GOC - ISOMERISM

45

LEVEL - I
1. Propanone and propanal are : (a) geometrical isomers (c) functional isomers (b) chainisomers (d) position isomers.

2.

Which of the following is not an isomer of 1-butyne ? (a) but-2-yne (b) buta-1, 3-diene (c) but-2-ene (d) methyl cyclopropene Which of the following in not a cyclic isomer of C4H7OH ? (a) Cyclobutanol (b) cyclopropyl methanol (c) 1-methyl cyclopropanol (d) none of these The total number of isomers of C4H11N would be : (a) 4 (b) 8 (c) 5 (d) 10

3.

4. 5. 6.

In which of the following molecules carbon does not involve sp3 hybridisation . (b) CH2N2 (c) CH2F2 (d) CF2Cl2 (a) CH2Cl2 A compound with molecular formula C8H14, contains 12 secondary and 2 tertiary H atoms . The compound is :

(a) 7. 8. 9.

(b)

(c)

(d)

The total number of structural isomers possible for structure C3H6 are : (a) 1 (b) 2 (c) 3 (d) 4 How many geminal dihalides with different formula are possible for C3H6Cl2 ? (a) only one (b) two (c) three (d) four The compounds (CH3)3N and CH3CH2CH2NH2 represent : (a) chain isomerism (b) position isomerism (c) functional isomerism (d) all of the above The number of isomeric aldehydes and ketones with formula C5H10O are : (a) 7 (b) 6 (c) 5 (d) 8 Nitroethane can exhibit one of the following kind of isomerism : (a) Metamerism (b) Optical activity (c) Tautomerism (d) Position isomerism

10. 11. 12.

Which of the following is not an isomer of CH3CH2CH2CH2OH ? (a) CH3CH(CHO)CH3 (b) (CH3CH2)2O (c) CH3OCH2CH2CH3 (d) CH3CH(OH)CH2CH3. A . (D+ is catalyst) , compound A is :

13.

OH

O

O

OH

(a) CH3 – C = CH – C – OC2H5 OD O

(b) CH3 – C – CH = C – OC2H5

OH

O

(c) CH3 – C = CH – C – OC2H5

(d) CH3 – C = CH – C – OC2H5

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46

GOC - ISOMERISM

14.

Tautomerism is not shown by : (a) CH3COCH2CN (c) CH3CH=NOH

(b) HCN (d) CH3CN (d) 5

15. 16.

How many isomers are possible for methyl anthracene ? (a) 2 (b) 3 (c) 4 Cyclohexane floats on water because : (a) it has low density (c) it has cyclic structure

(b) it has boat conformation (d) it has planar structure

17.

Which among the following compounds will show tautomerism ? (a) 2, 2-dimethyl propanal (b) 2, 2-dimethyl-1-nitropropane (c) Acetyl acetone (d) Benzophenone Which of the following can show tautomerism ?

18.

(a)

(b)

(c)

(d) all of these 19. Which of the following can show tautomerism ?

(a)

(b)

(c)

(d)

20. 21.

Which of the following can show tautomerism ? (a) (CH3)3 CNO (b) (CH3)2NH (c) R3CNO2 Which will not show tautomerism ?

(d) RCH2NO2

(a)

(b)

(c)

(d)

22.

Which will not show Tautomerism ? (a) CH3CH2CH2CH2NO2 (c) CH3 –CH2CH3

(b) (CH3)2–CH–CH2NO2 (d) (CH3)3C–NO2

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GOC - ISOMERISM

47

23.

Which will not show Tautomerism ? (a) (b)

(c) 24.

(d)

Which of the following compound show tautomerism ? (a) (H3C)2CCl–CH=CH2 (c) (H3C)2C(NO2)–CH=CH–CHO (b) C=O

H (d) None of these

25.

Which of the following is not an example of tautomeric equilibrium ? (a) (b) (c) (d)

26.

For which one of the following does the position of equilibrium lie to the left ? (a) (b) (c) (d)

OH |

OH |

27.

Which of the following will have highest percentage of enol content ?
O O || || (a) C6 H 5 − C − CH 2 − C − OC 2 H 5

O || (b) CH 3 − C − O − C2 H 5
O O || || (d) CH 3 − C − CH 2 − C − CH 3

O O || || (c) CH 3 − C − CH 2 − C − OCH 3
28.

Which among the following compounds will give maximum enol content in solution ? O O || || (a) C6H5– C –CH2––CH3 (b) CH3– C –CH2––CH3 O O || || (c) CH2– C –CH2–CH2–CH3 (d) CH3– C –CH2–COOC2H5

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48

GOC - ISOMERISM

29.

The enol form of acetone, after treatment with D2O, gives :

OD | (a) CH 3 – C = CH 2
OH | (c) CH 2 = C – CH 2D

O || (b) CD 3 – C – CD 3 OD | (d) CD 2 = C – CD 3

30.

Correct order of enolization is : (a) CH3COCH3 < CH3COCH2COOC2H5 < φCOCH2COOC2H5 < CH3COCH2CHO (b) CH3COCH2COOC2H5 < φCOCH2COOC2H5 < CH3COCH2CHO < CH3COCH3 (c) φCOCH2COOC2H5 < CH3COCH2CHO < CH3COCH3 < CH3COCH2COOC2H5 (d) CH3COCH2CHO < CH3COCH3 < CH3COCH2COOC2H5 < φCOCH2COOC2H5

31.

I

II

III

Among the ketones which of the following is the correct order of the ease of their enolization . (a) I > II > III (b) III > II > I (c) II > I > III (d) III > I> II

32.

I

II

III

Among these compounds which of following is the correct order of % enol content . (a) I > II > III (b) III > II > I (c) II > III > I (d) I > III > II 33. Compound H3C–CH–CH2–CH–OH is : (a) (b) (c) (d)
O tautomers of 3-oxobutanal and also show structural isomerism tautomer of butanoic acid compound does not show any isomerism the compound can show structural isomers except tautomerism

34.

CH2OH O OH H Glucose is a hemiacetal and its structure is . H OH H OH OH H Which of the following is correct ? (a) glucose show structural as well as stereo isomerism (b) diastereomer is convert to other diastereomer by ring chain tautomerism (c) both (a) and (b) (d) glucose conversion can not be predicted by its structure H
Chloretone has a oscillating hydrogen due to (a) Keto-enol tautomerism (c) due to presence of chlorine (b) H-bonding (d) all of these

35.

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GOC - ISOMERISM

49

36.

Which of the following can show tautomerism ?

O
(a)

CH3 O CH3

(b)

(c)

(d) All

37.

Which of the following compound have higher enol content ?

O || C
I

O || C

CH3 OH

II

CH3 OH

(a) II 38.

(b) I

(c) I = II

(d) none of these

Which of the following compound have higher enol content ?
O O

I
NO2

II
OCH3

(a) I 39.

(b) II

(c) I = II

(d) none of these

Which of the following compound have less enol content ? I
N | H O

II N O | H (c) both (a) & (b)

(a) I 40.

(b) II

(d) none of these

Highest percentage of enol form is possible in :

(a)

(b)

(c)

(d)

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50

GOC - ISOMERISM

41.

All of the compounds shown are present together in various amounts at equilibrium. The most abundant isomer is the one in which the least stabilized carbonyl group is enolized. Show that you understand the fundamental principles of enolization as well as the meaning of the preceding sentence by picking the species present in greatest amount at equilibrium.

(a) 42.

(b)

(c)

(d)

The addition NOCl on alkene the carbon can bear ‘NO’ group only if:(a) that carbon can contain hydrogen (b) that carbon can not contain hydrogen (c) depends upon the hydrogen (d) the stability depends upon the no of C carbon atoms.

O || C
43. The compound can show :

N H
(a) Amido-Imidol tautomerism (c) a prototopic tautomerism (b) Nitro acinitro tautomerism (d) Ring chain tautomerism Cl C 44. Phthalonyl chloride is also represented by the structure C O (a) Dehydrated form of Phthalonyl chloride (c) It is not a form of Phthalonyl chloride .. .. O O .. .. (b) Tautomerism. (d) Metamerism – .. O O + .. ..
..

Cl O . This is an example of :

45.

Conversion of

is :

(a) (b) (c) (d)

A B Example of valance tautomerism The compound B is more stable than A Compound ‘A’ is colourless and compound ‘B’ is red coloured compound. All of these are right.

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GOC - ISOMERISM

51

46.

This compound is an example of :
H

HO—C— H H—C—OH HO—C—H H—C—OH H—C H—C—H OH
(I) (a) (I) and (III) are epimers (c) (I) and (III) are anomers 47. The erythrose is a example of :

O C H—C—OH

H—C—OH H—C—OH HO—C—H H—C—OH H—C H—C—H OH O

O

HO—C—H H—C—OH H—C—OH H—C—H OH

(II) (III) (b) (I) (II) ring chain tautomerism (d) All of these

O OH H H H—C—C—C—C—OH H OH H
(a) resonance (c) anionotropy 48.

OH H OH H

H HH OH

(b) ring chain tautomerism (d) None of these

% enol content of acetyl acetone in H2O is 15% and is hexane is 92% because: (a) more intramolecular hydrogen bonding in water (b) more intramolecular hydrogen bonding in hexane (c) less intermolecular hydrogen bonding in water (d) more intermolecular hydrogen bonding in hexane The percentage of enolic form is:

49.

H
I

H

O | C Me C H

O || C Me

II Me

O | C C Me

O || C Me

(a) equal

(b) I > II

(c) II > I

(d) can not be predicted

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52

GOC - ISOMERISM

O 50. I (a) (b) (c)

O

OH

O enol form is more stable due to :

II decrease the dipole dipole repulsion double bond in Ring is more stable hydrogen bonding is possible in enol form O Na⊕ +

(d)

none of these

51.

O Na⊕

NaOH H2O

O

H⊕/H2O

OH
+

OH

(Minor) (Major) (Major) (Minor) Reason of this conversions : (a) In acid catalysed enolization, more stable alkene is formed (b) In base catalysed enolization, less stable alkene is formed due to the resonance with primary carbanion (c) Both (a) and (b) (d) Reason is not appropriate 52. Phenolphthalein is a example of
OH OH OH O

I

C O C || O

II

C OH C || O

(a) tautomerism

(b) resonance

(c) acid-base reaction
O

(d) none of these

O
53.

are :

N Isatin H Lactam

O

N H Lactim

OH

(a) (b) (c) 54. 55.

Tautomerism This tautomerism is also known as amido Both (a) and (b)

imidol tautomerism (d) None of these (d) 2,2,3,3-tetramethylbutane

The highest boiling point is expected for : (a) iso octane (b) n-octane

(c) n-butane

Which pair of isomerism is not possible together ? (a) Chain and position (b) Functional and position (c) Tautomerism and functional (d) All of these

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53

56. 57.

An isomers of ethanol is : (a) methanol (b) acetone

(c) diethyl ether

(d) dimethyl ether

Which of the following statement is not true ? (a) Homologues cannot be isomers but isomers can be homologues (b) Isomers can not be homologous (c) The number of paired and unpaired electrons in various resonating forms is equal Aldehyde show with each other : (a) Chain isomers (c) Functional isomers Compound C4H10O can show : (a) Metamerism (c) Functional isomers Acetamide is isomer of : (a) 1-amino ethanol (c) Ethyl amine (b) Position isomers (d) Both (a) and (b) (b) Functional isomers (d) All above (b) Formamide (d) Acetaldehyde oxime (d) 5

58.

59.

60.

61. 62.

How many isomers of C5H11OH will be primary alcohols : (a) 2 (b) 3 (c) 4

Which of the following is an example of position isomerism ? (a) Isopentane and neopentane (b) Glucose and fructose (c) Ethanol and dimethyl ether (d) α-Naphthol and β-naphthol O-Cresol and benzyl alcohol are : (a) Functional (b) Position CH3CONH2 & HCONHCH3 are called : (a) Position (b) Chain Choose the homologues (c) chain (c) Tautomers OH (d) All (d) Functional

63. 64. 65.

CH3
(a) & (b)

CH2OH
&

(c) CH3NH2 & (CH3)2NH

(d) All the above

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54

GOC - ISOMERISM

LEVEL - II
1. The stability of compounds is : (i) (ii) (iii)

A

(iv)

(a) (iv) > (iii) > (i) > (ii) (c) (ii) > (iii) > (i) > (iv) 2. Stability order of carbocation :

(b) (i) > (iii) > (ii) > (iv) (d) (iv) > (i) > (iii) > (ii)

C3H7 (I)

C

(II)

(III) C3H7 C3H7

(IV) H2C=CH– CH2

(a) I > III > II > IV (c) III > II > I > IV 3. Stability of carbocation : I F3C – CH2 (a) III > II > I 4.

(b) II > III > I > IV (d) III > I > II > IV

II F3C – CH2 – CH2 (b) I > II > III (c) II > I > III

III F3C (d) III > I > II

The most stable radical : O (a) C6H5• (b) H3C – C – O

H3C (c) H3C C • H3C

CH3
(d) C6H5– C

CH3

5.

Arrange the following alkenes in decreasing order of reactivity towards electrophilic addition ClCH2CH = CH2 (HC3)2C = CH2 H3C – CH = CH2 H2C = CH – Cl (i) (ii) (iii) (iv) (a) (i) > (iii) > (ii) > (iv) (b) (iv) > (iii) > (ii) > (i) (c) (ii) > (iii) > (i) > (iv) (d) (ii) > (iii) > (iv) > (i) Consider the following three halides : (1) CH3 – CH2 – Cl (2) CH2 = CH – Cl (3) C6H5 – Cl Arrange C—Cl bond length of these compounds in decreasing order : (a) 1 > 2 > 3 (b) 1 > 3 > 2 (c) 3 > 2 > 1 (d) 2 > 3 > 1 C , C double bond length is minimum in : (a) CH3 – CH = CH2 (c) CCl3 – CH = CH2 (b) CH2Cl – CH = CH2 (d) CCl3 – CH = CH – CCl3 (d) NH3

6.

7.

8.

Which one of the nitrogen containg compounds is an electropile ? (a) NH2 – NH2 (b) NH2 – OH (c) NF3

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GOC - ISOMERISM

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9.

Which among the following compounds behave both as an electrophile as well nucleophile . O O CH2 = CH2 1 (a) only 1 CH3 – C – CH3 2 (b) 1 and 2 CH2 = CH – CH2 3 (c) 3 and 4 CH3 – C – Cl 4 (d) 1 , 2 , 3 and 4

10.

Ethyl alcohol is miscible with water in all proportions because : (a) of its acidic nature (b) it is neutral (c) it reacts with water (d) it forms H-bonds. The pKa of acetylsalicylic acid (aspirin) is 3.5. The pH of gastric juice in human stomach is about 2 − 3 and pH in the small intestine is about 8. Aspirin will be : (a) unionised in the small intestine and in the stomach (b) completely ionised in the stomach and almost unionised in the small intestine (c) ionised in the stomach and almost unionised in the small intestine (d) ionised in the small intestine and almost unionised in the stomach . What is true about the following equilibrium ?
⊕ ΘK

11.

12.

H + H3C–C

CH

H H + H3C–C
||

CΘK⊕

|||

(a) (b) (c) (d) 13.

It will be almost completely shifted to the left It will be almost completely shifted to the right The equilibrium constant is very close to one The equilibrium constant is zero

Use resonance arguments to rank the following in order of increasing acidity .

(a) Hc < Ha < Hb 14.

(b) Ha < Hb < Hc

(c) Hb < Hc < Ha

|

The acidity of the protons H is : (i) (a) i > ii > iii (ii) (b) ii > i > iii (iii) (c) ii > iii > i (d) iii > i > ii

15.

Which one of the hydrocarbon is the most acidic ?
H3 C H3C
|

|

|

| ||

|

|

|

|

|

H3C

H

CH3

CH3

H3C H H3C CH3

(a)

(b)

(c)

|

|

|

(d)

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|

|

(d) Hc < Hb < Ha

CH3 CH3

H3 C H3C

CH3 CH3
|

56

GOC - ISOMERISM

16.

1,3-cyclopentadiene has a pKa = 15 whereas simple cycloalkanes have pKa > 50 with respect to their conjugate bases . This is because : (a) 1, 3-cyclopentadiene is aromatic. (b) 1, 3-cyclopentadiene is anti-aromatic. (c) 1, 3-cyclopentadine is non-aromatic. (d) 1, 3-cyclopentadiene is non-aromatic with an aromatic conjugate base. The Ka values of alcohols, water and phenol are of order 10–17, 10–14 and 10–10 respectively . Which of the following reaction is possible ? (a) C6H5O– + H2O → C6H5OH + OH– (b) C2H5O– + H2O → C2H5OH + OH– (c) both (a) and (b) (d) neither of the two. The pKa of the conjugate acids of : (i) (ii)
N | H
..

17.

18.

(iii)

(a) i > ii > iii 19.

(b) i > iii > ii

(c) ii > i > iii

(d) ii > iii > i

Which of the following represents the increasing order of pKa values of the C − H acids . CH 3 − C ≡ C − H (i) (a) ii < iii < i < iv

O O || || CH 3 − C − CH 2 − C − OEt
(ii) (b) ii < i < iv < iii

CH3COOEt

Ph − CH 3 (iv) (d) iii < ii < iv < i

(iii) (c) iv < ii < iii < i

20.

What is the correct order of acidity of the following compounds .

(1) CH3CO2H (4) Me2CH−CO2H

(2) CHBr2 CO2H (5) Me − CH − CO 2 H | N+ R 3

Cl | (3) H 3C − CH CO 2 H

(a) 2 > 5 > 3 > 1 > 4 (c) 1 > 2 > 5 > 4 > 3 21. Among the following compounds ,

(b) 5 > 3 > 2 > 1 > 4 (d) 2 > 5 > 1 > 3 > 4

I

II Et 3N

III

IV

the order of basicity is : (a) IV > III > II > I (c) III > IV > II > I 22. Which is maximum basic in nature ? (a) (b)

(b) II > I > III > IV (d) I > II > III > IV

(c)

(d)

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57

23.

The correct order of basicities of the following compounds is : I (a) II > I > III > IV (c) III > I > II > IV II CH3 − CH2 − NH2 III (CH3)2 NH (b) I > III > II > IV (d) I > II > III > IV (d) HOCH2 COOH IV

24. 25.

Which of the following is most acidic compound ? (a) CH3COOH (b) Cl CH2COOH (c) CH3OCH2COOH Which among the following has strongest acidic character ? (a) Cyclohexanol (b) 3-nitrocyclohexanol (c) 4-methylcyclohexanol (d) 4-ethylcyclohexanol Which one of the following is most acidic ? (a) Phenol (b) 2-chlorophenol Most acidic compound of the following is : (c) 3-chlorophenol

26. 27.

(d) 4-chlorophenol

(a) 28.

(b)

(c)

(d)

Which of the following is least basic ? (a) methyl lithium (c) methyl magnesium chloride

(b) dimethyl zinc (d) methyl sodium

29.

Rank of the following three compounds in decreasing order of basicity .

I (a) III > I > II 30.

II (b) III > II > I

III (c) II > I > III (d) II > III > I

Least basic character is shown by which compound amongst the following is :

(a)

(b)

(c)

(d) all are equally basic

31.

Which of the following carbocations is expected to be most stable ?
CH3 CH3
CH3 CH3

(a)
X H

(b)
X H

(c)
X

H

(d)
X

H

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58

GOC - ISOMERISM

32.

Which of the following species is/are aromatic ?
Ph

(a)

(b)

SbCl6

(c)
Ph

(d) H

33.

Which of the following has the most acidic hydrogen ? (a) 3-hexanone (b) 2, 4-hexanedione (c) 2, 5-hexanedione (d) 2, 3-hexanedione. Of the following order of reactivity of Cl with AgNO3 , which one is correct ? (a) CH2 = CH –CH2Cl > CH3CH2CH2Cl > CH3CH = CHCl (b) CH2 = CH – CH2Cl > CH3CH2CH2Cl < CH3CH = CHCl (c) CH2 = CHCH2Cl < CH3CH2CH2Cl > CH3CH = CHCl (d) CH2 = CHCH2Cl < CH3CH2CH2Cl < CH3CH = CHCl. What is the decreasing order of stability of the ions ? I II III

34.

35.

(a) I > II > III 36.

(b) II > III > I

(c) III > I > II (b) (d)

(d) II > I > III

Which of the following orders is not correct regarding the –I effect of the substituents ? (a) – I < – Cl < – Br < – F (c)

37.

Which compound has maximum solubility in water ? (a) C6H6 (b) CH2=CH2 (c) CH3– –CH3 Hydrogen bonding between NH3 and H2O is shown as : (a) (b)

(d) CH3CH2CHO

38.

(c)

(d)

39.

Which of the following statements is true about this molecule ?

(a) (b) (c) (d)

C5-N bond is longer than C1-N and C3-N bonds. C5-N bond is shorter than C1-N bond and latter is shorter than C3-N bond. All three C-N bonds are of same length. C1-N and C3-N bonds are of same length but they are longer than C5-N bond.

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GOC - ISOMERISM

59

40. (a) (b) (c) (d) 41.

Which of the following statements is true about this molecule . C1-C2 and C3-C4 bonds are of same length. C1-C2 bond is shorter than C3-C4 bond. C1-C2 bond is longer than C3-C4 bond. C1-C2 and C2-C3 bonds are of same length.

H–O–C≡N H–N=C=O (Cyanic acid) (Isocyanic acid) Loss of proton from these two acids produces : (a) same anion (b) different anions (c) same cation

(d) different cations

42.

A highly important canonical structure of this molecule is :

(a)

(b)

(c)

(d)

43.

I

II

III

Resonance energies of the cations are in the order : (a) II > I > III (b) I > II > III (c) III > II > I

(d) III > I > II

44.

I

II

III

Resonance energies of these compounds are in the order as : (a) I > II > III (b) III > II > I (c) II > I > III 45.

(d) III > I > II

II CH2–CH=OH I CH2=CH–OH On moving from gas phase to water as solvent, the contribution of II in resonance hybrid (a) increases (b) decreases (c) remains constant (d) question is not correct I II III

46.

The order of the ease of ionization of these compounds to produce carbocations and (a) I > II > III (b) II > I > III (c) I > III > II (d) III > II > I
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is :

60

GOC - ISOMERISM

47.

Identify the major contribution in following resonance structures: NH 2 | NH2– C− NH 2

(a)

&

NH 2 | NH2– C =
O || CH3– C –CH=

(b)

O || CH3– C –

O || – C –CH3

&

–CH3

(c)

&

(d) 48.

CH3–

–OH

&

CH3– = –H

Which of the following statements is NOT true ? (a) Resonance forms must obey normal valency rules (b) Resonance forms are in equilibrium (c) The hybrid is more stable than the individual resonance forms (d) Resonance forms differ only in the distribution of electrons I CH 2 = CH − CH = CH − CH = CH 2
⊕ Θ

49.

II CH 2 = CH − C H − CH = CH − C H 2

Θ

III C H 2 − CH = CH − CH = CH − C H 2 Among these three canonical structures (through more are possible) what would be their relative contribution in the hybrid : (a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II 50. Consider the three compounds below (i) CH3CH2OCH2CH3 (ii) CH3CH2CH2CH2CH3 (iii) CH3CH2CH2CH2OH The two most similar in boiling point are ________ and the two most similar in solubility in water are ________ . (a) i and iii , ii and ii (b) i and ii , i and iii (c) ii and iii , i and ii (d) i and iii , i and iii Match the boiling points with the following three isomers of C4H10O2. CH 3OCH 2CH 2OCH 3 CH3CH2OCH2CH2OH HOCH2CH2CH2CH2OH (a) 85ºC 230ºC 135ºC (b) 230ºC 85ºC 135ºC (c) 85ºC 135ºC 230ºC (d) 135ºC 230ºC 85ºC Which substance would be expected to exhibit the greatest surface tension at 25°C . (a) CH – O – CH (b) C H – OH (c) CH – CH – (OH) – CH (d) HO – CH – CH – OH
3 3 2 5 3 3 2 2

51.

52.

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GOC - ISOMERISM

61

53.

Which of the following should have the lowest boiling point ?

HO
(a)

OH
Cl
(b)

(c)

|

(d)

54.

Which of the following are more viscous ? (a) (b) (c) (d)

55.

The hydrocarbons having high vapour pressure is : (a) 2 – methyl hexane (b) heptane (c) 3, 3 – dimethyl pentane (d) 2,2,3,3 – tetramethyl butane If the dipole moment of toluene and nitro benzene are 0.43 D and 3.93 D, then what is the expected dipole moment of p-nitro toluene ? (a) 3.50 D (b) 2.18 D (c) 4.36 D (d) 5.30 D The compound having lowest dipolemoment is : (a) CH2 = CH − Cl (b) CH ≡ C − Cl (c) CH3 − CH2 − Cl (d)

56.

57.

58.

Which one of the following compounds will have the highest dipolemoment .

(a)

NO

2

(b)

(c)

|

59.

Which of the following options are correct for dipolemoment of the following compounds ? NO2 H3C (A) (a) µA > µB (b) µA = µB Cl (B) (c) µA < µB (d) 2 µA = µB NO2 CH3

|

60.

The dipole moment of

|

Cl

(d)

Cl Cl
is 1.5 D . The dipole moment of is :

Cl
(a) 0 D (b) 1.5 D (c) 2.86 D

Cl

(d) 2.25 D

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62

GOC - ISOMERISM

LEVEL - II
1. Which will not give AgCl on reaction with AgNO3 . (a) H2C = CH – CH2Cl CH2–Cl (b) 2. (c)

B

Cl
(d) Cl (4) Benzoic acid (d) 4 > 3. > 1 > 2 CH3 CH3

Arrange pH of the given compounds in decreasing order : (1) Phenol (2) Ethyl alcohol (3) Formic acid (a) 1 > 2 > 3 > 4 (b) 2 > 1 > 4 > 3 (c) 3 > 2. > 4 > 1

3.

Consider the given compounds (1) CH3 – CH2 – NH2 (2) CH3 – CH = NH (4) C2H5 – NH – C2H5 (3) CH3 – C ≡ N Arrange basicity of these compounds in decreasing order : (a) 4 > 1 > 2 > 3 (b) 1 > 2 > 3 > 4 (c) 1 > 4 > 2 > 3 (d) 4 > 1 > 3 > 2 Which of the following halides undergo solvolysis most easily ? (b) CH2 = CH – CH2Cl (a) C6H5CH2Cl (d) (C6H5)3CCl (c) CH2 = CH – CHCl – CH3 Which nitrogen in LSD is most basic ? (1) H—N (2) N CH3 (a) 1 (b) 2 (c) 3 (d) All are equally basic

4.

5.

(3) C—N(C2H5)2

O

6.

Which is is the most basic among following pairs of compounds ? (A) (B) (I) (C2H5)3N (I) CH3CH2NHCH2CH3 & & (II) (II)
N H

N

O
(C) H2N— C —NH2 &

NH NH2—C—NH2 (b) A - I , B - I , C - I (d) A - II , B - II , C - II

(a) A - I , B - II , C - I (c) A - II , B - I , C - II

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GOC - ISOMERISM

63

7.

Among I H3CO III O2N COOH COOH(III) II IV Cl COOH

COOH NO2

The correct order of increasing acid strength is : (a) I < III < II < IV (b) I < II < III < IV (c) II < I < III < IV (d) II < III < I < IV 8. Match the pKa with the appropriate phenol .

(a) (b) (c) (d) 9.

10.8 10.3 10.0 9.4

10.3 8.0 9.4 10.2

10.2 9.4 10.3 8.0

10.0 10.2 8.0 10.0

9.4 10.0 10.2 10.3

Which vertical column correctly matches the pKa values ? pK a 1.0 43 10.0 15.8 4.2

43

1.0

4.2

4.2

15.8

10.0

4.2

15.8

43

10.0

15.8

10.0

43

1.0

1.0

4.2 (a) 10. Identify the most acidic structure –

15.8 (b)

1.0 (c)

10.0 (d)

43 (e)

(a)

(b)

(c)

(d)

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64

GOC - ISOMERISM

11.

Which balanced equation best describes the hydrolysis of the compound shown ? The reaction is carried out at a pH of 2 .

(a)
O || CNHCH3 + H3O+ O || + CNH3 + CH3OH

(b)

(c)

(d) 12. Which one of the following contains most acidic hydrogen atom ?

(a) 13.

|

(b)

|

(c)

(d)

The decreasing order of basicity of the following ethers towards BF3 is : (i) (C 2 H 5 )2 O (ii) (CH 3 )2 O (iii)  CH 3 − CH − O  (iv)   |   CH 3  2 (b) i > ii > iii > iv (c) iii > i > ii > iv (d) iv > ii > iii > i

(a) iv > ii > i > iii 14.

Match the pKa with the appropriate ammonium ion .
+NH3 | | CN

(a) (b) (c) (d)

4.0 4.6 5.4 2.4

4.6 4.0 2.4 5.1

2.4 5.1 4.0 4.6

5.1 2.4 4.6 5.4

5.4 5.4 5.1 4.0

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65

15.

T he conjugated acid of , CH3−

CH2−CH2−NH−CH2−CH2−NH

NH2 is :

(a)

CH3−

CH 2−CH 2 −NH−CH 2−CH 2−NH

NH 2

(b)

CH3−

CH 2−CH 2−NH−CH2−CH 2−

NH 2

(c)

CH3−

CH 2−CH 2−NH−CH 2−CH 2−NH

(d) 16.

CH3−

CH 2−CH2−

−CH 2−CH 2−NH

NH 2

Which of the following compound would be the most acidic ?
H C H

H
(b) H C H (c)

H C
(d)

(a) 17.

For which one of the following does the position of equilibrium lie to the right ? (a) + NH3
O || CO¯ + NH4+

|

(b)

+ NH3

+ NH4+

(c)

+ NH3

+ NH4+ + NH4+

(d) 18.

+ NH3

Which of the following is the strongest acid ?
+

(a)

(b)

CH2CH2NH3

(c)

(d)

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|

66

GOC - ISOMERISM

19.

Conjugate acid of

–CH .. N–C H H

is :

(a) H–N

(b) :N

+ NH2–CH

(c) :N

.. N–C H H2

||

(d) none of these

20.

2 moles NaNH 2       → A . The product (A) will be : 

(a)

(b)

(c)

(d)

21.

From the following reactions : HC ≡ CH + LiNH2 NH3 + HC ≡ CLi and H2O + HC ≡ CLi H — C ≡ C — H + LiOH. Predict which of the following facts regarding the basic strength is correct. (a) Li NH2 > HC ≡ C Li > LiOH (b) Li NH2 > LiOH > HC ≡ CLi (c) HC ≡ C Li > LiNH2 > LiOH (d) HC ≡ C Li > LiOH > LiNH2 Which one of the following is the weakest base ? (a) 2-methyl-3-nitroaniline (b) 2-methyl-5-nitroaniline (c) p-nitroaniline (d) 3, 4-dinitroaniline

22.

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||

GOC - ISOMERISM

67

23.

Which one of the amines is the least basic ? (a) (b)

(c) 24. Which of the following is strongest base ?

(d)

(a)

(b)

(c)

(d)

25.

Strongest base among the following is : (a) (b) (c) (CH3)3N: (d)

26.

Which is the most basic among following pairs of compounds: (A) I (C2H5)3 N & II (B) I CH3 CH2 NH CH2 CH3 & II

(C) I & II (a) (A) - I , (B) - II , (C) - I (c) (A) - II , (B) - I , (C) - II 27. Which is more basic ? H (a) N .. (b)
N .. H

(b) (A) - I , (B) - I , (C) - I (d) (A) - II , (B) - II , (C) - II

H

(c)
N H ..

(d)

N ..

(W) HO
28. The most acidic ‘H ’

(Z) OH H O CH2OH(X) OH (Y)
(c) Z (d) W is :

O

Vitamin-C
(a) X 29. (b) Y

I CH2=CH–OH II On moving from gas phase to water as solvent, the contribution of II in resonance hybrid (a) increases (b) decreases (c) remains constant (d) question is not correct

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68

GOC - ISOMERISM

30.

(CH3)3COH is less acidic than (H3C)3SiOH because : (a) Carbon is more electronegative than Si (b) (CH3)3SiOΘ is stabilized due to back bonding (c) Bigger size of silicon than carbon
8 7 6 5 10 4 9 1 2 3

(d)

None of these

31.

The most reactive positions for electrophilic substitution reaction of anthracene are

(a) 1 & 4

(b) 1 & 2

(c) 2 & 3

(d) 9 & 10.

32.

I

II

III

The order of the C − N bond lengths among these compounds is : (a) III > I > II (b) II > I > III (c) III > II > I (d) I > II > III 33. Among the following compounds which has longest C – O bond :

(a) 34.

(b)

(c)

(d)

The order of the ring − N bond lengths among these compounds is :

I (a) III > I > II

II (b) III > II > I (c) I > II > III

III (d) II > III > I

35.

I

II

III

The stability order of these canonical structures is : (a) I > II > III (b) II > III > I (c) I > III > II 36. I II III IV

(d) III > I > II

Among these compounds the order of the π-electrons energies is : (a) IV > II > III > I (b) III > IV > II > I (c) III > I > IV > II (d) I > II > IV > III 37. I II III

Which of the following choice is the correct order of resonance energy of these molecules ? (a) I > II > III (b) II > I > III (c) III > I > II (d) III > II > I

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GOC - ISOMERISM

69

38.

I

II

III

Which of the following choice is the correct order of resonance energy of these molecules ? (a) I > II > III (b) III > II > I (c) II > I > III (d) III > I > II
• O
• •

39.

I

II CH2=CH– CH2

III CH2=CH– CH–CH=CH2

Which of the following choice is the correct order of resonance energy of these radicals ? (a) I > II > III (b) I > III > II (c) III > I > II (d) III > II > I 40. Which of the following has highest Kb value ? (a) Ph–NH2, (b) (c) (d)

41.

Ease of ionization to produce carbocation and compounds :

will be maximum in which of the following

(a) 42.

(b)

(c)

(d)

Ease of ionization to produce carbocation and compounds : (a) (b) (c)

will be maximum in which of the following

(d)

43.

Ease of ionization to produce carbocation and compounds : Br (a) (b) (c)

will be maximum in which of the following

(d)

Br

44.

I

II

III

IV

Rotation about indicated bonds is easiest in which of these molecules : (a) I (b) II (c) III (d) IV
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70

GOC - ISOMERISM

45.

Which is the most stable resonance form ?

(a)

(b)

(c)

(d)

46.

Which is the most aromatic in character ? (a) N H (b)
S

(c)
O

(d)

N

47.
II

CH2 III I

CH2

HC

CH IV

Rotation about indicated bonds is easiest in which of these molecules (a) I (b) II (c) III (d) IV

48.

Cl

(a) Cl 49.

(b) Cl ⊕

(c) Cl*

(d) none

Which of the following compounds will be aromatic on treatment will LiAlH4 : (a) (b) (c) (d)

50.

An improvement in basic strength due to hydrogen bonding is observed in :

NH2 NH2
(a) (b)
NH2

O || (c) H 2 N – C – NH 2

(d) None of these

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71

LEVEL - III
1. (i) (ii) (iii) (iv) (v) (v) Fill in the blanks : The positively charged carbon of carbonium ion contains ________ valence electrons . NO2+ is/an ________ reagent . The negatively charged carbon of carbanion is ________ hybridized . Acetic acid is ________ acid than formic acid due to ________ effect of methyl group. Free radical is paramagnetic while carbonium and carbanion ion is ________ – – – Amongst CH2CHO , CH 3 and CH2 —NO2, the most stable carbanion is ________

(vi) (vii) (viii) (ix) (x) (xi) (xii) (xiii) (xiv) (xv) (xvi)

  The boiling point of dioxane is ________ than thioxane  

  . 

They type of delocalization involving sigma bond orbitals is called ________ Hydroperoxide ion a stronger ________ but weaker ________ than hydroxide ion. A reaction which occurs through a single transition state is called a ________ reaction. Free radicals are ________ but carbanions are ________ Amongst isomeric butenes ________ is the most stable. In ethyl acetoacetate, it is the ________ form which is more stable while in acetylacetone, it is the ________ form which is more stable. In propionic acid , the central carbon atom is _______ while in α-bromopropionic acid it is _______. An organic compound with the formula CH3CH2CH2OH shows functional, isomerism with compound of the structural formula ________ Alkenes can exhibit position, chain and ________ isomerism. Ketones must contains at least ________ carbon atoms in order to exhibit metamerism .

(xvii) The number of isomers of molecular formula C8H10 containing benzene ring are ________ (xviii) The possible number of dichloro derivatives of propane are ________ (xix) 2. (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) (ix) Ethyl benzene is ________ isomer to xylenes. True and false sp hybrid orbital is more electronegative than sp2 hybrid orbital. The size of sp3 hybrid orbital of carbon is smaller than that of sp hybrid orbital. The resonating structure differ in the number of unpaired electrons. The resonance energy is defined as the difference between the enthalpy of formation of the molecule and that of resonating structure having the largest energy. Benzene has about 78 per cent contribution from Kekule’s structures. Metamerism is due to the different arrangement of groups attached to a functional group. Tautomers of a compound are in equilibrium with each other. Chain isomers are possible for alkanes having four or more carbon atoms. Maleic acid has zero dipole moment.

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72

GOC - ISOMERISM

(x) (xi) (xii) (xiii) (xiv) (xv) (xvi)

Of ethane, ethene and ethyne, the ethynic hydrogens are most acidic. Propandiene has both sp and sp2 hybrid carbon atoms. Methyl group belongs to –I group. The − OCH3 group belongs to + I group. Resonance and tautomerism refer to one and the same phenomenon. The − OH and − NH2 groups attached to aromatic ring have only resonance effects. BF3 acts as a Lewis base. CH3COO¯ + H+, CH3COOH and CH3COO¯

(xvii) Stronger acids have lesser values of pKa as compared to weaker acids. (xviii) In an equilibrium reaction CH3COOH constitute conjugate pair of acid and base. (xix) (xx) (xxi)

In a carboxylic acid RCOOH, the factor stabilising the carboxylate anion, RCOO¯, relative to RCOOH increases the acidity of the acid. + I group attached to carboxylic group weakens the acidity of carboxylic acid. The resonate stabilisation of formate anion makes formic acid stronger acid than acetic acid.

(xxii) Nucleophilic substitution reactoin involving SN1 mechanism is always associated with the inversion of configuration of carbon atom (xxiii) The addition across C = O group is an electrophilic addition reaction. (xxiv) Aryl halides are less reactive than alkyl halides towards nucleophilic reagents. (xxv) In acylium ion, the structure R—C ≡ O : is more stable than R— C = O, (xxvi) The stability of carbonium ions is influenced by both resonance and inductive effect. –I effect reduces the stability while + I effect increases the stability fo carbonium ion. (xxvii) m-chlorobromobenzene is an isomer of m-bromochlorobenzene. (xxviii) Dichlorocarbene (:CCl2) is a nucleophile. (xxix) Free radicals are produced by homolytic cleavage of covalent bonds. (xxx) All electrophiles are positively charged. (xxxi) Amongst CH3O¯ , HO¯ and CH3COO¯ ions nucleophilicity parallels basicity. (xxxii) Simple carbanions are isoelectronic and isostructural with ammonia. 3. Choose the correct answer : (a) If both A and R are TRUE, and is the CORRECT explanation of A. (b) If both A and R are TRUE, but R is not the CORRECT explanation of A. (c) If A is TRUE but R is FALSE (d) If both A and R are FALSE. Assertion (A) (i) Tertiary carbonium ion are generally formed more easily than primary carbonium ions. Singlet carbene has a linear structure. Carbanions like ammonia have pyramidal shape. Reason (R) Hyperconjugative as well as inductive effect due to additional alkyl groups stabilize tertiary carbonium ions The carbon atom in singlet carbene is sp2hybridized. The carbon atom carrying negative charge has an octet of electrons.

(ii) (iii)

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GOC - ISOMERISM

73

Assertion (A) (iv) The carbocation CF3– C H2 is less stable than C F3.

Reason (R) In case of CF3– C H2, the strongly electron withdrawing –CF3 group intensifies the +ve charge but in case of C F3, the lone pair of electrons on each of the three F-atoms overlap with the empty p-orbital of the carbocation carbon thereby dispersing the +ve charge.

(v) (vi) (vii) (viii) (ix)

Methylene has sextet of electrons around carbon but bears no formal charge. N3¯ is a weaker base than NH2¯. Allyl free radicals is more stable than a simple alkyl free radical. Enol form of cyclohexane-1,3,5-trione is more stable than its keto-form. Metamers can also be chain or position isomers All the carbon atoms in but-2-ene lie in one plane All the hydrogen atoms in CH2=C=CH2 lie in one plane C2H5O2N shows functional isomerims as well as tautomerism. Both ethyl acetoacetate and acetylacetone exhibit keto-enol tautomerism but the amount of enolic form is much higher in acetylacetone than in acetoacetic ester. Ethyl acetoacetate gives reddish violet colour on treatment with ferric chloride. Benzaldehyde forms two oximes on reacting with NH2OH. Cyclobutane is less stable than cyclopentane. Pick out the correct match (i) Aseptic distillation (ii) acetaldehyde (iii) Yeast (iv) Dipole moment measurement

Methylene behave as a nucleophile. The lone pair of electrons in on N atom in N3¯ is a in a sp2-orbital while in NH2¯ it is in an sp3-orbital. The allyl free radical is stabilized by resonance. It contains α-hydrogen atoms The term tautomerism was introduced to explain the reactivity of a substance according to two possible structures. All the carbon atoms of but-2-ene are sp2hybridized All the carbon atoms in it are sp2-hybridised Nitroethane shows tautomerism due to presence of α-hydrogens and functional isomerism with ethyl nitrite. Keto group is a much better electron withdrawing group than an ester group.

(x) (xi) (xii)

(xiii)

(xiv) (xv) (xvi)

It exists predominantly in the keto-form The two oximes arise due to geometrical isomerism. Presence of ‘bent bonds’ causes loss of orbital overlap.

4.

(A) (B) (C) (D)

separation of keto and enol tautomers high percentage of enol conversion of D-glucose to L-glucose distinguishing optical isomers

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74

GOC - ISOMERISM

LEVEL - IV SU BJEC TIV E
1. Arrange the following according to their stability and give reason of your answer .
C 6 H 5 C H 2 , (CH 3 ) 3 C , C Cl3 , C H 3 , ( CH 3 ) 2 C H

2. 3. 4.

Explain why boiling point of acetone is more than that of propanaldehyde although both have same molecular weight ? CH3Cl and CH3OH both are polar compounds but CH3OH is soluble in water where as CH3Cl is not. Why ? Explain why bp of RX is in the following order : R—I > R—Br > R—Cl > R—F although dipole-dipole attraction is maximum in R—F and minimum in R—I: Alkane has a molecular weight of 72 and monochlorination prduces one product only . What is the compound. Write down the structure of close homologous of heptane having in their molecular one of quaternary carbon atom and the other having two tertiary carbon atom. When propane reacts with Cl2, the reaction yield two compounds of the molecular formula C3H7Cl, One compound has a b.p. of 46.6ºC and the other b.p. of 36.5ºC. When the compound with boiling point 46.6ºC is allowed to react with Cl2, the reaction gives three isomeric compounds of molecular formula C3H6Cl2. When the compound with b.p. 36.5º reacts with Cl2, only two isomers of formula C3H6Cl2 are formed. Give the structure of all products. Why allylic free radical CH2 = CH – C H 2 is more stable than CH3– CH2 – C H 2 , while both are primary free radicals .
H
4
• •

5. 6. 7.

8.

O H
1

O H
2

9.
H OH
3

Arrange all these numbered H in order of their decreasing acidic strength. 10. Arrange the following compounds in order of increasing basicity. CH3
+ –

(a) Cl3C , H3C 11.

N

CH3 , CH 3 — O — CH3

(b) N H 4 , N H 2 , NH 3

Which of the following C—I bond is weak and why? CH3 (a) CH 3O — CH 2 — I (b) H3C N CH2 I

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GOC - ISOMERISM

75

12.

Account for the following .
– (a) CCl3 is less basic than CF3– .

(b) I – is weaker base than F– .

13.

Explain the following (a) (b) (c) NC — CH 2 — CN is a stronger acid than CH 3 — CO — C 2H 5 . CH 3 — CO — C 2H 5 is more acidic than CH 3 — CH = CH 2 . CH 3 — CH = CH — OH is more acidic than CH 2 = CH — CH 2 — OH .

14. 15. 16.

O O || || H3C– C –CH3 Acetone shows slow rate of reaction as compare to the H3C– C –H . Why ? Molecular weight of ICl (162.5) and Br2 (160) are nearly same but boiling point of ICl is 40° higher than Br2. Why ? Explain (a) N-methylpyrrolidine has a boiling of 81°C , and piperidine has a boiling point of 106 °C .

(b) 17. 18. 19. 20. 21.

Tetrahydrofuran has a boiling point of 88 °C and its isomer cyclobutanol has a boiling point of 141 °C.

Indane 1 , 2 , 3 trione and diphenyl propane trione having high hydration constant value . Explain. Cyclobutadiene exist as a dimer . Justify . Write metamers of OCH2CH3

C4H9NO2 has different isomeric nitroalkanes . Which will form tautomers ? Write the structure of two alkanes of molecular formula C8H18 having following structural features – Four 1° carbon atoms – Two 2° carbon atoms – Two 3° carbon atoms – Two asymmetric centres. Write the structure of a compound having following structural features : – molecular formula = C5H9N – a five membered ring – N is 3° and asymmetric Write the structure of a compound having following structural features : – molecular formula = C4H9NO – a π bond between N and O – no tautomerization Structural isomers and contributing structures are different . Why ? Phosgene has smaller dipolemoment than formaldehyde . Explain. Write the structure of isomers C4H6 and identify the structures that has highest dipole moment. How can you explain the fact that fluoromethane (CH3F, µ = 1.81D) has a smaller dipole moment than chloromethane (CH3Cl, µ = 1.87D), even though fluorine is more electronegnative than chlorine ?

22.

23.

24. 25. 26. 27.

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28.

Explain : (a) Although boron trifluoride in soluble in trimethylamine, it does soluble in triphenylamine. (b) Which CX2(X = F, Cl, Br, I) is the most stable radical and why ? Sulphanilic acid although has acidic as well as basic group, it is soluble in alkali but insoluble in mineral acids. Explain. Write equations for the acid base reaction that would occur when each of the following compounds of solution are mixed. In each case label the stronger acid and stronger base, and the weaker acid and weaker base. (a) NaNH2 is added to acetylene (b) gaseous NH3 is add to ethyl lithium in hexane (c) (d) C2H5OH is added to a solution of HC ≡ NaH is added to H3COH in liquid NH3.

29. 30.

31. 32. 33. 34.

Cyclohexanol is more soluble in water then 1-hexanol 1 , 5-Pentanediol is soluble and 1-pentanol is slightly soluble in H2O. Justify the statement. 1º and 2º amides tend to exist as dimer in solid and pure liquid state. Explain the following: (a) p-Chlorobenzene is more soluble in n-propyl alcohol than methyl alcohol , while o-dichlorobenzene is less soluble in n-propyl alcohol than methanol. (b) Heterolytic cleavage requires more energy than homolytic cleavage. How many isomer of molecular formla C3H7NO are posiible while all isomer should have ‘amide’ group and one of the isomer different properties. Name that isomer and give reason of different characteristics. Write down the all possible amides of formula C3H7NO and show one among these isomers, show exceptionally behaviour. Draw the structure of that isomers and give reason for this exception. Explain enol form of acetoacetic ester is said to be more volatile thath keto form. Explain the α-methyl acetyl acetone undergoes enolization to a smaller extent than acetyl acetone .

35.

36.

37. 38.

O
39..

O

Why CH3 – C – CH2 – C – CH3 is known as active methylene compound ?

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IIT-JEE PROBLEMS
Fill in the blanks :
1. 2. 3. 4. 5. Among the given cations , ________ is most stable . [ sec-butyl carbonium ion ; tert-butyl carbonium ion ; n-butyl carbonium ion ] The compound having both sp and sp2 hybridized carbon atoms is ________ . [ Propane , propane , propadiene ] ________ ring is most strained . (Cyclopropane , Cyclobutane , Cyclopentane) The terminal carbon atom in butane ________ hybridised . [ 1981 ] [1981 ] [ 1981 ] [ 1985 ]

Isomers which are ________ mirror images are known as ________ [ superimposable , non-superimposable , enantiomers , diastereomers , epimers ] [ 1988 ] The valence atomic orbitals on carbon in silver acetylide is ________ hybridised . The kind of delocalization involving sigma bond orbitals is called ________ . Among PCl3, CH3+, NH2¯ and NF3 , ________is least reactive towards water . [ 1990 ] [ 1994 ] [ 1997 ]

6. 7. 8.

True/false :
1. 2. 3. 4. Iodide is a better nucleophile than bromide . [ 1985 ] An electron donating substituent in benzene orients the incoming electrophilic group to the meta position . [ 1987 ] 2 , 3 , 4-Trichloropentane has three asymmetric carbon atoms . [ 1990 ] During SN1 reaction , the leaving group leaves the molecule before the incoming group is attached to the molecule . [ 1990 ]

Multiple Choice Questions
1. The bond order of individual carbon-carbon bonds in benzene is : (a) one (b) two (c) between one and two (d) one and two, alternately Molecule in which the distance between the two adjacent carbon atoms is largest is (a) Ethane (b) Ethene (c) Ethyne (d) Benzene The compound which is not isomeric with diethyl ether is (a) n-propyl methyl ether (b) butan-1-ol (c) 2-methylpropan-2-ol (d) butanone

[ 1981 ] [ 1981 ]

2. 3.

[ 1981 ]

4.

Among the following, the compound that can be most readily sulphonated is (a) benzene (b) Nitrobenzene (c) toluene (d) Chlorobenzene [ 1982 ] The compound 1, 2-butadiene has : (a) only sp hybridized carbon atom (c) both sp and sp2 hybridized carbon atoms (b) only sp2 hybridized carbon atoms (d) sp, sp2 and sp3 hybridized carbon atoms [ 1985 ]

5.

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6.

An isomer of ethanol is : (a) methanol (b) diethyl ether

(c) acetone

(d) dimethyl ether [ 1987 ]

7.

Out of the following compounds, which will have a zero dipole moment ? (a) 1, 1-dichloroethylene (b) cis-1, 2-dichloroethylene (c) trans-1, 2-dichloroethylene (d) None of these compounds . The bond between carbon atom (1) and carbon atom (2) in compound N ≡ C — CH = CH2 involves the hybrids as :
1 2

[ 1987 ]

8.

(a) sp2 and sp2 9. 10.

(b) sp3 and sp

(c) sp and sp2

(d) sp and sp [ 1987 ]

The number of isomers of C6H14 are : (a) 4 (b) 5

(c) 6

(d) 7

[ 1987 ]

The Cl–Cl–Cl angle in 1,1,2,2-tetrachloroethene and tetrachloromethane respectively will be about (a) 120º & 109.5º (b) 90º & 109.5º (c) 109.5º & 90º (d) 109.5º & 120º [ 1988 ] In CH3CH2OH, the bond that undergoes heterolytic cleavage most readily is : (a) C − (b) C − O (c) C − H (d) O − H The compound which has one isopropyl group is : (b) 2 , 2 - dimethylpentane (a) 2 , 2 , 3 , 3 - tetramethylpentane (c) 2 , 2 , 3 - trimethylpentane (d) 2 - methylpentane The C – H bond distance is the longest in : (b) C2H4 (a) C2H2 (c) C2H6 (d) C2H2Br2 [ 1989 ] [ 1988 ]

11. 12.

[ 1989 ]

13.

14.

The number of sigma and pi - bonds in 1 - buten - 3 - yne are : (a) 5 sigma & 5 pi (b) 7 sigma & 3 pi (c) 8 sigma & 2 pi

(d) 5 sigma & 4 pi [ 1989 ]

15.

The compound which gives the most stable carbonium ion on dehydration is : CH3 (a) CH3—CH—CH2OH (b) CH3—C—OH CH3 (d) CH3—CH—CH2—CH3 [ 1989 ]

CH 3
(c) CH3—CH2—CH2—CH2OH

OH
16. 17. The hybridization of carbon atom in C – C single bond of HC ≡ C – CH = CH is : (a) sp3–sp3 (b) sp2–sp3 (c) sp–sp2 (d) sp3–sp [ 1991 ]

Read the following statement and explanation and answer as per the options given below : Statement (S) : Aryl halides undergo nucleophilic substitution with ease. Explanation (E) : The carbon-halogen bond in aryl halides has partial double bond character. (a) Both S and E are true, and E is the correct explanation of S (b) Both S and E are true, and E is not the correct explanation of S (c) S is true but E is false. (d) S is false but E is true. [ 1991 ]

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79

18.

The products of combustion of an aliphatic thiol (RSH) at 298 K are : (a) CO2(g), H2O (g) and SO2(g) (b) CO2(g), H2O(l) and SO2(g) (c) CO2(l), H2O(l) and SO2(g) (d) CO(g), H2O(l) and SO2(l) [ 1992 ] Allyl isocyanide has : (a) 9σ and 4π bonds (c) 9σ, 3π and 2 non-bonded electrons

19.

(b) 8σ and 5π bonds (d) 8σ, 3π and 4 non-bonded electrons [ 1995 ]

20.

Arrange in order of decreasing trend towards SE reactions : (I) Chlorobenzene (II) benzene (III) Anilinium chloride (IV) toluene (a) II > I > III > IV (b) III > I > II > IV (c) IV > II > I > III (d) I > II > III > IV [ 1995 ] Most stable carbonium ions is : (a) p—NO2—C6H4—CH2+ (c) p—Cl—C6H4—CH2+ In the following compounds OH (I) (II) (b) C6H5CH2+ (d) p—CH3O—C6H4—CH2+

21.

[ 1995 ]

22.

OH
(III)

OH
(IV)

OH

NO2
CH3
The order of acidity is : (a) III > IV > I > II (b) I > IV > III > II 23. (c) II > I > III > IV
NO2

(d) IV > III > I > II [ 1996 ]

Arrange the following compounds in order of increasing dipole moment I Toluene II m-dichlorobenzene III o-dichlorobenzene IV p-dichlorobenzene (a) I < II < III < IV (b) IV < III < I < II (c) III > II > I > IV (d) IV > II > I > III [ 1996 ] In the following groups : (I) — OAc (II) — OMe The order of leaving group ability is : (a) I < IV < II < III (b) IV < I < II < III (III) — OSO2Me (c) III > II > I > IV (IV) — OSO2CF3 (d) II > III > IV > I [ 1997 ]

24.

25.

Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is : (a) MeCOCl (b) MeCHO (c) MeCOOMe (d) MeCOOCOMe [ 1997 ] In the compound CH2 = CH – CH2 – C ≡ CH, The C2–C3 bond is of the type. (a) sp – sp2 (b) sp3 – sp3 (c) sp – sp3 (d) sp2 – sp3 [ 1999 ] Which of the following has the highest nucleophilicity ? (a) F¯ (b) OH¯ (c) CH3¯ (d) NH2¯ [ 2000 ]

26. 27. 28.

The order of reactivities of the following alkyl halides for a SN2 reaction is : (a) RF > RCl > RBr > RI (b) RF > RBr > RCl > RI (c) RCl > RBr > RF > RI (d) RI > RBr > RCl > RF

[ 2000 ]

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29.

Which of the following has the most acidic hydrogen ? (a) 3-Hexanone (b) 2, 4-Hexanedione (c) 2,5-Hexanedione (d) 2,3-Hexanedione [ 2000 ] Read the following statement and explanation and answer as per the options given below : Assertion : Phenol is more reactive than benzene towards electrophilic substitution reaction. Reason : In the case of phenol, the intermediate carbocation is more resonance stabilized. (a) If both assertion and reason are CORRECT and reason is the CORRECT explanation of the assertion. (b) If both assertion and reason are CORRECT, but reason is NOT the CORRECT explanation of the assertion. (c) If assertion is CORRECT, but reason is INCORRECT. (d) If assertion is INCORRECT, but reason is CORRECT. [ 2000 ] The number of isomers for the compound with molecular formula C2BrClFI is : (a) 3 (b) 4 (c) 5 (d) 6 [ 2001 ]

30.

31. 32.

An SN2 reaction at an asymmetric carbon of a compound always gives (a) an enantiomer of the substrate (b) a product with opposite optical rotation (c) a mixture of diastereomers (d) a single stereoisomer [ 2001 ] Which of the following acids has the smallest dissociation constant ? (b) FCH2CH2COOH (a) CH3CHFCOOH (c) BrCH2CH2COOH (d) CH3CHBrCOOH Identify the correct order of boiling point of the following compounds . (2) CH3CH2CH2CHO (3) CH3CH2CH2COOH (1) CH3CH2CH2CH2OH (a) 1 > 2 > 3 (b) 3 > 1 > 2 (c) 1 > 3 > 2 (d) 3 > 2 > 1 [ 2002 ] Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds
CH3

33.

[ 2002 ]

34.

35.

Cl
(3) (c) 2 > 1. > 3 > 4 (4)

NO2

(1) (a) 1 > 2 > 3 > 4 36.

(2) (b) 4 > 3 > 2 > 1

(d) 2 > 3 > 1 > 4 [ 2002 ]

Which of the following hydrocarbons has the lowest dipole moment ? CH3 (a) C=C CH3 (b) CH3C ≡ CCH3 (d) CH2 = CH – C ≡ CH [ 2002 ]

H H (c) CH3CH2C≡CH 37.

Which of the following represents the given mode of hybridisation sp2–sp2–sp–sp from left to right ? (a) H2C = CH – C ≡ N (b) HC ≡ C – C ≡ CH CH2 (c) H2C = C = C = CH2 (d) H2C Among the following, the molecule with the highest dipole moment : (a) CH3Cl (b) CH2Cl2 (c) CHCl3 [ 2003 ] (d) CCl4 [ 2004 ]

38.

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81

39.

Which of the following resonating structures of 1-methoxy-1,3-butadiene is least stable ? (a) CH2 – CH = CH – CH = O – CH3 (c) CH2 – CH – CH = CH – O – CH3 (b) CH2 = CH – CH2 – CH = O – CH3 (d) CH2 = CH – CH = CH – O – CH3 [ 2005 ]

CH3 CH3 CH3
40.

CH3O H
will give :

NO2 compound on hydrolysis in aqueous acetone Cl CH3

CH3 CH3 CH3
(i)

CH3O H OH CH3 CH3 CH3 CH3

NO2

(ii)

CH3O OH H CH3 CH3 CH3 CH3

NO2

(iii)

CH3O H CH3 OH

NO2
(b) Mixture of (i) and (iii) (d) Only (i)

(a) Mixture of (i) and (ii) (c) Only (iii) 41.

[ 2005 ]

Arrange the following compounds in the order of increasing boiling point (I) Hydroxy benzene (II) ortho dihydroxy benzene (III) meta dihydroxy benzene (IV) para dihydroxy benzene (a) (IV) > (III) > (II) > (I) (b) (III) > (IV) > (II) > (I) (c) (II) > (III) > (I) > (IV) (d) (I) > (II) > (III) > (IV) [ 2006 ]

Multiple choice question . [ One or more than one correct answer(s) ]
1. Resonance structure of a molecule should have : (a) Identical arrangement of atom (b) nearly the same energy content (c) the same number of paired electrons (d) identical bonding Phenol is less acidic than : (a) acetic acid (b) p-methoxyphenol Dipole moment is shown by : (a) 1, 4-dichlorobenzene (c) trans 1, 2-dichloroethene (c) p-nitrophenol (d) ethanol [ 1986 ] 3. (b) cis 1, 2-dichloroethane (d) trans 1, 2-dichloro-2-pentene

[ 1984 ]

2.

[ 1986 ]

4.

Only two isomeric monochloro derivatives are possible for : (a) n-butane (b) 2, 4-dimethylpentane (c) benzene (d) 2-methylpropane

[ 1986 ]

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5.

Which of the following have asymmetric carbon atom ? Cl Br (a) H—C—C—H H H

H Cl
(b) H—C—C—Cl

H Cl
(c) H—C—C—H

H H
(d) H—C—C—CH2

H

H

H H

Br OH [ 1989 ]

6.

What is the decreasing order of strength of the bases OH¯, NH2¯, H – C ≡ C¯ and CH3 – CH2¯? (a) CH3 – CH2¯ > NH2¯ > H – C ≡ C¯ > OH¯ (b) H – C ≡ C¯ > CH3 – CH2¯ > NH2¯ > OH¯ (c) OH¯ > NH2¯ > H – C ≡ C¯ > CH3 – CH2¯ (d) NH2¯ > H – C ≡ C¯ > OH¯ > CH3 – CH2¯ [ 1993 ] Which of the following compounds will show geometrical isomerism ? (a) 2-Butene (b) propene (c) 1-phenylpropene (d) 2-methyl-2-butene [ 1998 ] Among the following compounds , the strongest acid is : (a) HC ≡ CH (b) C6H6 (c) C2H6 Tautomerism is exhibited by : (a) (d) CH3OH [ 1998 ]

7.

8. 9.

CH = CH – OH

(b) O O O

O

(c)
O

O

(d)

[ 1998 ]

10.

An aromatic molecule will : (a) have 4n π electrons (c) be planar

(b) have (4n + 2) π electrons (d) be cyclic

[ 1999 ]

SUBJETIVE PROBLEMS :
1. 2. Write structural formulae for all the isomeric alcohols having the molecular formula C4H10O. [ 1984 ] Arrange the following in : (i) Increasing reactivity towards HCN CH3CHO , CH3COCH3 , HCHO , C2H5COCH3 (ii) n-butane, n-butanol, n-butyl chloride, isobutane in increasing order of boiling point,. (iii) Benzene, toluene, methoxybenzene, chlorobenzene in increasing order of reactivity towards sulphonation with fuming sulphuric acid. I ClCH2COOH , II CH3CH2COOH , III ClCH2CH2COOH , IV (CH3)2CHCOOH , V CH3COOH (iv) Increasing reactivity in nucleophilic substitution reactions CH3F, CH3I, CH3Br, CH3Cl [ 1985 ] For nitromethane molecule, write structure(s) (a) showing significant resonance stabilization. (b) indicating tautomerism

3.

[ 1986 ]

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4.

Give reasons for the following : (a) Carbon oxygen bond lengths in formic acid are 1.23Å and 1.36 Å and both the carbon oxygen bonds in sodium formate have the same value i.e. 1.27Å. (b) Phenyl group is known to exert negative inductive effect. But each phenyl ring in biphenyl (C6H5 –C6H5) is more reactive than benzene towards electrophilic substitution. (c) Aryl halides are less reactive than alkyl halides towards nucleophilic reagents. (d) CH2=CH¯ is more basic than HC ≡ C¯ (e) Normally, benzene gives electrophilic substitution reaction rather than electrophilic addition reaction although it has double bonds. [ 1986 ] Discuss the hybridisation of carbon atoms in allene (C3H4) and show the π-orbital overlaps . [ 1999 ] Which one is more soluble in diethyl ether-anhydrous AlCl3 or hydrous AlCl3 ? Explain . [ 2003 ] Match the Ka values (a) (b) (c) (d) (e) Benzoic acid (i) Ka 3.3 × 10–5 10.2 × 10–5 30.6 × 10–5 6.4 × 10–5 4.2 × 10–5 [ 2003 ] H3C CH2 Write resonance structure of the given compound . OH Which of the following is more acidic and why ? [ 2003 ]

5. 6. 7.

O2N Cl H3CO H3C

COOH COOH COOH COOH

(ii) (iii) (iv) (v)

8. 9.

H3N
10. mobs =

,

H3N

F

[ 2004 ]

∑ µi x i
i

, where µi is the diople moment of a stable conformer of the molecule ,

Z – CH2– CH2 – Z and xi is the mole fraction of the stable conformer . [ Given mobs = 1.0 D and x (Anti) = 0.82 ] Draw all the stable conformers of Z – CH2 – CH2 – Z and calculate the value of µ(Gauche) . [ 2005 ]

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ANSWERS
LEVEL - I
1. 8. 15. 22. 29. 36. 43. 50. 57. 64. 2. 9. 16. 23. 30. 37. 44. 51. 58. 65. 3. 10. 17. 24. 31. 38. 45. 52. 59. 4. 11. 18. 25. 32. 39. 46. 53. 60. 5. 12. 19. 26. 33. 40. 47. 54. 61. 6. 13. 20. 27. 34. 41. 48. 55. 62. 7. 14. 21. 28. 35. 42. 49. 56. 63.

LEVEL - II A
1. 8. 15. 22. 29. 36. 43. 50. 57. 2. 9. 16. 23. 30. 37. 44. 51. 58. 3. 10. 17. 24. 31. 38. 45. 52. 59. 4. 11. 18. 25. 32. 39. 46. 53. 60. 5. 12. 19. 26. 33. 40. 47. 54. 6. 13. 20. 27. 34. 41. 48. 55. 7. 14. 21. 28. 35. 42. 49. 56.

LEVEL - II B
1. 8. 15. 22. 29. 36. 43. 50.
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2. 9. 16. 23. 30. 37. 44.

3. 10. 17. 24. 31. 38. 45.

4. 11. 18. 25. 32. 39. 46.

5. 12. 19. 26. 33. 40. 47.

6. 13. 20. 27. 34. 41. 48.

7. 14. 21. 28. 35. 42. 49.

GOC - ISOMERISM

85

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