AVS College of Arts & Science

(Recognized under Section 2(f) & 2 (B) of UGC Act 1956 and Accredited by NAAC)

(Affiliated to Periyar University, Salem)

Attur Main Road, Ramalingapuram, SALEM – 636106

DEPARTMENT OF UG CHEMISTRY
Students Study Material
2020-2021
Title of the Subject INORGANIC CHEMISTRY

Paper Code 17UCH08

Year & Class III B.Sc CHEMISTRY

Batch 2018-2021

Semester EVEN

Subject In-charge HOD PRINCIPAL

 UNIT-I

1.1. Bioinorganic Chemistry-Essential and trace elements in Biological

processes- Biological role of Haemoglobin and Chlorophyll (elementary idea of
structure and mechanism of their action )

1.2. Metal carbonyls-Bonding in carbonyls-Mono and binuclear Carbonyls of Ni,

Fe, Cr, Co and Mn-Hybridisation and structure.Preparation, properties and
uses.

1.3. Silicates-classification and structure–examples. Composition, properties and

uses of asbestos, talc, mica, andzeolite.

BIOINORGANIC CHEMISTRY INTRODUCTION:

• Bioinorganic chemistry is a field that examines the role of metals in biology.

Bioinorganic chemistry includes the study of both natural phenomena such
as the behavior of metalloproteins as well artificially introduced metals,
including those that are non-essential, in medicine and toxicology.
• As a mix of biochemistry and inorganic chemistry, bioinorganic chemistry is
important in elucidating the implications of electron-transfer proteins,
substrate bindings and activation, atom and group transfer chemistry as well
as metal properties in biological chemistry.

Essential and trace elements in Biological processes:

1. Metal ion transport and storage covers a diverse collection of ion

channel, ion pumps (e.g. NaK ATP ase), vacuoles, siderophores, and
other proteins and small molecules whose aim is to “carefully control
the concentration of metal ions in the cell” (sometimes referred to as
metallome).
2. Hydrolase enzymes include a diverse collection of proteins that interact
with water and substrates. Examples of this class of metalloproteins are
carbonic anhydrase, metallophosphatases, and metalloproteinases

Metal-containing electron transfer proteins are organized into three major classes:

• iron-sulfur proteins such as rubredoxins, ferredoxins, and Rieske proteins

• blue copper proteins
• cytochromes
These electron transport proteins are complementary to the non-metal electron
transporters nicotinamide adenine dinucleotide (NAD) and flavin adenine
dinucleotide (FAD).

3. Oxygen transport and activation proteins make extensive use of metals

such as iron, copper, and manganese. Heme is utilized by red blood
cells in the form of hemoglobin for oxygen transport and is perhaps the
most recognized metal system in biology. Other oxygen transport
systems include myoglobin, hemocyanin, and
hemerythrin.Somemetalloproteins are designed to protect a biological
system from the potentially harmful effects of oxygen and other reactive
oxygen-containing molecules such as hydrogen peroxide. These systems
include peroxidases, catalases, and superoxide dismutases. A
complementary metalloprotein to those that react with oxygen is the
oxygen evolving complex present in plants. This system is part of the
complex protein machinery that produces oxygen as plants perform
photosynthesis.
4. Bioorganometallic systems such as hydrogenases and methylcobalamin
are biological examples of organometallic compounds. This area is
more focused on the utilization of metals by unicellular organisms.
Bioorganometallic compounds are significant in environmental
chemistry.
5. The nitrogen metabolism pathways make extensive use of metals.
Nitrogenase is one of the more famous metalloproteins associated with
nitrogen metabolism.
6. Metals in medicine is the study of the design and mechanism of action
of metal-containing pharmaceuticals, and compounds that interact with
endogenous metal ions in enzyme active sites. This diverse field
includes the platinum and ruthenium anti-cancer drugs, chelating agents,
gold drug chaperones, and gadolinium contrast agents.
7. In mental health inorganic compounds have been found to treat certain
disorders. For example, lithium carbonate has been used to treat the
manic phase of bipolar disorder.

Biological role of Haemoglobin:

Synthesis

Hemoglobin (Hb) is synthesized in a complex series of steps. The heme part is

synthesized in a series of steps in the mitochondria and the cytosol of immature red
blood cells, while the globin protein parts are synthesized by ribosomes in the
cytosol. Production of Hb continues in the cell throughout its early development
from the proerythroblast to the reticulocyte in the bone marrow. At this point, the
nucleus is lost in mammalian red blood cells, but not in birds and many other
species. Even after the loss of the nucleus in mammals, residual ribosomal RNA
allows further synthesis of Hb until the reticulocyte loses its RNA soon after
entering the vasculature (this hemoglobin-synthetic RNA in fact gives the
reticulocyte its reticulated appearance and name).

Biological role of Hemoglobin

Structure

• A heme group consists of an iron (Fe) ion (charged atom) held in a heterocyclic
ring, known as a porphyrin.
• It is an octahedral complex of Fe (II).
• The center of haemoglobin is occupied by Fe(II) and the four corners of the
square base are occupied by four N-atoms of the heme group.
• This porphyrin ring consists of four pyrrole molecules cyclically linked together
(by methine bridges) with the iron ion bound in the center.
• The iron ion, which is the site of oxygen binding, coordinates with the four
nitrogens in the center of the ring, which all lie in one plane.
• The iron is bound strongly (covalently) to the globular protein via the imidazole
ring of F8 histidine residue (also known as the proximal histidine) below the
porphyrin ring.
• A sixth position can reversibly bind oxygen by a coordinate covalent bond
completing the octahedral group of six ligands.
• Oxygen binds in an "end-on bent" geometry where one oxygen atom binds Fe
and the other protrudes at an angle. When oxygen is not bound, a very weakly
bonded water molecule fills the site, forming a distorted octahedron.
• It is a conjucated protein having molecular weight of 64,000.
• Fe atom in hemoglobin is in thehigh spin state (Fe2+=3d6=t2g4eg2). Thus Fe(II)
has four unpaired electrons in hemoglobin molecule.
• In adult humans, the most common hemoglobin type is a tetramer (which
contains 4 subunit proteins) called hemoglobin A, consisting of two α and two β
 subunits non-covalently bound, each made of 141 and 146 amino acid residues,
respectively. This is denoted as α2β2.
• The subunits are structurally similar and about the same size. Each subunit has
a molecular weight of about 16,000 daltons, for a total molecular weight of the
tetramer of about 64,000 daltons (64,458 g/mol). Thus, 1 g/dL =
0.1551 mmol/L. Hemoglobin A is the most intensively studied of the
hemoglobin molecules.
• In human infants, the hemoglobin molecule is made up of 2 α chains and 2 γ
chains. The gamma chains are gradually replaced by β chains as the infant
grows.
• The four polypeptide chains are bound to each other by salt bridges, hydrogen
bonds, and the hydrophobic effect.

APPLICATIONS

➢ Hemoglobin concentration measurement is among the most commonly

performed blood tests, usually as part of a complete blood count.
➢ If the concentration is below normal, this is called anemia. Anemia is
classified by the size of red blood cells, the cells that contain hemoglobin in
vertebrates. The anemia is called "microcytic" if red cells are small,
"macrocytic" if they are large, and "normocytic" otherwise. Hematocrit,
➢ 100ml of the blood of a normal male contains 15g of hemoglobin.
➢ It is a carrier of O2 and CO2. Hemoglobin takes up large volume of O2 in the
lungs and carries to the tissues. In the same way CO2 is also transported from
the tissues to lungs.
➢ It also maintains acid-base balance of the body.

CHLOROPHYLL

• Chlorophyll is vital for photosynthesis, which allows plants to absorb energy

from light.
• Chlorophyll molecules are specifically arranged in and around photosystems
that are embedded in the thylakoid membranes of chloroplasts.
• In these complexes, chlorophyll serves two primary functions. The function
of the vast majority of chlorophyll (up to several hundred molecules per
photosystem) is to absorb light and transfer that light energy by resonance
energy transfer to a specific chlorophyll pair in the reaction center of the
photosystems.
 • Chlorophyll is a magnesium porphyrine complex
• It is a green color matter present in green plants and algae
• It is a square planar complex containing Mg2+ as central atom.
• It is a naturally occurring chelated complex of Mg.
• It consist of two chemically related substances. They are
✓ Chlorophyll-a(blue green color)
✓ Chlorophyll-b(yellow green color)

The most abundant chlorophyll is chlorophyll-a.

• Its presence is essential for photo synthesis in plants.

• Chlorophyll causes the combination of CO2 and H2O in presence of sunlight
to form starch.

6 CO2+6 H2O→C6H12O6+6O2

Metal carbonyl:

The electronic configuration of CO molecule shows that it has a lone pair of

electrons on carbon and oxygen atom each.

Carbon atom can donate its electron pair to a transition metal atom (M),
forming OC→M coordinate bond. The compounds formed by the combination of
CO molecules with transition metals are known as metallic carbonyls.

Metal carbonyls are coordination complexes of transition metals with carbon

monoxide ligands.

TYPES OF CARBONYLS:

Depending on the number of metal atoms in a given carbonyl, carbonyls

have been classified

Mono nuclear or monomeric carbonyls:

These contain one one metallic atom per molecule and are of the type M(CO)y.

Ex: V(CO)6 ,Cr(CO) 6.

Poly nuclear carbonyls:

These contain two or more metallic atoms per molecule are of the type
Mx(CO)y.

Ex: poly nuclear carbonyls may be homonuclear [Fe3(CO)12] 0r

heteronuclear [MnCo(CO)9], [MnRe(CO)10].

Bonding in metal carbonyls:

The HOMO of CO is a σ MO

The LUMO of CO is a π* antibondingMO

Metal carbonyls generally have poor solubility with water.

• Carbon monoxide bonds to transition metals using "synergic π* back-

bonding."
 • The bonding has three components, giving rise to a partial triple bond.
• A sigma bond arises from overlap of nonbonding electron pair on
carbon with a blend of d-, s-, and p-orbitals on the metal.
• A pair of π bonds arises from overlap of filled d-orbitals on the metal
with a pair of π-antibonding orbitals projecting from the carbon of the
CO.
• The latter kind of binding requires that the metal have d-electrons, and
that the metal is in a relatively low oxidation state (<+2). The π-bonding
has the effect of weakening the carbon-oxygen bond compared with free
carbon monoxide. Because of the multiple bond character of the M-CO
linkage, the distance between the metal and carbon is relatively short,
often < 1.8 Â, about 0.2 Â shorter than a metal-alkyl bond.

The increased π-bonding due to back-donation from multiple metal centers results
in further weakening of the C-O bond

Nickel tetracarbonyl

Preparation:

Ni(CO)4 was first synthesised in 1890 by Ludwig Mond by the direct

reaction of nickel metal with CO.

Ni + 4 CO→NiCO4

It is conveniently generated in the laboratory by carbonylation of commercially

available bis(cyclooctadiene)nickel(0).

Structure and bonding:

Nickel carbonyl is a tetrahedral molecule with four carbonyl (carbon

monoxide) ligands attached to nickel. The CO ligands, in which the C and the O
are connected by triple bonds (often depicted as double bonds), are covalently
bonded to the nickel atom via the carbon ends. Nickel carbonyl has 18 valence
electrons, like many other metal carbonyls such as iron pentacarbonyl and
molybdenum hexacarbonyl. These metal carbonyls have symmetrical structures
and are charge-neutral, resulting in their high volatility. In Ni(CO) 4, the nickel
atom has a formal oxidation number of zero.
Properties and uses:

o IUPAC name: tetracarbonylnickel.

o Nickel carbonyl is the most toxic substance encountered in industrial
processes.
o It is the organonickel compound with the formulaNi(CO)4.
o NiCO4 is liquid at ordinary temperature.
o Melt at low temperatures.
o It is also typical covalent compound and for this reason it soluble in no-polar
solvent.
o The metals in carbonyls are in zero oxidation state.
o It is used as a catalyst.

Reactions with nucleophiles and reducing agents

Like other low-valent metal carbonyls, Ni(CO)4 is susceptible to attack by

nucleophiles. Attack can occur at nickel center, resulting in displacement of CO
ligands, or at CO. Thus, donor ligands such as triphenylphosphine react to give
Ni(CO)3(PPh3) and Ni(CO)2(PPh3)2. Bipyidine and related ligands behave
similarly. The monosubstitution of nickel tetracarbonyl with other ligands can be
used to determine the Tolman electronic parameter, a measure of the electron
donating or withdrawing ability of a given ligand

Reactions with electrophiles and oxidizing agents:

Nickel carbonyl can be oxidized. Chlorine oxidizes nickel carbonyl into

NiCl2, releasing CO gas. Other halogens behave analogously. This reaction
provides a convenient method for destroying unwanted portions of the toxic
compound.

Reactions of Ni(CO)4 with alkyl and aryl halides often result in carbonylated
organic products. Vinylic halides, such as PhCH=CHBr, are converted to the
unsaturated esters upon treatment with Ni(CO)4 followed by sodium methoxide.
Such reactions also probably proceed via oxidative addition. Allylic halides give
the pi-allyl nickel compounds, such as (allyl)2Ni2Cl2:

1 Ni(CO)4 + 2 ClCH2CH=CH2 → Ni2(μ-Cl)2(η3-C3H5)2 + 8 CO

HYBRIDISATION:

In this molecule Ni atom is SP3hybridised as shown in fig. Here too both the
electrons of 4S-orbitals to vacate 4S orbital.

Now 4S and three 4P-orbitals on mixing together give four SP3 hybrid
orbitals. The presence of all paired electrons confirms the diamagnetic character of
(NiCO)4 molecule.

Due to SP3hybridisation (NiCO)4has the expected tetrahedral shape.

Iron pentacarbonyl:
Preparation:

It is Prepared by treatment of finely divided, oxide-free iron powder with

carbon monoxide at room temperature.

Fe+5CO→Fe(CO)5 at 200oc and 100 atm.

STRUCTURE:
 ❖ Most metal carbonyls have 18 valence electrons, and Fe(CO)5 fits this
pattern with 8 valence electrons on Fe and five pairs of electrons provided
by the CO ligands.
❖ Fe(CO)5 adopts a trigonalbipyramidal structure with the Fe atom surrounded
by five CO ligands: three in equatorial positions and two axially bound. The
Fe-C-O linkages are each linear.

Properties and uses:

o It a yellow liquid which is soluble in alcohol,ether,benzene.

o It is insoluble in wate.
o Iron pentacarbonyl is one of the homolepticmetal carbonyls; i.e. CO is the
only ligand complexed with iron.
o Iron pentacarbonyl, also known as iron carbonyl, is the compound with
formulaFe(CO)5. Under standard conditionsFe(CO)5 is a free-flowing, straw-
colored liquid with a pungent odour.
o This compound is a common precursor to diverse iron compounds, including
many that are useful in organic synthesis.
o When it is burnt in air finally divided into ferric oxide is obtained which is
used as a pigment and polishing agent.

Chemical properties:

➢ Fe(CO)5→Fe(CO)3 +2PR3→Fe(CO)3(PR3)2.
➢ Fe2(CO)9→Fe2(CO)4+4NO→2[Fe(CO)2(NO)2]
➢ Fe(CO)5+NaOH+NH3/H2O→Na2+[Fe(CO)4]2-

Hybridization:

I. In this carbonyl Fe atom which is in zero oxidation state is dsp3hybridised as

shown in fig.
II. Here too both the electron from 4S orbital go to 3d orbital
III. Thus one 3d, 4s and all the three 4p orbitals on mixing together give 5 dsp3
hybrid orbitals.
IV. Since, all the electron are paired in iron pentacarbonyl. It is diamagnetic due
to dsp3 hybridization.
V. It has trigonalbipyramidal shape.

Chromium hexacarbonyl:
Preparation:

CrCl3+6CO→Cr(CO)6 in the presence of (C2H5)3Al in benzene

Structure and properties:

Chromium carbonyl, also known as chromium hexacarbonyl, is the chemical

compound with the formulaCr(CO)6.

At room temperature the solid is stable to air, although it does have a

highvapor pressure and sublimes readily.

Cr(CO)6 is zero valent, meaning that Cr has a formal charge of zero, and it is
called a homiletic complex, which means that all the ligands are the same.

The complex is octahedral with Cr-C and C-O distances of 1.91 and 1.14 Å,
respectively. The reaction of chromium carbonyl is

Cr(CO)6 + C6H5R → Cr(CO)3(C6H5R) + 3 CO

Hybridization:
 ➢ In this carbonyl Cr-atom which is in zero oxidation state is d2sp3
hybridized as shown in fig.
➢ Since the energy of 3d and 4s orbitals is not very different from each
other, both the electrons from 4s orbital go to 3d and 4s orbital is
empty. Now the 3d,4s and 4p orbitals are hybridized together to form
six d2sp3 hybrid orbitals.
➢ This is diamagnetic nature due to the presence of all paired electrons.

Dimanganesedecacarbonyl (Mn2(CO)10):

Synthesis:

The compound was first prepared in low yield by the reduction of manganese
iodide with magnesium under CO. A more efficient preparation entails reduction
of anhydrous MnCl2 with sodium benzophenoneketyl under 200 atmospheres of
CO. The availability of inexpensive methyl cyclopentadienyl manganese
tricarbonyl ("MMT") has led to a low pressure route to Mn2(CO)10.

Structure:

• The molecular weight of this compound indicates the

dimericformulaMn2(CO)10.
• The structure of this carbonyl in the solid state contains octahedrally
coordinated Mn atoms. Each Mn atom is linked with 5 CO groups and
is also directly bonded to the other Mn atom.
• Thus this carbonyl contains ten CO groups which are called terminal
CO groups and one Mn-Mn bond.
• Mn2(CO)10 has no bridging CO ligands: it can be described (CO) 5Mn-
Mn(CO)5.
Properties:

o Mn2(CO)10 is air stable as a crystalline solid, but solutions require

Schlenk techniques.
o It finds limited use in organic synthesis.

Characteristic reactions:

• Reduction of Mn2(CO)10 gives the manganese pentacarbonyl anion, which

can be isolated as a salt:

Mn2(CO)10 + 2 Na → 2 Na[Mn(CO)5]

The anion is a versatile nucleophile. Protonation gives the hydride [HMn(CO)5],

and methylation gives [(CH3)Mn(CO)5].

• Halogenation of Mn2(CO)10 proceeds with scission of the Mn-Mn bond.

Mn2(CO)10 + Br2 → 2[Mn(CO)5Br]

Hybridization:
d2sp3hybridisation, and this carbonyl also dia magnetic

Dicobaltoctacarbonyl

Synthesis, structure, properties

The high pressure carbonylation of cobalt(II) salts, often in the presence of

cyanide, affords this compound.

It is an orange-colored, pyrophoric solid that is thermally unstable.

 It exists as two isomers in solution:

• One of these forms has a bridged structure in which two CO groups

bridge two Co atoms which are also linked with each other by a sigma
bond.
• The other form has a non-bridged structure with a Co-Co sigma bond
linking twonCo(CO)4 groups.

Chemical properties:

➢ Co2(CO)8 + H2 → 2 HCo(CO)4
➢ Co2(CO)8 + 2 Na → 2 NaCo(CO)4
➢ 6 C6H5N + 1.5 Co2(CO)8 → [Co(C6H5N)6][Co(CO)4]2 + 4 CO
➢ 2 Co2(CO)8 → Co4(CO)12 + 4 CO

Hybridization:
The both structures are diamagnetic character and have the hybridization is
d2sp3.

Uses:

Dicobaltoctacarbonyl is the inorganic compoundCo2(CO)8.

This metal carbonyl is a reagent and catalyst in organometallic chemistry

and organic synthesis.
 It is used as a catalyst for hydroformylation, the conversion of alkenes to
aldehydes.

SILICATES:

Silicates may be regarded as the metal derivatives of the silicic acid, H2SiO4.

Silicates can be prepared by fusing metal oxides or metal carbonates with sand
(Si(O)2.

Ex: Na2CO3→Na2SiO4,(Na2SiO3)n (fuse with sand)

Properties:

I. Only some silicates of alkali metals are soluble in water while others are
insoluble.
II. The insolubility is due to the great strength of Si-O bond.
III. When silicates are treated with HF, Si-O bond is broken.

Types of silicates:

Silicates are classified according to the nature of linking between the

tetrahedral SiO42-anions. This basis of classification gives the following types of
silicates.

i. Orthosilicates
ii. Pyrosilicates
iii. Cyclic or ring silicates
iv. Chain silicates
v. Two-dimensional sheet silicates
vi. Three-dimensional silicates

Orthosilicates:

These silicates contain discrete SiO42- anion is also coordinated to the metal ion
impart electrical neutrality to the structure.

Ex: phenacite (Be2SiO4), zircon (ZrSiO4)

Pyrosilicates:

These silicates contain the discrete Si2O76- which is formed by joining two SiO4
tetrahedral units through one oxygen atom.

Ex: thorteveitite(Sc2(Si2O7)), hemimorphite.

Cyclic or ring silicates:

Such silicates contain the cyclic or ring anions like Si3O96- or Si6O1812-
Ex: benitoite, beryl

Chain silicates:
Such silicates contain the anions which are formed by the sharing of two oxygen
atom by each tetrahedran. The anions may be one of the types i. (SiO3)n2n-, ii.
(Si4O11)n6n-
Ex:spodimene, diapside
Two-dimensional sheet silicates:
when three o-atoms of each SiO4 tetrahedron are shared with adjacent SiO4
tetrahedra an infinite two dimensional sheet structure of the composition
(SiO5)n2n-
ex: Talc
Three dimensional silicates:
When all the four o-atoms of a SiO4 tetrahedraon are shared with adjacent
tetrahedral and the process is repeated an infinite three-dimensional structure.
Ex: quartz

ASPESTOS
COMPOSITION:
The composition of aspestoa is CaMg(SiO3)4. Aspestos is availabale in three
varieties namely,
1. Anthophylite- Mg,Fe,Silicate.
2. Amphibole-Ca2Mg5(OH)2.Si8O22.
3. Serpentine-Mg3Si2(OH)4O5.
PROPERTIES:
❖ It has a property of splitting in to fibres.
❖ It possess good insulating and acid resisting properties.
❖ It is available in Bihar, Orissa, Cuddapah and Chennai.
❖ The amphibole aspestos has high resistance to attack by acids it can
withstand near 1000oc.
USES:
➢ It is used for brake linings, heavy packings and gaskets.
➢ It is used for fine proof, wall innings, boiler pipe linings and electrical
insulating materials.
➢ Aspestas sheets are used for roofings.
➢ Aspestos ropes, cards and threads are used for varies putposes.

TALC
COMPOSITION:

It has a composition of Mg3Si4O10(OH)4

It is a magnesium silicate.

PRPPERTIES:

➢ It is extremely soft.
➢ The atoms within the layers are strongly bonded, so that the mineral is
highly stable both two acids and to heat talc is hydrated silicate water is
expected out when heated very strongly.
➢ Therefore it is regarded as basic the hardness of the mineral is greatly
increased by the action of heat.
➢ Talc imports greater resistance to mechanical stress.
USES:

i. It is widely used as raw material.

ii. It is mainly used in ceramics, paints and insecticides.
iii. In ceramic industry talc is used in many white ware bodies, table ware,
electrical porcelain high frequency insulation and glazed wall tiles.
iv. In paints talc is used as an extendure and as a pigment.
v. In the cosmetic industry it is used in toilet powder, soaps and creames.

MICA

COMPOSITION:

The micas of economic importants are muscovite and phtogophite. Muscovite

has the composition H2KAl3(SiO4)3.

Phtogophite has the composition H2Na2Al3(SiO4)3.

PROPERTIES:

➢ Most micas are monoclinic a few are hexagonal or triclinic.

➢ The mica structure is based on sheets of linked (SiAl)O4 tetrahedron. This
accounts for the characteristic cleavage commercial mica is two main types.

i. Sheet and punch

ii. Scrap or flake

USES:

1. High quality mica is used as dielectric mica in radio and radar

circuits capacitors.
2. Scrap mica is ground and used in paints, decorative inks, rubber
filler and coating on roofing material and waterproof fabrics
3. Large quantities are ground mica used in the manufacture of
wallpaper.
4. It is used for carrying photographic film.
5. It is also used for various optical instruments.
6. It is used as a protective coating for pictures and historical document.

Zeolite

COMPOSITION AND PROPERTIES:

 • Zeolites have a porous structure that can accommodate a wide variety of
cations, such as Na+, K+, Ca2+, Mg2+ and others.
• These positive ions are rather loosely held and can readily be exchanged for
others in a contact solution.
• Some of the more common mineral zeolites are analcime, chabazite,
clinoptilolite, heulandite, natrolite, phillipsite, and stilbite. An example
mineral formula is: Na2Al2Si3O10·2H2O, the formula for natrolite.
• Naturally occurring zeolites are rarely pure and are contaminated to varying
degrees by other minerals, metals, quartz, or other zeolites. For this reason,
naturally occurring zeolites are excluded from many important commercial
applications where uniformity and purity are essential.
• Zeolites are the aluminosilicate members of the family of microporous solids
known as "molecular sieves."
• The term molecular sieve refers to a particular property of these materials,
i.e., the ability to selectively sort molecules based primarily on a size
exclusion process.
• This is due to a very regular pore structure of molecular dimensions. The
maximum size of the molecular or ionic species that can enter the pores of a
zeolite is controlled by the dimensions of the channels.

USES:

• Zeolites are microporous, aluminosilicateminerals commonly used as

commercial adsorbents.
• Zeolites are widely used in industry for water purification, as catalysts, for
the preparation of advanced materials and in nuclear reprocessing. Their
biggest use is in the production of laundry detergents.
• They are also used in medicine and in agriculture.
• Zeolites are widely used as ion-exchange beds in domestic and commercial
water purification, softening, and other applications.
• Synthetic zeolites are widely used as catalysts in the petrochemical industry,
for instance in fluid catalytic cracking and hydrocracking.
• Zeolites have uses in advanced reprocessing methods, where their micro-
porous ability to capture some ions while allowing others to pass freely
allow many fission products to be efficiently removed from nuclear waste
and permanently trapped.
• Zeolites can be used as solar thermal collectors and for adsorption
refrigeration.

QUESTION BANK
2-marks

1. What are the bulk and trace metals found in biological system(apr-2014)
2. How are Ni(CO)4 and Fe(CO)5 prepared by direct method(apr-2014)
3. State the essential role of chlorophyll and haemoglobin(nov-2014)
4. What are metal carbonyls? How are they classified?(nov-14)
5. Write any two uses of talc(apr-13,nov-15)
6. What are the metal carbonyls give an example(N0v-15)
5-marks

1. Discuss the hybridization and structure of Ni(CO)4 (Apr,Nov-2014,nov-15)

2. What are silicates? give an account on the structure of silicate(Apr,Nov-2014,Nov-2015)
3. Give brief account of structure on biological role on chlorophile(Apr-14,Nov-15)
4. What are silicates? How are they classified(Nov-16,18)
5. Give brief account of structure on biological role on haemoglobin(Apr-17)
10-marks

1. Give the preparation properties and structure of Ni(CO)4 and Fe(CO)5 (Apr-14,Nov-15)
2. Give the reactions of Ni(CO)4 and Fe(CO)5,Co(CO)8 on heating explain the structure of
Fe3(CO)12
3. What are silicates? Draw and explain the different type of silicate.(Apr-13,Nov-18)
4. Write a note on Zeolite, ultramarine and aspestos(Apr-18).

UNIT II

2. Organometallic compounds

2.1 Definition-classification-ionic, σ-bonded and ∏-bonded organometallic

compounds-examples- nature of carbon-metal bond.

2.2 General methods of preparation. General properties of organometallic

compounds -physical and chemical characteristics.

2.3 Organometallic compounds of Lithium & Boron-preparation,

properties, structure and uses.

2.4 Olefin complexes –Zeisels salt –synthesis and structure

2.5. Cyclopentadienyl complexes -Ferrocene- preparation, properties, structure

and uses.
2.6. Uses of organometallic compounds.

ORGANOMETALLIC COMPOUNDS
The compounds containing at least one direct metal carbon bond are called
organometallic compound and the branch of chemistry which deals with such
compounds is called organometallic chemistry, the term metal in this definition
includes all those elements which are less electronegative than carbon
e.g.: CH3MgI, CH3Li, (CH3 CH2)4Pb, ferrocene

Structure and properties

The metal-carbon bond in organometallic compounds is generally of character

intermediate between ionic and covalent.

Primarily ionic metal-carbon bonds are encountered either when the metal is
very electropositive (as in the case of Group 1 or Group 2 metals) or when the
carbon-containing ligand exists as a stable carbanion.

Carbanions can be stabilized by resonance (as in the case of the

aromaticcyclopentadienyl anion) or by the presence of electron-withdrawing
substituents (as in the case of the triphenylmethyl anion).

Hence, the bonding in compounds like sodium acetylide and

triphenylmethylpotassium is primarily ionic.

On the other hand, the ionic character of metal-carbon bonds in the

organometallic compounds of transition metals, post-transition metals, and
metalloids tends to be intermediate, owing to the middle-of-the-road
electronegativity of such metals.

Two important classes are organolithium and Grignard reagents. In certain

organometallic compounds such as ferrocene or dibenzenechromium, the pi
orbitals of the organic moiety ligate the metal.

In metal carbonyl and metal alkenes, back bonding (pi bonding) of electron
density from metal to ligand antibonding orbitals makes stronger synergistic bonds.

➢ The physical and chemical properties of organometallic compounds vary

greatly.
➢ Most are solids, particularly those whose hydrocarbon groups are ring-
shaped or aromatic, but some are liquids and some are gases.
➢ Their heat and oxidation stability vary widely.
➢ Some are very stable, but a number of compounds of electropositive
elements such as lithium, sodium, and aluminum are spontaneously flammable.
➢ Many organometallic compounds are highly toxic, especially those that are
volatile.

Classification of organometallic compounds:

organo metallic compounds are classified according to the nature of

bonds present in them. They are classified as,

i. Ionic organo metallic compounds

ii. Covalent organo metallic compounds
iii. Complex organo metallic compounds

Ionic organo metallic compounds

The carbon atom of the alkyl group carries negative charge. This
negatively charged carbon is linked to a metal cation by a strong electro
static force of attraction called ionic bond. They exhibit the properties of
ionic compounds.
e.g: CH3Na
Covalent organo metallic compounds

The alkyl or aryl carbon of these compounds are linked to a metal by a

co valent bond. They possess the properties of co valent compounds.

e.g. (C2H5)Pb, B(CH3)3,C6H5OLi

Complex organo metallic compounds

These compounds are formed by the reaction of alkenes, alkynes and

aryl group with the metals. The metal ions in these compounds are linked to the
alkyl or aryl carbon by a π bond or co-valent bond.

e.g: K[Pt (C2H4)Cl3, Li2[Mg(C6H5)4], [Cr (C6H5)2

Organo Lithium Compounds

Alkyl And ArylLithium Compounds

Preparation:

i. by direct reaction of lithium with alkyl or aryl chloride in benzene or

petroleum.
2Li+MeBr→LiMe+LiBr
 ii. Reduction of alkyl halide with metallic lithium can afford simple alkyl
and aryl organolithium reagents.

iii. Vinyl , allyl other unsaturated derivatives can be obtained by

transmetallation
iv. Methyl lithium is also prepared by exchange through the interaction of
n-butyl lithium and methyl iodide in hexane at low temperature where it
precipitates as insoluble white crystals.
v. By metal-metal exchange in petroleum or benzene:
Excess of lithium and reacts with an organomercury compound forming
lithium organomettalic compound.
Properties:

i. Organolithium compounds tend to be thermally unstable and most of

them decompose to LiH and an alkene on standing at room temperature
or above
ii. They are generally liquids or low melting solids and are found in
molecular association .
iii. Organolithium compounds are typical covalent substances soluable in
hydrocarbons are other non- -polar liquids.
iv. They react ability with oxygen and are usually spontaneously flammable
in air, with illiquid water and water vapours.
v. LiMe and LiBu are usually synthetic reagents and have been increasingly
used in organic synthesis has polymerization catalysts is alkylating
agents and free cursors to metalated organic reagents.

USES

i. Organolithium compounds are has reactive as Grignard reagents.

Hence, many useful organic compounds can be prepared using
organolithium compounds.
ii. Some of the most common applications of organolithium reagents in
synthesis include their use as nucleophiles, strong bases for
deprotonation, initiator for polymerization, and starting material for the
preparation of other organometallic compounds.
STRUCTURE

Lithium alkynes are polymeric and generally oxide as tetrameric units such
as ( LiCH3) 4.
 In lithium methyl there is a tetra hedral set of four lithium atoms with a
methyl group place a symmetrical above each Li3 face.

The structure involves a methyl group merging three lithium atoms and the
carbon atoms have coordination no 7 being bonded directly to 3 hydrogen and 4
lithium atoms.

Li – C distance is 231 pm. The Li – Li distance is 268 pm.

ORGANO BORON COMPOUNDS

Organoborane or organoboron compounds are chemical compounds that

are organic derivatives of BH3,

for example trialkylboranes. Organoboron chemistry or organoborane

chemistry is the chemistry of these compounds.
]
Organoboron compounds are important reagents in organic chemistry
enabling many chemical transformations, the most important one called
hydroboration.

Synthesis

From Grignard reagents

Simple organoboranes such as triethylborane or

tris(pentafluorophenyl)boron can be prepared from trifluoroborane (as the ether
complex) and the ethyl or pentafluorophenylGrignard reagent.

Properties:

1. Lower boron alkenes are reactive substance but boron aryls are stable.
2. The compound Li (Bme4) M.P 463 K. is readily soluble in benzene and can
be sublimated. In solution only an ion pair, Li+BMe4- is present. It is
polymeric in the solid state.
3. Boronic acids RB(OH) 2 are quite stable and water soluble there acidities
are depend on the nature of the alkyl or aryl group. dehydration of boronic
acid by heat yields a boronic anhydride or trialkyl are aryl boroxime.
4. Hydrolysis of alkyl boron forms many organic compounds the nature of
products depends on the regeants.
5. It reacts with carbon monoxide forms aldhydes and ketones.
6. Alkyl boranes joints among themselves to produce alkelnes in the presense
of alkylene silver nitrate
 7. Sodium tetra phenyl borate is soluble in water and is stable in weekly acid
solution it gives insoluble precipitates with larger cation such as K+, Rb+,
Me4N+ that are suitable for gravimeric analysis. The ion (B[C6H5)4] can also
act as a ligand where in one phenyl ring is bound in n arene complexes as in
figure.

Structure of trialkylboroxines

Trialkyl or aryl boroxides (RBO), have trimeric, cyclic structures with

plannar rings of alternating boron and oxygen atoms. The alkyl groups are also in
the plane of the ring. Boron can also be incorporated into numerous carbon ring
systems.

Structure of BMe3

It is monomeric in solid p phase and has trigonal planar shape with B-C
distance 158 pm.

Structure of Li(BMe4)

It is an unusual type of methyl bridge occurs in adition to the conventional

type of found in (BeMe2)nIn Li-C = 212 pm and C- B = 151 pm.

Properties

• It is organic solids, aromatic.

• It gives mono and acetyle derivatives by means of fridel and craks reaction
under satiable condition on sulphonation with conc H2SO4 in acetic
anhydrides solvent it gives mono and di sulphonic acids.
Structure

• Ferrocene consists two penta di enyl ligands lying parallel to each other with
an iron atom sandwiched between them.
• The molecule possess a centre of symmetric cyclopentadienyl is weak
acid.thecyclopendadienyl ion C5H5 has the aromatic sixtets of π electrons
and forms salts with the number of bases. The other cyclodienylpenta
compounds are first row transition methods are those of ruthenium and
osmium. Compounds with more that to cyclopentadienyl rings are also
known.
Examples

• Cis (cyclopentadieneyl) titanium

• Trans (cyclopentadieneyl) uranium
A few compounds with only one cyclopendaeneyl ring per metal atoms are known.

Example

• Sodium cyclopendtadiennide
• Cyclopentadienyl thallium (I).
Zeise's salt:

Zeise's salt, potassium trichloro(ethene)platinate(II), is the chemical

compound with the formula K[PtCl3(C2H4)]·H2O.

The anion of this air-stable, yellow, coordination complex contains anη2-

ethyleneligand. The anion features a platinum atom with a square planar geometry.

The salt is of historical importance in the area of organometallic chemistry

as one of the first examples of antransition metal alkene complex.

Preparation:

This compound is commercially available as a hydrate. The hydrate is

commonly prepared from K2[PtCl4] and ethylene in the presence of a catalytic
amount of SnCl2. The water of hydration can be removed in vacuo.

Structure:

In Zeise's salt and related compounds, the alkene rotates about the metal-
alkene bond with a modest activation energy.

Analysis of the barrier heights indicates that the π-bonding between most
metals and the alkene is weaker than the σ-bonding.

In Zeise's anion, this rotational barrier cannot be assessed by NMR

spectroscopy because all four protons are equivalent.

Lower symmetry complexes of ethylene, e.g. CpRh(C2H4)2, are, however,

suitable for analysis of the rotational barriers associated with the metal-ethylene
bond.
FERROCENE

❖ Ferrocene is an organometallic compound with the formula Fe(C5H5)2.

❖ It is the prototypical metallocene, a type of organometallicchemical compound
consisting of two cyclopentadienyl rings bound on opposite sides of a central
metal atom.
❖ Such organometallic compounds are also known as sandwich compounds.
❖ The rapid growth of organometallic chemistry is often attributed to the
excitement arising from the discovery of ferrocene and its many analogues.

Structure and bonding

• The carbon-carbon bond distances are 1.40 Å within the five-membered rings,
and the Fe-C bond distances are 2.04 Å.
• In terms of bonding, the iron center in ferrocene is usually assigned to the +2
oxidation state, consistent with measurements using Mössbauer spectroscopy.
• Each cyclopentadienyl (Cp) ring is then allocated a single negative charge,
bringing the number of π-electrons on each ring to six, and thus making them
aromatic.
• These twelve electrons (six from each ring) are then shared with the metal via
covalent bonding. When combined with the six d-electrons on Fe2+, the
complex attains an 18-electron configuration.

Properties
 ➢ It is an orrange coloured crystalline compound.
➢ The melting point is 1730C.
➢ It is diamagnetic and it is thermally stable.
➢ It decomposes above 5000C in absence of air.
➢ Ferrocene stable in air and water.
CHEMICAL PROPERTIES

➢ Ferrocene undergoes many reactions characteristic of aromatic compounds,

enabling the preparation of substituted derivatives.
➢ A common undergraduate experiment is the Friedel-Crafts reaction of
ferrocene with acetic anhydride (or acetyl chloride) in the presence of
phosphoric acid as a catalyst.

Applications of ferrocene

Fuel additives:

Ferrocene and its derivatives are antiknock agents used in the fuel for petrol
engines; they are safer than tetraethyllead, previously used.

It is possible to buy at Halfords in the UK, a petrol additive solution which

contains ferrocene which can be added to unleaded petrol to enable it to be used in
vintage cars which were designed to run on leaded petrol.

The iron-containing deposits formed from ferrocene can form a conductive

coating on the spark plug surfaces.
Pharmaceutical:

Some ferrocenium salts exhibit anticancer activity, and an experimental drug

has been reported which is a ferrocenyl version of tamoxifen.

The idea is that the tamoxifen will bind to the estrogen binding sites, resulting
in a cytotoxicity effect.

Materials chemistry:Ferrocene, being readily decomposed to iron nanoparticles,

can be used as a catalyst for the production of carbon nanotubes.

The vinylferrocene from ferrocene can be made by a Wittig reaction of the

aldehyde, a phosphonium salt and sodium hydroxide.

The vinyl ferrocene can be converted into a polymer which can be thought
of as a ferrocenyl version of polystyrene (the phenyl groups are replaced with
ferrocenyl groups).

Uses of organometallic compounds.

➢ Organometallics find practical uses in stoichiometric and catalytic processes,

especially processes involving carbon monoxide and alkene-derived
polymers.
➢ All the world's polyethylene and polypropylene are produced via
organometallic catalysts, usually heterogeneously via Ziegler-Natta
catalysis.
➢ Organolithium, organomagnesium, and organoaluminium compounds are
highly basic and highly reducing. They catalyze many polymerization
reactions, but are also useful stoichiometrically.
➢ III-V semiconductors are produced from trimethylgallium, trimethylindium,
trimethylaluminium and related nitrogen / phosphorus / arsenic / antimony
compounds.
➢ These volatile compounds are decomposed along with ammonia, arsine,
phosphine and related hydrides on a heated substrate via metalorganic vapor
phase epitaxy (MOVPE) process for applications such as light emitting
diodes (LEDs) fabrication.
➢ Organometallic compounds may be found in the environment and some,
such as organolead and organomercury compounds are a toxic hazard
QUESTION BANK

2-marks

1. Define organometallic ompound(N0v-14,15)

2. What are Ziesel salt? Write it is structure(apr-14,nov-15)
3. Give the reaction of ferrocene with acetylene(Apr-14)
4. Write any 2 uses of organo metallic compound(Nov-18)
5. What are olefin complexes?(apr-2018)
5-marks

1. Explain the classification of organometallic compounds(Apr-13,Nov-15)

2. Explain ionic organo metallic compounds(Apr-14)
3. Discuss the structure of ferrocene(Apr-18)
4. Give the general preparation and uses of organometallic compounds(nov-19)
5. Explain about Ziesel salt with example(Apr-18)
10-marks

1. Elaborate the band theory conductors and insulaters

2. Discuss the preparation and properties of ferrocene(Apr-16,18)
 UNIT-III
3.1. Solids: Band theory of conductors , semiconductors and
insulators
3.2. Imperfections ina crystal-Outline ofSchottky defects, Frenkel
defects, metal excess and metal deficiency defects and line defects.
3.3. Nano materials – an elementary study.
SOLIDS:

• Solids are definite shape and volume.

• Each solids melts at a fixed temperature.
• Mild distorting forces cannot change their shape.
• These are rigid and virtually incompressible.
• They diffuse extremely slowly.

The attractive forces b/w the constituent particles are relatively strong.

a) Amorphous solids

b) Crystalline solids

Crystalline solids:

If the process of cooling is slow so as to allow the particles to arrange

themselves in a well ordered array the resulting solid is said to be crystalline solid.

Amorphous solid:

If the cooling is very rapid, there is a greater change that the particles get
frozen in a chaotic state, the resulting solid with constituent particles arranged in a
random fashion is termed amorphous solids

BAND THEORY

This theory is the quantum mechanical treatment of the metallic crystal and
is similar to molecular orbital theory of covalent molecules.

According to this theory metallic bonding results from the delocalization of

the free electron orbitals of all the atoms of a metal structure.

In metallic crystal very large number of the metal (1023 atoms) are combine
together to form metallic (1023 molecular orbitals). The energies of those molecular
orbitals are so closely spaced that they appear to be a continuum called “quasi-
continuous energy band”.Hence the name band theory.
 These molecular orbitals are delocalized (ie) the electrons in a molecule are
considered to belong to the crystal as a whole and not to individual or any pairs of
atoms.

Eg:

Li-crystal.

Electronic configuration:1S22S1

If n atoms are allowed to combine to form Li-crystal theywill form the

following energy bands.

1S-Band:

This band is formed by the combination of ‘n’ 1S atomic orbitals and hence
contains ‘n’ energy levels all of which are completely filled. Total number of
electrons in this completely filled 1S band is 2*n=2n.

2s band:

The 2s-orbitals are the valence energy levels. This is half filled the lower
half of this band is completely filled and is called conduction band.

2p band:

The 2p band contains no electrons. Since 2s and 2p levels are near in energy.
Therefore 2s and 2p bands overlap. The position where 2s and 2p bands overlap is
called overlap bond or overlap zone.

The electronic energy bands where the electrons can move is called
permitted bond. These are also called as Brillouin zone. Two Brillouin zones are
separated from each other by empty bands which are called forbidden zones.
 It is known as non-conducting band or non-conduction band

“A”represents the overlap zone where 2s and 2p bands overlap.

MERITS OF THE THEORY:

(i) Thermal and electrical conductivity of metals:

In terms of energy bands the conduction band of a conductor is
partially filled and contains very large number of electrons. These
electrons can be promoted to the nearby vacant orbital in the same band
by electrical and thermal energy.
Conductors:

Conductors are those materials having an excess of free electrons which act
as the charge carriers which means that they have high electrical conductivity. In
conductors the energy Band gap between the valance band and the conduction
band is very small it is below .5ev.the valance band is partially filled. Therefore the
free electrons in the conduction band increases the conductivity.
Semiconductors:

Semiconductors are solids that are insulators at absolute zero but with
conduct electricity by the passage of electrons at normal temperatures. Unlike
normal metallic conductors the conduction of a semiconductor increases with
raise in temperature . thus they are insulators at low temperatures and are
conductors can be can be explained by the band theory ofgsolids.accordind to this
theory solids have both permitted zones or brillouin zones and forbidden zones . in
a semiconductor all low energy permitted zones are completely occupied by
electrons.

i) Insulator in with the forbidden band is wide.

ii) Semiconductors in with the forbidden band is narrow.
Bands are completely flled up at low temperature the electrons fail to conduct
electrically , as sufficient energy is not available for them to cross the forbidden
zone and and jump to the next empty permitted zone . when the temperature is
raised the thermal energy of the electrons increase some valence electrons cross
the forbidden band and reach the higher permitted empty band is called
conduction band .

Thus when an electric field is applied these few electrons are free to flow
through crystal. Thus the semiconductors exhibit a limited electrical conductance
at the higher temperature.

Insulators:

Substance with donot conduct electricity at all conditions are called

insulators. According to the band theory of solids all low energy bands of these are
completely occupied. So the electrons in them are not in a position to move. So
hence do not conduct electricity. The forbidden zone in these is too wide, such that
the electrons are not in a position to jump over it and goes into empty conduction
band even , when the temperature is raised .Thus they remain non conducting
always.

CRYSTAL DEFECTS:

➢ Perfect crystal is one in which all the atoms or ions are lined up in a precise
geometric pattern.
➢ But crystals are never actually perfect.
➢ Real crystals that we find in nature or prepare in the lab always contain
impurfections in the formation in the crystal lattice.
➢ These crystal defect affect the physical and chemical properties of a solid,
➢ The common crystal defects are
1. Vacancy defect
2. Industrial defect
3. Impurity defect
 ➢ These defects pertaining to lattice sites or points are called point defects.
(i). VACANCY DEFECT:

▪ When crystal site is rendered vacant by removal of a structural unit in the

lattice. The defect is referred to as the vacancy defect.
▪ In one ionic crystals a cation and an ion may leave the lattice to cause
two valances. Such a defect which involves a cation and an anion
vacancy in the crystal lattice is called SCHOTTKY DEFECT. This
defect is found in the crystals of NaCl and CsClpaint

(ii). INTERSTITIAL DEFECT:

▪ Here an ion leaves its regular site to occupy a position in the space
between the lattice sites/interstitial position. This causes a defect known
as interstitial defect or Frenkal defect.
▪ Ordinary the cation moves as it is smaller than the anion and can easily
fill into the vacant spaces in the lattice. Thus in AgCl crystal Ag + ion
occupies an interstitial position leaving a vacancy or hole at the original
site.
 iii. Metal excess defects:
In the metal excess defect the +ve charge is in excess. These defects may arise in
two ways:

When there are same unoccupied lattice points. The unoccupied points are called
vacancies or holes. If a –ve ion is missing from its lattice site, it leaves a hole.

Iv. Metal deficiency defects or non- metal excess defects:

This type of defects occur mainly in transition metals because this type
requires variable valency of the metal. This may occur in two ways.

i) A +ve metal ion is missing from its lattice site and the charges are
equalized by an adjacent metal ion having two charges (instead of one) as
shown in fig.
ii) An extra –ve ion is present in the interstitial position. The charges are
balanced by means of an extra charge on an adjacent metal ion.

Defects due to impurities:

Some crystal are defective because of the presence of small amounts of

impurities in the crystal lattice eg., silicon or germanium containing a small
amount of arsenic, antimony or boron.

Conductors in ionic solids – electrical and magnetic properties:The direct

consequence of the defects in solids is that they become conductors of electricity.
As a consequence of schottky&frenkel defects, the crystal is able to conduct
electricity to a small intent by an ionic mechanism. When an electric field is
applied a nearby ion mores from its lattice site to occupy a hole. Now another hole
is created & another ion nearby moves into the newly created hole. The process
continues. The hole moves from one of the crystal to the other end. Thus the
crystal conducts electricity.

As the consequence of metal excess and metal deficiency defects the crystal is
able to conduct electricity by an electronic mechanism. In metal excess defects the
crystal contains free electrons .Thus the electrons migrate and conduct electricity .
In metal deficiency defects electrons move from one ion tom another. Thus the ion
metal + charges to M2+. Thus it appears that the ion M2+ moves.

As the result ion impurities in sod they become conducting. Thus defects
solids directly lead to a new world of conductors. However the conduction of these
conductors would be small when compared to conduction of metals fused salts or
salt solutions.so such conductors with conduct electricity to as small extent are
called semiconductors.

Semiconductors:

They are solids wiwth are insulators at absolte zero. But with conduct
electricity by the passage of electrons at normal temperatures. EgGe and silicon.

Different types of semiconductors:

Semiconductors are two types:

I) Intrinsic semiconductors
II) Extrinsic semiconductors
Intrinsic semiconductors:

A semiconductor is an extremely pure form is known as intrinsic semiconductors.

Ex: Si and Ge.

Explanation of semiconductor behavior based on covalent bond concept:

The crystalline structure of both Si and Ge is the tetrahedral pattern where in

each atom shares four of its valence electrons with each of the four neighboring
atoms. Such bonding is known as covalent bonding. All absolute zero temperature
all the valence electrons are tightly bound to the nuclei and there are no free charge
carriers (ie) the material behaves as an insulator.

The energy required to break a covalent bond is about 1.1 eV for Si and
about 0.7eV for Ge at room temperature.

When such a sufficient energies are given some of the covalent bonds are
broken and the electrons are ejected from their normal sites. These electrons can
migrate leaving behind a +ve holes. Now the electrical conduction takesplace by
the migration of both free electrons and positive holes.
Extrinsic conductors:

These are those if which the pure semiconductors materials have some
impurity or depending agents which increases the conductivity. When pentavalent
or trivalent impurity atoms are introduced into the crystalline structure of a
semiconductor Si or Ge there is a very high increase in the concentration of free
electrons or holes and also in the conductivity of the material.

Pentavalent elements commonly used are N,P,Ar and Sb while trivalent

element are B,Al,Ga,In.

Types of extrinsic semiconductors:

Depending on the nature of impurity added (pentavalent/trivalent) the

extrinsic semiconductors are classified into the following types

I. N-type semiconductor
II. P-type semiconductor
n-type semiconductor:

When a trace of v-A group element namely As(pentavalent) is added to

Si,As atom enters into the crystal lattice of Si. The Si containing trace of As is
called Arsenic doped silicon.

The pentavalent impurity atom has five valence electrons only four of whole
participate in the covalent bonding with neighboring Si atoms. The remaining one
electron is free to conduct electricity.

In this case As is called a donor impurity or n-type impurity because it

donates an extra electron to the conduction band of pure Si.
 Since current is carried by excess electrons (ie) electrons are the majority
charge carriers and the holes are the minority charge carriers.

Therefore this type of semiconductor are called n-type semiconductors (n-negative

charged electrons)

p-type semiconductors:

When a trace of III-A group element namely Ga is added to Si the GA atom

enters into the crystal lattice of Si. The Si containing a trace of gallium is called
“Ga doped Si”.

The three valence electrons of the trivalent atom from covalent bonds with the
neighboring Si atom while the fourth unfilled bond creates a +ve hole in the
valence band of Si.
 The holes occupy the level called acceptor impurity level which exists close to
the filled valence band Si-crystal.

Electron from the filled valence band can thermally promoted to this empty
acceptor impurity level of the holes.(ie) the adjacent electron move into these holes
leaving a hole at that position similarly these holes then move randomly in the
crystal structure. Thus the migration of such the holes conduct electrically.

In this case Ga is called acceptor impurity or p-type impurity because it

accepts an electron from the valence band of pure Si.

Since the current is carried by +ve holes. That is holes are the Mmjority
carriers and electrons are the minority carriers. Therefore this type of
semiconductors are called p-type semiconductor (p used for +ve holes)

Distinction b/w Intrinsic & Intrinsic semiconductors:

INTRINSIC EXTRINSIC SEMICONDUCTORS
SEMICONDUCTORS

They contain atoms of two types.

1. They contain atoms of (E.g) Ge+In&

single type.
(E.g) Ge& Si. Ge+AS

These contain either e – ns or (+) ve holes.

2. In this e –ns move in one

direction & (+) ve holes
in the other direction.

More

3. Conduction is less.

NANO MATERIALS

• Nanomaterials describe, in principle, materials of which a single unit is sized

(in at least one dimension) between 1 and 1000 nanometers (10−9 meter) but
is usually 1—100 nm (the usual definition of nanoscale).

Fullerenes

• The fullerenes are a class of allotropes of carbon which conceptually are

graphene sheets rolled into tubes or spheres. These include the carbon
nanotubes (or silicon nanotubes) which are of interest both because of their
mechanical strength and also because of their electrical properties.
 • In April 2003, fullerenes were under study for potential medicinal use:
binding specific antibiotics to the structure of resistant bacteria and even
target certain types of cancer cells such as melanoma. The October 2005
issue of Chemistry and Biology contains an article describing the use of
fullerenes as light-activated antimicrobial agents. In the field of
nanotechnology, heat resistance and superconductivity are among the
properties attracting intense research.

USES

• A common method used to produce fullerenes is to send a large current

between two nearby graphite electrodes in an inert atmosphere. The resulting
carbonplasma arc between the electrodes cools into sooty residue from
which many fullerenes can be isolated.
• There are the possibilities to use those materials in organic material based
optoelectronic devices such as Organic solar cells, OLEDsetc
• Nanoparticles or nanocrystals made of metals, semiconductors, or oxides are
of particular interest for their mechanical, electrical, magnetic, optical,
chemical and other properties.
• Nanoparticles have been used as quantum dots and as chemical catalysts
such as nanomaterial-based catalysts. Recently, a range of nanoparticles are
extensively investigated for biomedical applications including tissue
engineering, drug delivery, biosensor.
• Copper nanoparticles smaller than 50 nm are considered super hard
materials that do not exhibit the same malleability and ductility as bulk
copper.
• Ferroelectric materials smaller than 10 nm can switch their magnetisation
direction using room temperature thermal energy, thus making them useless
for memory storage
• Nanostructured materials with small particle size such as zeolites, and
asbestos, are used as catalysts in a wide range of critical industrial chemical
reactions. The further development of such catalysts can form the basis of
more efficient, environmentally friendly chemical processes.

QUESTION BANK

2marks

1. Why don’t some materials conduct electricity?(apr,2014)

2. What are CCP&HCP arrangements?(apr,2014)
3. Give two examples for semi conductors.(nov,2014)
4. Define non-
5. Give the structure of NaCl(apr,2014)
6. What are bragg;s equation (apr,2014)
7. What do you mean by line effect(nov,2018)
 8. What are insulators? Give an example(nov,2019)

5marks

1. Write a note on semiconductors (apr,2014)

2. Outline schottky defect &frenkel defect (apr,2014)
3. How does band theory account for insulators &conductors (nov,2014)
4. State the principle of X-ray diffraction analysis of crystal structure. Give
a brief note on the structure of NaCl(nov,2014)
5. Derive the bragg’s equation (apr,2013)
6. Elucidate the structure of ZnS(apr,2016)
7. What is frenkel defect? Explain (nov,2018)
8. Give account on nano materials (nov,2019)

10marks

1. What is meant by imperfection in crystals? Discuss non stoichiometric

defects.( apr,2014)
2. What is bragg;s law? Describe X-ray diffraction analysis&structure of
NaCl(apr,2014)
3. Write a note on band theory with an examples(apr,2017)
4. Discuss the stoichiometric defects in metals.( apr,2018)
5. Elaborate the band theory conductors, semi conductors& insulators
(nov,2019)

UNIT IV
Some Special compounds
4.1.1.Classification and structure of carboranes.
4.1.2.Boron Nitride-Borazole-metal Borides ( elementary idea)
4.2.Interhalogen Compounds-Naming of the compounds-
Types.Preparation,properties,structure and uses of ICl,BrF3 IF5,IF7. Basic
properties of Iodine.
4.3.Pseudohalogens-Definition,similarities and dissimilarities between halogen and
pseudohalogen,cyanogens,thiocyanogen- Preparation,properties and uses.

Carboranes:

Carboranes are cluster compounds with carbon and boron vertices. The
best known is orthocarborane, with the formula C2B10H12. Although they have
few commercial applications, carboranes have attracted much attention as
precursors to reagents and new materials. Anionic derivatives, dicarbollides,
e.g., [C2B9H11]2− are ligands that behave like cyclopentadienide
Boron Nitride (BN):
It is prepared by heating boron to a white heat in an atmosphere of
nitrogen or NO.
2B+N2→2BN
5B+3NO→3BN+B2O3
(ii) By heating B2O3 with Hg(CN)2, KCN or NH4Cl.
B2O3+HgCN2→2BN+CO+CO2+Hg
(iii). BN can also be prepared by passing N2 gas through a mixture of B2O3
and carbon heated in an electric furnace.
B2O3+3C+N2→2BN+3CO(gas)
Properties:
❖ It is a white powder of density 2.34
❖ It melts under pressure at 3000o c
❖ It is very stable and unreactive substance
❖ It remains unaffected by mineral acids, solutions of alkali and Cl2
at red heat.
❖ Decomposition:
(I). It gets decomposed when heated in steam evolving NH3
BN+3H2O→B(OH)3 or H3BO3+NH3
(II). It is decomposed but slowly,by HF, forming ammonium
borofluoride.
BN+4HF→NH4BF3
Structure:
Uses:
❖ BN possesses same hardness as diamond and can withstand temperature
of more than 300 degree Celsius.
❖ Due to this property it is used for coating crucible linings.
BORAZOLE (B3N3H6):
This compound is iso-electronic with benzene and has been called
“inorganic benzene”.
Preparation:
(i). by stock’s method:
B2H6+2NH3→B2H6.2NH3
2B2H6.2NH3→2B3N3H6+12H2
(ii). By heating BCl3 with NH4Cl:
3LiBH4+3NH4Cl→B3N3H6+ 3LiCl+9H2
Properties:
➢ Borazine is a colourless.
➢ Its boiling point is 630c.
➢ Its melts at -58oc.
Structure:
SOME IMPORTANT INTERHALOGEN COMPOUNDS:
IODINE MONO CHLORIDE: ICl

Preparation:

It is prepared as a dark red liquid by passing Cl2 over I2 or by heating I2 with

KClO3.

Properties:

• It solidifies on standing even at room temperature (15-25º). From

these compound two forms of the compound may be obtained. These are a) α form
which is ruby red. It is a stable form. (m.pt 27.2º)
• Form which is red-rhombic. It is a Meta stable form. (m.pt14º, b.pt
97.4 º).
• These can be identical in the gaseous state and is separated by cooling the
liquid ICl below 14º and by adding to the liquid a crystal of either of the two
forms.
• It is also dissolves in alkalies to form I2, iodate and chloride.

Uses:

• A solution of ICl in glacial acetic acid is used for the determination of iodine
number which measures the unsaturation oils and fats.
• It is used to iodate and chlorinate organic compounds.
• The solution of ICl is used as a catalyst in oxidizing As2O3 by Ce(SO4)2.
• It is also used to prepare polhalides.
• ICl is used as an electrophilic a iodinating agent. For example it converts
acetonitride into 4 iodoacetonitride and salicylic acid into 3,5-di iodo
salicylic acid and nitro benzene.

BrF3

Preparation:
 i) By mixing Br2vapuor with F2 in the presence of N2.

Br2 + F2→ BrF3

ii) By the action of ClF3 on Br2 at 10ºC.

ClF3 + Br2→ BrF3

iii) By the action of F2 on HBr:

F2+ HBr→ BrF3

Properties:

i) BrF3 is a straw coloured fuming liquid with boiling point 125.8ºC and
melting point 8.8 ºC and is very reactive.
ii) It is a corrosive liquid and hence it is used as a non-aqueous solvent to
carry out many reactions. It is a non-protonic ionizing solvent.
iii) Auto ionization of BrF3:
It has high specific conductance (onm-1m-1 at 298 K) and hence
undergoes auto ionization which takesplace in the following manner.
iv) Neutralization reactions involving acids and bases in liquid BrF3:

A neutralization reaction is that in which a compound containing BrF2+

ions react with that having BrF4- ions and a salt and BrF3 (solvent) are
formed.

v) Neutralization reactions involving an acidic anhydride and a base or

basic anhydride and an acid:
In these reactions salt and solvent are produced.
vi) Fluorination reactions:
BrF3 is a very reactive solvent and convert many metals, metallic and
non metallic halides, oxides, carbonates, iodates etc into their fluorides.
Thus BrF3 is a useful fluorinating agent.
vii) Redox reactions:
When alkali metals and other metals like Nb, Ta, Au etc react with liq
BrF3, they are oxidized and BrF3 is reduced to Br2.
viii) Hydrolysis:
It is hydrolysed by water to form BrOF3.
Uses:

• The reaction of liq BrF3,with covalent fluorides/ ionic halides gives

polyhalides.
• It is used to prepare a number of complex compounds which are difficult to
prepare by other methods.
• It is used as a flourinatng agent.
• Fluro complexes of many metals like Au(III), Ge (IV), As (V) etc have been
prepared.
Iodine penta fluoride IF5:

Preparation:

It is formed

a) By the direct combination of I2 and F2 (excess)

I2 + F2 (excess)→ IF5

b) By the action of F2 on I2O5

I2O5+ F2→ IF5

c) By heating I2 with AgF.

I2 + AgF→ IF5
Properties:

• It is a colourless liquid (b.pt=98º, m.pt= 9.6ºC)

• Self ionization : it is a good conductor of electricity.
• Action of I2O5:
IF5 reacts with I2O5 to form iodine oxy fluoride IOF3, which is a solid and
decomposes on heating at 110ºC.
IF5+ I2O5→IOF3
• Hydrolysis: hydrolysis gives halogen acid and oxy acid of the larger
halogen atom.
• Action of F2:

When IF5 is heated with F2 and 250-300ºC IF7 is formed.

IF5+ F2→ IF7

• It decomposes on heating to I2 and IF7:

Iodine hepta fluoride IF7:

 Only one compound of this type viz., IF7 (called iodine hepta fluoride) has been
formed and characterized. The reason of the formation of IF7 molecule is that
iodine atm has the largest size among halogens, while F atom has the smallest size.

IF7 is prepared by the action of F2 on IF5, KI or PbI2.

IF5+ F2→ IF7

Properties:

• It is a gas at ordinary temperature. Like ClF3 and BrF3 it is also highly

reactive.
• It reacts with most metals (except platinum group), non metals including Cl2
and I2, water to give per iodate and fluoride ions, many inorganic
compounds and a variety of organic materials.
• It explodes when heated with hydrogen.
• 2 of fluorine atoms present in IF7 can easily be reduced.
• Action of SiO2 and pyrex glass: SiO4 is formed.
• Formation of adducts: it forms adduct with SbF5 and AsF5. These adducts
are ionic compounds having the structure [IF6]+ [SbF6]- and [IF6]+ [AsF6]-
respectively.
• Hydrolysis:Vapours of IF7 are hydrolysed by water, giving HF and H5IO6.

Basic principles of iodine:

Preparation:

NaI reacts with MnO2 and H2SO4, iodine is liberated.

Physical properties:

i) Iodine is a grey black solid and its crystals possess a metallic lusture.
ii) Its vapour is however in violet in colour.
iii) It melts at 113.17ºC and boils at 184.35ºC. iodine is only slightly soluble
in water giving a light brown solution. It is soluble in carbon tetra
chloride or carbon disulphide forming a violet solution.
iv) Iodine produces stains on the skin.
v) Its vapour is pungent and irritating and dangerous to inhalide.

Chemical properties:
 i) With many metals and non metals it gives iodides like FeI3, HgI2, PbI2,
S2I2, MI3 (M = P, As, Sb), HI. Iodine does not combine with O2.
ii) With dilute cold alkalis it gives NaI and NaIO while with concentrated
hot alkaliesNaI and NaIO3 are formed.
iii) On dissociation at 1750ºC with bromine it gives constituent atoms.
iv) It oxidizes H2S to S, Na2S2O3 to Na2S4O6, SO2 to H2SO4, Na2SO3 to
Na2SO4.
v) Its reaction with Na2S2O3 is quantitative in nature and is employed for the
estimation of I2.
vi) Some of its additional reactions are that:
• It turns freshly prepared starch solution blue.
• With concentrated ammonia, NI3.NH3 is formed

Pseudohalogen

• The pseudohalogens are polyatomic analogues of halogens, whose

chemistry, resembling that of the true halogens, allows them to substitute for
halogens in several classes of chemical compounds.
• Pseudohalogens occur in pseudohalogen molecules, inorganicmolecules of
the general forms Ps–Ps or Ps–X (where Ps is a pseudohalogen group),
such as cyanogen; pseudohalide anions, such as cyanide ion; inorganic
acids, such as hydrogen cyanide; as ligands in coordination complexes, such
as ferricyanide; and as functional groups in organic molecules, such as the
nitrile group.
• Well-known pseudohalogen functional groups include cyanide, cyanate,
thiocyanate, and azide.

Similarities between halogens and pseudohalogens:

i) Volatile and dimeric nature:

Like halogens, pseudohalogens are also dimeric and fairly volatile (with
the exception of polymeric thio cyanogen) in the free state.

ii) Pseudohalogens are isomorphous to halogens when in the free or solid

state. For example Cl2 is isomorphous to (CN)2 and similarly Br2 is
isomorphous with (SCN)2.
iii) Addition to ethylenic double bond:
Like halogens, pseudo halogens also add to ethylenic double bond
linkage.
For example:
 iv) Reaction with alkalies:
Like halogens, pseudohalogens are also react with alkalis.
v) Formation of mono basic hydracids:
Like halogens, pseudohalogens also combine with hydrogen to form
mono basic hydracids.
Dissimilarity between halogens and pseudohalogens:

Pseudohalogens undergo polymerization and form polymerized

species. For example Halogens have no tendency to undergo polymerization.

Thiocyanogen

STRUCUTURE:

PREPARATION:

A suspension of anhydrous Pb(SCN)2 is treated with bromine in glacial acetic

acid to afford a 0.1M solution of thiocyanogen that is stable for days.
Alternatively, a solution of bromine in methylene chloride is added dropwise to a
suspension of Pb(SCN)2 in methylene chloride at 0 °C followed by filtration under
argon to give a solution of thiocyanogen that should be used immediately

Pb(SCN)2 + Br2 → (SCN)2 + PbBr2

PROPERTIES:

Chemical formula C2N2S2

Molar mass 116.16 g mol−1

❖ Thiocyanogen, (SCN)2, is a pseudohalogen derived from the

pseudohalidethiocyanate, [SCN]−.
❖ This hexatomic compound exhibits C2point group symmetry and has the
connectivity NCS-SCN.[1]
❖ The oxidation ability is greater than bromine.
❖ It reacts with water:

(SCN)2 + H2O → HSCN + HSCNO

Cyanogen

STRUCTURE:

Preparation

➢ Cyanogen is typically generated from cyanide compounds. One laboratory

method entails thermal decomposition of mercuric cyanide:

2 Hg(CN)2 → (CN)2 + Hg2(CN)2

➢ Alternatively, one can combine solutions of copper(II) salts (such as

copper(II) sulfate) with cyanides, an unstable copper(II) cyanide is formed
which rapidly decomposes into copper(I) cyanide and cyanogen.

2 CuSO4 + 4 KCN → (CN)2 + 2 CuCN + 2 K2SO4

➢ Industrially, it is created by the oxidation of hydrogen cyanide, usually using

chlorine over an activated silicon dioxidecatalyst or nitrogen dioxide over a
copper salt. It is also formed when nitrogen and acetylene are reacted by an
electrical spark or discharge.

PROPERTIES:

Chemical formula C2N2

Molar mass 52.04 g·mol−1

Appearance Colourless gas

Odor pungent, almond-like

Density 950 mg mL−1 (at −21 °C)

Melting point −28 °C (−18 °F; 245 K)

Boiling point −21.1 °C; −6.1 °F; 252.0 K

 Solubility in water 45 g/100 mL (at 20 °C)

Solubility soluble in ethanol, ethyl ether

➢ Cyanogen is the chemical compound with the formula (CN)2. It is a

colorless, toxic gas with a pungentodor.
➢ The molecule is a pseudohalogen.
➢ Cyanogen molecules consist of two CN groups – analogous to diatomic
halogen molecules, such as Cl2, but far less oxidizing.
➢ The two cyano groups are bonded together at their carbon atoms:
N≡C−C≡N, although other isomers have been detected.
➢ Certain derivatives of cyanogen are also called "cyanogen" even though they
contain only one CN group. For example cyanogen bromide has the formula
NCBr.
➢ Cyanogen is the anhydride of oxamide:

H2NC(O)C(O)NH2 → NCCN + 2 H2O

althoughoxamide is manufactured from cyanogen by hydrolysis:

NCCN + 2 H2O → H2NC(O)C(O)NH2

QUESTION BANK

2marks

1. Give two methds of preparation for diborane(nov,2014)

2. Write a note on boron nitride (apr,2014)
3. What are pseudo halogens? Give two examples(nov,2014)
 4. How will diborane react with H2O&NH3(nov,2014)
5. Give any two uses of cyanogens.(nov,2015)
6. Write the preparation methods of ICI(nov,2018)
5marks

1. Explain the basic property of iodine with example(nov,2014,2015)

2. Write a note on carboranes& their classification (nov 2013,2014&2015)
3. Give brief account for structure of closocarboranes(apr,2014)
4. Discuss the properties and uses of borazole(apr,2018)
5. Discuss the properties and uses of borides(apr,2018)
10marks

1. What ar inter halogen compounds? How are they classified? Discuss the
preparation & structure of BrF3Discuss the properties and uses of
borazole(nov,2014)
2. What are the similarities between halogens& pseudo halogens? Give the
preparation & properties of cyanogen (apr,2018)
3. Explain the preparation, properties and structure of IF7

UNIT V
5.1. Symmetry Elements and Symmetry operations – point
groups-point groups of simple molecules like H2, HCl, CO2, H2O &
NH3.
5.2. Magnetic properties of molecules: Magnetic
susceptibility. Types of magnetic behaviour- diamagnetism and
paramagnetism, Temperature and magnetic behaviour, Ferromagnetism
and antiferromagnetism-Temperature independent paramagnetism-
determination of magnetic moment using Guoy Balance-Applications of
magnetic measurements.
SYMMETRY:
 Symmetry helps us understand molecular structure, some chemical
properties, and characteristics of physical properties (spectroscopy) – used
with group theory to predict vibrational spectra for the identification of
molecular shape, and as a tool for understanding electronic structure and
bonding.

symmetry operation – an operation performed on an object which

leaves it in a configuration that is indistinguishable from, and
superimposable on, the original configuration.

symmetry elements – the points, lines, or planes to which a symmetry

operation is carried out.

Element Operation Symbol

Identity Identity E

Plane of symmetry Reflection in the plane σ

Inversion center Inversion of a point x,y,zto-x,-y,-z I

Proper axis Rotation by (360/n)° Cn

1. Rotation by (360/n)°
Improper axis 2. Reflection in plane perpendicular to
Sn
rotation axis
 Group means a set of entities related to each other by certain
rules a large number of groups can be visualized and each group has its own
set of group.
g-the order of group.
SUBGROUP:
This is a group which in a group if any selection or subset of the
element of a group satisfied the definition of a group.
g-the order of group. And s is the subgroup.
1. Plane of symmetry (σ):
 It is defined as an imaginary plane with in the molecule which divides
into two parts which are mirror images to each other.
 The plane of symmetry and the reflection operation on it are
represented as σ. The can be classified into three types.
i. The plane passing through the principal axis and one of the subsidiary
axis is called vertical plane, represented as σv.
ii. The plane perpendicular to the principal axis is called horizontal
plane, represented as σh.
iii. The plane passing through the principal axis but passing in between
two subsidiary axis is called dihedral plane, represented as σd.
e.g. a. H2O molecule posses two σv plane, in which one of the
σv passes through O and in between two H atoms (yz plane). The
other is the molecular plane passing through oxygen and two
hydrogen atoms.

2. Centre of symmetry (i):

 This is an imaginary point in the centre of the molecule, through
which the reflection of each atom can be carried out to result in its
coincidence with an equivalent atom.
 In other words, it any atom it the molecule is connected with the
centre of symmetry and extended equally on the other side , it meets
another equivalent point.
 The centre of symmetry is the element and the process of reflection
through it leading to an equivalent orientation is a symmetry
operation.
Example:
3. Axis of symmetry (Cn) :
 This is an imaginary axis passing through the molecule, over which
rotation can be carried out to take the molecule from one orientation
to another equivalent orientation.
 This is represented by Cn, where n is the order of the axis, i.e., the
number of times the equivalent orientation occurs on rotation through
360ₒ.

For example,

I. H2 is rotated 360ₒ, it leaves the molecule identical to the starting

structure of the molecule.
HA-HB → HB-HA → HA-HB.
II. BF3:
In case of BF3, the original planar BF3 molecule, the axis
passing through boron and perpendicular to the trigonal is an axis of
three fold symmetry (C3).

III. In H2O molecule the axis passing through oxygen atoms and in
between two hydrogen atoms has order 2 or its axis of two –fold
symmetry (C2). The molecule has to be rotation by 180ₒ to get
the equivalent orientation.

4. Rotation reflection axis or axis of improper rotation (Sn):

 It is an imaginary axis on which the molecule has to be rotated and
then reflected on a plane perpendicular to the rotation axis to attain an
equivalent orientation.
Example :
 5. Identity:(E):

All molecule possesses an identity element which does not do anything to

the molecule.

Point symmetry of molecule:

A short hand notation which gives information about the number of symmetry
operations possible on the molecule is called point symmetry.

1. Point group of H2:

➢ H-H is a linear structure.
➢ The following symmetry elements are present
Cn ,σv, σh, I (Linear with i)
➢ C∞ perpendicular to Cn
➢ The point group of H-H is D∞h.
2. Point group of CO2:
➢ It is a linear structure.
➢ The following symmetry elements are present
Cn ,σv, σh, I (Linear with i)
➢ The point group of O=C=O is D∞h.
3. Point group of H2O:
➢ In H2O molecule the axis passing through oxygen atom and in
between two hydrogen atoms has order 2 of its axis two fold-
symmetry C2. The molecule has to be rotated by 180 ₒ to get
equivalent orientation.
➢ It contains two σv plane of symmetry.
➢ So, it belongs to C2v point group i.e, (C2+2σv)=C2v.
4. Point group of NH3 :
➢ Ammonia belongs to C3v point group.
➢ It contains C3 as the rotational axis of the highest order and three
planes all containing C3 axis. In NH3, there are six symmetry
 operation possible E,C31,C32,3σv. The point group is (C3+3σv) =
C3v.
5. Point group of HCl:
➢ Linear without center of symmetry.
➢ The symmetry elements are E,C∞ and ∞ σv.
➢ It belongs to the C∞v point group.

MAGNETIC PROPERRTIES OF MOLECULES:

MAGNETIC FLUX:

A total lines of magnetic forces or the total magnetic field passing through an
object is called total magnetic flux. The lines of magnetic forces per unit area is
called the flux density, denoted by B. It is also called magnetic induction.

Intensity of magnetisation (I):

➢ This is also intensity of magnetism ot it is the magnetic moment for unit

volume in the direction of the field.
➢ If H is the strength of a magnetic field the relationship between H and I
given is by

I=kH

Where k is the volume susceptibility.

Magnetic permeability:

 Let two magnetic poles of strength m1 and m2 be separated by a distance r,

in any medium, then the force F acting between them is given by
 F = 1/μ = m1m2/r2
 Where μ is a constant called magnetic permeability. It is a constant for a
given medium and it gives a measure of the tendency of magnetic lines of
force to pass through the medium in comparision with air or vacuum. For air
or vacuum μ is taken as unity.

Magnetic susceptibility:
  If H is the strength of a magnetic field the product μH is called the magnetic
induction B in a given medium. This magnetic induction is related to the
intensity of magnetisation I (also called magnetic moment per unit volume)
induced by the magnetic field in that medium, as follows.
B=4пI + H ........................................(1)
 Therefore μH = 4пI + H
And μ = 4пI/H +I ..........................(2)
 The relationship between the field strength H and intensity of magnetisation
I, or magnetic moment per unit volume induced by the magnetic field in that
medium is defined by,
I α H; I=kH ; k=I/H ..........................(3)
Sub. (3) in (2) we get
kH=4п + I
where k (kappa) is called the volume susceptibility.
 For practical purposes we define another term mass susceptibility or specific
susceptibility (kai) X, which is defined as
X = k/P
Where P is the density of the medium.
k= xp..........................................(5)
sub. (5) in (4) we have

μ = 4пxp + I
x = μ-I/4пp

 Further molar magnetic susceptibility. Xm is given by Xm = xM

 Where M is the molecular weight of the compound. Magnetic susceptibility
is a measure of the tendency of a compound to be acted on by the magnetic
field or it is a measure of a compound to be affected by the magnetic field.

Diamagnetism:

Magnetic permeability, μ of a substance is a measure of the tendency of

magnetic lines of force to pass through that substance in comparisons with air or
vacuum. For air or vacuum μ is taken as unity. Thus it is clear that different
substance will have different permeabilities. Depending the values of
permeabilities we have three different types of substances.

i. Diamagnetic substances
ii. Paramagnetic substances and
iii. Ferro magnetic substances.
DIA MAGNETISM

➢ Diamagnetic substances are characterized by paired electrons—except in the

previously-discussed case of transition metals, there are no unpaired
electrons.
➢ According to the Pauli Exclusion Principle which states that no two identical
electrons may take up the same quantum state at the same time, the electron
spins are oriented in opposite directions.
➢ This causes the magnetic fields of the electrons to cancel out; thus there is
no net magnetic moment, and the atom cannot be attracted into a magnetic
field. In fact, diamagnetic substances are weakly repelled by a magnetic field
as demonstrated with the pyrolytic carbon sheet in the following Figure

Levitating pyrolytic carbon: A small (~6 mm) piece of pyrolytic graphite

levitating over a permanent neodymium magnet array (5 mm cubes on a piece of
steel). Note that the poles of the magnets are aligned vertically and alternate (two
with north facing up, and two with south facing up, diagonally).

How to tell if a substance is paramagnetic or diamagnetic?

The magnetic form of a substance can be determined by examining its electron

configuration: if it shows unpaired electrons, then the substance is paramagnetic; if
all electrons are paired, the substance is diamagnetic. This process can be broken
into four steps:
 1. Find the electron configuration
2. Draw the valence orbitals
3. Look for unpaired electrons
4. Determine whether the substance is paramagnetic (one or more electrons
unpaired) or diamagnetic (all electrons paired).

EXAMPLE

Are chlorine atoms paramagnetic or diamagnetic?

SOLUTION

Follow the four steps outlines above.

Step 1: Find the electron configuration

For Cl atoms, the electron configuration is 3s23p5

Step 2: Draw the valence orbitals

Ignore the core electrons and focus on the valence electrons only.

Step 3: Look for unpaired electrons

There is one unpaired electron.

Step 4: Determine whether the substance is paramagnetic or diamagnetic

Since there is an unpaired electron, [Math Processing Error] atoms are

paramagnetic (but weakly since only one electron is unpaired)
2. Paramagnetism :

The substance for which the magnetic permeability (is more than I) are
called paramagnetic. When these substance are placed in a magnetic field , lines
of force prefer to travel through the substance than through vacuum. That is , the
lines of force tend to coverage in the substance.(fig a). Because, of this , when a
paramagnetic substance is placed in a magnetic field it will set itself with its
length parallel to the field so that the lines of force travel the maximum distance
through the substance.

 Further we know that the magnetic susceptibility X is given by

X= μ-1 / 4пp

 For paramagnetic substance μ > 1. Therefore R will be positive. This is

because of the magnetic induction B is more within the substance than it
would be in a vacuum.
 Paramagnetic compounds contain one or more unpaired electrons in their
molecules.
 e.g Al (s), Mg(s), CuCl2 (s), NO (g) , Mn (s), MnS(s), UCl3 (s), O2 (g),
NiCl2 (s), CoI2(s), CdSO4 (s), FeSO4 (s), FeCl2 (s), MnSO4 .5H2O(s).
etc.,
3. Ferro magnetism :
 The substance for which the magnetic permeability is thousand times
more than that in paramagnetic substance are called ferromagnetic. That
is , when these substance are placed in a magnetic field, the intensity of
lines of force within the substance is thousand times more than that in
paramagnetic substances. E.g, Fe,Co, Ni and their corresponding alloys.
 Ferromagnetic substances are abnormal in their behaviour. The
susceptibility decreases with increase in temperature and above a certain
critical temperature called Curie point or Curie temperature they become
paramagnetic. Above this Curie temperature no ferromagnetism is
observed.
4. ANTIFERRO MAGNETISM:
✓ In materials that exhibit antiferromagnetism, the magnetic moments of
atoms or molecules, usually related to the spins of electrons, align in a
regular pattern with neighboring spins (on different sublattices) pointing in
opposite directions.
✓ This is, like ferromagnetism and ferrimagnetism, a manifestation of ordered
magnetism.
 ✓ Generally, antiferromagnetic order may exist at sufficiently low
temperatures, vanishing at and above a certain temperature, the Néel
temperature (named after Louis Néel, who had first identified this type of
magnetic ordering). Above the Néel temperature, the material is typically
paramagnetic.

Antiferromagnetic ordering

PROPERTIES:

• Synthetic antiferromagnets (often abbreviated by SAF) are artificial

antiferromagnets consisting of two or more thin ferromagnetic layers
separated by a nonmagnetic layer.
• Due to dipole coupling of the ferromagnetic layers results in antiparallel
alignment of the magnetization of the ferromagnets.
• It is not possible to construct a network where each spin is surrounded by
opposite neighbour spins.
• . This type of magnetism is sometimes called speromagnetism.

Applications:

• Antiferromagnets are very interesting in nature but do not have a wide range
of applications as other magnetic materials do. This is due to their lack of
spontaneous magnetization.
• However because their structural magnetization is closely related to
ferrimagnets they can be used along with ferromagnets to test theoretical
models used to explain ferrimagnetism.
• The lack an overall magnetic moment which makes them suitable for
providing magnetic reference points in magnetic sensors since the structure
of antiferromagnets is not sensitive to external fields.
• A growing theory and source of research on Antiferromagnets is their
contribution to superconductivity. There are materials that exhibit
antiferromagnetic and ferromagnetic transition states.
Comparison between paramagnetism and diamagnetism/ paramagnetic
substance and diamagnetic substances.

Property Paramagnetism/ Diamagnetism /

paramagnetic substance diamagnetic substance

Similarity

Dependence on Independent Independent

magnetic field
intensity

Differences

1. Magnetic >1 <1

permeability μ
(more permeable to magnetic (less permeable)
lines of force than vacuum)

2. Value of Large positive Small negative

magnetic
susceptibility
X
3. Origin Angular momentum Electronic charge

(electron spin )

4. Dependence on Decreases with an increase in Independant

temperature temperature

Comparison between paramagnetism and ferromagnetism/ paramagnetic

substance and ferromagnetic substances.

Property Paramagnetism/ Ferromagnetism/

paramagnetic ferromagnetic
substance substance
 Similarities

1. Dependence on Dependent Dependent

temperature
2. Sign of X Positive Positive

Differences

1. Value of magnetic Large Very large

susceptibility X
2. Origin Electronic charge Dipole exchange

3. Dependence on Independent Dependant

magnetic field
intensity

Determination of magnetic susceptibility:

Guoy balance method

A schematic diagram of the Guoy balance is given in fig. 1.

  In one arm of the balance a long cylinder C, is suspended. The lower
end of the cylinder lies in the middle of the two poles of an
electromagnet. A pan is suspended in other arm of the balance.

Experiment :

Application to structural problems:

 We have seen that some substances are paramagnetic because they

have one or more unpaired electrons: some substances are diamagnetic
because they have no unpaired electrons in their molecules. Since organic
compounds have no unpaired electrons in general, they are diamagnetic.
Inorganic compounds may or not have electrons in their molecules.
 QUESTION BANK
2marks
1. State symmetry operation (apr,2014& nov2015)
2. Define nano particles (apr,2014)
3. GIve the symmetry point groups & symmetry operations ofNH3 molecule(nov,2014)
4. List any two paramagnetic compound.(nov,2015)

5marks

1. Explain symmetry elements (nov,2014)

2. Write a note on diamagnetism &paramagnetism(nov,2014)
3. Explain elements of symmetry (nov,2014)
4. Write a note on nano material (nov,2013)
5. Write short note on ferromagnetism (apr,2017& nov,2018)
6. Identify the various symmetry elements present in water molecule and deduce its point
groups(nov,2019)

10marks

1. Describe Guoy;s method of determining magnetic moment (apr,2014)

2. Define magnetic susceptibility. How is it experimentally measured by Guoy;s
method(apr,2018)
3. Describe the construction working and applications of Guoy;s balance(nov,2019)