3.

Chemistry of the
Important Classes
CHM 211 Inorganic Chemistry
 Hydrogen
Electronic structure [H] 1s1.
Hydrogen is the lightest element, most abundant in the universe, but is rare on earth,
non-toxic, odourless, colourless and highly combustible gas.
Hydrogen is the simplest element, but has a rich chemistry

The structure of hydrogen atom

• is the first element in the periodic table and is unique

What does hydrogen mean? From the Greek words hydro and genes, which together
mean "water forming."

Who discovered hydrogen: Scientists had been producing hydrogen for years before it
was recognized as an element.

Records indicate that Robert Boyle produced hydrogen gas as early as 1671 while
experimenting with iron and acids.

Hydrogen was first recognized as a distinct element by Henry Cavendish in 1766.

 Hydrogen
Electronic structure [H] 1s1.
Hydrogen is the simplest element , but has a rich chemistry

The structure of hydrogen atom

• is the first element in the periodic table and is unique
• is in some ways like the alkali metals (G-1), removing one electron
from the outer shell
• However, H2 is a gas, and is in some ways like that of halogens (G-
17) one electron short to the a noble gas structure.
• is in some ways resembles that of group 14, half filled shell of
electrons (LiH, LiMe, NH3, NMe3; SiH4, SiMe4)

Abundance of hydrogen : 92%

Compounds containing hydrogen : water, living matter

(carbohydrate, proteins, organic compounds, ammonia, acids)
• Hydrogen attains stability in three different ways:

• 1. Forming an electron pair (covalent bond), typically with

nonmetals e.g. H2, H2O, HCl, CH4

• 2. Loosing an electron to form H+ (proton).

H+ is always associated with other atoms or molecules e.g.
in water or aqueous solutions H3O+, H9O4+ or H(H2O)n+. H+
is very small and has a high polarizing power and
therefore distorts the electron cloud towards other atoms.

• 3. Gaining an electron to form H- (hydride).

H- is formed with highly electropositive metals such as LiH
(all of Group 1 and the heavier elements of Group 2)
 Preparation of Hydrogen
1. Water Gas Shift Process
C(s) + H2O Catalyst
Δ CO (g) + H2(g)
Passing steam over red hot coke, forming water gas (mixture of CO and H2)
CO is liquified at low temperature and high pressure, thus separating it from
the H2. Difficult to obtain pure H2

2. Reaction of steam with metal

Fe (s) + 4H2O Fe3O4 (s) + 4H2 (g)

3. Electrolysis of water or solutions of NaOH or KOH

2H2O(g) electrolysis 2H2 (g) + O2 (g)
(bond energy 564 kJmol-1; High purity H2 (99.9%)
Expensive method, due high energy consumption
 Preparation of Hydrogen

4. Catalytic Cracking of Hydrocarbons

CnH2n+2 Δ, catalyst CnH2n (g) + H2 (g)

5. In laboratory:
Zn + dil. H2SO4 ZnSO4 + H2
2Al + 2NaOH + 6H2O 2Na[Al(OH)4] + 3H2
 Properties of Hydrogen
• It’s a colourless, odorless gas, lightest gas known, almost insoluble in
water.

• Exist as a diatomic molecule (H2), with strong covalent bond (bond

energy 435.9 kJmol-1).

H-H bond has to be broken prior to reacting with another element.

• Many reactions with hydrogen are slow (H2 has a high activation
energy).
High temperatures and catalysts are often required.

• Able to react with most elements under appropriate conditions.

• Mixtures of O2 and H2 are often explosive in (2:1, H2:O2)

 Compounds of Hydrogen
• Binary compounds of Hydrogen are called Hydrides.
• Compounds of Hydrogen are found in three possible
oxidation states
+1, -1 and 0.

• Three classes of hydrides are :

1. Covalent or molecular hydrides

2. Ionic or salt-like (saline) hydrides
3. Metallic or interstitial hydrides
 Hydrides
s-block
p-block
1 18
1 2
H 2 13 14 15 16 17 He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
d-block
11 12 13 14 15 16 17 18
Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 1
38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89 104 105 106 107 108 109 110 111
Fr Ra Ac** Rf Ha Sg Ns Hs Mt

f-block
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 92 91 93 94 95 96 97 98 99 100 101 102 103
Th U Pa Np Pu Am Cm Bk Cf Es Fm Md No Lr

Saline hydrides Covalent hydrides

Metallic hydrides intermediate hydrides

 Covalent hydrides
The oxidation state of hydrogen in these compounds is +1 (most important
oxidation state).

Hydrogen is combined with more electronegative elements (p-block elements)

Preparation of Covalent hydrides

Direct action of an element with hydrogen
Δ,
3H2 + N2 2NH3 (Haber Process)
catalyst

H2 + Cl2 2HCl (pure HCl) Oxidation State of an

atom: is the charge
Reaction of a halide with Li[AlH4] that an atom would
carry if the
4BCl3 + 3Li[AlH4] 2B2H6+ 3AlCl3 + 3LiCl3
compound were
Treatment of binary compounds with acid purely ionic.
FeS + H2SO4 H2S + FeSO4
Al4C3 + 12HCl 3CH4 + 4AlCl3

Converting one hydride into another by pyrolysis

B4H10 B2H6 + by products
Ionic or salt-like (Saline) hydrides

The oxidation state of H is -1 in these compounds.

•Hydrogen is combined with the less electronegative metals of Group 1 (all alkali metals)
and the heavier metals of Group 2 (alkaline earth metals) Ca, Sr and Ba. They contain the
hydride ion H- (NaH and CaH2).

The evidence that they are ionic is: high m.p.; conducts electricity; H2 liberated at the
anode (H-).

•Li is more polarizing and more likely to form covalent compounds.

•Group 1 hydrides are more reactive than the corresponding Group 2 hydrides and
reactivity of these hydrides increase down a group.

•Ionic (saline) hydrides all react with water.

CaH2 + 2H2O Ca(OH)2 + H2

LiH + H2O LiOH + H2

Definition (Heat of Formation): the heat released or absorbed (enthalpy change) during
the formation of a pure substance from its elements at constant pressure.
Metallic (interstitial) hydrides

Hydrogen reacts with many d-block elements, and the lanthanide and actinide (f-block)
elements forming metallic hydrides.

Elements in the middle of the d-block do not form hydrides; this part of the periodic table
is called the “hydrogen gap”

Usually prepared by heating the metal with hydrogen under high pressure.

Oxidation state of hydrogen in these compounds is 0.

These are hard brittle substances, conduct electricity, have magnetic properties and have a
metallic luster.

They are nonstoichiometric e.g. TiH1.8, LaH2.87, PdH0.7.

Uses of Metallic hydrides

Finely divided metals may be used as catalysts.

Used in metallurgy in powder fabrication, and zirconium hydride has been used as a
moderator in nuclear reactors.
 Intermediate hydrides

A few hydrides can not be classified, these are the

intermediate hydrides

CuH, ZnH, CdH2, and HgH2

 Hydrogen bonding

Hydrogen bonds are formed only with the

most electronegative atoms (F, O, N and
Cl).

H-bonding has a major effect on the

physical properties such as melting
points, boiling points, enthalpies of
vaporization and sublimation.
 Hydrogen bonding
H2O

In the series HF, HCl, HBr and HI there is a

progressive increase in the molar mass and HF

thus an increase in the boiling point is

expected. This trend is observed for HCl, HBr

Boiling point
HBr

and HI. The unexpectedly high boiling point SnH4

for HF is attributed to H-bonding between HF

HCl
molecules. GeH4

SiH4
Group 14 hydrides CH4, SiH4, GeH4 and SnH4
change smoothly since they do not contain CH4
hydrogen bonds. Molar Mass
 Group 16(VI) Elements (Chalcogens)
Element Electronic m.p. (ºC) 1st ionization potential Common
configuration (kJmol-1) oxidation states

O (8) [He]2s22p4 -219 1314 -II, (-I)

S (16) [Ne} 3s23p4 119 999 -II, (II), IV, VI

Se (34) [Ar}3d104s24p4 221 941 (-II), II, IV, VI

Te (52) [Kr}4d105s25p4 450 869 II, IV, VI

Po(84) [Xe}4f145d106s26p4 254 813 II, IV

Bold:-most important oxidation states

(brackets):- unstable oxidation states
Normal type:-Other well characterized but less common oxidation states
 Oxygen
O2 is the 3rd most abundant element in the universe, highly reactive (like to pair and form
compounds with most other elements). Pale shade of blue in pure liquid or solid form.
Most abundant element in the earths crust ( ~ 45% consists of o-atoms).
Air consists of ~ 20% oxygen by volume and 66% of human body is oxygen

Preparation of oxygen

Distillation of liquid air

Air from the atmosphere is compressed until it liquifies.
Fractional distillation is then used to separate gaseous nitrogen (b.p.-
196ºC) and liquid oxygen (b.p-183ºC)

Electrolysis of H2O
2H2O(g) electrolysis 2H2 (g) + O2 (g) (bond energy 564 kJmol-1)
Thermal decomposition of KClO3 (potassium chlorate)

2KClO3 (s) 2KCl (s) + 3O2 (g)

Properties: Dioxygen O2
O O O O

 colorless, odourless diatomic gas (O=O)

 Paramagnetic (unpaired electrons), i.e. weakly attracted by a magnetic

field.

 Liquefies at -183ºC and freezes at -219ºC

 Forms compounds with all other elements except noble gases

 Exhibits Allotropy (existence of more than one form in the same

physical state) O2 and O3
Properties Ozone O3 O

O O
Triatomic allotrope of oxygen
Angular molecule bond angles of 116º
Unstable blue gas, having a sharp smell
Diamagnetic (no unpaired electrons) with b.p,-112ºC
Thermodynamically unstable and decomposes to O2

Uses:
Disinfectant for purifying drinking water
Oxidizing agent:

S + H2O + O3 H2SO4
Compounds of Oxygen:

Except for oxygen in the fluorides such as O2F2 and OF2, the oxidation state of oxygen in
atoms is negative (oxidation state of F-atom in all of its compounds is -1).

The common oxidation states for the O-atom are: - ½, -1, -2

Oxidation State (-½)

Heavier elements of Group1 (K, Rb & Cs) react with oxygen to form compounds of the type
MO2, known as the Superoxides. They consist of M+ and O2- ions.

Superoxides react with water to produce O2 and H2O2

2MO2(s) + 2H2O(l) 2M+ + O2 + H2O2 + 2OH-

2KO2(s) + 2H2O(l) 2KOH + O2 + H2O2

Oxidation State (-1)

These are known as the as Peroxides.

Solid peroxides are formed by Group 1 & 2 elements e.g.

Na2O2, BaO2.

In acid solutions; these peroxides decompose to produce

hydrogen peroxide.
BaO2(s) + H2SO4 BaSO4 + H2O2
 Hydrogen peroxide
Physical properties
Pure H2O2 pale blue, syrupy liquid; stable in the pure form, but decomposes in the
presence of impurities
2H2O2(l) O2(g) + 2H2O(l)
More hydrogen bonded than water; thus has a higher b.p. (152ºC)
More denser (1.4g cm-3) than water O
H 98o48'
Chemical properties
Acts as a strong oxidizing agent
98o48'
O
H2O2 + 2I- + H+ I2 + 2H2O
H
In dil aq solutions it is more acidic than water, it’s a weak acid
Non-planar molecule
The two OH groups
H2O2 HO2- + H+ Ka= 1.5 × 10-12 don’t lie in the same
plane (this minimizes
Uses:
the repulsion between
• Used as a bleaching agent
lone pairs on the O-
• Used to prepare organic peroxides, which are used in
atoms)
polymerization reactions
• Liquid H2O2 together with Hydrazine is used for rocket fuel
• As and antiseptic to treat wounds.
Oxidation State -2

This is the common oxidation state of oxygen in compounds.

Oxides can also be classified according to their acid-base properties.

Metallic Oxides (basic oxides)

Most metal oxides are metallic and contain the O2- ion.
These are oxides of the most electropositive metals namely, Groups 1& 2 and the
lanthanides.

When they react with water, the O2- ion is converted to OH-

Na2O + H2O NaOH

When a metal exists in more than one oxidation state, and thus form more than
one oxide e.g CrO, Cr2O3, CrO3, PbO, PbO2, the lowest oxidation state is the most
ionic and the most basic.
Molecular oxides (acidic oxides)

These usually have covalent bonds between oxygen and another element (usually p-block
elements).

Many occur as discrete molecules (CO2, SO2, NO).

They are acidic and react with water to produce acidic solutions.
SO2 + H2O H2SO3 H+ + HSO3-

In cases where the element exists in more than one oxidation state
e.g. N2O3 and N2O5, SO2 and SO3 the higher oxidation state is more acidic.

N2O3 + H2O HNO2 (N =+3)

N2O5 + H2O HNO3 (N =+5)

The higher the oxidation state (electron deficient) of the central atom the more it will
attract electrons thus weakening any O-H bonds and facilitate the release of H+.
Amphoteric Oxides

Some metal oxides can’t be classified as acidic or basic,

since they are able to neutralize both acids and bases.
These are the amphoteric oxides

e.g. BeO, Al2O3, Ga2O3, SnO, PbO, ZnO, TeO2.

Al2O3 + 6HCl 2Al2+ + 6Cl- + 3H2O

Al2O3 + 2OH- 2[Al(OH)4]- + 3H2O

 Carbon
Group 14 (IVA) Elements

Element Electronic m.p. 1st ionization Common

configuration (ºC) potential oxidation
(kJmol-1) states
C (6) [He]2s22p2 3500 1086 IV

Si (12) [Ne] 3s23p2 1420 786 (II), IV, V

Ge (32) [Ar]3d104s24p2 945 760 II, IV

Sn (50) [Kr]4d105s25p2 232 707 II, IV

Ph (82) [Xe]4f145d106s26p2 327 715 II, IV

Bold:-most important oxidation states

(brackets):- unstable oxidation states
Normal type:-Other well characterized but less common oxidation states
 Carbon
Allotropes: Diamond, Graphite; Fullerenes
Diamond:
Each C-atom (sp3) is tetrahedrally surrounded by
four other C-atoms. The tetrahedra are linked
together into a 3-dimensional giant molecule.
Density 3.52 gcm-3. It’s the hardest naturally
occurring substance
Poor conductor of electricity
Thermodynamically unstable (favourable for
diamond to change to graphite; this does not
occur due to the high activation energy of the
process)
Uses: as an abrasive for sharpening very hard
tools, in dies for manufacturing tungsten
filaments for electric light bulbs.
Graphite:
It’s composed of flat sheets of C-atoms (sp2).
Each sheet is a hexagonal net of C-atoms. The
sheets are held together by weak van der
Waals forces.
Density 2.22 gcm-3; It’s soft and slippery (sheets
are easily broken and are moved easily relative
to one another)
Good conductor of electricity (presence of
double bonds means that mobile electrons are
present)
Thermodynamically more stable than diamond
Uses: as a lubricant, in “lead” pencils, as the
anode material in electrolysis processes
This fig show the structures of all the diamond and graphite and compare it with
silica. Both diamond and silica are 3 D structure while graphite is 2D (sheets)
Fullerenes

The soot produced between graphite electrodes (in argon atmosphere) contains
significant amounts of a C60 cluster compound called fullerenes.

Unlike diamond and graphite fullerenes are discrete molecules, C60 molecule
looks like a soccer ball (“bucky ball”).

It consists of a fused system of five and six membered rings.

They are covalent, soluble in organic solvents

Used to prepare K3C60; this compound behaves as a superconductor below 18K

(it carries an electric current with zero resistance)

Buckminsterfullerene
 Carbon Monoxide CO

Colourless, oudorless, poisonous gas (it forms a stable complex with haemoglobin
preventing haemoglobin from carrying oxygen through the body)

Prepared in the laboratory by dehydration of formic acid with H2SO4

HCOOH + H2SO4 CO + H2O
Can be detected; because in burns with a blue flame

Reduces an aqueous PdCl2 solution to metallic Pd PdCl2 + H2O + CO Pd + CO2 + 2HCl

Reduces a solution of I2O5 to I2 I2O5 + 5CO 5CO2 + I2

It’s sparingly soluble in water and is a neutral oxide

Uses:
Good reducing agent (reduces metal oxides to metal)
Fe2O3 + 3CO 2Fe+ 3CO2
CuO + CO Cu + CO2

Used as industrial fuels eg. Water gas

CO is an important ligand:-it donates an electron pair to many transition metals
 Carbon dioxide CO2
Colourless, odourless gas
Obtained as a by-product in the manufacture of H2 (Water Gas Shift H2O + CO CO2 + H2
Process)

Fermentation processes in breweries C6H12H6 yeast 2C2H5OH + CO2

Gases evolved from calcining limestone and from flue gases CaCO3 strong heat CaO + CO2

By action of dilute acids on carbonates CaCO3 + 2HCl CaCl2 + CO2 + H2O

By burning C in excess of air C + O2 CO2

Can be recovered by absorbing it in aqueous Na2CO3 Na2CO3 + CO2 +H2O 2NaHCO3

Detection of CO2 :
by its action on lime water Ca(OH)2, as a Ca(OH)2 + CO2 CaCO3 + H2O
white insoluble precipitate of CaCO3. if white precipitate

more CO2 is passed through the mixture, CaCO3 + CO2 H2O + Ca(HCO3)2
soluble

the cloudiness disappears as the soluble

bicarbonate is formed.
CO2 + H2O H2CO3
CO2 is acidic oxide, and reacts with bases
forming salts; dissolves in water, but only
slightly hydrated to carbonic acid H2CO3.

Uses:
• solid CO2 (dry-ice) to freeze foods (-78.5 oC)
• to carbonate drinks;
• in fire extinguishes;
• as an aerosol propellant;
CO2 SiO2
Properties Properties
•Colourless gas at room temp. •High melting point solid
•C-O multiple bonds •Has SiO single bonds
•Discrete linear molecule •Infinite 3-dimensional structure with
•Liquidfied under pressure between -57ºC to +35ºC tetrahedral Si
•Solid CO2 is produced by expanding the gas from •Requires high temperatures to soften
cylinders •Two basic crystal forms quartz and
Uses cristobalite
•Refrigerant (coolant) •Uses
•To carbonate cool drinks •Glass manufacturing
•In the manufacture of Urea •Optical components
•In fire extinguishes •Filtration material
•Neutralization of alkalis •Impure SiO2-semi precious stones
Reactions •Reactions
Acidic Oxide: SiO2 almost unreactive, reacts only with HF
CO2 + H2O H2CO3 and very slowly with alkalis
Ca(OH)2 + CO2 CaCO3 + H2O SiO2 + 4HF SiF4 + 2H2O
white precipitate

SiO2 is an acidic oxide: it dissolves slowly in aqueous alkali, and more rapidly in fused alkalis MOH or
fused carbonates M2CO3, forming silicates. This reaction accounts for ground glass stoppers sticking
to reagent bottles containing NaOH.

SiO2 + NaOH (Na2SiO3)n and Na4SiO4

 Carbon disulphide CS2
Most important sulphide of carbon; colourless volatile liquid (b.p. 46ºC);
very flammable (flash point 30ºC) and ignites spontaneously at 100ºC
Very poisonous, it affects the brain and nervous system

Produced by reacting natural gas with sulphur, catalyzed by Al2O3 or silica gel

Uses: CH4 + 4S 600ºC CS2 + 2H2S

Manufacture of CCl4
CS2 + 3Cl2 CCl4 + S2Cl2

Used a solvent to dissolve sulphur in the cold vulcanization of rubber

CS2 is a linear molecule similar to CO2

CS2 forms complexes more readily that CO2. [Pt(CS2)(PPh3)] is structurally similar to
[Co(CO2)(PPh3)3]
Differences Between Carbon and the Remaining Elements
in the Group
In general the 1st element differs remarkably from the rest of the group; as a result of
its smaller size and higher electronegativity. These result in the first element having a
higher ionization energy, being more covalent and less metallic character than the rest
of the group.

The 1st element is limited to only four covalent bonds (it only has s- and p-orbitals
available for bonding). Thus the coordination number is limited to four while the other
elements show higher coordination numbers.

Carbon has the ability to form multiple pπ - pπ bonds e.g. C=C, C≡C, C=O, C=S, C≡N.
The later elements don’t form pπ - pπ bonds, because their orbitals are too large and
too diffuse to obtain effective overlap. The later elements can form multiple bonds by
utilizing their empty d-orbitals.

Si for example forms multiple bonds between itself and N or O using dπ - pπ bonding.
This accounts for the fact that trisilylamine, N(SiH3)3 is planar (pπ - dπ bonding) while
trimethylamine, N(CH3)3 is trigonal pyrimidal (no π bonding).
In (CH3)3N the arrangement of electrons is sp3-hybridization occurs giving a
tetrahedral arrangement in which the three unpaired electrons form bonds
with CH3 groups, while the one lone pair occupies the fourth sp3-hybrid
orbital.
H3Si SiH3

1s 2s 2p
N
N
CH3 CH3
SiH3
CH3

In (SiH3)3N three sp2 orbitals are used for σ-bonding, giving a plane triangular
structure.
The lone pair occupy a p-orbital at right angles to the plane triangle. This
overlaps with empty d-orbitals on each of the three Si-atoms and results in
pπ - dπ bonding, because it is a full p-orbital to an empty d-orbital. This
shortens the N-Si bond lengths.

Similar pπ - dπ bonding is impossible in (CH3)3N because carbon does not

have d-orbitals and hence the molecule is pyrimidal
 Differences Between Carbon and the Remaining
Elements in the Group
Unlike the other elements Carbon can’t expand it coordination number;
this accounts for the fact that C-halides are resistant to hydrolysis while
those of the other elements are not e.g. compare CCl4 vs SiCl4.

CCl4 + H2O No reaction

SiCl4 + H2O Si(OH)4 + 4HCl

The above is observed despite the fact that Si-Cl bond is stronger than
C-Cl bond. This is accounted for by the ability of Si to expand its
coordination number (has d-orbitals) and form the Si-intermediate
below.
Cl Cl
Cl
Si + H2O H2O Si
Cl Cl
Cl
Cl Cl
 Differences Between Carbon and the
Remaining Elements in the Group
Carbon has the ability to form chains (catenation); because C-C bonds are very stable
(strong C-C bonds). The Si-Si, Ge-Ge and Sn-Sn bonds are much weaker and decrease in
strength down the group.

C-C (348 kJmol-1); forms chains of great lengths

Si-Si (297 kJmol-1); forms few chains Si8 in hydrides
Ge-Ge (260 kJmol-1); forms very few chains e.g Ge6
Sn-Sn (240 kJmol-1); forms the dimer Sn2H6 only

Complexes
The formation of complexes is favoured by a high charge, small size and availability of
empty orbitals.
In four-covalent compounds of carbon, the outer shell has 8 electrons which resembles
that of a noble gas, as a result the compounds are stable and do not form complexes.

Four-covalent compounds of the subsequent elements can form complexes due to the
availability of d-orbitals, thus they increase their coordination number from 4 to 6.
SiF4 + 2F- [SiF6]2-
SnCl4 + 2Cl- [SnCl6]2-

Thus the corresponding Carbon-analogue does not exist.

 Group 15 (VA) Elements
Element Electronic m.p. (ºC) 1st Common oxidation
configuration ionization states
potential
(kJmol-1)
N (7) [He]2s22p3 210 1043 -III, -II, -I, 0, III, IV,
V
P (15) [Ne} 3s23p3 44.1 1012 III, V

As (33) [Ar}3d104s24p3 sublime 940 III, V

Sb (51) [Kr}4d105s25p3 631 834 III, V

Bi (83) [Xe}4f145d106s26p3 271 703 III, V

Bold:-most important oxidation states

(brackets):- unstable oxidation states
Normal type:-Other well characterized but less common oxidation states
 Nitrogen
Discovered by Daniel Rutherford at 1772.
Origin of name: from the Greek words "nitron genes" meaning "nitre" and
"forming" and the Latin word "nitrum" (nitre is a common name for potassium
nitrate, KNO3).
N2 comprises 78% of earth’s atmosphere,
Nitrogen is an essential constituent of amino acids and proteins (17% N)
N2 is commercially produced by condensing air into the liquid state, then
fractionally distilling the liquid air.
The N2 has a lower boiling point than O2 and distills off first. (N2, O2, Ne, Ar, Kr
and Xe are all obtained in this way).

Uses of N2:
N2 used as an inert atmosphere
Liquid N2 is used as a refrigerant
Used in the manufacture of NH3 in the Haber Process
Manufacturing of fertilizers
 Phosphorus
Major source is from phosphorus rock, mined as fluoroapatite [3Ca3(PO4)2CaF2] some
found as hydroxyapatite [3Ca3(PO4)2Ca(OH)2] and some as chloroapatite
[3Ca3(PO4)2CaCl2]

Allotropes of Phosphorus:

• White phosphorus: structurally contains P4 tetrahedral units

• Red phosphorus: prepared by heating white phosphorus in an inert atmosphere at

270ºC. Its structure is not with certainty, it is macromolecular and denser than white
phosphorus.

• Black phosphorus: obtained by subjecting white phosphorus to high pressures and

temperatures 200ºC under inert conditions. It’s macromolecular, with each
phosphorus atom surrounded by three more atoms. Its denser than red phosphorus.
Uses of Phosphorus:

Manufacture of phosphoric acid

Manufacture of fertilizers (in the form of phosphates)
Production of match heads (P4S3)
Production of organo-phosphates used to manufacture insecticides

Compounds of Nitrogen
Nitrogen can exist in a variety of oxidation states (V → -III). The ( –III)
is one of the more stable states.

Hydrides of Nitrogen

NH3 Ammonia -III

N2H4 Hydrazine -II
NH2OH hydroxylamine -I
Oxidation state (-III): Ammonia, NH3
NH3 is the most common example of the N-atom in the (–III) oxidation state.
NH3 is prepared industrially by the Haber process. N2 and H2 are reacted together at high
pressures (250 atmospheres) in the presence of a finely divided iron catalyst at 500ºC.
Under these conditions only 15% of the gases are converted to NH3. The gases are
cooled while still under pressure, and the liquid NH3 is removed; the unreacted N2 and
H2 are recycled for further conversion into NH3.

N2 + 3H2 500ºC; high pressure 2NH3

NH3 (b.p. -33ºC) very soluble in water as a result of intermolecular hydrogen-bond

formation.

NH3 molecule is pyrimidal in shape, the lone pair of electrons can bond to a proton to
form the tetrahedral ammonium ion NH4+.

Many transition metals form complexes with NH3 e.g. [Ni(NH3)6]2+ and [Co(NH3)6]3+ which
are octahedral in shape.
Oxidation State (-II): Hydrazine N2H4

Colourless, covalent liquid, unstable with respect to disproportionation

N2H4 (l) N2 (g) + 2NH3 (g) + H2 (g)

Burns readily in air giving off a large amount of heat.

N2H4 (l) + O2 (g) N2 (g) + 2H2O (g) Δ H= -621 kJmol-1

It act as a base in aqueous solutions and can add one or two electrons to the unshared
electron pairs.
H +
H H
+
N N H + H N N H
H H H H

Each N-atom (sp3 hybridized) is tetrahedrally surrounded by one N, two H and a lone pair.
The two halves of the molecule are rotated 95o about the N-N bond.
 N2H4 Uses:

• used as rocket fuel

• As “blowing agents” for manufacturing blown plastic

products

• As agricultural chemicals

• Treatment of boiler feed water to prevent oxidation of

boilers and pipes
Oxidation State (-I): Hydroxylamine NH2OH

NH2OH forms colourless crystals (m.p.33ºC),

Thermally unstable decomposing easily to NH3, N2, HNO2 and N2O.
NH2OH is a weaker base than NH3 or N2H4. the salts contain the hydroxylammonium ion,
[NH3OH]+.
In aqueous solutions H+ becomes attached to the N-atom.

NH2OH + H+ [NH3OH]+
NH2OH has donor properties (like NH3 and N2H4): the N-atom can form coordinate bonds
and complex with metals.

Uses:
In organic reactions for introducing N-atom into molecules
Used as starting material in the synthesis of Nylon-6
 Oxides of Nitrogen (positive oxidation states)
Nitrous Oxide (dinitrogen oxide) N2O
Oxidation state +1 1.19A
Linear triatomic molecule N N O
Colourless gas; not very reactive
Used as an anaesthetic

Nitric Oxide (nitrogen monoxide) NO 1.15A

Oxidation State +2 N O
Colourless, paramagnetic gas
O O
Dinitrogen trioxide N2O3
Oxidation State +3 N N
Blue solid (m.p.-101ºC); O
dissociates into NO and NO2 in the gas phase

Nitrogen dioxide NO2 Dinitrogen tetroxide) N2O4 O O

N 1.18A
Oxidation State +4 1.19 A Oxidation State +4 N N
o
Brown, reactive, paramagnetic gas O
134
O Colourless liquid(m.p.-11ºC) O O
Dimerizes to N2O4 In equilibrium with NO2

Dinitrogen pentoxide N2O5

O O O
Oxidation State +5
N N
Colourless ionic solid [NO2][NO3](m.p.32ºC)
Unstable in the gas phase
O O