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ETOOS Comprehensive Study Material


For JEE- Main & Advanced
CHEMISTRY FOR JEE MAIN & ADVANCED

Reaction : Breaking of old bond and formation of new bond is known as chemical reaction

A B + X Y A X + B Y

Old bonds New bonds

A sequential account of each step, describing details of electron movement, energetics during bond cleavage and
bond formation, and the rates of transformation of reactants into products (kinetics) is referred to as reaction mechanism.
Species on which reagent is attacking is known as substrate or reactant.
Species which attack on substrate, is known as reagent.

Type of cleavage of bond


(A) Heterolytical cleavage/fission
(B) Homolytical cleavage/fission

(A) Cleavage in which unequal distribution of electrons takes place during the bond cleavage is known as
heterolytical cleavage. Due to unequal distribution of electrons, ions are formed. That’s why it is also known
as ionic cleavage or heterolytical cleavage.

(B) Cleavage in which equal distribution of e–s takes place during the chemical reaction is known as homolytical
cleavage.

C × Z C + × Z

• Due to equally distribution of electrons, without charge unpaired electrons species is formed, which is known
as free radical and cleavage is known as unionic cleavage/homolytical fission.
• By both cleavage [ionic/non ionic] three type of species are formed [One carrying positive charge, other
carrying negative charge and third one is neutral with unpaired electrons] is known as reaction intermidiate.

220
CHEMISTRY FOR JEE MAIN & ADVANCED

Ambident nucleophile : Nucleophiles which have two sites of electron rich centre or in which two or more atoms
bear an unshared pair of electrons.
  ••
Ex. K—O—N O, NH2—OH, K CN

Resonating structures are also abmbident nucleophile.


Amphiphile : Molecule containing a multiple bond between carbon and a more electronegative atom can act both
as electrophiles or nucleophiles.
Ex.

>C O CH 3 C N

electrophilic nucleophilic electrophilic nucleophilic

S.No. Electrophile Nucleophile

1 Accepts the electron pair Supplies the electron pair


2 Electron deficient Electron rich
3 Attacks the points of high electron density Attacks the point of low electron density
4 Lewis acid Lewis base

Possess an empty orbital to receive the Possess an electron pair which is loosely held and
5
electron pair can be supplied easily

6 Usually positively charged species Usually negatively charged species


7 Forms an extra bond with the nucleophile Increases its covalency by one unit

ELECTRONIC EFFECTS
There are four effect which affect the chemical reaction are –
(1) Inductive effect (2) Mesomeric effect (3) Hyper conjugation (4) Electromeric effect
(1) INDUCTIVE EFFECT
• Polarity developed in Carbon–chain due to the shifting of  bond electron by the group or atom present
on carbon-chain is known as inductive effect,.
• Discovered by scientist Ingold.
• It is effective upto 3 or 4 carbons. After 3 or 4 carbons it becomes neutralized.
1
So Magnitude of I effect ∝
dis tance
• Inductive effect is measure with respect to hydrogen atom that means inductive effect of hydrogen is
always zero.
• It is a permanent effect.
• Some atoms or groups have a greater tendency to attract the shared electron of the covalent bond. Such
atoms or groups acquire partial negative charge by receiving electron density from the covalent bonds
of the chain. Therefore, these are classified as the groups exerting negative inductive (– I) effect.

222
CHEMISTRY FOR JEE MAIN & ADVANCED

1. All the +ve charge species are electrophile except H3O+ and NH4+.
2. Relative electron withdrawing order (–1 order)
–NO2 > –CN > –COOH > –F > –OR > –OH > –C6H5 > –CH = CH2
3. + I order
–NO– > –O > –COO– > 3° alkyl > 2° alkyl < 1° alkyl
4. Greater the number of -Hydrogen, more stable is carbocation and free radical due to hyperconjugation.
(A) Carbocation
   
> (Ph)3 C > (Ph)2 C H > Ph – CH 2 > CH2 = CH – CH 2
     
(CH)3 C > (CH3)2 C H > CH3 CH 2 > CH3 > CH2 = C H > CH  C

(B) Free radical  


 
(Ph)3 C > (Ph)2 C H > Ph C H 2 > CH2 = CH – C H 2 >
  
(CH3)3 C > (CH3)2 C H > CH3 C H 2

(C) Carbanion
    
(Ph)3 C > (Ph)2 C H > Ph – C H 2 > CH2 = CH – C H 2 > C H3 >
  
CH3 CH 2 > (CH3)2 C H > (CH3)3 C

5. Acidic Strength
(i) H2O > CH  CH > NH3
(ii) CH  CH > CH2 = CH2 > CH3 – CH3

OH

(iii) R–SO3H > R–COOH > > R–OH

(iv) HCOOH > CH3COOH > CH3CH2COOH


(v) CCl3COOH > CHCl2COOH > CH2ClCOOH
(iii) CH3–CH2–CH–COOH > CH3–CH–CH2–COOH > CH2–
|
CH2CH2COOH | |
F F F

OH
(vii) C 6H 4 Phenol > m > p > 0
CH 3

OH
(viii) C6 H 4 p > o > m > Phenol
NO2

264
CHEMISTRY FOR JEE MAIN & ADVANCED

SOLVED EXAMPLES
Ex.1 Find the stability order of the following compounds
   
C  CH3 3 , C H  CH 3  2 , C H 2  CH 3  , C H 3

CH3
   
Sol. CH3 C  CH3 CH   CH3 CH2   CH3

CH3 CH3
3° 2° 1°
Reason : More no. of +I group.
more stable carbocation.

Ex. 2 Ethyl amine is more basic then aniline, why ?


Sol. Due to the + I effect of ethyl group.

Ex. 3 Cl–NH2 is less basic then methyl amine, why ?


Sol. Due to – I effect of –Cl group and p–d conjugation.

Ex. 4 Correct basic order of the following different amine in chlorobenzene medium is -

NH2
(A) CH3 – CH2 – NH2 (B) (C) (D)
N N
CH3 H
Sol. (C > D > B > A)

Ex. 5 Which is most basic among the following :


(A) CH3NH2 (B) CH3CH2NH2 (C) NH3 (D) (CH3)2CHNH2
Sol. (D)
Ex. 6 Which is most acidic compound –

OH OH OH OH
NO2
(A) (B) (C) (D)
NO2
NO2
Sol. (B)
Ex. 7 Draw the resonating structures of the following compounds and mention the most stable resonating structure :
..  
OH CH 2 CH 2
(a) (b) (c)

.
C H CH 2
(d) (e)
O
..
NH 2
..
(f) N (g)
H

266
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 1 [Single Correct Choice Type Questions]

1. Which of the following group shows +I-effect :


(A) –Br (B) –COOH (C) –OR (D) –COO–
2. Which of the following alkyl groups has the maximum +I effect ?
(A) (CH3)2CH– (B) (CH3)3C– (C) CH3CH2– (D) CH3–
3. Decreasing –I effect of given groups is :
(i) CN (ii) NO2 (iii) NH2 (iv) F
(A) iii > ii > i > iv (B) ii > iii > iv > i (C) iii > ii > iv > i (D) ii > i > iv > iii

4. Inductive effect involves :


(A) Delocalisation of  - electrons (B) Partial displacement of  - electrons
(C) Delocalisation of  - electrons (D) Displacement of lone pair electrons.
5. Select correct statement about I effect?
(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.

6. Which of the following is the strongest -  group :


  
(A) – N (CH3)3 (B) – N H3 (C) – S (CH3)2 (D) – F

7. In which of the following species, incorrect direction of Inductive effect is shown ?

CH3 O O
C OH C O
-
H3 C CH2–CH3
(A) (B) (C) (D) C

O
CH3

8. During delocalization, which statement is incorrect :


(A) Net charge remains same (B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same (D) Energy of resonating structures always remains same
9. Which of the following statements is incorrect ?
(A) The energy of resonance hybrid is always less than that of any resonating structure.
(B) The resonance energy is the difference between the enthalpies of formation of the molecule and the resonating
structure having maximum energy.
(C) The resonance structures are hypothetical structure and they do not represent any real molecule.
(D) In delocalized structure of benzene the -charge cloud is spread equally above and below the plane of molecule.

10. Which of the following statement regarding resonance is NOT correct ?


(A) the different resonating structures of a molecule have fixed arrangement of atomic nuclei.
(B) the different resonating structures differ in the arrangement of electrons.
(C) the hybrid structure has equal contribution from all the resonating structures always.
(D) None of the individual resonating structure explains all characteristics of the molecule.

270
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 2 Part # I [Multiple Correct Choice Type Questions]

1. Which of the hybrid species are correct?


(A) (B)

(C) (D)

2. In which of the following pairs of resonating structures first resonating structure is more stable than second?

(A)  (B) 

(C)  (D) 

3. In which of the following pairs of compounds will second structure have more contribution to resonance hybrid
than first ?

(A) & (B) &

(C) & (D) &

4. Which statement is/are true about resonance ?


(A) It decreases the energy of system.
(B) The hybridisation of atoms do not change due to resonance
(C) Resonance hybrid is more stable than any resonating structure.
(D) Resonanting structures can not be isolated at any temperature
5. Which of the following statement is incorrect about resonance ?
(A) The most stable structure explains all the characteristics of a species.
(B) All resonating structures remain in equilibrium.
(C) Resonance hybrid has maximum similarity with most stable resonating structure.
(D) Resonance hybrid is real.

296
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 3 Part # I [Matrix Match Type Questions]


1. Column-I Column-II
(Stability order) (Responsible effect)

(A) (p) Inductive effect

(B) > (q) Resonance

(C) CH3–CH2– > (r) Hyperconjugation

(D)  > CH3–CH2 (s) Mesomeric effect

2. Match the following


Coulmn - I Coulmn - II
(Compounds) (Characteristics)

(A) (p) Mesomeric effect / resonance

(B) Ph–CH=CH–CH3 (q) Inductive effect.

(C) (r) Hyperconjugative effect

(D) (s) Nonpolar

(t) Polar
3. Match the column
Column – I Column – II
(A) (p) The enolic form has geometrical isomers

(B) (q) The enol form is chiral

(C) (r) Its tautomer gives 2,4–DNP test positive

(D) (s) Keto-enol tautomerism results into racemisation.

314
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 4 [Subjective Type Questions]


1. In how many of the following cases, the negative charge is delocalised?

.. – CH3

..

2. Observe the following compound and write the number of hydrogen atom involved in hyperconjugation ?

3. Write that resonating structure of given carbocation in which all atoms have complete octet.

4. The central carbon-carbon bond in 1, 3-butadiene is shorter than that of n-butane. Why ?
5. Write decreasing order of electron density in aromatic ring in following compounds.

6. Identify the number of compounds in which positive charge will be delocalised ?

7. Find the number of carbon atoms including the given structure which can have negative charge in resonating
structures. (The structures with charge separation are not acceptable).

322
GENERAL ORGANIC CHEMISTRY

Exercise # 5 Part # I [Previous Year Questions] [AIEEE/JEE-MAIN]

1. In the following benzyl/allyl system R – CH = CH2 and (R is alkyl group)

Then decreasing order of inductive effect is : [AIEEE-2002]


(A) (CH3)3 C— > (CH3)2CH— > CH3CH2— (B) CH3CH2— > (CH3)2CH— > (CH3)3C—
(C) (CH3)2CH— > CH3CH2— > (CH3)3C— (D) (CH3)3C— > CH3CH2— > (CH3)2CH—

2. The increasing order of stability of the following free radicals is : [AIEEE-2006]


• • • •
(A) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
• • • •
(B) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
• • • •
(C) (CH3)2 C H < (CH3)3 C < (C6H5)3 C < (C6H5)2 C H
• • • •
(D) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C

3. The electrophile, E  attacks the benzene ring to generate the intermediate -complex, which of the following
-complex have lowest energy ? [AIEEE-2008]

NO2 NO2 NO2


H
H
+ E
(A) (B) + E (C) + (D) +
H
E
H E

4. Arrange the carbanions, (CH3)3 C , C Cl3 , (CH3)2 C H, C6H5 C H2 in order of their decreasing stability :
[AIEEE-2009]
(A) (CH3)2 CH > CCl3 > C6H5 CH2 > (CH3)3 C (B) CCl3 > C6H5 C H2 > (CH3)2 C H > (CH3)3 C
(C) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCCl3 (D) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH

5. The strongest acid amongst the following compounds is : [AIEEE-2011]


(A) CH3COOH (B) HCOOH
(C) CH3CH2CH(Cl)COOH (D) ClCH2CH2CH2COOH
6. Identify the compound that exhibits tautomerism. [AIEEE-2011]
(A) 2-Butene (B) Lactic acid (C) 2-Pentanone (D) Phenol

7. The order of stability of the following carbocations : [JEE(Mains)-2013]

; ; is :

(A) III > II > I (B) II > III > I (C) I > II > III (D) III > I > II

331
CHEMISTRY FOR JEE MAIN & ADVANCED

MOCK TEST

SECTION - I : STRAIGHT OBJECTIVE TYPE


1, Select correct statement about I effect?
(A) I effect transfers electrons from one carbon atom to another.
(B) I effect is the polarisation of  bond electrons.
(C) I effect creates net charge in the molecule.
(D) I effect is distance independent.

2. Which of the following group shows +I-effect :


(A) –Br (B) –COOH (C) –OR (D) –COO–

3. Which of the following alkyl groups has the maximum +I effect ?


(A) (CH3)2CH– (B) (CH3)3C– (C) CH3CH2– (D) CH3–

4. During delocalization, which statement is incorrect :


(A) Net charge remains same (B) Number of paired electrons remain same
(C) Number of unpaired electrons remain same (D) Energy of resonating structures always remains same

5. Which of the following statements is incorrect ?


(A) The energy of resonance hybrid is always less than that of any resonating structure.
(B) The resonance energy is the difference between the enthalpies of formation of the molecule and the resonating
structure having maximum energy.
(C) The resonance structures are hypothetical structure and they do not represent any real molecule.
(D) In delocalized structure of benzene the -charge cloud is spread equally above and below the plane of molecule.

6. The correct stability order of the following resonance structures is :

(A) (IV) > (I) > (III) > (II) (B) (II) > (IV) > (I) > (III)
(C) (III) > (II) > (IV) > (I) (D) (I) > (IV) > (III) > (II)

7. Which of the following is least stable resonating structure ?

(A) (B)

(C) (D)

8. The longest C — N bond length in the given compound is :

(A) x (B) y (C) z (D) w

336
11th Class Modules Chapter Details

Physics Chemistry Mathematics


5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1


1. Physical World and Units 1. Mole Concept 1. Basic Maths and Logarithm
& Dimensions 2. Atomic Structure 2. Quadratic Equation
2. Basic Maths & Vector 3. Chemical Bonding 3. Sequence and Series
3. Kinematics 4. Gaseous State
Module-2
Module-2 Module-2(PC) 1. Trigonometric Ratio and
1. Thermodynamics Identities
1. Newton’s Law of Motion 2. Trigonometric Equation
& Friction 2. Thermochemistry
3. Chemical Equilibrium 3. Properties & Solution
2. Work, Energy & Power of Triangle
4. Ionic Equilibrium
Module-3 Module-3
Module-3(IC)
1. Centre of Mass & Collisions 1. Periodic Table & Its Properties 1. Permutation & Combination
2. Rotational Motion 2. Redox Reaction & Equivalent 2. Binomial Theorum
3. Gravitation Concepts 3. Complex Number
3. Hydrogen & Its Components
Module-4 4. S-Block Module-4
1. Straight Line
1. Mechanical Properties 2. Circle
of Matter Module-4(OC)
1. Nomenclature of 3. Conic Section
2. Thermal Properties of Matter (Parabola,Ellipse & Hyperbola)
Organic Compounds
Module-5 2. Isomerism
3. General Organic Chemistry Module-5
1. Simple Harmonic Motion 1. Mathematical Induction
2. Wave Motion Module-5(OC) 2. Mathematical Reasoning
3. Measurement Error 1. Reaction Mechanism 3. Statistics
& Experiment 2. Hydrocarbon
3. Aromatic Hydrocarbon
4. Environmental Chemistry

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12th Class Modules Chapter Details

Physics Chemistry Mathematics


5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1


1. Solid State 1. Sets & Relation
1. Electrostatics
2. Solutions and 2. Function
2. Capacitance
Colligative Properties 3. Inverse Trigonometric Function
3. Electro Chemistry 4. Probability
Module-2
1. Current Electricity Module-2(PC) Module-2
2. Magnetic Effect of Current 1. Chemical Kinetics and
and Magnetism Nuclear Chemistry 1. Limit
2. Surface Chemistry 2. Continuity
Module-3 3. Differentiability
Module-3(IC) 4. Method of Differentiation
1. Electromagnetic Induction
2. Alternating Current 1. Metallurgy
2. P- Block Module-3
Module-4 3. Transition Elements 1. Indefinite Integration
(d & f block) 2. Definite Integration
1. Geometrical Optics 4. Co-ordination Compound 3. Area Under the Curve
2. Wave Optics 5. Salt Analysis & Qualitative
Analysis Module-4
Module-5
Module-4(OC) 1. Application of Derivative
1. Modern Physics
1. Alkyl Halides & Aryl Halides 2. Matrix
2. Nuclear Physics
2. Alcohol, Phenol & Ether 3. Determinant
3. Solids & Semiconductor
Devices 3. Carbonyl Compound
Module-5
4. Electromagnetic Waves
5. Principle of Communication Module-5(OC) 1. Differential Equation
1. Carboxylic Acid & Their 2. Vector & 3-Dimensional
Derivatives
2. Biomolecules & Polymers
3. Chemistry in Everyday Life

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