Assignment(Including Extra Questions) Haloalkane and Haloarenes

Syllabus 6 Marks
Haloalkanes: Nomenclature, nature of C–X bond, physical and chemical properties, optical rotation mechanism of substitution reactions.
Haloarenes: Nature of C–X bond, substitution reactions (Directive influence of halogen in monosubstituted compounds only). Uses and
environmental effects of - dichloromethane, trichloromethane, tetrachloromethane, iodoform, freons, DDT.

1 MCQ’s A/R 2 Marks 3 Marks Case Study 5 Marks

Sample Paper 2024 2 0 0 2(Internal C) 0 0
2024 (Compartment) 1 0 1 1 0 0
2024 (March) 0 0 1 1 0 1Mark Q

Multiple Choice Questions:

1. What The order of reactivity of following alcohols with halogen acids is ___________.

(i) (A) > (B) > (C) (ii) (C) > (B) > (A) (iii) (B) > (A) > (C) (iv) (A) > (C) > (B)
2. Which of the following alcohols will yield the corresponding alkyl chloride on reaction with concentrated HCl at room temperature?

3. Identify the compound Y in the following reaction

4. Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and para halo compounds. The reaction is
(i) Electrophilic elimination reaction (ii) Electrophilic substitution reaction
(iii) Free radical addition reaction (iv) Nucleophilic substitution reaction
5. Which of the following is halogen exchange reaction?

6. Which reagent will you use for the following reaction?

CH3CH2CH2CH3 → CH3CH2CH2CH2Cl + CH3CH2CHClCH3
(i) Cl2 /UV light (ii) NaCl + H2 SO4 (iii) Cl2 gas in dark (iv) Cl2 gas in the presence of iron in dark
7. Arrange the following compounds in the increasing order of their densities.

(i) (a) < (b) < (c) < (d) (ii) (a) < (c) < (d) < (b) (iii) (d) < (c) < (b) < (a) (iv) (b) < (d) < (c) < (a)
Assignment(Including Extra Questions) Haloalkane and Haloarenes

8. Arrange the following compounds in increasing order of their boiling points.

(i) (b) < (a) < (c) (ii) (a) < (b) < (c) (iii) (c) < (a) < (b) (iv) (c) < (b) < (a)
9. In which of the following molecules carbon atom marked with asterisk (*) is asymmetric?

(i) (a), (b), (c), (d) (ii) (a), (b), (c) (iii) (b), (c), (d) (iv) (a), (c), (d)
10. Which of the following is an example of vic-dihalide?
(i) Dichloromethane (ii) 1,2-dichloroethane (iii) Ethylidene chloride (iv) Allyl chloride
11. The position of –Br in the compound in CH3CH==CHC(Br)(CH3 ) 2 can be classified as ____________.
(i) Allyl (ii) Aryl (iii) Vinyl (iv) Secondary
12. Chlorobenzene is formed by reaction of chlorine with benzene in the presence of AlCl 3 . Which of the following species attacks the benzene ring
in this reaction?
(i) Cl – (ii) Cl + (iii) AlCl3 (iv) [AlCl4 ] –
13. Ethylidene chloride is a/an ______________.
(i) vic-dihalide (ii) gem-dihalide (iii) allylic halide (iv) vinylic halide
14. What is ‘A’ in the following reaction?

15. A primary alkyl halide would prefer to undergo _____________.

(i) SN1 reaction (ii) SN2 reaction (iii) α–Elimination (iv) Racemisation
16. Which of the following alkyl halides will undergo SN 1 reaction most readily?
(i) (CH3)3C—F (ii) (CH3)3C—Cl (iii) (CH3)3C—Br (iv) (CH3)3C—I
17. Which is the correct IUPAC name for
(i) 1-Bromo-2-ethylpropane (ii) 1-Bromo-2-ethyl-2-methylethane (iii) 1-Bromo-2-methylbutane (iv) 2-Methyl-1-bromobutane
18. What should be the correct IUPAC name for diethylbromomethane?
(i) 1-Bromo-1,1-diethylmethane (ii) 3-Bromopentane (iii) 1-Bromo-1-ethylpropane (iv) 1-Bromopentane
19. The reaction of toluene with chlorine in the presence of iron and in the absence of light yields ____________.

(iv) Mixture of (ii) and (iii)

20. Chloromethane on treatment with excess of ammonia yields mainly
(i) N, N-Dimethylmethanamine (ii) N–methylmethanamine (iii) Methanamine (iv) Mixture containing all these in equal proportion
21. Molecules whose mirror image is non superimposable over them are known as chiral. Which of the following molecules is chiral in nature?
(i) 2-Bromobutane (ii) 1-Bromobutane (iii) 2-Bromopropane (iv) 2-Bromopropan-2-ol
22. Reaction of C6H5CH2Br with aqueous sodium hydroxide follows ____________.
(i) SN1 mechanism (ii) SN2 mechanism (iii) Any of the above two depending upon the temperature of reaction (iv) Saytzeff rule
23. Which of the carbon atoms present in the molecule given below are asymmetric?

(i) a, b, c, d (ii) b, c (iii) a, d (iv) a, b, c

Assignment(Including Extra Questions) Haloalkane and Haloarenes

24. Which of the following compounds will give racemic mixture on nucleophilic substitution by OH – ion?

(i) (a) (ii) (a), (b), (c) (iii) (b), (c) (iv) (a), (c)
25. Note: In the questions 25 to 28 arrange the compounds in increasing order of rate of reaction towards nucleophilic substitution.

(i) (a) < (b) < (c) (ii) (c) < (b) < (a) (iii) (a) < (c) < (b) (iv) (c) < (a) < (b)
26.

(i) (a) < (b) < (c) (ii) (a) < (c) < (b) (iii) (c) < (b) < (a) (iv) (b) < (c) < (a)
27.

(i) (c) < (b) < (a) (ii) (b) < (c) < (a) (iii) (a) < (c) < (b) (iv) (a) < (b) < (c)
28.

(i) (a) < (b) < (c) (ii) (b) < (a) < (c) (iii) (c) < (b) < (a) (iv) (a) < (c) < (b)
29. Which is the correct increasing order of boiling points of the following compounds? 1-Iodobutane, 1-Bromobutane, 1-Chlorobutane, Butane
(i) Butane < 1-Chlorobutane < 1-Bromobutane < 1-Iodobutane (ii) 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane < Butane
(iii) Butane < 1-Iodobutane < 1-Bromobutane < 1-Chlorobutane (iv) Butane < 1-Chlorobutane < 1-Iodobutane < 1-Bromobutane
30. Which is the correct increasing order of boiling points of the following compounds?
1-Bromoethane, 1-Bromopropane, 1-Bromobutane, Bromobenzene
(i) Bromobenzene < 1-Bromobutane < 1-Bromopropane < 1-Bromoethane
(ii) Bromobenzene < 1-Bromoethane < 1-Bromopropane < 1-Bromobutane
(iii) 1-Bromopropane < 1-Bromobutane < 1-Bromoethane < Bromobenzene
(iv) 1-Bromoethane < 1-Bromopropane < 1-Bromobutane < Bromobenzene
Assertion and Reason Type:
1. Assertion : Phosphorus chlorides (tri and penta) are preferred over thionyl chloride for the preparation of alkyl chlorides from alcohols.
Reason : Phosphorus chlorides give pure alkyl halides.
2. Assertion : The boiling points of alkyl halides decrease in the order : RI > RBr > RCl > RF
Reason : The boiling points of alkyl chlorides, bromides and iodides are considerably higher than that of the hydrocarbon of comparable
molecular mass.
3. Assertion : KCN reacts with methyl chloride to give methyl isocyanide Reason : CN– is an ambident nucleophile.
4. Assertion : tert-Butyl bromide undergoes Wurtz reaction to give 2, 2, 3, 3-tetramethylbutane.
Reason : In Wurtz reaction, alkyl halides react with sodium in dry ether to give hydrocarbon containing double the number of carbon atoms
present in the halide.
5. Assertion : Presence of a nitro group at ortho or para position increases the reactivity of haloarenes towards nucleophilic substitution.
Reason : Nitro group, being an electron withdrawing group decreases the electron density over the benzene ring.
6. Assertion : In monohaloarenes, further electrophilic substitution occurs at ortho and para positions.
Assignment(Including Extra Questions) Haloalkane and Haloarenes

Reason : Halogen atom is a ring deactivator.

7. Assertion : Aryl iodides can be prepared by reaction of arenes with iodine in the presence of an oxidising agent.
Reason : Oxidising agent oxidises I2 into HI.
8. Assertion : It is difficult to replace chlorine by –OH in chlorobenzene in comparison to that in chloroethane.
Reason : Chlorine-carbon (C—Cl) bond in chlorobenzene has a partial double bond character due to resonance.
9. Assertion : Hydrolysis of (–)-2-bromooctane proceeds with inversion of configuration.
Reason : This reaction proceeds through the formation of a carbocation.
10. Assertion : Nitration of chlorobenzene leads to the formation of m-nitrochlorobenzene Reason : —NO2 group is a m-directing group.
Naming Based Questions
1. Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl
halides:

2. Give the IUPAC names of the following compounds:

(i) CH3CH(Cl)CH(Br)CH3 (ii) CHF2CBrClF (iii) ClCH2C≡CCH2Br (iv) (CCl3)3CCl (v) CH3C(p-ClC6H4)2CH(Br)CH3 (vi) (CH3 ) 3CCH=CClC6H4 I-p
3. Write the structures of the following organic halogen compounds.
(i) 2-Chloro-3-methylpentane (ii) p-Bromochlorobenzene (iii) 2-Bromobutane (iv) 1-Chloro-4-ethylcyclohexane
(v) 2-(2-Chlorophenyl)-1-iodooctane(vi) 4-tert-Butyl-3-iodoheptane (vii) 1-Bromo-4-sec-butyl-2-methylbenzene (viii) 1, 4-Dibromobut-2-ene
All Chemical Reactions:
1. How will you bring about the following conversions?
(i) Ethanol to but-1-yne (ii) Ethane to bromoethene (iii) Propene to 1-nitropropane
(iv) Toluene to benzyl alcohol (v) Propene to propyne (vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone (viii) But-1-ene to but-2-ene (ix) 1-Chlorobutane to n-octane
(x) Benzene to biphenyl. (xi)Propene to propan-1-ol (xii) Ethanol to propanenitrile
(xiii) 1-Bromopropane to 2-bromopropane (xiv) Benzyl alcohol to 2-phenylethanoic acid
(xv) Benzene to 4-bromonitrobenzene (xvi) Aniline to chlorobenzene (xvii) But-1-ene to n-butyliodide
(xviii) 2-Chlorobutane to 3, 4-dimethylhexane (xix) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xx) Ethyl chloride to propanoic acid (xxi) 2-Chloropropane to 1-propanol (xxii) Isopropyl alcohol to iodoform
(xxiii) Chlorobenzene to p-nitrophenol (xxiv) 2-Bromopropane to 1-bromopropane
(xv) Chloroethane to butane (xxvi) tert-Butyl bromide to isobutyl bromide (xxvii) Aniline to phenylisocyanide
2. Write the equation for preparation of1-iodobutane from
(a) 1-butanol (b) 1-chlorobutane (c) but-1-ene
3. Write the structure of the major organic product in each of the following reactions:
𝐴𝑐𝑒𝑡𝑜𝑛𝑒 𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑊𝑎𝑡𝑒𝑟
(i) CH3 CH2 CH2 Cl + NaI (ii) (CH3)3CBr + KOH > (iii) CH3CH(Br)CH2CH3 + NaOH >
𝐻𝑒𝑎𝑡 𝐻𝑒𝑎𝑡
𝐴𝑞 𝐸𝑡ℎ𝑎𝑛𝑜𝑙
(iv) CH3CH2Br + KCN (v) C6H5ONa + C2H5Cl → (vi) CH3CH2CH2OH + SOCl2 →
𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒
(vii) CH3CH2CH = CH2 + HBr > (viii) CH3CH = C(CH3) 2 + HBr →
4. Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b). Compound (b) is reacted with HBr to give (c) which is an
isomer of (a). When (a) is reacted with sodium metal it gives compound (d), C8H18 which is different from the compound formed when n-butyl
bromide is reacted with sodium. Give the structural formula of (a) and write the equations for all the reactions.
5. What happens when
(i) n-butyl chloride is treated with alcoholic KOH
(ii) bromobenzene is treated with Mg in the presence of dry ether
(iii) chlorobenzene is subjected to hydrolysis
(iv) ethyl chloride is treated with aqueous KOH
(v) methyl bromide is treated with sodium in the presence of dry ether
(vi) methyl chloride is treated with KCN
6. Identify A, B, C, D, E, R and R1 in the following:
 Assignment(Including Extra Questions) Haloalkane and Haloarenes

7. Draw the structures of major monohalo products in each of the following reactions:

Theory Based Questions From Previous year Board Papers

Prepration of Haloalkane and Haloarenes:
1. How the haloalkanes are classified? What are geminal and vicinal dihalides?
2. Discuss the role of Lewis acids in preparation of aryl bromides and chlorides in dark.
3. Predict all the possible monochloro structural isomers to be formed on the free radical chlorination of (CH3)2CHCH2CH3 .
4. Among the isomeric alkanes of molecular formula C5H12 , identify the one that on photochemical chlorination yields: (i) A single
monochloride(ii) Three isomeric monochlorides (iii) Four isomeric monochlorides.
5. A hydrocarbon C5H10 does not react with chlorine in the dark but gives single monochloro derivative C 5H9Cl in bright sunlight. Identify the
hydrocarbon.
6. Explain why thionyl chloride method is preferred f or preparing alkyl halide from alcohols.
7. Haloalkane can be easily prepared from alcohols by replacement of –OH group by halogen atom, why cannot we prepare haloarenes from
phenols? (Or) Why an aryl halide not prepared by the reaction of HCl with phenol in the presence of anhydrous ZnCl 2.
Physical Properties of Haloalkane and Haloarenes:
1. Haloarenes /Haloalkanes are insoluble in water but soluble in benzene explain why? (CBSE 2011)
2. Why alkyl halide have higher boiling point than hydrocarbons?
3. n- Butyl bromide has higher boiling point than t- butyl bromide. Why? (CBSE 2015)
4. Arrange the following in increasing order of boiling point
5. Bromoethane, Bromoform, Chloromethane, Dibromomethane
6. 1-Chloropropane, Isopropylchloride, 1- Chlorobutane
7. Why does p-dichlorobenzene have higher melting point and lower solubility than o and m dichlorobenzene? (CBSE 2009)
8. Which of the following will have the highest dipole moment? (a) CH2Cl2 (b) CHCl3 (c) CCl4
9. Why dipole moment of chlorobenzene is lower than that of cyclohexyl chloride. (CBSE 2010,16)
10. What will be the effect of resonance on the dipole moment of vinyl chloride?
Chemical Properties of Haloalkane and Haloarenes:
1. Why haloalkanes are more reactive than haloarenes towards nucleophillic reactions. (CBSE2009)
(OR) Why the C-X bond length in haloarenes is smaller than C-X bond length in haloalkanes (CBSE2016)
(OR) Why chlorobenzene is less reactive towards nucleophillic substitution reactions.
(OR) Why alkyl halide undergo hydrolysis more easily than haloarenes.
2. Although chlorine is electron withdrawing group yet it is o and p directing in electrophilic substitution reactions. Explain (Or) In haloarenes
why electrophillic substitution takes place at o and p position.Explain. (CBSE 2015)
3. Why KCN forms cyanide while AgCN forms isocyanide with haloalkanes.
4. Cyanide act as ambident nucleophile from which end it act as a stronger nucleophile in aqueous medium. Give reason (Or) What is
ambident nucleophile? Explain with example. (CBSE 2014)
5. Why KNO2 forms alkyl nitriles while AgNO2 forms nitro compounds?
Assignment(Including Extra Questions) Haloalkane and Haloarenes

6. How and why the product differ when ethyl bromide react separately with aqueous and alcoholic KOH.(OR) The treatment of alkyl chloride
with aqueous KOH leads to the formation of alcohols but in the presence of alcoholic KOH alkene is the major product. Explain (CB2024)
7. Why Grignard’s reagent must be prepared in anhydrous conditions. (CBSE 2012,2024)
8. Diphenyls are potential threat to the environment. How are these produced from aryl halides?
9. Allyl chloride is hydrolysed more readily than n-propyl chloride. Why? (Or) Allyl chloride is more reactive than n-propyl chloride towards
nucleophilic substitution reactions. Explain
10. Why vinyl chloride is less reactive than ethyl chloride?
11. The presence of nitro group at o and p position increases the reactivity of haloarenes towards nucleophillic substitution. (Or) Nucleophillic
substitution of p-nitrochlorobenzene is easier than that of chlorobenzene.
12. Predict the product formed by dehydrohalogentaion of (a) 1-Bromo-1-methylcyclohexane
13. 2,2,3- Trimethyl-3-bromopentane. Identify the major product formed.
14. Write a chemical reaction to replace diazonium group with iodine ion. (CBSE 2008)
SN1 and SN2 Mechanism and Stereochemical aspects:
1. Diffrentiate between SN1 and SN2 mechanism by giving examples. (CBSE 2010)
2. Racemisation occurs in SN1 mechanism. Why?
3. Which of the following will undergo SN2 faster and Why?: (a) CH3Br or CH3I (b) (CH3)3CCl or CH3Cl
1. How do polar solvents help in the first step in SN1 mechanism?
2. Arrange the following according to their reactivity in SN2 (CBSE 2011)
(a) 2-Bromo-2-methylbutane, 1-Bromopentane, 2- Bromopentane.
(b) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 3-Bromo-2-methylbutane
(c) 1- Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane,1-Bromo-3-Methylbutane.
3. Which can undergo SN2 faster:
(a) (c)

(b) (d)

4. Which one is optically active and why?: (a) (b) (CBSE 2018)
5. Tert-butyl bromide reacts with aq. NaOH by SN1 mechanism while n-butyl bromide react SN2 mechanism. Why?
6. Out of C6H5CH2Cl and C6H5CHClC6H5 which is more easily hydrolyzed by aqueous solution of KOH. (CB 2010,12)
7. Explain with examples: (1) Chirality (CBSE 2012) (2) Racemic mixture (CBSE 2011)
8. What are enantiomers? Draw the structure of the possible enantiomers of 3-methylpent-1-ene.
9. Give reason- (±) Butanol is optically inactive. (CBSE 2013)
10. Give the difference between (a) enantiomers and diasterioisomers. (b) Retention and inversion.
11. Write the structure of an isomer of compound C4H9Br which is most reactive towards SN1. (CBSE 2016)
12. SN1 is accompanied by racemization in optically active halides. Give reason (CBSE 2016)
13. (a)Can optical isomer be optically inactive.
14. (b)Optically active 2-iodobutane on treatment with NaI in acetone gives product which does not Show optical activity.
Some Important Compounds and Test to Distinguish:
1. Why chloroform is stored in dark coloured bottles? (CBSE 2019)
2. Write the formula and IUPAC name of DDT/ BHC and give structure also.
3. Why the use of DDT banned in India and other counteries.
4. Explain why a small amount of alcohol is added to chloroform bottle?
5. Write the product of chlorination of benzene in the presence of U.V light.
6. Give the uses of: Freon, DDT , CCl4 , Iodoform.
7. Give a chemical test to distinguish between (a) Chlorobenzene and cyclohexyl chloride
(b) C2H5Br and C6H5 Br (c) C2H5Br and C2H5Cl
(d) Chlorobenzen and Benzyl chloride (e) Chlorofrom and Carbon tetrachloride
Additional Question (HOTS):
1. Give reason (a) Boiling point of alkyl bromide is higher than alkyl chloride.
2. Alkyl halide is better solvent than aryl halide.
3. Iodoform has appreciable antiseptic property
4. How can you convert chloroform into tear gas?
5. Iodoform gives white ppt with silver nitrate on heating while chloroform does not. Explain
6. (Or) How we can check the purity of chloroform.(Or)Chloroform contains chlorine but do not react with AgNO 3 ?
Assignment(Including Extra Questions) Haloalkane and Haloarenes

7. What are meso compounds give example.

Important Reactions:
1. Groove’s process. 7. Hunsdiecker’s reaction 13. Finkelstein reaction
2. Swart’s reaction 8. Williamson’s reaction 14. Mendius reaction
3. Sandmeyer’s reaction 9. Gattermann reaction 15. Wurtz reaction
4. Balz-Schiemann reaction 10.Wurtz-Fittig reaction 16. Fittig reaction
5. Ulmann reaction 11. Dow’s process 17. β-Elimination
6. Friedel craft’s Alkylation/Acylation 12. Diazotisation 18. Allylic substitution
Rules for Major Products:
1. SaytZeff Rule 2. Markovnikov’s Rule 3. Anti Markovnikov’s Rule
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