8.

d AND f BLOCK ELEMENTS Structure of chromate and dichromate ion

Two types of magnetic behaviour are observed-
 diamagnetism
 paramagnetism
Diamagnetic substances- Repelled by the applied field
Paramagnetism-
 Substances are attracted by the magnetic field
 due to the presence of unpaired electrons.
 The spin only magnetic moment, μs is determined The oxidation state of Cr in chromate and
by the number of unpaired electrons and is given dichromate is + 6
by the spin only formula Uses of potassium dichromate
μs = √n(n+2) 1.Strong oxidising agents
where n is the no. of unpaired electrons. 2.Used as a primary standard in volumetric analysis
 The magnetic moment increases with increase in Potassium Permanganate , KMnO4
the number of unpaired electrons. Preparation
 The unit is Bohr Magneton (B.M). Fusion of MnO2 with an alkali metal hydroxide and
Formation of coloured ions or compounds an oxidising agent
 because of d-d transition of electrons due to 2MnO2 + 4KOH + O2 → 2K2MnO4
incompletely filled d orbitals. K2MnO4 disproportionates in a neutral or acidic
 When an electron from a lower energy d orbital solution to give permanganate.
is exited to higher d level, it absorbs energy , So MnO4 2– + 4H+ → 2MnO4 – + MnO2
the colour observed is the complementary colour Commercial preparation
of the light absorbed. Alkaline oxidative fusion of MnO2 followed by the
Formation of Complexes electrolytic oxidation of manganite (MnO42- )(Vl).
This is due to:  Potassium permanganate forms dark purple
 comparatively smaller sizes of the metal ions (almost black) crystals which are
 high ionic charges isostructural with those of KClO4
 availability of d orbitals for bond formation.
Catalytic activity
 Ability to adopt multiple oxidation states
 Form complexes.
Examples
 Vanadium(V) oxide (in Contact Process),
 Finely divided iron (in Haber’s Process),
 Nickel (in Catalytic Hydrogenation)
Two important compounds of transition metals
Potassium chromate (K2Cr2O7), Potassium
Permanganate (KMnO4) Uses of KMnO4
Potassium dichromate , K2Cr2O7 1.Oxidising agent
Preparation 2.Primary standard in volumetric analysis.
1. Conversion of chromite ore to sodium chromate 3.It is used for the bleaching and decolourisation .
FeCr2O4 + Na2CO3 + O2 8 Na2CrO4 lanthanide contraction
2. Acidification of sodium chromate to sodium The overall decrease in the atomic and ionic radius
dichromate of lanthanides ( La to Lu)
Na2CrO4 + H+ → Na2Cr2O7 cause of lanthanide contraction
3. Conversion of sodium dichromate to potassium Poor shielding effect of 4f orbitals.
dichromate
Na2Cr2O7 + KCl K2Cr2O7

1
 Ambidentate ligands:
Consequences of lanthanide contraction Ligate through two different atoms.
1) Due to Lanthanide Contraction the 2nd and 3rd row e.g., -NO2 , -ONO and -SCN, -NCS
transition series elements have similar radii.( Zr and Hf NOMENCLATURE
have similar radius) (i) The cation is named first.
2) Lanthanides have similar physical properties and they (ii) The ligands are named in alphabetical order
occur together in nature, hence separation is difficult. before the name of the central atom/ion.
3) The basic character of their hydroxides decreases. (iii) Prefixes mono, di, tri, etc., or bis (2), tris (3),
(La(OH)3 is more basic than Lu(OH)3) tetrakis (4) are used to indicate the number of
Some Applications of d- and f- Block elements ligands.
 Iron and steels - Construction materials. (iv) Oxidation state of the metal is indicated by
 TiO is used in the pigment industry. Roman numeral in simple bracket.
 Zn, Ni, Cd and MnO2 are used in battery cells. (v) If the complex ion is a cation, the central atom is
 As catalyst in different reactions. named same as the element.
V2O5 – Contact process (manufacture of H2SO4) (vi)If the complex ion is an anion, the name of the
Ziegler catalysts –(TiCl4 with Al(CH3)3) -manufacture metal ends with the suffix –ate.
of polythene.
Iron catalysts- Haber Process ( production of ammonia) ligand Name
Ni, Pd and Pt -catalyst in hydrogenation reactions. H2O Aqua
PdCl2- Wacker process (oxidation of ethyne to ethanol) NH3 Ammine
AgBr - photographic industry -OH -
Hdroxido
9.CO-ORDINATION COMPOUNDS NO2 Nitrito-N, Nitrito-O
In co-ordination compounds, according to Werner’s SO4 2- Sulphato
theory of complexes metals show two types of 2- Carbonato
CO3
valencies
a) Primary valency b) Secondary valency Cl- Chlorido
ii) Primary valency CN- Cyanido
 Ionisable en Ethane-1,2 -diamine
 Satisfied by negative ions CO Carbonyl
iii) Secondary valency 2- Oxalato
C2O4
 non-ionisable, SCN - Thiocyanato
 satisfied by neutral molecules or negative ions. 1. [Cr(NH3)3(H2O)3]Cl3
Ligands : The neutral molecules or ions that are triamminetriaquachromium(III) chloride
attached directly to the central atom or 2.[Co(H2NCH2CH2NH2)3]2(SO4)3
ion in a complex. tris(ethane-1,2–diamine)cobalt(III) sulphate
Types of ligands 3. [Ag(NH3)2][Ag(CN)2]
(i)Monodentate Ligands : Ligand bound through a diamminesilver(I) dicyanidoargentate(I)
single donor atom. 4.K2[Zn(OH)4]
Eg : NH3, H2O, CN- Potassium tetrahydroxidozincate(II)
(ii) Didentate: Ligand bound through two donor 5.[CoCl2(en)2]+
atoms. Dichloridobis(ethane-1,2-diamine)cobalt(III)
6.[Pt(NH3)2Cl(NO2)]
Diamminechloridonitrito-N-platinum(II)
7.[Co(NH3)5(CO3)]Cl
Ethane-1,2 diamine oxalate Pentaamminecarbonatocobalt(III) chloride
(iii) Polydentate:Ligand bound through a several donor 8.Hg[Co(SCN)4]
atoms. Mercury (I) tetrathiocyanatocobaltate(III)
e.g., ethylene diamine tetraacetate ion [EDTA]4-.

2
 trans isomer: Isomer in which the same ligands are
Isomerism in co-ordination compounds on the opposite side
a) Structural Isomerism
b) Stereo Isomerism
A Structural Isomerism
(i) Linkage isomerism: arises in a compound
containing ambidentate ligand.
e.g., [Co(NH3)5(NO2)]Cl2 [Co(NH3)2Cl2] [Co(NH3)4Cl2]+
[Co(NH3)5(ONO)]Cl2
(ii) Coordination isomerism:arises from the
interchange of ligands between
cationic and anionic entities of different metal ions
present in a complex. [Co (en)2Cl2]+
e.g., [Co(NH3)6][Cr(CN)6] Fac-mer isomerism: It is a type of geometrical
[Cr(NH3)6][Co(CN)6] isomerism occurs in octahedral co-ordination entities
(iii) Ionisation isomerism: arises due to the inter of the type
change of ions between the inside and outside of [Ma3b3].
coordination sphere. If similar ligands occupy three adjacent positions of
e.g., [Co(NH3)5SO4]Br and an octahedral face, it is called facial (fac) isomer.
[Co(NH3)5Br]SO4 Eg. [Co(NH3)3(NO2)3].
(iv) Solvate isomerism
Solvate isomers differ in the no. of solvent molecule
which are directly bonded to the metal ion as ligand
e.g., [Cr(H2O)6]Cl3, [Cr(H2O)4Cl2]Cl.2H2O
(In this case water is involved as a solvent.
-hydrate isomerism)
Stereoisomerism
These are isomers which differ only in the spatial When the positions are around the meridian of the
arrangement of ligands around the central atom. octahedron, it is called meridional (mer) isomer.
These are of two types:
(i) Geometrical isomerism (ii) Optical isomerism
i) Geometrical Isomerism: It arises due to the different
arrangements of the ligands around the central atom.
cis isomer :Geometrical isomer in which the same
ligands are on the same side of the central metal atom .
Optical Isomerism
Optical isomers or enantiomers are non
superimposable mirror images. These molecules or
ions are called chiral.
Eg: [CoCl2(en)2]+, only the cis-isomer shows optical
activity.

[Co(NH3)2Cl2] [Co(NH3)4Cl2]+

[Co (en)2Cl2]+

3
 Importance and Applications of Coordination
3+
[Co(en)3] Compounds
 Coordination compounds find use in many
qualitative and quantitative chemical analysis
EDTA ( estimation of hardness of water)
DMG (dimethylglyoxime), cupron.
 Extraction processes of silver and gold, make
use of complex formation
 Purification of metals –vapour phase refining
[PtCl2(en)2]2+ of impure nickel
 Biological importance
Chlorophyll Photosynthesis Mg
Haemoglobin Oxygen carrier Fe
in blood
Vitamin B12 or Pernicious Co
cyanocobalamine, anaemia factor
Carboxypeptidase A, Enzymes
Magnetic properties
Carbonic anhydrase
 The magnetic moment of coordination
compounds can be measured by the magnetic
 Used as catalysts for many industrial
susceptibility experiments.
processes.
 The results can be used to obtain information
Wilkinson catalyst [(Ph3P)3RhCl]- hydrogenation of
about the structures adopted by metal complexes
alkenes
 Electroplating
d orbital Metal ions Unpaired
 In black and white photography, Silver
electronic electrons
complexes are used
configuration
 Medicinal chemistry
d orbitals are available for octahedral hybridization
 Excess of copper and iron are removed by the
d1 Ti3+ 1 chelating ligands D–penicillamine and
2 3+
d V 2 desferrioxime B via the formation of
d3 Cr3+ 3 coordination compounds.
d orbitals results only after pairing of electrons for  EDTA is used in the treatment of lead
octahedral hybridisation poisoning.
d4 Cr2+, Mn3+ 2  cis–platin and related compounds effectively
5 2+ 3+
d Mn ,Fe 1 inhibit the growth of tumours..
d6 Fe2+ ,Co3+ 0

Magnetic data of d6 ions

Compound Magnetic No: of

nature unpaired
electrons
[Mn(CN)6]3–, Paramagnetic 2 Inner orbital
[Fe(CN)6]3– Paramagnetic 1 d2sp3
[Co(C2O4)3]3– Diamagnetic 0
[MnCl6]3– Paramagnetic 4 outer orbital
[FeF6]3– Paramagnetic 5 sp3 d2
[CoF6-]3– Paramagnetic 4

4
 14. BIOMOLECULES Methods used for the preparation of glucose
Classification of carbohydrates based on their 1. From sucrose
behaviour on hydrolysis
1) Monosaccharides- cannot be hydrolysed into
simpler units
glucose, fructose, ribose, galactose Commercial method
2) Oligosaccharides- two to ten monosaccharide 2.From starch
units on hydrolysis. Hydrolysis of starch by boiling with dilute H2SO4
e.g. Sucrose, maltose, lactose Anomers
Sucrose - glucose and fructose Molecules differing in the configuration of C1 atom.
maltose - two molecules of glucose Denaturation of protein
lactose - glucose and galactose.  Loss of biological activity of protein due to
3) Polysaccharides -large number of change in temperature or pH
monosaccharide units on hydrolysis.  During denaturation secondary and tertiary
E.g. starch, cellulose, glycogen etc. structures are destroyed but primary structure
Classification of carbohydrates classified based on remains intact.
their reducing character e.g. coagulation of egg white on boiling, curding of
Reducing sugar –sugars that reduces fehling’s soln milk etc.
Non-reducing sugar- sugars that do not reduce Nucleic acids
fehling’s soln Polymers of nucleotides which consist of a base,
Glycosidic linkage- linkage (C-O-C) between a pentose sugar and phosphate
monosaccharide units
Inversion of cane sugar (Sugar + phosphate + nitrogen base)n
Sucrose is dextro rotatory but after hydrolysis
the mixture is laevorotatory. This is called inversion
of cane sugar and the product formed is called invert
sugar.
Examples of polysaccharides Examples of nucleic acid
Starch,cellulose and glycogen deoxyribonucleic acid (DNA) and ribonucleic acid
Starch (RNA).
Polymer of α-glucose and consists of two Complete hydrolysis of DNA (or RNA) yields a
components -Amylose and Amylopectin pentose sugar, phosphoric acid and called bases.
Amylose DNA
 Water soluble Sugar- deoxyribose
 Long unbranched chain Bases- A, T,G,C
 Glucose units held together by C1– C4 Adenine (A), Guanine (G), Cytosine (C) and
glycosidic linkage. Thymine (T).
Amylopectin RNA
 Water insoluble Sugar-ribose
 Branched chain polymer with C1–C4 Bases -A,U,G,C
glycosidic linkage RNA contains Adenine (A), Guanine (G), Cytosine
 branching occurs by C1–C6 glycosidic (C) and Uracil (U).
linkage. Biological functions of nucleic acids
Glycogen: 1. Transmission of hereditary characters.
 The carbohydrates are stored in animal body 2. Protein synthesis
as glycogen.
 It is also known as animal starch because its
structure is similar to amylopectin and is
rather more highly branched.

5
 15.POLYMERS 2. Condensation polymers (step growth
Polymers classified based on Source polymers): Polymers formed by condensation
1. Natural polymers: found in nature. Eg.proteins, polymerisation reaction.Eg., terylene (dacron),
cellulose, starch, natural rubber. nylon 6, 6 and nylon 6
2. Semi-synthetic polymers: Cellulose derivatives Polymers classified based on the Molecular
Eg. cellulose acetate (rayon) and cellulose nitrate Forces
3. Synthetic polymers: man-made polymers. 1. Elastomers: elastic properties .E.g.natural rubber,
E.g. polythene, poly styrene, PVC etc. buna-S, buna-N, neoprene, etc.
Classification Based on Structure of Polymers 2. Fibres: have high tensile strength and high
1.Linear polymers-Consist of long and straight modulus.E.g. Nylon-6,6, Nylon-6, terylene etc.
chains. Eg:high density polythene, polyvinyl chloride 3.Thermoplastic polymers:Softens on heating and
hardens on cooling.
Eg. polythene, polystyrene, polyvinyls, etc.
4. Thermosetting polymers: Stiffens on heating
2.Branched chain polymers-Contain linear chains Eg.bakelite
having some branches, e.g., Differences between thermoplastics and
low density polythene. thermosetting plastics
Thermoplastics Thermosetting plastics
3. Cross linked or Network polymers 1.Softens on heating 1. Stiffens on heating
Contain strong covalent bonds between various and hardens on cooling.
linear polymer chains, e.g. bakelite, melamine, etc. 2.Can be reused 2.cannot be reused
3. linear or slightly 3.Cross linked or
branched long chain heavily branched
molecules molecules,
Natural rubber (cis-1, 4 -Polyisoprene)
Polymers classified based on mode of It is a linear polymer of isoprene ( 2 methyl 1,3
Polymerisation butadiene)
1. Addition polymers: Polymers formed by addition Vulcanisation of rubber
polymerisation reaction.  Heating of natural rubber with Sulphur to
E.g. polythene, polypropene, polystyrene, polyvinyl improve the physical properties.
chloride etc.  Sulphur forms cross links and gets stiffened
Biodegradable Polymers
Polymers which can be decomposed by micro
organisms.
Eg.PHBV, Nylon 2–nylon 6

POLYMER PREPARATION PROPERTIES AND USES

ADDITION POLYMERS
Low density Polymerisation of ethene  Branched chain
polythene  1000 to 2000 atm  Chemically inert and tough but flexible and a poor
(LDPE)  350 K to 570 K conductor of electricity.
 peroxide initiator  Used in the insulation of electricity carrying wires
and manufacture of squeeze bottles, toys and
flexible pipes.
High Polymerization of ethene  Consists of linear molecules and has a high density
density  6-7 atmospheres. due to close packing.
polythene  333 K to 343 K  Chemically inert and more tougher and harder.
(HDPE)  Ziegler-Natta catalyst  Used for manufacturing buckets, dustbins, bottles,
pipes, etc.
6
Polystyrene Addition polymerization of As insulator, wrapping material, manufacture of toys,
Styrene radio and television cabinets.
Poly vinyl Addition polymerisation of Vinyl Manufacture of rain coats, hand bags, vinyl flooring,
choride chloride water pipes
(PVC)
Polytetra Addition Polymerisation of  It is chemically inert and resistant to attack by
fluoroethene tetrafluoroethene with a free corrosive reagents.
(Teflon) radical or persulphate catalyst at  used in making oil seals and gaskets and also used
high pressures for non – stick surface coated utensils.
CONDENSATION POLYMERS
Nylon 6,6 Condensation polymerisation Used in making sheets, bristles for brushes and in textile
of hexamethylene diamine with industry.
adipic acid .
Nylon 6 By heating caprolactum with Used for the manufacture of tyre cords, fabrics and ropes.
water at a high temperature.

16 CHEMISTRY IN EVERYDAY LIFE Antimicrobial drugs

Antacids- The chemicals used to reduce the acidity in
stomach.
E.g. NaHCO3, metal hydroxides, ranitidine etc.
Neurologically active drugs
 Tranquilizers
 Analgesics
Tranquilzers-Reduce stress and tension by inducing a
sense of well-being.
E.g. Iproniazid, phenelzine ,Equanil, derivatives of
barbituric acid
Analgesics- Reduces pain
Two types of analgesics
(i)Narcotic analgesics:
 Reduces pain and induces sleep.
 Used for the relief of postoperative pain,
cardiac pain and pains of terminal cancer, and
in child birth
Eg:morphine, heroin, codeine
(ii) Non-narcotic analgesics:
 Non addictive
 Reduce pain
 Inhibits the synthesis of prostaglandins which
stimulate inflammation in the tissue and cause
pain.
 relieves skeletal pain due to arthritis.
E.g. aspirin, paracetamol, novalgin etc.
Aspirin
 Reduces fever (antipyretic)
 Prevents platelet coagulation.
 Because of its anti blood clotting action, finds
use in prevention of heart attacks.
Drugs that destroys or inhibit microbial growth.
 Antibiotics
 Antiseptics
 Disinfectants
Antibiotics- In low concentrations, destroys or
inhibits the growth microorganisms and can be taken
inside the body. Eg: penicillin
Antibiotics based on its spectrum of action.
(i)Broad spectrum antibiotics - Effective against a
wide range of Gram-positive and Gram-negative
bacteria.
Eg.,Ampicillin and Amoxycillin, Vancomycin
and ofloxacin, Chloramphenicol
(ii)Narrow spectrum antibiotics- Effective against
Gram-positive or Gram-negative bacteria.
Eg.,Penicillin G
(iii)Limited spectrum antibiotics. -Effective against
a single organism or disease.
Antibiotics based on the killing (cidal) effect or
static (inhibitory) effect
 Bactericidal-Kills microbes
Eg: Penicillin, Ofloxacin
 Bacteriostatic- Inhibits microbial growth
Eg: Tetracycline Chloramphenicol
Antiseptics- Can be applied to the living tissues such
as wounds to destroy the microorganisms.
Eg: Dettol, 0.2 % phenol
Disinfectants- Can be applied to nonliving tissue or
inanimate objects to destroy the microorganisms .
Eg: Cl2, SO2, 1% solution of phenol

7
8