INORGANIC CHEMISTRY

THE BRAINS PREPA, CHEM HOD

(Dr.) MBAKE COLLINS NYAMA

University Lecturer, Digital Marketer,
PharmD Ongoing
Introduction
This document provides a comprehensive overview of inorganic chemistry, covering
fundamental concepts and specific groups of elements. We will begin with an introduction
to the periodic table, including its history, structure, and the physical states of elements.
The discussion will then focus on S-block elements (Groups 1 and 2), exploring their
general properties, physical and chemical characteristics, and practical applications.

Next, we will examine Group IV elements, with a particular emphasis on the unique
properties of carbon and its compounds. The document will also delve into transition
metals, discussing their electronic structure, physical properties, and chemical behavior,
including the nomenclature of complex ions and the characteristics of ligands.

Furthermore, we will investigate the properties and uses of halogens (Group 17), including
their physical and chemical properties, compounds, and applications. Finally, the document
will touch on the chemistry of nitrogen and sulfur, highlighting their importance in various
chemical processes and applications. Through this exploration, we aim to provide a
thorough understanding of inorganic chemistry principles and their relevance to various
fields.

S-BLOCK ELEMENTS
1.1.1.Characteristics of alkali metals
The common feature of alkali metals (Table 1) is a valence shell composed
ofones-orbital with only one electron (ns1). The valency of the alkali metals is constant. They
always occur in the +I oxidation state. This is related to the persistence of theconfiguration on
shells closer to the kernel (Table 2). Beginning with lithium, the electron is farther from the nucleus
in each successive alkali metal. The detachment with the increase of the atomic mass of the
element. Lithiums have the lowest electronegativity among elements of theperiodic table. Their
electronegativities of this electron is therefore easier,therefore the reactivity of alkali metals
increases are correspondingly: Li–1.0; Na–0.9; K–0.8; Rb –0.8; Cs–0.7, it decreases as the
distance of the valence electron increases.
1.1.1.1. Physical properties of alkali metals
- Structure crystalline.
- Gloss metallic.
- Electrical conductivity very good.
- Colour silvery white.
- Density –very light –lithium, sodium and potassium are less dense than water.
- Melting points –low (30 –180°C).
- Hardness: very soft.
Alkali metals are extremely reactive. To prevent alkali metal from reacting with environment, it is
stored in a container with kerosene or other non-reactive liquid. In the case of rubidium and cesium,
this is not enough. They react with the liquid. Both metals are stored in vacuum glass ampoules
filled with inert gas.
1.1.1.2. Chemical properties of alkali metals
Lithiums are the most reactive chemical elements (the strongest reducing agents).
Lithium has the lowest standard potential (Table 3) because it has a very high hydration energy.
1.1.1.3. Identification of alkali metal salts by flame method
The excited atoms of the elements give a spectrum in the range of visible waves, which are known
as the flame test is used to identify the elements as they colour the flame in a characteristic colour:
-rubidium: violet-pink,
−sodium: yellow,
- lithium : carmine,
−potassium: purple,
−caesium: blue.
1.1.1.4. The reactions of alkali metals
1. Combustion
Only with lithium, the normal product of combustion in air is a simple oxide.
4Li + O2---- Li2O (lithium oxide)
2Na + O2----- Na2O2 (sodium peroxide)
K + O2----- KO2 (potassium superoxide)
Sodium peroxide reacts with carbon dioxide to form sodium carbonate and free
oxygen:
This process is used to remove CO2from the air in submarines and breathing apparatus
2Na2O2 + 2CO2----- 2Na2CO3 + O2
2. Reaction with water (Me any lithium metal)
2Me + 2H2O 2MeOH + H2
Sodium peroxide reacts violently with water to give off hydrogen peroxide:
2Na + H2SO3 Na2SO3+ H2
Dioxidaneis a 3% hydrogen peroxide solution, while its 30% solution is perhydrol. Concentrated
80% hydrogen peroxide (so-called Ignolina) was used in rocket engineering and turbine propulsion
(e.g. during World War II, V1 and V2 rockets and for torpedo propulsion).
3. Reactions with acids: All alkali metals react with acids to give salts and hydrogen:
2Li + 2HCl ----2LiCl + H2
Na2O2 + 2H2O---- 2NaOH + H2O2
6K + 2H3PO4------- 2K3PO4 + 3H2
2.1.1.5. The use of alkali metals:
- Lithium (Li) –additive to alloys, deoxidizer in the production of other metals, for the
production of anodes in batteries with a long life (lithium cell), in medicine (lithium
carbonate used in the treatment of depression);
−Sodium (Na) –metallurgy, soda glass production, fertilizers, coolant in nuclear
reactors, bleaching agents and detergents, kitchen;
- Potassium (K) coolant in nuclear reactors, fertilizers, covering the inside
ofphotocells, grey soap;
−Rubidium (Rb) –component of fluorescent lamps, geochronology and photocells;
- Caesium (Cs) scintillation counters (it is an ionizing radiation detector), catalysts,
photocells;
−Francium (Fr) –uranium ore presence indicator.
1.1.2. Characteristics of alkaline earth metals
They have the ns2 electron configuration –two valence electrons on the s subshell.
As a result of excitation, one of the s electrons goes to the p subshell. Compared to alkali
metals, they have a smaller volume (the greater charge of the nucleus attracts more electrons)
and a greater density (which results from the previous one).The reactivity of alkaline earth
metals, although lower than that of alkali metals, is significant and increases with increasing
atomic number. All beryllium are in the +II oxidation state. They show strong reducing
ofberyllium for the rest of the group, it tends to form covalent bonds, while other metals with
properties. Due to the small size of the atom and the relatively high electronegativity
much larger atom sizes and lower electronegativity occur mainly in ionic compounds.
1.1.2.1. Physical properties of alkaline earth metals (Table 4)
−Metals.
−Silvery white colour.
−Low density.
−Easily fusible.
- Soft (except beryllium).

1.1.2.2. Occurrence of alkaline earth metals

Alkaline earth metals are not free because they are highly reactive. Magnesium and calcium are
common in the earth's crust. Strontium and bar are less common, aberyl is even less common.
Radium occurs only in trace amounts (about 6·107ppm) in uranium ores.
1.1.2.3. Chemical properties of alkaline earth metals
Flame colouring:
−Calcium (Ca) brick red,
- Strontium (Sr)–carmine red (intense red),
−Barium (Ba)yellow green.
1.1.2.4. Beryllium amphoterism
Beryllium is the only s-block element showing an amphoteric character, the rest
are basic in character.

Be + 2HCl ------BeCl2 + H2
Be + 2NaOH + 2H2O------ Na2[Be(OH)4] + H2
All beryllium compounds taste sweet and are highly poisonous. Inhalation
ofberyllium and its compounds may cause serious respiratory diseases, and contact of soluble
beryllium compounds with the skin may cause inflammation.
Group 4 Elements
Carbon, Silicon, germanium, tin and lead

Elements symbol
Carbon C
Silicon Si
Germanium Ge
Tin Sn
Lead Pb
Physical properties
▪ Carbon and silicon are nonmetals.
▪ Germanium is a metalloid
▪ Tin and lead are metal

Electron configuration
General electron configuration of group 4 elements is ns2np2

Oxidation states
The common oxidation state of group IV elements is +2 and +4

Stability of oxidation states

Oxidation state +2 become more stable down the group
Oxidation state +4 become less stable down the group.

For instance carbon burns in oxygen to form carbon (IV) oxide (CO2) whereas lead form
Lead (II) oxide (PbO).

Secondly, CCl4 is stable whereas PbCl4 easily decomposes on heating giving lead (II)
chloride and chlorine
PbCl4 (g) (heat) →PbCl2 (s) + Cl2 (g)

Reasons for variation of stability of oxidation states

Down the group IV; +2 oxidation state become more stable due to inert pair effect i.e. the
two s-electron do not participate in the bonding due to increase in the energy difference
between ns and np electrons.

Properties of compound with +2 and +4 oxidation states

(i) Compounds in oxidation state +4 are predominantly covalent because formation M4+
requires a lot energy whereas compound in oxidation state +2 are ionic

This explains the fact that PbCl4 is soluble in organic solvents like ethanol whereas PbCl2
does not.
 Note that
a. covalent compounds are soluble in organic solvents whereas ionic compounds do
not.
b. Covalent compound have low melting and boiling points whereas ionic compounds
have high melting and boiling point.
c. Covalent compounds do not conduct electricity whereas ionic compounds do. On
this basis compound in oxidation state +4 show properties of covalent compounds
because they are predominately covalent.
Chemical properties
(a) Reaction with water
Carbon does not react with cold water but reacts with steam to form water gas
C(s) + H2O(g) → CO(g) + H2(g)

Silicon, germanium and Tin do not react with water up to 100 0C because they are
protected by thin layer of oxide. But they react with steam at very high temperatures to
form dioxides

Ge(s) + 2H2O(g) → GeO2(s) +2H2(g)

Lead reacts with soft water (water that contains oxygen) to form lead II hydroxide.
Pb(s) + 2H2O(g) + O2(g) → Pb(OH)2(s)

Reaction with acids

(i) Dilute non oxidizing acid like HCl.
C, Si, and Ge do not react

Sn liberates hydrogen
Sn(s) + 2H+(aq) Sn2+(aq) + H2(g)

Pb lead does not react with dilute hydrochloric acid and sulphuric acid due to
formation of insoluble salts.

(ii) Nitric acid

With concentrated nitric acid.

C, Si, Ge and Sn react to form dioxide

C(s) + 4HNO3(aq)→ CO2(g) +4NO2(g) + 2H2O(l)

Pb reacts to form lead II nitrate and nitrogen dioxide.

Pb(s) + 4HNO3(aq) → Pb(NO3)2(aq) + 2NO2(aq)+ 2H2O(l)

With 50% nitric acid.

 Pb reacts to form lead II nitrate and nitrogen monoxide.
3Pb(s) + 8HNO3(aq) → 3Pb(NO3)2(aq) + 2NO(aq)+ 4H2O(l)

(iii) With sulphuric acid Dilute sulphuric acid

C, Si and Ge do not react.
Sn and Pb reacts dilute concentrated sulphuric acid liberating hydrogen.
Pb (s) + H2SO4(aq) → PbSO4(s) + H2(g)

With hot Concentrated sulphuric acid

C, Si and Ge react to form dioxides
C(s) + 2H2SO4(aq) → CO2(g) + 2SO2(g) +2H2O(l)

Sn and Pb reacts hot concentrated sulphuric acid liberating sulphur dioxide .

Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) +2H2O(l)

Sn(s) + 2H2SO4(aq) → SnSO4(s) + SO2(g) +2H2O(l)

(iv) With acetic or ethanoic acid C, Si Ge and Sn do not react.

Pb reacts ethanoic acid in presence of air giving lead II ethanoate and
water Pb (s) + 4CH3COOH(aq) + O2(g) → Pb(CH3COO-)2(aq)
+2H2O(l)

Reaction with sodium hydroxide C

does not react.

Si Ge and Sn react liberating hydrogen and silicate (IV), germates (IV) and stannates
(IV) respectively

Si (s) + 2NaOH(aq) + H2O(l) → Na2SiO3(aq) + 2H2(l)

Lead reacts to form plumbates (II).

Pb(s) + 2NaOH(aq) → Na2PbO2(aq) + 2H2(g)

Unique characteristics of carbon

1. Forms gaseous oxides, the rest form solid oxides

Note that
a. Carbon dioxide is a gas because its molecules are bonded by weak van der Waal
forces.

b. Silicon dioxide is a solid of high melting point because each silicon atom is bonded
to four oxygen atom by strong covalent bonds.
 2. Catenation: carbon forms chains, rings and branches with single, double and triple
bonds while others do not

3. Forms compounds mainly with oxidation sate (IV); other elements form compounds
with oxidation states +2 and +4.

4. Carbon tetrachloride and carbon tetrahydride do not hydrolyze in water. Chlorides of

other elements hydrolyze in water.

5. Carbon form CF4 and not CF6-2

Reason for uniqueness of carbon

❖ Has a very small atomic radius
❖ Has high electronegativity
❖ Lacks easily accessible d-orbital in its valence shell.

Allotropes of carbon
Allotropy is the existence of two or more different physical forms in the same state of a
chemical element.

An allotrope is any of the different physical form in the same state into which a chemical
element can exist.

Carbon exists in two main allotropes, i.e. graphite and diamond.

a. Graphite
In graphite, each carbon atom is covalently bonded to 3 carbon atoms to form a layer of
hexagons. Each layer is bonded to another by weak van der Waal forces.

Properties of graphite as a result of its structure

1. Has open structure and low density.
2. It is slippery and used as a lubricant.
3. Has unbonded π-electron that is free to move about making graphite a good
conductor of electricity and heat

b. Diamond
Structure of diamond
Each carbon atom is bonded tetrahedrally to four carbon atoms to form a 3D compact
structure by strong covalent bonds. As a result diamond has a high density, melting and
boiling point. It is the hardest substance known.

Diamond is used as an ornament, and to drill and cut other substances.

Differences between diamond and graphite

1. The density of graphite (2.3 gcm-3) that of diamond (3.5 g cm-3)
2. Diamond is very hard while graphite is soft
3. Graphite is slippery while diamond is not
4. Graphite conducts electricity while diamond does not.

Experiment to show that graphite and diamond are allotropes of carbon

When equal masses of graphite and diamond are burn in air, they give equal volume of
carbon dioxide.

Compounds of carbon
1. Hydrides: they include alkanes, alkenes, alkyne and aromatic compounds studied in
organic chemistry
2. Halides of carbon
Carbon forms all the four tetrahalides: CF4, CCl4, CBr4 and CI4
Comments
a. The melting points of halides increase with molecular. All tetrahalides are volatile
liquids
b. The stability of the halides decrease from CF4 > CCl4 > CBr4 > CI4 due to decrease
in the bond strengths as electronegativity of the halogen decrease.
c. CCl4 is a good solvent, being very stable and heavier than air; is used in fire
extinguisher to protect the burning substance from oxygen.
d. CCl4 is not hydrolyzed by water due to lack of accessible d-orbital to accommodate
the lone pair of electron from water and weaken the C-X bond.

3. Oxides f carbon
(a) Carbon monoxide (CO)

Preparation
 By dehydration of methanoic acid with concentrated sulphuric acid.
HCO2H(l) + Conc. H2SO4(l) → CO(g) + H2O(l)

Uses of carbon monoxide

(i) It reduces most metal oxides to metals.
Fe2O3 (s) + 3CO (g) → 2Fe (s) + 3CO2 (g)
NiO (s) + CO (g) → Ni (s) + CO2 (g)

This property is employed industrially in the extraction of iron and nickel.

It is used to purify nickel: it forms a volatile carbonyl that decompose to give a pure
metal 900C
Ni (s) + 4CO(g) Ni(CO)4(g)
1800C
Ni(CO)4(g) Ni (s) + 4CO (g)

(ii) It is used preparation of carbonyl chloride that is used in the production of

polyurethane form of plastics and pesticides.
CO (g) + Cl2 (g) → COCl2 (g)
[carbonyl chloride]

(iii) It reacts with fused NaOH under pressure to give sodium methanoate.
Methanoic acid is produced from this salt by the addition of dilute HCl.

NaOH (l) + CO (g) → HCOONa (s)

then HCOO- (aq) + H+ (aq) → HCOOH (l)

Methanoic acid is used to produce insecticides and for dyeing, tanning, and
electroplating.

(b) Carbon dioxide (CO2)

Preparation
By decomposition of calcium carbonate
CaCO3(s) (heat) → CaO(s) + CO2(g)
Limestone quick lime

Uses of carbon dioxide

a. Flavors fizzy drinks.
b. It is heavy and stable so is used in fire extinguishers to displace oxygen from burning
objects.
Carbonic acid
Preparation
By reacting carbon dioxide and water. There is however, equilibrium in solution of carbonic
acid, hydrogen ions, hydrogen carbonate and carbonate ions.
CO2 (g) + H2O (l) ↔ H2CO3 (aq)
H+(aq) + HCO3- (aq) ↔ 2H+ (aq) + CO32- (aq)

Structure of carbonic acid

Has 3 resonance hybrid whose bond lengths are intermediate between a C=O and C-O
bonds

Carbonates and hydrocarbonate

✓ Both react with acids to liberate carbon dioxide
CO32- (aq)+ 2H+ (aq) → H2O (l) + CO2 (g)
HCO3- (aq)+ H+ (aq) → H2O (l) + CO2 (g)
✓ CO32- forms white ppt with Mg2+ whereas HCO3- does not.

Silicon
Existence
Exists as silica, SiO2 or sand used for building or making glass.

Chemical properties of SiO2

Reaction with NaOH
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
SiO2(s) + 2-OH (aq) → SiO32- (aq) + H2O (l).

Chemical properties of SiO2

(a) Reaction with NaOH
SiO2(s) + 2NaOH(aq) → Na2SiO3(aq) + H2O(l)
SiO2(s) + 2-OH (aq) → SiO32- (aq) + H2O (l).

(b) Reaction with HF

SiO2(s) + 4HF(g) → SiF4(aq) + H2O(l)
SiF4(aq) + 2HF(aq) → H2SiF6(aq)

(c) Reaction of silicon with acids

Silicon does not react with most acids under normal conditions but is dissolved by
hydrofluoric acid, HF, to form fluorosilicic acid, a reaction apparently driven by the stability of the
Si(IV) fluoride complex
 [SiF6]2-.
Si(s) + 6HF(aq) → 2H2(g) +H2SiF6 (aq) (fluorosilicic acid)

Germanium, tin and lead

Points to note
a. They form compounds with oxidation states +2 and + 4. The stability of compounds with
oxidation states +2 increases down the group due to ‘inert pair effect’ while those of
oxidation states +4 decreases down the group.

b. Compounds with oxidation state +2 are reducing. For instance tin II ions reduce iron III
ions to iron II ions.
Sn2+(aq) + Fe3+(aq) → Sn4+(aq) + Fe2+(aq)

c. Compounds with oxidation state +4 are oxidizing. For instance lead IV oxide ions
oxidizes HCl ions to chlorine
PbO2 (s)+ 4HCl (aq) → PbCl2(s) + 2H2O (l) + Cl2 (g)

d. Compounds with oxidation state +4 are predominantly ionic whereas those in oxidation
state +4 are predominantly covalent. This explains the fact that PbCl 2 is soluble in water
but insoluble in ethanol whereas PbCl4 is soluble in ethanol

Chemical properties
The principal reactions of germanium and tin are similar, both elements exhibiting oxidation
state of 4

The principal reactions of lead are summarized below

a. Lead IV halide
Lead forms ionic Pb4+(F-)4, and covalent liquid PbCl4.
The tetra-bromide and tetra-iodide do not exist, presumably because bromine and iodine
are not sufficiently strong oxidizing agents to convert Pb2+ to Pb4+.

Lead IV chloride Preparation

By reacting lead IV oxide with cold concentrated hydrochloric acid.
PbO2 (s) + 4 HCl (aq) (conc. and cold) → PbCl4(aq) +2H2O(l)

Effect of Heat on Lead (IV) chloride

Decomposes on heating liberating chlorine
PbCl4 (g) (heat) → PbCl2 (s) + Cl2 (g)

Hydrolysis of lead (IV) chloride

Lead tetrachloride is readily hydrolyzed by water (white fumes of HCl and brown
precipitate of PbO2 are observed)
PbCl4 (s) + 2H2O (l) → PbO2 (s) + 4HCl (aq)
Reaction of lead (IV) chloride with sodium hydroxide solution
Lead(IV) chloride react with sodium hydroxide to produce lead(IV) oxide, sodium chloride and water.
Sodium hydroxide - diluted solution.

PbCl4 + 4NaOH → PbO2 + 4NaCl + 2H2O

The compound PbO2 reacts with the sodium hydroxide to produce the hexahydroxoplumbate (IV)
ion [Pb(OH)6]2−, soluble with the water.
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]

b. Lead II halide
Preparation
By reacting soluble salt like lead nitrate with soluble halide
Pb2+(aq) + 2X-(aq) → PbX2(s) ( X = F, Cl, Br, I).
E.g. Pb2+(aq) + 2Cl-(aq) → PbCl2(s)

Properties
Except the iodide, which is yellow, they are white solids. Lead (II) chloride forms
 chlorocomplexes, e.g., [PbCl4]2-, with Cl- ions and because of this, it is soluble in
concentrated hydrochloric acid.

Reaction of lead (II) chloride with sodium hydroxide solution

Lead II chloride reacts with sodium hydroxide solution to form lead (II) hydroxide which
dissolves in excess sodium hydroxide to form sodium plumbate (II)
PbCl2 (s) + 2OH-(aq) Pb(OH)2(s) + 2Cl-(aq)
Then
Pb(OH)2(s) + 2OH-(aq) Pb(OH)42-(aq)

c. Lead IV oxide Preparation

(i) Lead (IV) oxide, PbO2, is a brown solid obtained by oxidation of a soluble lead (II)
salt with hot sodium chlorate (I).

Pb2+(aq) + H2O(l) + ClO- (aq) → PbO2(s) + Cl-(aq) + 2H+(aq)

(ii) By action of nitric acid on trilead tetra oxide, Pb3O4.

Pb3O4 (s) + 4HNO3 (aq) → 2Pb(NO3)2(aq) + PbO2(s) + 2H2O(l)

Chemical properties of lead (IV) oxide

(i) Decomposes on heating
2PbO2 (s) + heat → 2PbO (s) + O2 (g)
(ii) Reacts with cold concentrated hydrochloric acid to form a yellow liquid lead (IV)
chloride and water
PbO2(s) + 4HCl (aq) → PbCl4(l) + 2H2O(l)
Lead(IV) chloride react with ammonium chloride to form a yellow solid of ammonium
hexachloridoplumbate(IV).
PbCl4 + 2NH4Cl → (NH4)2[PbCl6]

(iii) Oxidize hot concentrated hydrochloric acid to chlorine PbO 2(s) + 4HCl(aq) → PbCl2
(s) + 2H2O(l) + Cl2(g)

React with the sodium hydroxide to produce the hexahydroxoplumbate (IV) ion [Pb(OH)6]2−, soluble
with the water.
PbO2 + 2NaOH + 2 H2O → Na2[Pb(OH)6]

Qualitative analysis of Pb2+

1. Forms a white precipitate with sodium hydroxide soluble in excess
Pb2+(aq) + 2OH-(aq) → Pb(OH)2 (s) + 2OH-(aq) → Pb(OH)42- (aq)
2. Forms white precipitate with ammonia solution insoluble in excess
Pb2+(aq) + 2OH-(aq) → Pb(OH)2 (s)
3. Forms yellow precipitate with potassium iodide Pb2+(aq) + 2I-(aq) →
PbI2 (s)
4. Forms white precipitate hydrochloric acid soluble on warming Pb 2+(aq) +
2CI-(aq) → PbCI2 (s)
5. Forms white precipitate with sulphate ions
Pb2+(aq) + SO42-(aq) → PbSO4 (s)
 TRANSITION METALS
The transition metals are elements in the d-block of the periodic table with a partially filled
d-orbital. They lose electrons to form positive ions with the s-orbital electrons being removed
first.

All transition metals have similar physical properties including atomic radius, high densities
and high melting and boiling points. They all also have special chemical properties:

● They form complexes

● They form coloured ions
● Variable oxidation states
● Good catalysts.

Complexes
These form from transition metals, consisting of a central metal ion or atom surrounded by
ligands.

They can also be represented in formulas using square brackets.

Ligands
These are molecules or ions with a lone electron pair that is able to form a coordinate bond
to the central metal ions by donating this electron pair. Common ligands include:

● Cl-
● H2O
● NH3
Coordination Number
This is equal to the number of coordinate bonds formed around the central metal ion. Silver
complexes have a coordination number of 2 and platinum complexes commonly have a
coordination number of 4.

3.2.5.2 - Ligand Substitution Reactions

The ligands NH3 and H2O are similar in size and are both uncharged. This means they can be
exchanged without a change in coordination number via a ligand substitution reaction.

Example:

With copper complexes and NH3 in excess, this substitution is incomplete and the complex
formed has a combination of water and ammonia ligands.

Example:

This complex ion product forms as a deep blue solution.

The Cl- ligand is much larger than the NH 3 and H 2O ligands meaning substitution with this
ligand results in a change in coordination number for that complex.

Example:

Complexes with just Cl- ligands always have a coordination number of four, producing a
tetrahedral shaped complex.
Bidentate Ligands
These ligands are able to form two coordinate bonds to the central metal ion as they have two
lone electron pairs. There are two common bidentate ligands:

● Ethanedioate ions - a lone electron pair on two of the oxygen atoms

● Ethane-1,2-diamine - a lone electron pair on each of the nitrogen atoms

These can replace two unidentate ligands but the coordination number remains at six as six
coordinate bonds still form.

Example:
Multidentate Ligands
These ligands are able to form up to six coordinate bonds to the central metal ion as they
have multiple lone electron pairs. The most common multidentate ligand is EDTA
(ethylenediaminetetraacetic acid). It forms six coordinate bonds in a ligand substitution reaction.

Example:

Haem, a component of haemoglobin is another common multidentate ligand. It consists of six

coordinate bonds around a central Fe2+ ion. Its shape and structure allow it to transport oxygen
around the body.

Example:

Carbon monoxide is toxic to humans as it replaces the oxygen in the haem complex thus
preventing it from being transported around the body.

The Chelate Effect

In ligand substitution reactions, a positive entropy change is favourable as it means a more
stable complex is being formed. Therefore it is favourable to have more moles on the right than
the left.
This is achieved by substituting unidentate ligands with bidentate or multidentate ligands, known
as the chelate effect.

The greater the entropy change, the more negative the free energy change (∆G) will be,
therefore meaning the reaction is more favourable.
Enthalpy Change
The enthalpy change (∆H) for ligand substitution reactions is very small as the bonds being
formed are very similar to the bonds that were broken. Therefore overall enthalpy change is
near zero.

3.2.5.3 - Shapes of Complex Ions

Octahedral Complexes
Transition metal complexes with H2O and NH3 ligands commonly form octahedral complexes
with a bond angle of 90o.

Example:

Cis-trans Isomerism
This type of isomerism is shown by octahedral complexes with different types of unidentate
ligands. Ligands of the same type can either be next to or opposite each other. The trans
isomer has two of the same ligands opposite each other and the cis isomer has them next door
to each other.

Example:
Optical Isomerism
This type of isomerism is shown by octahedral complexes with bidentate ligands. The two
isomers are mirror images of each other.

Example:

Tetrahedral Complexes
When complexes form with larger ligands such as Cl-, they form tetrahedral complexes with a
bond angle of 109.5o. Tetrahedral complexes can also show optical isomerism.

Example:

Square Planar Complexes

Platinum and Nickel complexes form in a square planar shape. This consists of four
coordinate bonds with a bond angle of 90o.

Example:
Linear Complexes
Silver complexes always have a linear shape with two coordinate bonds around the central
metal ion. The bond angle is 180o.

Example:

This is the type of complex present in Tollen’s reagent, [Ag(NH3)2]+.

Cisplatin
This is the cis isomer of a square planar complex of platinum. It is commonly used as a
cancer therapy drug.

Cells in the natural world are chiral so only one isomer of the drug will be the correct orientation
to ‘fit’ the cells. Therefore only this single isomer will work and cure the disease.

Cisplatin can cause serious side effects such as hair loss, meaning it has to be administered in
small amounts to try and reduce these effects.
 HALOGENS
Introduction
Halogens are elements of group VII of the periodic table. Halogens are also
known as salt formers because they readily react with metals to form
salts. They have an outer electronic configuration of ns2 np5.
The elements include fluorine, chlorine, bromine, iodine and astatine
NB; astatine does not occur nationally because it is a radioactive element

PHYSICAL PROPERTIES OF HALOGENS

A) Physical state and structure; halogens consist of diatomic molecules

in which the two halogen atoms are joined together by Joined by a
single covalent bond. They all exist in simple molecular structures with
with the molecules held together by weak van der Waals forces.
Fluorine is a pale yellow gas, chlorine is a greenish yellow gas,
bromine is a red liquid while iodine is a shiny black solid. the trend in
physical state from gas to liquid and then to solid down the group is
due to an increase in the strength of Van der waals forces which
increases with molecular mass and the number of electrons.
B) Boiling points; Halogens are volatile. This is because the molecules
are held by weak van der waals forces. The boiling points increases
down the group from fluorine to iodine due to an increase in van der
waals forces.
C) Electron affinity; the electron affinity increases from fluorine to chlorine
and then decreases to iodine.
The exceptional low value of Fluori6is die to the repulsion of the non
bonding electrons as a result of their close proximity. The decrease
from chlorine to iodine is due to the decrease in effective nuclear
attraction
D) Solubility; all halogens except fluorine are slightly soluble in water.
Fluorine is a powerful oxidizing agent. Its oxidises water to oxygen.
The halogens being non-polar simple molecules are more soluble in organic
solvents. The colour of the solution depends on the particular halogen
and solvent. in non polar solvent such as the tetrachloromethane and
cyclohexane, chlorine is colourless, bromine is red and iodine is violet.
In these solvents’ the element exists as relatively free molecules as in
the gas phase. In polar solvent in (electron donating) solvents such as
water and ethanol, chlorine is colourless, bromine gives a yellow
orange solution while iodine gives a reddish brown solution.
 LABORATORY PREPARATION OF HALOGENS
All halogens are poisonous and therefore they should be prepared in a fume
cupboard.
Flooring is difficult to prepare. the other halogens can be prepared by
oxidising the appropriate hydrogen halide. the usual oxidising agents
are manganese dioxide or potassium permanganate.
Chlorine is prepared by heating a mixture of concentrated hydrochloric
acid and manganese (IV) oxide or potassium permanganate. the acid
is oxidised to liberate chlorine.
MnO2(s) + 4HCl(aq) ---- MnCl2(aq) + 2H2O(l) + Cl2(g)
Bromine is prepared by warming a mixture of potassium iodide,
manganese (IV) oxide and concerntrated sulphuric acid.
Bromine is separated from the reaction mixture by distillation
2KBr(s) + MnO2(s) + 2H2SO4(aq) - K2SO4(aq) + MnSO4(aq) + 2H2O(l) +
Br(l)
Iodine is prepared by warming a mixture of potassium iodide, manganese
(IV) oxide and concerntrated sulphuric acid. Iodine is separated from
the reaction mixture by sublimation.
2KI(s) + MnO2(s) + 2H2SO4(aq) K2SO4(aq) + MnSO4(aq) + 2H2O(l) +
I2(s).
 OXIDATION STATES

CHEMICAL PROPERTIES OF HALOGENS

The reactivity of halogens decreases down the group due to decrease in
election affinity. the exceptional high reactivity of fluorine is due to it
very low bond the dissociation entherapy and ability to form very stable
 bonds with other elements. the F-F bond is weak because of the small
size of the fluorine atom brings the lone pairs of elections closer
together than in other halogens. as a result, repulsion between the
lone pairs of electron weakens the F-F bond.

OXIDIZING PROPERTIES
Halogens are highly oxidizing and will oxidize both metals and non metals. the
oxidizing power decreases down the group due to a decrease in
hydration energy and electronegativity.
a) Displacement reactions
The difference in their oxidizing power is illuminated by the displacement
of the halogens lower in the group from their salts in solution.
• Fluorine will oxidize chloride, bromide and iodine ions
• Chlorine will oxidize bromide and iodide ions
• Bromine will oxidize iodide ions
b) Reaction with water
Fluorine oxidizes water to oxygen
2F2(g) + 2H2O (l) 4HF(aq) + O2(g)
Chlorine reacts less readily. It dissolves in water and then reacts to produce a
mixture of hydrochloric acid and chloric (I) acid.
C) Reaction with alkalis
Fluorine reacts with cold dilute alkalis to form oxygen difluoride
with warm concentrated alkali, oxygen is formed.
Chlorine, bromine and iodine undergo disproportionation with alkalis. The
products depend on the reaction conditions.
Disproportionation reaction is a redox reaction in which a molecule, ion or
atom is simultaneously reduced and oxidized.

COMPOUNDS OF HALOGENS
1. Hydrogen halides; the hydrogen halides are HF, HCl, HBr, and HI.
They are all gases at room temperature except hydrogen fluoride which is a
liquid due to hydrogen bonding between the molecules.
a.Laboratory preparation;
Hydrogen chloride and hydrogen fluoride are prepared by the
action of concentrated sulphuric acid on metal halides.
Sulphuric acid is less volatile due to its high boiling point and there
fore displaces hydrogen chloride and hydrogen fluoride from the
corresponding metallic halides
Hydrogen bromide and hydrogen iodide are prepared by ;
A) Hydrolysis of phosphorous trihalides
The element is reacted with red phosphorus in water. Phosphorus reacts with
the element to form PX3 which is immediately hydrolyzed
B) Reaction between a halide and concerntrated phosphoric acid.
Concentrated phosphoric acid is used to produce the halides because it is
relatively non volatile and is a poor oxidizing agent. Concentrated
Phosphoric acid reacts with alkali metal halides to produce hydrogen
halides
b. Melting and boiling points;
The melting and boiling points increase from HCl to HI due to an increase in
van der waals forces which increase with molecular mass and the
number of electrons . The exceptional high value of HF is due to the
strong intermolecular hydrogen bonds between the molecules.
 NITROGEN
Nitrogen is found in group V of the periodic table. It is a diatomic gas and
make up about 7i% by volume of the air. It exists in an uncombined
state because of its small atomic radius and high electronegativity

OXIDATION STATES
Nitrogen exhibit oxidation states of -3 to +5 in it's compounds

COMPOUNDS OF NITROGEN
A) Ammonia
Manufacture
Ammonia is manufactured by the Haber process. This involves the direct
combination of nitrogen and hydrogen.
The reaction is reversible and it is exothermic.
Nitrogen is obtained by fractional distillation of liquid air. Hydrogen is obtained
from natural gas
The gases are passed on activated charcoal or zinc oxide to purify them by
removing carbon monoxide, water vapour and sulphur compounds
 which may poison the catalyst.

Properties of ammonia
a. Basic properties ; the lone pair of electrons on nitrogen in ammonia
permits it to behave as a Lewis base.
b. As reducing agents; It is oxidized to nitrogen in the reaction with
chlorine and some heated metal oxides

Uses of ammonia
1 used in thee manufacture of fertilizers
2 used to soften hard water
3 used in the manufacture of nitric acid

B) Nitric acid
Nitric acid is manufactured by the catalytic oxidation of ammonia in the
Ostwald process.
Ammonia obtained from the Haber process is mixed with excess dust free air.
The reaction is exothermic and the head evolved keeps the catalyst chamber
at the temperature of the reaction.
The gases are cooled and mixed with excess air.
Properties of nitric acid
a. Acidic properties; it is a very strong acid, it neutralizes bases and
alkalis to form metallic nitrates and water.
b. As an oxidizing agent ; the oxidizing power is due to its ability to
accept electrons. .
Uses of nitric acid
1 use in the manufacture of drugs
2 as a rocket fuel
3 in the manufacture of fertilizers

SULPHUR
Sulphur is found in group VI of the periodic table.
It has an atomic number of 16
OXIDATION STATES

Allotropes of sulphur
Sulphur have two main allotropes which are;
1 Rhombic : a yellow transparent octahedral crystal.
2 Monoclinic sulphur; amber colour, long, thin needle shape crystal.

Reactions of sulphur
A with metals
Sulphur combines directly with most metals to form sulphides when
heated in the absence of air
B with non metals
Sulphur burns with a blue flame when heated in oxygen to produce sulphur
dioxide
C with acids
Sulphur is oxidized by concentrated nitric and sulphuric acid which are
strong oxidizing agents.
 COMPOUNDS OF SULPHUR
Hydrogen sulphide
Hydrogen sulphide is a colourless and highly toxic gas with a rotten egg
small, prepared by the action of dilute hydrochloric acid on iron (II)
sulphide in the Kipp's apparatus
Sulphuric acid
sulphuric acid is a corrosive, colourless and oily acid manufactured by the
contact process.
Sulphur obtained from the frasch process is roasted in air to produce sulphur
dioxide
The sulphur dioxide is mixed with excess air and the gaseous mixture is
purified by passing it through electrostatic dust precipitators to remove
dust and other impurities like arsenic compounds which may poison
the catalyst.

Properties of sulphuric acid

1 Acidic properties ; it is a strong acid in aqueous solution

2 Dehydrating properties; concentrated sulphuric acid acts as a dehydrating
agent, it remove chemically combined water or elements of water from
a compound with the formation of a new one.

Uses of sulphuric acid

• Manufacture of sulphate fertilizers
• Electrolyte in lead accumulator
• Petroleum refining mostly in the extraction of alkenes
• Production of acid