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09. HALOALKANES and HALOARENES


(AP and TS EAMCET PYQS)
1. This question contains statement − I : and statement-II, of the four choices given after
the statements. Choose the one that best describes the two statements.
Statement- I : Aromatic acids do not undergo Friedel-Crafts reaction.
Statement- II : −COOH is m-directing group.
(1) Statement-I is false, Statement-II is true
(2) Statement-I is true, Statement-II is true, Statement-II is correct explanation of
statement - I
(3) Statement-I is true, Statement-II is true, Statement-II is not a correct explanation of
statement - I
(4) Statement - I is true, Statement − II is false#[TS EAMCETCG PET-22.05.2022]#

2. On the surface of polar stratospheric clouds, hydrolysis of chlorine nitrate gives A


and B while its reaction with HCl produces B and C . A, B and C are,
respectively
(1) HOCl, HNO3 , Cl2

(2) Cl2 , HNO3 , HOCl

(3) HClO2 , HNO2 , HOCl

(4) HOCl, HNO2 , Cl2O #[TS EAMCET[JEE Main-27.06.2022, Shift-I]]#

3. In Friedel-Crafts alkylation of aniline, one gets


(1) Alkylated product with ortho and para substitution.
(2) Secondary amine after acidic treatment.
(3) An amide product.
(4) Positively charged nitrogen at benzene ring.#[TS EAMCET JEE Main-29.06.2022,
Shift-II]#

4. The correct order of nucleophilicity is


(1) F−  OH−
¨
(2) H2 O  OH
¨
(3) R O H  RO
(4) NH 2−  NH 2 #[TS EAMCET JEE Main-26.06.2022, Shift-I]#

5. Identify the major product formed in the following sequence of reactions:

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(1)

(2)

(3)

(4) #[TS EAMCET JEE Main-28.06.2022, Shift-I]#

6. Which one of the following compounds is inactive towards S N 1 reaction?

(1)

(2)

(3)

(4) #[TS EAMCET JEE Main-28.06.2022, Shift-I]#

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7. The major product (P) in the reaction

(1)

(2)

(3)

(4) #[TS EAMCET JEE Main-28.06.2022, Shift-I]#

8. Identify the product formed in the following reaction sequence

(1)

(2)

(3)

(4) #[AP EAMCET-06.07.2022, Shift-II]#

9. The major products P and Q of the following reactions respectively are

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+
I. n − Pentylbromide ⎯Zn ⎯⎯ /H
→P
II. n − Pentylbromide ⎯⎯⎯⎯Na
Dry Ether
→Q
(1) Pentane; Decane
(2) Pent-1-ene; Decane
(3) Pentane; Pentane
(4) Pentane; 1-Decene#[AP EAMCET-06.07.2022, Shift-II]#

10. The order of decreasing reactivity towards an electrophilic reagent, for the following
compounds, is
I. Benzene II. Toluene
III. Chlorobenzene IV. Phenol
(1) I  II  III  IV
(2) II  IV  I  III
(3) IV  III  II  I
(4) IV  II  I  III#[TS EAMCET-19.07.2022, Shift-II]#

11. Sodium tertiary butoxide on reaction with methyl bromide produced the product P .
Sodium methoxide upon reaction with tertiary butyl bromide generated the product Q
.
The products P and Q are

(1)

(2)

(3)

(4) #[TS EAMCET-19.07.2022, Shift-I]#

12. The order of reactivity of the following compounds towards dilute aqueous KOH in
S N 1 reaction is
CH3CH 2CH 2CH 2Br H 3CCH 2CHBrCH (CH3 ) CHCH 2Br (CH 3 )3 CBr
I II III IV
(1) I  IV  III  II
(2) IV  II  III  I
(3) III  II  I  IV
(4) I  III  II  IV#[TS EAMCET-18.07.2022, Shift-II]#

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13. The most suitable solvent for Wurtz reaction is


(1) Dry acetonitrile
(2) Dry dichloromethane
(3) Dry ethanol
(4) Dry ether#[TS EAMCET-18.07.2022, Shift-II]#

14. 1-chlorobutane on treatment with alcoholic potash forms .......... .


(1) 2-butanol
(2) 1- butene
(3) 1- butanol
(4) 2-butene#[AP EAMCET (Engg.) 21.09.2020, Shift-I]#

15. Which among the following is most common in alkyl halides?


(1) Nucleophilic substitution
(2) Electrophilic substitution
(3) Electrophilic addition
(4) Nucleophilic addition#[AP EAMCET (Engg.) 17.09.2020 Shift-I]#

16. Which one of the following is more reactive towards SN 2 reaction?


(1) ( CH3 )3 CX
(2) CH3CH2 X

(3) ( CH3 )2 CHX


(4) CH3X #[AP EAMCET-2017]#

17. The reactivity of alkyl bromides.

I. CH3CH2 Br II. III. IV. CH3Br


towards iodide ion in dry acetone decrease in the order
(1) IV  I  II  III
(2) I  IV  II  III
(3) III  II  I  IV
(4) III  II  IV  I#[TS EAMCET-2017]#

18. Which one of the following has highest boiling point?


(1) CH3CH2CH2CH2Cl

(2) ( CH3 )2 CHCH 2Cl

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(3) ( CH3 )3 CCl

(4) #[TS EAMCET-2016]#

19. What is Z in the following sequence of reaction?


2-methyl-2-bromopropane ⎯⎯⎯⎯ Mg
Dry ether
→ X ⎯⎯⎯
H2O
→Z
(1) Propane
(2) 2-methyl propene
(3) 2-methyl propane
(4) 2-methyl butane#[AP EAMCET - 2016]#

20. The correct order of reactivity of hydrogen halides with ethyl alcohol is
(1) HF  HCl  HBr  HI
(2) HCl  HBr  HF  HI
(3) HBr  HCl  HI  HF
(4) HI  HBr  HCl  HF #[AP EAMCET-2008]#

21. C2H5Cl ⎯⎯⎯


Moist
Ag 2O
→ A ⎯⎯⎯
Al 2O3
360 C
→ B ⎯⎯⎯
S2Cl 2
→C
In the above sequence of reactions, identifying
(1) chloretone
(2) cloropicrin
(3) mustard gas
(4) lewisite gas#[AP EAMCET (Medical) - 2007]

22. Which one of the following is more readily hydrolyzed by S N 1 mechanism?


(1) ( C6 H5 )2 C ( CH3 ) Br
(2) C6 H5CH2 Br

(3) C6 H 5CH ( CH 3 ) Br

(4) ( C6 H5 )2 CHBr #[AP EAMCET (Engg.) -2014]#

23. Which of the following can give a Grignard reagent when reacted with magnesium in
dry ether?
(1) C2 H6

(2) C2 H5Cl

(3) C2 H5OH

(4) C2 H5CN #[AP EAMCET (Medical), 2006]#

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24. Finkelstein reaction is used for the synthesis of


(1) RF
(2) RI
(3) RCI
(4) RBr #[AP EAMCET-04.07.2022, Shift-I]#

25. Identify the most suitable reagents (I) and (II) for the following sequence of reactions:

(1) (I) → conc. H2SO4 (II) → HBr


(2) (I) → aq. KOH (II) → HBr / peroxide
(3) (I) → alc. KOH (II) → HBr / peroxide
(4) (I) → alc. KOH (II) → HBr #[AP EAMCET 25-08-2021 Shift - I]#

26. The compound which readily under goes bimolecular nucleophilic substitution reaction
with aqueous KOH is

(1)

(2)

(3)

(4) #[TS EAMCET 10.08.2021, Shift-I]#

27. What is Y in the following reaction?


C2H5I + NaOC2H5 ⎯⎯
→ X + NaI

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X + 2HI ⎯⎯ → 2Y + H 2 O

(1) C2H6
(2) C2 H5I
(3) C2H4
(4) C2H5OC2H5 #[AP EAMCET-2007]#

28. Match of the following columns.


Column I (Reactants) Column II(Products)

(A) C2 H5Cl , moist Ag2O (1) CH3CH2ONO


(B) C2 H5Cl aqueous ethanolic AgCN (2) C2H4
(C) C2 H5Cl , aqueous ethanolic AgNO2 (3) CH3CH2OH
(D) C2 H5Cl , ethanolic KOH (4) CH3CH2 NC
(5) C2H6

Codes
(1) A-5, B-3, C-4, D-1
(2) A-1, B-2, C-3, D-4
(3) A-3, B-4, C-1, D-2
(4) A-4, B-1, C-2, D-5 #[AP EAMCET-2007]#

29. Which of the following is added to chloroform to slow down its aerial oxidation in
presence of light?
(1) Carbonyl chloride
(2) Sodium hydroxide
(3) Ethyl alcohol
(4) Nitric acid#[AP EAMCET-2006]#

30. Identify A, B and C in the following reactions


+
CH3Cl ⎯⎯⎯
KCN
→ A ⎯⎯⎯⎯
hydrolsis
H O
→ B ⎯⎯⎯⎯⎯
C2H5OH / H

→C
3

(1) A − CH3 NC , B − CH 3 NHCH3 , C − CH 3 − N ( CH 3 ) − C2H 5

(2) A - CH3CN, B - CH3CONH2 , C - CH3CO2H


(3) A- CH3CN , B- CH3CO2H , C - CH3CO2C2H5
(4) A - CH3CN, B - CHCO2 H, C - ( CH3CO )2 O #[AP EAMCET (Engg.) - 2010]#

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31. Which one of the following is not a method for preparing chloroform?
(I) Heating ethyl alcohol with chlorine and alkali.
(II) Heating acetone with bleaching powder and water.
(III) Heating chloral hydrate with aqueous sodium hydroxide.
(IV) Distillation of acetone over iron filing and water.
(1) II
(2) I
(3) III
(4) IV#[AP - EAMCET(MEDICAL) - 2009]#

32. Hydrogen chloride and SO2 are the side products in the reaction of ethanol with thionyl
chloride. Which of the following is the main product in this reaction?
(1) C2H5OC2 H5
(2) C2H6
(3) CH3Cl
(4) C2 H5Cl #[AP EAMCET (Engg.)-2005]#

33. C2H2 + 2HCl → C2H4Cl2 is an example of ......... reaction.


(1) addition
(2) hydrogenation
(3) substitution
(4) chlorination#[AP EAMCET (Engg.)-2005]#

34. The chlorination of ethane is an example for which type of the following reactions?
(1) Nucleophilic substitution
(2) Electrophilic substitution
(3) Free radical substitution
(4) Rearrangement#[AP EAMCET (Engg.) - 2012]#

35. C − Cl bond in chlorobenzene a comparison to C − Cl bond in methyl chloride is


(1) longer and weaker
(2) shorter and weaker
(3) shorter and stronger
(4) longer and stronger #[ AP EAMCET (Engg.) 17.09.2020, Shift-I]#

36. What by product is formed in the process of making phenol from cumene ?

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(1) propan-2-ol
(2) n-propanol
(3) propanal
(4) propan-2-one#[AP EAMCET (Engg.) 21.09.2020, Shift-I]#

37. Which among the following statements is true about reactivity of haloarenes towards
nucleophilic substitution reactions?
1.Haloarenes are very reactive towards nucleophilic substitution reaction.
2.In haloarenes, the C − X bond acquires partial doubled bond character.
3.The C − X bond in haloarenes is longer than the C − X bond in haloalkanes.
4.In haloarenes, the phenyl cation formed as a result of self-ionisation is stable.
(1) 1
(2) 2
(3) 3
(4) 4#[AP EAMCET (Engg.) 18.9.2020 Shift-I]#

38. With respect of chlorobenzene, which of the following statements is not correct?
(1) Cl is ortho/para directing
(2) Cl exhibits + M effect
(3) Cl is ring deactivating
(4) Cl is meta directing#[AP EAMCET (Engg.) - 2012]#

39. Identify the major product of the following reaction

(1)

(2)

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(3)

(4) #[AP EAMCET-05.07.2022, Shift-I]#

40. From the following


C2H5OH + 4I2 + 3Na2CO3 → X + HCOONa + 5NaI + 3CO2 + 2H2O
in the above reaction, 'x' is :
(1) diiodomethane
(2) triiodomethane
(3) iodomethane
(4) tetraiodomethane#[AP EAMCET (Engg.) 2015]#

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ANSWER
1. 3 2. 1 3. 4 4. 4 5. 3
6. 3 7. 3 8. 1 9. 1 10. 4
11. 2 12. 4 13. 4 14. 2 15. 1
16. 4 17. 1 18. 1 19. 3 20. 4
21. 3 22. 1 23. 2 24. 2 25. 4
26. 4 27. 2 28. 3 29. 3 30. 3
31. 4 32. 4 33. 1 34. 3 35. 3
36. 4 37. 2 38. 4 39. 4 40. 2

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EXPLANATION
1. (C) : Aromatic carboxylic acids do not undergo Friedel-crafts reaction because the -
COOH group is deactivating and the catalyst AlCl3 gets bonded to COOH group.
−COOH group is Meta directing because it is electron withdrawing group with − R effect.
There is +ve charge on ortho and para positions. So, electrophilic substitution takes place at
Meta position. Here, both statements are true but statement II is not correct explanation of
statement I.
2. (A) : On the surface of polar stratospheric clouds, hydrolysis of chlorine nitrate reaction
is given below-
ClONO2 + H2O → HOCl + HNO3
A B
Reaction of chlorine nitrate with HCl-
ClONO2 + HCl → Cl 2 + HNO3
C B
So, the correct option is (a)
3. (D) : Infriedel-crafts alkylation of aniline, one gets positively charged nitrogen at
benzene ring.


4. (D) : The correct order of nucleophilicity is NH 2  NH3
Nucleophilicity referred as nucleophile strength. A nucleophile is a chemical species that forms

bonds by donating an electron pair. Here, NH 2 is stronger nucleophile than NH3 because of
the charge on the amide ion.
5. (C)

6. (C) :

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is inactive towards SN1 reaction because halogen is attached to bridge head carbon atom,
where formation of carbocation is not possible.
7. (C) :

So, the correct option is (c)


8. (A) :

9. (A) :
(i) CH 3 − ( CH 2 )4 − Br ⎯⎯⎯ → CH 3 − ( CH 2 )2 − CH 3 + HBr
+
Zn / H

Pentane

Alkyl halide (except Fluorides) on reduction with zinc dilute hydrochloric acid give alkanes.
Hence, n-pentyl bromide gives pentane.
(ii) CH 3 − ( CH 2 )4 − Br ⎯⎯⎯ → CH 3 − ( CH 2 )8 − CH 3 + HBr
+
Zn / H

Decane

When two alkyl halides are reacted with sodium metal in dry ether solution to form a higher
alkane.
10. (D) : The structure of compound are given below

As we know that electrophile attack that position in which the electron density will be more.
CH3 , OH are ring activating group. It increases electron density on benzene ring that's why it
has more reactivity towards electrophilic reagent. So, the overall electrophilic reagent towards
reactivity as given below:-
Phenol (IV) > Toluene (II) > Benzene (I) > Chlorobenezene (III)

11. (B) :

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12. (D) : When these compound are react towards aqueous KOH it is a nucleophilic
substitution reaction which result in formation of carbocation.
Stability of carbocation is 3  2  1
So, the correct option is I  III  II  IV
13. (D) : Dry ether is the most suitable solvent forwurtz reaction.
Wurtz are also known as warts coupling. It is method used to synthesize higher alkanes by a
reaction between alkyl halides and metallic sodium I the presence of dry ether.
14. (B) : Alc. KOH act as a dehydrohalogenation agent by reacting with an alkyl halide and
forms alkene as a product. The reaction is-
CH3CH 2CH 2CH 2Cl ⎯⎯⎯⎯ Alc.KOH
→ CH3CH 2CH = CH 2
1-chlorobutane 1-butene
Hence, option (b) is correct.
15. (A) :

Alkyl halides readily undergo nucleophilic substitution like SN 2 and S N 1 .

Here a stronger nucleophile, Nu substitutes a weaker nucleophile (leaving group : X − ) from


an alkyl halide.
16. (D) : CH3X is more reactive toward SN 2 reaction because less hindered species are
more reactive.
17. (A) : The reactivity of alkyl bromides towards iodide ion in dry acetone reaction follow
SN 2 mechanism. In SN 2 mechanism, less hindered are more reactive towards nucleophile
(Iodide ion).

18. (A) : The boiling point of alkyl halides decreases due to alkyl branching. Branching of
chain makes the molecule more compact and surface area decreases.
The highest boiling point is CH3 − CH2 − CH2 − CH2Cl .
19. (C) :

In the following sequence ( Z ) is 2-methyl propane.


20. (D) : On moving from top to bottom in a halogen family size of halide is increase, its
reactivity towards ethyl alcohol also increases. Thus, the order of reactivity of hydrogen halides
are-
HI  HBr  HCl  HF .

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21. (C) : Ethyl chloride react with moist Ag2O (silver oxide) to give the ethanol ( C 2 H 5 OH )
and ethanol further react with Al2O3 to a temperature of 360 C and form the ethene. Ethene
on reaction with S2Cl2 , mustard gas is formed.
C2 H 5Cl ⎯⎯⎯
Moist
Ag 2O
→ C2 H 5 − OH ⎯⎯⎯
Al 2O3
360 C
→ CH 2 = CH 2 ⎯⎯⎯
S 2Cl 2
→ ClCH 2 − CH 2 − S − CH 2 − CH 2Cl
Ethyl chloride Ethanol eEthene Mustard Gas

22. (A) : For SN1 , rate of reaction  stability of carbocation

(a)

(b)

(c)

(d)
On the basis of stability of carbocation,
(a)  (d)  (c)  (b)
( C6 H5 )2 C ( CH3 ) Br is more readily hydrolyzed by SN1 mechanism.
23. (B) : When ethyl chloride reacted with magnesium in dry ether then the Grignard
reagent is formed.
CH 3 − CH 2 − Cl + Mg ⎯⎯⎯ ⎯
Dryether
→ CH 3CH 2MgCl
Ethylchloride Ethylmagnesium chloride

24. (B) : It is used for easy production of alkyl iodide. It can be used as a qualitative test to
determine from which class an unknown alkyl halidebelong to synthesis of chrysochlamic acid
is also done by finkelstein reaction.
25. (D) : The given sequence of reactions give the following product-

26. (D) :

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In above compound −NO2 group is electron withdrawing group so the bond strength is
decreases between benzene ring and Cl . So the compound undergo ( SN 2 ) bimolecular
nucleophilic substitution reaction.
27. (B) :

C2H5I + NaOC2H5 ⎯⎯ → C2H5OC2H5 + NaI
( x)

C2H5OCH5 + 2HI ⎯⎯
→ 2C2 H5I + H 2O
(x) ( x)

28. (C) :
Reactants Products

i) C2H5Cl , moist Ag2O CH3CH2OH


C2 H5Cl aqueous ethanolic AgCN CH3CH2 NC
(iii) C2 H5Cl , aqueous ethanolic CH3CH2ONO
AgNO2
C2 H5Cl , ethanolic KOH C2H4
29. (B) : Ethyl alcohol is used to as a negative catalyst for the aerial oxidation of chloroform
to allow down its aerial oxidation in presence of light. Chloroform vapour slowly reacts with
oxygen in the presence of light to generate phosgene, a highly toxic gas.
30. (C) : The sequence of reaction give the following product-
+
CH 3Cl ⎯⎯⎯
KCN
→ CH 3CN ⎯⎯⎯⎯
Hydrolysis
H O+
→ CH 3COOH ⎯⎯⎯⎯⎯
C2 H5OH / H

→ CH 3COOC2H 5
3
Acetonitrile ( A ) EthanoicAcid ( B ) Ethylethanoate ( C )

31. (D) : Distillation of acetone over iron filings and water cannot produce chloroform.
32. (D) : The reaction of ethanol withthionylchloride gives the ethyl chloride ( C 2 H 5Cl ) ,
hydrogen chloride and SO2 .
C2H5 − OH + SOCl 2 → C2H5Cl + SO2 + HCl
Ethylalcohol Thionyl Ethylchloride
chloride

33. (A) : The given reaction is :


H − C  C − H + 2H − Cl ⎯⎯ → C2H 4Cl 2
The above reaction is the example of addition reaction because reagent add with the substrate.
34. (C) : Free radical halogenations is a type of halogenations. This chemical reaction is
typical of alkanes and alkyl substituted aromatics under application of UV light. The reaction
is used for the industrial synthesis of chloroform ( CHCl3 ) , proceeds by a free radical chain
mechanism.

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Chlorination of ethane involves free radical substitution in the presence of light to form ethyl
chloride.
35. (C) :

Because of + R effect of Cl -atom with the ring, C − Cl bond in chlorobenzene gets a double
bond character and it becomes shorter and stronger than the C − Cl bond of in methyl chloride
( CH 3 − Cl ) , which does have such effect.
36. (D) : Cumene (isopropyl benzene) is oxidised in the presence of air to form cumene
hydroperoxide. On treating with dilute acid, it is converted to phenol and acetone.

37. (B) : Because of + R effect of halogen atom X , the C − X bond of haloarene acquires
partial double bond character C − X bond becomes shorter than that in haloalkanes) and
nucleophilic substitution becomes difficult.

38. (D) : The lone pair of electron on chlorine is involved in delocalization with benzene
ring and increase the electron density at ortho and para position. So, Cl is not meta directing.
It so, + M effect due to non-bonding electron and it is deactivating due to high electro
negativity.
39. (D) :

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40. (B):
C2H5OH + 4I 2 + 3Na2CO3 → CHI3 + HCOONa + 5NaI + 3CO2 + 2H 2O
( X)

In the above reaction x is CHI3 (Triiodomethane).

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