CHE 102 BASIC GENERAL CHEMISTRY II (4 UNITS)

Course synopsis.

Historical survey of the development and importance of Organic Chemistry; nomenclature and classes of organic
compounds and purification of organic compounds. Qualitative and quantitative analysis in organic chemistry;
stereochemistry. Determination of structures of organic compounds. Electronic theory in organic chemistry,
saturated hydrocarbons; alkanes, unsaturated hydrocarbons; alkenes, alkynes and aromatics. Functional groups;
carbonyls, halides, carboxylic acids and hydroxyls. Periodic Table and Periodic properties; periodic law, Morseley’s
Law, valence forces, structure of solids, molecular and ionic forces. Chemistry of selected metals and non-metals.
Quantitative analysis.

Inorganic Chemistry.

This is the chemistry of all the elements in the Periodic Table; their compounds and interaction with each others.
This aspect covers all the elements in the Periodic Table. It involves the electronic structures, physical properties,
reactions under various conditions; pressure, temperature and in vacuo. The only exceptions are the compounds
of carbon which forms the basis of Organic Chemistry. This is not as systematic as Organic chemistry; each
element/compound has its own unique characteristic.

Periodic Table.

Periodic Table is the systematic arrangement of elements in a chart according to their atomic numbers. The
development of periodic Table was initially based on atomic weight by Mendeleev in the late 19 th Century.
However, later discoveries and development made use of atomic number, Z, according to the observation of
Morseley using information obtained from the α-scattering experiments.

Morseley in 1913 discovered a correlation between atomic number Z of an element and the frequency ν of x-ray
generated by bombarding an element with high energy electrons. Morseley noted that the frequency ν of x-ray
emitted from elements can be correlated by this equation

√𝑣 = a(Z – b)

Where v = frequency, a and b are constants that are same for all elements and Z = atomic number.

This is known as the Morseley’s Periodic Law.

It was observed that all elements within the same vertical column share similar outermost electronic configuration
and subsequently same physical and chemical properties. This column is known as the Group. The horizontal row
known as the Period that displays elements with increasing atomic number Z and the progressive filling of their
outermost orbital shell. According to the sub-shell being filled, elements can be divided into categories;
representative elements (Main), the noble gases, transition (or d-orbital) elements and the Lanthanides and
Actinides (also known as f-orbital or rare earth elements).

The Main Group or Representative elements are the elements in Group IA, IIA, and IIB to VIIB. All these elements
have incomplete s- or p-orbitals/sub-shells of the highest principal quantum number. Noble gases in Group 0, VIIIB
or 18 have completely filled p-orbital with exception of He that has completely filled s-orbital. The transition
metals are the elements that have completely filled s-orbitals, f-orbital and partially filled d-orbital and are in
Group IIIA (3) to VIIIB. They readily form cations with incompletely filled d-sub shells or orbitals. The Lanthanides
and Actinides have partially filled f-orbital and they are called rare earth or f-orbital or inner transition elements.
The elements in these two classes are characteristically radioactive.

Each group is unique in that it has characteristic outermost electronic configuration and hence similar chemical
properties. For instance, all elements in Group IA – Alkali metals have similar outermost electronic configuration;
each has a noble gas core and ns1 outer electron. Similarly, Group IIA known as Alkaline-Earth elements has core
noble gas and ns2 outer electron configuration. These outer electrons are usually the ones involved in chemical
bondings and they are called the VALENCE ELECTRONS. In the same vein, the elements in Group 14 or IVA have the
same outer electron configuration of ns2np2.

Periodic Law.

Periodic Law in Chemistry states that many of the physical and chemical properties of the elements tend to recur
in a systematic manner with increasing atomic number.

Progressing from the lightest to the heaviest atoms, certain properties of the elements approximate those of their
precursors at regular intervals of 2, 8, 18 and 32. For instance, the second element He is similar in chemical
behavior to the 10th (Ne) as well as to the 18th (Ar), 36th (Kr), 54th (Xe) and the 86th (Rn). Similarly the chemical
family of halogens comprising of element 9 (F), 17 (Cl), 35 (Br), 53 (I) and 85 (At) show similar properties.

Valence Forces.

The electrons in the outermost configurations of elements are usually involved in bonding during chemical
reactions and these electrons are known as the valence electrons. Elements with low ionization energies tend to
form cations by losing their valence electrons to elements with high electron affinities that tend to form anions. As
a rule, the elements most likely to form cations are the alkali and alkaline-earth elements and the elements most
likely to form anions are halogens and oxygen.

An ionic bond is electrostatic or electrovalent and electrostatic force holds the ions together in ionic compounds.
For instance, reaction between Li (1s22s1) and F (1s22s22p5) leads to each of the participating atoms to assume inert
gas configuration in forming ionic compound. Li will lose one electron to F

Li + F → Li+ + F-

1s22s1 1s22s22p5 1s2 1s22s22p6

The force between the ions formed is electrostatic. Since the reaction occurs as a result of ions, the valence force is
therefore electrovalent or electrostatic.

On the other hand, reaction between two electronegative elements leads to the sharing of electrons by the
participating atoms to form covalent compounds Covalent compounds contain only covalent bonds.

F F
In such reactions, formation of molecules illustrates Octet Rule.

Octet Rule

Octet Rule states that an atom other than hydrogen tends to form bonds until it is surrounded by eight valence
electrons.

O : : C : : O or O=C=O

The valence force holding covalent molecules together is van der Waal force.

Comparison of some properties of an ionic and covalent compound.

Property NaCl CCl4

Appearance White solid Colourless liquid

Melting Point 0C 801 -23

Molar heat of fusion (kJ/mol) 30.2 2.5

Boiling Point 0C 1413 76.5

∆H vaporization (kJ/mol) 600 30

Density (g/cm3) 2.17 1.59

Solubility in H2O High very low

Electrical conductivity

Solid Poor Poor

Liquid Good Poor

The attractive force operating between molecules is called the intermolecular force and is usually weak. Intra-
molecular forces hold atoms together in a molecule.

General Properties of ionically and covalently bonded compounds.

Electrovalent compounds having ionic linkages are made up of positive and negative ions arranged together in a
regular way in a LATTICE. The attraction between the ions is electrostatic and non-directional and extends equally
in all directions. Thus, considerable amount of energy is required to melt the solid and this has to break the
lattices. This explains why these solids have high melting and boiling points and they are usually hard.

Covalent compounds are made up of discrete molecules. The bonds are directional and strong covalent forces exist
between atoms in the molecules. In solid, the only force between molecules is weak van der Waal forces. This
explains why little heat is needed to overcome these forces and melt and boil the compounds. Hence, most
covalent compounds are gases, liquids and soft solids with low melting points. However, in cases of diamond and
silica, SiO2, three-dimensional covalent structures are formed. In these cases, there are strong forces operating in
all directions. Hence, these materials are very hard with high melting and boiling points.

Structures of solids.

Solids can be divided into 2 categories; crystalline and amorphous. Crystalline solid possesses rigid and long-ranged
orders; its atoms, molecules or ions occupy specific positions. The arrangement of such particles in crystalline
solids is such that the net intermolecular attractive forces are at their maxima. The forces responsible for the
stability of crystal can be ionic, van der Waal forces, hydrogen bond or a combination of these forces. A unit cell is
the basic repeating structural unit of a crystalline solid.

Amorphous solids such as glass lack well-defined arrangement and long-ranged molecular orders.

Types of crystals.

The structure and properties of crystals such as melting and boiling points, density and hardness are determined
by the kind of forces that hold the particles together. Crystals can be classified into ionic, covalent, molecular or
metallic.

Ionic crystals.

There are two characteristics that mark out ionic crystals out and these are; (a) they are composed of charged
species and (b) the constituting anions and cations are of different sizes. There are types of ionic structures;

1. Cubic close-packed structure

2. Hexagonal close-packed
3. Body-centre cubic arrangement.

Example of isomeric crystal like iron pyrite

Isometric Crystal
Isometric crystals, such as the pyrite shown here, have three perpendicular axes of equal
length. The cubic-isometric structure is the most symmetrical of all the crystals. The pyrite
crystal system forms rocks that are fairly hard, but quite brittle. Pyrite is also known as
fool’s gold because of its yellow color and metallic luster.
Dorling Kindersley
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.

Hexagonal Crystal
A hexagonal crystal such as beryl, shown here, has four axes of symmetry. Three of the
axes are of equal length, and are symmetrically placed in one plane. The fourth axis is
perpendicular to the others.
Dorling Kindersley
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.

Face-centre cubic structure includes that of NaCl.

Ionic Bonding: Salt

The bond (left) between the atoms in ordinary table salt (sodium chloride) is a typical ionic
bond. In forming the bond, sodium becomes a cation (a positively charged ion) by “giving
up” its valence electron to chlorine, which then becomes an anion (a negatively charged
ion). This electron exchange is reflected in the size difference between the atoms before and
after bonding. Attracted by electrostatic forces (right), the ions arrange themselves in a
crystalline structure i
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.
Tetragonal Crystal
This Siberian idocrase has a tetragonal crystal structure. Its axes are all perpendicular and
two are of equal length. Idocrase is grouped with rocks such as zircon, rutile, and wulfenite,
which are rocks of medium hardness that may possess a diamondlike fire.
Dorling Kindersley
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.

Covalent Crystals

In this the atoms are held in an extensive 3-dimensional network entirely by covalent bond. 2 allotropes of carbon
vividly illustrates this; diamond and graphite. These two have different crystal structures. The differences are as
illustrated in the Table below.
Allotropic Forms of Carbon
Atoms of the element carbon can link together in several ways to form substances with very
different properties. In diamond, the atoms form a three-dimensional network that extends
throughout a crystal and makes diamond the hardest naturally occurring substance.
Graphite is made up of layers of carbon that can slide over each other easily, making
graphite a useful lubricant. In the family of substances called fullerenes, the atoms link to
form spherical or cylindrical surfaces.
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Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.
Properties of Diamond and Graphite.

Property Diamond Graphite

Hardness Very hard, in fact the hardest Soft and slippery

Known substance

Hybridization sp3 with no ∏ electrons sp2 hybridized like benzene with ∏ electrons.

Melting point 3930 0C 3000 0C

Structure Tetrahedrally bonded in Layer structure with fused rings

all directions.

Density (g/cm3) 3.51 2.22

Conductivity Insulator Good electrical conductor due to mobile ∏ electrons

Convertibility - Graphite can be converted to diamond at 1600 0C by a

pressure of 50 – 60,000 atmospheres.

Uses Jewelry, cutting of glass Lubricant, conducting electrodes and lead pencil.

Forces Strong covalent force van der waal force

Molecular crystals

Typical examples of molecular crystals are solid SO 2, I2, P4 S8 and ice. The lattice points are occupied by molecules
rather than atoms. The attractive forces are van der waal and or hydrogen bonding. Intermolecular attractive force
is due to dipole-dipole interaction. Most melt at temperature below 100 0C.

Metallic crystals.

In metals, the lattice points are occupied by atoms of the same metal. Metallic crystals are generally body-centred
cubic or hexagonally packed structures. Metallic elements are very dense. In a metal, the bonding electrons are
delocalized over the entire crystals. In fact, atoms in a metal have an array of positive ions immersed in a sea of
delocalized valence electrons. The great cohesive force resulting from delocalization is responsible for a metal’s
strength. Mobility of the delocalized electrons makes metals good conductor of electricity and heat.
Metallic Bonding
Silver, a typical metal, consists of a regular array of silver atoms that have each lost an
electron to form a silver ion. The negatively charged electrons distribute themselves
throughout the entire piece of metal and form nondirectional bonds between the positive
silver ions. This arrangement, known as metallic bonding, accounts for the characteristic
properties of metals: they are good electrical conductors because the electrons are free to
move from one place to another, and they are malleable (as shown here) because the
positive ions are held together by nondirectional forces. A force applied to a malleable
substance shifts the positions of the atoms without breaking the bonds that hold them
together.
© Microsoft Corporation. All Rights Reserved.
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.
General properties of crystals.

Crystal type Forces General properties Example

Ionic Electrostatic Hard, brittle, high MP & BP NaO, LiF, MgO, CaO

attraction conductors of heat and

electricity

Covalent Covalent bond Hard, High MP & BP, poor C (diamond) SiO 2

Conductors of heat and (quartz)

Electricity

Molecular Dispersion Soft, low MP & BP, poor Ar, CO 2, I2, H2O,

Forces, dipole- heat & electricity. Sucrose, C12H22 O11

Metallic Metallic bonds. Soft to hard, low to high MP & All metallic elements e.g. Na

BP, good conductors of heat and Fe, Cu, Zn, Hg, Ca, Mg

Electricity.

Reactivity Series
Chemists can list metals according to how quickly they undergo chemical reactions, such as
burning or dissolving in acids. The result is called a reactivity series. A metal at the top of
the series generally reacts more vigorously than those that are below it in the series, and
the more reactive metal can take their place (or displace them) in various compounds or in
solution. In some reactions, however, such as reduction reactions, the order of reactivity is
reversed.
© Microsoft Corporation. All Rights Reserved.
Microsoft ® Encarta ® 2009. © 1993-2008 Microsoft Corporation. All rights reserved.

Chemistry of selected elements.

To fully appreciate Inorganic Chemistry, some elements or groups of elements are selected to illustrate the
behaviours of these substances. Two metallic groups and three non-metals will be discussed. The metals of
interest are Alkali and Alkaline-earth metals, while halogens, hydrogen and oxygen are the non-metals slated for
discussions.

ALKALI METALS.

These are Group IA or 1 elements reputed to be the most reactive and electropositive elements. This group
consists of lithium, sodium, potassium, rubidium, caesium and francium. They have one electron each in their
respective outermost electronic shell or sub-shell. Information on francium is scanty since it only exists in nuclear
reactor with short half life of few seconds

Table: Properties of Alkali metals.

Element Configuration Atomic radius Ǻ ionic radius Ǻ M P 0C S. G Ionization energy (kJ mol-1)

Li [He] 2s1 1.23 0.60 181 0.54 520

Na [Ne] 3s1 1.57 0.95 98 0.97 496

K [Ar] 4s1 2.03 1.33 63 0.86 419

Rb [Kr] 5s1 2.16 1.48 39 1.53 403

Cs [Xe]6s1 2.35 1.67 29 1.87 375

From this table, it is obvious that the behaviours of the elements follow some trends. For instance, the atomic and
ionic radii of univalent cations as well as the specific gravity increase down the group from Li to Cs. On the other
hand, the melting point and the first ionization energy decrease down the group from Li to Cs.

The alkali metals are very important. Sodium and its compounds are of great importance. The metallic sodium, Na,
as Na-Pb alloy is used to make tetra-ethyl lead in anti-knocking principles of oil. There are other important
industrial uses. The hydroxides, carbonates, sulphates, tetrapolyphosphate and silicate of sodium among the top
50 industrial chemicals being produced in the U. S.A. Potassium salts, usually sulphate are used in fertilizer. Lithium
is used mainly in the synthesis of lithium alkyls. Both Na+ and K+ are of physiological importance in animals and
plants; cells can differentiate between Na+ and K+ ions probably in some types of complexing mechanisms. Lithium
salts are used in the treatment of certain mental disorders. .
Preparation and properties of metals.

Lithium and sodium are obtained by the electrolysis of their fused salts or low melting eutectics such as CaCl 2-NaCl.
Due to low melting point and ready vaporization of K, Rb and Cs; they are rather made by treating their molten
chlorides with Na vapour. Li, Na, K and Rb are silvery metals while Cs has a golden-yellow cast. These metals are
highly electropositive and they react readily with most other elements and many compounds on heating. Li is
usually the least and Cs being the most reactive.

Li react slowly with water at 25 0C and will not replace the weakly acidic H in C6H5C=CH while other metals do. Li
however, is uniquely reactive with N2, slowly at room temperature, but rapidly at 400 0C to form ruby-red nitride
Li3N like Mg that gives Mg3N2 with N2. Li can be used to absorb N2.

2Na + 2H2O → 2NaOH + H2

2Li + 2H2O → LiOH + H2

Na, K, Rb and Cs react violently with water at room temperature. They tarnish rapidly in air to form M 2O oxides
with oxygen. They form oxides with oxygen.

4Na + O2 → 2Na2O

4Li + O2 → 2Li2O

In air or O2 at 1 atmosphere of pressure, the metals burn. In this instance Li gives Li2O and traces of Li2O2 while
sodium forms peroxide Na2O2 with ability to take further O2 under pressure to form NaO2. K, Rb and Cs form
superoxide MO2.

All these elements react with alcohols to from alkoxides.

2C2H5OH + 2 Na → 2C2H5 ONa + H2

The metals dissolve in ammonia to give a blue solution when dilute and copper colour solution when the ammonia
is concentrated. These solutions have extremely high conductivities like those of liquid metals. They also react with
ammonia to form amide and hydrogen.

2NH3 + 2Na →NaNH2 + H2.

Compounds.

Binary compounds are formed with halogens, hydrogen and metals.

2Na + Cl2 → 2NaCl

Li + H → LiH

The chlorides and hydrides are highly electropositive and ionic. However, Li forms covalent halides with halogens.
Lithium shares some diagonal relationship with Mg in Group IIA making it uniquely different from other elements
in its group. The compounds are white and form colourless solutions with water with the exception of their
complexes that are coloured e. g. K2ClO4, KMnO4, K2PtCl6 and NaZn(UO2)(CH3COO)9 (sodium zinc uranyl acetate)
Hydroxides.

These are formed by the dissolution of metals or their oxides in water.

2Na + 2H2O → 2NaOH + H2

K2O + H2O → 2KOH

Li2O + H2O → 2LiOH

They readily absorb CO2 from air to form carbonates.

2KOH + CO2 → K2CO3 + H2O.

The hydroxides are easily neutralized by mineral acids to form salts and water.

KOH + HCl → KCl + H2O

2NaOH + H2SO4 → Na2SO4 +2H2O

CH3COOH + NaOH → CH3COONa + H2O.

Halides.

These metals react readily with halogens to form ionic halides.

2Na + Cl2 → 2NaCl

2K + F2 → 2KF

2Cs + I2 → 2CsI

2Rb + Br2 → 2RbBr

The halides are also formed by reactions between metal oxides, hydroxides and carbonates with halo-halide acids
or hydrogen halides. These halides dissociate in water to form cations M + and halide anions.

K2CO3 + 2 HCl → 2KCl + CO2 + H2O

Na2O + 2HF → 2NaF + H2O

RbOH + HI → RbI + H2O

CsHCO3 + HBr → CsBr + CO2 + H2O

Carbonates and hydrogen carbonates.

The carbonates and bicarbonates are formed by reactions between metal oxides, hydroxides and CO2. The
carbonates and bicarbonates are very soluble in water and they decompose at high temperatures. Both carbonates
and bicarbonates react with acids to form salts, water and liberate CO2. Bicarbonates are thermo labile giving
carbonates, water and CO2 on heating.
K2O + CO2 → K2CO3

K2CO3 + H2O + CO2 → 2KHCO3

2NaOH + CO2 → Na2CO3 + H2O

Na2CO3 + 2HCl → 2NaCl + H2O + CO2

KHCO3 + HCl → KCl + H2O + CO2

2NaHCO3 → Na2CO3 + CO2 + H2O

Sulphate

Their metals, oxides, hydroxides, carbonate and bicarbonate form sulphates with sulphuric acid. The sulphate salts
are very soluble in water.

2Na + H2SO4 → Na2SO4 + H2

Na2O + H2SO4 → Na2SO4 + H2O

2KOH + H2SO4 → K2SO4 + H2O

2CsCO3 + H2SO4 → Cs2SO4 + H2O + CO2

2KHCO3 + H2SO4→ K2SO4 + 2CO2 + 2H2O

Nitrates

The metals, oxides, hydroxides, carbonates and bicarbonates react with nitric acid to form nitrates. The nitrates
are very soluble in water.

2HNO3 + K2O → 2KNO3 + H2O

Na2CO3 + 2HNO3 → 2NaNO3 + H2O + CO2

LiOH + HNO3 → LiNO3 + H2O

However, the reaction of metals with this acid is very violent, hence not to be indulged in. The nitrates are also
thermo-labile giving nitrites and oxygen on pyrolysis.

2NaNO3 → 2NaNO2 + O2

2KNO3 → 2KNO2 + O2.

Hydrides.

The metals react directly with hydrogen to form ionic and electrovalent hydrides. These hydrides however react
with water to form hydroxides and hydrogen.

2K + H2 → 2KH

2Li + H2 → 2LiH

2Na + H2 →2NaH

2LiH + H2O →LiOH + H2

GROUP 2 OR IIA OR ALKALINE-EARTH METALS.

The members of this group include Beryllium, magnesium, calcium, strontium, barium and radium. They all have
two valence s-electrons in their outermost orbitals. They form divalent cations by losing their 2s-electrons to
electronegative elements. They form colorless ionic compounds.

Properties of Alkaline-earth metals.

Element Configuration Atomic radius Ǻ Ionic radius Ǻ Density M. P. oC Ionization energy (KJ/Mol)

Be [He] 2s2 0.89 0.31 1.8 1277 1757

Mg [Ne] 3s2 1.36 0.65 1.7 650 1450

Ca [Ar] 4s2 1.74 0.99 1.6 838 1143

Sr [Kr] 5s2 1.91 1.13 2.6 768 1064

Ba [Xe] 6s2 1.98 1.35 3.5 714 965

Ra [Rn] 7s2 1.50 5.0 700 773

The compounds are less basic than those in Group IA.

Occurrence: Mg and Ca are abundant and are among the eight most abundant elements in nature/earth crust.
Beryllium occurs in traces in silicate minerals; phenacyte BeSiO4 and beryl Be3Al2Si6O18. Mg occurs in seawater as
deposit of Magnesite MgCO3, dolomite MgCa(CO3)2, Kieserite MgCl3.6H2O. CaCO3 is found extensively as Calcite
and Limestone. Barium occurs as Barite BaSO4. Radium only occurs in nuclear reactor with a half-life of seconds.

Chemical Properties.

The metals being less reactive than those in Group IA, react with water, especially steam to form hydrogen and
hydroxides.

Mg + 2H2O → Mg(OH)2 + H2
The basic strength increases from Mg to Ba down the group. The bases absorb CO2 from air to form carbonates and
bicarbonates.

Ca2+ + (OH-)2 + CO2 → CaCO3 + H2O + CO2 ↔ Ca2+ + (HCO3-)2

Bicarbonates are only stable in solution and they are able to decompose back to carbonates and water on heating.

The metals burn in air to form basic oxides. Oxides are also formed from the decomposition of carbonates,
nitrates, sulphates and hydroxides.

2Mg + O2 → 2MgO

MgCO3 → MgO + CO2

Ca(OH)2 → CaO + H2O

Ba(NO3)2 → BaO + 2NO2 + O2

CaSO4 → CaO + SO2 + O2

The stability of the carbonates to heat increases from Be to Ba e. g BeCO 3< 100 0C, MgCO3 – 540 0C, CaCO3 – 900
0
C, SrCO3 – 1290 0C and BaCO3 – 1360 0C.

Halides are formed from reactions between metals and halogens or between metal oxides, hydroxides and
halogen or hydrogen halides.

Ca + Cl2 → CaCl2

MgO + 2HCl → MgCl2 + H2O

Sr(OH)2 + 2HCl → SrCl2 + H2O

Ba + 2HF → BaF2 + H2

BeO + 2HCl→ BeCl2 + H2O

Nitrates are formed by reactions between metals, metal oxides, carbonates, bicarbonates and hydroxides and
nitric acid.

MgCO3 + 2HNO3 → Mg(NO3)2 + CO2 + H2O

CaO + 2HNO3 → Ca(NO3)2 + H2O

Sr(OH)2 + 2HNO3 → Sr(NO3)2 + 2H2O

Ca + 3HNO3 → Ca(NO3)2 + NO2 + H2O

The nitrates are thermo-labile decomposing to oxides, nitrogen oxides and oxygen on heating.

2Ba(NO3)2 → 2BaO + 4NO2 +O2

2Sr(NO3)2 → 2SrO + 4NO2 + O2

2Mg(NO3)2 → 2MgO + 4NO2 + O2

2Be(NO3)2 → 2BeO + 4NO2 + O2

Sulphates are formed by reactions between metals, metal oxides, hydroxides, carbonate, bicarbonates and
sulphuric acid.

Ca + H2SO4 → CaSO4 + H2

Mg(OH)2 + H2SO4 → MgSO4 + 2H2O

BaO + H2SO4 → BaSO4 + H2O

SrCO3 + H2SO4 → SrSO4 + CO2 + H2O.

Be(HCO3)2 + H2SO4 → BeSO4 + 2CO2 + 2H2O

The sulphates are not generally soluble in water and their solubility decrease down the group from Be to Ba. The
sulphates are equally thermo-labile with stability to heat increasing down the group from Be to Ba. In this instance
the decomposition temperature increases down the group with BeSO4 – 580 0C, MgSO4 – 895 0C, CaSO4 – 1149 oC
and SrSO4 – 1374 oC.

MgSO4 → MgO + SO3

CaSO4 → CaO + SO3

They all form ionic hydride by direct reaction of metals with hydrogen

Mg + H2 →MgH2

Sr + H2 → SrH2

Ca + H2 → CaH2

Be + H2 → BeH2

Ba + H2 → BaH2

They also form ionic carbides by direct reaction of metal oxides with carbon at high temperature. The carbides
form hydroxides and acetylene with water.

CaO + 3C → CaC2 + CO

Ca + 2C → CaC2

CaC2 + 2H2O → C2H2 + Ca(OH)2

Calcium carbide react atmospheric nitrogen to form calcium cyanide.

CaC2 + N2 → Ca(CN)2

Ca(CN)2 + 4H2O → CaCO3 + NH4OH

HYDROGEN.

This is the first member of the Periodic Table with atomic number 1, and has only one proton devoid of neutron in
its nucleus. It is the simplest known element. Atomic hydrogen only exists at high temperature. Solid hydrogen has
good conductivity as it exists in the planet, Jupiter.

H(g) + H(g) → H2(g)

Molecular hydrogen H2 is colorless, odourless and non-toxic gas. At one atmosphere, liquid boils at -252.9 0C. It is
the most abundant element in the universe. It is also the tenth most abundant element in the earth crust where it
is found in combination with other elements.

Hydrogen has many industrial applications such as in the synthesis of ammonia, hardening of fats and unsaturated
hydrocarbon and in the fuel cells.

On the ground state, hydrogen has a configuration of 1H. It partly resembles the alkali metals in its oxidized
aqueous state of H+ ion. On the other hand, hydrogen resembles the halogens in its uni-negative hydride ion H-;
which is isoelectronic with He (1s2). It occurs in a large number of covalent compounds. Hydrogen occurs in 3
isotopic forms; 1H, 21D and 31T. Its isotopes have their unique names; proton, deuterium and tritium.

Preparation.

Laboratory scale preparation can be accomplished with reaction between metals and dilute mineral acids.

Zn + 2HCl → ZnCl2 + H2

H2SO4 + Mg → MgSO4 + H2

Electrolysis of water, dilute HCl, NaOH and NaCl is also another way of producing hydrogen. In fact, some industrial
processes are by electrolysis. Commercially, hydrogen can be obtained from reaction between propane and water
at 900 0C in presence of a catalyst. Also by passing steam over heated coke.

C3H8 + 3H2O → 3CO + 7H2

C(s) + H2O(g) → CO(g) + H2(g)

Properties.

1. Hydrogen reduces oxides of metals lower than it in the electrochemical series.

3H2(g) + Fe2O3 → 2Fe + 3H2O.

2. Hydrogen reacts with unsaturated hydrocarbons to produce saturated contemporary with a catalysts.
CH2=CH2 + H2 → CH3CH3

Hydrides.
There are three types of binary hydrides; ionic, covalent and interstitial hydrides.
1. Ionic hydrides are formed when molecular H2 react with alkali and alkaline earth metals. These hydrides
are solid with high melting point temperatures. The hydrides are strong Bronsted bases that accept
protons from donors like water.
2Li + H2 →2LiH
Mg + H2 → MgH2
H-(aq) + H2O → OH- + H2
LiH + H2O → LiOH +H2
2. Covalent hydrides are formed with elements in Groups IIIA to VIIA. Examples include CH4, H2S, NH3, PH3,
HCl Some are polymeric like boranes, silanes and hydrocarbons.
3. Interstitial hydrides are the non-stochiometric hydrides usually formed with transitional metals like iron,
vanadium, nickel e.t.c. In this case the molecular hydrogen dissolves in metals only to be released on
heating e.g. TiH1.8, TiH2.8

Halogens.

Halogens are reactive non-metals belonging to Group VIIA; and these include fluorine, chlorine, bromine, iodine,
astatine and lately, unuseptium.

Properties of halogens.

Property F Cl Br I

Valence electron 2s22p5 3s23p5 4s24p5 5s25p5

Configuration

Melting point oC -223 -102 -7 114

Boiling point oC -187 -35 59 183

Atomic radius (Ǻ) 0.71 0.99 1.14 1.33

Ionic radius (Ǻ) 1.36 1.81 1.95 2.16

Ionization energy 1680 1251 1139 1003

(kJmol-1)

Electronegativity 4.0 3.0 2.8 2.5

Electrode potential (V) 2.82 1.36 1.07 0.53

Bond energy 80.6 242.7 192.5 151.0

X-1(kJmol-1)

Element Astatine (At) is unstable. Molecular halogens occur in diatomic X2 forms.

Preparation.

1. Electrolysis of fluorides and chlorides. At anode: 2F- → F2(g) + 2e

 At cathode: 2H+ + 2e → H2(g)
Overall 2HF(l) → H2(g) + F2(g)
Electrolysis of brine 2NaCl + 2H2O through electrolysis → 2NaOH(l) + H2(g) + Cl2(g).
2. Reaction between NaCl and MnO2
2NaCl + MnO2 + 2H2SO4 → MnSO4 + Na2SO4 + 2H2O + Cl2.

Compounds of halogens.

1. Hydrogen halides can be prepared by direct combination of the elements.

H2 + F2 → 2HF

H2 + Cl2 →→ 2HCl

H2 + Br2 → 2HBr

H2 + I2 → 2HI

These reactions can be rapid and explosive especially with fluorine. HCl and HF can also be prepared from reaction
between metal halides and concentrated H2SO4.

CaF2 + H2SO4 → 2HF + CaSO4

2NaCl + H2SO4 → Na2SO4 + 2HCl

However HI and HBr cannot be produced likewise. This can be achieved by reacting bromine with phosphorus and
then dissolve in water.

P4 + 3Br2 → 4PBr3

PBr3 + 3H2O → 3HBr + H3PO4

Aqueous solutions of hydrogen halides are acidic with acid strength reducing down the group HF>HCl>HBr>HI.

Metallic halides.

These metallic halides can be prepared by reaction between metals and halogen directly.

2Na + Cl2 → 2NaCl

2Fe + 3Cl2 → 3FeCl3

Mg + F2 → MgF2

The metal halides are ionic salts. These metallic halides can also be prepared by reactions between metals, oxide
or hydroxides and hydrogen halides.

2Na + 2HF → 2NaF

K2O + 2HCl → 2KCl + H2O

Ca(OH)2 + 2HCl → CaCl2 + 2H2O

Uses of halogens.

Chlorine plays an important role in human body. It is used as a bleaching agent In the textile and paper industries.
Chlorine is also used in water treatment, production of organochlorine insecticides and in plastic industries in form
of polyvinyl chloride (PVC).

Fluorine is useful in the production of refrigerant Freon and Teflon (Polytetrafluoroethylene) It is also used in the
separation of 235U and 238U isotope in form of UF6.

Bromine is used in the production of insecticide (BrCH 2CH2Br), ethylene dibromide and as AgBr for developing
photographic films.

Iodine is a constituent of thyroid hormone, thyroxin. 50% alcohol solution of iodine known as tincture of iodine is
used as antiseptic. A salt of iodine with silver AgI is used in seeding clouds for artificial rainfall.

NITROGEN AND PHOSPHORUS.

Element Electronic configuration Oxidation State Abundance M. P. 0C B. P. 0C

Nitrogen [He]2s22p3 -3, -2, -1,0, 1, +3, +5 19mg/kg -210 -196

Phosphorus [Ar]3s23p3 +3, +5 1120mg/kg 44 281

Nitrogen and phosphorus are very important elements to life and agriculture in that they are major element of
fertilizers, nitrogen is a major component of the body building block; protein and nitrogen is responsible for
nitrogen fixation in plants. Phosphorus on the other hand, is a major component of nucleic acids that play
important role in genetics and metabolism. Phosphorus in form of calium salt is a major component of bones. They
are both non-metals. Nitrogen occurs freely in the atmosphere where it is a major component of air in which it
constitutes 78% by volume of air. In the earth crust, it occurs as Saltpetre, KNO 3 in India and as Chile Saltpetre
NaNO3 found in the Atacama Desert of Chile. Phosphorus occurs mainly in form of Phosphate mineral like
phosphate rock Ca3(PO4)2.
PDF Compiled by Michael Cole