...
...
...
Elements of Group 1A through 8A (or Groups 1, 2, and 13 through 18) are called
representative elements. Their chemical properties are determined by the electron
configurations of the valence-shell ns and np orbitals. They consist of metals, semi-metals (or
metalloids), and nonmetals. In general, metals react with nonmetal to form ionic compounds,
but there are exception where molecular compounds may also be formed between certain
metals and nonmetals. On the other hand, reactions between nonmetals or between semi-
metals and nonmetals invariable form molecular compounds.
For example, the following trends are observed for alkali metals:
Atomic radii: Li < Na < K < Rb < Cs;
Ionization energy: Li > Na > K > Rb > Cs;
Reactivity: Li < Na < K < Rb < Cs.
1
Abundance, Occurrence and Isolation
Oxygen is the most abundant element in the Earth’s crust (49.5% by mass). It occurs as
molecular oxygen in the atmosphere (23% by mass or 21% by volume), as H 2O in the
ocean, and mainly as silicate and carbonate minerals in rocks and soils.
Aluminum is the third most abundant element and the most abundant metal in the
Earth’s crust. It occurs mainly as alumina (Al2O3) in bauxite, which is the primary source
of aluminum.
Calcium carbonate (CaCO3), which occurs in limestone and seashells, is the most
abundant mineral on Earth and, therefore, an important source of calcium metal.
Sodium, potassium and magnesium are the next three elements in terms of natural
abundance. The ocean is the primary source for these metals. Although sodium is also
obtained from salt mine and dolomite (a mineral containing MgCO3 and CaCO3) is also a
major source of magnesium.
In the living materials, the eight most abundant elements in decreasing order are as follows:
Oxygen, carbon, hydrogen, nitrogen, calcium, phosphorus, magnesium, and potassium.
Oxygen, carbon, hydrogen, nitrogen, and phosphorus form the basis for all biologically
important molecules and biopolymers. Calcium phosphate forms the major structural
component of bones and teeth.
Since most metals occur as mixtures of minerals in ores, their isolations involve the most
innovative processes since ancient time. Metallurgy or the process of extracting metal from
ores involves the following steps:
mining the ores;
pre-treating the ores, such as by magnetic attraction, cyclone separation, floatation
method, or leaching, to separate the minerals from sand, rocks, and soil;
converting the minerals to compound, such as by roasting;
reducing the compound by chemical or electrolytic processes to obtain the metals.
Refining such as by electrorefining or zone refining;
Alloying, such as making steel.
Isolation of nonmetals:
Nitrogen and oxygen, which occur in abundance as free elements in the atmosphere, are
isolated directly by fractional distillation of liquefied air.
Chlorine is mainly derived from NaCl and MgCl2, where the ocean is the major source.
Bromine and iodine are produced by chemical reduction of NaBr and NaI with Cl 2; the
ocean is also their major source of these elements.
Fluorine is derived from fluoride containing minerals such as fluorospar (CaF2) and
fluoroapatite (Ca5(PO4)3F).
Sulfur is obtained from sulfur deposit and phosphorus is extracted from the phosphate
rocks fluoroapatite, Ca5(PO4)3F.
2
19.2 Group 1A(1): The Alkali Metals
This group contains elements with the largest atomic size and the lowest first ionization
energy. The relatively weak effective nuclear charge makes it easier to remove the single
electron in the valence shell. Thus, alkali metals are the most reactive of all metals. Compounds
of alkali metals are invariably ionic, except for organo-lithium compounds, such as alkyl lithium,
where lithium metal is covalently bonded to a carbon atom of the alkyl group. Alkali metals are
light and soft – they can easily be cut with a knife. They have low melting points and low heat
of atomization (Hatom). Lithium and sodium have a relatively high specific heat for metals.
Lithium carbonate, fluoride, hydroxide, and phosphate are less soluble in water than are
the corresponding compounds of the other alkali metals.
Lithium is the only alkali metal that forms a simple oxide (Li2O) and nitride (Li3N).
(1) 4Li(s) + O2(g) 2Li2O(s);(2) 6Li(s) + N2(g) 2Li3N(s)
Sodium forms peroxide, while potassium and other metals form superoxide (MO2)
Lithium reacts with organic halides to form alkyl lithium, which are covalent compounds .
2Li(s) + CH3CH2Cl(g) CH3CH2CH2Li(s) + LiCl(s)
Lithium carbonate and lithium hydroxide are decomposed by heat to form the oxide.
The carbonate and hydroxide of other alkali metals are thermally stable.
To a large extent, the special properties of lithium compounds can be attributed to the high
charge density of Li+. (The charge density is the ratio of the ionic charge to the ionic volume.)
The properties of lithium and lithium compounds show some similarity with those of magnesium
and magnesium compounds. This diagonal relationship probably results from the roughly
similar ionic radii of Li+ and Mg2+.
Potassium is produced by the reaction of molten KCl and liquid sodium vapor:
KCl(l) + Na(l) K(g) + NaCl(l);
3
Alkali metals have few important uses. Because of its high specific heat, good thermal
conductivity, low density, low viscosity, and low vapor pressure, liquid sodium is suitable
for use as a heat transfer medium in certain types of nuclear reactors.
A small quantity of sodium vapor is used in sodium vapor lamps for out-door lighting.
The most important chemical use of sodium metal is as a reducing agent in the
production of refractory (high melting point) metals, such as Ti, Zr, and Hf, and in the
isolation of potassium metal from molten KCl.
An important use of potassium is its conversion to the superoxide, KO 2, which is used as life-
support system in a confined area to produce O2 by reaction with CO2 gas.
Lithium is used to make lightweight batteries such as those used in cameras, pacemakers, and
computers. Lithium is a desirable battery electrode because of its lightness and produces high
voltage when combined with proper oxidizing agent. For example, lithium iodide batteries that
are used in cameras produce a voltage of about 3.5 V, whereas a normal alkaline battery
produces only 1.5 V. Lithium is also used in alloys with other light metals; it imparts high-
temperature strength to aluminum and ductility to magnesium when added in small quantities.
A possible future application is the production of tritium (3H) for use in nuclear fusion reactors.
2. Reaction with oxygen gas to form different types of oxides: lithium forms a simple oxide,
Li2O; sodium forms peroxide, N2O2; potassium and the other form superoxide:
3. Alkali metals react with hydrogen gas to form ionic (salt like) hydrides:
2Li(s) + H2(g) 2LiH(s); 2Na(s) + H2(g) 2NaH(s);
4
Uses of Certain Alkali Metal Compounds:
1. Sodium chloride is the most important alkali halide. It is the source of sodium metal and
chlorine gas and the starting material in the manufacture of sodium hydroxide.
(a) In the Downs process, electrolysis of molten sodium chloride produces Na and Cl2:
electrolysis
2NaCl(l) > 2Na(l) + Cl2(g)
(b) In the Chlor-alkali process for NaOH production, brine solution (concentrated NaCl
solution) is electrolyzed to produce NaOH, H2, and Cl2:
electrolysis
2NaCl(aq) + H2O(l) > 2NaOH(aq) + H2(g) + Cl2(g)
(c) NaCl reacts with conc. sulfuric acid to form sodium sulfate and hydrogen chloride gas:
2NaCl(s) + H2SO4(aq) Na2SO4(aq) + 2HCl(g)
(d) Sodium sulfate is an important ingredient in paper industry; HCl is used in steel,
plastics, textile and food production.
2. Sodium hydroxide and chlorine gas are used for making household bleaching solution:
2NaOH(aq) + Cl2(g) NaOCl(aq) + NaCl(aq) + H2O(l)
(bleach)
3. LiCl and LiBr are used in dehumidifiers and air-conditioning units because of their positive
heat of solution. Li2CO3 is used to make porcelain enamels, in glass making to produce
tough glasses, and used as a drug for treating manic-depression.
4. Na2CO3 is used in glass manufacture and as industrial base. NaHCO 3 is used as baking
powder and in fire extinguishers because it decomposes to produce CO 2 gas and the
reaction is endothermic, therefore reduces heat.
____________________________________________________________________________
5
19.3 Hydrogen
Hydrogen is the most abundant element in the universe, but it accounts for less than
1% (by mass) in the Earth’s crust. It is the third most abundant element in the living system.
There are three naturally occurring isotopes of hydrogen: the most abundant isotope is
hydrogen (1H) – sometimes referred to as protium, which comprises 99.9844% of the naturally
occurring hydrogen. This is the only atom that is devoid of neutron. Deuterium ( 2H or D), which
contains a proton, a neutron and an electron, makes up 0.0156% of the naturally occurring
hydrogen. Most hydrogen occurs as H2O, hydrocarbon, and biological compounds.
Deuterium exhibits significant isotope effects on the physical and chemical properties when it
substitutes hydrogen in the compounds. For example, heavy water (D 2O) has a melting point of
3.81oC and boiling point of 101.42oC. It density at 25oC is 1.104 g/mL, compared to 0.997
g/mL. Isotope effect is also observed in the rate of reactions that involve hydrogen.
3
The third isotope, tritium ( 1 H), is radioactive with a half-life of 12.3 years and occurs only in
trace amount. It is continuously formed in the upper atmosphere in nuclear reactions induced
by cosmic rays. It can also be synthesized in nuclear reactors by neutron bombardment of
lithium-6.
6 1 3 4
3 Li + 0 n 1 H + 2 He
3 3 0
Tritium decays by beta-emission to form helium-3: 1 H 2 He + 1 .
Hydrogen is a colorless gas with m.p. = -259 oC (14 K) and b.p. = -253 oC (20 K). Like other
nonmetals, hydrogen has a relatively high ionization energy (I.E. = 1311 kJ/mol), and an
electronegativity of 2.1 is lower than many nonmetals, but higher than metals.
The hydrides are very reactive and act as a strong base. Metal hydrides react violently with
water to produce hydrogen gas and hydroxides:
Fluorine is the only element that reacts with hydrogen at room temperature to form hydrogen
fluoride gas. The reaction is very exothermic and explosive.
H2(g) + F2(g) 2HF(g), Horxn = -546 kJ
Hydrogen fluoride gas dissolves in water to form hydrofluoric acid solution.
6
A mixture of H2 and O2 gases may remain indefinitely without reacting until a spark is
introduced, which will cause an explosive reaction:
2H2(g) + O2(g) 2H2O(l), Horxn = -572 kJ
The reaction is very exothermic, but it also has a very high activation energy. A mixture of
hydrogen and oxygen gas will not spontaneously react unless initiated by a flame or spark.
Once initiated, the reaction is violently explosive.
A convenient laboratory method of preparing hydrogen gas by reacting less reactive metals,
such as magnesium and zinc with dilute hydrochloric or sulfuric acid (but not nitric acid):
Hydrogen gas can be produced by passing steam over hot iron or over burning coke (carbon).
The latter reaction actually produces a mixture of carbon monoxide and hydrogen gases, called
“syngas”. At one time this gas mixture was used as fuel, but the practice was stopped because
of health hazardous (CO gas is toxic).
Industrial production of hydrogen gas involves the steam reformation of methane gas. The
reaction is normally carried out in the presence of Ni-catalyst at about 1100 oC and 7 atm.
CH4(g) + H2O(g) CO(g) + 3H2(g); Ho = +206 kJ
The reaction is endothermic, but has a positive entropy change. The reaction becomes
spontaneous and goes to completion when carried out at high temperature (>900 oC). More
hydrogen can be obtained if the CO gas is piped into another reactor where it is further reacted
with steam in a reaction known as the water-gas shift reaction. This reaction is exothermic:
CO(g) + H2O(g) CO2(g) + H2O(g); Ho = –41 kJ
(The CO2 gas can be absorbed by calcium oxide, CaO, thus leaving a fairly pure hydrogen gas.)
Hydrogen can also be produced by the electrolysis of water, but the operation is too costly for a
large-scale production:
electrolysis
2H2O(l) > 2H2(g) + O2(g); Ho = –572 kJ
7
Primary Uses of Hydrogen Gas
1. Production of ammonia:
The largest portion of hydrogen gas produced is used to manufacture ammonia by the
Haber process:
The industrial process is carried out at temperature of about 250oC and a pressure of 150 – 200
atm and in the presence of catalyst.
2. Production of methanol:
The reaction between hydrogen and carbon monoxide to make methanol is normally
carried out at about 300 oC and 150 atm over pellets of Cr2O3-ZnO catalyst:
8
19.4 The Alkaline Earth Metals (Group 2A or 2)
The alkaline Earth metals (Be, Mg, Ca, Sr, Ba, and Ra) have the valence-shell electron
configuration ns2.
They are generally harder than alkali metals and have higher melting and boiling points,
as well as a greater ionization energy due to greater effective nuclear charge.
Metallic bonds in alkaline Earth metals are stronger than that is the alkali metals due to
the presence of two valence electrons compared to only one in alkali metals.
They are less reactive than their alkali metal in the same period.
These metals are strong reducing agents, with reactivity increasing down the group.
With the exception of beryllium, alkaline Earth metals react with oxygen and halogens to
form ionic compounds. The oxides are alkaline – they form basic aqueous solution.
Like lithium, compounds of beryllium are mainly molecular. Even BeF2 is not completely
ionic, as indicated by its relatively low melting point and the low conductivity.
Magnesium and calcium are produced by the electrolysis of molten MgCl 2 and CaCl2,
respectively. Seawater contains Mg2+ at concentration of about 0.055 M and is an important
source of magnesium. The extraction of magnesium metal from seawater is carried out in the
Dow process. Quick lime (CaO) produced by the decomposition of calcium carbonate (CaCO 3) is
added to the seawater containing Mg2+. This reaction causes Mg2+ to form precipitate of
Mg(OH)2.
The precipitate is washed, filtered, and converted to MgCl2 by treating with dilute HCl.
Mg(OH)2(s) + 2HCl(aq) MgCl2(aq) + 2H2O(l)
9
The resulting solution of MgCl2 is evaporated to dryness and the solid MgCl2. Magnesium is
produced by the electrolysis of molten MgCl2, which also produces Cl2 as the by-product. The
latter is converted to HCl and recycled.
electrolysis
MgCl2(l) > Mg(l) + Cl2(g)
Production of magnesium by the Dow process consumes a lot of energy – about 300 MJ per
kilogram of Mg produced. In contrast, it takes only 7 MJ (7000 kJ) of energy to melt and recast
1 kg of recycled magnesium. Thus, recycling of magnesium is especially cost effective.
9 4 12 1
4 Be + 2 6 C + 0 n (The alpha particles are produced by
radium.)
Magnesium is a low density metal. Lightweight aircraft parts are manufactured from
alloys composed of magnesium, aluminum, and other metals.
Magnesium is the reducing agent in the extraction of beryllium and titanium.
TiCl4(l) + 2Mg(s) Ti(s) + 2 MgCl2(s)
Except for BeO, all oxides of alkaline earth metals are basic. BeO is amphoteric:
BeO(s) + 2HCl(aq) BeCl2(aq) + H2O(l);
BeO(s) + NaOH(aq) NaHBeO2(aq)
4. The reactivity of alkaline Earth metals with water increases as we go down the group. While
Be and Mg do not react with water, Ca, Sr, and Ba do so to form hydroxides and H2 gas. Mg,
but not Be, will react with hot steam to form Mg(OH) 2 and H2:
10
Mg(s) + 2H2O(g) Mg(OH)2(s) + H2(g);
Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g);
5. They react with halogens to form ionic halides, except for beryllium that forms molecular
halides:
Ca(s) + F2(g) CaF2(s); Mg(s) + Cl2(g) MgCl2(s); Be(s) + Cl2(g) BeCl2(g)
6. Except for beryllium, all alkaline earth metals react with hydrogen to form ionic hydrides:
Mg(s) + H2(g) MgH2(s)
The hydrides react with water to produce hydrogen gas and can be a source of fuel:
MgH2(s) + 2H2O(l) Mg(OH)2(s) + 2H2(g);
7. All carbonates of alkaline earth metals undergo thermal decomposition to the oxide:
CaCO3(s) CaO(s) + CO2(g)
CaO, which reacts with water to form Ca(OH)2, is used for making cement and mortar.
MgCO3 - manufacture of refractory bricks, glass, inks, rubber reinforcing agent, dentifrices,
cosmetics, antacids, and laxatives
MgCl2 - source of magnesium metal; manufacture of textiles and paper; fireproofing agents,
cements; refrigeration brine
MgO - Refractory (furnace linings), a component in ceramics and cement, for SO 2 removal
from stack gases
MgSO4 - Fireproofing, textile manufacturing, ceramics, fertilizers, cosmetics, dietary
supplements.
Limestone is a naturally occurring form of calcium carbonate, which is the most widely used
calcium compound. Although some limestone is used as building stones, most of it is used to
manufacture other building materials.
Portland cement is a complex mixture of calcium and aluminum silicates obtained by
heating limestone, clay, and sand in a high-temperature rotary kiln.
Ordinary soda-lime glass (the same one used to make bottles and windows) is a
mixture of sodium and calcium silicates formed by heating limestone, sand, and sodium
carbonate together.
Limestone is used in the metallurgy of iron and steel to produce liquefied mixture of
calcium silicates called slag, which removes impurities from the molten metal.
Pure CaCO3 is extensively used as a filler, providing bulk materials such as paint,
plastics, printing inks, and rubber. It is also used in toothpastes, food, cosmetics, and
antacids. Added to paper, calcium carbonate makes the paper bright, opaque, smooth,
and absorbs ink well.
The calcination of limestone produce calcium oxide (CaO), which is used as base in steel
production.
11
Calcination process is carried out at high temperature (about 1000 oC) with continuous removal
of CO2.
CaO is an important ingredient in the manufacture of Portland cement.
CaO is used during the early step of the Dow process in the extraction of magnesium
from seawater. CaO reacts with water to form calcium hydroxide, Ca(OH) 2, also called
slaked lime. The latter reacts with Mg2+ ions to form magnesium hydroxide precipitate.
If CO2 is bubbled through a suspension of slake lime, pure calcium carbonate is formed.
Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O
Quicklime and slaked lime are the cheapest and most widely used bases. Lime is used to
treat acidic soils of lawns, gardens, and farmland, and to treat excess acidity in lakes.
CaO(s) + 2H+(aq) Ca2+(aq) + H2O(l)
Quicklime is also used in air pollution control. Coal used as fuel in power plant contains
sulfur, which is converted to SO 2, during the combustion process. To prevent the release
of SO2 gas during the combustion of coal, powdered coal is mixed with powdered
limestone. During combustion limestone decomposes to CaO and CO 2, and CaO then
reacts with SO2 gas to form calcium sulfite.
12
19.5 Group 3A (13) Elements
The Group 3A elements exhibit a wide range of physical and chemical properties. For
example, boron is a metalloid and forms a covalent network solid, which makes it the hardest
element in the group; it has extremely high m.p. and b.p. Other elements in the group are
metals. Boron has the smallest atomic size and the highest ionization energy. Ionization energy
in kJ/mol are: B(800), Al(577), Ga(579), In(558), and Tl(589). The trend in ionization energy is
rather inconsistent due to the irregular trend in the effective nuclear charges. The number of
protons increases by 8 from B to Al, but increases by 18 from Al to Ga and from Ga to In
(because of transition metals), and from In to Tl the number increases by 32 (because of
transition metal and lanthanide series. These additional charges found among the heavier
metals of Group 3A results in a lower increase of atomic size than would be expected if the
transition and lanthanide series were not present. As a result, the increase in density are
relatively large between Al (d= 2.70 g/cm 3) and Ga (d = 5.90 g/cm 3), and between In (d= 7.31
g/cm3) and Tl (d= 11.85 g/cm3).
All elements react with oxygen gas, especially at high temperature, to form oxides:
(a) 4B(s) + 3O2(g) 2B2O3(s); (b) 4Al(s) + 3O2(g) 2Al2O3(s);
(c) 4Tl(s) + O2(g) 2Tl2O(s)
The properties of oxides vary from being weakly acidic (B 2O3) to amphoteric (Al2O3), mildly
basic (Ga2O3 and In2O3), and to very basic (Tl2O).
Boric acid, B(OH)3, when dissolved in water does not release hydrogen ion, but it acts as
a Lewis acid by accepting a pair of electron from water, and the reaction produces H +:
B(OH)3(aq) + H2O(l) ⇄ B(OH)4–(aq) + H+(aq);
Boron and nitrogen form a covalent network boron nitride (BN), a compound that is
structurally similar to graphite.
In many hydrides of boron (such as diboranes, B 2H6), boron attains the octet state by
forming two bridges via the hydrogen atoms.
13
Dehydration of the boric acid yields diboron trioxide, B2O3:
2 B(OH)3(s) B2O3(s) + 3 H2O(g)
Boron oxide (B2O3) is weakly acidic, which dissolves in water to form boric acid. B 2O3 is also a
component in borosilicate glasses. Elemental boron is obtained from the oxide by reduction with
magnesium:
B2O3(s) + 3 Mg(s) 2 B(s) + 3 MgO(s)
Aluminum
Aluminum is commercially the most important metal of Group 3A elements. Pure
aluminum is malleable, ductile, silvery-colored, and light, with a density of 2.70 g/cm 3 (only
about a-third that of steel). Pure aluminum is not very strong, but its alloys with copper,
magnesium, or silicon are very strong and light, suitable for the construction of aircraft parts.
Over 5 million tons of aluminum is produced yearly in the United State; most of it is used for
making lightweight alloys.
Production of Aluminum
Aluminum is the third most abundant element and the most abundant metal in the
Earth’s crust., with a relative abundance of 8.3% by mass. It is found in soils as aluminum
silicates and in bauxite. The latter is the commercial source of aluminum. The first pure
aluminum was only produced in 1825 by the work of Hans Oersted. For the next several
decades it remained a semi-precious metal used mostly in jewelry and artwork.
The major breakthrough in the production of aluminum occurred in 1886. Two important
individuals, Charles Martin Hall of the United States and Paul Heroult of France discovered
relatively an inexpensive method to produce pure aluminum by electrolysis of molten Al 2O3-
cryolite (Na3AlF6) mixture. The Hall-Heroult process uses bauxite as the source of aluminum,
which is first treated with NaOH to separate Al 2O3 from Fe2O3, the major impurity. The base
dissolves Al2O3, which is amphoteric, but not Fe2O3.
A solution containing [Al(OH)4]- is separated from the insoluble “red mud” (mostly Fe 2O3),
diluted with water and slightly acidified to precipitate the hydroxide, Al(OH) 3.
Al(OH)3 decomposes to Al2O3 when heated to about 1200 oC. Since the melting point of
aluminum oxide is too high (> 2000oC), electrolysis is not carried out on pure Al 2O3. Instead,
Al2O3 is dissolved in molten cryolite, Na3AlF6, which melts at a significantly lower temperature
(<1000oC) and it also serves as the electrolyte. The electrolysis cell uses a carbon-lined steel
cell as the cathode and large carbon anodes. The overall electrolysis reaction is as follows:
Aluminum production requires a great deal of energy - about 54 000 kJ per kg of Al. To produce
one of steel requires only one-fifth this much energy. However, it takes only 5% as much
energy to re-cycle aluminum as to produce it by electrolysis from bauxite.
14
The oxide forms thin impervious film that prevent further oxidation. Thus, aluminum resists
corrosion due to its protective oxide coating.
Aluminum reacts with dilute HCl(aq) and H2SO4(aq) to form AlCl3 and Al2(SO4)3, respectively.
Reaction with nitric acid produces Al2O3, which forms a protective coating and prevent further
oxidation by the acid.
Aluminum is highly combustible and the reaction is very exothermic; powdered Al is used as a
component in rocket fuels, explosives, and fireworks.
Aluminum is used to make beverage cans, cookware, and aluminum foil. However, most of the
aluminum produced is used in structural materials, usually alloyed with other metals to impart
greater strength. Most modern aircrafts use aluminum alloys, as do some automobile engines.
Because of its excellent electrical conductivity and low density, aluminum is widely used in the
electrical industry. High-power transmission lines in the United States are now made mostly of
aluminum alloys.
Aluminum Compounds
Among the halides, only AlF3 is strictly ionic. It has a high melting point (1090 oC) and
the molten form is a good electrical conductor. In contrast, AlCl 3 has a low melting point
(193oC) and the liquid is a poor conductor; it is soluble in water as well as in some organic
solvents, such as ethanol, diethyl ether, and carbon tetrachloride. In the liquid and gaseous
state, aluminum chloride exists as dimeric, Al2Cl6 molecules, in which two AlCl 3 units are linked
together by two chloride bridges.
Al2(SO4)3 is the most important industrial compound. It is prepared by the reaction of hot
aqueous H2SO4 with Al2O3; the product crystallizes as Al2(SO4)3.18H2O
About half of the aluminum sulfate produced in the United States is used in water treatment,
where it is used as flocculants. In this application, the pH of the water is raised to a point at
which Al(OH)3 precipitates.
As it settles, the gelatinous Al(OH)3 traps and removes suspended particulates from the water.
Besides being the source of aluminum metal, aluminum oxide, Al 2O3, is also used in the
manufacture of ceramic materials. Aluminum oxide (Al 2O3) is the major constituent in bauxite,
which is the natural source of Al metal. It is used as abrasive in sand paper, sanding and
cutting tools, and toothpaste. It is also used to strengthen ceramics and metal.
Aluminum oxide reacts with H 2SO4 to form aluminum sulfate, Al2(SO4)3, which is used in water
purification.
Al2O3(s) + 3H2SO4(aq) Al2(SO4)3(s) + 3H2O(l)
15
Aluminum sulfate and CaO form a colloidal mixture in water and is used in water treatment
plant for removing suspended particulates. Aluminum metal is produced by electrolysis of
molten Al2O3 in cryolite (Na3AlF6):
electrolysis
2Al2O3/Na3AlF6(l) + 3C(s) > 4Al(s) + 3CO2(g)
Compounds of the other members of Group 3A elements are ionic with a significant covalent
characteristic. For example, the halides of aluminum can exist in the gas phase as covalent
dimers and its oxide is amphoteric. Lithium aluminum hydride, LiAlH4, is a reducing agent in
many organic reactions;
16
19.6 Group 4A(14) Elements – Valence-shell Configuration: ns2np2
This group contains a nonmetal (C), two metalloids (Si & Ge), and two metals (Sn & Pb).
Carbon exhibits the most interesting and versatile chemical properties. Carbon is the most
important element in organic, molecular, and polymer chemistry, where it forms the primary
structural features of these compounds. Silicon is the second most abundant element in the
Earth’s crust and it shares some of the chemical characteristics of carbon, such as the ability to
form polymer molecules.
The types of bonding found among elements of Group 4A affect some of their physical
characteristics, such as hardness, m.p. and b.p. The large decrease in m.p. between C and Si,
where both form covalent network solids, is due to the longer and weaker bonds in Si-
structure; while the large decrease in m.p. from Ge and Sn is due to the change from covalent
network to metallic bonding. The large increase across the period between Al and Si is also due
to the change from metallic bonding to covalent network bonding.
Allotropes
Carbon exists in three different allotropes, namely, diamond, graphite, and the “bucky-
ball”. Diamond and graphite are physically very different; whereas the former is very hard, the
latter is soft and flakes off rather easily. This difference is due to the different types of covalent
bonds found in diamond and graphite. In diamond, each carbon atom has sp 3-hybrid orbitals
that form covalent (sigma) bonds with four other carbon atoms, thus forming an extensive
covalent network solid. This makes diamond the hardest natural substance on Earth. It is used
as cutting materials, such as in drill bits used for drilling rocks.
In graphite, each carbon atom has sp2 hybrid orbitals, which enable each atom to form covalent
(sigma) bonds with three other atoms in a planar geometry. Carbon atoms in graphite are
arranged in layers; within each layer atoms are covalently bonded to each other, but
interactions between one layer to other layers of carbon atoms are through weak dispersion
(London) forces. These weak forces holding carbon layers make graphite soft and the layers
flake off rather easily. Because of this property, graphite is used as lubricants and pencil leads.
The third allotrope of carbon that was only discovered in 1980s is called buckminsterfullerene
(or the “bucky-ball”). The basic feature of this allotrope is its soccer ball-like molecule
containing 60 carbon atoms that are covalently bonded to each other. Interest in the physical
and chemical properties of the bucky-ball has been growing quite steadily since its discovery,
especially in its selective conductivity potentials.
Group 4A(14) elements also display a wide range of chemical behavior, from the covalent
compounds of carbon to the ionic compounds of lead. Like carbon, Si and Ge also form covalent
compounds with nonmetals; whereas Sn and Pb form ionic as well as covalent compounds. Tin
and lead can acquire the oxidation states of +2 and +4. Compounds in which Sn and Pb have
the +2 oxidation state are primarily ionic, as indicated by their high m.p. and the ability of the
molten compounds and their aqueous solutions to conduct electric current. Compounds in which
Sn or Pb have the +4 oxidation state are primarily covalent, as indicated by their low m.p. and
the melt does not conduct electricity. For example, SnCl 2 and PbCl2 are primarily ionic – they
are white solid with high m.p., and their aqueous solution or the molten form conducts
electricity. SnCl4 is a volatile liquid, soluble in organic solvents, such as benzene and ether;
PbCl4 is an oily substance and it is also soluble in organic solvents. The physical properties of
SnCl4 and PbCl4 suggest that they are covalent compounds. The oxides, SnO and PbO are
primarily ionic and basic, whereas SnO2 and PbO2 are covalent and acidic.
17
Important Features in Carbon Chemistry.
Carbon is the most versatile element in the periodic table; it can bond with many
elements as well as with itself. Carbon exhibits the sp3, sp2, and sp hybridizations, and
therefore, can form single, double and triple bonds. As a result, carbon can form chain,
branching, and ring structure that lead to myriad of structures containing carbon skeletons. The
entire organic and biological compounds are based on carbon skeletons. A wide array of organic
compounds containing only carbon and hydrogen (thus called hydrocarbon) are found in nature.
The small atomic size of carbon enables the formation of -bonds between carbon atoms, in
addition to -bonds. This leads to carbon-carbon multiple bond formation. The formation of -
bond by sidewise overlap of unhybridized p-orbitals does not occur in other elements of Group
4A because their atomic size is too large. For example, whereas CO 2 is a discrete molecule in
which carbon is double bonded to each oxygen in the molecule, SiO 2 is a network solid; -bond
between Si and O atom cannot form because Si atom is too large for effective sidewise
overlaps.
Metal carbonates, especially calcium carbonate (CaCO 3), are the most important inorganic
compounds that contain carbon. CaCO3 makes up the limestone, marble, coral, and chalk.
CaCO3 is the starting material in the production of quicklime (CaO), which is used for making
cement and mortar. It is also an ingredient in common antacid formulation to neutralize
stomach acid:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
Similar reactions with sulfuric acid and nitric acid protect lakes bounded by limestone deposits
from the harmful effects of acid rain.
Carbon reacts with oxygen gas to form CO and CO 2; the former gas is toxic and the latter gas is
essential for plant life. Plants absorb CO 2 gas and water to manufacture carbohydrates during
photosynthesis. CO2 gas in the atmosphere also helps keep our Earth environment warm and
livable, but too much CO2 may lead to global warming.
Carbon also reacts with halogens to form a wide array of compounds, such as carbon
tetrachloride (CCl4), dichloromethane (CH2Cl2) and chloroform (CHCl3), which are important
organic solvents. The chlorofluorocarbons (CFCs, or freon) have important industrial uses, but
their exceptional stability and persistent presence in the upper atmosphere catalyzes the break
down of ozone and the depletion of ozone layer.
2. CO2 is essential in photosynthesis to make carbohydrates and produce O 2 gas. CO2 is the
final oxidation product of carbon-based fuels; it is a green house gas. CO 2 is used in
industry as a refrigerant gas, blanketing gas in fire extinguishers, and effervescence gas in
beverages. NH3 and CO2 are reactants in the production of urea, which is an organic
fertilizer as well as used in the manufacture of plastic monomers.
18
6. Methane, CH4, is the primary component is natural gas and used as fuel; it is also a reactant
in the industrial production of hydrogen gas, which is an important constituent in the
manufacture of ammonia, methanol, in the hydrogenation of vegetable oil to make
margarine and other solid shortening; it is also used as reducing agent in the production of
tungsten.
7. C3H8, C4H10, and C8H18 are important fuels; C6H14 and C6H6 are important organic solvents;
8. C2H4, C2H3Cl, CF4, H2N(CH2)6NH2, and ClOC(CH2)4COCl (among others) are important
monomers in polymer industries, such as plastic, PVC, Teflon, and nylon.
1. Silica, SiO2, is a covalent network solid, in which the SiO2 units are linked to one another by
the -Si-O- linkages. SiO 2 is the source of silicon used in the electronic industries. Silicon
production involves the reaction of silica with purified coke, which produces crude silicon.
This crude silicon is then converted to silicon tetrachloride, SiCl 4, by reaction with chlorine
gas.
SiO2(s) + 2 C(s) Si(s) + 2 CO(g)
Si(s) + 2 Cl2(g) SiCl4(g)
Volatile silicon tetrachloride is distilled and then reduced to pure silicon using a very pure
magnesium or zinc. The final purification is carried out by zone refining.
2. Silicate minerals are the most abundant substance outside the living systems. The building
unit of silicates is the tetrahedral orthosilicate group, —SiO4—. Some of the well known
minerals contain single SiO44- ions or a number of them linked together, such as in the
gemstone zircon, ZrSiO4; hemomorphite, Zn4(OH)2Si2O7.H2O, and in beryl, Be3Al2Si6O18.
3. Silicone Polymers are synthetic polymers containing short to long chains of —Si—O— units.
A key starting material in the formation of silicone is dimethylsilicon dichloride, which is
formed by catalytic reaction of silicon with methyl chloride:
Si(s) + 2CH3Cl(g) + Cu-catalyst (CH3)2SiCl2(l)
A major difference between silicon and carbon polymers is that, whereas carbon polymers
contain C-C backbone chains, silicone polymers contain repeating –(-Si-O)- units.
19
Important Compounds of Silicon
1. Silica (SiO2) occurs in many amorphous (glassy) and crystalline forms, quartz being the
most common. It is used to make glass and an inert support material in thin layer and
column chromatography.
2. Silicon carbide, SiC, or “carborundum”, is a major industrial abrasive and used for making
tough and temperature resistant ceramics.
3. Silica and silicates are common constituents in ceramics, and glass is the most common
form of ceramic products.
Over half of the lead produced is used as electrodes in lead storage batteries. Other uses
include the manufacture of solders, lead shot, and radiation shields.
A significant difference between tin and lead is that the +4 oxidation state is more stable in tin
than in lead. For example, when tin is heated in air, the product is SnO 2, whereas lead forms
PbO as the primary product. Tin reacts with chlorine gas to form SnCl 4 (bp. 115oC). Lead reacts
with chlorine gas to form PbCl 2 (bp.501oC). Tin reacts with sulfur to form both SnS and SnS 2,
but PbS is the only product in the reaction of lead with sulfur.
20