GrADE- XI

CHEMISTRY NOTES
VoL-ii
(2022- ’23)

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 Chapter 8: Redox reactions

Main points:

Oxidation:

 According to this concept oxidation is the process of addition of oxygen/electronegative element to a

substance or removal of hydrogen/electropositive element from a substance. (Classical Concept)
 Oxidation is the process of removal (losing) of electron. (electronic concept)
 In oxidation, there is an increase in the oxidation number.

Reduction (Classical Concept):

 Reduction is the process of removal of oxygen/electronegative element from a substance or addition of

hydrogen/electropositive element to a substance. (Classical Concept)
 Reduction is the process of addition (gaining) of electron.
 In reduction, there is a decrease in the oxidation number.

Reducing agent:

 Substance which is oxidised is called reducing agent.

 A substance that donates electron is called a reducing agent.
 A reagent which lowers the oxidation number of an element in a given substance is called reductant or
reducing agent.

Oxidising agent:

 The substance which is reduced is called an oxidising agent.

 A substance that accepts electron is called an oxidising agent.
 A reagent which can increase the oxidation number of an element in a given substance is called an
oxidant or oxidising agent.

Redox reaction:

 If oxidation and reduction take place simultaneously, the process is called Redox reaction.
i.e. reduction + oxidation → Redox reactions
 E.g. Zn + CuO → ZnO + Cu. Here Zn is converted to ZnO. i.e oxygen is added to Zn. So, it is oxidised and
hence the reducing agent. CuO is converted to Cu. i.e. oxygen is removed from Cu. So, it is reduced and
hence it is the oxidising agent.
 Other examples are: FeCl3 + H2 → FeCl2 + 2HCl
Here the electronegative Cl atom is removed from FeCl3. So, it is reduced. H2 is oxidised since an
electronegative Cl atom is added to it. FeCl3 is the oxidising agent and H2 is the reducing agent.
 2 H2S(g) + O2 (g) → 2 S (s) + 2 H2O (l)
Here H2S is oxidised and O2 is reduced.
 A redox reaction is the process of exchange of electrons between two or more substances.
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 E.g. In the reaction Zn + Cu2+ → Zn2+ + Cu, Zn loses two electrons and forms Zn2+. So, it is oxidised.
Cu2+ gains two electrons and forms Cu. So, it is reduced. Here Zn is the reducing agent and Cu2+ is the
oxidising agent.
 Other examples are reaction between Cu and Ag+ ; Cu + Ag+ → Cu+2 + Ag. Here Cu loses two electrons.
So, it is oxidised and is the reducing agent. Ag+ accepts an electron. So. it is reduced and is the oxidising
agent.
 In the first example, Cu is reduced while in the second reaction it is oxidised. So, the oxidation or
reduction of a metal depends on the nature of the metal to which it is combined.
 The series in which the different metals are arranged in the decreasing order of their reactivity is called
electrochemical series or reactivity series. Generally, a metal lying above in the reactivity series can
displace another metal from its salt solution.
 For example, Zn can displace copper from an aqueous solution of copper sulphate, since Zn lies above
Cu in the electrochemical series.
 In the reaction between cobalt and nickel ion Co + Ni2+ → Co2+ + Ni, Co is oxidised to Co2+ and Ni2+ is
reduced to Ni.

Oxidation number (Oxidation state):

 Oxidation number of an element in a compound is the residual charge on the element when all the
other atoms are removed from it as ions.
 For example, oxidation number of Mn in KMnO4 is the residual charge on Mn when one K atom and
four O atoms removed from it as K + and O2- ions respectively.
 Oxidation number denotes the oxidation state of an element in a compound ascertained according to a
set of rules. These rules are formulated on the basis that electron in a covalent bond belongs entirely to
the more electronegative element.

Rules for assigning oxidation number to an atom:

 Oxidation number of Hydrogen is always +1 (except in hydrides, it is -1).

 Oxidation number of oxygen in most of compounds is -2. In peroxides it is (-1). In superoxides, it is (-1/2).
In OF2 oxidation number of oxygen is +2. In O2F2 oxidation number of oxygen is +1 Oxidation number of
fluorine is -1 in all its compounds.

Calculation of oxidation number:

 Oxidation state of all the elements in their elemental form (in standard state) is taken as zero. Oxidation
number of elements in Cl2, F2, O2, P4, O3, Fe(s), H2, N2, C(graphite), Na(s) is zero.
 Common oxidation state of elements of group one (1st) is +1. Common O.S. of elements of group two
(2nd) is +2.
 For ions composed of only one atom, the oxidation number is equal to the charge on the ion.
 The oxidation number of oxygen in most of its compounds is –2. But, in peroxides (e.g., H2O2, Na2O2), each
oxygen atom is assigned an oxidation number of –1, in superoxides (e.g., KO2, RbO2) each oxygen atom is
assigned an oxidation number of (–½). In oxygen difluoride (OF2) and dioxygen difluoride (O2F2), the
oxygen is assigned an oxidation number of +2 and +1 respectively.
 The oxidation number of hydrogen is +1 but in metal hydride its oxidation no. is–1.
 In all its compounds, fluorine has an oxidation number of –1.
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 The algebraic sum of the oxidation number of all the atoms in a compound must be zero.
 In polyatomic ion, the algebraic sum of all the oxidation numbers of atoms of the ion must equal the
charge on the ion.

Stock-notation:

 The oxidation number is expressed by putting a Roman numeral representing the oxidation number in
parenthesis after the symbol of the metal in the molecular formula. Thus aurous chloride and auric
chloride are written as Au(I)Cl and Au(III)Cl3. Similarly, stannous chloride and stannic chloride are written
as Sn(II)Cl2 and Sn(IV)Cl4.

Balancing of redox reactions- Oxidation Number Method:

Write the net ionic equation for the reaction of potassium dichromate (VI), K2Cr2O7 with sodium
sulphite,Na2SO3, in an acid solution to give chromium(III) ion and the sulphate ion.

Step 1: The skeletal ionic equation is-

Cr2O72– (aq) + SO32–(aq) → Cr3+(aq) + SO42–(aq)

Step 2: Assign oxidation numbers for Cr and S

+6 –2 +4 –2 +3 +6 –2
Cr2O7 (aq) + SO3 (aq) → Cr (aq) + SO42–(aq)
2– 2– 3+

Step 3: Calculate the increase and decrease of oxidation number and make them equal

Change in O.N.= [(+3) – (+6)] x 2 = - 3

Change in O.N. of S atom = (+6) – (+4) = 2

+6 –2 +4 –2 +3 +6 –2
Cr2O7 (aq) + 3SO3 (aq) → 2Cr (aq) + 3SO42–(aq)
2– 2– 3+

Step 4: Balance the number of oxygen atoms by adding water molecule.

Cr2O72– (aq) + 3SO32–(aq) → 2Cr3+(aq) + 3SO42–(aq) + 4H2O(l)

Step 5: Balance the number of hydrogen atoms by adding H+as the reaction occurs in the acidic medium,

Cr2O72– (aq) + 3SO32–(aq) + 8H+→ 2Cr3+(aq) + 3SO42–(aq) + 4H2O(l)

Half- Reaction Method:

balance the equation showing the oxidation of Fe2+ ions to Fe3+ ions by

dichromate ions (Cr2O7)2– in acidic medium wherein Cr2O72– ions are reduced to Cr3+ ions.

Step 1: Write unbalanced equation for the reaction in ionic form:

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Fe2+ (aq) + Cr2O72– (aq) → Fe3+ (aq) + Cr3+(aq)

Step 2: Separate the equation into half reactions:

Oxidation half-cell reaction: Fe2+ (aq) → Fe3+ (aq) (increase in O.N of Fe from +2 to +3)

Reduction half- cell reaction: Cr2O72–(aq) → Cr3+ (aq) (decrease in O.N. of Cr from +6 to +3)

Step 3: Balance the atoms other than O and H in each half reaction individually.

Cr2O72– (aq) → 2Cr3+ (aq)

Fe2+ (aq) → Fe3+ (aq) (already balanced)

Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H+ to balance H atoms.
Cr2O72– (aq) +14 H+→.2Cr3+ (aq) + 7H2O (l)

Step 5: Add electrons to one side of the half reaction to balance the charges. If need be, make the number
of electrons equal in the two half reactions by multiplying one or both half reactions by appropriate
coefficients

[Fe2+ (aq) → Fe3+ (aq) + e– ] x 6

6Fe2+ (aq) →6 Fe3+ (aq) +6 e–

Cr2O72– (aq) +14 H+(aq) + 6e– → 2Cr3+ (aq) +7H2O

Step 6: Add the two half reactions and cancel the electrons on each side. This gives the net ionic equation

6Fe2+(aq) + Cr2O72– (aq) + 14H+(aq) → 6 Fe3+(aq) +2Cr 3+(aq) + 7H2O(l)

Redox couple:

 A redox couple is defined as having together the oxidised and reduced forms of a substance taking part
in an oxidation or reduction half reaction represented as Zn2+ /Zn and Cu2+ /Cu.
 Electrochemical cells are the devices which are used to get electric current by using chemical reaction.

Standard Electrode Potential:

 The potential associated with each electrode is known as electrode potential. If the concentration of each
species taking part in the electrode reaction is unity (if any gas appears in the electrode reaction, it is
confined to 1 atmospheric pressure) and further the reaction is carried out at 298K, then the potential of
each electrode is said to be the Standard Electrode Potential.
 SHE (Standard Hydrogen Electrode) is used to measure electrode potential and its standard electrode
potential is taken as 0.00 V.

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 Chapter 12: Organic Chemistry- Some Basic Principles and Techniques

Key points:

Reasons for Large Number of Organic Compounds:

(a) Catenation: It is the tendency of self- combination and is maximum in carbon. A carbon atom can
combine with other carbon atoms by single, double or triple bonds. Thus, it forms more compounds than
the others.
(b) Tetravalency and small size: Carbon being tetravalent, is capable of bonding with four other C atoms or
some other monovalent atoms. Carbon can form compound with oxygen. hydrogen. chlorine, sulphur,
nitrogen and phosphorus. These compounds have specific properties depending upon the nature of the
element or group attached with the carbon.
Furthermore, these compounds are exceptionally stable because of the small size of carbon.

Tetravalency of carbon: Carbon is always tetra covalent, i.e. it forms 4 covalent bonds with other atoms of
carbon. Due to tetravalency of carbon it has a tetrahedron shape.

Catenation: The self- linking property of carbon is known as catenation.

General Characteristics of Organic Compounds:

1. These are the compounds of carbon with H, 0, N, S, P, F, CI, Br and 1.
2. These are generally found in living organisms. e.g., carbohydrates, proteins etc.
3. These may be gases, liquids or solids.
4. Being covalent in nature, these have low boiling point and melting point and soluble in organic solvents.
5. These are generally volatile and inflammable.
6. They do not conduct electricity because of the absence of free ions.
7. They possess distinct colour and odour.

Classification of Carbon Atoms:

1. On the Basis of Number of C Attached

(i) Primary carbon atom: When carbon atom is attached with one other carbon atom only, it is called
primary or 1° carbon atom.

(ii) Secondary carbon atom: When carbon atom is attached with two other carbon atoms, it is called
secondary or 2°carbon atom.

(iii) Tertiary carbon atom: When carbon atom is attached with three other carbon atoms, it is called
tertiary or 3° carbon atom.

(iv) Quaternary carbon atom: When carbon atom is attached with four other carbon atoms, it is called
quaternary or 40 carbon atom.

Reactivity order of carbon atoms is as follows 3° > 2° > 1°.

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2. On the Basis of Position of Functional Group:
(i) α – carbon: Carbon which is directly attached to the functional group.
(ii) β- carbon: Carbon which is directly attached to the n-carbon.

Classification of Hydrogen Atoms:

 1°-hydrogen (primary): attached to 10 carbon,
 2°-hydrogen (secondary): attached to 2°carbon.
 3°-hydrogen (tertiary): attached to 3°·carbon.
 α- hydrogen(s): Hydrogens which are attached to n-carbon atom.
 β – hydrogen(s): Hydrogens which are attached to ~-carbon atom.

Classification of Organic Compounds:

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Functional Group:
 A functional group may be defined as an atom or a group of atoms present in a molecule which largely
determines the chemical properties.
 The atom e.g., -CI, -Br etc., or group of atoms e.g., -COOH, – CHO, which is responsible for the chemical
properties of the molecule, is
called functional group.
 Double and triple bonds are also functional groups.


R is called alkyl group, it contains only single bond; alkenyl group if contains double bond and alkynyl group
if contains triple bond.

Homologous Series:
 The series in which the molecular formula of adjacent members differ by a – CH2 unit, is called
homologous series and the individual members are called homologous.
 Homologous series is defined as a family or group of structurally similar organic compounds all
members of which contain the same functional group.
 The homologous series of alkene group is

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 The general characteristics of this series are :
 All the homologues contain same functional group. That’s why their chemical properties are almost
similar.
 All the members of a series have same general formula, e.g.,

3. All the members can be prepared by almost similar methods.

4. With increase in the molecular weight of a series, the physical properties varies gradually.

Representation of Different Formulae: An organic compounds can be represented by the following ways:

1. Complete formula: In it, all the bonds present between any two atoms are shown clearly.

2. Condensed Formula: In it, all the bonds are not shown clearly.

3. Bond Line Formula:

 In it, every fold and free terminal represents a carbon and lines represent the bonds. e.g.,

 In such formulae, it is assumed that required number of H-atoms are present, where ever, they are
necessary (to satisfy tetravalency of carbon) e.g.,

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Nomenclature of Organic Compounds:

IUPAC System:
 The IUPAC (International Union of Pure and Applied Chemistry) system, given in 1957, is superior
and widely used. IUPAC amends these rules from time to time. Here. we are following the 1993
recommendations of IUPAC nomenclature.
 Following rules are used to write the IUPAC name of an organic compound:

Rule 1:
 Longest chain rule: The chain containing the principal functional group, secondary functional group
and multiple bonds as many as possible is the longest possible chain.
 In the absence of functional group, secondary group and multiple bonds, the chain containing the
maximum number of C-atoms will be the longest possible chain e.g

 Choose the word root from the table given below for the longest possible chain.
 Word Root for Carbon Chain

Rule 2:
 Lowest number rule Numbering is done in such a way so that
 branching if present gets the lowest number.
 the sum of numbers of side chain is lowest.
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  principal functional group gets the lowest number.
 Select the principal functional group from the preference series :

 Functional group other than the principal functional group are called substituents.

Rule 3: Naming the prefixes and suffixes:

 Prefix represents the substituent and suffix is used for principal functional group.
 Primary prefixes are cycle, bicycle, di, tri, tetra, tries. tetrakis etc.
 Primary suffix are ene, ane, or yne used for double, single and triple bonds respectively.
 Secondary suffixes are tabulated below :

 Hence, according to the rules. given above, the IUPAC name of a compound can be written as
 Prefixes + Root word + Suffixes
OR
 Primary prefix + secondary prefix + Root word + primary suffix + secondary suffix

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  If more than two similar functional groups are present, all the groups are considered as substituent,

Naming Alicyclic Compounds:

 For alicyclic compounds, prefix cyclo is used e.g.,

 If the alkyl chain contains a greater number of C-atoms than the ring, the ring is designated as
substituent, e.g.,

 If side chain contains a multiple bond or a functional group, the ring is treated as a substituent e.g

 Other examples are

Naming Spiro Compounds:

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  Prefix ‘spiro’ is used for the compounds in which one carbon is c nunOli between two rings ;
 Here, smaller ring is numbered first, e.g.,

Naming Bicyclo Compounds:

 Prefix ‘bicycle’ is used for such compounds e.g.,

 In bicycle compounds, numbering is done first in larger ring, then in smaller ring.

Naming Aromatic Compounds:

 IUPAC accepted their common trivial names e.g.,

Isomerism:
 The compound having same molecular formula but differ in properties are known as isomers and
the phenomenon is known as isomerism.

 There are two main types of isomerism i.e.,

1. Structural Isomerism:
 In this type of isomerism, compounds have same molecular formula but different structures.

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  It can further be of following types:
(i) Chain Isomerism:
 It arises when two or more compounds have similar molecular formula but different carbon
skeletons, e.g.

(ii) Position Isomerism:

 When two or more compounds have same molecular formula but different position of functional
groups or substituents, they are called positional isomers and the phenomenon is called position
isomerism

(iii) Functional group Isomerism:

 It arises when two or more compounds have the same molecular formula but different functional
group. e.g., C3H6O represents an aldehyde and a ketone as shown below

(iv) Metamerism:
 It arises due to different alkyl groups on either side of the same functional group in a molecule, e.g,

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(v) Tautomerism:
 It is a special type of functional group isomerism which arises in carbonyl compounds containing α –
H atom e.g.,

2. Stereoisomerism
 The compounds having same molecular formula but different spatial arrangement of atoms or
groups are called stereoisomers and the phenomenon is called stereoisomerism.

 Stereoisomerism is of three types: optical isomerism, geometrical isomerism and conformational

isomerism

(i) Optical Isomerism:

 Compounds having similar physical and chemical properties but, differ only in behaviour towards
plane polarised light are called enantiomer (optical isomers) and the phenomenon is known as
optical isomerism. e.g.,

 The isomer which rotate the plane of polarised light towards right (clockwise) is known as
dextrorotatory or d-form while that which rotates towards left (anticlockwise) is known as
laevorotatory or l-form.
 Generally, asymmetric or chiral compounds show optical isomerism.
 Chiral compounds are those which contain chiral centre i.e., chiral carbon, the carbon all the four
valencies of which are satisfied by four different groups.
 Allenes, spiranes and biphenyl compounds, although have absence of chiral centre, but are
asymmetric. That’s why they are also optically active.
 Number of optical active isomers = 2n (where, n = chiral carbon).
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  If two end are similar number of optical active isomers = 2n – 1 (if n = even) and meso form = 2n – 2 / 2.
 If n = odd, number of optical active isomers = 2n – 1 – 2(n – 1) / 2.

Geometrical Isomerism:
 The isomers having same molecular formula but different spatial arrangement of atoms about the
double bond are known as geometrical isomers and this phenomenon is called geometrical
isomerism, e.g.,

 For exhibiting geometrical isomerism, the essential conditions are :

 The compound must contain at least one double bond.
 The groups present at the double bonded carbon atoms, must be different. However, one
similar group should be present at the adjacent double bonded carbon atoms.
 Number of geometrical isomers (if two ends are not similar = 2n where, n = number of double
bonds).

Types of Geometrical Isomers:

 (a) Cis-trans isomers: In cis-isomer, similar groups are present on the same side of the double bond
and in trans- isomer, similar groups are present on the opposite side of the double bond. e.g.,

(b) Syn-anti isomers compounds containing C=N bond (as in aldoxime), N=N bond (as in H2N2O) exhibit
this type of isomerism.

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 (c) E-Z isomers In E-isomer, bulkier (heavier) groups are present on the opposite side of the double
bond and in Z-isomer, heavier groups are present on the same side of the double bond. E is entgegen
means opposite and Z is Zusammen means together, e.g.,

(iii) Conformational Isomerism:

 In conformational isomerism because of the free rotation of carbon-carbon single bond, different
arrangement of atoms in space are obtained. These arrangements are called conformers or
rotamers.

 Different Conformers:
 (a) Staggered conformation: In it, the atoms or groups bonded to carbons at each end of a C-C
bond are as far apart as possible.

 In staggered conformation, the dihedral angle between the bonds at each of the C-C bonds is 180°.

(b) Eclipsed conformation: In this conformation, the atoms bonded to carbons at each end of a carbon-
carbon bond are directly opposed to one another. i.e., they are as close as possible

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  In this conformation, the dihedral angle is 0°.

(c) Skew or Gauche conformation: All other conformations in between eclipsed and staggered
conformations are called Skew or Gauche conformations.

Fission of a Covalent Bond: Cleavage of covalent bond can happen in two ways, homolytic and heterolytic

1. Homolytic Fission:
 In this, one of the electrons of the shared pair in a covalent bond goes with each of the bonded
atoms. The neutral chemical species thus formed, is called free radical. Generally, homolytic fission
takes place in non-polar, covalent molecules in the presence of sunlight or high temperature.

 Free radicals are highly reactive, neutral and electron deficient species

2. Heterolytic Fission
 In this, the bond breaks in such a fashion that the shared pair of electrons goes with one of the
fragments.

 Carbon bearing a positive charge is called carbocation and carbon bearing negative charge is called
carbanion.
 Heterolytic fission generally takes place in polar covalent molecules but in non-polar molecules, it
takes place in the presence of catalyst like AlCI3) (anhy.), FeCl3)(anhy.)etc.

Attacking Reagent: These are of two types-

1. Electrophiles or Electrophilic Reagents:

 These are electron deficient species i.e., behave as Lewis acids. The following species behave as
electrophiles :
 All non-metal cations and metal cations which have vacant d- orbitals. e.g., CI+, NO+2, CH3CO+ etc.
 Lewis acids (incomplete octet) e.g., BF3, ZnC12 (anhydrous), FeCl3 (anhydrous), AlCl3 (anhydrous),
:CH2 etc.
 Non-metal (acidic) oxides e.g., CO2, SO2 etc.

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2. Nucleophiles or Nucleophilic Reagents:
 These are electron rich species i.e., behave as Lewis bases.
 These attack at electron deficient area.
 The following species behave as nucleophiles :

 In case of same nucleophilic site, nucleophilicity parallels basicity i.e, as the basicity increases,
nucleophilicity also increases.
 (if nucleophilic sites (or attacking atoms) are different nucleophilicity varies inversely with
electronegativity)

3. Amphiphile:
 These species behave like both electrophiles as well as nucleophiles. Organic compounds containing
a multiple bond between carbon and a more electronegative atom can act as amphiphiles, e.g.,

Reaction Intermediates:
 These are formed as an intermediate during the course of a reaction.
 These are short lived and highly reactive.
 Free radicals, carbocations, carbanions, carbenes and nitrenes are important reactions
intermediates.

1. Free Radicals:
 These are the product of homolytic fisson and contain an odd electron. These are highly reactive
planar species with Sp2 hybridisation.
 Their order of stability is

2. Carbocations:

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  These are the product of heterolysis and contain a carbon bearing positive charge. These are
electron deficient species. Carbocations contain six electrons in the valence shell.
 These are also planar chemical species i.e., sp2 hybridised with an empty p-orbital

 The stability order of carbocations is

3. Carbanions:
 These are also the product of heterolysis and contain a carbon bearing negative charge and 8
electrons in its valence shell
 These have pyramidal shape with Sp3 hybridised carbon (having one lone pair)
 The order of stability of carbanions is

4. Carbenes:
 These are divalent carbon species having two non-bonding electrons along WIth two bond pairs.
 These are obtained by photolysis or pyrolysis. e.g.,

 These being electron deficient behave as Lewis acids. These are of two types:

(i) Singlet carbine: In it, the C-atom is Sp2 hybridised. Then Hybridised orbitals contain no electrons and
a hybridised orbital contains two electrons.

 Singlet carbene has bent structure and is less stable than triplet carbene.
 The order of stability of singlet carbenes is

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 (ii) Triplet carbene In it, the central C-atom is sp-hybridised. The sp – hybridised orbitals contain 1
electron each .

 Triplet carbene has linear geometry.

5. Nitrene:
 These are neutral monovalent nitrogen species in which N atom has two unshared pair of electrons
with a monovalent atom or group attached.

 These are obtained by thermolysis of azides and as reactive as carbenes.

6. Arynes:
 It contains a formal carbon-carbon triple bond in aromatic molecule.

 The additional bond is formed between two neighbouring C-atoms by sideways overlapping of two
Sp2 orbitals. The new bond lies along with side of the ring and has little interaction with the 1t
electron cloud lying above and below the ring.
 The sideways overlapping is weak and thus, makes the benzene more reactive.

Inductive Effect:
 It is just like shifting of shared pair of electrons in polar covalent molecules. If shared pair is more
shifted towards the more electronegative atom, the less electronegative atom acquires slight
positive charge and more electronegative atom acquires partial negative charge, e.g.,

 It is a permanent effect and propagates through carbon chain.

 Atoms or groups having greater electron affinity than hydrogen. are said to have electron attracting
or negative inductive effect (- I) while that having, smaller electron affinity than hydrogen are said
to have electron releasing or positive inductive effect (+ I) e.g.,

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  Here, Cl has – I effect and alkyl group has + I effect.
 Order of groups producing – I effect is

 Order of groups producing + I effect is

Applications of Inductive Effect:

 Presence of groups showing + I effect increases the stability of carbocation while presence of
groups showing – I effect decreases their stability.
 Strength of acid increases with the attachment of group showing – 1 effect and decreases with the
attachment of group showing + I effect.
 Presence of + I showing groups increases the basic strength of amines.
 Reactivity of carbonyl compound is increased by – I showing groups.
 Reactivity of alkyl halides towards SN 1 is increased by + 1 showing groups.

Electromeric Effect:
 It is defined as the polarity produced in a multiple bonded compound as a reagent approaches it. In
the presence of attacking reagent, the two π electrons are completely transferred to any of the one
atom. This effect is temporary.
 When the electron pair moves towards the attacking reagent, it is termed as the +E effect.
 The -E effect can be found in reactions when the electron pair moves away from the attacking
reagent.
 In + E type displacement of electron pair is away from the atom or group.
 In – E type the displacement is towards the atom or group. e.g.,

Hyperconjugation:

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  It involves delocalisation of σ electron of a C – H bond of an alkyl group attached directly to an atom
of unsaturated system or to an atom with an unshared p-orbital.

 This effect is also called no bond formation or Baker Nathan effect.

Applications of Hyperconjugation:
 Stability of alkenes: More the number of a-hydrogen atoms, more stable is the alkene.

 Stability of carbocation: Greater the number of alkyl groups attached to a positively charged
carbon atom, the greater is the stability.

Resonance Effect:
 The polarity produced in the molecule by the interaction of two pi bonds or between a pi bond and
lone pair of electron present on an adjacent atom is known as resonance.

 It involves delocalisation of π electrons. This effect may be of + R type or – R type.

 When all the properties of a molecule cannot be shown by a single structure and two or more
structures are required to show all the properties of that molecule, then the structures are called
resonating structures or canonical forms and the molecule is referred as resonance hybrid.
 The arrangement of atoms must be identical in all the canonical forms.
 The energy content of all the canonical forms must be nearly same.
 Each canonical form must have the same number of unpaired electrons.

Positive Resonance Effect (+R):

 In this effect the transfer of electrons is away from an atom or substituent group attached to the
conjugated system.
 Electron donating groups with respect to conjugate system show +R effect. Central atom of
functional groups should be more electronegative than the surrounding atoms or groups to show
+R effect. e.g., halogens, -OH. -OR, -OCOR, -NH2,-NHCOR etc.

23
  Electron donating groups producing + R effect are ortho and para directing. ‘They activate the
benzene ring towards the electrophilic Substitution reactions except halogens.
 Halogens slightly deactivate the benzene ring towards the electrophilic substitution reaction.
 More the electron donating group, more is the basic nature.

Negative Resonance Effect (-R):

 In this effect the transfer of electrons is towards the atom or substituent group attached to the
conjugated system.
 Electron withdrawing groups with respect to conjugate system show – R effect. Central atom of
functional groups should be less electronegative than surrounding atoms or groups to show – R
effect. e.g., halogens, – COOH, - COOR, - CHO, - CN, -NO2 etc.

 Electron withdrawing groups producing – R effect are meta directing. They deactivate the benzene
ring towards the electrophilic substitution reaction.
 More the electron withdrawing group, more is the acidic nature.

Resonance Energy:
 Number of π bonds ∝ contributing structures ∝ resonance energy ∝ stability.
 In benzene, resonance energy is 36 kcal/mol.

Stability of Canonical Forms: It can be judged by the following rules-

 Non-polar structure is more stable than the polar structure.

 Among polar structures, structure with maximum number of covalent bonds is most stable.
 The structure with maximum charge separation is more stable.
 Structure with positive charge on more electropositive element and negative charge on more
electronegative element is more stable.

Resonance and Bond order:

Methods of Purification of Organic compounds:

 Sublimation: This method is used to separate the sublime able compounds from non- sublimable
compounds.

24
 Crystallisation: This method is based on the difference in the solubilities of compound and impurities in
a suitable solvent. The impure compound is dissolved in a solvent and heated at higher temperature. On
cooling the hot and conc. Solution, pure compounds crystallizes out.
 Distillation: This method is used to separate volatile liquids from non- volatile liquids and liquids having
sufficient difference in their boiling points.
 Fractional distillation: If the difference in the boiling points of two liquids is not much, they are
separated by fractional distillation.
 Distillation under reduced pressure: This method is used to purify liquids having high boiling points and
decomposes at or below their boiling points.
 Steam distillation: This method is used to separate substances which are steam volatile and are
immiscible with water.
 Differential Extraction: When an organic compound is present in an aqueous medium it is separated by
shaking it with organic solvent in which it is more soluble than in water. The aqueous solution is mixed
with an organic solvent in a separating funnel and shaken for sometimes and then allowed to stand for
some time. When organic solvent and water form two separate layers the lower layer is run out by
opening the tap of funnel and organic layer is separated, the process is repeated several times and pure
organic compound is separated.
 Chromatography: This technique is used to separate mixtures in to their components, purify the
compounds and test the purity of compounds. It is classified as follows:
 Adsorption Chromatography: It is based on the fact that different compounds are adsorbed on
an adsorbent to different degrees. Silica gel or alumina is used as adsorbents.
 Partition Chromatography: It is based on the continuous differential portioning of components
of a mixture between stationary and mobile phases.

Qualitative Analysis of Organic Compounds:

Detection of Carbon and Hydrogen:

 The carbon and hydrogen present in the organic compound are detected by heating the compound with
Copper II oxide in a hard glass tube. Carbon present in the compound is oxidized to CO2 which can be
tested with lime water and hydrogen is converted to water which can be tested with anhydrous copper
sulphate which turns blue.
C + CuO 2Cu + CO2
2H + CuO Cu + H2O
CO2 +Ca (OH)2 2 CaCO3 + H2O
5H2O + CuSO4 CuSO4.5H2O

Detection of other elements:

 Sodium Fusion Extract:

 A small piece of dry Sodium metal is heated with an organic compound in a fusion tube for 2 -3
minutes and the red-hot tube is plunged in to distilled water contained in a china dish. The
contained of the china dish is boiled, cooled and filtered. The filtrate is known as Sodium fusion
extract.

 Test for Nitrogen: The sodium fusion extract is boiled with iron II sulphate and then acidified with Conc.
sulphuric acid, the formation of Prussian blue colour confirms the presence of nitrogen.
6CN- + Fe2+ [Fe(CN)6] 4-
3[Fe(CN)6] 4-+ 4Fe3+ + xH2O Fe4[Fe(CN)6] 3.xH2O
25
 Test for Sulphur: the sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A
black precipitate of lead sulphide indicates the presence of sulphur.
S2- + Pb2+ PbS
Black

 Test for halogens:The sodium fusion extract is acidified with nitric acid and then treated with silver
nitrate. A white precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a
yellowish ppt. sparingly soluble in ammonium hydroxide shows the presence of bromine, a yellowish
ppt. insoluble in ammonium hydroxide shows the presence of iodine.
X- + Ag+ AgX

Quantitive Analysis :

1. Carbon and Hydrogen:

Let the mass of organic compound be m gm. Mass of water and carbon dioxide produced be m1 and m2 gm
respectively.
% of carbon = 12 x m2 x 100 /44 x m
% of hydrogen = 2 x m1 x 100/ 18 x m

2. Nitrogen:

 Dumas Method: A known mass of organic compound is heated with excess of CuO in an atmosphere of
CO2, when nitrogen of the organic compound is converted into N2 gas. The volume of N2 thus obtained is
converted into STP and the percentage of nitrogen determined by applying the equation:
Volume of Nitrogen at STP = P1V1 x 273 760 x T1
%N = 28 x vol of N2 at STP x 100/ 22400 x mass of the substance taken

 Kjeldahl’s Method:

A known mass of organic compound is heated with conc. H2SO4 in presence of K2SO4 and little CuSO4 or
Hg in a long -necked flask called Kjeldahl’s flask. When nitrogen present in the organic compound is
quantitatively converted into (NH4)2SO4. (NH4)2SO4 thus obtained is boiled with excess of NaOH solution
to liberate NH3 gas which is absorbed in a known excess of a standard acid such as H2SO4 or HCl. The vol
of acid unused is found by titration against a standard alkali solution. From the volume of the acid used,
the percentage of nitrogen is determined by applying the equation,

%N= 1.4 x Molarity of the acid x Basicity of the acid x Vol of the acid used/ Mass of the substance taken

Halogens:

 Carius method: A known mass of an organic compound is heated with fuming nitric acid in the presence
of silver nitrate contained in a hard glass test tube known as carius tube in a furnace. Carbon and
hydrogen present in the compound are oxidized to carbon dioxide and water. The halogen present
forms the corresponding silver halide. It is filtered, dried, and weighed.

26
 Chapter 13: Hydrocarbons

Key points:

Hydrocarbons are the organic compounds containing carbon and hydrogen only, e.g., alkane, alkene and
alkynes.

Classification of Hydrocarbons:

Alkanes:
 Alkanes are saturated, open chain hydrocarbons containing carbon-carbon single bonds. e.g., methane
(CH4), ethane (C4H6) propane (C3H8), etc.
 These hydrocarbons are inert under normal conditions [i.e.,do not react with acids. bases and other
reagents).
 Alkanes exhibit chain isomensm, position isomerism and conformational isomerism.
 C–C bond length 1.154 A0
 sp3 hybridization

Methods of Preparation of Alkanes:

i) From hydrogenation of alkenes and alkynes:

 Ease of hydrogenation depends on the steric crowding across the multiple bond.
 More is the steric crowding, the less is the
 reactivity towards hydrogenation.

(ii) By sodalime: Decarboxylation of sodium or potassium salts of fatty acids [decarboxylation reaction]

27
 This reaction is used for descending of series as the alkane obtained has one carbon less than the parent
compound.
 CaO is more hygroscopic than NaOH and it keeps NaOH in dry state.

(iii) By Wurtz reaction:

 This reaction is used to increase the length of the carbon chain.

(iv) By reduction of alkyl halides:

 Reducing agents like Zn/HCl, HI/Red P, H2/Pd can also be used.

(v) By Kolbe’s electrolysis:

 Only alkanes with even number of carbon atoms can be formed.

 Alkane and CO2 are liberated at anode while H2 is liberated at cathode.

(vi) Clemmensen’s reduction:

(vii) From compounds containing oxygen: Alcohols, aldehydes ketones, carboxylic acids and their
derivatives give alkane when treated with hot conc HI and red P in a sealed tube.

28
(viii) Wolff-Kishner reduction:

(ix) From carbides:

(x) Corey-House synthesis: This method can be used to prepare alkanes having odd number of carbon
atoms.

Physical Properties of Alkanes:

 The first four members are colourless gas, next thirteen members are colourless liquids and next higher
members are colourless solids.
 It can be explained on the basis of magnitude of force of attraction i.e vanderWaals force.
 Boiling point of alkanes decreases on branching as the surface area decreases.
 BP ∝ VAF (van der Waals’ forces) ∝ molecular mass or VAF ∝ SA (surface area). So, boiling point order
can be given as n-octane > iso-octane> 2, 2, 3, 3-tetramethyl butane.
 Alkanes with even number of carbon atoms have higher melting points as compared to next higher or
lower alkanes with odd number of carbon atoms.
 Alkanes being non-polar in nature, soluble in non-polar solvents but insoluble in polar solvent such as
water.

Chemical Properties of Alkanes:

(i) Halogenation of alkanes:

(a) Chlorination:

29
(b) Bromination of alkanes proceeds in the same way but not so easily.

(c) Iodination:

 Mechanism of halogenation of alkanes is free radical in nature, i.e., the attacking reagent is a halogen
free radical X.
 It is a chain reaction.

(ii) Combustion:

 Due to the evolution of a large amount of heat during combustion, alkanes are used as fuels.

(iii) Controlled oxidation:

(iv) Isomerisation:

30
(v) Aromatisation:

Reactions for Methane (CH4):

31
  Methane cannot be prepared by Wurtz reaction, Kolbe’s electrolytic process and by reduction of
alkenes or alkynes.

Reactions for Ethane(C2H6):

Conformations of Alkanes:
Alkanes have C-C sigma (σ) bonds and rotation about C-C single bond is allowed. This rotation results in
different spatial arrangements of atoms in space which can change into one another, such spatial
arrangements are called conformations or conformers or rotamers.

Conformations of ethane:

(i) Sawhorse projections:

32
(ii) Newman projections:

 Intermediate conformation between eclipsed and staggered are known as skew (gauche)
conformations.
 Eclipsed form is least stable but staggered form is most stable due to greater distance between the
bond pairs or lesser torsional strain.
 The energy difference between the two extreme forms is of the order of 12.5 kJ mol-1.

Alkenes:

 Alkenes are also called olefins which indicates their high reactive nature.
 Alkenes have general formula Cn H2n, where n = 2,3,4 …
C2H4 (ethene), C3H6 (propene), etc.
 The carbon-carbon double bond in alkenes is made up of one σ and one π-bond.
 Alkenes are more reactive than Alkanes. This is due to the availability of n electrons
 These are unsaturated non-cyclic hydrocarbons which have sp2 -hybridisation with 120° bond angle.
 In ethylene the carbon atoms are sp2 hybridized- They are attached to each other by a π bond and a σ
bond. The σ bond results from the overlap of two sp2 hybrid orbitals. The π bond is formed from overlap
of the unhybridized p-orbitals. Ethylene is a planar molecule.

33
Methods of Preparation of Alkenes:

(i) From aIkynes:

Mechanism of 1,2-elimination or β-elimination:

34
  Predominant formation of a substituted alkene is formed according to Saytzeff’s rule.

Physical Properties of Alkenes:

 Alkene as a class resemble alkanes in physical properties, except in types of isomerism and difference in
polar nature.
 C1 to C3 are gases, the next fourteen are liquids and the higher members are solids.
 Alkenes show a regular increase in boiling point with increase in size.

Isomerism in Alkenes:
 Alkene show both structural isomerism and geometrical isomerism.
 Structural isomerism exhibited by alkenes are chain isomerism and position isomerism.
 Alkenes also exhibit stereoisomerism as geometrical (cis-trans) isomerism.

Chemical Properties of Alkenes:

(i) Addition of halogens:

(ii) Addition of hydrogen halides:

 HCI, HBr, HI add up to alkenes to form alkyl halides as per their reactivity order
 HI > HBr > HCI
 Addition reaction of HBr to unsymmetrical alkenes (Markownikoff’s rule):
 According to Markownikofrs rule, the negative part of the addendum (adding molecule) gets
attached to that carbon atom which possesses lesser number of hydrogen atom.
35
 Anti-Markownikoff addition or peroxide effect or kharash effect:
 In the presence of organic peroxide, addition of only HBr molecule on unsymmetrical alkene
takes place contrary to the Markownikoffs rule.

(v) Oxymercuration-demercuration:

 This reaction is an example of hydration of alkene according to Markownikoffs rule.

 It is an anti-addition reaction.
 It is better than catalytic hydration by dil. H2SO4, as it avoids rearrangement.

(vi) Hydroboration oxidation:

 This reaction involved syn-addition of reagent.

36
(vii) Oxidation:
 Alkenes decolourise cold dilute aqueous solution of potassium permanganate (Baeyer’s reagent).
 It is used as a test for unsaturation.

 Acidic KMnO4 or acidic K2Cr2O7 oxidise alkenes to ketones and/or acids depending upon the nature of
alkene and the experimental conditions.

(viii) Ozonolysis:

(ix) Polymerisation:

(x) Reaction with sulphur monochloride:

37
(xii) Diels-Alder reaction:

(xiii) Substitution reactions:

 These occur at very high temperature at allylic position

Reactions for Ethene [Ethylene] (C2 H4):

38
Conjugated dienes:
 Dienes having alternate single (-) and double bonds (=) are called conjugated alkenes.
 These give Diels Alder reaction.

Alkynes:
 These are unsaturated hydrocarbons with general formula C nH2n – 2 e.g., C2H2 (ethyne), C3H4 (propyne).
 Alkynes also exhibit electrophilic addition reaction but less reactive than alkenes because the
dissociation of x-electron cloud requires more energy.
 In alkynes, position of triple bond is determined by ozone (O3).
 H – C = C – H contains 3σ and 2π – bonds and bond length is 120 pm. In acetylene. H – C – C bond angle
is 180°.
 The σ -bond results from the overlap of two sp hybrid orbitals. The π bonds are formed from the
separate overlap of the two p-orbitals from the two adjacent carbon atoms.
 The other sp hybrid orbital of each carbon atom forms a σ bond with another carbon or hydrogen atom.
 Ethyne is a linear molecule.
 Like alkenes, alkynes undergo addition reaction. These reactions are due to the availability of more
exposed π electrons.

39
Methods of Preparation of Alkynes:

(i) From calcium carbide:

(ii) From vicinal dihalides:

(iii) From tetrahalides:

Physical Properties of Alkynes:

 The rust two members are gases next eight members (C5 – C12) are liquids and higher members are
solids.
 They are all colourless and odourless with the exception of acetylene which has slightly garlic odour due
to the presence of PH3 and H2S as impurities.
 Alkynes are insoluble in water but soluble in organic solvents like ethers, carbon tetrachloride and
benzene.
40
 Melting point, boiling point and density increase with increase in molar mass.

Chemical Properties of Alkynes:

 Alkynes show electrophilic as well as nucleophilic addition reactions.

(i) Acidic character of alkyne:

 Acetylenic hydrogens are acidic in nature due to 50% a-character in sp-hybridised orbitals.
 Acidity of alkynes is lesser than water.

 These reactions are not shown by alkenes, alkanes and non-terminal alkynes, hence used for distinction
between alkane, alkene and alkyne.
 The order for acidic behaviour is as follows:

(ii) Electrophilic addition reactions:

 The addition product formed depends upon the stability of vinylic cation. Addition on unsymmetrical
alkynes takes place according to Markovnikov’s rule.

(a) Addition of dihydrogen:

41
(b) Addition of hydrogen halides:

(c) Addition of halogens:

(d) Addition of water:

(iii) Cyclic polymerization:

42
(iv) Reaction with AsCl3 (Arsenic trichloride):

(v) Oxidation:

Ozonolysis:

 Higher alkynes give diketones which are further oxidised to carboxylic acid.

(vi) Linear polymerization:

Reactions for Acetylene (C2 H2)

43
Benzene:
 The parent member of the family of aromatic hydrocarbons is benzene (molecular formula: C6H6).
 It has hexagonal ring of six carbon atoms with three double bonds at alternate positions.
 It is resonance stabilised and the structure may be represented as given ahead.

Resonance Structure of Benzene:

 The phenomenon in which two or more structures can be written for a substance which involve
identical positions of atoms is called resonance.
 In benzene’s Kekule’s structures (A) and (B) represent the resonance structures. Actual structure – of
the molecule is represented by hybrid of these two structures.

Orbital structure of benzene:

 All six carbon atoms in benzene are sp2 hybridized. The sp2 hybrid orbitals overlap with each other and
with s orbitals of the six hydrogen atoms forming C—C and C—H σ-bonds.

44
 X-Ray diffraction data indicates that benzene is a planar molecule.
 The data indicates that all the six C—C bond length are of the same order (139 pm) which is
intermediate between (C—C) single bond (154 pm) and C—C double bond (133 pm).
 Thus the presence of pure double bond in benzene gives the idea of reductance of benzene to show
addition reaction under normal condition. Thus, It explains the unusual behaviour of benzene.

Methods of Preparation:

(i) Cyclic polymerisation of ethyne:

(ii) Decarboxylation of aromatic acids:

Physical Properties of Benzene:

 Aromatic hydrocarbons are non-polar molecules and are usually colourless liquids or solids with a
characteristic aroma.
 Aromatic hydrocarbons are immiscible with water but readily miscible with organic solvents.
 Aromatic compounds burn with sooty flame.

45
Chemical Reactions of Benzene:
 Benzene gives electrophilic substitution reactions.

Mechanism of electrophilic substitution reactions:

 All electrophilic substitution reactions follow the same three step mechanism.

Step 1. Formation of an electrophile:

Step 2. The electrophile attacks the aromatic ring to form a carbonium ion or carbocation:

Step 3. Loss of proton gives the substitution product:

(i) Nitration:

(ii) Halogenation:

46
(iii) Sulphonation:

(iv) Friedel-Craft’s alkylation reaction:

 When Friedel-Craft alkylation is carried out with CH3CI, the product obtained is C6H5CH3.
 In case the alkylation is carried out with higher alkyl halide, e.g., n-propyl chloride, then the electrophile
is n-propyl carbocation (CH3 – CH2 – +CH2) which is a primary carbocation and rearranges to form more
stable secondary carbocation (iso-propyl carbocation).Tthe main product formed will be iso-propyl
benzene.

(v) Friedel-Crafts acylation reaction

(vi) Chlorination (With Cl2 ): In excess of chlorine, benzene yields hexachlorobenzene [C 6CI6].

47
Vii) Addition reaction: Benzene also undergoes addition reactions e.g.,

Viii) Combustion reaction: 2C6H6 + 15O2 → 12CO2 + 6H2O

Reactions for Benzene:

Petroleum:
 It is a dark coloured oily liquid with offensive odour, found at various depths in many region below the
earth’s surface.
 It is also called rock oil, mineral oil or crude oil It is covered by an atmosphere of a gaseous mixture
known as natural gas.
 It contains mainly alkanes, cycloalkanes, aromatic hydrocarbons, sulphur, nitrogen and oxygen
compounds.
48
 When subjected to fractional distillation, it gives different fractions at different temperatures.

LPG (Liquified Petroleum gas):

 It is a mixture of butane and isobutane with a small amount of propane.

 A strong foul smelling substance, called ethyl mercaptan (C2H5SH) is added to LPG cylinders, to help in
the detection of gas leakage.

CNG (Compressed Natural Gas)

49
 It consists mainly of methane (95%), which is a relatively unreactive hydrocarbon and makes its nearly
complete combustion possible.

Artificial Methods for Manufacturing Petrol:

 From higher alkanes, petrol or gasoline is obtained by cracking or pyrolysis.
 From coal, petrol can be synthesized by following two processes :

(i) Bergius process:

(ii) Fischer- Tropsch process:

 The best catalyst for this process is a mixture of Co, thoria, magnesia and kieselguhr.
 The overall yield in this process is slightly higher than Bergius process.

Octane Number:

 The quality of petrol is expressed in terms of octane number which is defined as the percentage of iso-
octane by volume in a mixture of iso-octane and n-heptane which has the same antiknock properties as
the fuel under test.
 The octane number is 100 for iso-octane (2, 2, 4-trimethylpentane).
 Natural gas has octane number 130.
 TEL (tetraethyl lead) is used as antiknocking compound.
 Octane number is increased by isomerisation, alkylation or aromatisation.

Cetane Number:
 Quality of diesel oils is measured in terms of cetane number which is defined as the percentage of
cetane (hexadecane) by volume in a mixture of cetane and a-methyl naphthalene which has the same
ignition property as fuel oil under similar experimental conditions.
 It is 100 for cetane and 0 for α – methyl naphthalene.

Aromaticity:
 It is a property of the sp2 hybridized planar rings in which the p orbitals allow cyclic delocalization of π
electrons.

Conditions for Aromaticity:

 An aromatic compound is cyclic and planar.
 Each atom in an aromatic ring has a p orbital. These p orbitals must be parallel so that a continuous
overlap is possible around the ring.
 The cyclic π molecular orbital (electron cloud) formed by overlap of p orbitals must contain (4n + 2) π
electrons. Where n = integer (0, 1, 2, 3, etc.). This is known as Huckel rule.
 Some Examples of Atomic Compounds are given below:

50
Directive influence of a functional group in monosubstituted benzene:

1. Ortho and para directing groups and activating:

 These group activates the benzene ring for the attack by an electrophile.
 Example are —OH; —NH2, —NHR, —NHCOCH3, —OCH3 —CH3 —C2H5 etc.

2. Meta directing group and deactivating:

 These group because of strong —I effect, decreases overall electron density on benzene ring and makes
further substitution difficult in the benzene ring.
 Examples are –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.

51
3. Ortho and para directing groups and deactivating:
 Halogens because of their strong – I effect, decreases overall electron density on benzene ring.
However, due to resonance the electron ensity on o– and p– positions is greater than that at the m-
position. Hence, they are also o– and p– directing groups

Carcinogenicity and Toxicity:

 Some polynuclear hydrocarbons containing more than two benzene rings fused together become toxic
and they are having cancer producing property.
 They are actually formed due to incomplete combustion of some organic materials like tobacco, coal
and petroleum, etc.
 Some of the carcinogenic hydrocarbons are given below:

52