G. C. E. (Advanced Level) Chemistry Grade 12: Unit 6: Chemistry of S, P and D Block Elements
G. C. E. (Advanced Level) Chemistry Grade 12: Unit 6: Chemistry of S, P and D Block Elements
G. C. E. (Advanced Level) Chemistry Grade 12: Unit 6: Chemistry of S, P and D Block Elements
(Advanced Level)
CHEMISTRY
Grade 12
Department of Science
Faculty of Science and Technology
National Institute of Education
www.nie.lk
I
Chemistry
Resource Book
Grade 12
Department of Science
Faculty of Science and Technology
National Institute of Education
Sri Lanka
II
Message from the Director General
The National Institute of Education takes opportune steps from time to time for the
development of quality in education. Preparation of supplementary resource books for
respective subjects is one such initiative.
Supplementary resource books have been composed by a team of curriculum developers of the
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are in line with the G. C. E. (A/L) new syllabus implemented in 2017, students can broaden
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I wish to express my sincere gratitude to the staff members of the National Institute of
Education and external subject experts who made their academic contribution to make this
material available to you.
III
Message from the Director
Since 2017, a rationalized curriculum, which is an updated version of the previous curriculum
is in effect for the G.C.E (A/L) in the general education system of Sri Lanka. In this new
curriculum cycle, revisions were made in the subject content, mode of delivery and curricular
materials of the G.C.E. (A/L) Physics, Chemistry and Biology. Several alterations in the
learning teaching sequence were also made. A new Teachers’ Guide was introduced in place
of the previous Teacher’s Instruction Manual. In concurrence to that, certain changes in the
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events, assessment and evaluation.
When implementing the previous curricula, the use of internationally recognized standard
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to the contradictions of facts related to the subject matter between different textbooks and
inclusion of the content beyond the limits of the local curriculum, the usage of those books was
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overcome that issue.
As this book is available in Sinhala, Tamil, and English, the book offers students an opportunity
to refer the relevant subject content in their mother tongue as well as in English within the
limits of the local curriculum. It also provides both students and teachers a source of reliable
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This book authored by subject experts from the universities and experienced subject teachers
is presented to you followed by the approval of the Academic Affairs Board and the Council
of the National Institute of Education. Thus, it can be recommended as a material of high
standard.
Dr. A. D. A. De Silva
Director
Department of Science
IV
Guidance
Dr. (Mrs.) T. A. R. J. Gunasekara
Director General
National Institute of Education
Supervision
Dr. A. D. A. De Silva
Director, Department of Science
National Institute of Education
Mr. R. S. J. P. Uduporuwa
Former Director, Department of Science
National Institute of Education
Subject Leader
Mrs. M. S. Wickramasinghe
Assistant Lecturer, Department of Science
National Institute of Education
Mrs. G. G. P. S. Perera
Assistant Lecturer, Department of Science
Mr. V. Rajudevan
Assistant Lecturer, Department of Science
Writing Panel
Dr. M.N. Kaumal - Senior Lecturer, Department of Chemistry,
University of Colombo (Unit 6)
V
Mrs. H.M.D.D. D. Manike - SLTS-1, Viharamhadevi Balika Vidyalaya,
Kiribathgoda
Mr. S. Thillainathan - SLTS-1 (Rtd), Hindu Ladies College, Colombo 06
Miss. S. Veluppillai - SLTS-1 (Rtd), Hindu Ladies College, Colombo 06
Mrs. M. Thirunavukarasu - SLTS-1 (Rtd), Hindu Ladies College, Colombo 06
Mrs. S. Rajadurai - SLTS-1 (Rtd), St. Peters' College, Colombo 04
Language Editing
Dr. Chandra Amarasekara
Consultant, National Institute of Education
Mr. M. A. P. Munasinghe
Chief Project Officer (Rtd.), National Institute of Education
Cover Page
Mrs. R. R. K. Pathirana
Technical Assitant, National Institute of Education
Supporting Staff
Mrs.Padma Weerawardana
Mr. Mangala Welipitiya
Mr. Ranjith Dayawansa
VI
Content
s Block Elements
4.1 Group 1 elements………………………………………………………………….122
4.1.1 Group trends
4.1.2 Reactions of Group 1 elements
4.1.3 Thermal stability of salts
4.1.4 Solubility of Group 1 salts
4.1.5 Flame test
4.2 Group 2 elements………………………………………………………………….126
4.2.1 Group trends
4.2.2 Reactions of alkaline earth Group 2 elements
4.2.3 Thermal stability of salts
4.2.4 Solubility of Group 2 salts
4.2.5 Flame test
p Block Elements
4.3 Group 13 elements…………………………………………………………………130
4.3.1 Group trends
4.3.2 Aluminium
4.4 Group 14 elements…………………………………………………………………132
4.4.1 Group trends
4.4.2 Diamond and graphite
4.4.3 Carbon monoxide and carbon dioxide
4.4.4 Oxoacid of carbon
4.5 Group 15 elements…………………………………………………………………135
4.5.1 Group trends
4.5.2 Chemistry of nitrogen
4.5.3 Oxoacids of nitrogen
4.5.4 Ammonia and ammonium salts
4.6 Group 16 elements…………………………………………………………………140
4.6.1 Group trends
4.6.2 Hydrides of Group 16
4.6.3 Oxygen
4.6.4 Sulphur
4.6.5 Oxygen containing compounds
4.6.6 Hydrogen peroxide
4.6.7 Sulphur containing compounds
4.6.8 Oxoacids of sulphur
4.7 Group 17 elements…………………………………………………………………147
4.7.1 Group trends
4.7.2 Simple compounds of Group 17
4.7.3 Reactions of chlorine
VII
4.8 Group 18 elements…………………………………………………………………152
4.8.1 Group trends
4.8.2 Simple compounds of group 18 elements
4.9 Periodic trends shown by s and p block elements……………………………….153
4.9.1 The valence electron configuration
4.9.2 Metallic character
4.9.3 Reactions of third period oxides with water, acids and bases
4.9.4 Acid, base and amphoteric nature of hydroxides and hydrides
4.9.5 Nature of the halides across the third period
d Block Elements
4.10 Transition elements………………………………………………………………158
4.10.1 Occurrence
4.10.2 Properties of fourth period d block elements
4.10.3 Oxides of d block oxides
4.10.4 Chemistry of some selected d block oxides
4.10.5 Coordination compounds of transition metal ions
4.10.6 Nomenclature of simple complex ions and compounds
4.10.7 Factors affecting the colour of the complexes
4.10.8 Importance of d block elements
4.10.9 Identification tests for selected cations of d block elements
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
4. Chemistry of s, p and
d Block Elements
Content
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Introduction
This section describes the physical and chemical properties of elements in s, p and d
blocks. This section will help to identify trends and patterns among elements in the
periodic table.
s Block Elements
Sodium can be found naturally as various salts such as NaCl (rock salt) and
Na2B4O7·10H2O (borax). Some examples of naturally occurring potassium salts are KCl
(sylvite) and KCl·MgCl2·6H2O (carnallite).
Li Na K Rb Cs
Ground state electronic
[He]2s1 [Ne]3s1 [Ar]4s1 [Kr]5s1 [Xe]6s1
configuration
Metallic radius/ pm 152 186 231 244 262
Melting point/ °C 180 98 64 39 29
Radius of M+/ pm 60 95 133 148 169
1st ionization energy/ kJ mol-1 520 495 418 403 375
2nd ionization energy/ kJ mol-1 7298 4562 3052 2633 2234
Increase in the atomic radius from Li to Cs makes the ionization energy of these elements
to decrease down the group, and this can be used to explain the chemical properties of
Group 1 elements. Reactivity of the Group 1 elements increases down the group.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Li Na K Rb Cs
Vigourously
Gently Vigorously Explosively Explosively
with ignition
Lithium reacts non-vigorously with water or with water vapour available in the air to
produce lithium hydroxide and hydrogen gas. However, both sodium and potassium react
vigorously with water to produce metal hydroxide and hydrogen gas. These reactions are
highly exothermic except with Li.
Group 1 metal oxides react with water to produce metal hydroxides as shown below.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
When heated, lithium forms lithium nitride with nitrogen. Only lithium forms a stable
alkali-metal nitride. With water, lithium nitride produces ammonia and lithium hydroxide.
Group 1 hydroxides react with carbon dioxide to produce relevant carbonates. These
carbonates can further react with carbon dioxide to produce metal hydrogen carbonates.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Decomposition of carbonates
Carbonates are stable and they will melt before they decompose into oxides. However,
Li2CO3 is less stable and decomposes readily.
Decomposition of bicarbonates
Decomposition of bicarbonates of Group 1 is shown below.
Solubility of Group 1 halides increase down the group is shown in Table 4.2.
Variation in the solubility can be understood using the energy cycle for the solvation of
ionic solids. The solubility can be explained using Gibbs free energy. For almost all ionic
solids of Group 1, are soluble in water due to the negative Gibbs free energy in the
solvation process.
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Enthalpy and entropy cycles for the solvation process are shown below.
Figure 4.1 Enthalpy and entropy cycles for the solvation process
Using these two energy cycles, enthalpy and entropy change of solvation can be
calculated and these calculated values are given in Table 4.3. Free energy is calculated
using the equation,
ΔGϴ = ΔHϴ - T ΔSϴ
Calculated Gibbs free energies match with the solubility trend for the sodium halides. The
free energy change gets more negative from sodium fluoride to sodium iodide.
Elements of Group 2 have higher densities and stronger metallic bonds compared to the
Group 1 metals. This is due to the availability of a greater number of electrons to form a
stronger metallic bond and their smaller size in atomic radii.
The first ionization energies of Group 2 elements are higher than that of Group 1 elements
due to their electron configuration of ns2. Elements become more reactive and produce
+2 oxidation state easily down the group. The properties of Group 2 elements are given
in Table 4.4.
Be Mg Ca Sr Ba
Ground state electronic
[He]2s2 [Ne]3s2 [Ar]4s2 [Kr]5s2 [Xe]6s2
configuration
Metallic radius/ pm 112 160 197 215 224
Melting point/ °C 1560 923 1115 1040 973
Radius of M2+/ pm 30 65 99 113 135
1st ionization energy/ 899 736 589 594 502
kJ mol-1
2nd ionization energy/ 1757 1451 1145 1064 965
kJ mol-1
3rd ionization energy/ 14850 7733 4912 4138 3619
kJ mol-1
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Decomposition of carbonates
Thermal stability of these carbonates increases down the group. Thermal stability of these
carbonates increases with the size of the cation. The polarizing power of the cation
decreases down the group due to the decrease of charge density of the cation. Carbonate
anion attached to Mg2+ cation is highly polarized than that of carbonate attached to Ba2+.
Highly polarized carbonate anion can undergo decomposition easily and this explains the
lower decomposition temperature of MgCO3 than that of BaCO3.The general
decomposition of metal carbonates is shown below.
MCO3 MO + CO2
Decomposition temperature increases from 540 °C for MgCO3 to 1360 °C for BaCO3.
Decomposition of bicarbonates
Group 2 hydrogen carbonates are only stable in aqueous solutions and solid Group 2
hydrogen carbonates are not stable at room temperature.
Salts of Group 2 metals with uninegative anions, such as chloride and nitrates are
generally soluble. However, salts formed with anions containing more than one negative
charge, such as carbonates and phosphates, are insoluble. All carbonates are insoluble
except BeCO3. Hydrogen carbonates are more soluble than carbonates. The solubility of
Group 2 sulphates changes from soluble to insoluble when comparing solubility from
MgSO4 to BaSO4. On the other hand, hydroxides change solubility from insoluble to
soluble when moving down the group. For example, Mg(OH)2 is sparingly soluble
whereas Ba(OH)2 is soluble and produces a strongly basic solution.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
p Block Elements
configuration
Metallic radius/ pm - 143 153 167 171
Covalent radius/ pm 88 130 122 150 155
Melting point/ °C 2300 660 30 157 304
3+
Radius of M / pm 27 53 62 80 89
st
1 ionization energy/
799 577 577 556 590
kJ mol-1
2nd ionization energy/
2427 1817 1979 1821 1971
kJ mol-1
3rd ionization energy/
3660 2745 2963 2704 2878
kJ mol-1
**Not a part of current G. C. E. (A/L) syllabus
4.3.2 Aluminium
Aluminium is the third most abundant element in the earth crust. The exposed surface of
aluminium produces a layer of Al2O3. This layer makes aluminium resistant to further
reactions with oxygen. Due to this impermeable layer, Al can be considered as a non-
reactive element with air.
Reactions of aluminium
Aluminium reacts readily with O2 and halogens. Also, it reacts with N2.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Aluminum is less reactive than Groups 1 and 2 elements. Similar to beryllium, aluminium
reacts with both acids and bases. The equations for the reactions of Al with acids and
bases are given below.
Group 13 elements can have six electrons in their valence shell by forming three covalent
bonds due to their ns2np1 electron configuration. As a result, many of the Group 13
covalent compounds have an incomplete octet, so can act as Lewis acids to accept a pair
of electrons from a donor. These compounds with incomplete octet are called electron
deficient compounds. Both B and Al compounds with incomplete octet form dimers in
the gaseous phase to satisfy the octet rule (Figure 4.2).
Cl Cl Cl
Al Al
Cl Cl Cl
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Carbon can be found in nature mainly in coal, crude oil, calcite (CaCO3), CO2 in air,
magnesite (MgCO3) and dolomite (CaCO3·MgCO3). Graphite, diamond and fullerenes
are the allotropic forms of carbon. Fullerenes are recently found, and most well-known
fullerene is C60, buckminsterfullerene (or bucky-ball). Carbon is the basis of life and the
most important element in organic chemistry. Silicon and germanium are mainly used in
the semiconductor industries. In addition, silicon is heavily used in inorganic polymer
industry.
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Fullerenes are another series of carbon allotropes. In fullerenes, carbon atoms are
connected in a spherical manner. Structures of graphite, diamond and fullerene (C60) are
shown in Figure 4.4.
Figure 4.4 Structures of (a) graphite, (b) diamond and (c) fullerene (C60)
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Carbon monoxide is mostly used as a reducing agent in the production of iron. Also, CO
plays an important role in many catalytic reactions as a ligand due to the lone pair of
electrons on the C atom.
Carbon dioxide (Figure 4.6) solidifies due to London forces at low temperatures and/ or
under high pressures. Solid CO2 (dry ice) sublimes to produce gaseous carbon dioxide
under normal atmosperic conditions. It is commonly used as a freezing agent in the food
industry and to produce artificial rain.
Hydrogen atom which is directly connected to oxygen atom can be released as a proton
to the solution by exhibiting the acidic property of carbonic acid.
Carbon dioxide reacts with bases to produce carbonates showing its acidic property. In
the presence of excess CO2 thus formed carbonates of Group 1 and 2 produce hydrogen
carbonates.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Since nitrogen is an inert gas its chemical reactions occur under strong conditions. For an
instance nitrogen gas reacts with oxygen in the presence of external energy from an
elctrical spark. This reaction naturally occurs in lightening.
Nitrogen shows oxidation states from –3 to +5. Compounds with these oxidation states
are shown in Table 4.9.
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-2 Hydrazine N2H4
-1 Hydroxylamine NH2OH
0 Dinitrogen N2
+1 Dinitrogen N2O
monoxide
+2 Nitrogen NO
monoxide
+3 Dinitrogen N2O3
trioxide
+4 Nitrogen NO2
dioxide
+4 Dinitrogen N2O4
tetroxide
+5 Dinitrogen N2O5
pentoxide
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Nitrous acid can undergo disproportionation to produce nitric acid and nitrogen monoxide
which is a colourless gas.
Futher reaction of nitrogen monoxide with oxygen forms nitrogen dioxide which is redish
brown in colour.
Nitric acid (Figure 4.9) is an oily and hazardous liquid. This acid is a strong oxidizing
agent and can undergo vigorous chemical reactions.
Due to the light-induced decomposition, nitric acid produces oxygen and nitrogen
dioxide.
hν
4HNO3(aq) 4NO2(g) + O2(g) + 2H2O(l)
Due to this reason concentrated nitric acid is stored in brown colour glass bottles in
laboratories.
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The reactions of conc. HNO3 acting as an oxidizing agent with non metals such as carbon
and sulphur are given below.
Like any other base it reacts with dilute acids to produce aqueous salts.
Hydrolysis of the ammonium ion in aqueous solution produces the conjugate base,
ammonia.
Reactions of ammonia
Ammonia acts as a reducing agent with chlorine, and the products vary with the amount
of ammonia and chlorine used. In the presence of excess ammonia, chlorine produces
nitrogen gas as one of the products. However, with excess chlorine, nitrogen trichloride
is produced as one of the products, which is used for water disinfection.
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The formed HCl further reacts with unreacted ammonia to form NH4Cl. excess chlorine,
Nitrogen trichloride is a covalent chloride. It reacts with water to produce ammonia and
hypochlorous acid. Due to the ability to produce hypochlorous acid, nitrogen trichloride
is used as a water disinfecting agent.
Gaseous ammonia reacts with hydrogen chloride to produce a white smoke of solid
ammonium chloride. This can be used as a confirmation test for ammonia.
Ammonia can act as an oxidizing agent as well as an acid with metals under dry condition.
However, anions in some ammonium salts can oxidize the ammonium ion to produce
many products upon heating.
Reactions of nitrate
Reaction of nitrate with iron(II)/ conc. sulphuric acid can be used to identify nitrate ion.
This test is known as brown ring test. The brown coloured [Fe(NO)]2+ ring formed in the
test tube, confirms the presence of nitrate.
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H2 O H2 S H2Se H2Te
Melting point/ °C 0.0 -85.6 -65.7 -51
Boiling point / °C 100.0 -60.3 -41.3 -4
Bond length/ pm 96 134 146 169
Bond angle/ ° 104.5 92.1 91 90
Due to the extensive hydrogen bonding, H2O shows abnormally high boiling and melting
points than the other hydrides of the group. Water is the only non-poisonous hydride
among all the other hydrides of the group.
The observed varation in bond length of covalent hydrides is due to the increase of size
of the central atom. Therefore, bond length increases down the group.
The covalent bond angle decreases as you come down in the group due to the less
repulsion of the bonding electrons as a result of electronegativity of the central atom
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
decreases down the group. In H2S, H2Se and H2Te the bond angles become close to 90°.
This may also suggest that almost pure p orbitals on selenium and tellurium especially
are used for binding with hydrogen.
4.6.3 Oxygen
Oxygen has two allotropes, dioxygen (O2) and trioxygen (ozone, O3). Dioxygen is a
colourless and an odourless gas which is slightly soluble in water. Ozone has a pungent
odour. Ozone has a bond angle of 111.5°. Structure of these two allotropes are shown
below.
(a) (b)
Metals react with dioxygen to produce metal oxides. Ozone is a powerful oxidizing agent
stronger than dioxygen. Ozone is used to disinfect water in many developed countries to
kill pathogens. Unlike chlorine, ozone does not produce any harmful byproducts in the
disinfection process.
4.6.4 Sulphur
Sulphur can be classified as it is explained below.
Sulphur
Crystalline Amorphous
Unlike oxygen, sulphur forms single bonds with itself rather than double bonds. The most
commonly occurring allotrope is rhombic sulphur which is referred to as α-sulphur (α-
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
S8). It has a crown shape with eight-membered ring that has a cyclic zigzag arrangement
as shown below. When heated above 93 °C, α-S8 changes its packing arrangement to the
other commonly found form of monoclinic sulphur, β-sulphur (β-S8). These two forms
are allotropes of each other.
Figure 4.12 (a) crown form of S8 (b) Rhombic sulphur (c) Monoclinic sulphur
Crystalline form of rhombic and monoclinic sulphur consist of S8 rings in the shape of
crown. These can be packed together in two different ways to form rhombic crystals and
to form needle shaped monoclinic crystals as shown above. Below 95 °C the rhombic
form is the most stable allotropic form of sulphur.
(a) (b)
Water is the most widely used solvent. Water ionizes as follows. This is reffered to as
self-ionization of water.
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An amphiprotic molecule can either donate or accept a proton. Therefore, it can act as an
acid or a base. Water is an amphiprotic compound since it has the ability to accept and
release a proton. The amphoteric nature of water is shown below
Due to the extensive hydrogen bonding, H2O2 is a viscous liquid H2O2 can act as an
oxidizing as well as a reducing agent. It oxidizes to oxygen and reduces to water.
Reducing half-reaction;
Oxidizing half-reaction;
Disproportionation;
Reactions of H2O2
H2O2 as an oxidizing agent;
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2KMnO4(aq)+3H2SO4(aq)+5H2S(g) K2SO4(aq)+5S(s)+2MnSO4(aq)+8H2O(l)
K2Cr2O7(aq)+4H2SO4(aq)+3H2S(g) K2SO4(aq)+Cr2(SO4)3(aq)+3S(s)+7H2O(l)
Sulphur dioxide
Sulphur dioxide is a colourless gas and soluble in water. Sulphur dioxide can act as an
oxidizing and a reducing agent.
As a reducing agent;
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Sulphuric acid
Sulphuric acid is a strong diprotic acid. Sulphur trioxide reacts with water to produce
sulphuric acid.
With metals,
With nonmetals,
Dilute sulphuric acid is a strong acid which can protonate to give two H+ ions to water as
shown below.
H2SO4(aq) + 2H2O(l) SO42-(aq) + 2H3O+(aq)
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Sulphurous acid
Due to the air oxidation of sulphurous acid, it always contains a small amount of sulphuric
acid. The reaction of gaseous sulphur dioxide and water produces sulphurous acid. The
sulphurous acid reacts with dissolved oxygen in water to produce sulphric acid. Structure
of the sulphurous acid is shown below. This acid is a weaker acid than sulphuric acid.
Thiosulphuric acid
Only the salts of thiosulphuric acid are stable and thiosulphate ion can oxidize as well as
reduce to give sulphur and sulphur dioxide as its products. Thiosulphuric is a weak acid.
In aqueous solutions, thiosulphuric acid can decompose to produce a mixture of sulphur
containing products.
Structures of thiosulphuric acid and thiosulphate ion are shown below. The oxidation
state of the central sulphur atom is +4 where as the terminal sulphur is zero in both
structures.
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
Oxidizing ability of halogens decreases down the group. Fluorine is a powerful oxidizing
agent. The reactivity of halegons decreases down the group. This can be explained by
using the displacement reactions of halegons.
Fluorine and chlorine are gases with pale yellow and pale green colours respectively at
room temperature. Bromine is a red-brown fumming liquid and iodine is a violet-black
solid with lustrous effect.
The bond energy of F2 (155 kJ mol-1) is less than that of Cl2 (240 kJ mol-1) due to repulsion
between the non-bonded electron pairs of fluorine atoms. This is a reason for the high
reactivity of fluorine gas. Down the Group 17 bond energies show a gradual decrease
(Cl2 = 240 kJ mol-1, Br2 = 190 kJ mol-1 and I2 = 149 kJ mol-1).
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G.C.E. (A/L) CHEMISTRY: UNIT 6 Chemistry of s, p and d block elements
F Cl Br I **At
Ground state
electronic [He]2s22p5 [Ne]3s23p5 [Ar]3d104s24p5 [Kr]4d105s25p5 [Xe]4f145d106s26p5
configuration
van der Waals 135 180 195 215 -
radius/ pm
Ionic radius X-/ pm 133 181 196 220 -
Covalent radius/pm 71 99 114 133 -
Melting point/ °C -220 -101 -7.2 114 -
Boiling point/ °C -188 -34.7 55.8 184 -
Pauling 4.0 3.2 3.0 2.7 -
electronegativity
Electron gain -328 -349 -325 -295 -
enthalpy/ kJ mol-1
X(g) + e X-(g)
**Not relevant to the current G. C. E. (A/L) Chemistry Syllabus
HF is a weak acid whereas the other hydrogen halides are strong acids in the aqueous
medium. HF has the high bond energy (strongest covalent bond), which makes it difficult
to dissociate in water to produce H+ ions readily. The acidic strength of hydrogen halides
increases down the Group 17. This can be explained using the same fact mentioned above.
Some selected properties of Group 17 hydrogen halides are shown in Table 4.13.
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HF HCl HBr HI
Melting point/ °C -84 -114 -89 -51
Boiling point / °C 20 -85 -67 -35
Bond length/ pm 92 127 141 161
Bond dissociation energy/ kJ mol-1 570 432 366 298
Silver halides
Silver halides can be used to identify the halides (chloride, bromide, and iodide) using the
colour of the precipitate. Few selected properties are shown below.
+3 ClO2-
+5 ClO3-
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Chlorine forms four types of oxoacids. The acidic strength increases with the increasing
oxidation number of the chlorine atom. The stuctures and the oxidation states of oxoacids
are given in the Table 4.16.
The oxidation state of chlorine in HClO, HClO2, HClO3, HClO4 respectively are +1, +3, +5
and +7. The higher the oxidation state the stronger the acid will be. Therefore the variation
of acidic strength is HClO < HClO2 < HClO3 < HClO4.
Halides
Most covalent halides react vigorously with water. But CCl4 does not hydrolyze. Most
fluorides and some other halides are inert.
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In this reaction, zero oxidation state of chlorine (Cl2) oxidize to +1 (HOCl) and reduce
to -1 (Cl¯).
Reactions of oxoanions
ClO ̅ is stable at low temperatures and disproportionates at high temperature to produce
Cl ̅ and ClO3 ̅ . However, both BrO ̅ and IO ̅ are not stable even at low temperatures
and undergo disproportionation.
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Under acidic conditions, HOCl is more stable than ClO ̅ , which makes disproportionation
predominant under basic conditions.
He Ne Ar Kr Xe
Ground state
electronic 1s2 [He]2s22p6 [Ne]3s23p6 [Ar]3d104s24p6 [Xe]4d105s25p6
configuration
Atomic radius/ pm 99 160 192 197 240
1st ionization energy/ 2373 2080 1520 1350 1170
kJ mol-1
Electron gain 48.2 115.8 96.5 96.5 77.2
enthalpy/ kJ mol-1
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+2 XeF2
+4 XeF4
+6 XeF6
+6 XeO3
+8 XeO4
Group number 1 2 13 14 15 16 17 18
1 2 2 1 2 2 2 3 2 4 2 5
Valance shell ns ns ns np ns np ns np ns np ns np ns2np6
electron
configuration
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The third period shows a gradual increase in melting point and then a decrease across the
period. Most abundant elemental form, type of bonding between similar atoms and the
melting point of the third period elements are shown below.
Table 4.19 Most abundant elemental form, type of bonding between similar atoms and
the melting point of the third period elements
Na Mg Al Si P4 S8 Cl2 Ar
Melting point/ °C 98 649 660 1420 44 119 -101 -189
Bonding type M M M NC C C C -
Metallic – M, Network covalent – NC, Covalent - C
Across the third period variation of type of bonding in oxides in which the elements are
at their highest oxidation number are given below.
Oxides with the highest oxidation number are considered to compare the chemical nature.
The nature from strong basic on the left to strong acidic to the right can be seen.
Amphoteric nature can be seen in the middle of the series.
4.9.3 Reactions of third period oxides with water, acids and bases
Oxides of sodium and magnesium react with water to produce hydroxides.
As these two oxides are basic, they react with acids to produce salt and water.
Aluminum oxide is amphoteric and it reacts with acids as well as with bases to produce
salts.
SiO2 is weakly acidic and reacts with strong bases. Also, SiO2 shows no reaction with
water.
P4O10, SO3, and Cl2O7 are acidic and produce acids when dissolved in water. Those
reactions are shown below.
These oxides also react with bases to produce salts and water.
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Nature of hydrides of third period varies from strong bases to strong acids across the
period. Amphoteric nature can be seen in the middle of the series.
Hydrides of sodium and magnesium react with water to produce basic solutions.
PH3 is weakly soluble in water and produces a neutral solution. H2S and HCl are acidic
and aqueous solutions are also acidic.
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Group 15 can be used to understand the variation of properties down the group. Down a
group the ionization energy decreases, and the metallic nature increases. Use the
information given for the Group 15 and correlate the variation in ionization energies with
the increase of metallic properties down the group. Both N and P are nonmetals and
produce acidic oxides. However, As and Sb oxides are amphoteric and bismuth oxide is
basic.
Reactions with water of group 15 halides are given in the respective section under the
halides of group 17.
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d Block Elements
Both Zn and Sc are d block elements (last electron is filled to a 3d orbital). However, Zn
is considered as a non-transition element due to the absence of a partially filed d subshell
at the elemental stage and Zn2+ ion. Sc can be considered as a transition element since Sc
contains partially filed d subshell at the elemental stage.
Group 3 4 5 6 7 8 9 10 11 12
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Pauling 1.3 1.5 1.6 1.6 1.5 1.9 1.9 1.9 1.9 1.6
electronegativity
Atomic 162 147 134 128 127 126 125 125 128 137
radius/pm
Covalent 144 132 122 118 117 117 116 115 117 125
radius/pm
Ionic radius (M2+)/ - 100 93 87 81 75 79 83 87 88
pm
Transition metal ions have less variation in atomic radii across a period than that of the
main group elements. Across the period of the transition metals shown in Table 4.23, the
atomic radii decrease slightly and then increase. Across the period, to each d electron
added nuclear charge is also increased by one. The decrease of the atomic radii at the
middle of the period (from Sc to Ni) occurs due to the predominance of attraction power
of nuclear charge increase than the repulsion among the electrons. However, at the end of
the period (Cu and Zn), radii of the atoms increase due to greater repulsion among
electrons as electrons are paired in d orbitals.
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4.10.1 Occurrence
Elements on the left of the 3d series (fourth period d block elements) exit commonly in
the nature as metal oxides and cations combined with anions.
Element Example
Ti FeTiO3 (Ilmenite) and TiO2 (Rutile)
Fe Fe2O3 (Haematite), Fe3O4 (Magnetite) and FeCO3 (Siderite)
Cu CuFeS2 (Copper Pyrite)
The highest possible oxidation number that a d block element can show is the sum of 4s
and 3d electrons. Transition metals are also capable of producing variable oxidation states
similar to p block elements and show the ability to interconvert among their oxidation
states. Therefore, they can act as oxidizing as well as reducing agents.
First five elements achieve the maximum possible oxidation state by losing all 4s and 3d
electrons. With the filling of more 3d electrons, towards the right end of the period, the
3d orbitals become greater in energy as the nuclear charge of the atom increases. This
makes d electrons are harder to remove. The most common oxidation state for these
elements is +2 due to the loss of 4s electrons.
Reactivity
d block elements do not react with the water while s block elements react with water
vigorously. The 4s electrons of the d block elements are tightly bound to the nucleus due
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to the higher nuclear charge than that of the s block elements. First ionization energy of
d block elements lies between the values of those of s and p block elements.
Ionization energies of fourth period d block elements are higher than that of the s block
elements in the same period. The first ionization energies of d block elements are increase
slightly across the period when move from left to the right of the period. Variation of the
first ionization energy across the d block is less than that of s and p block elements.
Increase in the nuclear charge across the fourth period d block elements expect to be
increase the first ionization energies due to the greater attraction towards the 4s electrons.
However, in all d block elements, extra electrons are inserted in to the 3d orbital moving
from left to right across the period, and these d electrons shield the 4s electrons from the
inward attraction of the nucleus. Because of these two counter effects, the ionization
energy of d block elements increases slightly across the period. Successive ionization
energies of the fourth period d block elements are shown in the table given below.
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Table 4.27 Successive ionization energies of fourth period d block metals, K and Ca.**
** For K, only first and second ionization energies are given to understand the energy
increase due to removal of an electron from an inner orbital.
First ionization energies of d block elements are higher than those of s block elements in
the same period. This explains the less reactivity of d block elements than the s block
elements.
All d block elements are metals because 4s electrons in d block elements can be released
easily to form cations. Metallic character of the d block elements increases down the
group.
All d block elements in the fourth period are solids with high melting and boiling points.
Melting and boiling points of d block elements are extremely high as compared to those
of s and p block elements. d block elements are moderately reactive.
Except metal ions with 3d0 and 3d10 configurations, d block metal compounds produce
characteristic colours. This means transition metal ion complexes can produce coloured
compounds. Most d block metal ions form complex compounds.
Electronegativity
Table below provides the electronegativity of d block elements and can be used to
understand the variation of electronegativity of d block elements in the fourth period.
Electronegativity increases with the atomic number. However, Mn and Zn are deviated
from the trend due to their stable electron configuration. Due to the higher nuclear charge,
d block elements have higher electronegativity than that of the s block elements.
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Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6
When an atom exhibits variable oxidation states, the higher oxidation state has higher
electronegativity.
Catalytic properties
Most transition metals and compounds can act as catalysts due to the presence of partially
filed and empty d orbitals. This makes d orbitals to accept or donate electrons. This
property makes them effective components of catalysts. Pd for hydrogenation, Pt/Rh for
oxidation of ammonia to nitrogen oxide, and V2O5 for oxidation of SO2 to SO3 and
TiCl3/Al(C2H5)6 for the polymerization of ethene are some examples for the use of d block
element and its compound as a catalyst. Some popular organic reactions such as alkylation
and acylation are done in the presence of transition metal ion as the catalyst.
Table 4.28 Colours of d block metal ions and oxoanions in aqueous solutions. The
number of 3d and 4s electrons are shown in brackets next to the metal ion.
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Generally, if the metal is in a lower oxidation state, the oxide is basic. Also, if the metal
is in a moderate oxidation state, the oxide is amphoteric and metal oxides with higher
oxidation state are acidic. This explains why the compounds in Tables 4.29 and 4.30 with
lower oxidation states are more metallic while compounds with higher oxidation states
are more non-metallic in properties.
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Even without partially filled d subshells (Cr at +6 oxidation state), both chromate and
dichromate produce colours due to the electron charge transfer between Cr and O ligands.
However, the explanation of this phenomena is not a part of the current syllabus.
The reduction of Cr6+ to Cr3+ happens only in acidic medium. In acidic medium, CrO42-
ions will dimerized and converted into Cr2O72- ions. Therefore in acidic medium Cr6+
present only as Cr2O72-.
In CrO42-, oxidation number Cr is +6. Therefore it can act as an oxidizing agent. Under
acidic conditions, Cr(IV) can be reduced to Cr(III).
Compound Colour
MnO2 Dark brown/black
KMnO4 Purple
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Ligands (Lewis bases) can donate electrons to the central metal ion (Lewis acid) to form
dative bonds with it.
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[Ni(NH3)6]Cl2 = 2Cl ̶
In this example, ammonia molecules are bonded as ammine ligands to the central metal
ion of Ni2+. The charge of the complex ion can be easily determined using the following
equation.
Oxidation number of
The charge of the Total charge of
= the central metal atom +
complex all ligands
or the ion
Example 6.1
Calculate the oxidation number of the central metal ion in [Ni(H2O)3Cl3] ̅
complex ion.
Answer:
Oxidation number of
The charge of the Total charge
= the central metal atom +
complex of all ligands
or the ion
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Naming of ligands
Name of an anion acting as a ligand in the complex ion can be obtained by removing the
last letter of the anion name and adding ‘o’ letter to the end. Neutral molecules acting as
ligands are usually given the name of the molecule. However, there are some exceptions
and those are not discussed in the current G. C. E. (A/L) Chemistry syllabus.
Number of a particular ligand is indicated by prefixes. The used prefixes are di – two, tri
– three, tetra – four, penta – five, hexa – six, etc.
Complex anions
For negatively charged complex ions (complex anions) the suffix ‘ate’ must be used after
the name of the metal.
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Name of a complex compound must have the name of the cation first and the anion name
second. These two names must be separated by a space.
Coordination number
The number of coordination bonds formed between the central metal ion and ligands is
defined as coordination number. Since some ligands can form more than one coordination
bond with the central metal ion, it is incorrect to define the coordination number as the
number of ligands coordinated to the central metal ion. The coordination number depends
on the size, charge, nature of ligands and the electronic configuration of the central metal
ion.
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Table 4.34 Colours of transition metal ion complexes depends on the factors
Ability to form coloured compounds is a unique property of the transition metal elements.
Colours of some common metal complexes are given in Table 4.33.
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With excess
OH-
[Zn(OH)4]2-
Colourless
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Reactions of [Cr(H2O)6]3+
With aqueous NH3, the violet colour [Cr(H2O)6]3+ aqueous solution will be turned into a
blue-green gelatinous precipitate.
Reactions of [Co(H2O)6]2+
With strong base (NaOH); the pink colour [Co(H2O)6]2+ aqueous solution turns into pink
precipitate.
Co(OH)2 is a pink precipitate. With excess concentrated hydroxide ion solutions, a deep
blue solution is formed.
With NH3
Initially, the pink colour [Co(H2O)6]2+ forms a pink colour Co(OH)2 precipitate with
limited amount of concentrated NH3 and on further addition of concentrated NH3 it forms
a yellow colour [Co(NH3)6]2+ complex ion. However due to the auto-oxidation,
[Co(NH3)6]2+ complex convert to a brown colour [Co(NH3)6]3+. Because of this, the
solution appears as yellowish-brown solution.
With conc. HCl, pink colour solution turns into a blue colour solution.
Reactions of [Ni(H2O)6]2+
With a strong base, the green colour [Ni(H2O)6]2+ aqueous solution turns into a green
precipitate.
With excess NH3(aq), the green colour [Ni(H2O)6]2+ solution turns into a deep blue
solution.
With concentrated HCl, green colour solution turns into a yellow colour solution.
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Reactions of [Mn(H2O)6]2+
With strong base, pale pink colour [Mn(H2O)6]2+ aqueous solution turns to a white/ cream
colour precipitate.
With aqueous NH3, the pale pink colour solution turns into a white/ cream colour
precipitate.
Reactions of [Fe(H2O)6]3+
With strong base, yellow colour [Fe(H2O)6]3+ aqueous solution turns into a reddish-brown
precipitate.
With aqueous NH3, yellow colour [Fe(H2O)6]3+ aqueous solution turns into a reddish-
brown precipitate.
Reactions of [Cu(H2O)6]2+
With strong base, the blue colour [Cu(H2O)6]2+ aqueous solution turns into a blue
precipitate.
With a limited amount of aqueous NH3, blue colour solution turns into a blue precipitate.
With excess aqueous NH3, blue colour solution turns into a deep blue colour complex.
With concentrated HCl, blue colour solution turns into a yellow colour solution.
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Reactions of [Zn(H2O)6]2+
With limited amount of strong base, colourless [Zn(H2O)6]2+ aqueous solution turns into
a white precipitate.
With excess strong base; white precipitate turns into a colourless clear solution.
The colourless solution turns into a white precipitate, then with excess base, the
precipitate dissolves to form a colourless solution.
1. Fe2+
Formation of KFe[Fe(CN)6], a dark-blue precipitate of with K3[Fe(CN)6], can
be used to identify Fe2+.
2. Fe3+
Formation of Fe4[Fe(CN)6]3, Prussian-blue complex of with K4[Fe(CN)6], can
be used to identify Fe3+.
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3. Cr3+
Oxidation of Cr3+ to yellow colour solution of CrO42¯
Addition of excess of sodium hydroxide to a Cr3+ solution followed by a few
milliliters of 6% hydrogen peroxide form a yellow colour solution of CrO42¯.
Reference:
Atkins, P. Overton, T. Shriver and Atkins' Inorganic Chemistry, 5th Edition, 2010.
Brown, T. E. LeMay, H. E. Bursten, B. E. Chemistry: The Central Science, 13th Edition,
2015
Prakash, S. Advanced Inorganic Chemistry, 2000
Sodhi, G. S. Principle of Inorganic Chemistr, 2nd Edition, 2015
Svehla, G. Vogel's Qualitative Inorganic Analysis, 6th Edition, 1987
Tuli, G. D. Madan, R. D Malik, W. U Selected Topics in Inorganic Chemistry,
5th Edition, 2014
NOMENCLATURE OF INORGANIC CHEMISTRY (IUPAC Recommendations
2005)
Rayner-Canham, Geoff Descriptive Inorganic Chemistry, 6th Edition, 2013.
Lee, J. D. Concise inorganic chemistry, 5th Edition, 1996.
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