Coursebook of Inorganic Chemistry 1 2016-Rev2020

i
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Course Book for Bilingual Learning
Inorganic Chemistry 1:
Chemistry of Non Metallic Elements
I Wayan Karyasa
ISBN 978-602-6428-01-1
First Edition, August 2016
Publisher:
UNDIKSHA PRESS
Addreses Jalan Udayana Singaraja 81116 Bali
Printed by:
Unit Penerbitan dan Percetakan
Universitas Pendidikan Ganesha
Singaraja Bali Indonesia
Cover designer
I Wayan Karyasa
Hak Cipta dilindungi undang-undang.

Dilarang memperbanyak atau mengutip sebagian atau seluruh isi buku ini
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Dalam bentuk apa pun termasuk ilustrasi, tanpa ijin dari penulis dan penerbit.
COURSE BOOK
FOR BILINGUAL LEARNING
INORGANIC CHEMISTRY 1:
CHEMISTRY OF NON METALLIC ELEMENTS
I Wayan Karyasa
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PREFACE
It is important to realize that chemistry especially in the branch of inorganic chemistry
has developed very fast. Today, inorganic chemistry goes forward in a dynamic body of
knowledge and stimulates other branches of chemistry as well as natural sciences and
technology. In other side, the advancement of information technology (e.g. online
learning resources) gives people especially higher education civities challenge to fullfill
their desires on information and knowledges, so does for inorganic chemistry, most of
them, however, written in English. Lack of English comprehension for non-native
English speaker countries may cause difficulties to understand the contents as well as
context of the information and knowledges thus they may be difficult to choose the
correct ones. Most of mis-conception constructed by learners of non-native English
speakers may be contributed from the such matter. The simple English written course
book of Inorganic Chemistry I is aimed to give students as well as lecturers basic
comprensive concepts extracted from several prominent textbooks as well as student
books in this area, thus they can have a guide to develop their knowledge by adding
correct chosen further materials avaiable in online manner.
The first edition of the course book is purposed to bilingual learning of students
at the Chemistry Education Department of Mathematics and Natural Science Faculty,
Ganesha University of Education, Singaraja. The book contains 11 chapters which is
started with introduction to inorganic chemistry and continued to the chapters for
chemistry of non-metallic elements: hydrogen, noble gases, halogen, oxygen, sulfur,
nitrogen, phosphorus, carbon, silicon, and boron.
The Faculty of Mathematics and Natural Sciences of Ganesha University of
Education is highly aknowledged for financial support in drafting the book.
Singaraja, August 26th, 2016
I Wayan Karyasa
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TABLE OF CONTENTS
PREFACE i
TABLE OF CONTENTS ii
CHAPTER 1
INTRODUCTION TO INORGANIC CHEMISTRY 1
1.1 INTRODUCTION 1
1.2 WHAT IS INORGANIC CHEMISTRY? 1
1.3 TRENDS OF ELEMENTAL PROPERTIES ON PSE 3
1.4 INORGANIC SUBSTANCES 6
1.5 INORGANIC REACTIONS 7
1.6 ACID AND BASE THEORIES 10
1.7 SUMMARY 12
1.8 STUDY QUESTIONS 12
CHAPTER 2
CHEMISTRY OF HYDROGEN 13
2.1 INTRODUCTION 13
2.2 HYDROGEN AND ITS PROPERTIES 13
2.3 ISOTOPES OF HYDROGEN 16
2.4 HYDROGEN GAS PRODUCTION AND ITS USES 17
2.5 COMPOUNDS OF HYDROGEN AND PROPERTIES 18
2.6 SUMMARY 20
CHAPTER 3
CHEMISTRY OF NOBLE GASES 21
3.1 INTRODUCTION 21
3.2 ELEMENTS OF NOBLE GASES AND THEIR PROPERTIES 21
3.3 COMPOUNDS OF NOBLE GASES 24
3.4 SUMMARY 27
CHAPTER 4
CHEMISTRY OF HALOGEN 28
4.1 INTRODUCTION 28
4.2 THE ELEMENTS OF HALOGEN 28
4.3 THE PRODUCTION WAYS OF HALOGEN GASES 30
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4.4 PROPERTIES OF OXIDES OF HALOGEN 31
4.5 HALIDE ACIDS AND OXYHALIDE ACIDS 33
4.6 INTERHALOGEN COMPOUNDS 35
4.7 SUMMARY 36
CHAPTER 5
CHEMISTRY OF OXYGEN 37
5.1 INTRODUCTION 37
5.2 ELEMENTAL OXYGEN 37
5.3 ISOTOPES OF OXYGEN 38
5.4 OXYGEN GAS PREPARATION 38
5.5 OZONE 39
5.6 OXIDES 42
5.7 WATER 43
5.8 SUMMARY 44
CHAPTER 6
CHEMISTRY OF SULFUR 45
6.1 INTRODUCTION 45
6.2 ELEMENTAL SULFUR 45
6.3 COMPOUNDS OF SULFUR 48
6.4 SUMMARY 52
CHAPTER 7
CHEMISTRY OF NITROGEN 53
7.1 INTRODUCTION 53
7.2 NITROGEN AND ITS PROPERTIES 53
7.3 PREPARATION OF NITROGEN 54
7.4 AMMONIA 56
7.5 NITRATE AND NITRITE 57
7.6 NITROGEN CYCLE IN NATURE 58
7.7 SUMMARY 59
CHAPTER 8
CHEMISTRY OF PHOSPHORUS 61
8.1 INTRODUCTION . 61
8.2 PHOSPHORUS AND ITS ALLOTROPES 61
8.3 HYDRIDES OF PHOSPHORUS 64
8.4 HALIDES OF PHOSPHORUS 65
8.5 OXIDES OF PHOSPHORUS 60
8.6 OXOACIDS OF PHOSPHORUS 70
8.7 USES 72
8.8 SUMMARY 73
CHAPTER 9
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CHEMISTRY OF CARBON 75
9.1 INTRODUCTION 75
9.2 ELEMENT OF CARBON 75
9.3 COMPOUNDS OF CARBON 78
9.4 SUMMARY 82
CHAPTER 10
CHEMISTRY OF SILICON 83
10.1 INTRODUCTION 83
10.2 SILICON AND ITS PROPERTIES 83
10.3 SILICON PREPARATION 85
10.4 SILICON HYDRIDES (SILANES) 85
10.5 SILICIDES 86
10.6 SILICON CARBIDE 87
10.7 SILICA AND SILICATES 88
10.8 SUMMARY 89
CHAPTER 11
CHEMISTRY OF BORON 91
11.1 INTRODUCTION 91
11.2 BORON AND ITS PROPERTIES 91
11.3 BORON-OXYGEN COMPOUNDS 93
11.4 BORON HALIDES 95
11.5 BORANES 95
11.6 SUMMARY 99
REFFERENCES 101
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1
CHAPTER 1
INTRODUCTION TO INORGANIC
CHEMISTRY
1.1 INTRODUCTION
The basic competences of the first chapter are to understand elements periodicity on the
Table of Periodic System of Elements and to understand some types of chemical reactions.
Obtaining those basic competences, the lesson should be conducted to reach indicators of
learning, i.e. students should be able to:
a. explain how elements were grouped in the system of periodicity;

b. describe periodicities of element‘s properties;
c. explain some types chemical reactions with their examples; and
d. explain acid base theory.
This chapter will discuss briefly the elements and their groups, periodicity of
element‘s properties, types of chemical reactions, and acid base theories.
1.2 WHAT IS INORGANIC CHEMISTRY?

Tradisionally, learning inorganic chemistry is identical to learning chemistry of
elements. Chemistry of elements ranges from the boarder of traditional organic
chemistry, i.e. primarily the chemistry of carbon in combination with hydrogen, oxygen,
nitrogen, phosphorus, sulfur, halogens, and others related to organic compounds. The
chemistry of elements often discusses also a broader physical chemistry of each
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elements, namely physical properties and quantitative behaviour of the elements.
Consequently, we learn most of all elements in the Periodic System of Elements (PSE).
Thus, inorganic chemistry courses are often divided into chemistry of chemistry of non
metallic elements, chemistry of metals, chemistry of main group elements, and
chemistry of transition group elements.
What are the differences between organic and inorganic chemistry? As an
illustration, we are often see in our surroundings, organic and inorganic wastes or
gabbages as depicted in Figure 1.1.
INORGANIC WASTE:
ORGANIC WASTE:
• plastic
• leaf • paper
• stem/wood • carton boxes
• vegetable • metallic can
• fruits • rubber
• flower • metal things
• rice • battery
• grass • pen/balpoint
• meet
MUCH DIFFERENT IN CHEMISTRY KNOWLEDGE: paper (sellulose), plastic (polyetylene)
and rubber are grouped as organic compounds (consisting C-C and C-H with addition C-O or C-
N bonds). But DON‘T THROW PAPER IN THE ORGANIC CABBIN!
Figure 1.1 Organic and Inorganic Wastes Cabbines and Their Contents
The illustration in Figure 1.1 above implys that there is a different meaning of organic
and inorganic matters between a common view and a chemistry knowledge view.
Let we compare organic and inorganic chemistry in more detail. Firstly, organic
chemistry concerns mainly molecular substances created from carbon and other
elements, but inorganic chemistry concerns not only molecules, but also atomic gases,
molecular gases, ionic as well as molecular liquids and solids. Thus, inorganic
chemistry studies a greater variety of substances than does organic chemistry. Secondly,
organic substances mainly have a maximum coordination number of 4, for examples
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CH4, C2H6, and NR4+, but inorganic substances have coordination numbers 4 and
frequently more than 4, for examples PCl5, FeF6-3, and [Nd(H2O)9]+3.
1.3 TRENDS OF ELEMENTAL PROPERTIES ON PSE

The properties of elements are related to their electronic configurations, hence
they tend to have periodical trends. In order to understand the trends of elemental
properties on PSE lets us doing the group discussion activity as follows.
Task 1.1. A Jigsaw Group Discussion
• Please divide the class become 4 expert groups (4-member of A,B,C,D groups).
• Discuss the topics as given worksheet.
• Rearrange the groups to become 5 groups- each 4 members from the expert groups
to compose working group namely group I, II, III, IV and V.
• Every one from expert groups explain his/her understanding of the topic to members
of his/her new working groups.
• Make a report of the working group and present in front of the class
• Try to communicate in English as much as possible and should be effectively.
• Don‘t worry to make mistakes, practices make masters.
Worksheet A
Aims:
To describe the table or/and graph of periodic properties of elements:
Ionization energies
Table and Graph of Ionization Energies:
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Discussion:
1. What is ionization energy of elements?
2. Explain the periodicity of ionization energy of each group of elements as well
as each period of elements!
3. Why the periodicity is that? What of the implications of that?
Worksheet B
Aims:
To describe the table or/and graph of periodic properties of elements:
electron affinities
Table and Graph of Electron Affinities :
Discussion:
1. What is electron affinity of elements?
2. Explain the periodicity of electron affinity of each group of elements as well as
each period of elements!
3. Why the periodicity is that?
4. What of the implications of that?
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Worksheet C
Aims:
To describe the table or/and graph of periodic properties of elements: Electronegativity
Table and Graph of Electronegativity:
Discussion :
1. What is electronegativity of elements?
2. Explain the periodicity of electronegativity of each group of elements as well as
each period of elements!
3. Why the periodicity is that?
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Worksheet D
Aims:
To describe the table or/and graph of periodic properties of elements: Covalent and
Ionic radii
Table of Covalent and ionic radii:
Discussion:
1. What are covalent and ionic radii of elements?
2. Explain the periodicity of covalent and ionic radii of each group of elements as
well as each period of elements!
3. Why their periodicity is that?
1.4 INORGANIC SUBSTANCES

Inorganic Substances can be classified into four groups, namely elements, ionic
compounds, molecular compounds, and network solids or polymers.
1.4.1 Elements
Inorganicly, elements have variety structures and properties. They can be as
atomic gases such as Ar, Kr, and Xe; molecular gases such as H2, O2, and N2; molecular
solids such as P4, S8, and C60, extended molecules or network solids suc as diamond and
graphite, solid metals: W, Co, and Fe, and liquid metals such as Hg, and Ga.
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1.4.2 Ionic Compounds
Ionic compounds can be as simple ionic compounds such as NaCl, KBr, and
CaCl2, ionic oxides such as ZrO2, and MgAl2O4, other binary halides, carbides, sulfides,
and similar materials such as AgCl, Al4C3, ZnS, GaAs, and BN, and compounds
containing polyatomic ions such as Na2SiF6, and K3Fe(CN)6.
1.4.3 Molecular compounds
Inorganic molecular compounds may be solid, liquid, or gaseous state. Some
molecular compounds include simple ionic, binary compounds such as PF3, SO2, UF6,
complex metal-containing compounds such as PtCl2(P(CH3)3)2 and
RuH(CO2CH3)(P(C6H6)3)3, and organometallic compounds such as Ni(CO)4,
Zr(CH2C6H5)4 and U(C8H8)2.
1.4.4 Network solids, or polymers
Networks solids or polymers include inorganic polymers such as poyphosphates
containing P-O-P linkage, silicone, a linear or chain polymer containing –R2Si-O-SiR2-
O- repeating units.
1.5 INORGANIC REACTIONS

Commonly, the chemical reactions can be classified into four basic reactions, i.e
synthesis, decomposition, single subtitution, and double or polysubstitution. The four
types of reactions can be detailed as follows.
Synthesis reaction is a chemical reaction in which two or more substances
directly combine each other to form more complex compound. Two or more substances
react to form one new substance. It can be shown that the synthesis reaction is already
happened. For examples are:
2 H2 + O2 H2O ............................................................................................(1.1)
N2 + 3 H2 2 NH3 .........................................................................................(1.2)
Decomposition reaction or analysis reaction is a reaction in which a more
complex compound is broken into two or more simple compounds. For example:
2 CaCO3 → CaO + CO2 ................................................................................(1.3)
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In a single substitution reaction, a single element subsitutes other single element
in a compound to produce the new single element and a new compound. For example,
sodium metal reacts to hidrochloride acid to form sodium chloride and hydrogen as
shown below.
2 Na(s) + 2 HCl(aq) → 2 NaCl(aq) + H2(g) ...................................................(1.4)
Double substitution reaction is a reaction in which two compound exchange
their ions to form two new compounds. To understand the double substitution reaction
let us consider two examples below.
Pb(NO3)2(aq) + 2 KI(aq) → PbI2(s) + 2 KNO3 (aq) .......................................(1.5)
NaCl(aq) + AgNO3(aq) → NaNO3(aq) + AgCl(s) .........................................(1.6)
There are a lot of chemical reactions studied in inorganic chemistry. Some of
them are classified to 12 types as follows: acid-base (neutralization), addition,
elimination, oxidation-reduction (redox), insertion, substitution (displacement),
rearrangement (isomerization), metathesis (exchange), solvolysis, chelation, cyclization
and condensation, and nuclear reactions. The explanation of those reaction types are as
follows.
a. Acid-base (neutralization)
According to Arrhenius, the neutralization of the H+ ions (from an acid) with the
OH- ions (from a base) to form water molecules. The acid-base reaction happen in water
solution.
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(aq) ...............................................(1.7)
By the definition of Bronsted-Lowry, the neutralization of a proton donor by a proton
acceptor. For example:
NH3 + H2SO4 → (NH4)2SO4 ..........................................................................(1.8)
According to Lewis, the formation of an adduct between an electron-pair donor and an
electron-pair acceptor. For example:
NH3 + BF3 → NH3BF3 ...................................................................................(1.9)
By the Lux-Flood definition, the reaction of an oxide ion acceptor with an oxide ion
donor. For example:
CaO + SiO2 → CaSiO3 ……………………………………………...……..(1.10)
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b. Addition reaction
A reaction in which a group, molecule, or ion combines with another. Common
examples are addition across a multiple bond and addition to an atom that is able to
undergo coordination sphere expansion (an increase in occupancy). For example:
C2H4 + H2 → C2H6 ........................................................................................(1.11)
PCl3 + Cl2 → PCl5 .........................................................................................(1.12)
c. Elimination reaction
A reaction in which a group, molecule, or ion is separated from another.
Examples are dehydrogenations, and eliminations from metal centers that are able to
undergo coordination number reduction (a decrease in occupancy). For example:
C2H4 → C2H2 + H2 ......................................................................................(1.13)
Cu(H2O)6SO4 + 4 NH3 → Cu(NH3)4SO4 + 6 H2O ........................................(1.14)
d. Oxidation-reduction (redox) reaction:

A reaction in which oxidation (a lost of electrons, corresponding to an increase
in oxidation state) and reduction (a gain of electrons, corresponding to a decrease in
oxidation state) undergo simultaneously.
2 S2O32−(aq) + I2(aq) → S4O62−(aq) + 2 I−(aq) ............................................(1.15)
e. Insertion reaction
The interposition of a new molecule, group, or ion between atoms in a structure
such that the added molecule, group, or ion separates the two parts of the structure that
were formerly bonded together. For example:
W + C → WC ...............................................................................................(1.16)
Pd + H2 → PdH2 ...........................................................................................(1.17)
f. Substitution reaction
A reaction in which a group, molecule, or ion is gained by another by occupying
its place of bonding. Substitution can be single or double as explained before (see also
the examples 1.4; 1.5; and 1.6).
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g. Isomerization reaction
One of two or more substances can be called isomer if they are structurally and
physically different but which have the same elemental composition. Isomerization
reaction is defined as a conversion of one isomer to another. For example, cis-
diaquodiamin cuprum (II) sulphate and trans-diaquodiamin cuprum (II) sulphate have
the sam composition and formula of [Cu(H2O)2(NH3)2]SO4.
h. Metathesis (exchange)
An exchange of comparable groups, such that two compounds form two new
ones.
AX + BY  AY + BX ………………………………………………….…(1.18)
For example:
KBr + AgNO3  AgBr + KNO3 …………………………………….…….(1.19)
i. Solvolisis
A reaction with solvent; when solvent is water, it is called hydrolysis. For
example:
HCl(g) + H2O(l)  H3O+(aq) + Cl-(aq) ………………………….........…..(1.20)
j. Chelation
A reaction in which a chelate is bounded to a central metal atom of complex ion.
A chelate is a ligand that is able to bond to a central metal atom simultaneously through
more than one donor atom. For example:
Cu(NH3)4SO4 + 2K2C2O4  K2[Cu(C2O4)2] + NH3 + K2SO4 .................(1.21)
k. Cyclization and condensation

Cyclization reaction is a reaction that leads to the formation of rings.
Condensation is a reaction that leads to combine some small groups, molecules or ions
become a big condensed molecule.
l. Nuclear reaction
Nuclear reaction is a reaction that changes the atomic number or mass number of
an atom.
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1.6 ACID AND BASE THEORIES
Acid base theories should be discussed including the definition of acid-based
after Arrhenius, Bronsted-Lowry, Lewis, Lux-Flood, and Pearson. Arrhenius definition
of acid and base is the oldest one. According to Arrhenius, acid is a substance which can
give H+ in water, base is a substance which can giv OH- ions in water solution.
Bronsted-Lowry theory implys that acid is a substance that supplies proton (H+) donor,
and base is a proton (H+) acceptor. Meanwhile, according to Lewis, acid is electron pair
acceptor, and base is electron pair donor. For example, :NH3 is a Lewis base because it
has a pair electron that can be donated to other substance, but BF3 is a Lewis acid
because it can accept a pair of electron. The reaction of NH3 with BF3 to form NH3BF3
is an acid-base recation after Lewis. Another acid-base theory is in accordance to Lux-
Food definition of acid-base substances. Accordingly, an acid is defined as an oxide ion
acceptor and a base is an oxide ion donor. For example:
CaO + H2O  Ca(OH)2 ……………….…………..……………………….(1.22)
CO2 + H2O  H2CO3 ..…………………………….……………………...(1.23)
CaO serves as a basic anhydride and CO2 serves as an acid anhydride. The reaction of
Ca(OH)2 and H2CO3 is a neutralization reaction to produce CaCO3 and water according
to reaction below.
Ca(OH)2 + H2CO3  CaCO3 + 2 H2O ……………...........……………….(1.24)
Without solvent (water) or anhydrous reaction, CaO can directly react with CO2 to
produce CaCO3 where CaO can accept an oxide ion, thus it can be called as a base
because donate oxide ion to CO2 to become CO3-2, thus CO2 is an acid because of
accepting oxide ion.
CaO + CO2  CaCO3 ……………………………………………….…….(1.25)
It is important to define acid-base according to solvent system because solvent
has a significant autoionization. A solute can increase the cationic species to the solvent
is an acid, one can increase the anionic species in the solvent is a base. The solvent of
BrF3 can ionize to BrF2+ kation and BrF4- anion. The reaction of BrF2AsF6 with KBrF4
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can give result of KAsF6 salt and BrF3 solvent. The ionic reaction can be written as
follows.
BrF2+ + AsF6- + K+ + BrF4-  K+ + AsF6- + 2 BrF3 …………………..….(1.26)
The (BrF2+ + AsF6-) species are acid, and the (K+ + BrF4-) is base.
Pearson observed that two types of metals ions according to their preference for
various ligands i.e type (a) and type (b) metal ions, Type (a) metal ions are small,
compact, and not very polarizable. For the type (a) metal ions, complexes are more
stable with the lightest ligands and less stable as the ligands decended. The type (a)
metals ions (acids) are prefered ligands (bases) that are also small and less polarizable.
The acids and bases are called ―hard‖ acids-bases. Contrastly, the type (b) metal ions are
opposite characteristics to type (a) metal ions (acids). They are polariable, not compact
and wide in size parameters. They also prefer to interact with the polarizable, not
compact, and big size of ligands (bases). Thus, hard acids prefer to combine with hard
acids, soft acids prefer to react with soft bases.
In other words, hard acids are electron pair acceptors, have no low lying or low
energy unfilled orbitals (LUMO), do not ready to form covalent bond with bases. Hard
bases are electron pair donors, have no high lying or high-energy orbital (HOMO), not
readily for covalent bonds with acids.Soft acids do tend to have low-energy unfilled
orbitals (a low LUMO), readily enter to form covalent bonds, soft bases do tend to have
high-energy filled orbitals (a high HOMO), easily to form covalent bonds.
Acids:
Hard: H+, Li+, Be2+, Mg2+, Al3+, Ga3+, In3+, As3+, BF3, AlMe3, AlCl3, SO3.
Borderline: Sn2+, Pb2+, Bi3+, BMe3, SO2, NO+, GaH3.
Soft: Tl+, Hg+, Te4+, Tl3+, TlMe3, BH3, GaMe3, GaCl3, InCl3, I+, I2.
Bases:
Hard: H2O, OH-, F-, SO42-, Cl-, CO32-, ClO4-, NO3-, NH3.
Borderline: N3-, Br-, NO2-, SO32-, N2.
Soft: H2S, I-, SCN-, R3P, CN-, CO, H-.
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1.7 SUMMARY
Inorganic chemistry deals with a wide ranges of substances formed by almost all
of elements, which spreads from simple until complex compounds, from atomic
elements to polymers. Although there are various reactions can undergo inorganicly, but
they can be divided into four primarily reactions, namely synthesis, decomposition,
single substitution and double substitution. For better understanding of structure,
properties and norganic reactions, trend of elemental properties on PSE should be taken
into account. Acid-base theories reserve understanding on acid and base substances,
their reaction, and effect of solvent and solute to the acidity as well as basic properties
of the system. ―Like dissolves like‖ can be applied on the hard soft acid base (HSAB) of
Pearson theory. Hard acids tend to make compounds to hard bases, soft acids tend to
react to soft bases.
1.8 STUDY QUESTIONS

1. Please make a list the different between organic and inorganic substances!
2. Please compare the methatesis reaction and substitution reaction!
3. What is the relationship between donor and/or acceptor ability of a solvent and its
ability to function as a solvent?
4. In liquid NH3 what are the species characteristics of acids? And bases?
5. State the Arrhenius, Lewis, and Bronsted-Lowry theories of acid-base?
6. Why is acetic acid not an acid in H2SO4?
7. To what sort of systems does the Lux-Flood concept apply?
8. Describe the origin of the concept of hard and soft acids and bases.
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CHAPTER 2
CHEMISTRY OF HYDROGEN
2.1 INTRODUCTION
The basic competence of the chapter 2 is to understand properties, production and uses
of hydrogen. Indicators of learning for reaching the basic competences should show that
students should be able to:
a. explain properties of hydrogen gas and its isotopes;
b. explain ways in producing hydrogen gas;
c. explain the uses of hydrogen gas; and
d. explain some compounds of hydrogen and their properties.
This chapter will explain briefly the properties of hydrogen, its isotopes,
hydrogen gas production, uses, as well as some compounds of hydrogen and their
properties.
2.2 HYDROGEN AND ITS PROPERTIES

Hydrogen atom consists of a nucleus with a single positive charge surrounded by a
single electron. Because of this simple structure, hydrogen may be the most important element
of all. In the sun, hydrogen (H) nuclei combine to form helium (He) nuclei in a processs that
provides nearly all the energy on earth. About 90 % of all the atoms in the universe are H
atoms, making it the most abundant element. On the earth, only tiny amount of the free element
occurs naturally as H2, but hydrogen is abundant in combination with oxygen in form of water.
Because of its simple structure and low molar mass, hygdogen is a nonpolar gaseous, colorless
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and odorless. Because of its extremely weak dispersion forces, hydrogen gas has very low
melting (-259 0C) as well as boiling points (-253 C).
Hydrogen has no perfectly suitable position in the Periodic System of Elements (PSE).
Because of its single valence electron and common + 1 oxidation state, it might almost fit in
Group 1 A. However, unlike alkali metal, hydrogen shares its electron with nonmetal rather than
losing it to them. Like a nonmetal, it has a relatively high ionization energy (1311kJ/mol) much
higher than that of lithium (520 kJ/mol) whose the ionization energy is the highest in Group 1A
and a much higher electronegativity as well (electronegativity of H is 2.1; electronegativity of
Li is 1.0)
On the other hand, hydrogen might almost fit in Group 7 A, like the halogens, it occurs
as diatomic molecule and fills its outer shell either by electron sharing or gaining one electron
from a metal to form a monoatomic anion, the hydride ion (H-, oxidation number of -1).
However, hydrogen has a lower electronegativity (EN) than any of the halogens and lack of
their three valence electron pairs. Moreover, the H- ion is rare and reactive, whereas halide ions
are common and stable. The hydrogen‘s unique behavior is due to its tiny size. It has a high
ionization energy because its electron is very close to the nucleus, with no inner electron to
shield it from the position charge. It has a low electonegativity (for a nonmetal) because it has
only one proton to attract bonded electrons.
Hydrogens is very reactive, in combining with nearly elements, so we focus here on the
three types of hydrides. The first, ionic (saltlike ) hydrides is the hydride with very reactive
metals, such as those in Group 1A and the larger members of 2A (Ca, Sr, and Ba). The ionic
hydrides are white, crystalline solids composed of the metal cations and the hydrides ions:
Li(s) + H2 (g) → 2 LiH (s) .................................................................................(2.1)
Ca(s) + H2 (g) → CaH2 (s) .................................................................................(2.2)
In water, H- is a strong base that pulls H+ from surrounding H2O molecules to form H2 and OH-:
NaH(s) + H2O (l) → Na+ (aq) + OH- (aq) + H2 (g) ............................................(2.3)
The inonic hydrides are also powerful reducting agents, for examples, LiH can reduce Ti (
group IV) to the free metal:
TiCl4 (l) + 4LiH (s) → Ti (s) + 4 LiCl (s) + 2 H2 (g) ...........................................(2.4)
The second is covalent (molecular) hydrides. They are nonmetal hydrides such as CH 4,
NH3, H2O, and HF. Most are gases consisting of small molecules, but many hydrides of boron
and carbon are liquids or solids that consist of much larger molecules. In most covalent
15 | 105 P a g e s
hydrides, hydrogen has an oxidation number of +1 because the other nonmetal has a higher
electronegativity than hydrogen. Conditions for preparing the covalent hydrides depend on the
reactivity of the other nonmetal. For example, with stable, triple-bonded N2 ,hydrogen reacts at
high temperature (± 400 oC) and pressure (± 250 atm), and the reaction needs a catalyst to
proceed at any practical reaction rate:
N2 (g) + 3H2 (g) → 2NH3 (g) ΔHo = -91.8 kJ ...............................................(2.5)
The third, metallic (interstital) hydrides form from many transition elements, in which
H2 molecules (and H atoms) occupy the holes in the metal‘s crystal structure. Thus, such
hydrides are not compounds but gas –solid solution. Also, unlike ionic and covalent hydrides,
interstitial hydrides, such as TiH1.7 , typically lack of a single, stoichiometric formula because
the metal can incorporate variable amounts of hydrogen, depending on the pressure and
temperature of the gas.
Normally, the boiling points of series of similar compounds containing elements in the
same periodic group increase with increasing molar mass. This increase in boiling point is due
to the increase in dispersion forces for molecules with more electrons. Hydrogen compounds of
Group 4A follow this trend. The lightest compound (CH4) has the lowest boiling point, and the
heaviest compound (SnH4) has the highest boiling point. However, hydrogen compounds of the
elements in Groups 5A, 6A, and 7A do not follow this trend. In each of these series, the lightest
compound (NH3, H2O, and HF) has the highest boiling point, contrary to our expectations based
on molar mass. This observation must mean that there are stronger intermolecular attractions in
NH3, H2O, and HF compared to other molecules in the same groups. In fact, this particularly
strong type of intermolecular attraction is called the hydrogen bond, which is a special type of
dipole-dipole interaction between the hydrogen atom in a polar bond, such as NH, OH, or
FH, and an electronegative O, N, or F atom. The interaction is written:
AH . . . B or AH . . . A
A and B represent O, N, or F, AH is one molecule or part of a molecule and B
is a part of another molecule, and the dotted line represents the hydrogen bond. Note
that the O, N, and F atoms all possess at least one lone pair that can interact with the
hydrogen atom in hydrogen bonding. The average strength of a hydrogen bond is
quite large for a dipole-dipole interaction (up to 40 kJ/mol). Thus, hydrogen bonds have
a powerful effect on the structures and properties of many compounds.
16 | 106 P a g e s
The strength of a hydrogen bond is determined by the Coulombic interaction
between the lone-pair electrons of the electronegative atom and the hydrogen nucleus.
For example, fluorine is more electronegative than oxygen, and so we would expect a
stronger hydrogen bond to exist in liquid HF than in H2O The boiling point of HF is
lower than that of water because each H2O takes part in four intermolecular hydrogen
bonds. Therefore, the forces holding the molecules together are stronger in H2O than in
HF, so that needs more energy to break H2O (4 intermolecular hydrogen bond) than in
HF (2 intermolecular hydrogen bond).
2.3 ISOTOPES OF HYDROGEN

Hydrogen has three naturally occurring isotopes, denoted 1H, 2H and 3H. Only hydrogen
that the isotopes has their different names. Protium (1H) is the most common hydrogen isotope
with an abundance of more than 99.98%. Because the nucleus of this isotope consists of only a
single proton, it is given the descriptive but rarely used formal name protium. Deuterium (2H),
the other stable hydrogen isotope, is known as deutrium and contains one proton and one
neutron in its nucleus. Deuterium is not radioactive, and does not represent a significant toxicity
hazard. Water enriched in molecules that include deuterium instead of normal hydrogen is
called heavy water. Deuterium and its compounds are used as a non-radioactive label in
chemical experiments and in solvents for 1H-NMR spectroscopy. Heavy water is used as a
neutron moderator and coolant for nuclear reactors. Deuterium is also a potential fuel for
commercial nuclear fusion. Tritium (3H) contains one proton and two neutrons in its nucleus. It
is radioactive, with a half-life of 12.32 years. Only very small percent of hydrogen occur as
tritium. Small amounts of tritium occur naturally because of the interaction of cosmic rays with
atmospheric gases; tritium has also been released during nuclear weapons tests. It is used in
nuclear fusion reactions. Tritium has also been used in chemical and biological labeling
experiments as a radiolabel.
2.4 HYDROGEN GAS PRODUCTION AND ITS USES

There are several ways to produce hydrogen gas. In the laboratory, H2 is usually
prepared by the reaction of dilute non oxidizing acids on some reactive metals such as zinc
Zn + 2 H+ → Zn2+ + H2 …….………………………………………………………(2.6)
17 | 105 P a g e s
Aluminium can also produce H2 upon treatment with bases:
2 Al + 6 H2O + 2 OH− → 2 Al(OH)− 4 + 3 H2 ................................................(2.7)
The electrolysis of water is a simple method of producing hydrogen. A low voltage
current is run through the water, and gaseous oxygen forms at the anode while gaseous
hydrogen forms at the cathode. Typically the cathode is made from platinum or another
inert metal when producing hydrogen for storage. If, however, the gas is to be burnt on
site, oxygen is desirable to assist the combustion, and so both electrodes would be made
from inert metals. (Iron, for instance, would oxidize, and thus decrease the amount of
oxygen given off.) The theoretical maximum efficiency (electricity used vs. energetic
value of hydrogen produced) is in the range 80–94%.
2 H2O(l) → 2 H2(g) + O2(g) ……………………………………………...….(2.8)
Industrially, hydrogen can be prepared by several different ways, but
economically the most important processes involve removal of hydrogen from
hydrocarbons. Commercial bulk hydrogen is usually produced by the steam reforming
of natural gas. At high temperatures (1000–1400 K, 700–1100 °C or 1300–2000 °F),
steam (water vapor) reacts wit h methane to yield carbon monoxide and H2.
CH4 + H2O → CO + 3 H2 ……………………………………………….….(2.9)
This reaction is favored at low pressure but it is nonetheless conducted at high pressure
(2.0 MPa, 20 atm or 600 inHg). The product mixture is known as "synthetic gas" or
―syngas‖ because it is often used directly for the production of methanol and related
compounds. Hydrocarbons other than methane can be used to produce synthetic gas
with varying product ratios. One of the many complications to this highly optimized
technology is the formation of coke or carbon:
CH4  C + 2 H2 ……………………………………………………………(2.10)
Consequently, steam reforming typically employs an excess of H2O. Additional
hydrogen can be recovered from the steam by use of carbon monoxide through the
water gas shift reaction, especially with an iron oxide catalyst.
CO + H2O  CO2 + H2 ……………………………………………………(2.11)
Other important methods for H2 production include partial oxidation of
hydrocarbons.
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CH4 + O2  2 CO + 4 H2 …………………………………………..(2.12)
Hydrogen gas is widely used in every sector in our life some of them likes: (1)
commercial fixation of nitrogen from the air in the Haber ammonia process; (2) hydrogenation
of fats and oils (Hydrogenation is the addition of hydrogen to compounds containing multiple
bonds,especially C═C and C C bonds); (3) methanol production, in hydrodealkylation,
hydrocracking, and hydrodesulphurization; (4) rocket fuel; (5) welding; (6) production of
hydrochloric acid; (7) reduction of metallic ores; and (6) for filling balloons (hydrogen gas
much lighter than air; however it ignites easily).
2.5 COMPOUNDS OF HYDROGEN AND PROPERTIES

Hydrogen has million kinds of molecules, hydrogen is also remarked as an atom that
has the most numbers of compounds in the universe, much more than carbon compounds.
However, here it will be explained some compounds of hydrogen that have important
properties.
Water is so common substance on Earth that we often overlook its unique
nature. All life processes involve water. Water is an excellent solvent for many ionic
compounds, as well as for other substances capable of forming hydrogen bonds with
water. The reason is that to raise the temperature of water (that is, to increase the
average kinetic energy of water molecules), we must fi rst break the many
intermolecular hydrogen bonds. Thus, water can absorb a substantial amount of heat
while its temperature rises only slightly.
The most striking property of water is that its solid form is less dense than its
liquid form ice floats at the surface of liquid water. The density of almost all other
substances is greater in the solid state than in the liquid state. To understand why water
is different, we have to examine the electronic structure of the H2O molecule, there are
two pairs of nonbonding electrons, or two lone pairs, on the oxygen atom.
Although many compounds can form intermolecular hydrogen bonds, the

difference between H2O and other polar molecules, such as NH3 and HF, is that each
19 | 105 P a g e s
oxygen atom can form two hydrogen bonds, the same as the number of lone electron
pairs on the oxygen atom. Thus, water molecules are joined together in an extensive
threedimensional network in which each oxygen atom is approximately tetrahedrally
bonded to four hydrogen atoms, two by covalent bonds and two by hydrogen bonds.
This equality in the number of hydrogen atoms and lone pairs is not characteristic of
NH3 or HF or, for that matter, of any other molecule capable of forming hydrogen
bonds. Consequently, these other molecules can form rings or chains, but not three
dimensional structures.
The highly ordered three-dimensional structure of ice (tetrahedral) prevents the
molecules from getting too close to one another. But consider what happens when ice
melts. At the melting point, a number of water molecules have enough kinetic energy to
break up of the intermolecular hydrogen bonds. These molecules become trapped in the
cavities of the three-dimensional structure, which is broken down into smaller clusters.
As a result, there are more molecules per unit volume in liquid water than in ice. Thus,
because of its density 5 mass/volume, the density of water is greater than that of ice.
2.6 SUMMARY
From that we can conclude that hydrogen is very familiar and most abundant element in
the universe, because of its remarkable properties. It can bind a lot of atoms to form millions of
compounds. Hydrogen can also form hydrogen bond with NH3, H2O, and HF mollecules that
make these molecules show different properties.
2.7 STUDY QUESTIONS
1. Explain the properties of atomic as well as molecule diatomic of hydrogen.

2. Explain the properties and natural abundances of three isotopes of hdrogen.
3. Explain the properties and uses of hydrogen gas.
4. Explain what is hydrogen bonding and what factors affecting the strength of the
hydrogen bonding.
5. Explain the misceleneaous properties of water.
6. Explain three types of hydride compounds.
20 | 106 P a g e s
CHAPTER 3
CHEMISTRY OF NOBLE GASES
3.1 INTRODUCTION
The basic competence of the chapter 3 is to understand properties, and compound
preparations of noble gases. Indicators of learning for reaching the basic competences should
show that students should be able to:
a. explain properties and uses of noble gases; and
b. explain ways in preparing compounds of noble gases.
This chapter will explain briefly the properties of noble gases, their uses, as well
as some compounds of nobles and their ways of preparation.
3.2 ELEMENTS OF NOBLE GASES AND THEIR PROPERTIES

Noble gases are a special group because it is the most stable group in the
periodic table. Noble gases have electron valence configuration s2p6, except helium with
electron valence configuration s2. This structure cause noble gases are unreactive.
Although noble gases are stable and unreactive but, it could form compounds with some
mechanisms. Beside that, noble gases are useful in human life. In this essay will explain
briefly the properties of noble gases, their uses, as well as some compound of noble
gases and their ways of preparation.
In periodic table, group of VIIIA also called noble gases group. In one period,
the noble gas has smallest atomic radii. The elements of the noble gas group are not
very reactive because they are stable (have eight electrons in the valence shell). The
21 | 105 P a g e s
noble gases are, in fact, comparatively unreactive, but some (especially xenon and
krypton) are not ―inert‖ even though that label was once applied to the noble gas.
Elements belonging to noble gases are He, Ne, Ar, Kr, Xe, and Rn. Some properties of
noble gases can be seen in the following table.
Table 3.1 Some Properties of Noble Gas Elements
Property He Ne Ar Kr Xe Rn
Atomic number 2 10 18 36 54 86
Atomic mass 4.0026 20.183 39.948 83.80 131.30 222
Electron 1 s2 [He] 2s2 [Ne] 3s2 [Ar] 3d10 [Kr] 4d10 [Xe] 4f14
configurations 2p6 3p6 4s2 4p6 5s2 5p6 5d10 6s2
6p6
Melting point (K) 0.95 24.5 83.78 116.6 161.3 202
Boiling point (K) 4.22 27.1 87.29 120.8 166.1 211

Ionization potential 2372 2081 1520 1351 1170 1037
(kJ mol-1)
Atomic radius (0pm) 122 160 191 198 218 -220
Density (bg L-1) 0.1785 0.900 1.784 3.73 5.88 9.73
Solubility in H20 (103 7.12 8.73 30.2 57.0 105 230
x X c)
Abundance in nature 0.00052 0.0015 0.92 0.00011 0.0000087 0.0778613
(%)
Color of spectrum Colorless Red Violet Weak Blue Colorless
purple violet green
(Resource: House, 2008)
Elements belonging to noble gases are He, Ne, Ar, Kr, Xe, and Rn. First is
helium (He), this element was named helium the Greek word helios, its mean ―sun‖. In
1968 Pierre Jansen found evidence of He during the total solar eclipse when he detected
a new line in the solar spectrum. In 1895, Ramsay discovered He in the uranium mineral
cleveite. At the same time, the Swedish chemists Cleve and Langlet discovered He in
cleveite. In 1907 Rutherford and Royds demonstrated that alpha particles are He nuclei.
It has long been related to nuclear chemistry because of the formation of alpha particles
(𝛼 = 4He2+) during the decay of heavy nuclei.
Second is neon (Ne), in 1898 Ne was discovered by William Ramsay and Morris
Travers. This element was named neon the Greek word neos, its mean ―new‖. In nature,
it was produced by some of the stars from the nuclear reactions that occur in the star. Ne
is naturally present in the form of isotopes. There are three stable isotopes of Ne are Ne-
20, Ne-21 and Ne-22.
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Third is argon (Ar), Ar was discovered in 1885 by Sir William Ramsay as a
constituents in the residual gas after O2 and N2 were removed from air. The name comes
from the Greek argos, which means ―inactive‖. Argon is generated by the electron
capture decay of 40K .
Fourth is krypton (Kr) and xenon (Xe), in 1898 Ramsay and Travers discovered
a new substance that is Kr and Xe. Kr and Xe were founded in the residue left after
almost all of liquid air evaporating. This element was named Kr the Greek word
kryptos, its mean ―hidden‖ and Xe the Greek word xeneus its means ―stranger‖.
The last is radon (Rn), in 1900 Rn was by discovered Friedrich Dorn, called
emanation (emission) of radium. In 1908, Ramsay and Gray, named niton, isolate these
elements and determine its density, and then it was known that this element is the
heaviest gas of all the elements that have been found at that time. Rn is inert and
occupies the last position in the group of noble gases in the periodic table. Rn was
235
produced in the three naturally occurring decay series of U, 238U, 232Th. Each of that
series consists of numerous steps before stable nuclide results, but the final product is
Rn in each case. All of the isotopes are radioactive and decay by 𝛼-emission to produce
isotopes of polonium.
All noble gases present in the atmosphere and used in human life. Here are the
benefits of each element of the noble gas. He was used to fill the balloon, as a mixture
of gas for sea dives in lieu of N2. He also used to substitute N2 as heliox gas mixture
(He-O2) in vitro oxygen to divers, because it is unreactive, very light weight and
solubility in body tissues less than N2. Liquid He was used for cooling the metal coil in
the scanner, because a low boiling point. It was also used for heat transfer medium in
nuclear reactors.
Neon was used as billboards and lights on the runway. Ne produces high-
intensity light when an electric current pass. This light can be seen from a far and
through the mist. Red is the characteristics color of Re. However, the use of fluorescent
tubes with powder can produce other colors. Ne also used in TV tubes, gas lasers, high-
voltage indicators and liquid it was used as a coolant.
23 | 105 P a g e s
Argon was used in light bulbs replace the O2 because it is unreactive so that the
filaments are not easily broken. The use of Ar enables heating the filament at a higher
temperature thus obtained is more white light. Ar was used as an inert atmosphere in
welding, metal production in industry and in laboratory experiments. This is because Ar
was unreactive that metal will not oxidize as if the process takes place in the open air.
Ar used for laser to produce a variety of light with blue-green waves. Lasers can be used
for live entertainment and medical purposes, such as eye surgery and hardening dental
fillings.
Krypton (Kr) was used in light aircraft on the runway, the lighthouse, the light
high-speed photography, fluorescence and laser for treating eye retina. Kr-85 is the
isotope, Kr was used for industry to control the thickness of the paper industry, because
it is radioactive, it can remove particles of β (Beta).
Xenon (Xe) was used to flash (flash gun) and vacuum tubes. In a vacuum tube, it was
produced a very bright white light. Xenon is the only noble gas that is anesthesia/ drugged at
atmospheric pressure. Xe was considered as an ideal anesthetic among other anesthetics. It was
also use in nuclear reactor.
Radon (Rn) was used for cancer therapy. Rn that is radioactive put in a small tube
sealed and placed near the tissue affected by cancer. It also used for earthquake warning system.
Rn comes from the decay of U and Ra in rocks. As the plates move, Rn levels will increase due
to the release of Rn of rocks. Rn levels are an indicator of the earthquake.
3.3 COMPOUNDS OF NOBLE GASES

Although elements of the noble gas group are stable, there was a noble gas
elements are capable forming compounds or bonded with other elements. For example
compound that consists of xenon such as XeF2, XeF4, XeF6 and other noble gas
chemistry such as KrF2.
Linus Pauling (1933) speculated about the reaction of O2 with PF6 mentioned
earlier suggested that a similar reaction with xenon might be successful in light of the
similarity in ionization potentials. It should be apparent that if Xe is to react, it should
be with an extremely strong oxidizing agent, and F2 is a suitable candidate. By this
24 | 106 P a g e s
means, the difluoride and tetrafluoride of xenon were prepared as a mixture of the
elements was heated or subjected to electromagnetic radiation.
Xenon difluorides is made by interaction of Xe with a deficiency of F2 at high
pressure. The deficiency of F2 insures exclusive formation of the difluoride.
Xe(g) + F2(g) → XeF2(s) …..……………………….…………………….….(3.1)
It dissolves in water to give solutions with a pungent odor of XeF2. Hydrolysis is slow
in acid solution, but rapid in the pressure of bases, due to
1
XeF2 + 2 OH- →Xe + 2 O2 + 2 F- + H2O …………...........…………………(3.2)
Xenon tetrafluorides is easy to prepare. When preparing XeF4, a mixture

0
containing a 5 : 1 ratio of fluorine to xenon was heated at 400 C and subjected to
several atmospheres pressure about 6 atm.
XeF2(g) + F2(g) → XeF4(s) …………………………………...…………….(3.3)
Xenon heksafluorides at a higher ratio of fluorine to xenon was used, XeF 6 can
be obtained. Xenon heksafluoride (XeF6) is obtained by the interaction of XeF4 and F2
at temperature above 2500C and pressure greater than 50 atm.
`XeF4(g) + F2(g) → XeF6(s)...............................................................................(3.4)
Monomeric XeF6 in the liquid or the vapor has a distorted octahedral structure because
of a lone of electrons at Xe.
Reactions of Xenon Fluorides and Oxyfluorides, many of the reactions that
xenon fluorides undergo are similar in some ways to those of interhalogens. However,
the xenon halides differ markedly in terms of their reactivity with XeF2 being much less
reactive than either XeF4 or XeF6. The difluoride reacts slowly with water,
2 XeF2(s) + 2 H2O(l) → 2 Xe(g) + O2(g) + 4 HF(aq)..........................................(3.5)
But in basic solution a different reaction takes place rapidly, which can be shown as
2 XeF2 + 4 OH- → 2Xe + O2 + 2 H2O + 4 F- ................................................(3.6)
Xenon tetrafluoride reacts rapidly with water by undergoing disproportionation,
6 XeF4 + 12 H2O → 2 XeO3 + 4 Xe + 3 O2 + 24 HF ....................................(3.7)
As xenon +4 is converted into xenon +6 and Xe. The oxide is an explosive compound
that is also produced by the hydrolysis of XeF6.
25 | 105 P a g e s
XeF6 + 3 H2O → XeO3 + 6 HF .....................................................................(3.8)
Xenon trioxide is formed in the hydrolysis of XeF4 and XeF6. The hydrolysis may take
place by the formation of XeOF4 as an intermediate (Cotton, 1930).
XeF6 + H2O → XeOF4 + 2 HF ........................................................................(3.9)
XeOF4 + 2 H2O → XeO3 + 4 HF ................................................................(3.10)
Some oxides of xenon are known, and like most other compounds of xenon, they
are usually obtained from the fluorides. The heat of formation of XeO3 is approximately
+ 400 kJ/mol so, it should be not surprise that the compound is a very sensitive material.
On evaporation of water, XeO3 is obtained as a white deliquescent solid that is
dangerously explosive. The structure of XeO3 can be shown as follows:
Xe Xe Xe
o o o o O o
o o o
The first structure shows only single bonds, thus the formal charge on Xe is +3
so contributions from structures showing double bonding are significant. In basic
solution, a reaction between OH- and XeO3 occurs and xenate ion (HXeO4-) is formed,
which can be shown as
XeO3 + OH- → HXeO4-- .............................................................................(3.11)
A reaction of HXeO4- in basic solution is very similar, and it can be shown as
2 HXeO4- + 2 OH- → XeO64- + Xe + O2 + 2 H2O ......................................(3.12)
Which produces an perxenate ion, XeO64-. Several solids containing perxenate
ion have been isolated, and the ion is the conjugated base of weak acid, H 4XeO6.
Therefore, the salts hydrolyze to produce basic solutions.
XeO64- + H2O HXeO63- + OH- ................................................................(3.13)
HXeO63- + H2O H2XeO62- + OH- .............................................................(3.14)
With the oxidation state of Xe in perxenates being +8, it is expected as a very
strong oxidizing agent. In an analogous reaction, xenon oxyfluorides are produced by
the reactions
XeF6 + 2 XeO3 → 3 XeO2F2........................................................................(3.15)
2XeF6 + XeO3 → 3 XeOF4 ............................................................................(3.16)
26 | 106 P a g e s
Krypton difluoride, as mentioned earlier krypton is known to form several
compounds, but they are fewer and less well characterized than the compounds of
xenon. The difluoride has been obtained by electric discharge through a mixture of Kr
and F2 at low temperature. Krypton difluoride is obtained when an electric discharge is
passed through a mixture of Kr and F2 at 1800C. As in the case of xenon difluoride, a
cation is produced in the reaction with a strong Lewis acid such as SbF5.
KrF2 + SbF5 → KrF+SbF6- ..........................................................................(3.17)
It resembles XeF2 being volatile white solid constructed of linear FKrF
molecules, but differs in that it is thermodynamically unstable.
KrF2(g) → Kr(g) + F2(g) ∆H0 = -63 kJ/mol ...................................................(3.18)
XeF2(g) → Xe(g) + F2(g) ∆H0 = 105 kJ/mol ..................................................(3.19)
Krypton difluoride has been prepared from the elements, but only at low
temperature using electric discharge. When irradiated with ultraviolet light, a mixture of
liquid krypton and fluorine reacts to produce KrF2.
The chemistry of krypton is well established, but is still much less extensive
than xenon. Although a rather extensive chemistry of the noble gases has developed, the
vast majority of the studies has dealt with the xenon compounds. As expected, radon
difluoride can be obtained, but because all isotopes of radon undergo rapid decay, there
is not much interest in the compound.
3.4 SUMMARY
Based on explanation above, it can be conclude than noble gases are a special
group because it is the most stable group in the periodic table. The elements of the noble
gas group are not very reactive because they are stable (have eight electrons in the
valence shell). Noble gas was useful in daily life such as in industry and health.
Although it is stable and very unreactive noble gases could still form compounds with
some mechanisms, for example the chemistry of xenon such as XeF2, XeF4, XeF6 and
other noble gas chemistry such as KrF2.
27 | 105 P a g e s
3.5 STUDY QUESTIONS
1. Explain the tendencies of properties of the noble gases from helium to radon.
2. Explain at least two uses of each noble gas from helium to radon.
3. Explain why do some noble gases can form compounds although they are noble and
inert.
4. Explain how to isolate the nobvle gases from air.
28 | 106 P a g e s
CHAPTER 4
CHEMISTRY OF HALOGEN
4.1 INTRODUCTION
The basic competence of the chapter 4 is to understand properties and preparation of
halogen gases and their compounds. Indicators of learning for reaching the basic competences
should show that students should be able to:
a. explain natural availability of halogen gases;
b. explain oxidative tendencies of halogen;
c. give examples showing halogen as oxidation agents;
d. explain the production ways of halogen gases;
e. explain properties of oxides of halogen;
f. explain the acid strengths of halide acids and oxyhalide acids; and
g. explain the formation of interhalogen compounds.
This chapter will explain briefly the natural availabilityof halogen gases, their
properties and preparation, as well aspreparation and properties of halogen compounds
such as halides, oxyhalides, and interhalogen.
4.2 THE ELEMENTS OF HALOGEN

The group VIIA elements are known as the halogens, a word that has its origin
in the Greek words halos meaning salt and genes meaning formed. In other words, the
halogens are the ―salt‖ formers‖, which at least partially describes their chemical
behavior. All of the elements in the periodic table (exception He, Ne and Ar) form
halides. Ionic or covalent halides are among the most important and common
29 | 105 P a g e s
compound. This essay will explain briefly the natural availability of halogen gases, their
properties and preparation, as well as preparation and properties of halogen compounds
such as halides, oxyhalides, and interhalogen.
Halogen elements namely fluorine, chlorine, bromine and iodine are not free in
nature, but are found in the form of compounds. Fluorine found as fluorspar CaF2,
cryolite Na3AlF6 in Greenland deposit, and fluorapatite Ca5(PO4)3F in the earth‘s crust.
In nature, chlorine found as NaCl, KCl, MgCl2 and so on in seawater, salt lakes, and as
deposits from the prehistoric evaporation of salt lakes. The largest natural amount of
bromine is in the ocean. Bromine is obtained from seawater through the reaction:
𝑝𝐻 ~3.5
2Br- + Cl2 2Cl- + Br2 ……….……………………………………….(4.1)
The first mineral founded containing bromine is AgBr. It was discovered in
Mexico (1841) and industrial production. Iodine found in the form of sodium and
potassium compounds on land and in sea. The first mineral of iodine (AgI) was
discovered in Mexico (1825). Astatine has isotopes-85, because of that astatine was
expected to be radioactive which have half-life of less than 1 min. Thus, the natural
211
availability of astatine is negligible. It was made by synthesizing the isotope At by
209
bombarding Bi with particles in a large cyclotron:
209
83 Bi + 42He → 211 1
85 At + 2 0𝑛 ………………………..………………………..(4.2)
A halogen is a strong oxidizing agent. The oxidator property of halogen from top
to bottom tends to decrease, so the halogen can oxidize ion of halide underneath it.
F2 + 2KCl → 2KF + Cl2 …………………………….………………..……..(4.3)
or can be written as
F2 + 2Cl- → 2F- + Cl2 ………………….…………….……………….……..(4.4)
Cl2 + 2Br- → 2Cl- + Br2 …………………..….……….…………….……….(4.5)
Cl2 + 2I- → 2Cl- + I2 ……………………….……………………….……….(4.6)
Br2 + 2I- → 2Br- + I2 …………………………………………….……….…(4.7)
From the reaction above, fluorine is the most reactive; it can oxidize chlorine,
bromine and iodine. Chlorine can oxidize iodine and bromine. Bromine only can
oxidize iodine. Iodine is the least reactive because it cannot oxidize fluorine, chlorine
and bromine. The reactivity of halogen elements follows the sequence below:
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fluorine > chlorine > bromine > iodine > astatine
Based on the electron configuration, a halogen element gets the stability by
accepting an electron. A halogen is an oxidizing agent (electron acceptor) and it is
reduced by gaining electron to form a halide ion.
X(g) + e- → X-(g) ……………………………….…………….…………….(4.8)
For example:
2 F2 + 2 H2O → 4 HF + O2 …………..…………………………...…………(4.9)
Based on the reaction above, fluorine is reduced. The oxidation number of
fluorine changes from 0 becomes -1. The oxidation strength of halogen increasing from
astatine to fluorine as the following order:
astatine < iodine < bromine < chlorine < fluorine
4.3 THE PRODUCTION WAYS OF HALOGEN GASES

Fluorine cannot be prepared directly by chemical methods; it is prepared in the
laboratory and on an industrial scale by electrolysis. In 1886, Moissan electrolyzed a
cooled solution of KHF2 in anhydrous liquid HF using electrodes of Pt/Ir.
Chlorine can be obtained in several ways. First, chlorine is obtained by
electrolyzing concentrated sodium chloride solution. This process was initially used
primarily for the production of sodium hydroxide. Second, it is obtained by
electrolyzing fused magnesium chloride or fused sodium chloride. Third, it is obtained
by electrolyzing hydrogen chloride. A mixture of hydrogen chloride with oxygen is
passed over a catalyst of copper (II) chloride containing one or more chlorides of rare-
earth metals on silica at temperature of 600-670 K (Chambers and Holliday; 1975). The
reaction is exothermic:
4 HC1 + O2 2H2O + C12 ……...…………………………………….…..(4.10)
In the laboratory, bromine is prepared by oxidizing bromide ion. The oxidation
is carried out by mixing solid potassium bromide with manganese (IV) oxide and
distilling with concentrated sulphuric acid with reaction:
2KBr + MnO2 + 3H2SO4 → Br2 + 2KHSO4 + MnSO4 + 2H2O ...................(4.11)
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On the industrial scale, bromine is obtained from sea water by using the displacement
reaction with chlorine:
2 Br- + Cl2 → 2 Cl- + Br2 …………………………………………….…….(4.12)
Iodine is prepared in the laboratory by using oxidation method of an iodide with
manganese (IV) oxide and sulphuric acid.
2NaI + MnO2 + 3H2SO4 → MnSO4 + 2NaHSO4 + I2 + 2H2O .....................(4.13)
Most iodine was produced from the sodium iodide (V) remaining after crystallizing
sodium nitrate from Chile saltpeter. First, the iodide (V) is reduced to iodide by blowing
sulphur dioxide into the solution:
IO3- + 3 SO32- → I- + 3 SO42- …………………………………………..…..(4.14)
Then, excess of iodide is added. The reaction as follow:
IO3- + 5 I- + 6 H+ → 3 I2 + 3 H2O ……...…………………………….…….(4.15)
The iodide is precipitated as copper (I) iodide by adding copper (II) sulphate, thus:
2 I- + 2 Cu2+ + SO32- + H2O → 2 CuI + SO42- + 2 H+ ..................................(4.16)
Then the iodine is liberated by heating the copper (I) iodide with sulphuric acid and iron
(III) oxide:
2 CuI + 6 H2SO4 + 2 Fe2O3 → 2 CuSO4 + 4 FeSO4 + 6 H2O + I2 ...............(4.17)
The copper (II) sulphate is recovered and used to precipitate more copper (I) iodide.
4.4 PROPERTIES OF OXIDES OF HALOGEN

4.4.1 Oxides of Fluorine
Compounds containing fluorine and oxygen are actually fluorides (e.g. O2F2 and
OF2) (James House; 2008). Oxygen difluoride, OF2 (m.p. -223,8oC, b.p. -145oC) is a
pale yellow, poisonous gas. The molecule has a bent structure and the bond angle is
103,2o. The reaction of OF2 with water can be shown as
H2O + OF2  O2 + 2 HF …………..………………………………………(4.18)
The reaction of OF2 with HCl produces HF and liberates chlorine. When heated to a
temperature above 250oC, OF2 decomposes into O2 and F2.
Dioxygen difluoride, O2F2, is a yellow-orange solid with a melting point of -
163oC. It is an extremely reactive fluorinating agent.
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4.4.2 Oxides of Chlorine
The compounds of oxides of chlorine to be discussed are (Greenwood and
Earnshaw; 1997):
1) Cl2O (m.p. -120,6 oC, b.p. 2,0 oC): a brownish-yellow gas at room temperature (or red-
brown liquid and solid at lower temperature); it explodes when heated or sparked.
2) Cl2O3: a dark-brown solid which explodes even below 0oC.
3) ClO2 (m.p. -59 oC, b.p. 11 oC): a yellow paramagnetic gas (deep-red paramagnetic liquid
and solid); the liquid explodes above -40oC and the gas at room temperature may explode at
pressures greater than 50 mmHg.
4) Cl2O4: a pale-yellow liquid, ClOClO3 (m.p. -117 oC, b.p. 44,5 oC (extrap)), which readily
decomposes at room temperature into Cl2, O2, ClO2 and Cl2O6.
5) Cl2O6 (m.p. 3,5 oC, b.p. 203 oC): a dark-red liquid which is in equilibrium with its monomer
ClO3 in the gas phase; it decomposes to ClO2 and O2.
6) Cl2O7 (m.p. -91,5 oC, b.p. 81 oC): a colorless oily liquid which can be distilled under reduced
pressure.
All the compounds are endothermic, having large positive enthalpies and free
energies of formation, so it is not possible to prepare them by direct reaction of Cl2 and
O2. For example Cl2O is best obtained by treating freshly prepared yellow HgO and Cl2
gas (diluted with dry air or by dissolution in CCl4):
2 Cl2 + 2 HgO  HgCl2.HgO + Cl2O(g) ....................................................(4.19)
It is very soluble in water; in fact the gas is the anhydride of hypochlorous acid.
Chlorine dioxide, ClO2 is a very reactive compound; it decomposes readily and
violently into its constituents; it is a powerful oxidizing agent. Dichlorine hexoxide,
Cl2O6, is a powerful oxidizing agent and reacts violently even with water with which it
forms a mixture of chloric (V) and chloric (VII) acids. Dichlorine heptoxide, C12O7, is
the most stable of the chlorine oxides.
4.4.3 Oxides of Bromine
Bromine oxides are unstable substances and little is known about them.
Dibromine monoxide, Br2O, is a dark brown liquid, m.p. -17 oC, which decomposes
rapidly at room temperature. It oxidizes I2 to I2O5, benzene to 1,4-quinone, and yields
33 | 105 P a g e s
OBr- in alkaline solution. Tribromine octoxide, Br3O8, is a white solid obtained when
ozone and bromine react together at 0oC at low pressure. It is unstable above -73oC in
the absence of ozone. It is known to exist in two forms, both soluble in water. Bromine
dioxide, BrO2, is a yellow solid, stable only below -43oC, decomposing above this
temperature to give oxygen and bromine.
4.4.4 Oxides of Iodine
Iodine forms the most stable oxides of the halogens. Diiodine pentoxide, I2O5, is
a white solid prepared by heating iodic acid (V) to 177oC:
2 HIO3  H2O + I2O5 ……………………………………………………..(4.20)
The equation indicates that it is the anhydride of iodic-acid(V), which is re-formed
when water is added to the pentoxide. Mixed with concentrated sulphuric acid and
silica, it is a quantitative oxidizing agent for carbon monoxide at room temperature:
5 CO + I2O5  5 CO2 + I2 …………………………………………………(4.21)
4.5 HALIDE ACIDS AND OXYHALIDE ACIDS

4.5.1 Halide Acids (Hydrogen Halides)
All the halogens form hydrides by direct combination of the elements. The
hydrogen halides formed are covalently bonded, and when pure are colorless gases at
room temperature.
Table 1. Properties of Hydrogen Halide (James House; 2008)
HF HCl HBr HI
Melting point, oC -83 -112 -88,5 -50,4
Boiling point, oC 19,5 -83,7 -6,7 -35,4
Dipole moment, D 1,74 1,07 0,788 0,382
Bond Energy, kJ mol-1 574 428 362 295
All the hydrogen halides are freely soluble in water and react according to the
general equation:
HX + H2O H3O+ + X- …………………………………............………(4.22)
The steps involved are (a) the breaking of the hydrogen-halogen bond; (b) the hydration
of the proton, and (c) the hydration of the halide ion. When HX is HCl, HBr or HI, the
energy liberated by the combined hydration energies of the proton and halide ion
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exceeds the bond dissociation energy, step (a), and all three are strong acids in water
with acid strength increasing from HCl to HI.
The bond dissociation energy of the hydrogen-fluorine bond in HF is so great
that the above equilibrium lies to the left and hydrogen fluoride is a weak acid in dilute
aqueous solution. In more concentrated solution, however, a second equilibrium
reaction becomes important with the fluoride ion forming the complex ion HF2-. The
relevant equilibrium are:
HF + H2O H3O+ + F- .............................................................................(4.23)
(HF)2 + H2O HF2- + H3O+ ......................................................................(4.24)
The second equilibrium is displaced to the right as the concentration of hydrogen
fluoride is increased and it is found that at a concentration of approximately 5-15 M, HF
is effectively a strong acid. In this way hydrogen fluoride differs from all the other
hydrogen halides.
4.5.2 Oxyhalide Acids
The existence of fluoric (I) acid (hypofluorous acid), HFO, formed by the reaction
of fluorine with water at 273 K. The acid forms colorless crystals, m.p. 156 K, is very
unstable and has, as expected, very strong oxidizing properties.
The acids of chlorine(I), bromine(I) and iodine(I) are weak acids, the pKa values
being 7.4, 8.7 and 12.3 respectively. They are good oxidizing agents, especially in acid
solutions. The acids decrease in stability from chloric(I) to iodic(I).
Only chlorine forms a +3 acid, HC1O2. This is also a weak acid and is unstable.
The +5 acids, HXO3, are formed by chlorine, bromine and iodine; which are strong
acids and are stable compounds.
The existence of chloric(VII) (perchloric) and iodic(VII) (periodic) acids has long
been known but bromic(VII) acid has only recently been prepared. The strengths of the
monobasic acids increase rapidly with increase in oxidation state of the halogen in
accordance with Pauling‘s rules (Greenwood and Earnshaw; 1997). The pKa values of
related acids increase in the sequence Cl < Br < I.
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4.6 INTERHALOGEN COMPOUNDS
One of the interesting attributes of the halogens is the fact that atoms of different
types readily form bonds, the compound known as an interhalogen (House; 2008).
Because the halogen atoms have seven valence shell electron, the outer shell is filled
when two atoms form a bond, but when an unshared pair is separated, two additional
bonding sites are available. A general formula for compounds containing two different
halogens is XX‘n, where X‘ is the lighter halogen and n is an odd number. The
maximum value for n is 7, but the only interhalogen having that formula is IF7. When
n=5, the known compounds are ClF5, BrF5 and IF5, and none of the pentachlorides are
stable. This is undoubtedly due to the effect of the larger size of the chlorine atom and
the fact that it is a weaker oxidizing agent than fluorine. Bonds between other halogens
and fluorine are also more polar, so there is some stability imparted by partial charges
on the atoms. As a result of these factors, the only XX‘7 compound is IF7.
Table 2 Summary of the properties of the interhalogens.
Formula m.p., oC b.p., oC µ, D
Type XX‘ ClF -156 -100 0,88
BrF -33 20 1,29
IF - - -
BrCl -66 -5 0,57
ICl 27 97 0,65
IBr 36 116 1,21
Type XX‘3 ClF3 -83 12 0,56
BrF3 8 127 1,19
IF3 - - -
ICl3 101 (16 atm) - -
Type XX‘5 ClF5 -103 -14 -
BrI5 -60 41 1,51
IF5 10 101 2,18
Type XX‘7 IF7 6,45 (triplept) - 0
Iodine monochloride (IC1), IBr, and IC13 are solids at room temperature, the
remainder being volatile liquids or gases. It‘s made by the direct combination of the
halogens concerned; all are covalent with the larger halogen occupying a central
position. With the exception of iodine pentafluoride, IF5, they are extremely reactive,
behaving (like halogens) as oxidizing agents and reacting with water.
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4.7 SUMMARY
Halogens are founded in nature in the form of its compounds. A halogen is a
strong oxidizing agent (electron acceptor) and it is reduced by gaining electron to form a
halide ion. The oxidator property of halogen from top to bottom tends to decrease
(fluorine > chlorine > bromine > iodine > astatine). Halogens gas can be produced by
electrolyzing process or oxidation method from its ion. Halogens with oxygen produce
its oxides. Oxides of fluorine are OF2 and O2F2; some oxides of chlorine are Cl2O,
Cl2O3, ClO2, Cl2O4, Cl2O6, and Cl2O7 (all the compounds are endothermic, having large
positive enthalpies and free energies of formation, so it is not possible to prepare them
by direct reaction of Cl2 and O2); oxides of bromine are unstable substances such as
Br2O, Br3O8, and BrO2; oxides of iodine are the most stable oxides of the halogens such
as I2O5. The halide acids strength increasing from HF to HI, and the strengths of the
monobasic acids increase rapidly with increase in oxidation state of the halogen in
accordance with Pauling‘s rules; the pKa values of related acids increase in the
sequence Cl < Br < I. One of the interesting attributes of the halogens is the fact that
atoms of different types readily form bonds, the compound known as an interhalogen. A
general formula for compounds containing two different halogens is XX‘n, where X‘ is
the lighter halogen and n is an odd number.
4.8 STUDY QUESTIONS

1. How is chlorine prepared from its chloride salt?
2. Why is it imposible to make iodides in high oxidation state from its element,
comparing to corresponding bromides and chlorides are known?
3. How may halides act as bridging ligands?
4. Why can iodine, which has very low solubility in water, dissolve readily in KI
aquous solution?
5. Why can F2 not be obtained by electrolysis of aquous solution of NaF, but Cl2 can
be from aquous solution of NaCl?
6. Write a balance equation of the hydrolysis of SeF6.
7. How can CF3NO be obtained from CF3I?
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CHAPTER 5
CHEMISTRY OF OXYGEN
5.1 INTRODUCTION
The basic competence of the chapter 5 is to understand properties, preparation
compounds of oxygen. Indicators of learning for reaching the basic competences should show
that students should be able to:
a. explain properties of oxygen and its isotopes;

b. explain ways in producing oxygen gas;
c. explain structure of ozon and chemicals, that can break away the ozon;
d. clasify various oxides; and
e. explain ways in reducing water hardness.
This chapter will explain briefly the properties, isotopes and preparation of
oxygen gas, as well as preparation and properties of ozone, oxides, and water.
5.2 ELEMENTAL OXYGEN

The mass of earth‘s crust contain about 50 % by weight of oxygen, 89% in water
and 21% in atmosphere. Oxygen is the main elements in earth crust. The discoveries of
oxygen are Carl Wilhelm Scheele and Joseph Priestly in 1773-1774. The oxygen term
invented by Antoine Lavoisier in 1777and succeeded in breaking down experiment with
oxygen Phlogiston theory of combustion and corrosion.The oxygen atom has the
configuration electron 1s2 2s2 2p6. The oxygen needs two electrons to achieve the
completion of the octet rules.The physical and chemical properties of matter are those of
38 | 106 P a g e s
the constituent molecules, and the transformation of matter into different materials
(compounds) is the result of their reactions to form new molecules. Only oxygen in the
group VI A is a gas formed in room temperature, odorless, and colorless. There are
16 17
three isotopes of oxygen in nature, such as O(99.759%), O(0.0374%) and
18
O(0.2039%). There are various oxides of oxygen based such as ionic oxides, covalent
or molecular oxides, and acid base properties of oxides ( basic oxides, acidic oxides,
amphoteric oxides, and other oxides). Oxygen has two allotropes there are dioxygen
(O2) and trioxygen or ozone (O3).
Oxygen is a diatomic gas, which is tasteless, odorless, and colorless. The
element oxygen has an atomic weight of 16. The oxygen has a density that is greater
than air and it has very low solubility in water. It dissolves to the extent of 3.08 cm 3
(STP) in 100 cm3 H2O at 200 and this drops to 2.08 cm3 at 500. Typical solubilities are
Et2O 45.0 CCl4 30.2, Me2CO 28.0 and C6H6 22.3. The bond dissociation energy of O2 is
493.4 kJ mol-1, this is substantially less than for the triply bonded species N2 (945.4 kJ
mol-1) but is much greater than for F2(158.8 kJ mol-). The melting and boiling point of
oxygen are 54.80K (-218.3 °C or -360.9 °F) and 90.2 K [182.9 °C or -297.2 °F). The
oxygen has critical temperature of 154.60K (-118.5 °C or 181.3 °F ) and the critical
pressure is 50.15 atm.
Oxygen is an extremely reactive gas which vigorously oxides many elements
directly, either at room temperature or above. Oxygen atoms react spontaneously with
the atoms of all elements except the noble gases to form polyatomic molecules via
covalent bonds. Linear 2-coordinate O occurs in the silyl ether molecule [O(SiPh3)2].
Planar 3-coordinate O occurs in the neutral gaseous molecular species OLi3, ONa3 and
in both cationic anioniccomplexes. It also occurs in to dimensional layer lattices such as
tunellite, [OB6O8(OH)2]2- and in the three dimensional rutile structure. Planar 4-
coordinate O occurs uniquely in NbO which can be considered as a defect NaCl and Nb.
39 | 105 P a g e s
5.3 ISOTOPES OF OXYGEN
Oxygen has three stable isotopes, namely 16O (99.759%),17O (0.0374%) and 18O
18
(0.2039%) (Sawyer, 1991). The isotope of O can be concentrated by fractional
distillation of water containing up to 97 % atom 18O. The oxygen isotopes have medical
applications. O16 is used in the production of radioactive N13, which is used for PET
imaging and myocardial perfusion. O17 can be used as a tracer in the study of cerebral
oxygen utilization. Large quantities of O18 are used for the production of F18. F18 is used
to produce 2-[18F] fluoro-2-deoxyglucose (FDG) which is used as a tracer in positron
emission tomography or PET. Millions of these FDG-PET medical procedures are
performed annually to investigate a range of diseases in various human organs.
5.4 OXYGEN GAS PREPARATION

The most frequently used method to prepare oxygen in the laboratory is through
the decomposition of potassium chlorate (KC1O3). The potassium chlorate is heated and
oxygen is evolved leaving KCl.
2 KClO3  2 KCl + 3 O2 .............................................................................(5.1)
The best method for the controlled preparation of very pure O2 is the thermal
decomposition of recrystallized, predict,degassed KMNO4 in a vacuum line. MnVIand
MnIVare both formed and the reaction can formally be represented as:
2 KMnO4  K2MnO4 + MnO2 +O2 .............................................................(5.2)
Manganese dioxide (MnO2) is added to the reaction as a catalyst. A catalyst is a
substance which speed up a reaction but is not changed after the reaction is completed.
The MnO2, causes the reaction to take place more rapidly at a lower temperature.
alternate methods of producing oxygen in the laboratory are sodium peroxide and water.
2 Na2O2 + 2 H2O  4 NaOH + O2 ...............................................................(5.3)
Hydrogen peroxide and manganese dioxide:
2 H2O2  2 H2O + O2 ..................................................................................(5.4)
Electrolysis of water:
2 H2O2  2 H2 + O2 ....................................................................................(5.5)
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5.5 OZONE
Ozone is a very reactive form of oxygen, acting as an oxidizing agent. Aside
from its use in purifying drinking water, ozone at low altitudes in the atmosphere is
usually considered an unwanted pollutant. On the other hand, the ozone layer that forms
at an altitude of approximately 27 km above the earth‘s surface is considered to be
essential and beneficial. Ozone is an irritating pale blue gas, heavier than the air, very
reactive and unstable, which cannot be stored and transported, so it has to be generated
―in situ‖. It is explosive and toxic, even at low concentrations. In the Earth‘s
stratosphere, it occurs naturally (with concentrations between 5 and 10 ppm), ozone
absorbs ultraviolet radiation very strongly in the region 220-330 nm. it is effective in
filtering out dangerous UV-B radiation, 290 nm < l < 320 nm (UV-A radiation, 320 nm-
400 nm, is relatively less harmful and UV-C radiation, < 290 nm does not penetrate to
the troposphere.) If UV-B were not absorbed by ozone, severe damage would result to
exposed forms of life on the earth (Ullmann‘s, 1991).
By analysis of the electronic structure, the molecule is considered to have the
following resonant structure:
O O
O O O O
It is worthy to mention the toxic character of ozone, specially at high

concentrations. While ozone is considered to be a toxic gas, there are factors which
mitigate the immediate danger to individuals working with it. Toxicity is dependent on
concentration and length of exposure. The ozone layer is beneficial because ozone
absorbs harmful ultraviolet radiation emitted by the sun.
There are two reactions by which stratospheric ozone is produced are,
O2 + hv  O + O (l < 242.4 nm) ..........................................................(5.6)
41 | 105 P a g e s
O + O2 + M  O3 + M (energy-absorbing N2 or O2) ................................(5.7)
and it is destroyed by photodissociation,
O3 + hv  O2 + O (l < 325 nm) .....................................................................(5.8)
and a series of reactions from which the net result is the following:
O + O3  2O2 ................................................................................................(5.9)
The principal cause of ozone depletion is the presence in the stratosphere of
chlorofluorocarbons (CFCs). Chlorofluorocarbons(CFCs) are small molecules with
halogen atoms bonded to central carbons. CFCs play a major role in ozone depletion.
Specific examples of CFCs include CFCl3 (CFC-11) and CF2Cl2 (CFC-12). These
compounds are nonflammable, relatively inert, volatile yet readily liquefied, and
nontoxic an extremely useful set of properties. CFCs have been used as coolants for
refrigeration, in foam plastics manufacture, as aerosol propellants, and as industrial
solvents. Unfortunately, the same properties that make them useful are also the reason
for their destructive effect on the stratospheric ozone.
Destruction of the stratospheric ozone layer by CFCs begins when a photon of
high enough energy breaks a carbon-chlorine bond in a CFC molecule. This produces a
chlorine atom, as shown here using CFC-12 as an example.
CF2Cl2(g) + hv  CF2Cl(g) + Cl(g) ..............................................................(5.10)
The chlorine atom, a free radical, then participates in what is called a chain
reaction mechanism. It first combines with an ozone molecule, producing a chlorine
monoxide (ClO) radical and an oxygen molecule.
First step : Cl(g) + O3(g)  ClO(g) + O2(g) ...........................................(5.11)
Second Step : ClO + ClO  ClOOCl .....................................................(5.12)
Third Step : ClOOCl + hv  ClOO + Cl .............................................(5.13)
Fourth Step : ClOO + hv  Cl + O2 ......................................................(5.14)
The net reaction obtained by adding two Step 1 reactions to Steps 2, 3, and 4 and
canceling species that appear as both reactants and products is the conversion of two
ozone molecules to three oxygen molecules.
Net reaction : 2O3(g)  3O2(g) ...................................................................(5.15)
42 | 106 P a g e s
This chain reaction increases the rate at which stratospheric ozone is destroyed,
but it does not affect the rate at which ozone is formed. It is called a chain reaction
because the reaction steps can repeat over and over. The two chlorine atoms that react
when Step 1 occurs twice are regenerated in Steps 3 and 4, so there is no net change in
concentration of chlorine atoms. It has been estimated that a single chlorine atom can
destroy as many as 100,000 molecules of O3 before it is inactivated or returned to the
troposphere (probably as HCl)
5.6 OXIDES
The oxygen has classify various oxide including ionic oxides, covalent or
molecular oxides, acid base properties of oxides (basic oxides, acidic oxides,
amphoteric oxides, and other oxides), andperoxide and superoxide, and. The classify
oxides according to their acid or base character in aqueous system. Generally, the
oxides of the metals are basic, whereas those of the nonmetals are acidic. There also a
number of important amphoteric oxides.
Ionic metal oxides formed, energy must also be expended to vaporize and to
ionize the metal. Those the stability of ionic metal oxides is a consequence only of the
high lattice energies that are obtained with the small and highly charged oxide ion.
Where the lattice energy is not sufficient to offset the energies for ionization and so on,
oxides with substantial covalent character are formed. Examples of oxides with some
covalent character are BeO, SiO2, and oxides of Boron such as B2O3. Another various
oxide are peroxide and superoxide.
Covalent or molecular oxides are compounds, such as CO2,SO2,SO3, and NO2,in
which covalent bonding is dominant.
The covalent oxides of the nonmetals are usually acidic, dissolving in water to
produce solution of acid. There are term acid anhydrides. An example in which N2O5 is
seen to be the acid anhydrides of nitric acid.
N2O5 + H2O  2H+ + 2NO3 .......................................................................(5.16)
43 | 105 P a g e s
Even when these oxides are in soluble in water, they will generally dissolve in
these.
Sb2O5 + 2OH- + 5H2O  2Sb(OH-)6 .........................................................(5.17)
Acidic oxide will often combine directly, by fusion with basic oxide to form salt.
Na2O + SiO2  Na2SiO3S ...........................................................................(5.18)
Consequently, only those ionic oxides that are insoluble in water are inert to it.
Basic oxides function as basic anhydrides. When insoluble in water they usually
dissolve in dilute acid. The reaction
MgO(s) + 2 H+(aq).  Mg2+ + H2O ...............................................................(5.19)
These oxides behave acidicly toward strong bases and as bases towards strong acid. It is
called amphoteric oxides. The example of ZnO is illustrated in reaction.
ZnO(s) + 2H+(aq)  Zn2+(aq) + H2O ................................................................(5.20)
ZnO + 2OH- + H2O  Zn(OH) ......................................................................(5.21)
There are some which are relatively inert, which dissolve in neither acid or
bases( N2O, CO, PbO2, MnO2). This is last classifying of acid and base oxides called
other oxides. When MnO2 and PbO2 do react with acid (HCl) they do so by a redoxs
rather than an acid base reaction.
MnO2(s) + 4 HCl  Mn2+ + 2Cl-+ Cl2 + 2H2O……………………….……(5.22)
Peroxides and superoxides are derived formally from 𝑂22− (peroxides) and 𝑂22−
(superoxides). Alkali metals, Ca, Sr, and Ba form ionic peroxides. For example is
sodium peroxide. Sodium peroxide is made commercially air Oxidation of sodium.
Sodium peroxide is a yellow powder that is very hygroscopic and stable in temperature
of 500 C. Ionic Superoxidesare formed by the interaction of O2 with K, Rb, or Cs as
yellow to orange crystals solids .
5.7 WATER
Water is the most abundant compound on earth‘s surface, covering about 70%
of the planet. In nature water exists in liquid, solid, and gaseous states. At room
temperature, it is a tasteless and odorless liquid, nearly colorless. Many substances
dissolve in water and it is commonly revered to as the universal solvent because of this
44 | 106 P a g e s
water in nature and in use is rarely pure and some of its properties may vary slightly
from those of the pure substance. Water is volatile, mobile liquid with many curious
properties, most of which can be ascribed to extensive H bonding. In the gas phase the
H2O molecule has a bond angle of 104.50 (close to tetrahedral) and an interatomic
distance of 95.7 pm. The dipole moment is 1.84 D.
Water is present in nature is never found as pure water. The water still contains
from ions Ca2+ and Mg2+ called hard water. Based on properties they, hard water is
divided into two types, namely hard water temporary and hard water remains.
Hard water temporary contains of ions Ca2+ and Mg2+ ions of bicarbonate so that
it can be removed by heating.The reactions :
Ca(HCO3)(aq) → CaCO3(s) + H2O(l) + CO2(g) ……………………..………(5.23)
Mg(CO3)2(aq) → MgCO3(s) + H2O(l) + CO2(g) …………………………..(5.24)
Hard water remains contain of ions Ca2+ and Mg2+ can be derived from sulfate
orchloride-soluble compounds. These ions can‘t be removed by heating, but with the
addition of a solution of Ca(OH)2 and Na2CO3 solution.The reactions:
Mg2+(aq) + OH-(aq) → Mg(OH)2(s) ……………………………………..……(5.25)
Mg2+(aq) + 𝐶𝑂32−(aq) → MgCO3(s) ……………………..…………………….(5.26)
Ca2+(aq) + 2OH-(aq) → Ca(OH)2(s) ……………………………………..…..(5.27)
Ca2+(aq) + 𝐶𝑂32−(aq) → CaCO3(s) ……………………………………………..(5.28)
5.8 SUMMARY
Oxygen is there in group of VI A. Oxygen has three isotopes, namely 16O, 17O,
18
O. Oxygen is a diatomic gas, which is tasteless, odorless, and colorless. The element
oxygen has an atomic weight of 16. Oxygen atoms react spontaneously with the atoms
of all elements except the noble gases to form polyatomic molecules via covalent bonds.
Ozone is a very reactive form of oxygen, acting as an oxidizing agent. Aside from its
use in purifying drinking water, ozone at low altitudes in the atmosphere is usually
considered an unwanted pollutant. The principal cause of ozone depletion is the
presence in the stratosphere of chlorofluorocarbons (CFCs). Oxygen has various
45 | 105 P a g e s
oxide,namely ionic oxide, covalent or molecular oxides, ionic oxide, basic oxides,
amphoteric oxide, and other oxide like peroxide and superoxide. Water is present in
nature is never found as pure water. The water still contains from ions Ca2+and Mg2+
called hard water. Based on properties they, hard water is divided into two types,
namely hard water temporary and hard water remains.
5.9 STUDY QUESTIONS

1. Write the Lewis structure of O2. Explain why O2 has paramagnetic properties
meanwhile from its Lewis structure all valence electrons are paired.
2. Describe the carbon-oxygen bond in acetone.
3. Describe the preparation of ozone in laboratory.
4. What is the difference between oxidation and oxygenantion?
5. Explain the role of oxygen and ozone molecules in protecting our earth from global
warming. Explain also the role of oxygen for living live.
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CHAPTER 6
CHEMISTRY OF SULFUR
6.1 INTRODUCTION
The basic competence of the chapter 6 is to understand properties and production of
elemental sulphur and its compounds. Indicators of learning for reaching the basic competences
a. explain properties of sulphur and its allotropes;

b. explain ways in producing sulphur from natural sulphur resources;
c. describe structures of sulphur oxides;
d. explain properties of sulphuric acid;
e. explain ways in producing sulphuric acid;
f. explain ways in preparing hydrogen sulphide gas and its properties;
g. explain ways in preparing sodium tiosulphate and its uses.
This chapter will explain briefly the properties, allotropes and preparation of
sulphur, as well as preparation and properties of compounds of sulphur oxides,
sulphuric acid, hydrogen sulphide, and sodium tiosulphate.
6.2 ELEMENTAL SULFUR

Sulfur is well known by the peoples because it is used in people‘s daily life. For
matches, gunpowder, detergents, fireworks, batteries are some of sulfur usefulness. Not
only its usefulness, but also it is needed to know or make the others know, the danger
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of sulfur itself. The usefulness and the danger are absolutely related into the science of
matter, chemistry. In chemistry term, sulfur can be analyzed in the periodic table of the
elements. Sulfur is placed at group VI A, and at the third period. Started from periodic
table, it can be known all about sulfur including its properties and its allotropes, ways in
producing sulfur, the kind of sulfur compounds and ways in producing or preparing
sulfur compounds. So, this essay is going to tell or explain sulfur including its histories,
its properties, allotropes, compounds and ways in producing sulfur compounds.
Sulfur was firstly known in China, in a natural form that the chinese had called
―brimstone‖ or shiliuhuang that was found in Hanzhong (Freshney, 2007). By the third
century, chinese discovered that sulfur can be extracted from pyrite. A Song Dynasty of
military treatise of 1044 AD described different formulas of chinese gunpowder, which
is a mixture of potassium nitrate (KNO3), carbon, sulfur. Early, alchemist gave sulfur its
own alchemical symbol which was a triangle at the top of a cross. In the late 1770s,
Antoine Lavoisier helped convince the scientific community that sulfur was an element
and not a compound. In 1867, sulfur was discovered in underground deposits in
Louissiana and Texas. The overlying layer of earth was quicksand, prohibiting ordinary
mining operation. Therefore, the Frasch process was utilized to produce sulfur.
In modern era, its specifically known the properties of sulfur and its allotropes.
Sulfur is classified into group VIA in periodic table or it is called chalcogen group.
Sulfur is also classified into non-metallic group. Sulfur has melting point at 388,36 K or
115,21o C. The melting point of S8 is actually a decomposition point. Just after melting
rings with an average of 13.8 sulfur atoms are formed and at higher temperature still
larger rings form. The in the high viscosity region there are giant macromolecules that
are probably chains with radical ends. At higher temperature, highly colored S3 and S4
molecules are present to the extent 1-3 % at the boiling point.. Then, sulfur also has
boiling point at 717,8 K or 444,6o C. Sulfur is normally seen in lemon yellow colour.
The density of sulfur is 2,08 gr/cm3 (alpha), 1,96 gr/cm3 (beta) and 1,92 gr/cm3 (gama).
Sulfur has allotropes. At least, twenty four sulfur allotropes has been identified.
Two of the most common sulfur allotropes are Orthorhombic sulfur (α-S8) and
Cyclohexasulfur or Rhombohedral sulfur (S6). The most stable allotrope form in room
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temperature is Orthorhombic sulfur (α-S8). Eight sulfur atoms bond covalently crown
like rings. The Cyclohexasulfur or Rhombohedral sulfur is the densest of the sulfur
allotropes and forms air sensitive orange red crystals containing chair shape, six
membered rings. The structure of Orthorhombic sulfur (α-S8) and Cyclohexasulfur are
shown in figure below.
(a) (b)
Figure 1. The structure of Orthorhombic (a) and Cyclohexasulfur (b). The
picture of (a) is taken from Garry L Miessller et al., ―Inorganic Chemistry‖.
The picture of (b) is taken from Bodie E. Douglas et al., ―Structure and
Chemistry of Crystaline Solid‖.
Sulfur occurs widely in nature as the element, as H2S and SO2, in metal sulfide
ores, and as sulfates [e.g., gypsum and anhydrite (CaSO4), magnesium sulfate and so
on](Cotton et al., 1995). Freshney (2007) mention sulfur can be found in pure form
(near hot springs and in volcanic regions) and in ores like cinnabar (HgS), galena (PbS),
alunite, barite (BaSO4), sphalerite (ZnS), and stibnite (Sb2S3). The main concern is the
existence of sulfur as element. Sulfur as element is found in Orthorhombic sulfur
structure (α-S8). Related with sulfur usefulness, it is made a system or prototype to
produce sulfur from natural sulfur resources.
In 1904, Frasch was successful to develop a method to extract sulfur from
natural sulfur resources. This method is known as Frasch method. In this process, metal
pipe with diameters of 15 cm which is consisted of two smaller concentric pipes inside
is buried until reach the sulfur layer. Extremely hot water vapor is pumped into the
sulfur layer through the pipe until the sulfur melt. Then, high pressure air is pumped
into the sulfur layer through small pipe until sulfur foam is formed and the sulfur foam
is pumped up into surface. On the surface, liquid sulfur is gathered in together in large
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vessel and let them freeze, produce solid sulfur with purity of 99,5%. The frasch method
is shown in picture below.
Figure 2. The pump in Frasch method. The picture is taken from C. Chambers
et al., ―Modern Inorganic Chemistry‖.
6.3 COMPOUNDS OF SULFUR

Sulfur has oxides, especially sulfur dioxide. The dioxides are commonly
produced by burning elements in the air. So, sulfur dioxides is produced when sulfur is
burned in the air. Sulfur dioxide is a gas with a pungent smell (Cotton et al., 1995). The
molecule is angular. Sulfur dioxide has lone pairs and can act as base according to
Lewis acid-base theory. The other sulfur oxides is sulfur trioxide. Sulfur trioxide is
obtained by reaction of sulfur dioxide with O2, a reaction that is thermodynamically
very favorable but extremely slow in the absence of a catalyst such as platinum sponge,
V2O5, on NO (Cotton et al., 1995). The sulfur trioxide molecule, in the gas phase, has a
planar, triangular structure involving both p-p an p-d S-O bonding and forms polymers
in the solid state.
The other compound of sulfur is Sulfuric Acid. Sulfuric Acid, H2SO4, corrosive,
oily, colorless liquid, with a specific gravity of 1.85. It is formed from hydrogen, sulfur,
and oxygen. Sulfuric acid melts at 10.36°C (50.6°F), boils at 340°C (644°F), and is
soluble in all proportions in water. When sulfuric acid is mixed with water, considerable
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heat is released. Unless the mixture is well stirred, the added water may be heated
beyond its boiling point and the sudden formation of steam may blow the acid out of its
container. The concentrated acid destroys skin and flesh, and can cause blindness if it
gets into the eyes. The best treatment is to flush away the acid with large amounts of
water. Despite the dangers created by careless handling, sulfuric acid has been
commercially important for many years.
Sulfuric acid is a strong acid, that is, in aqueous solution it is largely changed to
hydrogen ions (H+) and sulfate ions (SO42-). Each molecule gives two H+ ions, thus
sulfuric acid is dibasic. Dilute solutions of sulfuric acid show all the behavior
characteristics of acids. They taste sour, conduct electricity, neutralize alkalies, and
corrode active metals with formation of hydrogen gas. From sulfuric acid one can
prepare both normal salts containing the sulfate group, SO4, and acid salts containing
the hydrogen sulfate group, HSO4.
There are two major processes (lead chamber and contact) for production of
H2SO4, and it is available commercially in a number of grades and concentrations. The
lead chamber process, the older of the two processes, is used to produce much of the
acid used to make fertilizers; it produces a relatively dilute acid (62%-78% H2SO4). The
contact process produces a purer, more concentrated acid but requires purer raw
materials and the use of expensive catalysts. In both processes sulfur dioxide is oxidized
and dissolved in water. There are four steps to the contact process which starts with
elemental sulfur.
1. Step 1: Burning. Pure sulfur is burned in air to give sulfur dioxide (SO2), which is
familiar to as rotten egg gas. This reaction happens at about 10000C. The air used
for the burning must be dust free as the presence of dust in the second part of the
process will cause damage to the catalyst.
S(g) + O2(g)  SO2(g) ........................................................................................(6.1)
2. Step 2: Converting. The sulfur dioxide is passed into a tower made of stacked
vertical beds of catalyst material, usually vanadium oxide (V2O5) but sometimes
platinum. Here the sulfur dioxide reacts with oxygen once again to give sulfur
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trioxide. The purpose of the catalyst is to reduce the temperature needed for the
reaction to occur. This is used because the reaction of SO2 with O2is more
productive at the lower temperature of 3000C.Sulfur Trioxide cannot be immediately
converted into Sulfuric acid by absorbing water, as happens in acid rain. If allowed
to absorb water the SO3 becomes a fine mist that is very difficult to collect.
SO2(g) + ½ O2(g)  SO3(g) ...............................................................................(6.2)
3. Step 3: Absorption of sulfur trioxide. In order to produce sulfuric acid in liquid
form, the sulfur trioxide gas from the converter is bubbled through very high purity
liquid H2SO4. This is a very efficient process that results in virtually complete
absorption of the SO3 gas. The resulting liquid chemical is called oleum and has the
formula H2S2O7.
SO3(g) + H2SO4(l)  H2S2O7(l) .......................................................................(6.3)
4. Step 4: Hydration of the oleum. Finally the oleum is converted into highly
concentrated H2SO4 by the addition of dilute H2S2O7 and water. This reaction gives
off a lot of heat and so the resulting acid needs to be cooled before it is sent to
storage.
H2S2O7(l) + H2O(l)  H2SO4(aq) .....................................................................(6.4)
The other well-known of the sulfur compound is hydrogen sulfide (H2S).
Hydrogen sulfide is colorless gas, and known as rotten egg smell gas. In chemistry
terms, it can be said complete, if the structure and the chemical properties of hydrogen
sulfide is explained. When the sulfur and the other chalcogenides make a bond with
hydrogen, they form compounds with analogous formulas that may represented as H2Y
where Y, in this term is sulfur. The hydrogen chalconides molecules are angular, since
there are four groups of electrons on each central chalcogens. As one of the chalcogen,
the sulfur molecule is angular too. The properties of hydrogen sulfide such as melting
point, boiling point heat of fusion, heat of vaporization critical temperature dipole
moment and dielectric constant. The melting point of hydrogen sulfide is 190 K and the
boiling point of hydrogen sulfide is 213 K. Heat of fusion and heat of vaporization of
hydrogen sulfide in a row is 0,568 kcal/mole and 4,46 kcal/mole. The dipole moment of
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hydrogen sulfide is 0,931 debyes, and the dielectric constant of hydrogen sulfide at 212
K is 8,0.
As said before, Hydrogen sulfide is colorless gas, and known as rotten egg odor
gas. Hydrogen sulfide itself is a poisonus gas and its more poisonus than carbon
monoxide, but its bad odor allows it to be detected at low concentrations. In nature,
hydrogen sulfide is released into the air during volcanic eruption and by the
decomposition of organic matter in the absence of air that‘s rotten eggs smell of
hydrogen sulfide. Hydrogen sulfide is difficult to dissolve in water and its solution
become turbid because hydrogen sulfide is oxidized produce sulfur. In laboratory,
hydrogen sulfide is used as strong reductor. The reaction is shown below.
H2S + ½ O2  H2O + SO2 .............................................................................(6.5)
H2S + SO2  2 H2O + 3S ..............................................................................(6.6)
Brady (1990) mentioned that hydrogen sulfide can be prepared in laboratory by
reacting a metal sulfide with a strong monoxidizing acid, for example, HCl.
FeS(s) + 2H+(aq)  Fe2+(aq) + H2S(g) ................................................................(6.7)
Another method, generally used when one wants to generate the H2S in an
aqueous solution, is the hydrolysis of an organic compound called thioacetamide.
Thioacetamide(aq) + 2H2O  H2S(aq) + NH4+(aq) + acetate ion(aq) .................(6.8)
The advantage of this reaction is that it avoids the release of significant amounts
of toxic H2S into the atmosphere. Qualitatively, hydrogen sulfide can be analyzed with
paper which is tear-stained by salt solution of Pb2+ and produce black spot, because PbS
is formed.
H2S(g) + Pb2+(aq)  PbS + 2H+(aq) ...................................................................(6.9)
The last sulfur compound that will be explained is sodium thiosulfate (Na2S2O3).
Sodium thiosulfate is formed in reaction of sodium sulfites solutions and sulfur. The
reaction is shown below.
S(aq) + Na2SO3(aq)  Na2S2O3(aq) ...............................................................(6.10)
The sodium thiosulfate has characteristic as reductor and used in iodometric analysis,
according reaction:
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2 Na2S2O3 + I2  Na2S4O6 + 2 NaI ............................................................(6.11)
Specifically, the thiosulfates ion has the structure SSO32-, and may be considered to be
derived from sulfate by replacement of an atom by an S atom.
6.4 SUMMARY
Based on the explanation above, it can be concluded that sulfur is common
element that has several advantage and disadvantage for human being. Sulfur has
allotropes. Sulfur exists in nature in pure element and in compound form. Some of
sulfur compounds are sulfur dioxide, sulfuric acid, hydrogen sulfide and sodium
thiosulfate. Every sulfur compound has their own properties, structure and process to
prepare or making it.
6.5 STUDY QUESTIONS

1. Explain the species contructing sulfur solids in nature and what happen when the
solid is heated from below its melting point to above it melting point.
2. Discuss the aquous chemistry of H2S, SH-, and S2-.
3. Explain the contact process in synthesizing of H2SO4. Explain also the mechanism
of the V2O5 catalist working in the process.
4. Explain how to synthesize natrium tiosulfate from natrium sulfite. How tyo
determine the purity of the synthesis product.
5. Describe the preparation and uses of SF4 and SF6.
6. Why is it that SOCl2 can act both as a Lewis acid and as a Lewis base?
7. List the formula and draw the Lewis structures of sulfurous acid, thiosulfuric acid,
dithionic acid, disulfuric acid, peroxodisulfuric acid.
8. Explain why H2SO4 is a prominent substance for chemical industries.
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CHAPTER 7
CHEMISTRY OF NITROGEN
7.1 INTRODUCTION
The basic competence of the chapter 7 is to understand properties, preparation, and
compounds of nitrogen. Indicators of learning for reaching the basic competences should show
a. explain properties and preparation of nitrogen;
b. describe structures of nitrogen oxides;.
c. explain properties of ammonia and its production ways;
d. explain properties of nitrate and nitrite compounds and their uses; and
e. describe nitrogen cycle in nature
This chapter will explain briefly the properties, production and uses of nitrogen
gas as well as preparation and properties of compounds of nitrogen oxides, ammonia,
nitrate, nitrite, and nitrogen cycle.
7.2 NITROGEN AND ITS PROPERTIES

Nitrogen was discovered by the Scottish physician Daniel Rutherford in 1772. It
is the fifth most abundant element in the universe and makes up about 78% of earth‘s
atmosphere. At the earth surface the N2 molecules. Nitrogen is obtained from liquefied
air through a process known as factional distillation. In periodic table nitrogen included
in the group VA elements with phosphorus, arsenic, antimony and bismuth.
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Molecular nitrogen is characterized by its lack of reactivity. The nitrogen
molecule contains a triple bond and is the most stable diatomic molecule known. Only
14 15
two naturally occurring isotopes are found, N (99.635%) and N. The occurrence
14
mainly N is somewhat unusual in view of the fact that so few odd-odd nuclei are
stable. Nitrogen molecules are small, having a bond length of only 110pm (1.10Å)
owing to the strong triple bond holding the atoms together (945kl/mol). This very strong
and stable bond (the force constant is 22.4 mdyn Å-1) is partially responsible for the
explosive nature of some nitrogen compounds. The fact that nitrogen is a nonmetal
having an electronegativity of 3.0, but as mentioned earlier, the strong N-N bond
implies that there are no low-energy pathways for most reactions of the element. Liquid
nitrogen boils at -195.8 oC. The boiling point of nitrogen is 77.36 K (-195.79°C or -
320.44°F) and the melting point of nitrogen is 63.15 K (-210.00°C or -346.00°F). The
phase of nitrogen at room temperature is gases. Mass atomic relative of nitrogen is
14.0067 amu, with the density 0.0012506 grams/cm3.
7.3 PREPARATION OF NITROGEN

Nitrogen is most conveniently prepared from the atmosphere by distillation or
simply by removing the more reactive component, oxygen (active metals or elementary
phosphorus have been used as reducing agents). Such nitrogen contains a little more
than 1 percent of the rare gases, chiefly argon. Purer nitrogen is obtained by heating
ammonium nitrite, either dry or in solution:
NH4NO2 → N2 + 2H2O .................................................................................(7.1)
This is actually one of a group of reactions in which compounds having the –NH2
linkage are treated with nitrous acid. Similarly, primary organic amines such as aniline
(C6H5NH2) and organic amides such as urea (NH2CONH2) yield nitrogen. Such
reactions generally proceed through an intermediate ―N-nitroso‖ compound (with the
group –NH–N=O) which sometimes can be isolated and shown to yield nitrogen when
heated. (This reaction will be further discussed in connection with nitrous acid). Pure
nitrogen may also be prepared by high-temperature oxidation if ammonia with copper
(II) oxide.
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Nitrogen forms an extensive series of oxides: N2O (nitrous oxide), NO (nitric
oxide), NO2 (nitrogen dioxide), N2O4 (dinitrogen tetraoxide), N2O3 (dinitrogen
trioxide), and N2O5 (dinitrogen pentaoxide). These compounds are described as follow.
Dinitrogen monoxide is a colorless gas; it is relatively unreactive, being inert to the
halogens, alkali metals, and ozone at room temperature. The molecule has the geometric
structure N—N—O, and is a resonance hybrid of the two forms the molecular being
linier. Nitrogen monoxide is the most stable of all the oxides of nitrogen. The molecule
of nitrogen monoxide contains an odd number of electrons and can be represented as N
– N. This shows the unpaired electron on the nitrogen atom; it is in fact "shared' over
the whole molecule. Molecules such as nitrogen monoxide which contain unpaired
electrons are referred to as odd electron molecules. The presence of the odd electron can
be detected by magnetic experiments when such substances are found to be
paramagnetic, and they are attracted into a magnetic field. Molecules and ions
containing unpaired electrons are very weakly attracted by a magnetic field. In some
cases the total number of electrons may be even and yet the molecule may still be
paramagnetic; this is because some of the electrons are unpaired, for example oxygen is
paramagnetic. The presence of the unpaired electron explains why, chemically, nitrogen
monoxide is more reactive than dinitrogen oxide.
The structure of nitrogen dioxide contains an unpaired (odd) electron and the
molecule is consequently paramagnetic. The odd electron is not localized on any atom.
Both N—O bonds are of equal length. Unlike nitrogen monoxide, nitrogen dioxide has
properties more typical of an odd electron molecule. It is a colored (brown), reactive gas
which dimerises to the diamagnetic colorless gas dinitrogen tetroxide, N2O4, in which
the odd electron is paired. The structure of dinitrogen tetroxide.
Dinitrogen trioxide, N2O3, formally the anhydride of nitrous acid, is obtained by
interaction of stoichiometric amounts of NO and O2, or of NO and N2O4. It is an intensely blue
liquid or a pale blue solid. The stable form has a weak N-N bond. It exists only at low
temperature, and readily dissociates to give NO and NO2. The N2O3 molecule has an O2N - NO
structure in the gas phase and at low temperature, with an extremely long (1.89 Å) N - N bond
consistent with its easy dissociation.
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This oxide (N2O5) forms unstable colorless crystals. Dinitrogen pentaoxide is the
anhydride of nitric acid. I the solid state it exists as nitronium nitrate.
7.4 AMMONIA
Ammonia is a colorless gas with a distinctive sharp smell. It has the formula
NH3, it is less dense than air and is very soluble in water. Ammonia is distinctive in
producing an alkaline solution. It dissolves so well in water because it reacts. The
solution is partially dissociated into:
NH3 + H2O(aq) ⇌ NH4+(aq) + OH-(aq) ...............................................................(7.2)
Ammonia solution or gas will react with an acid to produce an ammonium salt,
for example: ammonia + sulphuric acid  ammonium sulphate
2NH3(g) + H2SO4(aq)  (NH4)2SO4(aq) ...........................................................(7.3)
ammonia + hydrochloric acid  ammonium chloride
NH3(ag) + HCl(aq)  NH4Cl(aq) ........................................................................(7.4)
To white smoke formed when NH3 and HCl fumes meet can be used as a simple
test for ammonia. Ammonium (NH4+) ion. The salts are all soluble in water.
Ammonia is produced in huge quantities, and it is by far the most common and
important compound of nitrogen and hydrogen. Approximately 30 billion pounds of
NH3 are used annually with a large portion being used as fertilizer or in the production
of nitric acid. Ammonia is produced by the Haber process, which can be shown as
N2 + 3H2⇌2NH3 ............................................................................................(7.5)
The raw materials used for the process are:

1. Air – which supplies the nitrogen
2. Natural gas (methane) – which is reacted with steam to produce hydrogen and is also
used as the heating fuel for the system.
3. Iron – which is used in a finely divided form as the catalyst.
Another ways, ammonia can make in the laboratory. Small amounts of ammonia
gas are produced when any ammonium salt is hated with an alkali. In the normal
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laboratory preparation, a solid mixture of calcium hydroxide and ammonium chloride is
heated:
Calcium hydroxide + ammonium chloride  calcium chloride + water
The water vapor is removed by passing the gas through a drying tube containing
calcium oxide. In general, this reaction between ammonium salts and alkali is used as
the chemical test for ammonium ions. The ammonia produced is detected because it
turns moist red litmus red paper blue.
7.5 NITRATE AND NITRITE

The example of nitrate and nitrite compounds is nitric acid and nitrous acid.
Nitric acid, the most important acid of nitrogen, is synthesized from NH3 on a large
scale as one of the common strong acids and for the production of N fertilizers.
Concentrated HNO3 is 15.7 M. it can be dehydrated and vacuum distilled to give
anhydrous HNO3. Nitric acid is strong oxidizing agent, commonly being reduced to NO
in dilute solution and to NO2 in concentrated solution. The Eo values are given for
comparison, but these refer to unit activities.
NO3- + 4 H+ + 3e ⇆ NO + 2H2O EÅ = 0.96 V ........................................(7.6)
NO3 + 2H+ + e ⇆ NO2 + H2O EÅ = 0.803 V ..................................................(7.7)
NO2 is the major reduction product only for concentrated HNO3. A strong reducing
agent such as Zn reduces NO-3 in dilute acidic solution to NH+4. Nitrate salts used
frequently for studies of metal cations because most metal nitrates are water-soluble and
the nitrate ion is weak ligand for complex formation.
Nitrous acid is unstable expect in dilute solution, which can be obtained from
H2SO4 + Ba(NO2)2 after removal of the BaSO4 precipitate. Nitrous acid oxidizes Fe2+ or
I- and reduces MnO-4. Alkali-metal nitrite salts can be prepared by thermal
decomposition of the nitrates or by reducing the nitrates with the carbon, lead, or iron.
Sodium nitrite is used as an additive in cured meats (hot dogs, hams, bacon, and cold
cuts), to which the presence of some NO from decomposition of NO-2 imparts an
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appealing red color, because of the formation of a bright red compound with
hemoglobin. Also, the NO-2 ion inbotulism. Nitrites are controversial food additives,
since they can be converted during cooking to nitrosamines (R2NN=O), compounds
considered to be carcinogens. However, nitrites have been approved as food additives.
HNO2 + H+ + e ⇆ NO + H2O Eo = 1,0 V ............................................(7.8)
HNO-3 + 3H+ + 2e ⇆ HNO2 + H2O Eo = 0.94 V ..........................................(7.9)
7.6 NITROGEN CYCLE IN NATURE

Nitrogen is essential for all life. It is present in proteins and nucleic acids, and so
is essential for growth and good health. Like carbon, another essential element, there is
a global cycle known as the nitrogen cycle. Nitrogen atoms are cycled between various
forms of life, and between the soil and the atmosphere, by a series of connected
chemical changes. Animals obtain the nitrogen they need for making proteins by
feeding on plants and other animals. Most plants obtain the nitrogen they require from
the soil, where it is found as nitrates. Nitrates are the soluble salts of nitric acid. The
solubility of nitrates is important, as they are absorbed in solution by plants through
their root systems. Nitrates occur in the soil through the effect of lightning on
atmospheric nitrogen and oxygen, and through the decay of dead plants and animals.
There are called nitrogen-fixing bacteria. Some plants are also able to ‗fix‘ atmospheric
nitrogen because their roots have nodules that contain nitrogen-fixing bacteria. These
plants are known as leguminous plants or legumes. They include beans and clover.
When soils are heavily cultivated, eventually they do not have enough nitrogen for good
plant growth (they become nitrogen-deficient). Crops are harvested and removed rather
than left to decay. Nitrates are used up or washed out of the soil by rain. Without decay,
the replacement of nitrates in the soil is insufficient and the soil becomes infertile.
Farmers need to add substances containing nitrates to the soil. Such substances are
known as fertilizers. Organic fertilizers, such as farmyard manure or compost, can be
use, but intensive agriculture has led to the production of artificial fertilizers on a very
60 | 106 P a g e s
large scale. One of the most commonly used fertilizers is ammonium nitrate, which is
made from ammonia gas and nitric acid.
Figure 7.1 Nitrogen Cycle
7.6 SUMMARY
Based on the explanation above, it can be concluded that nitrogen is the essential
element, located in group VA element and has triple bond in the molecular structure. It
can be obtained through fractional distillation process. Some compounds that included
in nitrogen oxides are N2O (nitrous oxide), NO (nitric oxide), NO2 (nitrogen dioxide),
N2O4 (dinitrogen tetraoxide), N2O3 (dinitrogen trioxide), and N2O5 (dinitrogen
pentaoxide). Ammonia is a compound of nitrogen that most frequently used in
industrially. Besides that, nitrate and nitrite compounds, for example nitrous acid and
nitric acid are useful in daily life. On the other hand like another essential elements,
there is a global cycle known as the nitrogen cycle. This cycle is useful for keep an
existence of nitrogen in the world.
61 | 105 P a g e s
7.8 STUDY QUESTIONS
1. Draw the Lewis structures, explain the geometry and hybridization at each atom in
N2, N3, N2O, NO, NO+, NO2+, NO2-, and NO3-.
2. What is hydrazin, how it is prepared, and what it can be used for?
3. Write balanced equations for hydrolisis of calcium nitride, lithium nitride,
dinitrogen pentaoxide and dinitrogen dioxide.
4. Draw the Lewis structure of the three isomers of N2O4.
5. Explain the conversion of NO2 into HNO3 as well as into NH3.
6. Explain the Haber-Bosch process in synthesizing ammonia.
7. Explain how to synthesis HNO3 from N2 of air.
8. Which oxide is the anhydride of HNO3?, of HNO2? Explain by using equation.
62 | 106 P a g e s
CHAPTER 8
CHEMISTRY OF PHOSPHORUS
8.1 INTRODUCTION
The basic competence of the chapter 8 is to understand properties, preparation, and
compounds of phosphor. Indicators of learning for reaching the basic competences should show
a. explain of phosphorus and its allotropes;

b. explain properties of hydrides of phosphorus;
c. explain the formation of PCl3 and PCl5;
d. describe the structures of phosphor oxides and phosphor oxyacids; and
e. explain the uses of some phosphate minerals.
This chapter will explain briefly the properties of element phosphor and its
allotropes, preparation of elemental phosphorus, oxides and other compounds of
phosphor as well as phosphate minerals and uses.
8.2 PHOSPHORUS AND ITS ALLOTROPES

Phosphor or phosphorus, symbolized as P is a member of the nitrogen family,
group 15 or VA on the periodic system of elements (PSE). Phosphorus was firstly
investigated by Henning Brand in the year of 1669 in Hamburg, Germany. Phosporus
has atomic number of 15, hence it has 5 valence shell electrons available for bonding.
63 | 105 P a g e s
Its valence shell configuration is 3s2 3p3. Phosphorus is a nonmetal, solid at room
temperature, and a poor conductor of heat and electricity. Phosphorus forms mostly
covalent bonds. There are many isotopes of phosphorus, only one of which is stable
(31P). The rest of the isotopes are radioactive with generally very short half-life, which
vary between a few nanoseconds to a few seconds. Two of the radioactive phosphorus
isotopes have longer half-life. 32P has a half-life of 14 days and 33P has a half-life of 25
days. This half-life is long enough to be useful for analysis and for this reason the
isotopes can be used to mark DNA.
Some properties of elemental phosphorus can be described in the Table 8.1
below.
Table 8.1. Some properties of Elemental Phosphorus
Atomic Symbol P
Atomic radii 1.28 Α
Atomic volume 17 cm3/mol
Atomic mass 30,9738
Boiling point 553 K ( 280oC)
Covalent radii 1.06 Α
Crystal structure Monoclinic
Melting point 317.3 K (44.20C)
Density (red phosphorus) 2.34 g/cm3
Density (white phosphorus) 1.823 g/cm3
Density (black phosphorus) 2.609 g/cm3
Density (element) 1.82g/cm3
Electrical conductivity 10 x 106 ohm-1cm-1
Electronegativity 2.19
Electron configuration [Ne] 3s23p3
Enthalpi 0.63kJ/mol
Potential ionization 10.486 V
Oxidation state 3,.5,.4
64 | 106 P a g e s
Phosphorus exists in minerals of apatite family, Ca9(PO4)6.CaX2 whereas X =
F,Cl, or OH. They are the main component of amorphous phosphate rock, millions of
tons of which are processed annually. Phosphorus is obtained by reduction of phosphate
rock with coke and sand in an electric furnace. These yield elemental phosphorus when
heated with a mixture of carbon and silica; the latter forms a fusible ―slag‖ with the CaO
formed during the reaction, and the phosphorus formed from reduction by the carbon is
distilled away from the mixture.
The elemental phosphorus has several allotropes, namely white phosphorus, red
phosphorus and black phosphorus. The well-known white (or yellow) phosphorus
(Figure 8.1) is volatile, (boiling point 2800), inflammable, and poisonous. The solid
structure of white phosphor consists of discrete molecules, almost certainly the P4
tetrahedral known to exist in the vapor phase. It is soft and waxy, but insoluble in water.
The soft, waxy solid becomes yellow on exposure to light; it is very poisonous, being
readily absorbed into blood and liver. White phosphorous is soluble in benzene but
virtually insoluble in water and it is stored under water to prevent oxidation.
White phosphorus is manufactured by reaction like below:
2Ca3(PO4)2 +6SiO2 + 10 C  P4 + 6CaSiO3 + 10 CO ................................(8.1)
P P
P
Figure 8.1 P4 Tetrahedral Form of White Phosphorus
The more highly colored forms of phosphorus (red, violet and two black forms),
are less volatile, far less reactive, and have more complicated structures than the white.
Red and black phosphorus are stable in air but will burn on heating. Red phosphorus
(Figure 8.2) is intermediate in reactivity between the white and black all allotropes. It is
not poisonous, insoluble in organic substance, does not react with aqueous alkali, and
65 | 105 P a g e s
ignite in air above 520K. It reacts with halogens, sulfur and metals, but less vigorously
than does white phosphorous.
P P P
P P P P P P P P
P P P
Figure 8.2 The Chain Structure of Red Phosphorus

The violet and crystalline black modifications appear actually to be different.
The black phosphorus produced at high temperatures under pressure, has a layer
structure. The structure of the violet form (which sometimes is more nearly red) is
different from that of the black, but has been determined only in part. Black phosphorus
is the most stable allotrope and it is obtained by heating white phosphorus under high
pressure. On melting, all allotrope give a liquid contain P4 molecules, and these are also
present in vapor, above 1070 K or at high pressure, P4 is in equilibrium with P2. Black
phosphorus is kinetically inert and does not ignite in air even at 670 K.
8.3 HYDRIDES OF PHOSPHORUS

The hydrides of phosphorus are analogous to ammonia, both formally and
structurally. However, they differ from NH3 in being far less stable, easily inflammable,
and extremely poisonous. Phosphine, PH3, is a much weaker base than ammonia, hence
the PH4+ ion is less stable than NH4+ ion. In water solution, PH4+ ion will be changed
into PH3.
PH4+ + H2O  PH3 + H3O+ ..........................................................................(8.2)
Phosphine can be prepared by action of water or dilute acid on a binary metal
compound of the parent element (e.g. Mg3P2).
Mg3P2 + 6 HCl  2 PH3 + 3 MgCl2 ..............................................................(8.3)
Phosphine is also produced by warming the white phosphorus with kalium hidroxide
solution.
P4 + 3 KOH + 3 H2O  PH3 + 3 KH2PO2 ....................................................(8.4)
66 | 106 P a g e s
Phosphine is a colorless gas. It is very toxic and garlic odor. Its boiling point is -88C.
The differences in boiling points of these substances are influenced by intermolecular
hydrogen bonding. It can form phophonium salt with hydrogen halogenides, for
example:
PH3 + HI  PH4I + H+ ..................................................................................(8.5)
The phosphonium salt can be decomposed in water solution.
PH4I + H2O  PH3 + H3O+ + I- ....................................................................(8.6)
It is interesting that a second hydride of phosphorus, P2H4 (diphosphine,
analogous to hydrazine), is described as being essentially nonbasic. Diphosphine is a
colorless liquid (boiling point of 52C. It is self inflammable and decomposed in light
and in heating through disproportionation to phosphine and hydrogen less phosphine.
There are also some well-known further phosphine such as P3H5, P5H5, P7H3, and
hydrogen phosphorus polymers.
8.4 HALIDES OF PHOSPHORUS

Phosphorus is reacted with all halogens to form halides. The most common
halides of phosphorus are phosphorus trihalides, phosphorus tetrahalides, and
phosphorus pentahalides as shown in Table 8.2 below.
Table 8.2. Phosphorus Halides
Compound F Cl Br I
Phosphorus Colorless gas Colorless Colorless Red
trihalides, PX3 liquid liquid crystalline
(trigonal pyramide)
Diphosphorus Colorless gas Colorless - Light red
tetrahalides, P2X4 liquid crystalline
(trans-conformation
with P-P single
bond)
Phosphorus Colorless gas Colorless Red yellowish Black
pentahalides, PX5, crystalline crystalline crystalline
(trigonal pyramide)
Resource: Riedel 2002: 497
67 | 105 P a g e s
Phosphorus trihalides, i.e PCl3, PBr3, and PI3 can be synthesized from their
elements, for example, hosphorus trichloride is prepared industrially by the reaction of
chlorine directly under reflux with continues take-off of PCl3 formed.
P4 + 6 Cl2  4 PCl3 .........................................................................................(8.7)
However, PF3 is synthesized through flourination of PCl3.
PCl3 + 3 HF  PF3 + 3 HCl ...........................................................................(8.8)
Some substitution reactions can undergoes on PCl3 leading to various organophosphorus
compounds, particularly PR3, PRnCl3-n, PRn(OR)3-n, (PhO)3PO, and (RO)3PS. Some
subtitution reactions can be depicted as follows:
2 PCl3 + 6 RMgBr  2 PR3 + 3 MgCl2 + 3 MgBr2 .......................................(8.9)
PCl3 + RP(OR)2  PRCl2 + P(OR)2Cl ........................................................(8.10)
PCl3 + R2POR  PR2Cl + P(OR)Cl2 ...........................................................(8.11)
PCl3 + 3 ROH  P(OR)3 +3 HCl .................................................................(8.12)
PCl3 + 3 R2NH  P(NR2)3 + 3 HCl .............................................................(8.13)
PCl3 + 3 NH3  P(NH2)3 + 3 HCl ................................................................(8.14)
PCl3 + 3 RSH  P(SR)3 + 3 HCl .................................................................(8.15)
2 PCl3 + 3 BaS  P2S3 + 3 BaCl2 ................................................................(8.16)
PCl3 + 3 AgNCO  P(NCO)3 + 3 AgCl ......................................................(8.17)
PCl3 + 3 AgCN  P(CN)3 + 3 AgCl ............................................................(8.18)
PCl3 + PF3  PCl2F + PClF2 ........................................................................(8.19)
PCl3 + PBr3  PCl2Br + PClBr2 ...................................................................(8.20)
PCl3 + 3 HI  PI3 + 3 HI .............................................................................(8.21)
PCl3 is also oxidized by some compounds to produced P(V) compounds. Some of them
can be depicted as follows:
2PCl3 + Cl2S2Cl2  2PCl5 + 2S ...................................................................(8.22)
PCl3 + ClO2  POCl3 + ClO ........................................................................(8.23)
PCl3 + S  PSCl3 .........................................................................................(8.24)
2PCl3 + 2 As2O3  P2O5 + AsCl3 + ClO + Cl2 ...........................................(8.25)
PCl3 + 3H2O  H3PO3 + 3HCl ....................................................................(8.26)
68 | 106 P a g e s
PCl3 + 3 RCO2H  3 RCOCl + H3PO3 .......................................................(8.27)
PCl3 + N2O4  Cl3P=NPOCl2 ......................................................................(8.28)
PCl3 + AlCl3 + CH3Cl  [CH3PCl3]+[AlCl4]- ..............................................(8.29)
PCl3 can undergo reduction reaction to P or P2X4, for example:
PCl3 + Sb  P + SbCl3 .................................................................................(8.30)
2 PCl3 + 2 I2/CH3CO2H  P2I4 + 3 Cl2 .......................................................(8.31)
The further most important halides of phosphorus are phosphorus pentahalides.
Phosphorus pentafluoride, PF5, is a colorless, sensitively hydrolizeable gas. It can be
synthesized through Cl-F substitution reaction of PCl5 and AsF5.
PCl5 + AsF5  PF5 + AsCl5 ..........................................................................(8.32)
Phosphorus pentachloride, PCl5 can be prepared by the chlorination of PCl3. The
reaction is as follows:
PCl3 + Cl2 PCl5 .....................................................................................(8.33)
It can be synthesized directlly from their elements, as shown below.
P4 + 10 Cl2  4 PCl5 ....................................................................................(8.34)
In the solid form, PCl5 is as salt of [PCl4]+ [PCl6]-. Other pentahalide of phosphorus, i.e
PBr5 analogue to PCl5 can be synthesized from their elements.
P4 + 10 Br2  4 PBr5 ....................................................................................(8.35)
Its solid is ionized as [PBr4]+ Br-, a litle bit different with the solid form of PCl5, but the
same as the solid of PI5 consisting of [PI4]+ I- ions.
PCl5 can undergo some reactions as follows. PCl5 reacts with water to give HCl
and H3PO4. It can give POCl3 if it reacts with water in equimolar amounts.
PCl5 + 4 H2O  H3PO4 + 5 HCl ...................................................................(8.36)
PCl5 + H2O  POCl3 + 2 HCl ......................................................................(8.37)
POCl3 can be also produced by reacting PCl5 with P4O10.
6 PCl5 + P4O10  10 POCl3 .........................................................................(8.38)
Some other reactions undergo to PCl5 as follows.
PCl5 + H2  PCl3 + 2 HCl ............................................................................(8.39)
PCl5 + 4 NH3  P(NH2)4+Cl- + 4 HCl .........................................................(8.40)
69 | 105 P a g e s
PCl5 + PhNH2  Cl3P=NPh + 2 HCl ...........................................................(8.41)
PCl5 + H2N-NH2  Cl3P=N-N=PCl3 + 4 HCl .............................................(8.42)
PCl5 + Ph3PO  Ph3P+-O-PCl5- ...................................................................(8.43)
PCl5 + R2POOH  R2POCl + POCl3 + HCl ...............................................(8.44)
PCl5 + BCl3  PCl4+BCl4- ............................................................................(8.45)
PCl5 + NH4Cl  (PNCl2)n + 4HCl ...............................................................(8.46)
PCl5 + (NH4)2SO4  Cl3P=NPOCl2 + H2SO4 .............................................(8.47)
PCl5 + 6 KF  KPF6 + 5 KCl ......................................................................(8.48)
PCl5 + P4S10  10 PSCl3 ..............................................................................(8.49)
So far, diphosphorus tetrahalides, P2X4, as depicted in Table 8.2, can be
described in more detail as follows. P2F4 can be synthesized by reacting PF2I with Hg at
room temperature under reduced pressure.
2 PF2I + 2 Hg  P2F4 + Hg2I2 ......................................................................(8.50)
P2F4 can hidrolyse to F2POPF2.
P2F4 + H2O  F2POPF2.+ 2H+ .....................................................................(8.51)
F2POPF2.can be also prepared directly through reacting P2F4 with oxygen.
2 P2F4 + O2  2 F2POPF2 .............................................................................(8.52)
Meanwhile P2Cl4 can be prepared by mixing of PCl3 and H2 in an electric discharege
under reduced pressure or by microwave discharge through PCl3 at 1 – 5 mmHg
pressure.
2 PCl3 + H2  P2Cl4 + 2 HCl .......................................................................(8.53)
2 PCl3  P2Cl4 + Cl2 ....................................................................................(8.54)
8.5 OXIDES OF PHOSPHORUS

Two of the most important oxides of phosphorus are Phosphorus (III) oxide,
P4O6 and phosporus (V) oxide, P4O10. They are related structurally to the P4 molecule
itself by exchanging P-P bonds to P-O-P bonds as shown in Figure 8.3 below.
70 | 106 P a g e s
Figure 8.3 The Ball and Stick Structure Models of P4O6 and P4O10
(Blue = P, Red =O)
The compound of P4O6 can be synthesized directly from their elements P4 and
O2. P4O6 is a colorless volatile compound and one of the most effective drying agents
known at temperatures below 1000 C. It reacts with water to form a mixture of
phosphoric acids whose composition depends on the quantity of water and other
condition. P4O6 is not nearly as important as the phosporus acid and phosphite salts
which are derived from it.
P4 + 3 O2  P4O6 .........................................................................................(8.55)
P4O6 + 6 H2O  4 H3PO3 ............................................................................(8.56)
Phosphorus (V) oxide (P4O10) is the commonest and most important phosphorus
oxides. It is almost always made by oxidation either of phosphorus itself or lower
oxides. It is made by burning phosphorus in excess oxygen. It can form phosphoric acid
when it is dissolved in water
P4 + 5 O2  P4O10 ........................................................................................(8.57)
P4O10 + 6 H2O  4 H3PO4 ...........................................................................(8.58)
Some reactions undergo to P4O6 as well as P4O10 as follows. P4O6 can be reacted
with some simple inorganic as well as organic compounds, but their products are rarely
isolated as reported by Heinze (1975) in Greenwood and Earnshaw (2003: 506). P4O6
can act as ligand for replacing ligand CO of the organometallic complex of [Ni(CO)4] to
[P4O6{Ni(CO)3}], [Ni(CO)2(P4O6)2], and [Ni(CO)(P4O6)3] succesively. Reacting P4O10
71 | 105 P a g e s
with diethyl ether can produce triethylphosphate. Furthermore, direct reaction of P 4O10
with alcohols gives mixed mono- and dialkyl phosphoric acids.
P4O10 + 6 Et2O  4 PO(Oet)3 ......................................................................(8.59)
P4O10 + 6 ROH  2 (RO)PO(OH)2 + 2 (RO)2PO(OH) ...............................(8.60)
The other oxides of phosphorus are the suboxide PO and the peroxide P2O6. PO
can be synthesized by slow reaction under reflux of POBr3 with Mg in Et2O as shown in
the reaction equation below.
2 POBr3 + 3 Mg  2 PO + 3 MgBr2 ............................................................(8.61)
P2O6 is prepared through reacting P4O10 and O2 in a heated discharge tube at low
pressure.
P4O10 + O2 2 P2O6.....................................................................................(8.62)
8.6 OXOACIDS OF PHOSPHORUS

The oxoacids of phosphorus have some features as summarized by Greenwood
and Earnshaw (2003: 510-511) as follows: (1) All P atoms in the oxoacids and
oxoanions are 4-coordinate and contain at least one P=O unit; (2) All P atoms in the
oxoacids have at least one P-OH and related anion P-O-; (3) Some of them have at least
one P-H, it can not be ionizable; (4) It undergoes catenation of P-O-P or P-P bonds; and
(5) It can form peroxo compounds feature either P-OOH groups or POOP. Some
oxoacids of phosphorus compounds can be depicted on Table 8.3 below.
Table 8.3 Oxoacid Compounds of Phosphorus
Nr. Name Formula Bonding description
1. Phosphinic acid H3PO2 H2POOH
(hypophosphorous acid) (two P-H, one P=O, one P-OH)
2. Phosphonic acid H3PO3 HPO(OH)2
(phosphorous acid) (one P-H, one P=O, two P-OH)
3. Ortho(phosphoric acid H3PO4 (HO)3PO
(one P=O, three P-OH)
4. Peroxomonophosphoric acid H3PO5 (HO)2PO(OOH)
(one P=O, two P-OH, one P-O-
OH)
5. Diphosphonic acid H4P2O5 H(HO)OP-O-PO(OH)H
(diphosphorous or (two P=O, two P-H, two P-OH,
pyrophosphorous acid) one P-O-P)
6. Isohypophosphoric acid H4P2O6 H (HO)OP-O-PO(OH)2
72 | 106 P a g e s
(diphosphoric(III, V) acid) (one P-H, three P-OH, two P=O,
one P-O-P)
7. Hypophosphoric acid H2P2O6 (HO)2OP-PO(OH)2
(diphosphoric(IV) acid) (four P-OH, two P=O, one P-P)
8. Diphosphoric acid H4P2O7 (HO)2OP-O-PO(OH)2
(pyrophosphoric acid) (four P-OH, two P=O, one P-O-P)
9. Peroxodisphosphoric acid H4P2O8 (HO)2OP-O-O-PO(OH)2
(four P-OH, two P=O, one P-O-O-
P)
10. Triphosphoric acid H5P3O10 (HO)2OPOP(O)(OH)OPO(OH)2
(five P-OH, three P=O,
two P-O-P)
11. Polyphosphoric acid Hn+2PnO3n+1 (HO)2OP-(OPO(OH))n-2PO(OH)2
(n up to 17
isolated)
12. Cyclo-trimetaphosphoric acid (HPO3)3 ((HO)OP-O-)3 (three P-OH, three
P=O, three P-O-P)
13. Cyclo-trtetrametaphosphoric acid (HPO3)4 ((HO)OP-O-)4
(four P-OH, four P=O, four
P-O-P)
14. Polymetaphosphoric acid (HPO3)n ((HO)OP-O-)n
(n P-OH, n P=O, n P-O-P)
The two lowest P valence state of phosphorus oxoacids are hypo phosphorous
acid, (H3PO2), and phosphorous acid (H3PO3). They are solids and have low-melting
points (bp H3PO2 at 27C and H3PO3 at 73C). Both acids are better reducing agent than
metallic tin, whereas H3PO2 is a better reducing agent than iron metal. In addition, since
both acids are better reducing agents than H2, aqueous solutions of them would not be
expected to be stable. It should be noted that the values for the ionization constant of
both hypo phosphorous and phosphorous acids (each about 10-2) are very close to that
for the first ionization constant of phosphoric acid. Using the principle forwarded by
Pauling one might infer that the number of ―nonhydrogenated oxygen atoms‖ per
molecule is the same for all three acids. If the structures on the left are correct, H3PO2
should be only a monobasic acid and H3PO3 a dibasic acid (since the P-H bonds
presumably do not ionize in aqueous media); such is indeed the case. Unlike the
structures of the right, the correct structures have no unshared electrons on the central
atoms, being in this respect different from other reducing oxy-acids such as :S(OH)2,
:N=O, and :Cl-OH. This is perhaps why the lower acids of phosphorous are sluggish
reducing agents in spite of their very high potentials, for reactions by direct nucleophilic
73 | 105 P a g e s
displacement, as has been shown to occur in reductions by sulfite cannot occur with
phosphite or hypophosphite.
A third ―lower‖ oxy-acid of phosphorus, hypo phosphoric acid, H4P2O6, is
somewhat less important than H3PO2 and H3PO3. Hypophosphate, the salt of H4P2O6, are
prepared by controlled oxidations of elemental phosphorus in solutions of high pH, and
each molecule of the acid is thought to contain one of the P-P bonds present in the
element itself. The acid, thus represented as (OH)2OP–PO(OH)2, disproportionate in
strongly acid solutions to form H3PO4 and H3PO3.
The familiar phosphoric acid, H3PO4, (melting point 43C ) is more specifically
ortho phosphoric acid, as distinct from pyro phosphoric acid, (OH)2 OP–O–PO(OH)2,
and from the ―less hydrated‖ derivatives of phosphorus pentoxide (often grouped
together as ―poly-phosphoric acids‖). In dilute solutions, H3PO4 is a tribasic acid whose
successive ionization constants descend in value in a ―typical‖ fashion. The values at
25C are: K1 = 8 x 10 -3, K2 = 6 x 10-8, and K3 = 10-13. It is important to note that the
value for K3 is so low that appreciable concentrations of PO4-3 may exist only in very
basic solutions. Tertiary phosphate, secondary (monohydrogen) phosphates, and
primary (dihydrogen) phosphates are known, and all three series of salts are important.
Most tertiary phosphates are only slightly water soluble, (e.g. NH4MgPO4. 6H2O,
Ag3PO4, FePO4. 4H2O), whereas the secondary and primary phosphates tend to be more
soluble (exceptions: FeHPO4.H2O, Zn(H2PO4)2. H2O and a few others).
The behavior of the phosphate in dilute solution is straightforward but in
concentrated solutions at low pH values and high temperatures, reactions become
complicated by condensation, i.e. linking together of PO4 groups by the sharing of
oxygen atoms. Such polymerization is similar to that described for the borates but the
polyphosphate unit is a tetrahedron whereas the polyborate unit is a triangle. The
chemistry of phosphate which result from systems of fused salts is particularly complex
since the properties (and almost certainly the structures) of the products depend to a
large degree on small variations in reaction conditions. The chemistry of the
polyphosphates is sufficiently complex to be deferred to more advanced works.
74 | 106 P a g e s
8.7 USES
Phosphorus and its compounds, especially its minerals, take important roles in
prominent industries, see Figure 8.4 depicted from Greenwood and Earnshaw (2003:
520).
Phosphate rock Phosphoric acid Fertilizer

(impure)
 Food phosphate
Elemental Phosphoric acid  Industrial phosphate
phosphorus (pure)  Detergent phosphate
 Pharmaceutical
 Phosphorus sulfides Metal treatment

 Phosphorus chlorides (e.g. pickling, cleaning,
 Organic P compounds rust proofing, polishing)
Figure 8.4 Production and Uses of Phosphoric Acid

The most important application of phosphorus is in phosphate fertilizer.
Phosphorus is an essential plant nutrient and up to 90% of phosphate rock mined is
consumed in the manufacture of phosphorus containing fertilizer. Insoluble phosphate
rock is treated with concentrated H2SO4 to generate soluble superphosphate fertilizer
containing Ca(H2PO4)2 mixed with CaSO4 and other sulfates such as reaction between
phosphate rock and H3PO4 gives triple superphosphate, mainly Ca(H2PO4). Phosphate
in run-off water which flows into lakes contributes to the excessive growth of algae and
eutrophication of lake.
Fertilizers are the major source of phosphate entering rivers and lake. However,
domestic and industrial waste water for example detergent manufacturing also contain
[PO4]3- and condensed phosphate, and the level must be removed before the waste can
be discharged are controlled by legislation. In most cases, phosphate are removed by
methods based on the precipitation and for Fe3+, Al3+, Ca2+ , they are most commonly
used to give precipitates that can be separated by filtration. Recent fields‘ studies
indicate that adding phosphate to acid lakes stimulates plant growth which in turn leads
to a production of [OH-] , which neutralize excess acid.
75 | 105 P a g e s
Most white phosphorus is converted to H3PO4 or to compound such as P4O10,
P4S10, PCl3, and POCl3. Phosphoric acid is industrially very important and is used on
large scale in the production of detergent and food additives. It also has responsibility
for the sharp taste of many soft drinks, and is used to remove oxide and scale from the
surfaces of iron and steel. Phosphorus trichloride is also manufactured in large scale. It
is a precursor to many organophosphorus compounds, including nerve agent, flame
retardant, and insecticides. Phosphorus is important in steel manufacture and phosphor
bronze. Red phosphorus is used in safety matches and in the generation of smoke for
example fireworks and smoke bomb.
8.8 SUMMARY
Based on the explanation above, it can be concluded that phosphorus exist in
group15 element whereas in minerals of the apatite family. It has several properties.
Phosphorus also has some allotropes. There are the well-known white (or yellow)
phosphorus, red, violet and two black forms. Besides, there are many isotopes of
phosphorus, only one of which is stable (31P). Phosphorus has hydrides namely, PH3
and P2H4. Phosphorus trichloride and phosphorus pentachloride are the chemical
compound of phosphorus and chlorine. Two of the most important oxides of phosphorus
are P4O6 and P4O10. While, the two simple oxy-acids having phosphorus in lower
valence states are hypo phosphorous acid, (H3PO2), and phosphorous acid (H3PO3). In
daily life, phosphorus has many roles. The most important application of phosphorus is
in phosphate fertilizer.
8.9 STUDY QUESTIONS
1. Why nitrogen elementally can be in form of N2 but phosphorus in P4?
2. Distinguish the structures and properties of three different colored phosporus

allotropes!
3. Draw the Lewis structure of all phosphorus oxoacid compounds depicted on Figure
8.3!
76 | 106 P a g e s
4. Why is pure phosphoric acid syrupy?
5. Compare the structure and properties of nitric and phosphoric acids.
6. Write a balanced equation of ammonolysis of PCl3.
7. Give the products to be expected on reaction of P4 with (a) an excess of Cl2, (b) a
deficiency of Cl2, (c) an excess of oxygen, and 9d) a deficiency of oxygen.
8. Explain what is superphaphate, double superphosphate, rhenaniaphosphate. Explain

also the solubility of those phosphat pertilizers.
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CHAPTER 9
CHEMISTRY OF CARBON
9.1 INTRODUCTION
The basic competence of the chapter 9 is to understand properties of elemental carbon
and its allotropes as well as carbon compounds. Indicators of learning for reaching the basic
competences should show that students should be able to:
a. explain properties of carbon and its allotropes according to their structures;

and
b. explain properties and reactions of oxides, cyanogenide, cyanide, sulphide
and halides of carbon as well as carbides.
This chapter will explain briefly the properties of carbon and its allotropes, its
oxides, cyanogenides, cyanides, sulphides, and halides as well as carbides.
9.2 ELEMENT OF CARBON

Carbon constitutes about 0.09 percent by mass of Earth‘s crust and it is an
essential element of living creature. Many essential compounds in organism are made
up from carbon. It is also a component of natural gas, petroleum, coal, and etc. It
combines with oxygen to form carbon dioxide in atmosphere and occurs as carbonate in
limestone and chalk. In nature, carbon also exists as allotropes. Most of its compounds
lie within the remit of organic chemistry. Nonetheless, compounds of C that are
formally classified as inorganic bound and extend to organometallic species. This essay
78 | 106 P a g e s
will explain briefly the properties of carbon and its allotropes, its oxide, cyanogenides,
cyanides, sulfides and halides as well as carbides.
Carbon has its own properties that differentiate it from other elements. It is a
nonmetal element and lied on 4A group and 3rd period in periodic table. The electronic
structure of C atom in its ground state is 1s22s22p2, so that to accommodate the normal
four covalent bonds, the atom must be promoted to a valence state 2s2px2py2pz. A
unique feature of carbon is its propensity for bonding to itself in chains or rings, not
only with single bonds (C-C) but also with multiple bonds (C═C or CC). The ion C4+
does not arise in any normal chemical process, but C4+ may possibly exist in some
carbides of most electropositive metal.
There are several allotropes of carbon, namely diamond, graphite, fullerenes,
and carbon nanotubes. Allotropes are different crystalline form of an element. It differs
in the way the atoms bond with each other and arrange them selves into a structure.
Therefore, allotropes have different physical and chemical properties. Diamond is the
hardest material known. In diamond, each carbon atom is sp3 hybridized so that it is
bonded to four other carbon atoms. The strong covalent bonds in three dimensions
contribute to diamond‘s unusual hardness and high melting point (3550°C). Diamond
has a higher density than graphite (ρgraphite = 2.25 g cm-3; ρdiamond = 3.5 g cm-3).
(Housecroft et al., 2008: 384) This allows artificial diamonds to be made from graphite
at high pressure (more than 100,000 times the atmospheric pressure at sea level) and
temperature (about 3000°C). High temperatures break the strong bonds in graphite so
that the atoms can rearrange themselves into a diamond lattice. Naturally, occurring
diamonds must have been formed when those conditions were provided by geological
processes. Diamonds will burn in air at 600-8000C but its chemical reactivity is much
lower than that of graphite.
In graphite, the atoms form planar or flat layers. Each layer is made up of rings
containing six carbon atoms. The rings are linked to each other in a structure that
resembles the hexagonal mesh of chicken wire. Bonds between atoms within a layer of
graphite are strong, but the forces between the layers are weak.
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Figure 9.1 The Structure of Diamond (left) and Graphite (Right)
Figure 9.2 The Structure of Carbon Nanotube (left) and Fullerene (right)
Therefore, the layers can slide over one another. Graphite is slippery to the touch
and is effective as a lubricant. It is also used in pencils and ribbons for computer
printers and typewriters. The loose layered structure of graphite allows molecules or
ions to penetrate the layers to form intercalation compounds with alkali metals. They
have compositions such as LiC6, LiC12, LiC18 or KC8, KC24, KC36, KC48. Depending on
the metal content, they have colors extending from a golden luster to black. They are
better electric conductors than graphite (Muller, 2006: 113).
Graphite can be rolled into tubes which are only few nanometers in diameter
which is called nanotubes. It consists of elongated cages of networks of fused 6-
membered rings. Nanotubes can be used to make threads and cables of extreme strength
called nanofibres(Ratcliff et al., 2008: 223).
Fullerenes are modifications of carbon that consist of cage-like molecules. The
family of molecular fullerenes includes C60, C70, C76, C78, C80, and C84. They can be
obtained by setting up an electric arc between two graphite electrodes in a controlled
80 | 106 P a g e s
atmosphere of helium and condensing the evaporated carbon, then recrystallizing it
from magenta-colored benzene solution. The main product is the fullerene C60 which is
called buckminsterfullerene. The C60 molecule has the shape of a soccer ball, consisting
of 12 pentagons and 20 benzene-like hexagons. Second in yield from this preparation is
C70, which has 12 pentagons and 25 hexagons and a shape reminiscent of a peanut.
Cages with other sizes can also be produced, but they are less stable. Independent of its
size, a fullerene molecule always has twelve pentagons. The crystals are as soft as
graphite. Similar to the intercalation compounds of graphite, potassium atoms can be
enclosed. They occupy the cavities between the C60 balls forming K3C60. This
compound has metallic properties and becomes superconducting when cooled below
18oK (Muller, 2006: 115).
9.3 COMPOUNDS OF CARBON

Beside allotropes, carbon can be found in the form of oxide, cyanogenides,
cyanides, sulfides and halides as well as carbides. The first is oxide of carbon. Carbon
forms two oxides, namely carbon monoxide (CO) and carbon dioxide (CO2). Carbon
monoxide is a colorless and odorless toxic gas. It is formed when carbon is burned in
limited supply of oxygen. The following equilibrium is found at all temperatures
2 CO(g) C(s) + CO2(g) ..................................................................................(9.1)
Carbon monoxide is also present in the exhaust fumes of cars due to the
incomplete combustion of petrol. Certain marine plants release CO and naturally
occurred in atmosphere. Industrially, CO is manufactured by reduction of CO2 using
along with hydrogen by partial combustion of hydrocarbon:
CO2 + H2 CO + H2O ..................................................................................(9.2)
Small-scale preparations involve the dehydration of methanoic acid
HCO2H  CO + H2O ....................................................................................(9.3)
Carbon monoxide is almost insoluble in water and does not react with aqueous
NaOH under normal condition but at high temperature and pressure, HCO2H and
Na[HCO2] are formed respectively. (Housecroft et al., 2008: 384) Although CO is the
81 | 105 P a g e s
anhydride of formic acid but it is not an acidic oxide. One of its important properties is
its ability to act as ligand toward transition metals. The metal─CO bond involves a
certain type of multiple bonding. This ability is shown when CO bind to Fe atom in
hemoglobin causing consequent inhibition of O2 transport in body. Under practical
condition, only iron and nickel react directly with CO. Despite of its toxicity, CO has
several uses in industry. Due to its ability to bond rapidly with oxygen makes it an
effective reducing agent and used in blast furnace extraction of iron from iron ore.
(Harwood, 2007: 227)
Fe2O3(s) + 3CO(g) → 2 Fe(s) + 3CO2(g) ............................................................(9.4)
A mixture of CO and H2 is very important commercially used in the hydroformylation
process and for the synthesis of methanol.
Carbon dioxide is also a colorless and odorless gas. Unlike CO, CO2 is nontoxic.
It is present in the atmosphere (300 ppm), in volcanic gases, and in supersaturated
solution in certain spring water. It is formed in all forms of combustion of carbon and
carbon compound in excess of O2. It is involved in geochemical cycle as well as
photosynthesis. Carbon dioxide can be prepared in laboratory by heating carbonate or
reacting it with acids.
CaCO3 + 2 HCl  CaCl2 + H2O + CO2 .........................................................(9.5)
Solid CO2 (sublimes -78.5oC) or dry ice can be produced at low temperature and high
pressure. Carbon dioxide is the anhydride of carbonic acid. When it dissolves in water,
some of the gas reacts to produce a weak acid, carbonic acid (H2CO3). The solution has
pH between 4 and 6.
CO2 + H2O  H2CO3 ....................................................................................(9.6)
Carbon dioxide is used in fire extinguisher since it is denser than oxygen, in refrigerant,
in manufacturing soda ash and baking soda. More recently, CO2 has gained international
attention due to its role in the greenhouse effect causing global warming.
The second compound is cyanogenides. Cyanogens ((CN)2) is one example of it.
This is a toxic and extremely flammable gas. It can be obtained from CN- by aqueous
solution using Cu2+.
2 Cu2+ + 4 CN-  2 CuCN + (CN)2 ................................................................(9.7)
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Cyanogen is able to resemble the halogen in the disproportianation in basic solution
(CN)2 + 2 OH-  CN- + OCN- + H2O ...........................................................(9.8)
This gas is able to produce one of the hottest flames known from a chemical reaction
when it is burned. (Cotton et al., 1995: 377)
The third is cyanides. Cyanide ions are extremely toxic because they bind almost
irreversibly to Fe(III) ion in cytochrome oxidase, a key enzyme in metabolic processes.
An example of cyanides is hydrogen cyanide (HCN). Like the hydrogen halides, HCN
is a covalent molecular substance but capable of dissociation in aqueous solution. It is a
colorless gas having the aroma of bitter almonds. This gas is extremely poisonous. A
few tenths of 1 percent by volume of HCN in air can cause death within minutes. Liquid
HCN is unstable and can polymerize violently in the absence of stabilizers. In aqueous
solutions, polymerization in induced by UV light. Hydrogen cyanide can be prepared by
treating sodium cyanide or potassium cyanide with acid:
NaCN + HCl  NaCl + HCN ........................................................................(9.9)
Because HCN solution is a very weak acid (Ka = 4.9 x 10-10), most of the HCN
produced in this reaction is in the nonionized form and leaves the solution as hydrogen
cyanide gas. For this reason, acids should never be mixed with metal cyanides in the
laboratory without proper ventilation. (Chang, 2010: 921)
The fourth is sulfide. Sulfide of carbon is a compound with C─S bond. One of
them is carbon disulfide (CS2). It is highly toxic liquid (b.p. 46oC ) with pale yellow
color and extremely flammable. Carbon disulfide is made by heating charcoal with
sulfur at 1200oK or by passing CH4 and sulfur vapor over Al2O3 at 950oK. (Housecroft
et al., 2008: 423)
CH4 + S CS2 + 2 H2S ............................................................................(9.10)
This compound is highly toxic (by inhalation and absorbption through skin) but it is an
excellent solvent used in the production of rayon and cellophane. Industrially, it is also
used to prepare CCl4
CS2 + 3 Cl2  CCl4 + S2Cl2 ........................................................................(9.11)
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Another type of carbon compound is halides. The carbon tetrahalides (CF4,
CCl4, CBr4, and CI4) differ from those of the group 4A elements. They are inert toward
water and dilute alkali as well as do not form complexes with metal halides. Carbon
tetrafluoride is colorless gas and synthesized from graphite-free calcium cyanamide and
CsF is added to prevent the formation of NF3. (Housecroft et al., 2008: 404)
CaNCN + 3 F2  CF4 + CaF2 + N2 ............................................................(9.12)
Carbon tetrachloride is colorless liquid and produced by chlorination of CH4 at 520-
670oK or by the sequence reaction in which CS2 is recycled.
CS2 + Cl2  CCl4 + S2Cl2 ..........................................................................(9.13)
CS2 + 2 S2Cl2  CCl4 + 6 S .........................................................................(9.14)
6 S +3C  3CS2 ...........................................................................................(9.15)
In the past, CCl4 had been widely used as solvent and for the chlorination of inorganic
compounds. However, its high toxicity and the fact that thermal decompositions results
in the formation of radicals has led to its manufacture and used being controlled by
environmental legislation. On the other side, CBr4 is colorless solid while CI4 is dark
red solid. Both of them are toxic and easily decomposed to their elements. Preparation
of CBr4, and CI4 can be done as follow:
3 CCl4 + 4 AlBrZ3  3 CBr4 + 4 AlCl3 .......................................................(9.16)
CCl4 + 4 C2H5I  CI4 + 4 C2H5Cl ..............................................................(9.17)
The last is carbide. Solid compounds of carbon with elements other than
hydrogen are generally called carbides. It can be classified into three types, namely
ionic carbides, interstitial carbides, and covalent carbides. (Cotton et al., 1995: 374)
Ionic carbides are formed by metals from group IA, IIA, and aluminum, for example
Na2C2, CaC2, and Al4C3. Carbon is in the form of C22− or C4- ions. These ions are strong
Brønsted bases and react with water as follows:
C22− (aq) + 2H2O(l) → 2OH-(aq) + C2H2(g) ...........................................................(9.18)
C4- (aq) + 4H2O(l) → 4OH-(aq) + CH4(g) ...........................................................(9.19)
Interstitial carbides are formed by heating C with d-block (transition group)
metals having rrmetal > 130 pm, e.g. Ti, Zr V, Mo, and W. Such materials are commonly
very hard, electrically conducting, and have very high melting points (3000-4800oC).
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Tungsten carbide (WC) is one of the hardest substances known and widely used in
cutting and dies tools. Transition metals with rrmetal < 130 pm ,e.g. Cr, Fe, Co, Ni give
carbides that are intermediate between typically ionic and interstitial carbides. This type
of carbides is hydrolyzed by water or dilute acid to give mixture of hydrocarbons and
H2. On the other hand, metalloids especially Si and B form SiC and B4C which are
covalent carbides. Silicon carbide is called carborundum and prepared as follows:
SiO2(s) + 3C(s) → SiC(s) + 2CO(g) ..................................................................(9.20)
Carborundum is also formed by heating silicon with carbon at 1500°C.
Carborundum is almost as hard as diamond and it has the diamond structure in which
each carbon atom is tetrahedrally bonded to four Si atoms and vice versa. It is used
mainly for cutting, grinding, and polishing metals and glasses.
9.4 SUMMARY
Based on the explanation, it can be concluded that carbon is nonmetal element
that has propensity for bonding to itself in chains or rings, not only with single bonds
(C-C) but also with multiple bonds (C═C or CC). There are several allotropes of
carbon, namely diamond, graphite, fullerenes, and carbon nanotubes. It differs in the
way the carbon atoms bond with each other and arrange themselves into a structure so
that each allotrope has different physical and chemical properties. Carbon can be also
found in the form of oxide, cyanogenides, cyanides, sulfides and halides as well as
carbides. Their properties are different and several of them are highly toxic.
9.5 STUDY QUESTIONS

1. Explain the correlation of structure and properties of carbon black, graphite, and
diamond.
2. Why can carbon build single C-C, double C=C, and triple CC bonding and can
undergo catenation as well?
3. Why is CCl4 unreactive in water but SiCl4 reactive and easily hydrolized?
4. List ways in which CO as well as CO2 can be prepared!
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5. HCN can give dimers, trimers, tetramers, pentamers, and polymers. Draw the Lewis
structures of those molecules. Explain why HCN is a weak acid in aquous solution
but a strong acid in its liquid.
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CHAPTER 10
CHEMISTRY OF SILICON
10.1 INTRODUCTION
silicon as well as its compounds. Indicators of learning for reaching the basic competences
a. explain properties of silicon and its preparation;

b. explain preparation and properties of silicon hydrides, silicides and
silicon carbide;
c. describe structures of silica and silicates; and
d. give some examples aluminosilicates and their uses of ceramics, talc,
zeolite and micas . in industries.
This chapter will explain briefly the properties of silicon and its preparation,
hydrides of silicon, silicides, silicon carbides, silica and silicates, aluminosilicates, and
their industrial prospects.
10.2 SILICON AND ITS PROPERTIES

Silicon is classified as metalloids (Kotz, et.al, 2009). It is the member of group
14 in periodic table, but there are specific differences from carbon. Silicon is much
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more reactive than carbon (Housecroft & Sharpe, 2008). Furthermore, Si displays little
or no tendency for catenation among its compounds (Cotton, et.al, 1995).
28 29
Silicon consists predominantly of Si (92,23%) together with 4,67% Si and
3,10% 30Si. No other of its isotopes are stable. In its ground state, the free atom Si has
the electronic configuration [Ne] 3s23p2. Furthermore, the physical properties are
summarized in the following table.
Table 10.1 Elemental Silicon Properties
Density (20oC)/gcm-3 2.53259
∆Hf (monoatomic gas)/kJ mol-1 454±12
r (covalent)/pm 117,59
r (―ionic‖)/pm 26(a)
Pauling electro negativity 1.8
(a)
this is a ―effective ionic radius‖ for 4-coordinate Si in silicates
Silicon in the massive, crystalline form is relatively unreactive except in high

temperatures. Si is insoluble in acids other than a mixture of concentrated HNO3 and
HF. Si also dissolves readily in hot aqueous alkali due to reaction below.
Si + 4OH-→ SiO44-+2H2 ..............................................................................(10.1)
Silicon form mostly covalent substances, as well as polyatomic ions and
oxoanions containing covalent bond. Si readily undergoes coordination number
expansion to a maximum covalence of six, namely 𝑆𝑖𝐹5− and 𝑆𝑖𝐹62−. At high
temperatures, Si combines with O2, F2, Cl2, Br2, I2, S8, N2, P4, C, and B to give binary
compounds. At room temperature, silicon can react only with F2. Si forms divalent
(lower) compounds only rarely, for example being the unstable SiF2. Silicon also forms
hydrides that are reactive and unstable, an example being SiH4, which is readily
hydrolyzed. Si forms molecular halides that are readily hydrolyzed. Si also forms an
oxide (SiO2) that is an acidic, covalent-network substance.
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10.3 SILICON PREPARATION
Commercial silicon is made by reducing pure silica (SiO2) with carbon (C) or
calsium carbida (CaC2) to approximately 3000oC in electric furnace. The SiO2 is kept in
excess to prevent the accumulation of SiC.
SiO2 + 2 C  Si + 2CO ..................................................................................(10.2)
2 SiO2(s) + CaC2  2 Si + CaCO3 + CO .........................................................(10.3)
2 SiC + SiO2(s)  3 Si + 2 CO ........................................................................(10.4)
The molten silicon is drawn off the bottom of the furnace and allowed to cool to a shiny
blue-gray solid. Meanwhile, pure silicon is made by several step. First, the silicon in the impure
sample is allowed to react with chlorine to convert the silicon to liquid silicon tetrachloride
(Kotz, Treichel, & Toensend, 2009)
Si(s) + 2Cl2(g)  SiCl4 (l) ................................................................................(10.5)
Silicon tetrachloride (boiling point of 57.6oC) is carefully purified by distillation and

then reduced to silicon using magnesium.
SiCl4 (g) + 2Mg (s)  2 MgCl2 (s) + Si (s) .......................................................(10.6)
The magnesium chloride is washed out with water, and the silicon is remelted and cast
into bars. A final purification is carried out by zone refining, a process in which a special
heating device is used to melt a narrow segment of the silicon rod. The heater is moved slowly
down the rod. Impurities contained in the silicon tend to remain in the liquid phase because the
melting point of a mixture is lower than that of the pure element. The silicon that crystallizes
above the heated zone is therefore of a higher purity.
In laboratorium, silico can be prepared through reducing silica powder with Mg

or Al.
SiO2 + 2 Mg  Si + 2 MgO .........................................................................(10.7)
3 SiO2 + 4 Al  2 Si + 2 Al2O3 ....................................................................(10.8)
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10.4 SILICON HYDRIDES (SILANES)
There are 3 general types of preparative route to the silanes and their derivatives.
First methods treated materials such as metal silicides which contained negatively
charged Siᵟ- with a protonic reagent such as an aqueous acid. The second general
preparative route involves treatment of compounds such as SiX4 with hydride reagent
such as LiH, NaH, LiAlH4, etc., in either solvent at low temperature, e.g. SinCl2n+2
(n=1,2,3) with LiAlH4 gives essentially quantitative yields of SiH4 , Si2H6, and Si3H8.
Then, the last the preparation of Si-H compounds involves direct reaction of HX or RX
with Si or a ferrosilicon alloy in the presence of a catalyst such as Cu when necessary.
This method are usually used in industry fields.
350 𝑜
Si + 3HCl SiHCL3+ H2 .........................................................................(10.9)
𝑜
𝐶𝑢 300
Si+2MeCl MeSiHCl2 +H2 +C ........................................................(10.10)
Combination of these various methods has led to a vast number of derivatives in which
H is progressively replaced by one or more monofunctional group such as F, Cl, I, Br,
NH2, etc.
Silanes is a colourless gas which is insoluble in water, reacts rapidly with alkalis
and explosively inflammable in air (Housecroft & Sharpe, 2008).
10.5 SILICIDES
Silicides are usually prepared by direct fusion of the element but coreduction of SiO2
and a metal oxide with C or Al is sometimes used. Heats of formations are similar to those of
borides and carbides but mps are substantially lower; e.g : TiC 3140o, TiB2 2980o, TiSi2 1540o,
and TaC 3800o, TaB2 3100o, TaSi2 1560o
Silicides of group 1 and 2 are generally much more reactive than those of the transition
element (cf carbide and borides). Hydrogen and/or silanes are typical product
𝑅𝑎𝑝𝑖𝑑 𝑎𝑛𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒

Na2Si+ 3H2O Na2SiO3 + 3H....................................................(10.11)
Mg2Si + 2H2SO4(aq)  2 MgSO4 + SiH4.........................................................(10.12)
Product also depend on the stoichiometry, in example structural types.
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Silicides have several properties, it written in the following properties
(a) The structures of the metal silicides (prepared by direct combination of the
elements at high temperatures) are diverse.
(b) The Si4- units present in the alkali metal silicides are noteworthy.
(c) The Si4- anion is isoelectronic with P4 and the solid state structures of several group
1 metal silicides contain tetrahedral Si4- units, but these are not isolated anions.
(d) Silicides are hard materials, but their melting points are generally lower than those
of the metal carbides.
10.6 SILICON CARBIDE

Silicon carbide exist in at least 200 crystalline modification based on hexagonal
α-SiC or cubic β-SiC. The complexity arises from the numerous stacking sequences of
the α and β ―layers‖ in the crystal. The α- form is more stable thermodynamically.
Industrially α-SiC is obtained as black, dark green or purplish iridescent crystal by
reducing high-grade quartz sand with a slight excess of coke or anthracite in electric
furnace at 2000-2500oC. It is simply written in the following equations:
SiO2 + 2C  Si + 2CO ...............................................................................(10.13)
Si + C SiC ...............................................................................................(10.14)
Very pure β-SiC can be obtained by heating grains of ultrapure Si with graphite
at 1500o or b gas phase plasma decomposition Me2SiCl2, MeSiCl3, or SiCl4/CH4
mixtures. Fibres of SiC are made by progressive pyrolysis of organosilicon polymer
such as –CH2SiHMe- or –CH2SiMe2-
Silicon carbide (carborundum) has several polymorphs. The 𝛽-form adopts the
wurtzite structure. It is extremely hard, resist wear, withstands very high temperature,
has a high thermal expansion. Recent development of suitable CVD methods has made
possible the deposition of 𝛽-SiC of >99.9% purity (Housecroft & Sharpe, 2008). Silicon
carbide is a IV-VI semiconductor (band gap = 2.98 eV) which has particular application
for high-frequency devices and for systems operating at high temperatures (Housecroft
& Sharpe, 2008). So, silicon carbide can use in manufacturing mirrors for laser radar
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system, high-energy laser, synchrotron X-ray equipment, astronomical telescopes and
blue-light emitting diodes (LEDs).
10.7 SILICA AND SILICATES

The simplest oxide of silicon is SiO2, its called silica. SiO2 is a network solid, which is
the preferred structure because the bond energy of two Si O (double bonds) is much less than
the bond energy of four Si O single bonds. Silica is an in volatile solid and occurs in many
different forms, nearly all of which posses 3-dimensional structures constructed from tetrahedral
SiO4 building blocks, often represented as in the following structure.
The structure is a polyhedral representation of the SiO4 unit, and is commonly used
when illustrating the connectivities of the building blocks in 3-dimensional silicate structures.
Each unit is connected to the next by sharing an oxygen atom to give Si O Si bridges
(Housecroft & Sharpe, 2008).
Silicates are readily formed by fusion of SiO2 and metal hydroxides, oxides or
carbonates (Housecroft & Sharpe, 2008). The overwhelming majority of silicates have
structures based on SiO4 tetrahedral. The following is the schematic representations of
the structures of selected silicates.
-
O O-
-
O O- -
Si
O
O O
O-
Si Si Si
O- O O
-
O O-
O O
Si Si Si - Si
-
O
- - O O
O O
O- -
O O- -
O O-
[SiO4]4- [Si3O6]6- [Si4O12]8-
By sharing O atoms, assemble into small groups such as cyclic motifs, infinite chains,
infinite layer or infinite 3-dimensional networks. Sharing an atom only involves corners of
tetrahedra; sharing an edge would bring two O2- ions too close together.
Silica is the basic structural feature of some of the earth‘s most important
minerals, particularly the clay minerals, mica, talc, and the chrysotile form of asbestos.
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However, these minerals do not contain just silicon and oxygen. Rather, they are often
referred to as aluminosilicates because they frequently have Al3+ ions in place of Si4+
(which means that other positive ions such as Na+, K+, and Mg2+ must also be present in
the lattice to balance the net negative and positive charges) (Kotz, et.al, 2009). Other
aluminosilicates include the feldspars, common minerals that make up about 60% of the
earth crust, and zeolites.
There are some interesting uses of clays. In certain cultures, clay is eaten for
medicinal purposes (Kotz, et.al, 2009). Mica is used to furnace windows and as
insulation and flecks of mica give the glitter to metallic paints. Zeolites can be used
asdrying agents to selectively absorb water from air or a solvent. Small amounts of
zeolites are often sealed into multipane windows to keep the air dry between the panes
(Kotz, et.al, 2009). Zeolite are also used as catalysts. ExxonMobil, for example has
patented a process in which methanol, CH3OH is converted to gasoline in the presence
of specially tailored zeolites. Zeolites also are added to detergents, where they functions
as water-softening agents because the sodium ions og the zeolite can be exchanged for
Ca2+ ions in hard water, effectively removing Ca2+ ions from the water (Kotz, et.al,
2009).
10.8 SUMMARY
Silicon have specific properties and preparations. Silicon is a non metal. It
displays little or no tendency for catenation among its compounds. Silicon forms mostly
covalent substances, as well as polyatomic ions and oxoanions. Silicon readily undrgoes
coordination number expansion to a maximum covalence of six, namely SiF5-, and
SiF62-. Silicon can form divalent compounds but unstable such as SiF2. Silicon forms
hydrides but the compounds normally are very reactive and unstable, SiH4 for example
is readily hydrolyzed. Silicon can form also halides but they are readily hydrolyzed.
Silicon forms an oxide called silica, SiO2, an acidic, covalent-network substance. be
found in its compounds, like silicon hydrides, silicides, silicon carbide, silica and
silicates. Silica is the basic structural feature of some of the earth‘s most important
minerals. However, these minerals do not contain just silicon and oxygen, they are often
93 | 105 P a g e s
contains aluminum, so called aluminosilicates. Aluminosilicates have been use largely
in industrial fields.
10.9 STUDY QUESTIONS

1. Compare and contrast the molecular structure of CO2 and SiO2.
2. Explain using an example reaction the acidic properties of silica.
3. Explain why carbon can undergo catenation but not for silicon.
4. Balance the equation for the reaction of SiCl4 with LiAlH4.
5. Balance the reaction equation of hydrolysis of SiF4.
94 | 106 P a g e s
CHAPTER 11
CHEMISTRY OF BORON
11.1 INTRODUCTION
boron as well as its compounds. Indicators of learning for reaching the basic competences
a. explain properties and preparation of boron;
b. explain properties of ortoborate acids;
c. explain properties of boron trihalides; and
d. explain properties of diborane, its preparation and structure.
This chapter will explain briefly the properties and preparation of boron, borates,
boron trihalides, and boron hydrides.
11.2 BORON AND ITS PROPERTIES

Boron is a unique and exiting element. Over the years it has proved a constant
challenge and stimulus not only to preparative chemists and theoreticians, but also to
industrial chemists and technologist. It is the only non-metal in the Group IIIA (13) of
periodic table and shows many similarities to its neighbor (carbon), its diagonal relative
(silicon) and only a few features in common with that of aluminum. Atomic number of
Boron is 5 and the configuration electron of Boron is [He]2s22p1. The melting point of
95 | 105 P a g e s
Boron is 24530K and the boiling point is 42730K. The first ionization energy of Boron is
800.6, the second ionization energy is 2427, and the third ionization energy is 3660.
Boron forms a number of alltropes that are difficult to purify because of the high
melting point of the solids (e.g., 22500C for the -rhombohedral form) and because of the
corrosive nature of the liquid.
It shows a marked propensity to form covalent, molecular compounds, but it differs
sharply than C and Si in having one less valence electron than the number of valence orbitals, a
situation sometimes referred to as ―electron deficiency‖.
Boron is most interesting element, in that it tends to form trivalent compounds
typical of most non-metallic elements but, in doing so, is left in a state of valency
unsaturation. In many ways, boron exhibits compounds that are in the il-defined region
between metallic and ―normal‖ covalent compounds. This is no more strikingly shown
than by the element and its binary compounds with metals, the so called borides.
Elemental boron exists in three different crystallographic forms, but all are
characterized by icosahedral B12 clusters linked together in a three-dimensional
network. The icosahedral is a regular polyhedron with 12 vertices and 20 faces. There
are two high-symmetry polyhedra with the same number of vertices, the cuboctahedron
has six square faces and eight triangular faces, while the icosahedron has only
equilateral triangular faces.
The chemical properties of boron, in comparison with aluminium and silicon,
has only a few features as follows. The oxide B2O3 and B(OH)3 are acidic, but Al2O3
and Al(OH)3 are basic, and show weak amphoteric properties by dissolving in strong
NaOH. Borates and silicates are built on similar structural principles with sharing of
oxygen atoms so that complicated chain, ring, or other structures result. The halides of
B and Si (except BF3) are readily hydrolyzed. The Al halides are solids and only partly
hydrolyzed by water. All act as Lewis acids.
The hydrides of B and Si are volatile, spontaneously flammable, and readily
hydrolyzed. Aluminium hydride is a polymer (AlH3)n.
11.2 ISOLATION AND USES

96 | 106 P a g e s
Boron is an element that is rarely to be found in the earth's crust, but are often
found in the compound as a borax salt or sodium tetraborate. The principal ores of
boron are ulexite NaCa[B5O6(OH)6]. 5 H2O, borax Na2[B4O5(OH)4].8 H2O, colemanite
Ca2[B3O4(OH)3]2. 2 H2O, and kernite Na2[B4O5(OH)4. 2 H2O.
Boron is made in 95-98% purity as an amorphous powder by reduction of the
oxide B2O3 with Mg.
B2O3 + 3 Mg  2 B + 3 MgO .............................................................(11.1)
The powder containing a mixture of boron and magnesium oxide is washed with
NaOH, HCl, and HF, thus boron can be separated from MgO. After washing, boron
metal is then purified throug placing electropositive metals in place of Mg.
Pure boron metal can be isolated through reducing boron trihalides with zinc at
900 C, as reaction below.
2 BCl3 + 3 Zn  3 ZnCl2 + 2 B ..........................................................(11.2)
The uses of boron are prominent in advancement of technology as well as
various industries. Boron is used in the manufacture of borosilicate glass (Pyrex brand
traded with) highly resistant heating at a high temperature. Addition of boron is also
used as a wash, detergent very effective at temperatures of 900C, which is a compound
of sodium peroksoborat (NaBO3). Boron is a key component in nuclear power because
of its ability to function as an absorber (absorber) neutrons; stir stick containing boron
lowered into the reactor to keep the nuclear reaction takes place at a pace that is being
desired.
11.3 BORON – OXYGEN COMPOUNDS

Boron is never found as the element and or even directly bonded to any other
element than oxygen, by exceptions of the generalization are ferrucite (NaBF4) and
avogadrite (K,Cs)BF4 (Greenwood and Earnshaw, 2003: 203). The chemistry of B-O
compounds is characterized by its complexity and diversity.
97 | 105 P a g e s
The principal oxide of boron is boric oxide, B2O3. It has melting point of 450C,
boiling point of 2250C, and the most difficult substance to crystallize, thus it is known
only in vitrious state.
Ortoboric acid or boric acid, B(OH)3 is the normal end product of hydrolysis of
most boron compounds. It is a white solid which partially soluble in water. Boric acid
can be obtained from the oxidation of elemental boron with hydrogen peroxide solution
(-30%). In acidic aqueous solution is weakly mono rather than acting as a proton donor
but as a Lewis acid, for example, received OH-being [B(OH)4]- according to the
equation:
B(OH)3(s) + H2O(l) [B(OH)4]-(aq) + H+(aq) ...............................................(11.3)
B(OH)3 acts as a strong acid in anhydrous H2SO4 according to the reaction below.
B(OH)3 + H2SO4  3 H3O+ + 2 HSO4- + [B(HSO4)4]- ................................(11.4)
Partial dehydration of B(OH)3 at 140C will produce monoclinic HBO2 which in rapid
quenching can produce orthorombic HBO2. Heating (OH)3 at 1750C can produce cubic
HBO2.
Heating boric acid to produce the oxide B2O3 melt like glass. The molten boric
acid dissolves the oxide - metal oxides produce borate glasses. Pyrex borosilicate glass
that contains of borosilicate compound. Dehydration boric acid will be produce acids
metaborate, HBO2. Boric acid has a circular structure with ground-plane layer hydrogen
bonds.
Boric acid is readily converted to alkyl or aryl orthoborates, B(OR)3, by
condensation with alcohols in the presence of sulfuric acid. These compounds are
usually colorless liquids that are converted, in ether solvents, by alkali metal hydrides to
the very useful reducing agents [HB(OR)3-]. The reactivity and selectivity of the latter
as reducing agents can be controlled by charging the R groups.
Ortoborate acids are usually colorless liquids that are converted, in ether solvents,
by alkali metal hydrides to the very useful reducing agents [HB(OR)3-].
Metal borates are known in which the structural unit is mononuclear, bi, tri, tetra
or penta-nuclear, or in polydimensional network of glass phases. There are some
structural principles of the bonding in metal borates as follows: (a) boron can link either
98 | 106 P a g e s
three oxygens to form a triangle or four oxygens to form a tetrahedron; (b) polynuclear
anions are formed by corner sharing of boron-oxygen triangles and tetrahedra; (c) in
hydrated borates, protonable oxygen atoms will be protonated in the following
sequence: available protons are first assigned to free O2- ions to convert these to free
OH-ions; additional protons are assigned to tetrahedral oxygens in the borate ion, and
then to triangular oxygens in the borate ion; finally any remaining protons are assigned
to free OH- ions to form H2O molecules; (d) the hydrated insular groups may
polymerize in various ways by splitting out water; (e) complex borate polyanions may
be modified by attachment of an individual side group, such as an extra borate
tetrahedron, an extra borate triangle, 2 linked triangels, and so on; and (f) isolated
B(OH)3 groups, or polymers of these, may exist in the presence of other anions.
11.4 BORON HALIDES

The boron trihalides are colorless, volatile, highly reactive, trigonal-planar,
monomeric molecular compounds which show no detectable tendency to dimerize.
Boron triflouride (BF3) is a colorless gas and boils at -101oC, whereas BCl3 and BBr3
are liquids (boiling points 12oC and 90oC) and BI3 is a solid and melts at 43oC.
The boron trihalides are typical and strong Lewis acids, capable of forming
complexes with the most molecules that contain nonbonding electrons. Except for BF3,
they undergo solvolysis by most compounds containing acid hydrogen; all, again except
BF3, undergo violent hydrolysis on contact with water.
Boron triflouride (BF3) is a colorless gas and boils at -101oC, whereas BCl3 and
BBr3 are liquids (boiling points 12oC and 90oC) and BI3 is a solid and melts at 43oC.
11.5 BORANES
The simplest hydride of boron exists as a gaseous dimer is diborane (B2H6).
Diborane, a colorless gas is clearly a highly covalent bond. It is melts at -164.85oC and
boils at -92.59 oC, that is spontaneously flammable in air and instantly hydrolyze by
H2O to H2 and boric acid. Besides that, the thermal stability of B2H6 is fairly stable at 25
o
C.
99 | 105 P a g e s
The structure of diborane, which was first determined by gas-phase electrone-
diffraction studies, is shown as bellow:
The bonds of diborane are required to explain the B-H-B bridges. The terminal B-H
bonds may be regarded as conventional (B-H) bonds. Thus, each boron atom uses two electrons
and two roughly sp3 orbitals to form (B-H) bonds to two hydrogen atoms. The boron atom in
each BH2 group still has one electron and two hybrid orbitals for use in further bonding. The
plane of the two remaining orbitals is perpendicular to the BH2 plane. When two such BH2
groups approach each other, as the picture above, with hydrogen atoms also lying in the plane of
the four empty orbitals, two B-H-B bonds are formed. The total of four electrons required for
these bonds is provided by the one electron carried by each H atom and by each BH2 group.
Diborane, a colorless gas is clearly a highly covalent bond. It is melts at -
164.85oC and boils at -92.59 oC, that is spontaneously flammable in air and instantly
hydrolyze by H2O to H2 and boric acid. Besides that, the thermal stability of B2H6 is
fairly stable at 25 oC. The original preparation of diborane trough hydrolysis of
magnesium.
There are 5 classes of boranes, namely closo-, nido-, arachno-. hypo-, and
conjucto-boranes.
(1) Closo-boranes have complete, closed polyhedral cluster of n boron atoms, for
example BnHn-2 (n = 6-12).
(2) Nido-boranes have non-closed structures in which the Bn cluster occupies n corners
of an (n+1)-cornered polyhedron, for examples, BnHn+4 e.g. B2H6, B5H9, B6H10,
B10H14, B8H12. There are also formula BnHn+3- formed by removal of 1 brigde
proton from BnHn+4, e.g. B5H8, B10H13-. Other formula is BnHn+22- e.g. B10H122-,
B11H132-.
(3) Arachno-boranes have even more oven clusters in whichbthe B atoms occupy n
continous corners of an (n+2)-cornered polyhedron. For examples are series of
BnHn+6 such as B4H10 and B5H11, BnHn+5- such as B2H7-, B3H8-, B5H10-, B9H14-, and
B10H15-.
100 | 106 P a g e s
(4) Hypo-boranes have the most open clusters in which the B atoms occupy n corner of
an (n+3)-cornered polyhedron. For examples are BnHn+8 series such as B8H16 and
B10H18.
(5) Conjuncto-boranes have structures formed by linking two (or more) of the
proceding types of cluster together. The formula of the series is BnHm. There are
five different structure types of interconected borane clusters are already identified:
(a) fusion by sharing a single common B atom, e.g. B15H23.
(b) Formation of a direct 2-centre B-B  bond between 2 clusters, e.g. B8H18 i.e.
(B4H9)2.
(c) fusion of 2 clusters via 2B atoms at a common edge, e.g. B13H19, B14H20,
B16H20, n-B18H22, i-B18H22.
(d) Fusion of two clusters via 3B atoms at a common face, no neutral borane
neither anion is yet known, but the solvated complex (MeCN)2B20H16.MeCN
has this structure.
(e) More extensive fusion involving 4 B atoms in various configurations, e.g.
B20H16, B20H182-.
The original preparation of diborane was proposed by Alfred Stock, the pioneer
of boron hydride chemistry. The process was effected trough hydrolysis of magnesium
boride. Now, it is routinely prepared by a variety of reaction of boron compounds with
complex hydries, the most convenient being the following:
(C2H5)2O
3LiAlH4 + 4BF3∙O (C2H5)2 2B2H6 + Li3AlF6 + 2AlF3 + 4(C2H5)2O ....(11.5)
CH3O(CH2CH2O)2 CH3
3NaBH4 + 4BF3 ∙ O (C2H5)2 2B2H6 +3NaBH4+ 4(C2H5)2O ..(11.6)
Boranes can be synthesized systematically by using the Lewis acid properties of

BX3 (X = F, Cl, Br) to abstract H- from borane anions such as BH4-, B3H8-, and so on.
BX3 + BH4-  HBX3- + (BH3)  ½ B2H6 ……...........…………………..........…(11.7)
BX3 + B3H8-  HBX3- + (B3H7)  ½ B4H10 + ½ B2H4 polymer .........................(11.8)
101 | 105 P a g e s
Electron counting for boranes as well as carboboranes uses Wade‘s rules in
order to catagories the numerous structure of baranes or carboboranes into the closo-,
nido-, or arachno-boranes. The formula is that.
F = 3b + 4c + h + x -2n
Where
F = the number of electrons avaiable for framework bonds,
b = the number of boron atoms,
c = the number of carbon atoms,
h = the number of hydrogen atoms,
x = the amount of negative charge on the ion,
n = the number of vertices, that is b +c.
Rule 1. When the value of F is equal to the quantity (2n+2), the substance should have a
closo structure.
nido structure.
arachno structure.
102 | 106 P a g e s
11.6 SUMMARY
Na2[B4O5(OH)4]• 8 H2O (borax) + heating Na2B4O7
B(OCOR)3 NH4BF4
+
H
H 2O
RCOCl
NH4HF2
-HCl
BCl3
H2O
Cl2
Na[HB(OR)3] B(OH)3 H2
B
ROH
 Cl2
NaH H2SO4 Mg C
-H2O or Fe
B(OR)3 B2O3
H 2O
ROH
O2
-2 HCl
-HCl
Cl2
+2 ROH +ROH
B2H6
Cl2B-OR -HCl Cl3B-O(H)-C2H5 C2H5OH
103 | 105 P a g e s
11.7 STUDY QUESTIONS
1. Boron is intersting because of its electron defisiency. It can build numerous
compound in wide diversity. Why can not we find BH3 but we have BF3 compound,
thus the simplest borane is diborane, B2H6? How would BF3 prepare in laboratory?
2. How does boric acid ionize in water? How strong an acid is it? Why is the activity of
boric acid increased by the addition of glycerol?
3. Draw the structure of diborane and describe its bonding. Give some chemical
equations for synthesizing diborane?
4. By giving one example for each of the structure type, please explain the closo-, nido-,
arachno-, hypo-, and conjunctio-boranes and carboboranes.
5. Apply the Wade‘s rules to classify the compounds: B5H9, C2B7H11, B6H62-, B7H72-,
and C2B8H10.
104 | 106 P a g e s
REFFERENCES
Alsfasser, R., Janiak, C., Klapoetke, T.M., Meyer, H. J. (2007). Moderne Anorganische
Chemie. Hrsg. E. Riedel. 3. Auflage. Belin: Walter de Gruyter.
Butler, I. S., and Harrod, J. F. (1988). Inorganic Chemistry Principles and Applications.
California:The Bejamin/Cummings Publishing Compani,Inc.
Chambers, C., & Holliday, A. (1975). Modern Inorganic Chemistry: An Intermediate
Text. Great Britain: Butterworth.
Cotton, F. A., Wilkinson, G., and Gaus, P.L. (1995). Basic Inorganic Chemistry. Third
Edition. New York: John Willey & Son.
Douglas,B., McDaniel, D. and Alexander, J. (1994). Concept and Models of Inorganic
Chemistry, 3rd edn. USA: Malloy Lithographing.
Gould, E. S. 1955. Inorganic Reactions and Structure. New York: Holt, Rinehart and
Winston, Inc.
Greenwood, N., & Earnshaw, A. (1997). Chemistry of The Elements: Second Edition.
Great Britain: Pergamon Press.
Holleman, A. F., and Wiberg, E. (1985). Lehrbuch der Anorganischen Chemie. 91-100
veberserte und stark erweitere Auflage von Nils Wiberg. Berlin: Walter de
Gruyter.
Housecroft, C. E., Sharpe, A. G. (2008). Inorganic Chemistry. London: Pearson edu
limited.
House, E. J. (2008). Inorganic Chemistry. Canada: Academic Press
Keith, P. and Kotz. J. (1980). An Introduction to Inorganic Chemistry. New York:
Saunders College.
Riedel, R. (2002). Anorganische Chemie. 5. Auflage. Berlin: Walter de Gruyter.
Steudel, R. (1998). Chemie der Nichtmetalle. 2. Auflage. Berlin: Walter de Gruyter.
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i

Hak Cipta dilindungi undang-undang.

a. explain how elements were grouped in the system of periodicity;

1.2 WHAT IS INORGANIC CHEMISTRY?

1.3 TRENDS OF ELEMENTAL PROPERTIES ON PSE

Table and Graph of Electronegativity:

1.4 INORGANIC SUBSTANCES

1.5 INORGANIC REACTIONS

d. Oxidation-reduction (redox) reaction:

k. Cyclization and condensation

1.8 STUDY QUESTIONS

2.2 HYDROGEN AND ITS PROPERTIES

2.3 ISOTOPES OF HYDROGEN

2.4 HYDROGEN GAS PRODUCTION AND ITS USES

2.5 COMPOUNDS OF HYDROGEN AND PROPERTIES

Although many compounds can form intermolecular hydrogen bonds, the

2.7 STUDY QUESTIONS

1. Explain the properties of atomic as well as molecule diatomic of hydrogen.

3.2 ELEMENTS OF NOBLE GASES AND THEIR PROPERTIES

Boiling point (K) 4.22 27.1 87.29 120.8 166.1 211

3.3 COMPOUNDS OF NOBLE GASES

Xenon tetrafluorides is easy to prepare. When preparing XeF4, a mixture

4.2 THE ELEMENTS OF HALOGEN

4.3 THE PRODUCTION WAYS OF HALOGEN GASES

4.4 PROPERTIES OF OXIDES OF HALOGEN

4.5 HALIDE ACIDS AND OXYHALIDE ACIDS

4.8 STUDY QUESTIONS

a. explain properties of oxygen and its isotopes;

5.2 ELEMENTAL OXYGEN

5.4 OXYGEN GAS PREPARATION

It is worthy to mention the toxic character of ozone, specially at high

5.9 STUDY QUESTIONS

a. explain properties of sulphur and its allotropes;

6.2 ELEMENTAL SULFUR

6.3 COMPOUNDS OF SULFUR

6.5 STUDY QUESTIONS

7.2 NITROGEN AND ITS PROPERTIES

7.3 PREPARATION OF NITROGEN

NH3 + H2O(aq) ⇌ NH4+(aq) + OH-(aq) ...............................................................(7.2)

The raw materials used for the process are:

7.5 NITRATE AND NITRITE

NO3- + 4 H+ + 3e ⇆ NO + 2H2O EÅ = 0.96 V ........................................(7.6)

NO3 + 2H+ + e ⇆ NO2 + H2O EÅ = 0.803 V ..................................................(7.7)

HNO2 + H+ + e ⇆ NO + H2O Eo = 1,0 V ............................................(7.8)

HNO-3 + 3H+ + 2e ⇆ HNO2 + H2O Eo = 0.94 V ..........................................(7.9)

7.6 NITROGEN CYCLE IN NATURE

Figure 7.1 Nitrogen Cycle

a. explain of phosphorus and its allotropes;

8.2 PHOSPHORUS AND ITS ALLOTROPES

Figure 8.2 The Chain Structure of Red Phosphorus

8.3 HYDRIDES OF PHOSPHORUS

8.4 HALIDES OF PHOSPHORUS

8.5 OXIDES OF PHOSPHORUS

8.6 OXOACIDS OF PHOSPHORUS

Phosphate rock Phosphoric acid Fertilizer

 Phosphorus sulfides Metal treatment

Figure 8.4 Production and Uses of Phosphoric Acid

8.9 STUDY QUESTIONS

1. Why nitrogen elementally can be in form of N2 but phosphorus in P4?

2. Distinguish the structures and properties of three different colored phosporus

5. Compare the structure and properties of nitric and phosphoric acids.

6. Write a balanced equation of ammonolysis of PCl3.

8. Explain what is superphaphate, double superphosphate, rhenaniaphosphate. Explain

a. explain properties of carbon and its allotropes according to their structures;