General Organic Chemistry

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 General Organic
Chemistry

Rules for Nomenclature of Simple

Hydrocarbons
General Organic
Chemistry IUPAC Rules
General Organic
Priority order for Functional groups
Chemistry
General Organic
Chemistry
 Metamerism
General Organic
Chemistry Compounds having same molecular formula but
different in alkyl groups present in the either side of
the same functional group are called metamers. The
phenomenon is called metamerism. Example :
Chain Isomerism
Structural
. . . . Alkyl Halides Isomerism

Note: Ethers, ketones, 20 amine, 30 amine, esters

etc. Show metamerism.

Functional Isomerism
Position Isomerism
Ring-Chain Isomerism
CH3 一CH=CH2 and
(propene)
 General Organic Geometrical Isomerism Number of Geometrical Isomers
Chemistry It arises due to restricted
rotation of atoms or groups
around a double bonded
system or cyclic system
Structural Isomerism

Tautomerism
It is a special type of functional isomerism in which there
is migration of α- hydrogen from carbon to electronegative
atom and vice-versa with necessary rearrangement of
covalent bonds. Eg . keto – enol tautomerism.

Cis and Trans Isomers

● Cis Isomers: Like atoms or groups attached at

the same side of double bonded C-atom
● Trans Isomers: Like atoms or groups are on the
opposite sides of doubly bonded carbon
 General Organic Number of optical Isomers
Chemistry
Optical Isomerism

Configurational homers which differ in their optical

activity

Meso Compounds
General Organic
Chemistry Enantiomers & Diastereomers

Racemic Mixture

● Equimolecular mixture of a pair of

enantiomers

● Optically inactive because of the

fact that in equimolecular mixture of
enantiomeric pairs, the rotation
caused by the molecules of one
enantiomer is cancelled by the
rotation caused by the molecules of
other enantiomer.

● Racemic mixture becomes optically

inactive because of external
compensation.

● The racemic mixture of a particular

sample is indicated by using the
prefix (d, I) or (±). For example,
racemic mixture of lactic acid is
represented as (±) lactic acid.
 General Organic
Inductive Effect
Chemistry
Displacement of an electron (shared) pair
along the carbon chain due to the
difference in electronegativity of the
Resonance groups present along with carbon chain

When two or more contributing structures of compound

can be drawn such that none of the structure alone can Types of Inductive Effect
explain all its properties then we draw an average
structure of all contributing structures called as
“Resonance Hybrid” and contributing structures are
called as “Resonating structures” OR “canonical
structures” and the phenomenon is called as
“Rosancne”
 General Organic +M & -M Effect
Chemistry

Hyperconjugation

● When a sigma C◻H bond of sp3 hybridised carbon is

in conjugation with 𝜋 bond at p-orbital, half filled
p-orbital or vacant p-orbital, then the bond pari e◻ of
sigma C◻H bond overlap with adjacent p-orbital. This
phenomenon is called hyperconjugation
General Organic
Chemistry

Carbocation
 General Organic
Chemistry
Carbanions

Free Radical

Carbon Free Radical is the intermediate of carbon

having an odd electron

Factors contributing to the stability of carbocations:

ERG increase stability while EWG decrease stability
Chemical Bonding and
Molecular Structure

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Chemical Bonding
Unit of rate Constant (k)
and Molecular
Structure
 Chemical Bonding and
Molecular Structure

Drawing Lewis structure

Chemical Bonding and Valence Shell Electron Pair Repulsion Theory
Molecular Structure
The electron pairs surrounding the central atom repel one another and
move so far apart from one another that there are no further repulsions
between them. As a result, the molecule has minimum energy and
maximum stability.
Chemical Bonding and Valence Shell Electron Pair Repulsion Theory
Molecular Structure
Chemical Bonding and Valence Shell Electron Pair Repulsion Theory
Molecular Structure
Chemical Bonding and Bent Rule
Molecular Structure
Atomic s character concentrates in orbitals directed towards
electropositive substituents

More E.N. ⟶ More p%

Less E.N. ⟶ More s%
L.P. occupies S-character more than double bond
 Chemical Bonding and Hybridisation
Molecular Structure

(i) Only those orbitals which have approximately

equal energies and belong to the same atom or
ion can undergo hybridisation.
(ii) Number of hybrid orbitals produced is equal
to the number of atomic orbitals mixed.
(iii) It is not necessary that all the half-filled
orbitals must participate in hybridisation.
Similarly, it is not necessary that only half-filled
orbitals should participate in hybridization. Even
completely filled orbitals with slightly difference
energies can also participate.
(iv) Hybridisation never takes place in isolated
atoms but it occurs only at the time of bond
formation.
(v) Type of hybridization indicates the geometry
of molecules. One can tell the shape of a
molecule by knowing the kind of hybridisation
involved.
(vi) The bigger lobe of the hybrid orbital always
has +ve sign while the smaller lobe on the
opposite side has a -ve sign.
 Chemical Bonding and
Molecular Structure

Hybridisation
Chemical Bonding and
Molecular Structure

Predicting Hybridisation
Chemical Bonding and Valence Bond Theory
Molecular Structure
Depending upon the type of overlapping, the covalent bonds are mainly of
two types:
Sigma (𝝈) Bond Pi(𝜋) Bond
(i) This bond is formed by overlap of (i) This is formed by by sideway
orbitals along their internuclear axis (end overlapping of orbitals (lateral
to end overlap). overlapping).
(ii) This is formed by overlapping between (ii) This is formed by the overlap of p-p
s-s, s-p or p-p orbitals. orbitals only
(iii) overlapping is quite large and hence (iii) overlapping is to a small extent.
sigma bond is a strong bond. Hence, 𝜋-bond is a weak bond.
(iv) Electron cloud in this case is (iv) Electron cloud of 𝜋-bond is
symmetrical about the line joining the two unsymmetrical.
nuclei. (v) Pi(𝜋) bond consists of two electron
(v) Sigma bond consists of only one clouds, one above the plane of atomic
electron cloud, symmetrical about the nuclei and the other below it.
internuclear axis. (vi) Free rotation about a 𝜋-bond is not
(vi) Free rotation about a 𝝈-bond is possible because on rotation, overlapping
possible. vanishes and so the bond breaks.
 Chemical Bond Parameters
Bonding and
Molecular Bond length Bond energy
Structure Factors affecting bond length Factors affecting bond energy
 Chemical Bonding and
Dipole Moment
Molecular Structure
The product of magnitude of negative or positive charge (q) and
the distance (d) between the centres of positive and negative
Bond Angle
charges is called dipole moment. It is usually denoted by μ.

Bond Order
 Chemical Bonding and
Molecular Structure Linear Combination of Atomic
Orbitals (LCAO)
MOT Homonuclear diatomic hydrogen molecule,
consisting of A and B atoms
Given by hund and Mulliken
Each hydrogen atom in ground state has one
● Two atomic orbital come nearer and then overlap each other electron in 1s orbital
to form two molecular orbitals (MO)
● Combination of two atomic orbital (AO) forms two molecular,
orbital (MO):

● Both orbitals can be filled by electron according to Aufbau

principle.
● Energy of BMO < Energy of ABMO.
● Order of energy in molecular orbitals of diatomic molecules.
 Chemical Bonding and
Molecular Structure
MOT

Energy level diagram for ❏ Order of energy in molecular orbitals of

diatomic molecules.
molecular orbitals ❏ From H2 to N2σ 1s < σ *1s < σ 2s < σ *2s < 𝜋 2px
= 𝜋 2py < σ 2pz < 𝜋 *2px = 𝜋 *2py < σ *2pz
❏ For O2 and F2; σ 1s < σ *1s ; < σ 2s < σ *2s < σ
2pz < 𝜋 2px = 𝜋 2py < 𝜋 *2px = 𝜋 *2py < σ *2pz
σ *, 𝜋 * = antibonding molecular orbital
σ, 𝜋 = bonding molecular orbital

Bond order = Nb - Na
Bond order =
2
Nb = No. of electron in bonding MO’s
Na = No. of electron in antibonding MO’s
 Chemical Bonding and
Molecular Structure
MOT

Energy level diagram for If bond order = 0, it means species does not exist.
Bond order of 1, 2 and 3 corresponds to a single bond,
molecular orbitals double and triple bond respectively.
Bond order ↑ stability of molecule ↑ bond length ↓

Nb - Na
 Chemical Bonding and MOT
Molecular Structure
● Ion induced dipole attraction - In this case a neutral
molecule is induced by an ion as a dipole as shown
in fig.
Vander Waal’s Forces

● Dipole - induced dipole attraction: In this case a

neutral molecule is induced as a dipole by another
dipole as shown in fig.

● Induced dipole - Induced dipole attraction or

London dispersion force between two non polar
molecules as in Cl2, He etc.
 Chemical Bonding and Fajan’s rule
Molecular Structure
Just as a covalent bond may have partial ionic character an ionic
bond may also show a certain degree of covalent character.
Hydrogen bonding

● It is an electrostatic force attraction

between polar-covalently bonded H atom of
one molecule and an electronegative (F, O, Factors Influencing Ion- Deformation or Increasing Covalent
N) atom of same or another molecule. Character
● it is of two types intermolecular hydrogen Charge on the ions: charge on the cation covalent character
bonding and intramolecular hydrogen Small cation and large anion: For a small cation and a large anion,
bonding covalent character increases
Cation with a pseudo-inert gas type of electronic configuration :A
cation with a 18 electron in outermost shell such as Ag+ ([Kr] 4d10)
polarizes anions more strongly than a cation with a 8 electron
arrangement as in K+.Thus AgI is more covalent than KI, although
Ag+ and K+ ions are nearly of the same size
 Chemical Bonding and
Molecular Structure

Hydrogen bonding

H-bond has serious consequences on

the physical properties. These are-
● H2O is liquid at room temperature
whereas H2S is gas at room
temperature Ice
● Ice is lighter than water, although it is
solid
● Alcohols have higher boiling points
than corresponding alkanes and
ethers of the same molecular mass
● o-nitrophenol is steam volatile and
less H2O soluble than its
corresponding para isomer due to
intramolecular H-bonds. Hydrogen bond
● Acetic acid has a molecular weight
of 60 in benzene and it shows a
very high boiling points. This is due
to dimerization of molecule.
 Hydrocarbons

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Hydrocarbons

HYDROCARBON
 Preparation
Hydrocarbons
of Alkanes

Kolbe Electrolysis
 Hydrocarbons Wurtz Reaction

Preparation
of Alkanes

Dehydration of Alcohols

● Alcohols when heated in presence of H2SO4,

H3PO4, P2O5 or Al2O3 undergo loss of water
molecules with the formation of alkene.
Hydrocarbons

Preparation of Alkenes
Hydrocarbons
Preparation of Alkenes
Hydrocarbons

Reactions of Alkenes
Hydrocarbons

Reactions of Alkenes
 Hydrocarbons Reactions of Alkenes

Additional f Hydrogen Halides

Hydrocarbons Preparation of Alkyne/Ethyne

Reactions of Alkynes
Hydrocarbons

Reactions of Alkynes
Hydrocarbons

Preparation of Benzene
Hydrocarbons

Properties of Benzene
Hydrocarbons

Properties of Benzene
Hydrocarbons

Substitution Reactions

● Most important reactions of benzene are electrophilic

substitution reactions.

● Halogenation:
Hydrocarbons

Substitution Reactions

● Nitration:

● Sulphonation:

● Alkylation:

● Acylation:
D and F Block Elements

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d & f - Block Elements

Some Important
d-block
elements
compound

The d-Block
Elements
d & f - Block Elements
 ● Four transition series: ● Ionisation potentials : The ionisation potentials of
(i) 3d series: From Sc (21) to Zn (30) d-block elements increase as we move across each
(ii) 4d series : From Y (39) to Cd (48) series from left to right, although the increase is not
(iii) 5d series: La (57), Hf(72) to Hg (80)
quite regular, e.g., in the first series, the values for
(iv) 6d series : Ac (89), Rf (104) to Cn (112)
Sc, Ti, V and Cr differ very slightly. Similarly the
● Electronic configuration: (n -1) d1-10 ns1-2
values Fe, Co, Ni and Cu are fairly close to one
● Atomic Size : Atomic and ionic radii of d-block another. The value for Zn is appreciably higher due
elements is smaller than s-block elements.
to the additional stability associated with completely
Atomic radii depends on effective nuclear charge
(Zeff) and screening effect (SE). filled 3d-level in Zn (Zn 🠆 3d104s2).
In 3d series : Sc 🠆 Cr (Zeff > SE) ∴ radius ● Standard electrode potential : values
decreases are more negative than values (except
Mn 🠆 Ni(Zeff = SE) ∴ radius remains constant ;
Cu 🠆 Zn(Zeff < SE) Cu). These metals (except Cu) evolve H2(g) and
∴ radius increases hence are oxidised easily when reacted with acid
Decrease in the radii with increase in atomic solutions is highest (+0.34) in first
number is not regular. Atomic radii tend to reach
transition series and does not liberate H2(g) from
minimum near at the middle of the series and
increase slightly towards the end of the series. acids. is highest (+ 0.34) in first transition series and
● Melting and boiling points : M.P. and B.P. of does not liberate H2(g) from acids.
d-block elements is greater than of s-block (the ● Cr is unreactive although high negative
reason is stronger metallic bond and presence of value due to the formation of non-reactive invisible
covalent bond formed by unpaired d-electrons).
layer of Cr203
● of Co and Ni is exceptionally high d & f - Block Elements
positive value due to high (negative) hydration enthalpy.
● Oxidation state: Shows variable oxidation states due to
involvement of (ns) and (n—I)d electrons in bonding.
● Magnetic property: Transition elements and many of their
compounds are paramagnetic. The magnetic moment (It)
can be calculated by using where 'n' is
the number of unpaired electrons in the metal ion
● Coloured compounds: Forms coloured compounds due
to d-d transition.
● Forms complexes: Due to small highly charged ions and
vacant d-orbitals
● Forms interstitial compounds: As they are able to
entrap atoms of elements having small atomic size like H,
C, N, B etc.
● Oxides: Oxides in lower oxidation states are basic,
whereas those with higher. oxidation state are acidic or
amphoteric
Lanthanoids: 14 elements from Ce to Lu General E.C: Colour : The lanthanoid ions have unpaired electrons in
6s2 5a0-1 4f-114 their 4f- orbitals. Thus these ions absorbs visible
Atomic and Ionic Sizes region of light can undergo f-f transition and hence
In the lanthanoid series with increasing atomic number,
there is a progressive 3+decrease in the size from exhibit colour.
lanthanum to lutetium (La to Lu3+). This contraction in
size is known as lanthanoid contraction. In these ● They are highly dense metals with high m.pts.
elements the added electron enters in the deep seated ● Ionisation Energies - The first I.E.'s are around
f-orbitals and therefore experiences considerable pull by
the nucleus. Such an electron cannot add to the size of 600 kJ mol-1' and second about 1200 kJ mol-1 which
the element and also because the intervening 5s2p6d1
electronic shells, have very little screening effect on the are comparable with those of calcium. The 3rd I.E.
outermost 6s2 electrons. Hence with increasing atomic
number, the enhanced nuclear charge leads to is low if it leads to stable empty, half-filled or
contraction in the size of atoms and ions. completely filled configuration. This is the reason
Oxidation states : All the lanthanoids attains +3 oxidation
state and only cerium, praseodymium, terbium, and for very low 3rd I.E. of La, Gd and Lu.
dysprosium exhibit higher oxidation state (+4).
Oxidation states + 2 and +4 occur particularly when they ● Electropositive character- High due to low I.P.
lead to
(a) A noble gas configuration e.g. CO4+ (f 0) ● Complex formation- Do not have much tendency
to form complexes due to low charge density
(b) A half filled `f ’ orbital e.g. Eu2+, TIP4+, (f 7)
(c) A completely filled ' f ' orbital e.g. Yb2+ (f14) because of their large size.
● Reducing Agent - They readily lose electrons so
they act as good reducing agents.
Due to lanthanide contraction, pairs of elements
such as Zr/Hf, Nb/Ta and Mo/W are almost identical
in size. They are used in the production of alloy
steel known as mirsch metal (Ln-95%, Fr-5% traces
of S, C, Ca & Al) which is used in making
Mg—based alloy to produce bullets, shell and
lighter flint.
Coordination Compound

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 Coordination Compound (c) Polydentate ligands: A ligand that is attached to a central metal
ion by bonds from two or more donor atoms.
(d) Chelating ligands: Polydentate ligands whose structures permit
(I) Perfect Complexes the attachment of two or more donor site to metal ion simultaneously,
The compounds in which complex ion is fairly stable thus resulting in cyclic structure are called chelating ligands and
and further dissociation is not possible or only feebly compound formed is known as chelate compound.
dissociation is possible in solution state. (e) Ambidentate ligands: Ligands which can ligate through two
(II) Imperfect Complexes
difference atoms present in it are called ambidentate ligands. At a
Those complexes in which complex ion is less stable
and is reversibly dissociates to give enough simple time only one atom can donate.
ions and thus respond to their usual qualitative test. (f) Flexidentate Ligands: Ligands which sometimes do not use all
Classification of Ligands the donor sites to get coordinated with central metal ion are known as
(A) Based on Charge flexidentate ligands.
(i) Neutral ligands H2O, NO, CO, C6H6 etc. (B) Based upon bonding interaction between the ligand and the
(ii) Positive ligands NO+, N2H5+
central atom.
(iii) Negative ligands (i) Classical or simple ligands: These ligand only donate the lone
pair of electrons to the central atom.
(a) Unidentate/monodentate ligands : Ligands
(ii) Non classical or 𝜋-acid or 𝜋-acceptor ligand: These ligand not
which donate one pair of electron to the central
metal are called unidentate ligands. only donate the lone pair of electrons to central metal but also accept
(b) Bidentate ligands: Ligands which have two the electron cloud from central atom. On the basis of nature of
donor atoms and have the ability to link with central donating electron cloud these ligands are following types.
metal ion at two position are called bidentate (a) 𝝈 donor 𝜋 acceptor Ex. CO, CN-
ligands. (b) 𝜋 donor 𝜋 acceptor Ex. C2H2, C6H6
Heading Spectrochemical Series
● A spectrochemical series is the arrangement of
common ligands in the increasing order of their Coordination Compound
crystal-field splitting energy (CFSE) values.
● The ligands present on the R.H.S of the series are
strong field ligands while that on the L.H.S are weak
field ligands.
● Also, strong field ligands cause higher splitting in the d
orbitals than weak field ligands.
I− < Br− < S2− < SCN− < Cl− < N3 < F− < OH− < C2O42− ∼
H2O < NCS− ∼ H− < CN− < NH3 < en ∼ SO32− < NO2− <
phen < CO
Rule For IUPAC Nomenclature
(a) Like simple salts, the positive part of the coordination
compound is named first.
Ex. K4[Fe(CN)6] the naming of this complex starts with
potassium.
(b) Then after ligands of the coordination sphere are to
be named.
(c) The ligands can be neutral, anionic or cationic.
(i) The neutral ligands are named as the molecule
Ex. C5H5N pyridine, (C6H5)3P Triphenylphosphine,
H2N一CH2一CH2一NH2 ethylene diamine.
CO carbonyl, NO nitrosyl, H2O Aqua, NH3 amine.
(ii) Anionic ligands ending with ‘ide’ are named by
replacing the ‘ide’ with suffix ‘O’.
 Coordination Compound

Crystal Field Theory

Valence Bond Theory
The drawbacks of VBT of coordination compounds are to a
(a) The metal ion under the influence of ligands can use its
considerable extent removed by the Crystal Field Theory).
vacant d(n-1), ns, np, nd orbitals for hybridisation.

Factors Influencing the Magnitude of C.F.S.E

1. Higher the CFSE value higher will be the stability of
complex
2. Chelated complexes are more stable than non-chelated
Stability of Coordination Compound
complexes given the donor atoms are same
The stability of a coordination compound [MLn] is measured in
3. Same charges on the cation but the number of
terms of the stability constant (equilibrium constant, Kf).
d-electrons is different
 Coordination Compound Classification of Isomerism
Type of Isomerism

Stereo Isomerism
They have same molecular formula, same
constitution, they differ only with respect to the
special orientation of ligands in space around the Structural isomerism
metal ion. Ionization
Geometrical Isomerism
(i) The ligands occupy difference positions around Hydrate
the central metal ion.
(ii) When two identical ligands are coordinated to the
metal ion from same side then it is cis isomers. Coordination
Geometrical isomers with coordination number =
4(Square planar complexes) Linkage
Ma4, Ma3b, M(AA)2, M(AA)a2, M(AA)ab, M(AB)a2,
M(AA)(AB), M(AA)(BB) can’t show GI.
[Pt(NH3)2Cl2] Cis(Cis-Platin) anti cancer Ligand

Stereo Isomerism

Geometrical

Optical
 Organo-metallic Compounds
Coordination Compound The compounds in which metal carbon linkage is present are known
as organo-metallic compounds.
1. 𝝈-bonded organometallic compounds 𝝈-bond between metal
Bonding in coordination compounds and carbon.
Due to presence of p acid ligands special type of 2. 𝜋-bonded organometallic compounds
bonding takes place in coordination compounds. It is (i) 𝝈-donar and 𝜋-acceptor [Ni(CO)4], [Fe(CO)5] etc.
known as synergic bonding. (ii) 𝜋-donar and 𝜋-acceptor [Fe(C2H5)2], [Cr(C6H6)2] etc.
Bonding in metal carbonyl Sidgwick Theory or Effective
Ex. [Fe(CO)5] ; [Ni(CO)4] ; [Cr(CO)6] Atomic Number Concept (EAN)
EAN = (atomic number of the metal-oxidation state of central metal) +
number of electrons gained from the donor atoms of the ligands.
Werner’s Co-ordination Theory
Werner’s co-ordination theory was the first attempt to explain the
bonding in co-ordination compounds.
Werner’s Representation of Complex
(i) Fe(NH3)6Cl3 Dotted lines indicate
primary valency and
continuous lines indicate
secondary valency of metal
ion.
 Solutions

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 SOLUTIONS 2. Concentration of Solutions

1. Types of solutions
Classification based on physical state:

● Gas in gas (Air)

● Gas in liquid (Soda water)
● • Gas in solid (Hydrogen in Pd)
● • Liquid in gas (Fog)
● • Liquid in liquid (Alcohol in water)
● Liquid in solid (Amalgams)
● • Solid in gas (Smog)
● Solid in liquid (Sugar in water)
● Solid in solid (Alloys)

Classification based on concentration

● Dilute solutions
● Concentrated solutions
● Saturated solutions
● Supersaturated solutions
 SOLUTIONS 4. Solubility
Maximum amount of a substance that can be dissolved in a specified
amount of solvent at a specified temperature it depends upon
• Nature of solute • Nature of solvent • Temperature • Pressure

Solubility of a solid in liquid Solubility of a gas in liquid

● Effect of nature of solute and ● Effect of temp ⇒ Follow same order

solvent ⇒ like dissolves like as in case of solid
● Effect of temp ⇒ Exothermic ● Effect of pressure ⇒ Henry’s law
3. Raoult’s Law process - increase with rise in states that the partial pressure of
(Ps = PAo + (PBo - PAo) xB temp. the gas in vapour phase (p)
● Endothermic process - decrease proportional to the mole fraction of
Ps = PAo + (PBo + PAo)xB where with rise in temp Effect of pressure the gas (x) in the solution” p = KHx
⇒ No effect KH ⇒ Henry’s law constant
Ps = Total
solubility = 1/KH
Pressure, PAo & PBo = vapour
pressure in pure state of two
constituents A and B in solution
 SOLUTIONS 5. Non-Ideal Solutions

6.Colligative Properties
These properties of a solution
depend on the total
concentration of all solute
particles, regardless of their
ionic or molecular nature,
charge, or size.
- No . of particles
- No. of molecules (in the
solution of
non-electrolytes)
- No. of ions (In the
solution of electrolytes)
SOLUTIONS 7.

8. Osmotic Pressure (𝜋)

● Osmotic pressure is the hydrostatic pressure
produced when a solution is separated from the
solvent by a semipermeable membrane.
● Osmotic pressure may be defined as the exceed
pressure which must be applied to a solution order
to prevent flow of solvent into the solution through
the semipermeable membrane.
Osmotic Pressure
For dilute solutions, osmotic pressure is found to
follow the equation
(Gay-Lussac-van’t Hoff law)
When w g of solute are dissolved in V litre of solutions
and M is the molar mass of the solute then,
SOLUTIONS

9. Van’t Hoff Factor (i)

 Electrochemistry

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 In corrosion, a metal is oxidised by loss of electrons to oxygen and
Electrochemistry forms metal oxide. Corrosion of iron (which is commonly known as
rusting) occurs in presence of water and oxygen (air).
Rusting of Iron: According to electrochemical theory, rusting can be
represented as:
Faraday’s Laws of Oxidation at Anode: Fe→ +Fe2+ + 2e- ; Eooxi = -0.44 V
Corrosion
Electrolysis Reduction at Cathode: CO2 + H2O → H+ + HCO3-
2H+(aq) + 2e → 2H
2H + ½ O2 → H2O
Faraday's First Law: When an electric current is
2H+ + ½ O2 + 2e → H2O ; Eored = 1.23 V
passed through an electrolyte, the amount of substance
deposited or liberated at an electrode is proportional to the Overall reaction of corrosion cell:
quantity of electric charge passed through the electrolyte. Fe + ½ H+ + ½ O2 → Fe2+ + H2O ; Eocell = 1.67 V
If W be the mass of the substance deposited by passing Q The ferrous ions so formed move through water and come at the
coulomb of charge, then according to the law, we have the surface of iron object where these are further oxidised to ferric state
relation. by atmospheric oxygen and constitute rust which is hydrated iron (III)
W∝Q oxide.
A coulomb is the quantity of charge when a current of one 2Fe2+ + ½ O2 + 2H2O → Fe2O3 + 4H+
ampere is passed for one second. Fe2O3 + xH2O → Fe2O3.xH2O
Q = current in amperes time in seconds = I ∝ t Rust

W∝I∝t Prevention of Corrosion

W=Z×I×t
● The metal surface is coated with paint which keeps it out of
where Z is a constant, known as electro-chemical contact with air, moisture etc.
equivalent, and is characteristic of the substance ● By applying film of oil and grease on the surface of the iron
deposited. Electro-chemical equivalent (Z) = tools and machinery
Equivalent wt.of element/96500 ● The iron surface is coated with non-corroding
 Regardless whether a cell is a voltaic or an electrolytic- cell,
Electrochemistry - The anode is the electrode at which oxidation occurs
- The cathode is the electrode at which reduction occurs
Voltaic Cell Electrolytic-cell
Anode Oxidation, Oxidation
Faraday’s Laws of Negative (-) terminal Positive (+) terminal
Electrolysis Cathode Reduction Reduction
Positive (+) terminal Negative (-) terminal

• Electrode Potential:
Faraday’s Second Law: It states that when same
quantity of electricity is passed through difference
electrolytes, then the quantity of deposit is directly • Nernst equation:
proportional to respective equivalent weight.
(Equivalent wt. Of electrolytes).
• For Reaction:

• Electrochemical Series: Arrangement of elements in order of

increasing value of Eored. Reducing nature decreases from top
Electrochemistry

Batteries
 • For weak electrolytes, λm increases as C decreases but does not
Electrochemistry reach a constant value even at infinite dilution. Hence, there λom
cannot be determined experimentally.
• Kohlrausch's Law:
Effect of Dilution Λ-eq = λo+ + λo-
Where = λo+ is the limiting equivalent conductivity of the cation and
λo- is the limiting equivalent conductivity of the anion. These
contributions are called limiting equivalent conductance at infinite
dilution. The above equation is, however, correct only for binary
electrolyte like NaCl, MgSO4 etc.
Plot of λm against C1/2 is a straight line with Applications of Kohlrausch's Law:
intercept equal to λmo and slope equal to '-A.' • Calculation of Molar Conductivity at Infinite Dilution for Weak
Thus, λm decreases linearly with √C, when C = 0, Electrolytes:
λm = λom and λom can be determined In order to calculate λ-m or λ-m of a weak electrolyte say CH3COOH,
experimentally. we determine permanently λmo values of the strong electrolyte
• For weak electrolytes, λm increases as C
decreases but does not reach a constant value
even at infinite dilution. Hence, there λom cannot
be determined experimentally.
 Conductance of Electrolytic Solutions:
Electrochemistry

• Calculation of the Degree of Dissociation:

λom is the molar conductivity of a solution
at any concentration C and λom the
conductivity t infinite dilution (i.e., zero
concentration), we will have
⍺=

• Calculation of dissociation Constant of a

Weak Electrolyte:
 Haloalkanes & Haloarenes

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Preparation: Properties:
● From alcohols:
Haloalkanes Physical properties
ROH + HX → RX + H2O & ● Lower alkyl halides are colourless with sweet
ROH + PCl5 → PCI + POCI + HCI smell or pleasant oily liquid, except CH3F,
ROH + SOCI2 → RCI + SO2 + HCl Haloarenes CH3Cl, CH3-CH2-F, CH3-CH2-CI which are
From hydrocarbons: gaseous in nature.
CH2 = CH2 + HX → CH3 CH2 X ● Alkyl halides having 18-carbon or more than
Order of reactivity HI > HCl > HF In case of it are solid in nature.
unsymmetrical alkenes addition occurs Haloalkanes
● These are completely soluble in organic
according to Markownikoff's rule only in case solvents but insoluble in H2O
of Hbr in presence of peroxides addition
● Reactivity order is RI > RBr > RCI > RF
occurs according to anti Markownikoff rule
● For same halide group, reactivity order is 3º
Chemical Properties:
(halide) > 2º (halide) > 1° (halide)
● Nucleophilic substitution:
● Polarity order is RF > RCI > RBr > RI
RX + KOH 🠆 ROH + KX
● Melting & Boiling points, for same alkyl group
RX + H2O 🠆 ROH + HX
the order is RI > RBr > RCI > RF
RX + NaOR 🠆 ROR + NaX
From halogen exchange ● Fluorides and chlorides are lighter than water
With Nal (Finkelstein reaction) whereas bromides and iodides are heavier
RX + LiAlH4 🠆 RH + LiX + AlH3
than H2O due to higher density of bromine
than oxygen.
● These reactions are of two types: ❏ Rate of reaction in SN2 mechanism depends
❏ SN1 type (Unimolecular nucleophilic
Haloalkanes on the strength of the attacking nucleophile.
reactions) proceeds in two steps: & ❏ Non-polar solvents, strong nucleophiles and
high concentration of nucleophiles favour
Haloarenes SN2 mechanism.

❏ Rate, r = k[RX]. It is a first order reaction.

❏ Reactivity order of alkyl halide towards Haloalkanes
SN1 mechanism 3° > 2° > 1°
❏ Polar solvents, low concentration of
nucleophiles and weak nucleophiles
favour SN1 mechanism. Grignard reagents are highly reactive and react
❏ In SN1 reactions, partial racemisation with any source of proton (H2O, alcohols, amines
occurs due to the possibility of frontal as etc. to give hydrocarbons.)
well as backside attack on planar
carbocation 2RC + 2Na 🠆 RR + 2NaX
● SN2 type (Bimolecular nucleophilic
substitution), these reactions proceed in
one step.
❏ It is a second order reaction with r =
k[RX] [Nu].
❏ During SN2 reaction, inversion of
configuration occurs
❏ Reactivity of halides towards S2
mechanism is 1° > 2° > 3°
Properties : Preparation:
Physical properties:
Haloalkanes
From arenes:
❖ Aryl halides are colourless liquids or &
colourless solids with characteristic
odour. Haloarenes From benzene diazonium Chloride:
❖ Boiling point generally increases with
increase in the size of aryl group or
halogen atom. Boiling point order
Ar-I>Ar-Br>Ar-Cl>Ar-F Haloarenes
❖ The melting point of p -isomer is more
than o- and m-isomer. This is because of ➢ Instability of phenyl
more symmetrical nature of p-isomer. carbocation.
❖ Due to resonance in chlorobenzene, C-Cl However, aryl halides having
bond is shorter and hence, its dipole electron withdrawing groups
moment is less than that of cyclohexyl (like NO2, -SO3H, etc.) at ortho
chloride. and para positions undergo
Chemical properties: nucleophilic substitution
❖ Nucleophilic substitution reactions: reaction easily.
Aryl halides are less reactive towards
nucleophilic substitution reaction. Their low
reactivity is attributed due to the following
reasons:
➢ Due to resonance, C-X bond has partial
double bond character.
➢ Stabilisation of the molecule by
delocalisation of electrons.
Polyhalogen compound: ● Electrophilic substitution reactions:
● Dichloromethane (CH2Cl2): It is useful as Haloalkanes Haloarenes are o, p-directing, due to +
solvent in industries. Mostly it is used as & I effect of halogen group electron
solvent in the production of chemicals
density increases at ortho and para
used in removal of colour. Haloarenes positions e.g., halogenation, nitration,
❏ It is Harmful to nervous system. If it
sulphonation, Friedel-crafts reaction etc.
comes in direct contact with eye it
Reaction with metals:
damages the cornea. In addition, if it
Wurtz fittig reaction:
comes in direct contact with skin, red
rashes are formed. Haloarenes
● Tetrachloromethane (CCl4): It is used in
the manufacture of refrigerants and
Fitting reaction:
propellants for aerosol cans.
❏ Used as a cleaning solvent, degreasing
agent and as fire extinguisher.
❏ It causes permanent damage to nerve
cells.
❏ In atmosphere, it depletes the ozone ❏ Freon 12 (CC12F2) is one of the most common freons in industrial use.
layer. ❏ Freon is able to initiate radical chain reactions that can disturb the natural
● Freons: Chlorofluorocarbon compounds ozone balance.
of methane and ethane are collectively ● DDT: It is a powerful insecticide.
known as freons and it is manufactured ❏ It is a persistent organic pollutant that is readily adsorbed to soils and
by swarts reaction using sediments, which can act both as sinks and as long-term sources of exposure
tetrachloromethane. affecting organisms.
❏ It is not metabolised very rapidly by animals.
Alcohols, Phenols and
Ethers

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 Classification of Alcohol
ALCOHOLS
Primary Alcohols : Hydroxyl group is attached to primary (1°) carbon
atom.
Alcohol
Alcohols are regarded as hydroxy derivatives
of hydrocarbons Secondary Alcohols: Hydroxyl group is attached to secondary (2°)
carbon atom.

Physical Properties of Alcohol Tertiary Alcohols: Hydroxyl group is attached with tertiary (3°)
Carbon atom.
● Alcohols are colourless liquids with
specific smell. They are soluble in water
due to H-bonding. These are partially
soluble in organic solvents.

● They are liquid in nature up to 12-carbon.

Preparation of Alcohol
● Boiling point ∝ molecular mass
From Alkanes Controlled Oxidation

● Boiling point of alcohols are higher than

equivalent ethers. It is due to
intermolecular H-bonding
 Classification of Alcohol
ALCOHOLS From Alkenes
(i) By acid catalysed hydration
Preparation of Alcohol
❖ From Alkyl halide
C2H5一Br + KOH(aq) 🠆 C2H5一OH + KBr
(ii) Oxymercuration-Demercuration
❖ From reactions involving Grignard reagent
❖ Reaction with methanal

In this reaction, methanal gives primary alcohol, while any

other aldehyde gives secondary alcohol. Addition-accordance with Markovnikov's rule without any
rearrangement
❖ Reaction with other aldehyde (iii) Hydroboration-Oxidation of alkenes

❖ Reaction with ketone

In this reaction, ketones form tertiary alcohols.
 Dehydration Reaction
ALCOHOLS
Secondary and tertiary alcohols undergo dehydration
under milder condition

Dehydration Reaction
● Dehydration means removal of a molecule of water
● Formation of either alkenes or ethers.
● Dehydration can be carried out either with protonic
acid such as H2SO4, Al2O3, P2O5.
● Primary alcohols when heated with conc. H2SO4 at
433-443 K, they undergo intramolecular dehydration Ease of dehydration of alcohols follows the order-3°
to form alkenes. alcohol > 2° alcohol > 1° alcohol
Dehydration of alcohol by Al2O2

Dehydration of alcohol by P2O5

Saytzeff Rule: The more highly substituted alkene is always

the major product
 ALCOHOLS

Test of Alcohol
Victor-Meyer Test
● This test used to distinguish whether a
given alcohol is primary, secondary or
tertiary.
● For the determination of this, a series of
reaction are done with the given sample of
alcohol.
● Colour of solution indicates the nature of
alcohol.
 Acidity of Phenol
PHENOL
Reaction which show acidic character of phenol
1. Reaction with metal (Na)

Introduction of Phenol
● Phenol contains OH group directly attached to 2. Ration with sodium hydroxide
carbon atom of an aromatic system.
● The simplest phenol is C6H5OH
● Phenols are classified as mono, di, trior polyhydric
depending upon whether they contain one, two,
three or many hydroxyl groups respectively in their
Resonance in Phenol
structures.
● In phenol the sp2 hybridised carbon of benzene ring which acts
as an electron withdrawing group.
● In resonance structure of phenol, oxygen of -OH group will be
positive.
 Preparation of Phenol
PHENOL
DOW’s Process
● This process involves alkaline hydrolysis of chlorobenzene.
● Large quantities of phenol are formed by heating chlorobenzene
with a 10% solution of caustic soda or sodium carbonate at 300°C
Acidity of Phenol under a very high pressure (200 atm)

Acidic Nature of Substituted Phenol

Electron withdrawing group - (-NO2, -COOH, -CN)
● Enhances the acidic strength of phenol
● This effect is more pronounced when such a Sodium phenoxide on treatment with mineral acid yields phenols.
group is present at ortho and para positions.
Electron donating group - (-OH, -OR, -NH2)
● Decreases the acidic strength of phenol.
From Diazonium Salts
● A diazonium salt is formed by treating an aromatic primary amine
with nitrous acid (NaNO2 + HCl) at 273-278 K
● When benzene diazonium chloride solution is warned with warm
water or dilute acids, phenol is formed with a evolution of
nitrogen.
 Preparation of Phenol
PHENOL Cumene Process
● Cumene (isopropylbenzene) is oxidised
in the presence of air to cumene
hydroperoxide which is converted to
phenol and acetone by treating with
dilute acid

Alkali fusion of sulfonates

● Sodium salt of benzene sulphonic acid is
fused with sodium hydroxide at 300-350°
C,
sodium phenoxide is formed.
● Sodium phenoxide on treatment with
dilute acid yields phenol.

From decarboxylation of sodium salicylate

with soda lime
 PHENOL Reaction of Benzene Ring
Bromination
Reaction of Benzene Ring ● The - OH group is ortho and para directing.
● Phenol activates the benzene nucleus towards electrophilic
Nitration substitution reactions at ortho and para-positions.
● Phenol activates the benzene nucleus towards ● When the reaction is carried out in solvents of low polarity such
electrophilic substitution reactions at ortho and as CHCl3 or CS2 and at low temperature, monobromo phenols are
para-positions. formed.
● With dilute nitric acid at low temperature (298 K),
yields a mixture of ortho and para nitrophenols.

When phenol is treated with bromine in water (high polarity) -2,4,6

-tribromophenol is formed as white precipitate
● Reaction with concentrated nitric acid.
● Phenol is converted to 2,4,6-trinitrophenol (picric
acid)
 PHENOL
Reimer-Tiemann Reaction
Reimer-Tiemann Reaction
● Reaction of phenol with chloroform in the presence of sodium
hydroxide.
● A-CHO group is introduce at ortho position of benzene ring.
Kolbe’s Reaction
Kolbe Reaction
● Reaction of sodium phenoxide with carbon
dioxide (weak electrophile)
● At 130-140°C under pressure of (4-7) atmospheres
followed by acid hydrolysis, salicylic acid
(o-Hydroxybenzoic acid) is formed.
 Preparation of Ether
ETHERS Williamson Synthesis
● Heating of alkyl halides with sodium or potassium alkoxides.
Introduction of Ether ● This is a very good method for the preparation of simple and
mixed ethers.
Organic compound having R-O-R’ as functional group ● Alkyl halide should be primary and alkoxide should be
are called ethers. secondary or tertiary.

CH3-O-CH3 C6H5-O-CH3 Preparation of Ether

C2H5-O-C2H5 CH3-O-C2H5
● When an excess of alcohol is heated at 140°C in presence of
Bond angle is slightly greater than the tetrahedral angle
protic acids, (H2sO4, H3PO4).
due to repulsive interaction between two bulky alkyl
● Two molecules of alcohol eliminate one molecule of water to form
groups.
symmetrical ether.

The dehydration of alcohols is in the order -

Primary > Secondary > Tertiary
 Biomolecules

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 Biomolecules Carbohydrates

Classification
Maltose: ● Monosaccharides: cannot be
● It is prepared by hydrolysis of starch with the enzyme hydrolysed further.
diastase. ● Oligosaccharides : yield two to ten
● It is reducing sugar. monosaccharides
● It hydrolyses into two ⍺-D-glucose molecules in the ● Polysaccharides : yield a large
presence of enzyme maltase. number of monosaccharide unit
Lactose:
● It is found in the milk.
● It is a reducing sugar.
● Lactose on hydrolysis gives equimolar quantities of
β-D-glucose and β-D-galactose.
Sucrose:
● It is obtained commercially from sugarcane or sugar beets.
● It is non-reducing sugar.
● Sucrose on hydrolysis gives equimolar mixture of
⍺-D-glucose or β-D-fructose.
 Nucleic Acids Properties
Biomolecules ● Play important role in replication and
protein synthesis polymer of nucleotides
Starch ● Nucleotide consist of a sugar unit,
● It is found exclusively in plants as stored as food. nitrogenous base and a phosphate group.
● It is a polymer of a-D-glucose and consists of two components, ● During formation of dinucleotide or
amylose and amylopectin. Amylose-water soluble, constitutes polynucleotide, nucleotide units are are
about 15-20% of starch. joined joined by.3' by.3' 5' phosphodiester
❏ It is a long unbranched chain with 200-1000 glucose units. linkages
❏ 1,4-a-glycosidic linkage is present. ● Nucleoside: Sugar+base
● Amylopectin-water insoluble, constitutes about 80-85% of starch. ● Structure of bases:
❏ It is a branched chain polymer of glucose units in which main
chain is formed by C1-C4 linkage where branching occurs by
C1-C6 glycosidic linkage.
Cellulose:
● It is the chief constituents of the cell walls of plant.
● It contains 1-4 glycosidic linkages.
● Cellulose on hydrolysis gives ẞ-D-glucose.
Glycogen:
● It is commonly known as animal starch.
● Its structure is similar to amylopectin.
● It is present in liver, muscles and brain.
 Glucose
Biomolecules

Enzymes
Proteins which are used as catalysts in biochemical
reactions are known as biocatalysts (enzymes).
Enzymes have following two
specific characteristics:
(i) Specificity of Enzymes: Limitations of the Open Chain Structure:
(a) Generally one enzyme can catalyze only one Glucose penta-acetate does not react with hydroxyl
biochemical reaction. (b) It can increase rate of reaction amine thus indicating the absence of free-CHO group.
upto 1020 times. Cyclic Structure of Glucose:
(ii) Efficiency of Enzymes:
(a) One molecule of enzyme can convert millions of
substrate molecules into product(s) per second.
eg. Carbonic anhydrase enzyme present in red blood
cells has a highest turnover number.
(b) Enzymes are denatured at higher temperature.
(c) Enzymes are very efficient and very specific in
nature. The optimum temperature for enzyme activity
lies between 40°C to 60°C.
 Amino acids Classification
Biomolecules ● Essential amino acids: cannot be synthesised in the body.
● Non Essential amino acids: can be synthesised in the body.
(i) Essential amino acids: These are as follows
(a) Leucine (b) Isoleucine (c) Lysine (d) Methionine
(e) Phenylalanine (f) Threonine
(ii) Non-essential amino acids: These are as follows
(a) Alanine (b) Asparagine (c) Aspartic acid (d) Cysteine
(e) Glutamic acid (f) Glutamine (g) Hydroxyproline (h) Glycine
(i) Proline (j) Serine (k) Tyrosine (l) Arginine
(m) Cystine
Properties
Enzymes
● They are fairly soluble in water, but insoluble in non-polar solvents like
The above properties point out
petroleum ether, benzene, or ether.
toward the salt like character ● Amino acids have much larger dipole moments than simple amines and simple
(dipolar ion structure) to amino acids.
acids. Actually, in the dry state,
amino acids exist as dipolar ions
(also known as zwitterions or inner ● Amino acids are less acidic than most carboxylic acids and less basic than most
salts), a form in which the carboxyl amines. In fact, the acidic part of the amino acid molecule is the -NH3+ group, not
group is present as a carboxylate a-COOH group, while the basic part of the amino acid is the -COO- group, and not
ion, -COO, and the amino a free -NH2 group.
group as an aminium ion, -NH3+.
 Proteins
Biomolecules ● Polymero of a-amino acids
● connected by peptide bond.
Classification
● Fibrous Protein Polypeptide chains run parallel and held together
Types of nucleic acid by hydrogen and disulphide bonds e.g kertin, myosin
● Globular Proteins: Polypeptide chain is folded, looped and twisted
e.g., albumin, haemoglobin.
Structure
DNA
● 1º structure: It is the unique sequence of amino acids in each kind
● Carries genetic information
or protein.
● Sugar unit is 2-deoxyribose
● 2º structure: Exist in two different type ⍺-helix and β-pleated.
● Bases are adenine, thymine, cytosine and guanine
● 3º structure: Overall folding of polypeptide chains
● It has double stranded structure In both chains, in
● 4° structure: Spatial arrangement of subunits (two or more
between A and T, 2 hydrogen bonds are present
polypeptide chain) with respect to each other.
while in C and G, 3 H-bonds are present. (A= T) (C°
The main forces which stabilise the 2º and 3°structures of proteins are
G)
hydrogen bonds, disulphide linkages, vander waals and electrostatic
RNA
force of attraction.
● Control protein synthesis
Denaturation of proteins:
● Sugar unit is ribose
● Bases are adenine, uracil, cytosine and guanine
● It has single stranded structure On the basis of
(Protein looses its biological activity)
their function RNAs mainly are of three types.
The denaturation causes change in 2 or 3° structures but 1º structure
Messenger RNA (m-RNA), Transfer RNA (t-RNA),
remains intact.
Ribosomal RNA (r-RNA)
Biomolecules Vitamins
It has been observed that certain organic compounds are
required in small amounts in our diet but their deficiency causes
specific diseases. These compounds are called vitamins.
Classification of Vitamins
Vitamins are classified into two groups depending upon their
solubility in water or fat.
(i) Fat Soluble Vitamins: Vitamins which are soluble in fat and
oils but
insoluble in water are kept in this group. These are vitamins A,
D, E and K. They are stored in liver and adipose (fat storing)
tissues.
(ii) Water Soluble Vitamins: B-complex and vitamin C are soluble
in water so they are grouped together. Water soluble vitamins
must be supplied regularly in diet because they are readily
excreted in urine and can not be stored (except vitamin B12) in
our body.