known are the alkali
metals (the Group 1A 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. The lightest known metal is lithium and has great chemical
reactivity. Lithium never occur naturally in elemental form and they are found with halide,
sulfate, carbonate, and silicate ions. Other properties of alkali metals are shown in Table 3.

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This module will discuss the chemistry of the two most important element in this group;
sodium and potassium.

Table 3. Properties of Alkali Metals (Chang & Goldsby, 2017)
Li Na K Rb Cs
( ( ( (
Valence electron 2𝑠 3𝑠 4𝑠 5𝑠 6𝑠(
configuration
Density (g/cm3) 0.534 0.97 0.86 1.53 1.87
Melting point 179 97.6 63 39 28
(°𝐶)
Boiling point 1317 892 770 688 678
(°𝐶)
Atomic radius 152 186 227 248 265
(pm)
Ionic radius (M+) 78 98 133 148 165
(pm)
Ionization 520 496 419 403 375
energy (kJ/mol)
Electronegativity 1.0 0.9 0.8 0.8 0.7

Sodium and Potassium
Electrolysis is the process where metallic sodium is ideally obtained from molten
sodium chloride. This compound (𝑁𝑎𝐶𝑙) has a high melting point (801°𝐶) where much
energy is needed to keep large amounts of the substance molten. Addition of 𝐶𝑎𝐶𝑙! , can
lower the melting point to about 600°𝐶 which is an ideal temperature for the electrolysis
process.
Metallic potassium is 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. Instead, it is usually obtained by the distillation of molten 𝐾𝐶𝑙
in the presence of sodium vapor at 892°𝐶. The reaction that takes place at this temperature
is
𝑁𝑎(𝑔) + 𝐾𝐶𝑙(𝑙) ⇔ 𝑁𝑎𝐶𝑙(𝑙) + 𝐾(𝑔)

Sodium and potassium are about 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. In a limited supply of oxygen, sodium burns to form
sodium oxide (𝑁𝑎2𝑂). However, in the presence of excess oxygen, sodium forms the pale-
yellow peroxide:

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2𝑁𝑎(𝑠) + 𝑂2(𝑔) → 𝑁𝑎2𝑂2(𝑠)

Sodium peroxide reacts with water to give an alkaline solution and hydrogen
peroxide:
𝑁𝑎2𝑂2(𝑠) + 2𝐻2𝑂(𝑙) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2𝑂2(𝑎𝑞)

Like sodium, potassium forms the peroxide. In addition, potassium also forms the
superoxide when it burns in air:
𝐾(𝑠) + 𝑂2(𝑔) → 𝐾𝑂2(𝑠)
2𝐾𝑂2(𝑠) + 2𝐻2𝑂(𝑙) → 2𝐾𝑂𝐻(𝑎𝑞) + 𝑂2(𝑔) + 𝐻2𝑂2(𝑎𝑞)

This reaction is applied in breathing equipment. Exhaled air contains both moisture
and carbon dioxide. The moisture reacts with 𝐾𝑂2 in the apparatus to generate oxygen gas
as shown in the preceding equation. Furthermore, 𝐾𝑂2 also reacts with exhaled 𝐶𝑂2, which
produces more oxygen gas:
4𝐾𝑂2(𝑠) + 2𝐶𝑂2(𝑔) → 2𝐾2𝐶𝑂3(𝑠) + 3𝑂2(𝑔)

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.
Rock salt is 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 chloride also occurs in nature as
the mineral halite.

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 𝑁𝑎! 𝐶𝑂+ 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. Bubbling carbon dioxide into the solution results in the precipitation of
sodium bicarbonate as follows:
𝑁𝐻+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻! 𝐶𝑂+ (𝑎𝑞) → 𝑁𝑎𝐻𝐶𝑂+ (𝑠) + 𝑁𝐻$ 𝐶𝑙(𝑎𝑞)

Sodium bicarbonate is then separated from the solution and heated to give sodium
carbonate:

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2𝑁𝑎𝐻𝐶𝑂+ (𝑠) → 𝑁𝑎! 𝐶𝑂+ (𝑠) + 𝐶𝑂! (𝑔) + 𝐻! 𝑂(𝑔)

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 is used in the manufacture of soap and many
organic and inorganic compounds. Potassium hydroxide is used as an electrolyte in some
storage batteries, and aqueous potassium hydroxide is used to remove carbon dioxide and
sulfur dioxide from air.
Sodium chloride (molten state), an ionic compound, can be electrolyzed to form
sodium metal and chlorine. The electrolytic cell contains a pair of electrodes connected to
the battery. The battery serves as an “electron pump,” driving electrons to the cathode,
where reduction occurs, and withdrawing electrons from the anode, where oxidation occurs.
The reactions at the electrodes are:
𝐴𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 2𝐶𝑙 3 (𝑙) → 𝐶𝑙! (𝑔) + 2𝑒 3
𝐶𝑎𝑡ℎ𝑜𝑑𝑒(𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 2𝑁𝑎N (𝑙) + 2𝑒 3 → 2𝑁𝑎(𝑙)

𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 2𝑁𝑎N (𝑙) + 2𝐶𝑙 3 (𝑙) → 2𝑁𝑎(𝑙) + 𝐶𝑙! (𝑔)

This process is a major source of pure sodium metal and chlorine gas.

Sodium Nitrate and Potassium Nitrate
Sodium nitrate decomposes with the evolution of oxygen at about 500°𝐶:
2𝑁𝑎𝑁𝑂+ (𝑠) → 𝑁𝑎𝑁𝑂! (𝑠) + 𝑂! (𝑔)

Potassium nitrate is prepared beginning with the “reaction”
𝐾𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝑁𝑂+ (𝑎𝑞) → 𝑁𝑎𝑁𝑂+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞)

Because 𝐾𝑁𝑂+ is the least soluble salt at room temperature, it is separated from the solution
by fractional crystallization. Like 𝑁𝑎𝑁𝑂3, 𝐾𝑁𝑂3 decomposes when heated ( a temperature
below 100°𝐶).
Gunpowder consists of potassium nitrate, wood charcoal, and sulfur in the
approximate proportions of 6:1:1 by mass. When gunpowder is heated, the reaction is
2𝐾𝑁𝑂+ (𝑠) + 𝑆(𝑙) + 3𝐶(𝑠) → 𝐾! 𝑆(𝑠) + 𝑁! (𝑔) + 3𝐶𝑂! (𝑔)

The sudden formation of hot expanding gases causes an explosion.

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

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alkaline earth metals in the combined form is almost always +2. Table 4. lists some common
properties of these metals. Radium is not included in the list because all of its isotopes are
radioactive and the study of its chemistry is expensive as well.

Table 4. Properties of Alkaline Earth Metals
Be Mg Ca Sr Ba
! ! ! !
Valence electron 2𝑠 3𝑠 4𝑠 5𝑠 6𝑠 !
configuration
Density (g/cm3) 1.86 1.74 1.55 2.6 3.5
Melting point 1280 650 838 770 714
(°𝐶)
Boiling point 2770 1107 1484 1380 1640
(°𝐶)
Atomic radius 112 160 197 215 222
(pm)
Ionic radius 34 78 106 127 143
(M2+) (pm)
First ionization 899 738 590 548 502
energy (kJ/mol)
Second 1757 1450 1145 1058 958
ionization
energy
Electronegativity 1.5 1.2 1.0 1.0 0.9

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 is a good source of magnesium and there
are about 1.3 g of magnesium in each kilogram of seawater. Metallic magnesium is 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:
Mg(s) + H2O(g) → MgO(s) + H2(g)

It burns in air to produce magnesium oxide and magnesium nitride:
2Mg(s) + O2(g) → 2MgO(s)
3Mg(s) + N2(g) → Mg3N2(s)

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This property makes magnesium (in the form of thin ribbons or fibers) useful in flash
photography and flares.
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:
MgO(s) + H2O(l) → Mg(OH)2(s)

Calcium
Calcium is about 3.4% by mas 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 is best prepared by the electrolysis of molten
calcium chloride (𝐶𝑎𝐶𝑙2).
Calcium (like strontium and barium) reacts with cold water to produce the
corresponding hydroxide, although the rate of reaction is much slower than those involving
the alkali metals:
𝐶𝑎(𝑠) + 2𝐻2𝑂(𝑙) → 𝐶𝑎(𝑂𝐻)2(𝑎𝑞) + 𝐻2(𝑔)

Calcium hydroxide [𝐶𝑎(𝑂𝐻)2] is 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:
𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

while slaked lime is produced by the reaction between quicklime and water:
𝐶𝑎𝑂(𝑠) + 𝐻2𝑂(𝑙) → 𝐶𝑎(𝑂𝐻)2(𝑎𝑞)

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. The ore is first heated in sodium (𝑁𝑎𝑂𝐻) solution to convert the silica
into soluble silicates:
𝑆𝑖𝑂! (𝑠) + 2𝑂𝐻3 (𝑎𝑞) → 𝑆𝑖𝑂+!3 (𝑎𝑞) + 𝐻! 𝑂(𝑙)

Aluminum oxide is also converted to the aluminate ion (𝐴𝑙𝑂!3 ):
𝐴𝑙2𝑂3(𝑠) + 2𝑂𝐻3 (𝑎𝑞) → 2𝐴𝑙𝑂!3 (𝑎𝑞) + 𝐻2𝑂(𝑙)

Unaffected iron oxide and titanium oxide by this treatment are filtered off.
To precipitate the insoluble aluminum hydroxide, the solution is treated with acid.
𝐴𝑙𝑂!3 (𝑎𝑞) + 𝐻+ 𝑂N (𝑎𝑞) → 𝐴𝑙(𝑂𝐻)+ (𝑠)

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After filtration, the aluminum hydroxide is heated to obtain aluminum oxide:

2𝐴𝑙(𝑂𝐻)3(𝑠) → 𝐴𝑙2𝑂3(𝑠) + 3𝐻2𝑂(𝑔)

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
𝑁𝑎+ 𝐴𝑙𝐹5 (melting point is 1000 °C), as the solvent for aluminum oxide (melting point is 2045
°C). The mixture is electrolyzed to produce aluminum and oxygen gas:
𝐴𝑛𝑜𝑑𝑒 (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛): 3[2𝑂!3 → 𝑂! (𝑔) + 4𝑒 3 ]
𝐶𝑎𝑡ℎ𝑜𝑑𝑒 (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛): 4[𝐴𝑙 +N + 3𝑒 3 → 𝐴𝑙(𝑙)]

𝑂𝑣𝑒𝑟𝑎𝑙𝑙: 2𝐴𝑙! 𝑂+ → 4𝐴𝑙(𝑙) + 3𝑂! (𝑔)

Oxygen gas reacts with the carbon anodes (at elevated temperatures) to form carbon
monoxide, which escapes as a gas. The liquid aluminum metal (melting point is 660.2 °C)
sinks to the bottom of the vessel, from which it can be drained from time to time during the
procedure.

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.
For the transition metals, the trends are different. Looking at Table 5 we see that the
nuclear charge, of course, increases from scandium to copper, but electrons are being added
to the inner 3d subshell. These 3d electrons shield the 4s electrons from the increasing
nuclear charge somewhat more effectively than outer-shell electrons can shield one another,
so the atomic radii decrease less rapidly. For the same reason, electronegativities and
ionization energies increase only slightly from scandium across to copper compared with
the increases from sodium to argon.

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Although the transition metals are less electropositive (or more electronegative) than
the alkali and alkaline earth metals, the standard reduction potentials of the first-row
transition metals suggest that all of them except copper should react with strong acids such
as hydrochloric acid to produce hydrogen gas. However, most transition metals are inert
toward acids or react slowly with them because of a protective layer of oxide.

Table 5. Electron Configurations and Other Properties of the First Row Transition Metals
Sc Ti V Cr Mn Fe Co Ni Cu
Electron
Configuration
(M) 4𝑠 . 3𝑑/ 4𝑠 . 3𝑑. 4𝑠 . 3𝑑0 4𝑠/ 3𝑑1 4𝑠 . 3𝑑1 4𝑠 . 3𝑑2 4𝑠 . 3𝑑3 4𝑠 . 3𝑑4 4𝑠/ 3𝑑/5
(M2+) --- 3𝑑. 3𝑑0 3𝑑6 3𝑑1 3𝑑2 3𝑑3 3𝑑4 3𝑑7
(M3+) [Ar] 3𝑑/ 3𝑑. 3𝑑0 3𝑑6 3𝑑1 3𝑑2 3𝑑3 3𝑑4
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.9 1.9
Ionization
energy (kJ/mol)
First 631 658 650 652 717 759 760 736 745
Second 1235 1309 1413 1591 1509 1561 1645 1751 1958
Third 2389 2650 2828 2986 3250 2956 3231 3393 3578
Radius (pm)
(M) 162 147 134 130 135 126 125 124 128
(M2+) --- 90 88 85 91 82 82 78 72
(M )
3+ 83 68 74 64 66 67 64 --- ---

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)
Concentrated sulfuric acid oxidizes the metal to Fe3+, but concentrated nitric acid
renders the metal “passive” by forming a thin layer of Fe3O4 over the surface. One of the best-
known reactions of iron is rust formation. The two oxidation states of iron are +2 and +3.

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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 (6.8𝑥103+ percent of Earth’s crust by mass), is found in nature
in the uncombined state as well as in ores such as chalcopyrite, CuFeS2. The reddish-brown
metal is obtained by roasting the ore to give Cu2S and then metallic copper:
2CuFeS2(s) + 4O2(g) → Cu2S(s) + 2FeO(s) + 3SO2(g)
Cu2S(s) + O2(g) → 2Cu(l) + SO2(g)
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. The +1 state is less stable and disproportionates
in solution:
2Cu+(aq) → Cu(s) + Cu2+(aq)
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).




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ASSESSMENT TASK

1. Define the following terms:
a) mineral
b) ore
c) metallurgy

2. List three metals that are usually found in an uncombined state in nature and
three metals that are always found in combined state in nature.

3. Write the chemical formulas for the following minerals:
a) calcite f) magnetite
b) dolomite g) beryl
c) fluorite h) galena
d) halite i) epsomite
e) corundum j) anhydrite

4. Describe the main step involved in the preparation of an ore.

5. Briefly discuss the steelmaking process.

6. Briefly discuss the nature of bonding in metals, insulators, and semiconducting
elements.

7. Briefly discuss the properties and characteristics of the following:
a) alkali metals
b) alkaline earth metals
c) aluminum




Reference:


Chang, Raymond and Kenneth A. Goldsby, (2017) Chemistry, (12th International Edition), New

York: McGraw-Hill]



SCI 401 –GENERAL CHEMISTRY