CHM 302

Semester 1 – 2022/23

Inorganic Chemistry III – 3 Units

Pre-requisite: CHM 212

Dr Thompson Izuagie
Where to find me:
Room C15, Department of Chemistry
[email protected]; [email protected]

Personal website: https://thomizuagie.com

LECTURE 1

Hydrogen
 Text books
• Inorganic Chemistry, 4th Ed by C. E. Housecroft and A. G. Sharpe;
Pearson Education Limited.
• Inorganic Chemistry, 6th ed. by M. T. Weller, T. Overton, J. Rourke, F.
Armstrong; Oxford University Press.
• Inorganic Chemistry, by James E. House; AP, Elsevier.
• Descriptive Inorganic Chemistry, 5th ed., by Geoff Rayner-Canham
and Tina Overton; W. H. Freeman and Company, New York.

Course materials
• There will be a handout for each lecture. Handouts can be
downloaded from my personal website: https//:thomizuagie.com or
will be made available to the Class Rep at the office of the Secretary
to the HOD at least a day before the lecture.
• Tutorials will provide valuable support.
• Other useful materials will be made available in due course.
 Outline
 Hydrogen
 Electronic structure, general properties and comparative study of
• Group 1
• Group 2 elements.
 Chemistry of
• Boron
• Carbon and Silicon
• Nitrogen and Phosphorus
• Oxygen and Sulphur
• The Halogens.
• Transition elements.
 The Noble gases
 Separation of metals.
 Co-ordination Chemistry.
 Ligand and Crystal field theories.
 Introduction to Radiochemistry
 Radioactivity and the periodic table.
 Objectives
• To develop a good understand of the elements, their
existence and extraction, properties and reactivities and
applications.
• To develop a good understand of trends in the properties
of elements in Groups 1, 2, 13, 14, 15, 16, 17 and 18.
• To become more familiar with the concepts and principles
of Co-ordination Chemistry.
• To become more familiar with Ligand and Crystal field
theories.
• To introduce the concept of Radiochemistry
 Review of CHM 212
 Chemistry of First row transition (d-block) metals

 Introduction to co- ordination chemistry including elementary

treatment of crystal field theory.

 Comparative Chemistry of the following elements:

a) Ga, In, TI,

b) Ge, Sn, Pb,

c) As, Sb, Bi

d) Se, Te, Po.

 Elementary introduction to Organometalic Chemistry.

 Role of metals in biochemical Systems.

 Periodic Table of the Elements
An Overview
s block p block
1-2 13 - 18
1 18
IA VIIIA
2 13 14 15 16 17
1A IIA
d block 8A
IIIA IVA VA VIA VIIA
3 - 12
2A 3A 4A 5A 6A 7A
3 4 5 6 7 8 9 10 11 12
IIIB IVB VB VIB VIIB VIII IB IIB
3B 4B 5B 6B 7B 8 1B 2B
 Hydrogen
 Hydrogen is the MOST ABUNDANT element in the Universe
 It is the TENTH most abundant element in the Earth’s crust, where it
occurs mainly in the form of water (e.g. in oceans), minerals, and in all
forms of life (e.g. as hydrocarbons, plant and animal materials).

Ocean Plants Animals

 The hydrogen atom has only one electron with a ground-state configuration
1s1
 Dihydrogen, H2 is the stable form of elemental hydrogen. It is colourless,
odourless gas, sparingly soluble in all solvents.
 Hydrogen is considered as the ‘FUEL OF THE FUTURE’, Why?
i. because it is very available from renewable resources (water and
sunlight)
ii. its clean and highly exothermic reaction with O2.
 Two disadvantages for its direct use as fuel are
 Its volatility and
 low energy density of H2.
 Isotopes of Hydrogen
 There are 3 isotopes of hydrogen:
Isotopes of hydrogen

Protium or hydrogen Deuterium Tritium

(1H) (D, 2H) (T, 3H)
is the lightest and is radioactive.
most abundant
 IR spectroscopy can be used to differentiate the different isotopes
in a compound due to their mass difference.
Deuterated compounds
 Compounds where the hydrogen have been replaced with Deuterium are called
DEUTERATED COMPOUNDS and are used for a number of purposes e.g.
solvents in NMR spectroscopy. E.g. D2O, CD3OD, CDCl3

QUIZ
 With reasons, where do you think is the best position for hydrogen in the periodic table?
 Why is dihydrogen inert? And how do we make it react?
 Properties and Reactions of Hydrogen
 Hydrogen has unique atomic properties that place it in a unique position
in the periodic table.
 It ranges in character from being a strong Lewis acid (as the hydrogen
cation, H+, the proton) like Group 1 elements to being strong Lewis base
(the hydride ion, H–) like the Group 17 elements.
 Dihydrogen undergoes 2 types of dissociation reactions catalyzed by
molecules or active surfaces.
Dissociation of H2

Homolytic dissociation Heterolytic dissociation

is induced by adsorption at certain is induced by adsorption on a
metal surfaces e.g. Pt or Ni metal. heteroatom surface, such as a metal
oxide (e.g. ZnO) or reaction with a
H2(g) → H(g) + H(g) ∆rHꝊ = +436 kJ mol–1
molecule that can provide both
Bronsted base and hydride acceptor
H2(g) → H+(g) + H–(g) ∆rHꝊ = +1675 kJ mol–1
 Reactions of Hydrogen
 Dihydrogen is quite an inert molecule due to a high bond enthalpy
(436kJmol–1) and a short bond length (74 pm) and its reactions require
a catalyst or initiation by radicals.
 Under suitable conditions of temperature (e.g. heating, uv), pressure and
catalyst (e.g. Pt), the following reactions of Hydrogen are possible:

1. With O2 2H2 + O2 → 2H2O

2. With Halogen, X2 H2 + X2 → 2HX X = F, Cl, Br, I

3. with Nitrogen, N2 3H2 + N2 → 2NH3

4. with metals, M M + H2 → MHn (not balanced)

 Production of Hydrogen
IN THE INDUSTRY
 Most H2 is produced from natural gas by using steam reforming.
 Increasingly, H2 is being produced by other methods, notably coal
gasification and thermally assisted electrolysis.
 In the future, H2 may be produced from entirely renewable sources such
as water, capturing the energy of sunlight.

SMALL-SCALE PRODUCTION
 In the laboratory, H2 is easily produced by the reactions of
electropositive elements with aqueous acid or alkali, or by hydrolysis of
saline hydrides.
Zn + 2HCl → ZnCl2 + H2
2Al(s) + 2 OH–(aq) + 6 H2O(l) → 2 Al(OH)4–(aq) + 3 H2(g)
NaH + H2O → NaOH + H2
 It is also produced by electrolysis. Electrolysis of heavy water is also a
convenient way to prepare pure D2.
 Uses of Hydrogen
 H2 is important both as a raw material for the chemical
industry and, increasingly, as a fuel.
 Although it is not present in significant quantities in the
Earth’s atmosphere or in underground gas deposits, there is
a high biological turnover, because various microorganisms
use H+ as an oxidant or H2 as a fuel.
 Most H2 is used close to its site of production, for the
synthesis of ammonia (the Haber process), hydrogenation of
unsaturated fats, hydrocracking of crude oil, and large-scale
manufacture of organic chemicals e.g. methanol.
 Reaction of ‘green’ H2 with CO2 or CO to produce liquid
hydrocarbon fuels would amount to a carbon-neutral
technology.
 The mixture of CO and H2 is known as water gas, which is
used for the production of fuel gas and H 2 for ammonia
synthesis.
 Hydrogen Bonding
 A hydrogen bond has been defined as a bond formed between H atom
attached to an electronegative atom, i.e. X─H and an electronegative atom that
possess a lone pair of electron, i.e. Y.
X─H∙∙∙∙Y Hydrogen bond
 Such interaction occurs because X─H acts as a proton donor to Y, which
acts as an acceptor
 A recently proposed definition by IUPAC is:
The hydrogen bond is an attractive interaction between the hydrogen
from a group X─H and an atom or a group of atoms Y, in the same or
different molecule(s), where there is evidence of bond formation.
 Hydrogen bonding exists in molecules like H2O, NH3, HF. The H-bonding in
water is illustrated as:

 Hydrogen bonding might be symmetrical or unsymmetrical (asymmetrical). In

symmetrical hydrogen bonding, the H atom is midway between the two nuclei, e.g.
in the bifluoride ion, [FHF]–, the H atom lies midway between the F atoms.
 In contrast, asymmetrical hydrogen bonding, is when the H atom is not midway
between the two nuclei, even when the heavier linked atoms are identical. For
example, [ClHCl]– ion is linear but the H atom is not midway between the Cl atoms.
 Hydrogen Bonding
 Symmetrical and asymmetrical hydrogen bonding are illustrated below:
Symmetrical
F∙∙∙∙H∙∙∙∙F in [HF2]- O∙∙∙∙H∙∙∙∙O in [H3O2]- N∙∙∙∙H∙∙∙∙N in [N2H7]+
Asymmetrical
Cl─H∙∙∙∙Cl in [HCl2]- N─H∙∙∙∙O in [NH4]+ ∙∙∙∙OH2 C─H∙∙∙∙O in CH4 ∙∙∙∙OH2
H2O H2S
Evidence for Hydrogen bonding
 Striking evidence for hydrogen bonding is provided by the bp(oC) 100 -60
trends in normal boiling points, which are unusually high for the NH3 PH3
strongly hydrogen-bonded molecules water, H2O (in which there
bp(oC) -33 -87
are O–H∙∙∙O bonds), ammonia, NH3 (containing N–H∙∙∙N
HF HCl
bonds), and hydrogen fluoride, HF (containing F–H∙∙∙F bonds).
 The relatively low boiling points of PH3, H2S, HCl, and the bp(oC) 19.5 -85
heavier p-block molecular hydrides indicate that these molecules
do not form strong hydrogen bonds.
 Collective hydrogen bonding interactions play a large part in
maintaining the structure of protein molecules.
 They are also responsible for the recognition between specific DNA
bases, adenine/thymine and guanine/cytosine, that underlies gene
replication.
 Similarly, solid HF consists of chain structures that survive partially even in the vapour.
 Binary Compounds of Hydrogen
 The binary compounds of hydrogen usually called ‘HYDRIDES’ fall into three classes,
although there is a range of structural types and some elements form compounds with
hydrogen that do not fall strictly into any one category. These are called intermediate
hydrides. Hydrides

Molecular hydrides Saline hydrides Metallic hydrides Intermediate

exist as individual, discrete Are formed when Group are nonstoichiometric, hydrides
molecules; they are 1 or 2 (except Be) electrically conducting these do not fall strictly
usually formed with p- metals are heated with solids with a metallic into any of the first three
block elements of similar H2. They are called ionic lustre. They are formed categories, and elements
or higher electronegativity hydrides. when hydrogen occupy for which binary hydrides
than H. Their E–H bonds Saline hydrides, such the interstitial holes in have not been
are best regarded as as LiH and CaH2, are many d- and f-block characterized.
covalent. Familiar nonvolatile, electrically metals. E.g. TiH1.7,
examples of molecular nonconducting, HfH1.98.
hydrides include methane, crystalline solids.
CH4, ammonia NH3 and
water, H2O.
 Hydrogen is also found in complex anions of some p-block elements, e.g. the BH 4–
(tetrahydridoborate, also known as boranate and in older texts as ‘borohydride’) in NaBH 4 and
the AlH4– ion (tetrahydridoaluminate, also known as alanate and in older texts as
‘aluminiumhydride’) in LiAlH .
 A pictogram of the properties Hydrogen from the Royal Society webpage in
celebration of the 2019 as International Year of the Periodic Table.