UNIT-1

BASICS CONCEPT OF ORGANIC

CHEMISTRY

Introduction:-

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Organic chemistry is the chemistry of carbon, an element that forms strongchemical bonds to other
carbon atoms as well as to many other elements like hydrogen, oxygen,nitrogen, and the halogens.
Because of its versatility in forming covalent bonds, more than a million carbon compounds are
known. Many are composed of only carbon and hydrogen, collectively called  hydrocarbons. Most
hydrocarbons are obtained from petroleum. Carbon always forms four covalent bonds (four shared
pairs of electrons) that may be present as four single bonds per atom, or two single bonds and one
double bond, or one single bond and one triple bond. With the ability of carbon to bond in different
ways, an important part of organic chemistry concerns the structure of compounds. For example, three
organic compounds have the identical molecular formula, C 5H 12, but they are different because each
connects the five carbon atoms together in a different arrangement. Compounds with the same
formula but different structures are called isomers. In organic chemistry, both structure and
composition are of prime importance.

Electron Displacement Effect :-

The organic reactions are not possible until and unless some charge or polarity is
developed on the reactants and they get attached to each other. This happens only when
there is a displacement of electrons due to which polarity develops within the reactant
molecules. Such effects involving the displacement of electrons in the substrate
(reactant) molecules are referred to as electron displacement effects .
These lead to a number of effects which are as follows:

1. Inductive effect
2. Electromeric effect
3. Resonance or Mesomeric effect
4. Hyperconjugation effect. Ki

Inductive Effect :-
The movement of electrons along the chain of the carbon due to the presence of polar
covalent bond at its one end. It is also known as Permanent Effect.

Types of inductive effect

 Negative inductive effect or -I effect
 Positive inductive effect +I effect

Negative inductive effect or -I effect.

When an electronegative atom, such as a halogen, is introduced to a chain of atoms (generally
carbon atoms), the resulting unequal sharing of electrons generates a positive charge which is
transmitted through the chain.

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 This causes a permanent dipole to arise in the molecule wherein the electronegative
atom holds a negative charge and the corresponding effect is called the electron-withdrawing
inductive effect, or the -I effect.

Positive inductive effect +I effect

When a chemical species with the tendency to release or donate electrons, such as an alkyl
group, is introduced to a carbon chain, the charge is relayed through the chain and this effect
is called the Positive Inductive Effect or the +I Effect.

Applications of Inductive effect:

Inductive effect is useful in explaining the strength of some organic acids and bases.

a) Effect of substituent on the acid strength of aliphatic acids.

HCOOH > CH 3COOH > (CH 3 ) 2CHCOOH

Reason : Acidic strength decreases as +I effect of the alkyl group increases.

b) O 2NCH 2COOH > FCH 2COOH >CICH 2COOH >BrCH 2COOH> ICH 2COOH >
CH 3COOH

Reason : Acidic strength decreases as -I effect of the group or halogen decreases.

 Electromeric Effect:-
The instantaneous formation of a dipole in the molecule of an organic compound due to the complete transfer
of shared pi electron pairs to one of the atoms under the influence of an attacking reagent is referred to as the
Electromeric effect.

This effect can be observed in organic compounds that contain at least one multiple bond. When the
atoms participating in this multiple bond come under the influence of an attacking reagent, one pi
bonding pair of electrons is completely transferred to one of the two atoms.
The electromeric effect is a temporary effect that remains as long as the attacking reagent is present
and exposed to the organic compound. Once this attacking reagent is removed from the system, the
molecule that was polarized goes back to its original state.

Types of electromeric effect

The electromeric effect can be broken down into two types. This classification is done based on the
direction in which the electron pair is transferred.

 Positive electromeric effect +E effect

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  Negative electromeric effect -E effect

Positive Electromeric effect +E effect

This effect occurs when the electron pair of the pi bond is moved towards the attacking
reagent. The +E effect can be observed in the addition of acid to alkenes. The attacking reagent
attaches itself to the atom which obtained an electron pair in the transfer.
The +E effect is generally observed when the attacking reagent is an electrophile and the pi
electrons are transferred towards the positively charged atom. An example where the +E effect
occurs is the protonation of ethene which is illustrated below.

Negative Electromeric effect -E effect

This effect occurs when the electron pair of the pi bond is moved away from the
attacking reagent. The attacking reagent attaches itself to the positively charged atom in the
molecule, i.e. the atom which lost the electron pair in the transfer.
The -E effect is generally observed when the attacking reagent is a nucleophile and
the pi electrons are transferred to the atom which the attacking reagent will not bond with. An
example where the -E effect occurs would be the addition of nucleophiles to carbonyl
compounds as illustrated below.

 Mesomeric effect
The polarity developed between atoms of a conjugated system by the electron transfer or
pi–bond electron transfer is known as the Mesomeric effect. In simple terms, we can describe
mesomeric effect occurs when π electrons move away from or towards a substituent group in a
conjugated orbital system.

The mesomeric effect can be subdivided into two types:

1. +M effect
2. -M effect
Positive mesomeric effect +M effect

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 When the electrons or the pi electrons are transferred from a particular group towards a
conjugate system, thus increasing the electron density of the conjugated system then such a
phenomenon is known as +M effect or positive mesomeric effect.

Example 1:

 For the +M effect, the group should have either a lone pair of electrons or should have a
negative charge.
 The +M effect gives negative charge to the conjugate system or it can be said that the
electron density increases on the conjugate system due to this. These conjugate systems show
more reactivity towards electrophiles and less reactivity towards a nucleophile.
Group showing +M effect
–NH, –NH2,–NHR, –NR2, – O, – OH, –OR, – F, – Cl, –O–COR, – NHCOR, –SH, – SR etc.

Negative mesomeric effect -M effect

When the pi-bond electrons are transferred from the conjugate system to a particular group
thus the electron density of the conjugate system is decreased, then this phenomenon is known as
negative mesomeric (–M) effect.

Example 1:

Example 2:

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  For –M effect, the group should have either a positive charge or should have a vacant orbital.
 –M effect makes the compound more reactive towards a nucleophile as it decreases the
electron density in the conjugate system and at the same time it is less reactive towards
electrophile due to same reasons.
The group which shows –M effect include :
–NO2, –CN, –COX, –SO3H, – CHO, –CONH2, –COR, –COOH, –COOR etc.

Resonance Effect
If two or more than two different structures can be drawn for a molecule or ion that are
having the same arrangement of atomic nuclei but differ in the distribution of electrons, this effect
can be termed as the resonance effect.

The different structures are called contributing or resonating structures. Not all the properties
of the molecule or ion are shown by the single resonating structure but the actual structure is a
resonance hybrid of all the resonating structures.

Understanding Resonance
There is charge transfer or electron migration from one part of the compound to the other
part. During this charge transfer, energy is released from the conjugate system due to which the
stability of the compound is enhanced.

This results in the formation of different structures. These structures are known as resonating
structures. These resonating structures have the same arrangement of atoms but only the charge/
electron distribution is different.

Although this effect is completely hypothetical it helps to understand and explain various
chemical mechanisms and reactions.

Characteristics of Resonance

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 i. In resonance effect, only electrons are delocalised not atoms.

ii. The number of lone pair electrons or number of unpaired in all resonating structures must be
equal.

iii. All the resonating structures must possess the same energy.

iv. This is a permanent effect.

v. All the resonating or canonical structures must conform to Lewis structures.

Resonance Energy
The difference between the calculated energies (heat of hydrogenation) and the experimental energy
which contributes to the stabilization of a conjugated compound, is known as the resonance or
delocalization energy. If there is more resonance energy better is the resonance stabilization.

 Hyperconjugation
Hyperconjugation effect is a permanent effect in which localization of σ electrons of C-H bond of an
alkyl group directly attached to an atom of the unsaturated system or to an atom with an unshared p
orbital takes place.

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 From the given figure, we observe that one of the three C-H bonds of the methyl group can align in
the plane of the empty p orbital and the electrons constituting the C-H bond in a plane with this p
orbital can then be delocalized into the empty p orbital.

We also observe that the hyperconjugation stabilizes the carbocation as it helps in the dispersal of
positive charges. Thus, we can say that the greater the number of alkyl groups attached to a
positively charged carbon atom, the greater is the hyperconjugation interaction and stabilization of
the carbonation. The relative stability on the basis of hyperconjugation is given as,

1.2- Nomenclature Of Organic Compound

The formation of a systematic name for an organic compound requires first selection and
then naming of a parent structure. This basic name may then be modified by prefixes, infixes
and in the case of a parent hydride, suffixes which convey precisely the structural changes
required to generate the compound in question from the parent structure. In contrast to such
systematic names, there are traditional names which are widely used both in industry and
academic circles. Examples are acetic acid, benzene and pyridine. Therefore when they meet
the requirements of utility and when they fit into the general pattern of systematic
nomenclature, these traditional names are retained.
A major new principle is elaborated and the concept of preferred IUPAC names is
developed and systematically applied. Up to now, the nomenclature developed and
recommended by IUPAC has emphasized the generation of unambiguous names in accord
with the historical development of the subject. In 1993 due to the explosion in the circulation
of information and the globalization of human activities it was deemed necessary to have a
common language that would prove important in legal situations with manifestations in
patents, export import regulations, environmental health and safety information etc.

There are two systems of naming :

1. Trivial system
2. IUPAC system

Trivial Nomenclature System

The Trivial Nomenclature system involves a non-systematic approach to the naming of
organic compounds. There do not exist any particular collection of rules for writing the trivial
naming of compounds. Names of organic compounds are simplified via this system. Examples of this
include phenol, acetic acid, and toluene. The compounds named via trivial nomenclature often have

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much shorter and simpler names than the corresponding IUPAC nomenclature of the same
compounds. For this reason, this system is still not obsolete today.

Common or Trivial Names of Some Organic Compounds

IUPAC Nomenclature System

IUPAC nomenclature of organic compounds refers to the systematic approach taken for the
nomenclature of organic compounds as per the recommendation of the International Union of
Pure and Applied Chemistry (often abbreviated to IUPAC).

The necessity for such a systematic approach arose due to the sheer quantity of new discoveries of
organic compounds which made the trivial nomenclature of organic compounds highly
inconvenient.However, the IUPAC nomenclature guidelines are not always followed by chemists
since some compounds have very long and extremely tedious names as per the IUPAC nomenclature
guidelines.

According to the Guidelines set by IUPAC, the nomenclature of compounds must follow
these steps:

1. The Longest Chain Rule : The parent hydrocarbon must be identified and subsequently
named. The parent chain belonging to the compound in question is generally the longest
chain of carbon atoms, be it in the form of a straight chain or a chain of any other shape.
2. The Lowest Set of Locants : The carbon atoms belonging to the parent hydrocarbon chain
must be numbered using natural numbers and beginning from the end in which the lowest
number is assigned to the carbon atom which carries the substituents.
3. Multiple instances of the same substituent : Prefixes which indicate the total number of
the same substituent in the given organic compounds are given, such as di, tri, etc.
4. Naming of different substituents : In the organic compounds containing multiple
substituents, the corresponding substituents are arranged in alphabetical order of names in the
IUPAC nomenclature of organic compounds in question.
5. The naming of different substituents present at the same positions : In the scenario
wherein two differing substituent groups are present at the same position of the organic
compound, the substituents are named in ascending alphabetical order.

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 6. Naming Complex Substituents : Complex substituents of organic compounds having
branched structures must be
Substituent Prefix named as substituted alkyl
group groups whereas the carbon
which is attached to the
‐F Fluoro substituent group is numbered
‐Cl Chloro as one. These branched and
‐Br Bromo complex substituents must be
‐NO2 Nitro written in brackets in the
IUPAC nomenclature of the
‐CH3 Methyl corresponding compounds.
-C2H5 Ethyl
The format of the IUPAC Name of
the Compound can be written as:
Prefix + Word root + Primary suffix + Secondary suffix

Prefix
Prefixes are added prior to the root of the compounds IUPAC nomenclature. Prefixes are very
useful since they indicate the presence of side chains or substituent groups in the given organic
molecule. These prefixes also offer insight into the cyclic or acyclic natures of the compounds in
question.

Thus, prefixes in IUPAC nomenclature can be broadly classified into primary prefixes and
secondary prefixes

Primary Prefixes  Indicate the cyclic or acyclic nature of the given compound. The prefix
‘cyclo’ is used for cyclic compounds.

Secondary Prefixes  Indicate the presence of side chains or substituent groups. An example
of these types of prefixes would be the ‘CH3’ group, which is called the methyl group.

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Thus, prefixes in IUPAC nomenclature can be broadly classified into primary prefixes and secondary
prefixes

Word Root
The Word root indicates the total number of carbon atoms present in the longest carbon chain
belonging to the compound. For example:-

Suffix
The suffix in IUPAC nomenclature is usually a functional group belonging to the molecule
which follows the root of the name. It can be further divided into the following types.

A Primary Suffix , which is written immediately after the word root as in the case of
alkanes, where the suffix is ‘ane’.

A Secondary Suffix,  which is generally written after the primary suffix is written. For
example, compounds having an alkane and alcohol group attached to it will be named as an alkanol,
with ‘ol’ being the secondary suffix for the alcohol group.

No. of carbon word root

atoms
1 Meth-
2 Eth-
3 Prop-
4 But-
5 Pent-
6 Hex-
7 Hept-
8 Oct-
9 Non-
10 Dec-

Example of some IUPAC nomenclature :

1)

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 5-(2-Ethylbutyl)-3,3-dimethyldecane

Step 1. Longest chain with more side chain is chosen. Since there are 10 C. So, Decane will
be root word
Step 2. Branched is name as 2-Ethylbutyl using the same procedure
Step 3. Name is written considering alphabet order of the side chain name
Finally, the Name is :
5-(2-Ethylbutyl)-3,3-dimethyldecane

2)

3-Ethyl-5-methylheptane

Step 1. Longest chain with more side chain is chosen. Since there are 7 C. So, heptane will be
root word
Step 2. Now two substituents are found in equivalent positions, the lower number is given to
the one coming first in the alphabetical listing
So, it is 3 -ethyl and 5 -methyl
Step 3. Name is written considering alphabet order of the side chain name:
3-Ethyl-5-methylheptane

IUPAC nomenclature of Functional Groups

The longest chain of carbon atoms containing the functional groups is numbered in such a
way that the functional group attached to the carbon atom gets the lowest possible number in the
chain. The name of the compound is decided by choosing the IUPAC suffix as below:

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 There are few functional group does not have any suffix, so they are treated as substituents
only
Class Structure IUPAC prefix
Halides -Cl or -BR or -I Halo
Ethers R-O-R Alkoxy

Poly-functional compounds are compounds which are having more than one functional group. For
naming poly functional compounds, one of the functional groups is chosen as the principal functional
group and the compound is then named on that basis. The remaining functional groups, which are
subordinate functional groups, are named as substituents using the appropriate prefixes. The choice
of principal functional group is made based on order of preference. The order of decreasing priority
for some functional groups is:
-COOH, –SO3H, -COOR (R=alkyl group), COCl, -CONH2 , -CN,-HC=O, >C=O, -OH, -NH2 ,
>C=C, -C≡C-

Here is the list with suffix and prefix both for poly-functional compound :-

Nomenclature of Substituted Benzene Compounds

Benzene is a hydrocarbon with the chemical formula C6H6. It has 6 carbon atoms joined in a
ring and has 1 hydrogen atom attached to each of the carbon atoms. By replacing one or more of the
hydrogen atoms with some functional group, we get several benzene compounds. While naming the
substituted benzene compounds, we prefix the name of the substituent to the word benzene. In this
article, we will learn the IUPAC nomenclature of the substituted benzene compounds.

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Mono-substituted Benzene Compounds

For the benzene compounds consisting of a single substituent, we simply prefix the name of
the substituent to benzene. Some examples along with their common names are listed below.

METHYLBENZENE OR TOLUENE HYDROXY BENZENE OR PHENOL

Di- substituted Benzene Compounds

When there are two substituents present in the compound, we
number each of the carbon atoms in such a manner that the substituents are attached to the lowest
possible numbered carbon atom.

1,3-DINITROBENZENE is the name of the following compound. Naming it as 1,5-

dinitrobenzene is incorrect because the carbon atom would not be numbered lowest.

1,3-DICHLOROBENZENE

Markovnikov Rule

when an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl halide,
the hydrogen adds to the carbon of the alkene that has the greater number of hydrogen
substituents, and the halogen to the carbon of the alkene with the fewer number of hydrogen
substituents

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 To simplify the rule, it can also be stated as – “Hydrogen is added to the carbon with
the most hydrogens and the halide is added to the carbon with least hydrogens”.
An example of a reaction that observes Markovnikov’s rule is the addition of hydrobromic
acid (HBr) to propene, which is shown below.

Mechanism :-
CH3 – CH= CH2 + HBR CH3 – CH – CH3

BR

STEP 1:- Generation of free Radical

H – BR H+ + BR-

STEP 2:- Attack of H+ on alkene and formation of carbocation.

CH3 – CH2 – CH2 (less stable) [1⁰ carbocation]

CH3 – CH = CH2 + H+

CH3 – CH – CH3 (more stable) [2⁰ carbocation]

Here, the secondary carbocation is more stable than primary carbocation therefore processed the
reaction at faster rate

1.3- Peroxide Effect

When HBr is added to unsymmetrical alkenes in the presence of peroxide, 1-
bromopropane is formed contrary to 2-bromopropane (according to Markovnikov’s rule).
This reaction is better known as anti-Markovnikov addition or Kharash effect after the
name of M. S. Kharash who first observed it. This reaction is also known as Kharash effect
or peroxide effect.
Anti Markovnikov addition is also an example of addition reaction of alkenes which is an
exception to the Markovnikov’s rule. It is one of the few reactions following free radical
mechanism in organic chemistry in place of electrophilic addition as suggested by
Markovnikov. This reaction is observed only with HBr, not with HCl or HI.

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 Mechanism of Anti Markovnikov addition
Anti Markovnikov addition reaction is found to follow a free radical mechanism. The
peroxide compound involved helps in the generation of free radicals. A general mechanism of
anti-Markovnikov addition reaction is discussed below:

1) Generation of free radical through homolytic cleavage of peroxide compound.

2) Attack of generated free radical on hydrogen halide to form halide radical through
hemolysis
3) Attack of generated halide radical on alkene molecule to form alkyl radical through
hemolysis.
4) Attack of a generated alkyl radical on hydrogen halide to form alkyl halide through
homolytic cleavage of hydrogen halide bond.

1.4- Saytzeff Rule :-

During Elimination reaction more than one alkene is possible than that alkene will be
preferred which is more alkylated.

Examples:

1. Dehydrohalogenation of 2-Bromobutane
.

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When 2-

bromobutane undergoes a dehydrohalogenation reaction it gives two products 1-butene and 2-butene.
Out of these two, 2-Butene is a major product since it is highly substituted and more stable

Mechanism of Saytzeff Rule:-

Step 1:
Sulfuric acid ionizes to give a proton
H2SO4 → H+ + HSO4–
Step 2:
Proton formed in step 1 reacts with OH group and forms OH2+ and loss of water gives positive
charge on the carbon atom and forms a tertiary carbocation.

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Step 3:
Removal of hydrogen adjacent to the tertiary carbocation gives alkene (Double bond formation).
Three alkene formations are possible as shown below,

1.5- Directive influence of functional group in mono-

substituted benzene :-
If mono-substituted benzene is subjected to further substitution then, the position of incoming
electrophile is determine by the functional group which is already present.

1. Ortho and Para directing group :- Ortho: minor

Para: major
These are the groups which directes the incoming electrophile at ortho and para position by
increasing the electron density at these position’s due to the resonance.

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 These groups are also called as ring activating group.

2. Meta directing group :-

These are the group which directes the electrophile toward Meta Position. These groups decreases
electron density at ortho and para position so, the electrophiles are directed to Meta position.

These groups are also called as ring deactivating group.

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UNIT-2
BASICS CONCEPT OF INORGANIC
CHEMISTRY

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 The word organic refers to the compounds which contain the carbon atoms in it. So the branch of
chemistry that deals with the study of compounds, which does not consist of carbon-hydrogen atoms
in it, is called ‘INORGANIC CHEMISTRY.’ In simple words, it is opposite to that of Organic
Chemistry. The substances which do not have carbon-hydrogen bonding are the metals, salts,
chemical substances, etc.

 Periodic trends of Element:

 Metallic and non- metallic character :-
Metallic Character: Tendency of donate electron.
Non-metallic Character: Tendency to gain electron.

Periodic Trends
1. On moving from top to bottom tendency to donate electron increases and tendency to gain
electron decreases so, metallic character increases and non-metallic character decreases.
2. On moving left to right tendency to donate electron decreases and tendency to gain electron
increases. So, metallic character decreases and non-metallic character increases.

 Oxidising and Reducing character :-

Oxidising Character: Tendency to oxidize others by reducing itself. Loss of electron:
Oxidization
Tendency to gain electron.
Gain of electron:
Reduction
Reducing Character: Tendency to reduce other by oxidizing itself.
Tendency to loose electron.

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Periodic Trends
1. On moving top to bottom in a group tendency to loose electron increases and tendency to gain
electron decreases. So, reducing character increases and oxidizing character decreases.
2. On moving left to right in a period tendency to loose electron decreases and tendency to gain
electron increases. So, reducing character decreases and oxidizing character increases.

 Nature of Oxide :-
Metallic oxide: Basic
Non-metallic oxide: Acidic

Periodic Trends
1. On moving top to bottom in a group metallic character increases and non-metallic character
decreases therefore, oxides become more basic and less acidic.
2. On moving left to right in a period metallic character decreases and non-metallic increases
therefore, oxides become less basic and more acidic.

 Atomic Radii :-
The distance from the centre of the nuclear to the outermost shell is called atomic radius.
Atomic radii is expressed in three different form:-
1. Covalent radius
2. Vanderwaals radii
3. Metallic radii

1. Covalent Radius:- The half of the distance between the centre of the
nucleus of the two atom bonded by single covalent bond.

2. Van der waals Radii:-Half of the distance between the nuclei of two
similar adjacent atom belonging to the two neighboring molecule is called
Vanderweals radius.

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 3. Metallic Radii:- Half of the distance between the centre of the nuclei of
the two adjacent atom in the metallic crystal.

Periodic Trends
1. On moving from top to bottom in a group atomic size increases due to addition of new shell.
2. On moving from left to right in a period atomic size decreases due to increase in nuclear
charge so electron are pulled towards the nucleus.

 Ionization enthalpy:-
The minimum energy required to remove the electrons from the isolated gaseous atom is called
ionization.

Factors affecting the ionization enthalpy

Atomic size:- with the increase in size ionization enthalpy decreases. This is because with
increase in size nuclear attraction to the outermost electron decreases and removal of electron
becomes easy.

Nuclear charge:- with the increase in nuclear charge nuclear attraction to the outermost electron
also increase so removal of electron become difficult and hence ionization enthalpy increases

Screening or shielding effect:- in multi electronic atoms, the inner electron act as screen
between nucleus and the outermost shell , so the electron present in outermost shell does not
experience complete nuclear attraction so, the removal becomes easier and hence ionization
enthalpy decreases.

Penetration effect:- it is difficult to remove the electron from the orbital which are more
penetrated towards the nucleus.

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 S>P>D>F

Greater the penetration more will be the ionization enthalpy.

Periodic Trends
1. On moving from top to bottom in a group atomic size increases and nuclear attraction to the
electron decreases so, the removal of electron becomes easy and hence I.E. decreases.
2. On moving from left to right in a period nuclear charge increases so we require more energy
to remove the electron hence, I.E. increases but some irregularities are there due to
symmetrical electronic configuration.

Symmetrical electronic configuration:-

We know that half filled and completely filled orbitals are more stable and removal of electron is
difficult from these orbitals hence, they have more ionization enthalpy.

 Electron gain enthalpy:-

The enthalpy change when extra electron is added to the isolated gaseous atom.

Easy the gain of electron more energy will released and del.egH will be –ve.

When energy will be given to remove the electron then del.egH will be +ve.

Factors affecting electron gain enthalpy:-

Atomic size:- with the increase in size nuclear attraction decreases so, gain of electron become
difficult hence, electron gain enthalpy becomes less –ve.

Nuclear charge:- with the increase in nuclear charge the gain of electron becomes more easy so
delegH become more –ve

Periodic trends
On moving from top to bottom in a grouo atomic size increases, gain of electron becomes difficult
so, electron gain enthalpy becomes less –ve.

On moving from left to right in a period gain of electron is easy so, electron gain enthalpy will be
more –ve.

 S, P, D and F Block Element:-

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S block element:-
In modern periodic table element of group 1 and 2 are called S-block element.

General electronic configuration:- ns1-2

Characteristics:-
1. All the element are soft metal.
2. They have low melting and boiling point.
3. Most of them impact characteristics colors to the flame.
4. The S-block element are good reducing agent.
5. All are good conductor of heat and electricity.

P-block element:-
In modern periodic table element of group 13 to 18 are P-block element because in these element last
electron enters into the P-subshell of outermost shell.

General electronic configuration:- ns2np1-6

Characteristics:-
1. P block element includes the both metal and non metals.
2. The compound of these element mostly forms covalent bond or compound.
3. Most of the element show variable oxidation state.
4. Elements of group 18 are called nobel gases, they are very least reactive.
5. Elements of group 17 are called halogen.(salt forming)
6. Elements of group 16 are called chalcogen(ore forming)
7. Elements of S block and P block together called Representative elements.

D-block element:-
It includes those element in which last electron enters in D orbital, since D orbital has max. 10
electrons.

General electronic configuration:- (n-1)d1-10ns1-2.

Characteristics:-
1. They are all metals with high melting and boiling points.
2. They form coloured compound.
3. They have mostly paramagnetic in nature.
4. A large no. of D block element are catalyst.

F-block element:-

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 In this block the filling of the last electron takes place in the (n-2) f-subshell(also called
antepenultimate sub shell ) however, (n-1)d sub shell may contain zero or one electron while ns sub
shell is having two electrons.

General electronic configuration:- (n-2)f1-14(n-1)d0-1ns2.

Characteristics:-
1. They are heavy metal.
2. They have generally high melting and boiling point.
3. They show variable oxidation state.
4. The compound of these elements are coloured.
5. Atomic no.-58-71 are called lanthanoid series.
6. 90-103 is called actinoid series.

 Concept of hybridisation:-
Hybridisation:-Intermixing of orbitals of same atom having small energy difference in order to
redistribute their energy and form same no. of new orbitals having equivalent energy and shape.

Arrangements:-

 Linear
 Trigonal planer
 Tetrahedral
 Trigonal bipyramidal
 Octahedral

Types of hybridization:-

1. SP hybridization:-
One S-orbital and one P-orbital hybridized and form two sp hybrid orbitals.

SP hybrid orbital:

Shape- Linear

Bond Angle- 180⁰

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S character- 50%

P character- 50%
Example of SP hybridization:-

 All compounds of beryllium like BeF2, BeH2, BeCl2

 All compounds of carbon-containing triple bond like C2H.
2. SP2 hybridization:-
One S-orbital and two P-orbital get hybridized and form three SP2 hybrid orbital.

SP2 Hybrid orbital:

Shape- Trigonal planer

Bond Angle- 120⁰

S character- 33.3%

P character- 66.7%

Example of SP2 hybridization:-

 All the compounds of Boron i.e. BF3, BH3

 All the compounds of carbon-containing a carbon-carbon double bond, Ethylene (C2H4).

3. SP2 hybridization:-
One S-orbital and three P-orbital get hybridized and form four SP3 hybrid orbitals.

 These are directed towards the four corners of a

regular tetrahedron and make an angle of 109°28’ with one
another.
 The angle between the sp3 hybrid orbitals is 109.280
 Each sp3 hybrid orbital has 25% s character and 75% p
character.
 Example of sp3 hybridization: ethane (C2H6), methane.

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 4. SP3D hybridization:-
One S-orbital three P-orbital and one D-orbital get hybridized and form five SP3D hybrid
orbitals

 The mixture of s, p and d orbital forms trigonal bipyramidal

symmetry.
 Three hybrid orbitals lie in the horizontal plane inclined at an
angle of 120° to each other known as the equatorial orbitals.
 The remaining two orbitals lie in the vertical plane at 90 degrees
plane of the equatorial orbitals known as axial orbitals.
 Example: Hybridization in Phosphorus pentachloride (PCl5).

5. SP3D2 hybridization:-
One S-orbital three P-orbital and two D-orbital gey hybridized and form six SP3D2
Hybrid orbital.

 These 6 orbitals are directed towards the

corners of an octahedron.

 They are inclined at an angle of 90 degrees

to one another.

 VSEPR THEORY:- (Valence Shell Electron pair Repulsion

Theory)
In a covalent molecule the central atom is surrounded by the shared pair or lone pair of electron,
these electron pair repel one another and the molecule tends to become unstable. According to
VSEPR theory the electron pair around the central atom arrange themselves at max. distance in order
to minimize the repulsion.
Main features of VSEPR Theory:-
1. The shape of molecule depends upon the no. of electron around the central atom.
2. Electron pair around the central atom tends to repel one another.
3. Electron pair in space tends to occupy such position that they are at max. distance.

Limitation of VSEPR Theory:-

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  This theory fails to explain isoelectronic species (i.e. elements having the same
number of electrons). The species may vary in shapes despite having the same number
of electrons.
 The VSEPR theory does not shed any light on the compounds of transition metals.
The structure of several such compounds cannot be correctly described by this theory.
This is because the VSEPR theory does not take into account the associated sizes of
the substituent groups and the lone pairs that are inactive.
 Another limitation of VSEPR theory is that it predicts that halides of group 2 elements
will have a linear structure, whereas their actual structure is a bent one.

 Writing Electronic Configuration:-

 Orbital: The three dimensional space around the nucleus where probability of finding the
electron as maximum. One orbital can contain max. 2 electron with opposite spin.

 Sub shell:

Sub shell Max. electron Orbitals

S 2
P 6
D 10
F 14
 Aufbau Principal:
According to this principal electron are filled in various subshell in order of their increasing
energy.
According to this principle, electrons are filled in the following order: 1s, 2s, 2p, 3s, 3p, 4s,
3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p…

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 Hund’s Rule:
According to this rule pairing of electron in a sub shell does not take place until each orbitals
are singly occupied.

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 UNIT-3
BASICS CONCEPT OF PHYSICAL
CHEMISTRY

Physical chemistry is the branch of chemistry devoted to the study of the behavior of matter at an
atomic or molecular level. It also involves the study of the properties of substances at different
scales, from the macroscopic scale which includes particles that are visible to the naked eye, to the
subatomic scale involving extremely small subatomic particles such as electrons.

Physical chemistry differs from other branches of chemistry because it employs the concepts and
principles of physics to understand chemical systems and reactions.

 Different Concentration Terms:-

Concentration:
It is the amount of solute present in given amount of solvent or solution.

Various ways to express the concentration:

 Strength
 Mass %
 Volume %
 Molarity

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 Molality
 Normality
 Mole fraction

1. Strength: Mass of solute in gram per liter or dm3 of the solution is called
strength.
Strength= mass of solute in gm/volume of solution in L
2. Mass %: It is no. of parts of mass of solute or solvent per 10 parts by mass of
the solution.
Suppose,
In a solution – Mass of solvent= WA
Mass of solute= WB
Then,
WA
Mass % of A = WA+WB ×100

WB
Mass % of B= WA+WB ×100
3. Volume %: It is no. of parts by volume if solute or solvent per 100 parts by
volume of its solution.
Suppose,
In a solution- volume of solvent=VA
Volume of solute=VB
Then,
VA
Volume% of A = VA +VB ×100

VB
Volume % of B = VA +VB ×100
4. Molarity: It is defined as the no. of moles of solute present in 1 liter of
solution.
No . of moles of solute
Molarity= vol. of solution(¿ L)
5. Molality: number of moles of a given substance per kilogram of solvent.
No . of moles of solute
Molality = mass of solvent (¿ Kg)

6. Mole fraction: Mole fraction of a component in a solution is defined as the

ratio of no. of moles of that component to the total no. of moles present in
solution.

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 na
Mole fraction of A (XA) = na+nb

nb
Mole fraction of B (XB) = na+nb

 Gaseous Law:-
 Boyle’s Law
 Charle’s Law
 Gay lussac’s Law
 Avogadro’s Law
Boyle’s Law:-
Boyle’s law states the relation between volume and pressure at constant
temperature and mass. It states that under a constant temperature when the
pressure on a gas increases its volume decreases. In other words according
to Boyle’s law volume is inversely proportional to pressure when the
temperature and the number of molecules are constant.

1
p ∝  V
1
p = k  V

k here is a proportionality constant, V is the Volume and p is the pressure

Let at constant temperature then the final volume and pressure shall be
p2 and V2. The initial volume and initial pressure here is p1 and V1 then
according to Boyle’s law: p1×V1 = p2×V2 = constant (k1)

p1 V2
p2
= V1

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Charlie’s Law:-
According to this law at constant pressure the volume of given mass of gas
increases or decreases by 1/273 times of its volume at 0⁰C for each degree
rise or fall in temperature.
T∝V
Let at 0⁰C volume of gas be Vc
At temperature T volume of gas be Vt
According to Charlie’s Law:-
Vt = Vc(1+t/273)
Vt = Vc(273+t/273)
Here,
273+t = Tt
273=T0
Vt/Vc = Tt/T0

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 Gay lussac’s Law:-
According to this law at constant volume, pressure of given mass of gas is
directly proportional to the Kelvin temperature.
p∝T
p=KT (k is constant)
p/T=constant or p1/T1=p2/T2

Avogadro’s Law:-
According to this law at constant temperature and pressure equal volume
of all the gases contain equal no. of molecules.
V∝n (no. of moles)
 Boiling and Freezing Point:-
Boiling Point:
Boiling point is the temperature at which the vapour pressure of liquid
become equal to atmospheric pressure.

Let Tb be the boiling point of pure

solvent, if some amount of non-volatile
solute is added the vapour pressure
decreases hence, it is to be heated to
higher temperature to make vapour
pressure equal to 1 atm.

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del Tb =Tb-T⁰b
by experiment it is found that,
del Tb∝m(molality)
del Tb=kb.m
where kb is constant called molal boiling point elevation constant or
ebullioscopic constant.
Freezing Point:
The temperature at which the vapour pressure of the liquid becomes
equal to the vapour pressure of the frozen substance. At this step the solid
phase is in dynamic equilibrium with the liquid phase.

Vapour pressure of solution containing non-

volatile solute is less than the pure solvent
so it freezes at lower temperature as
compare to the pure solvent.
This decreasing in the freezing point on
adding non-volatile solute is called
depresson in freezing point.
delTf = Tf⁰ - Tf
delTf∝ m(molality)
delTf = Kf.m
where Kf is the molal freezing point depression constant or
cryoscopic constant.

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