Thep-Block

Elements

Multiple Choice Questions (MCQs) 9. In nitrogen family. the H-M-H bond angle in the hydrides
graduallyExcomescloserto 900on going fromN to Sb.
Thisshowsthat gradually
DIRECTIONS: Thissectioncontainsmultiplechoice (a) Thebasicstrengthof the hydridesincreases
questions.Eachquestionhasfour choices (c)and (d) (b) Almost pure p-orbitals are used for M-H bonding
out of whichonly one is cornel. (c) Thebondenergiesof M-Hbondsincrease
Concentrated nitric acid. long standing. turns yellow (d) The bond pairs of electronsbecomenearer to the
brown due to the formation of centralatom
(a) NO (b) NO: (c) N20 (d) N204 10. The deepbluecolourproducedon addingexcessof
2. In the reaction ammonia to copper sulphate is due to presence of
HN03 + P40iO —41POg-X , the product X is
(a) Cu 2
(a) N20s (b) yo; (c) N02 (d)
3. Arnmm ia catalytic oxidation gives an oxide which
nitric acid is obtained. The oxide is
S —S bondis not presentin
(a) N203 (b) NO (e) N02 (d) N20s
4. The correct decreasing order ofbasic strength is: (a) (b) (c) (d) S207-
(a) > PH3 > NH3 12. Which of the following on thermal decomposition gives
(b) st,H3 > NIL oxygengas ?
(C) NH3>PH3 > AsH3 > SbH3 (a) Ag20 (b) Pbg04
(d) PHA > AsH3 >SbH3 > NHS (c) Pb0, (d) All of these
5. When orthophosphoric acid is heated to 600 0C. the rmxluct 13. In the preparation of HNOg, we get NO gas by catalytic
formedis oxidation of ammonia. The moles ofNO produced by the
(a) (b) (c) H,P03 (d) HPC), oxidation oftwo moles ofNH3 will be
6. The number OfP —O —P bonds in cyclic metaphosphoric
14. Fluorine exhibits an oxidation state of only —lbecause
acid is
(4) it canreadilyacceptan electron
(a) zero (b) two (c) three (d) four (b) it is very strongly electronegative
7. Nitrogen forms NY but phosphorus is converted into
(C) itis a non-metal
from P, the reason is
(d) it belongs to halogen family
(a) Triple bond is present between phosphorus atorn
15. Which of the followingis the best descriptionfor the
(b) pn —pa bonding is strong
behaviourofbrominein the reactiongivenbelow?
(c) pn —pn bonding is weak
H20+Brz HOBr+ HBr
(d) Multiple bond is formed easily (a) Proton acceptor only
8. Affinity for hydrogen decreases in the group from fluorine
to iodine.Whichofthe halogenacidsshouldhavehighest (b) Bothoxidizedand reduced
bond dissociation enthalpy? (c) Oxidized only
(a) HF (c) HBr (d) HI (d) Reducedonly
c-22 Chemistry
16. At temperature. HCI is a gas while HF isa low boiling 30. By mixing ammoniumchlorideto potassiumnitrite and
liquid. Thisis because heating, weget
(a) H- F bondis covalent (a) Ammoniumnitrate
(b) H- F bondis ionic (c) Nitrogen (d) Nitrogendioxide
(c) HFhasmetallicbond 31. If phosphorous
acid is allowedto react with sufficient
(d) HFhas hydrogenbond quantityof KOH.the productobtainedis
17. The oxidationstateof centralatomin the anionof (a) K,PO, (b) KH2P03
compound NaH2P02will (c) K2HP0g (d) Kl--1P03
32. In the preparation Ofcompounds ofXe, Bartlett had taken
18. correct cu•derofincreasing oxidising power is
ptF6¯as a basecompmtnd.This is because
(a) t»th and Xe havesamesize.
(b) both02 and Xe havesameelectrongain enthalpy
(c) C12> (d)
(c) both 02 and Xe have almost same enthalpy
19. Thecorrectorderofheatofformationof halogenacidsis (d) bothXe and 02 are gases.
33. Whichone of the followingpairs is obtainedon heating
ammoniumdichromate?
20. The reaction ofKMn04 and HCI results in
(a) oxidation of Mn in KMn04 and production ofC12 (a) y and (b) N,OandH20
(c) NOandH20 (d) NO and NOZ
(b) reduction of Mn in KMn04 and prcxluction of H:
34. Whichof the followingstatementsis wrong?
(c) oxidation of Mn in KMn04and productionofH2 (a) Single N— N bond is stronger than the single P —p
(d) reductionofMn in KMn04and prcxluctionofC12 bond.
21. Whichoneis moststableto heat (b) PHYcan act as a ligand in the formatiK_N1
ofcu»rdination
(b) HC102 compounds with transitionelements.
(c) HCIO, (d) HC104 N02 is paramagneticin nature.
(C)
22. Whichofthe followingis isoelectronicpair? (d) Covalencyofnitrogenin N:Oyis four.
35. Whichof the followingpropertiesof whitephosphorus
(c) CIO?BrF (d) CN-,q are shared by red phosphorus?
23. TheSequenceOfacidiccharacteris (a) It phosphorescences
in air
(b) It burnswhenheatedin air
(c) It dissolvesin CS,
(d) It reactswith NaOHto give PH,
36. Wh ich of the following crders regarding thermal stability
24. ThestructureofXeF is of hydrides MH, of group 15 is correct?
(a) Distortedoctahedral (b) Pyramidal (a) (b) e PH3<AsHg
(c) Telrahedral (d) NoneOfthe above.
25. The hydrolysis or trialylchlorosilanc RASiCl,yields
(a) R2Si0
37. Incorrect statement about PHs is:
(a) It is producedby hydrolysisofCa3P±
(c) Rs-Si-O-SiR3 (d)
(b) It gives black ppt. (CusP2) with CuS04 solution
26. Oxidation states ofP in H4P205 , H4P206 , and H4P207 , (c) Spontaneouslyburnsin presenceofP2H4
are respectively. (d) It notreactwith B
38. Sulphuricacid has greataffinityforWaterbecauseit
(a) Decomposeswater
27. Whichof the following
elementscanbe involvedin (b) Fonnshydratewith water
pn — Ex»nding?
(a) Carbon (b) Nitrogen (c) Hydrolysethe acid
(c) Phosphorus (d) Boron (d) Decomposes the acid
28. Whichone of the followinghalide doesnot hydrolyse 39. Whichoneof the followingstatementsis wrong?
(a) SbC13 (b) (c) PCI* (d) (a) SO: dissolves in water and forms sulphurous acid
29. Catalyticoxidationof NHA(passinga mixtureofNH,and (b) SO,actsas a bleachingagent
air overheatedPtgauge)gives (c) SO: has pungent odour
(a) U) (b) N20 (c) N203 (d) N20s (d) S02acts onlyas oxidisingagent
The p-BIock Elements c-23
40. Which ofthe followingis wrong? (c) Halogenmoleculesare boundedby strongforces
(a) Oxygenand sulphur belongto the Samegroup of (d) Halogen molecules are boundedby electrostatic
table forces.
(b) Oxygen is a gas while sulphur is solid 50. In the reaction:
(c) Bothoxygenand sulphurshow+2. +4 and +6
oxidation states (a) Oxidised (b) Reduced
(d) has no hydrogenbonding (c) Disintegrated (d) Disproportionated
41. Sulphur does not exist as S2 molecule because 51. The products ofthe chemical reaction between Na2S20
(b) It is less electronegative C12and 1--1.0
are
(b) It has ability to exhibit catenation (a) S.HCI. (b) S,HCLNa2S
(c) It is not able to constitute pr-P7t bond (c) S.HCI, (d) SNaC103
(d) It has the tendency to show variable oxidation s tates 52. Elementsof group- 15 formcompoundsin +5 oxidation
42. InsolidstatePC15isa state. Hoya•ver.bismuth forms only well characterised
(a) covalentsolid compound in +5 oxidation state. The compound is
(b) Octahedralstructure (d) Bi.ss
(c) ionicsolidwithI octahedraland [PCI (a) Bizos (b) BiF, (c)
tetrahedral 53. Electrongain enthalpywith negativesign offluorine is
(d) ionicsolidwith[PCIJ tetrahedraland less than that ofchlorine due to :
octahedra I (a) High ionizationenthalpyoffluorine
43. Which of the followingsolutionsdoes not change its (b) Smaller size of chlorine atom
colouron passingozonethroughit? (c) Smaller size of fluorine at(Nn
(a) Starchiodidesolution (d) Biggersize of2P orbitaloffluorine
(b) Alcoholicsolutionofbenzidine 54. In the case ofalkali metals, the covalent character decreases
(c) Acidicsolutionof in the order:
(d) AcidifiedsolutionofFeS04
44. In case of hydride of oxygen family, which ofthe following
physicalpropertychangeregularlyon movingdownthe
group.
(a) Meltingpoint (b) Thermalstability 55. Ofthe interhalogen AX3 compounds, CIF3 is reactive
(c) Boilingpoint (d) Criticaltempe•ature but BrF3 has higher conductance in liquid state, This is
45. The Correctsequence of decreasing numlxr of It-bonds in because
the structures ofH2S(h, H:S04 and H2S O, is : (a) BrF3has higher molecular mass
(b) CIF, is more volatile
(c) BrF3 dissociates into BrF2• and BrFd most easily
(d) Electrical conductance does not depend on

46. Thenumberof S—Sbondsin SOY.S20i- S206 and 56. XeF6on partialhydrolysiswith waterproducesa
respectively are compound•X'. Ille samecompound•X' is formedwhen
XeF6 reacts with silica. The compound •X' is :
(a) 1.0.0,1 (b) 1.0,
(a) xeF, (b) Xen (c) Xeon (d) xeog
(c) 0.1.1,0 (d) o, 1.0,1
57. Which compound is prepared by the following reaction?
47. A brown ring is formed in thering test for N03¯ion. It is
due to the formation of Ni vessel
Xe+2F2 673
(b) Fesog.N02 ( volumeratio)
(c) (ECOL (NO)212+ (d)
When S02 gas is passed through an acidified solution of
(a) xeFÅ (b) XeFd (C) xeF4 (d) xeOF2
K2C'%07
58. What are the products formed in the reaction of xenon
hexafluoridewithsilicondioxide?
(a) the solution becomes blue
(b) XeF:+SiF4
(b) the solutionbecomescolourless (d) XeoeSiF,
(c) S02 is reduced 59. Liquid flow from a higher to a lower level. Which ofthe
(d) green is formed following liquids can climb up the wall ofthe glass vessel
49. Volatile natureofhalogens is because in which it is placed?
(a) The halogen molecules are more reactive (a) Alcohol (b) Liquid He
(b) The forceexisting betweenthe moleculesare only (c) Liquid N: (d) Water
weakvander Waalforces
c-24 Chemistry
60. Helium-oxygenmixture is used bydeep sea diversin 72. Whichofthe followingcan be usedas an anaesthesia?
preferenceto nitrogen-oxygenmixturebecause (a) N20 (b) NO (c) NCI; (d) NO:
(a) Nitrogenis muchlesssolublein bloodthanhelium
(b) Heliumis muchless solublein bloodthannitrogen 73. The catalyst used in the manufactureof HN03 by
(c) Nitrogen is highly soluble in water Ostwald•s process is
(d) Due to high pressuredeep under the sea nitrogen (a) platinum gau;æ (b) vanadium pcntoxide
and oxygenreactto give poisonousnitric oxide, (c) finely divided nickel (d) platinum black
61. XeFodissolvesin anhydrous HF to give a good 74.
conductingsolutionwhichcontains: Which ofthe following is not tetrahedral in shape?
(a) NHI (b) SiC14
(a) HVand XeFi ion (b) HF2¯and XeF5
4 ions
(c) H,XeF6+
andF ¯ions (d) Noneof these 75. What is hybridization ofP in PCIS?
(a) spy (b) sp3d2 (c) spYd (d) sp2
62. Incorrect statement regarding fol lowing reactions is: 76. Maximum covalency ofnitrogen is .............„ .
*ExcessH O
X + HF
77. The bleaching action Ofchlorine is due to
xeF6
(a) reduction (b) hydrogenation
+2H20 (c) chlorination (d) oxidati(m
(a) •X' is explosi ve 78. At room temperature, HCI is a gas while I-IFis a
(b) 'Y' is an oxyacidofxenon liquid. This is because
(C) Both are example ofnon-redox reaction
(a) H-F bondis covalent (b) H-F is iomc
(c) HE has metallic bond (d) HE has hydrogen bond
(d) XeF6 can un dergo partial hydrolysis.
63. Ionicradii(in A) ofAsh SbS+
and followtheorder 79. Fluorineexhibitsan oxidationstateofonly—ltxcause
(a) Asy• > SbJ'> Bi3E (b) (a) it canreadilyacceptan electron
(b) it is very strongly electronegative
64. Strong reducing behaviour of H,P02 is due to (c) it is a non-metal
(a) low oxidationstateof phosphorus (d) it belongsto halogenfamily
(b) presence of two — OH groups and one P — H bond 80. Whichof the followingacidsformsthree seriesofsalts?
(c) presence of one — OH group and two P — H tX3nds (a) H3P02 (b) HYB03
(d) high electron gain enthalpy of phosphorus (C) H3P04 (d) HYPO*
65. Whichof the followingstatementsis not correctfor 81. Which element OutofHe, Ar, Kr and Xe forms least numtxr
nitrogen? of compounds ?
(a) Its electronegativity is very high (a) He (b) Ar (c) Kr (d) Xe
(b) d-orbitalsareavailablefcybonding 82. Theelementwhichhasnot yet beenreactedwith F2is
(c) It is a typical non-metal (c) Kr (d) Rn
(d) Itsmolecularsizeis small 83. Whichof the followingpairs ofionsare isoclectronicand
66. Collectivelythe elements of group 15 are called —
isostructural?
(a) pnicogens (b) pnicopens
(c) nicopen (d) Noneof these
67. On heatingleadnitrateformsoxidesof nitrogenand lead.
•nieoxidesformedare (c) SOö , NOC
(a) N20.PbO (b) N02.PbO 84. Whichof the followingis the life savingmixture for an
(c) NO.PbO (d) NO, Pb02 asthma patient
68. Whichoneofthefollowingelementsis mostmetallic? (a) Mixtureofheliumandoxygen
(b) As (c) Sb (b) Mixtureofneonand oxygen
69. The three important oxidation states ofphosphorus are (c) Mixtureofxenonand nitrogen
(a) —3,+3 and +5 (b) —3,+3 and —5 (d) Mixtureofargonand oxygen
(c) —3,+3 and +2 (d) —3,+3 and +4 85. Argon is used
70. Which ofthe following elements does not show allotropy? (a) in filling airships
(a) Nitrogen (b) Bismuth (b) to obtain low temperature
(c) Antimony (d) Arsenic (c) in high temperature welding
71. Hydrochloric acid at 250C is (d) inradiotherapy
fortreatment
ofcancer
(a) ionicandliquid (b) covalentand liquid 86. How many bridging oxygen atoms are present in P4010?
(c) ionic and gas (d) Noneof these
The p-Block Elements c-25
87. Which ofthe å.110'.üngnoble gases has thehighest positive 91. Assertion: Sulphur belongs to Same group in the pericxlic
electrongain enthalpyvalue? table as oxygen,
(a) Helium (b) Krypton Reason: S, has properties analogous to 02
(c) Argon (d) Neon 92. Assertion:Thiozonehas structurelike ozone.
88. PCI* reacts with water to form
Reason: Ozone has a lone pair which makes the molecule
(b) HYPO*andHC1 bent.
(d) H3P04 93. Assertion:S, is paramagneticin nature.
89. Which of the following group 15 element forms metallic Reason: The electrons in rt*3pxand CT*3pOrbitals in S:
bondsin elementalstate are unpaired.
94. Assertion: Sulphur has a greater tendency for catenation
(a) As (b) p
90. Whichof thesedoesn'texist? than oxygen.
Reason: 3d and 4s orbitals of Sulphur have same energy.
(b) PHs
(C) Lull* Case/Passage-II
The discoveryand preparationof severalof the interhalogen
> Case/Passage Based Questions compounds folloued shortly after the discovery Ofthe elements
themselves.
Sincethe halogensare all relativelystrongly
DIRECTIONS Followingare the case/passagebased electronegative elements. each lacking one electron to complete
question s. its outer shell. they form diatomicmoleculeswith a shared
electron-pair bond between them:
Case/Passage-l
In the last 10 years much has been learned about the molecular
structure of elemental sultirr. It is now known that many different In a very similar manner, interhalogen molecules are formed, the
types Ofrings are sufficientlymetastableto exist at room simplest type being represented by CIF, BrCl, IBr, etc., whose
temperature for several days. It is known that at high physical properties are intermediate between those Ofthe two
temperature. the equilibrium composition allows for a variety of elements involved. However, these prolxrties are not necessarily
rings and chains toexist in comparable concentration, and itis the averageofthoseof the twoparentelements.
known that at the boiling point and above, the vapor as well as Ofthe six possible uni-univalent halogen halides. five, all except
the liquid contains small species with three, four, and five atoms.
iodine flucyide.are knownto exist; the latter is probablytoo
Thesulfuratomhas the samenumberof valenceelectronsas unstable. since in the known iodine-fluorine compounds, iodine
oxygen- Thus, sulfur atoms S2 and Sg have physical and chemical alwayshas a valencegreaterthan l,
propertiesanalogousto thoseof oxygenand ozone.S: has a Considerably more interest from a structural standpoint are the
ground state of38 —'t3p 27t•3p I z n•3p l. interhalogencompounds
in whichoneof the halogenshas a
thiozonehas a well- knownuv spectrum.and has a Ernt valence greater than l. Three such series exist: ABS, AB and
Structure. analogous to its isovalent molecules O , and SS). AB? No compounds are knoull where an even number of atoms
ne chemistry of the two elements. sulphur and oxygen. differs ofone halogen combine with an odd number of another; such a
Ex-causesulfur has a pronounced tendency for catenation. The molecule would have an unpaired electron.
most frequentlyquotedexplanationis basedon the electron 95. Interhalogen compoundsare more reactive than the
structure ofthe atom, Sulfur has low-lying unoccupied 3dorbitals, individualhalogentwcause
and it is widely believed that the 4s and 3d orbitals of sulfur
(a) two halogens are present in place ofone
participate in [Mllding in a manner similar to the participati€yl of (b) they are more ionic
and 2P orbitals in carbon. (C) their tx»nd energy is less than the bond energy ofthe
Source: Meyer, B. (1976). Elemental sulfur Chemical Rev'ieus,
halogenmolecule
76(3),367-388. /cr60301a003) (d) theycarrymoreenergy
IFromCBSE QtæstionBank-2021| 96. Whichofthe followingstatementsare correct?
In the following questi»ns, a statement of assertion follo»ed by
a statementofreasonis given.Choosethe correctanswerout (i) Amonghalogens.radius ratio between and
fluorineismaximum.
of the followingchoicesonthe basisofthe abovepassage.
Leaving bond. all halogens have weaker
(a) Assertionand reasont»th are correctstatementsand
reasonis correctexplanationforassertion. bondthanX—X'bondin interhalogens.
(b) Assertionand reasonbothare correctstatementsbut (iii) Amonginterhalogencompoundsmaximumnumber
reason is not correct explanation for assertion. of atoms are present in iodine fluoride.
Assertionis correctstatementbut reasonis Wrong Interhalogen compounds are more reactive than
statement. halogen compounds.
Assertionis wrongstatementbut reasonis correct (a) (i) and (ii) (b) (i), (ii) and (iii)
statement. (c) (ii) and (iii) (d) (iii) and (iv)
c-26 Chemistry
97. Which of the following is not the characteristic of 104. Assertion : Both rhombic and moncx•linic sulphur existas
interhalogencompounds S butoxygenexistsas O
(a) Theyare morereactivethan halogens Reason : Oxygen Ix»nddue to small
(b) Theyare quite unstable but none ofthem is explosive size and small bond length but pa —p't bondingis not
(c) Theyare covalentin nature possible in sulphur.
(d) They have low boiling points and are highly volatile. 105. Assertion : Inert gases are monexrtomic.
DIRECI• IONS : Each ofthese questions contains an assertion Reason : Inert gases have stable configuration.
followedby reason.Read Themcarefullyand unsner the 106. Assertion : Fluorine exists only in —loxidation state.
question on the basis options. Youhave to select Reason : Fluorine has 2s22pSconfiguration.
the one thatbest describesthe tvvostatements. 107. Assertion : The fluorine has lower reactivity.
(a) If both Assertion and Reason are correct and the Reason Reason : F —Fbond has low bond dissociation energy.
is a correct explanation of the Assertion. 108. Assertion: F —F bond in F2 molecule is weak.
(b) If both Assertion and Reason are correct but Reason is Reason: F atom is small in size.
not a correct explanation of the Assertion. 109. Assertion: N2is lessreactivethan P
(c) Ifthe Assertion is correct but Reason is incorrect. Reason: Nitrogen has more electron gain enthalpy than
(d) Ifthe Assertion is incorrect but the Reason is correct. phosphorus.
110. Assertion: HNOSmakes iron passive
98. Assertion: interhalogen are reactiv• than Reason: HNOJ forms a protective layer offerric nitrate On
halogens(cxcept F)
the surface of iron.
Reason: bond strength in interhalogen compounds is 111. Assertion: HI cannot prepared by the reaction OfKl
weaker than halogen molecule except F—F. with concentrated H,SO
99. Assertion: CIF3 is used for the production OfUF6 in the
Reason:HI has lowestH — X bondstrengthamong
enrichment of U halogenacids.
Reason: CIF3 is hypergolic in nature.
112. Assertion : lcxline is more soluble in water than in carbon
tetrachloride.
> Assertion & Reason Reason : Iodine is a non-polar compound.
113. Assertion : At«ms in molecule undergo sp3hybridization
DIRECTIONS : Each ofthese questions contains an assertion and contain two tone pair on each atom.
followed by reason. Read themcure/ully and anvwerthe Reason : ss has a V-shape.
question on the basis ofjbllov.ing options. Youhave to select 114. Assertion: A mixture of He and 02 is used for respiration
the one that best describesrhe tun statements. for deepsea divers.
(a) Ifboth Assertion and Reason are correct and the Reason Reason : He is soluble in blood.
is a correctexplanationofthe Assertion.
(b) If bothAssertionand Reasonare correctbut Reasonis Match the Following
not a correct explanation of the Assertion.
(C) If the Assertion is correct but Reason is inc«rect. DIRECTIONS: Each questioncontainsstatementsgiven in
two columns nåich have to be matched. Statements (A, B. C. D)
(d) If the Assertion is incorrect but the Reason is correct.
in column-I have to be matched with statements (p. q. r; s) in
100. Assertion: Ozoneis thermodynamicallystable with colu
respect to oxygen.
Reason:Decompositionof Ozoneinto oxygenresults in 115. Match the columns
the liberation of heat ICBSE Sample 20211 Colunul-ll
101. Assertion : When a metal is treated with conc. HN03 it (A) High pressure favours
generally yields a nitrate, N02 and 1-420.
4N02 2PbO+ 02 the formation Of
Reason : Conc. HN03 reacts with metal and first produces
product
a metal nitrate and nascent hydrogen.The nascent
N2(g) + 02(g) (q) Product formed is acidic
hydrogen then further reduces HNOYto NOV
102. Assertion : Dinitrogen is inert at room temperature. 2NO(g) browngas
Reason : Dinitrogen directly combines with lithium to form NH4NO This reaction occurs at
ionic nitrides. N20 + 2H20 a high temperature
103. Assertion : Bond angle ofH2S is smaller than H.O. about 2000 K
Reason: Electronegativity
ofthe centralatomincreases,
(D) 3H2(g) (s) Product formed is a
bond angle decreases.
2NHg(g) neutralcolourlessgas
 ssertion: 1m trogen mert at roolll emperature_

Reason : Dimtrogcn directly cunbines with lithium to firm NH4N03 (r) Thisreactionoccursat
ionicnitrides. + 2H20 a high temperature
103. Assertion : Bondangle ofH2S is smaller than H.O. about 2000 K
ofthe centralatomincreases,
Reason: Electronegativity g) 3H2(g) (s) Productformedis a
bond angle decreases.
2NHg(g) neutralcolourlessgas

The p-Block Elements c-27

> Fill in the Blanks

DIRECTIONS: Completerhefol/ovvingslatementswithan
116.Matchthe columns appropriateword/ termto befilled in the blank space(s).
Column - I Colunul - Il
118. Nitrogenreactswithcalciumand carbonor whenN, gas
(A) Usedin manufacture (p) Ammcnia
is passed over heated calcium carbide (at 1070 K) it gives
Ofcalcium cyanamide which is an importantfertiliser marketed
Usedin manufacture Nitricacid underthenamenitrolium
ofnitricacid
119. Theleast numberof oxyacidsare ibrmedby
(C) Used in pickling of (r) Dinitrogen
stainlesssteel 120. Potassium chlorate on heating with conc H2S04 gives _.v
121. In the clathrates ofxenon with water. the nature ofbonding
c-(qj between xenon and water molecule is
A—(r), B — C 122. Instantaneous intermolecularforceis most
(d) A—(q), B C —(r) responsiblein allowingxenongas to liquibr,
Match the columns.

True I False
(Oxyacid) (Materialsfor
preparation)
(p) Red P ± alkali
DIRECTIONS: Readthefollowingstatementsand writeyour
HAP02
ansneras true or.false.
HAPO, (q) P4010+H20
P:03+ 123. NO is purified by absorbing in FeS04 solution.

H4P206 (s) White P + alkali 124. Ozone is an allotropic modification ofoxygen

125. HC103 does not have its hypo acid.
(b) (A) 126. FILKYineexhibit positive oxidation state is.

(c) 127. Helium can form clathrate compounds.

(d)
c-28 Chemistry

ANSWER KEY & SOLUTIONS

(b) The slow decomposition of HN03 is represented by And the lone pair of Bi remains in 6s orbital. The
the equation s-orbitalis closerto the nucleus,whichmeansthat the
4HN03 4N02 + 2H20 + 02 negativechargeofthe electronsis betterstabilised.
10. + 2NH40H
2. (paleblue)

4NO(g) + 6H20(g) excessNH40H

3. (b) 4NH3(g) + 502(g)
2NO(g) + 02(g) (deep blue)
3N02( g) + 2HN03(aq) + NO(g)
4. (c) As the sizeofcentralatomincreases,the lonepairof
o
electrons occupies a larger volume. In otherwords, 11. (d)
densityon the centralatomdecreasesand consequently
its tendency to donate a pair ofelectrons decreases along
12. (d) 2Ag20 (s) —i4Ag (s) + 02 (g)
with basic character from NH, to Bill*
(s) 6Pb0 (s) + (g)
(d)
6000
c 21-1P03 2Pb02 (s) + 02 (g)
-2H20
pt'"Rh gauge catalyst
13. (a) +502 (g)
6. (e) In cyclic metaphosporicacid, numberof 500K.9bar
bondsis three. 4NO(g) + 6H20(1)
TwomolesOf will produce2 moles OfNO on
catalytic oxidation.
(b) It is the most electronegative element.

15. (b) H20+Br2 —+10Br 4HBr

7. (c) Nitrogen fcrm (i.e. N=N) but phosphorus ferm P4, Thus. here oxidation number of Br increases from Oto +1
becausein P2,p, — tMndingis presentwhich is a and alsodecreases from Oto—I.'Illus. it isoxidised as well
weaker as reduced.
8. (a) Onmovingdownthe group,size of halogenatom 16. (d) Due to hydrogen bonding, HF is a liquid,
increaseshence.the H—X
bondlengthincreases.As a 17. (c) Let oxidation state of P in NaH2P02 is x.
result, bonddissociationenthalpydecreases.
Hence,the correctorderof bondenthalpyis :

9. (b) VSEPRtheorybreaksdownfor heavierelements.

There is no significant s—pmixing for PHs doum
the group. For PHs, there is very little contribution from
the Pss-orbital.We can assumethe P—Hbondsare
predominantly H bonds. Thus. the geometry around
P is determinedmostlybytheorientationofthe"-orbitals.
e.g. in Bills, the angle z 900
18. (d) Oxidising power decreases down the group
19. a)) On moving from top to bottom of halogen group the
bonddissociationenergyof hydrogenhalides decreases
and so the heat offormation ofhalogen acids also decreases.
20. (d) NCI -8H20+5C12
O.S OfMn changes from +7 to +2 hence reduction crcurs
andCll is formed.
21. (d) As the oxidation Stateof the centralhalogenatom
increases,the halogen-oxygenbondbecomesmoreand
morecovalent.As a result,the thermalstabilityof the
 a kopykitab.com

Notes 34 -of

The p-BIock Elements c-29

oxoacid increases. Thus. HCIO„ is most stable to heat, 35. (b) 36. (a)
whereas HCIO is least stable to heat. 37. (d) PH, (Lewis base) can react with B2H6(Lewis acid).
22. (b) Isoelectronicpair have same number of electrons 38. (b)
Total number of electrons for the given compounds : 39. (d) SO: acts as an oxidising agent as well as reducing
BrF2i agent.
35+288+1-52 35+9*2-1-52 40. (e) Oxygen does not show oxidation state +4 and +6.
IC12 41.
53+2* 17-87 17+16-33 35 9 44 42. (d) In solid state PCI, exists as an ionicsolid with thecatim
O, [PC141
W(tetrahedral) and the anion [PCIJ (extahedral).
80-24 43. (c) Ozone does not react with acidified solution of
23. (10 OutofN. S and C. nitrogen has the highest electrone-
K2C%O,.
gativity and it decrease in the order N S > C. Thus the
44. (b) Order ofM.P, ofB.P. or critical temixraturc •
oxide of nitrogen in its highest (+5) oxidation state is the
most acidic.
45. (c) Numberofft-bonds
Next to N205 in the decreasing order ofacidity will SO2
then CO, and finally CO which is neutral. O
24. (a) sp3d3hybridization will give pentagonal bipyramid
geometry with one trans position occupied by a lone pair
and shape of the molecule will be distorted octahedral.

XeF6 sp3d3hybridisation x H2S04-HO OH 2

25. (c) The hydrolysis of R3SiCl, yields R3Si(OH) which

condenses to give R. Si —O —SiR3 H2S03 - HO

26. 46. (c) o o

27. (c) Among carbon, nitrogen. phosphorus and boron only

-o 0'
(SOS)
phosphorus has vacant a-orbital hence, only phosphorus (Y O
has the ability to form pr. — bonding. (SOB)
28, (d) Duetohigh N—Fbondstrength. NFgis highly stable
and hence inert towards hydrolysis.
o
29. (A) 2NH3 +5/202 —Ä—QNO

30. (c) NH4Cl+KN02 —KCI ..N2 21120 04 Xo o/ iso

31. (c) H3P03+2KOH -K2HPOg 421120
32. (c) Bertletthad taken 024 Pt as a base compound because Hence (c) is the correct option.
02 and Xe tx»thhave almust same icmisation enthalpy 41. (a) When freshly prepared solution ofFeS04 is added to
an aqueous solution containing NOV ion. it leads to the
33. (a) (NHa)2 441120 cr203 formation of a brown coloured complex. This is known as
34. (a) The single N —N bond is weaker than the single brown ring test for nitrate ion.
P — P bond. This is why phosphorus show allotropy but
nitrogen docs not.
 Chemistry

NOR+3Fe -NO 3Fe3 *2H20 o

[Fe(H20 6)T+NO-.
Brown
Hypophosphorusacid
48. (d) K2C%07+H2S04 asoz 65. (b) In Caseofni trogen, d-orbitals are not available-
66. (a) Collectivelytheseelementsare calledpnicogensand
K2S04 4120
their compound pniconides.
67. On heating, lead nitrate producesbrowncoloured
49. (b)
nitrogen dioxide (N02)and lead (Il) oxide.

2Pb(N03 +2PbO 02
51.
52. (b) The only well characterised compound having + 5 68. (d) Metalliccharacterincreasesdownthe group,Bi is
oxidationstateof Bi is BiF,. It is dueto smallersize and most metal lic
high electronegativity
offluorine- 69.
53. (c) The electron gain enthalpy order for halogens is 70. (a) Nitrogendoes not show allotropydue to its small
size and high electronegativity.
The bondis weak
Dueto smallsizeoffluorinethe extraelectronto be added due to high inter—electronic repulsionsamong non-
feels more electron-electron repulsion. Therefore fluorine bonding electrons due to the small bond distance. Hence.
has lessvalueforelectronaffinitythanchlorine. it dex:s not show allotropy.
54. (c) Ml > MBr> MCI> ME As the size of the anion 71. (d) HCI acid at 25" C is a gas and polar in nature.
decreasescovalencydecreases. 72. (a) N20 is usedas an anaesthetic
55. (c) In liquid state BrFJ dissociates into BrF2•and BrFd 4NO+6H20
73. 4NH3+502
ions most easily.
74. (c) SF4 has sea-saw shape as shown below.
56. (c) xeF6 —Xeon 42HF(Partialhydrolysis)
xeF6+21120 —xe02F2
Si02 + 2XeF, —+2XeOF4
Xenonoxy tetra

57. (c)
58. 2XcF6 +Si02 ÄX'eOF4
59. (b) 60.(b) It has trigonal bipyramidal geometry having sp*d
hybridisation.
61. (b) HF+XeF6—xeF5+
75. (c) Hybridisationin PCI, ——(5 -0 5 : sp3d
+ExcessH Xeo,+
76. (C) Maximumcovalencyof nitrcæenis 4 in which One
62. (b) XeF electrcmis from s-orbital and 3 electrons are from p-€ybitals.
Xeo: Hence, total four electrons are available for bonding.
(Y) 77. (d) Bleachingactionof chlorineis due to oxidationin
presence of moisture.
Y is not an Oxyacid Of C12+H20 -QICI *HCIO
63. (d) Ionic radii increases down the group HCIO-9 HCI+O
64. (c) The acids which contain bondhave strong Colouring matter + O —+Colourless matter
reducing properties. Thus. HYPO:is a strong reducing 78. (d) Dueto hydrogenbonding.HFis a liquid.
agent due to the presence oftwo p — H bonds and one — 79. (b) It is the most e lectronegative element.
OHgroup 80. (c) Structure of H, P04 is
The p-Block Elements c-31

energetically favorable. It depends on size and orientation

Ofinteraction.
91. 0) Sulphurand oxygen belong to group 16of the
HO/ rNOH periodic table.
OH
HgP04has 3 —OHgroupsi.e., three ionisableH-atoms 92.
and hence, it forms three series Ofsalts: NaH2PO
Na2HP04 and Na;po. Ozone molecule is found to have bent shape because
81. (a) No compound of He as yet been reported. lone pair present on central oxygen atom repels the
82. (a) No compound of Ar as yet been reported with F: electronsofthe two bonds.
93. (a) S, also found to adopt bent shape.
(a) Both COi¯ and N03¯ have same
94. (c) Sulphur has a greater tendency for catenation than
oxygenbecauselonepair Ofoxygenrepelthe bond
O —O bond to a greater extent than the lone pairs of
NO/ 1=32 S —S bond. According to auibau principle. the 4s orbital is
lower in energythan the 3d orbital.
Hence, and NO; are isoelectronic. Also, both have
95. (c) The bond energy of interhalogen compounds is less
Same type of hybridization (sp2) and have trigonal planar
thanthe bondenergy ofhalogens.
structure. Hence, they are also isostructural.
96. (d) All halogens (leaving F-F) have stronger bond then
84. (a) Mixture of (He + O,) is used for asthma patient.
that in interhalogens.
85. (c) Argon is used in high temperature welding and other
97. (d) Interhalogen compounds are not highly volatile.
operations which require a non-oxidising atmosphere and
98. (a)
the absenceofnitrogen.
99. (b) Interhalogcn compounds are useful flucrinating agents.
100. (d) Ozone is thermcxlynamically less stable than oxygen
*6. due to large negative Gibb's free energy and decomposes
easily to form oxygen.

101.
(Melal) (Conc.) (Metalnitrate) (Nascenthydrogen)

2HN03+ 2H _eN02 -eH20

hydroga.)
102. (c) At higher temperatures, dinitrogen combines with
metals to form ionic nitrides.
bridging
oxygen bridging
103. (c) Bond angle of (920) •Z (104031). As the
oxygen electronegativity ofthe central atom decreases,bond angle
decreases. In the lyesent S is less electronegative than
oxygen- Thus, tx»nd pairs in H2S are more away from the
87. (d) Electron gain enthalpy for noble gases is positive central atom than in H.O and thus repulsi ve forces Ixtween
and it becomes less positive with increase in size Ofatom. bond are smaller, prcxhlcing smaller bond angle.
Value of electron gain enthalpy 104
He —48 kJ mow. Ne— 116 k.Jmol-I 105. (a) Inert gases are monoatomic because they have stable
Ar, Kr-96kJm01A.Xe-77kJmol-1 configuration as their cwtet is complete.
Hence, Ne has highest positive electron gain enthalpy, 106. (a) Fluorineexists in only—loxidationStatedueto the
88. (b) PC13+H20 POCl*+2HCl absenceof vacanta-orbital.
POC13+3H20 107. (e) Fluorine is a highly reactive non-metal due to its low
89. Bismuth forms metallic bonds in elemental state, bond dissociation energy.
90, g)) PHSdoes not exist because d-orbital of interacts 108. (a) Becauseofsmall size of F atoms. their is repulsion of
with s-orbital of H, Bond formed is not stable and not electrons in F2 molecule, Thus, F-F bond in F: molecule is
c-32 Chemistry
109. (c) N: isles reactivethan due to high valueofbond The salt is then treated with a strong non-oxidizing acid to
dissociation which is due to presence of triple give hypophosphorous acid.
bond two N-atoms ofN2 molecule. H2POÜ+ H,P02
110. (c) HN02makesiron passive due to formation ofpassive
form of oxide on the surface. Hence, Fe does not dissolve
in HNO, solution.
111. g)) HI cannot be preparedby the reactonOfKl with
concentratedH SO becauseHI is convertedinto 12on (red P) (dil.) (dil.)

reaction with H:SO,. Na2H2P206 can be converted to H4P206 by passing it in

112. (10 lcxline.Ixing a non-polarcompoundis moresoluble an ion exchange column.
in CCI„(non-polarcompound)than in water as "like 118. Calcium cyanamide
dissolves like". 119 . Flourine
120 . HC104, Kl•lS04. chlorine dioxide
113. (c) SS has puckered ring type structure.
3KC103 +3H2SOa 3KHS04 HC104 QC102 + 1120
114. (c) A mixture of He and 02 is used for respiration by
deep sea divers but Helium is not soluble in blood. 121. Dipole—induced dipole interaction.
IIS. (b) 122. Dipole-induced dipole,
123 . •n•ue.
116. (a) CaC2+ N2 CaCN24C 124 . •frue.
(B) NH3 is oxidized to NO, W'hich is used to prepare 125. True; Hypo form of'—ic•acid is derived from its pyro
nitric acid. and HClOg does not have its pyro form therefore its hypo
(C) Steel metal is dipped in a bath of nitric acid/ form is not possible.
hydrofluoricacid. It strips the surface layer of steel, 126. False; Fluorine is most electronegative element in pericxlic
removing impurities and free iron molecules; leaving an table and exhibits O.S. value of—I only.
even, satin like finish. 127. False
117. (a)
(white P) (hot) (calcium hypophosphite)
 Haloalkanes and
Haloarenes
6. In the preparation of chlorobenzene from aniline, the most
Multiple Choice Questions (MCQs) suitablereagentIs
(a) chlorine in the presence of ultraviolet light
(b) chlorine in the presence ofAlC13
DIRECTIONS: Thissectioncontainsmultiplechoice (c) nitrous acid followed by heating with Cu2C12
questions. Each question has four choices (c) and (d) (d) HClandCu,C12
out of which only one is correct. 7. Aryl halides can not be prepared by the reaction of aryl
Whentwo halogenatomsare attachedto samecarbon alcohols with PC13.PCISor SOCI, because
atom then it is : (a) phenols are highly stable compounds.
(a) vic-dihalide (b) gem-dihalide (b) carbon-oxygen bond in phenols has a partial double
(c) u. (0-halide (d) a,ß-halide bondcharacter
2. Identity A.B,C and D: ICBSE Sample 20211 (c) carbon-oxygen bond is highly polar
(d) all ofthese,
8. Ethyl alcohol reacts with thionyl chloride in the presence
AgCN
of pyridineto give
c C2HsCl ale. KOH A (a) H,O+S02
Aq. KOH (b) CHsCH2C1+HC1
(c) CH3CH2Cl+HCl+S02
(d) CHsCH2C1+S02+C12
(b) A-C2H501LB-C2Ha.C-C2H5CN,D-C2H5NC 9. Ethylene dichloride can be prepared byadding HCI to
(a) ethane (b) ethylene
(c) acetylene (d) ethylene glycol
(d) A-C,H50YLB-C2H C-C2H5NC,D-C2H5CN 10. Thebestmethodfor theconversionof an alcoholinto an
3. Which one of the following is not an allylic halide? alkyl chloride is by treating the alcohol with
(a) 4-Bromopent-2-ene (a) PCI,
(b) 3-Bromo-2-methylbut- I -ene (b) dry HCI in the presence of anhydrous ZnC12
(c) I-Bromobut-2-ene (c) SOC12in presence ofpyridine
(d) 4-Bromobut-l -ene (d) noneOfthese
4. IUPACname is 11, Arrange the following compounds in the increasing
(a) 2-bromo-l-chlorobutene oftheirdensities.
(b) I-chloro-2-bromobutene
(c) 3-chloro-2-bromobutene
(d) Noneof the above
Toluenereactswith a halogenin thepresenceofiron (111) (i)
chloridegivingorthoand parahalocompounds.The
reactionis
(a) electrophiliceliminationreaction
(b) electrophilicsubstitutionreaction
(c) free radical addition reaction (iv)
(d) nucleophilicsubstitutionreaction
 (b) I-chloro-2-bromobu
tene
(c)
(d) None of the abo ve
5. Toluene reacts with a halogen in the presence ofiron (Ill ) (i)
chloride giving ortho and para halo compounds.The
reactionis
(a) electrophilic elimination reaction
(b) electrophilicsubstitutionreaction
(C) free radical addition reaction (iii)
(d) nucleophilic substitution reaction

c-34 Chemistry

(i) (CH3)2CH-CH2Br
12, Which one is most reactive towards SNI reaction?
The mechanisms of reactions (i) and (ii) are respectively •
(c) (d) C6HsCH2Br
(a) SNI and SN2 (b) SNI and SNI
13. The order ofreactivities Ofthe following alkyl halides for a
SN2 reaction is
(C) SN2and S (d) SN2 and SNI
(a) (b) 20. + NaOH
14. Which among MeX, RCH:X, R2CHXandR3CX is most For which solvent rate ofSN2 will be maximum
reacti ve towards SN2reaction? (a) Benzene
(a) Mex (b) RCHrx (b) 1000/01120
(c) R2CHX (c) 100%acetone
Whichis the correctincreasingOrderof pointsof (d) H20+250/oacet(N1e
the following compounds? 21. Chloromethaneon treatmentwith of ammonia
I - bromocthane,I - bromopropane,
I - bromobutane. yields mainly

(a) Bromobenzene I - bromobutane < I - br«ncvrcvane (a) N,N-dimethylmethanamine

•z:l- bromoethane
< 1-
(b) Bromobenzene I - bromobutane (b) N-methylmethanamine — NH— CHO
bromopropane < I - bromobutane
(C) methanamine (CHsNH:)
(c) 1 - bromopropane < 1 - bromorpropane
< I - bromoethane
< Bromobenzene (d) mixture containing all these in equal proportion
(d) I - bromoethane < I - bromopropane 22. Which ofthe following is a primary halide?
< I - bromobutane
< Bromobenzene (a) Isopropyl iodide
(b) Secondarybutyliodide
16. (c) Tertiarybutylbromide
(d) Neohexylchloride
23. Whentwohalogenatomsare attachedfo samecarbon
atomthenit is :
(a) vic-dihali& (b) gem-dihalide
(C) a, CD-halide (d) u,ß-halide
24. The order of reactivity of the given haloalkanes towards
(b) nucleophile is :
(a) RI > RBr>KC1
(d) RIPRI>RCI
25. Which Oneofthe following is not an allylic halide?
(a) 4-Bromcvent-2-cne
(d) None of these (b) 3-Bronw2-methydbut- I-ene
17. Haloarenes are ortho and para directing due to (c) I-Bromobut-2-ene
(a) Resonancein arylhalide (d) 4-Bromc%ut-I-ene
(b) —Ieffectofhalogenatom 26. An organic compound A (C4HuCl)on reaction with Nal
(c) +1effectof halogenatom diethyl ether gives a hydrocarbonwhich on
(d) Both (a) and (b) monoch lorination gives only one chloro derivative, then
18. Reaction of C6HsCH2Br with aqueous sodium hydrox ide A is
„
K»llows (a) tert-butyl chloride (b) sec-butyl chloride
(a) SNI mechanism (c) iso-butyl chloride (d) n-butyl chloride
(b) SN2mechamsm 27. Which chloride is least reactive with the hydrolysis point
(c) Any of the above two depending upon the ofview?
temperatureofreaction (a) CHgC1 (b) CH3CH2C1
(d) Saytzeff rule (c) (CH3)3CC1 (d) CH2-CH-C1
19. Consider the reactions :
28. How many structural iscmers are possible for a compound
(i) (CH3)2CH -CH2Br with molecular formula C3H7Cl?
(CH02CH + HBr
 (a) SNI mechanism (c) iso-butylchloride (d) Il-butylchloride
(b) SN2 mechanism 27. Which chloride is least reactive with the hydrolysis point
(c) Any of the above two dependingupon the of view?
temperature of reaction (b) CHJCH2C1
(d) Saytzeffrule (c) (CHghCCI (d) CH:-CH-CI
19. Consider the reactions :
28. How many structural isomers are possible for a compound
(i) (CH3)2CH —CH2Br C:H'OH with molecular formula C,H7Cl
+ HBr

Haloalkanes and Haloarenes c-35

29. For the compounds 35. Benzene hexachloride is
CHYCI,CH3Br. and CHSF, (a) l, 2, 3, 4, 5, 6-hexachlonxyclohexane
the correct order of increasing C-halogen bond length is:
(c) I , 6-phenyl- I. 6-ch lorohexane
(d) l, I-phenyl-6, 6-chlorohexane
36. In the following groups :
-OAc(1)
30. The order of reactivity of following alcohols with halogen - OS02 Me (111)
acids is . the order of leaving group ability is
(A) CH3CH2CH2—OH

(B) CH3CH2-CHOH 37. Identity the compound Y in the following reaction.

N2C1
CH3

(O CH3CH2-COH
CH3

31. A set of compounds in which the reactivity of halogen (c)

atom in the ascending order is
(a) chlorotxnzene. vinyl ch loride. ch lorexthanc
(b) chloroethane. chlorobenzene. vinyl chloride
38. Which of the following is most reactive toward SN2
(c) vinyl chloride. chlorobcnzene. chlorcrthane
reaction?
(d) vinyl chloride. chloroethane. chlorotxnzene
32. The compound which contains all the four | 0, 20, 30 and 4
carbon atoms is
(c) Me—O C1
'A
(a) 2. 3-dimethylpcntane
(b) 3-ch10ro-2. 3-d imethylpentane O
(c) 2, 3, 4-trimethylpentane 39. The major pr€xiuct formed when I. I. I-trichloro-propane
(d) 3,3-dimethylpentane is treated with aqueous potassium hydroxide is:
33. The total number of acyclic isomers including the (a) Propyue (b) I-Propanol
Stereoisomers with the molecular formula C4H7Cl (c) 2-Propanol (d) propionic acid
Il (b) 12 40. Arrange the following halides in the decreasing order of
(d) 10 SNI reactivity :
34. Whichof the followingalcoholswill yield the CH3CH2CH2C1, CH2
corresponding alkyl chloride on reaction with concentrated
HCI at room temperature?
(a) CH3CH2 —OH

(b) CHsCH2 - CH -OH (b) 11>13111

41. Which reagent will you use for the following reaction?
CH3CH2CH2CH3 -OCH3CH2CH2CH2C1 + CH3CH2CHCICH3
(c) CHsCH2- CH—CH20H
(a) C12/tJV light
(b) NaCl + H2S0a
(c) C12gas in dark

CH3CH2--OH (d) C12gas in the presence ofiron in dark

 CH3CH2CH2CH3 -+CH3CH2CH2CH2C1+ CH3CH2CHCICH3
(c) CH3CH2- CH—CH20H
(a) C12/UV light
(b) NaCl+H2S04
(c) C12 gas in dark

CHsCH2 -OH (d) C12gas in the presence ofiron in dark

c-36 Chemistry
42. Which ofthe following will give vinyl chloride ? SO. Which ofthe following is an example ofvic-dihalide?
(a) CH2 -CH2 (a) Dichloromethane (b) l. 2-dichloroethane
KOH
(c) Ethylidenechl€ride (d) Allylchloride
(b) CICH2 —CH2C1 51. Whenm-chloronitrobenzeneis treatedwith scxlamidein
preseneofliquidammonia,mainproductis
(c) CH -CH+HCI (a) 0-Nitrcxmiline (b) p-Nitroaniline
(d) Allofthese (c) m- Nitroaniline (d) All of these
43. Commenton thefollowingreactions 52. Brominationoftoluenegives
(i) CH30H + NaCl (a) only m-substituted
(ii) CH30H+ HCI (b) only p-substituted
(a) Bothreactionstakeplaceeasily (c) mixtureof0-andp-substituted
(b) Only reaction (ii) takes place (d) mixtureof0-andm-substituted
(c) Reaction ( ii) takes places faster than (i) 53. Whatis the productof the followingreaction?
(d) Noneof the tworeactionsin possible
44. ConantFinkelsteinreactionfor the preparationOfalkyl
iodide is based upon the fact that
(a) Sodium iodide is soluble in methanol, while sodium
chlorideis insolublein methanol (a) N. N-dimethylaniline
(b) Sodium iodide is soluble in methanol. while NaCl and (b) phenyllithium (C6HsLi)
NaBrareinsolublein methanol (c) para-ch loro-N. N-dimethylanilinc
(C) Scxlium iodide is insoluble in methanol, while NaCl (d) meta-chloro-N,N-dimethylamline
andNaBrare soluble 54. is formedby reactionof chlorinewith
Chlorobenzene
(d) The three halogens differ considerably in their benzene in the presence ofAlC13. Which ofthe following
electronegativity
species attacks the benzene ring in this reaction?
45. Arrange the followingcompoundsin increasingorderof
their boilingpoints.
(c) AIC13 (d) [AIC14J-
55. Chlorolxnzene Canbe prepared by reacting anilineuith
(i) CH33>cH—CH2Br (ii) CH3CH2CH2CH2Br
(a) hydrochloricacid
CH3 (b) cuprous ch loride
(S) chlorine in presence of anhydrous aluminium chloride
(iii) H3C ¯ —CH3 (d) nitrous acid iöllowed by heating with cuprmaschloride
56. Aryl halidesare extremelyless reactivetowards
(a) < (iii) nucleophilic substitution than alkylhalides. Which ofthe
followingaccountsforthis
(c) (iii) <(ii) (i) Due to resonance in aryl halides.
46. When chl«ine is passed through propene at 400 0C, which (ii) In alkyl halides carbonatom in C—Xbond is sp2
ofthe followingis formed? hybridised whereas in aryl halides carbon atom in C—
(b) Allyl chloride X bond is sp3 hybridized.
(c) Alkylchlcride (d) l, 2-Dichlorcx•thane (iii) Due to stability of phenyl cation.
47. 2-Bromopentaneis heatedwith potassiumethoxide in Dueto repulsionthere are less chancesOf
ethanol. The major product obtained is nucleophileto approachelectronrich arenes.
(a) 2-ethoxypentanc (b) pentene-I (ii) and (iv) (b) (ii) and (iii)
(c) trans-2-pentene (d) cis-pentene-2 (c) (i) and (iv)
48. When CHYCH2CHC12
is treated with NaNHr the product 57. Whichofthe iöllowingsyntheticschemeswouldbe the
formedis tBt forthesynthesisofthecompound,2-bromo-l-chloro-
(a) CHs—CH-CH2 4-nitrotrnzene?

(C) CH3CH2CH (d) CH3CH2CH

49. Aryl fluoride may beprqured fr(Nnarale diuonium chloride

using ; 02
(a) HBF4/A (b) HBF4/NaN02,Cu. A
2-bromo-l e
(c) CuF/HF cu/HF
 using : N02
(a) HBF4/A (b)
2 -bromo- I -ch trobcnzene
(c) CuF/HF (d)

Haloalkanes and Haloarenes c-37

62. Eliminati(M1ofbfomine from 2-bromobutane results in the
Br2 HN03 formation of—
112S04 (a) predominantly 2-butyne
(b) predominantly I-butene
Bt2 (c) predominantly 2-butene
(b) FeBIÄ AIC1g (d) equimolar mixture of l- and 2-butenes

HN03 Br2
63. C3H8+C12 >C3H7Cl+HClisanexampleof
AIC13 H2S04 (a) substitution (b) elimination
(c) addition (d) rearrangement reaction
Br2 DIRECTIONS: In the questions64 ro 67. arrange the
AICI FeBr, 112S04 compoundsin increasing order o/ rate of reaction towards
58. Ethylidene chloride is a/an. nucleophilicsubstitution,
(a) vic-dihalide (b) gem-dihalide
(c) allylichalide (d) vinylichalide
59. The correctkineticrate equationforthe addition- 64. (1) (iii)
elimination mechanism ofnucleoph ilic aromatic sutstitution
(a) rate = k [aryl halide] [nucleophilel
(b) rate —k [aryl halide] (a) (i) < (ii) < (iii)
(e) rate = k [aryl halide] [nucleophilel 2 (c) (i) < (iii) (d) (iii)
(d) rate = k [ nucleophilel
60. What is 'A' in the following reaction?
65. (i) (iii)

4. HC•I A (a) < (iii)

(c)

02N NOZ
Cl
66. O) (iii)

N02
(b)
(a) (iii) < (ii) < (i)
(c) (i) < (iii)

—CHs 67. (i) (iii)

(a) (iii) < (ii) < (i)

(d) (c) (iii) < (ii) < (i)
H — CH2 — CHI 68. CH3-CH2-CH2-Cl
KOH ether
In the above sequence of reactions, the product D is
(a) propane (b) 2, 3-dimethylbutane
61. Whenhydrochloricacid gas is treatedwith propenein (c) hexane (d) allylbromide
69. In the followingsequenceof reactions
presence ofbenzoyl peroxide, it gives
(a) 2-chloropropane (b) allylchloride C2H5Br
(c) 'I-propyl chloride (d) No reaction occurs (a) "-propylamine (b) isopropyl amine
(c) ethyl amine (d) ethylmethyl amine
 — CH2 CHY 68. CHy—CHz-CHz-C1
KOH ether
In the abovesequenceof reactions.the productD is
(a) propane (b) 2, 3-dimethylbutane
(c) hexane (d) allylbromide
61. Whenhydrochloricacid gas is treatedwith propenein 69. In the followingsequenceofreactions
presenceofbenzoylperoxide,it gives
(a) 2-chloropropane (b) allylchloride CzHsBr
(c) "-propylchloride (d) NOreaction occurs (a) amine (b) isopropyl amine
(c) ethylamine (d) ethylmethyl amine

c-38 Chemistry
70. The reaction conditions leading to the Erst yield ofC2H5Cl 78. Gerndihalides treatmentwithalcoholicKOHgive :
(a) alkyne (b) alkene
(c) alkane (d) all ofthese
(a) C2H6(excess)+ 79. Whichof the following reactionsis an exampleof
nucleophilicsubstitution
reaction?
ternruature
(c) C + (excess) (b) RX+H2+RH+HX
(d) C2H6+C12 light (c) Mg-+RMgX
71. On sulphonation ofC6H Cl (d) RX'+KOH-.ROH+KX
(a) m-chlorobenzenesulphonic acid is formed 80. Which one ofthe töllowing is not an allylic halide?
(b) benzenesulphonic acid is formed (a) 4-Bromopent-2-ene
(c) 0-chlorobenzcnesulphonic acid is formed (b) 3-Bromo-2-methylbut-l-ene
(d) mixture Ofo- and p-chlorobenzenc sulphonic acid is (c) I-Bromobut-2-ene
(d) 4-Bromobut- I-ene
72. Whenchlorobenzene
is reactedwithacetylchloridein the 81. Whichof the followingalkyl halides will undergoSNI
presence of anhydrous AICI3, the major Kyrmedis reaction most readily?
(a) 2-chloroacetophenone
(b) 3-chloroacetophenone
(c) 4-chloroacetophenone 82. ich ofthe following is the correct method ofpreparation
(d) l. 4-dichlorobenzene
Ofmethyl fluoride?
73. Which ofthe following compounds will give racemic mixture
(a) + I-IF (b) CH30H+HF-*
on nucleophilicsubstitutionby OH ion?
(d) CH3Br+AgF+
83. Thestructureofthemajorproductformedin thefollowing
(i) (ii) —CHs reaction
C2H5 C2Hs c HSI
NWN
(üi) CHs CH — CH2Br is
DMV

C2H5
(b) (ii) and (iii) CH2C1
(c) (ii) and (iii) (d) (i) and (iii) (a)
74. Ethanol can be prepared more easily by which reaction ?
(i) —CH3CH20H
(ii) CH3CH2Br + Ag20 (in boiling water)
CH2Cl
(a) by(i) reaction
CH3CH20H
CNJQ
(b) by (ii) reaction
(c) Bothreactions at samerate
(d) by none 84. Identi$' Z in the following series
75. Thebestmethodforthe conversionofan alcoholinto an
Alc_ KOH
alkyl chloride is by treating the alcohol with
(a) PCI,
(a) CH3CH2CN' (b) NCCH2-CH2CN
(b) dry HCI in the presence of anhydrous ZnC12
(C) SOC12in presence of pyridine
(c) BrCH:-CH2CN (d) BICH=CHCN
(d) Noneof these 85. Whichis thecorrectIUPACnamefor
76. "-PropylbromideOntreatmentwith ethanolicpotassium CHs— CH —CH2—Br?
hydroxide produces C2H5
(a) propane (b) propene
1-trorno—2-ethylpropane
(c) propyne (d) propanol (b) I -brom yiethane
77. Aprimaryalkyl halide would prefer to undergo. (c) I -brcxno-2-methylEA1tane
(a) SNI reaction (b) SN2reaction (d) 2-methyl- I e
(c) CÆliminati(M (d) racemisation
 (a) I -tyomo-2-ethylpropane
(c) propyne (d) propanol (b) I-brorno-2-ethyl-2-mehylethane
77. A pnmary alkyl halide would prefer to undergo... (c) I -brcnno-2-methyltR1tane
(a) SN I reaction (b) SN2 reaction
(d) 2-methyl- I -bromolwtane
(c) a-eliminatim (d) racemisation

Haloalkanes and Haloarenes c-39

86. What should be the correct IUPAC name for 91. The major product of the following reaction is:
diethylbromomethane?
(a) I -bromo-l , 1-diethylmethane KOH
(b) 3-bromopentane
(c) I-H-omo- I-ethylpropane
(d) I-bromopentane
87. Amongthe followingcompounds,
which has the
shortest C —Cl bond?

(a) Hsc Cl

(b)
(c) HgC-C1

88. The major product ofthe followin g reaction is

CH,OH
-C - CHCH*
CHJ
(d)
CH3

(a) CH3 -C -CH- CH

Case/Passage Based Questions

CHs DIRECIIONS : F0110Uingare the case/pussage basedquestions.

(b) CHs-C - CHCHS Case/Passage-l

Nucleophilic substitutionreaction Ofhaloalkane can bc
CH3 conductedaccordingto both S I and S mechanisms.
However.whichmechanismit is basedon is relatedto such
(c) CHg-c -CH2CH
factors as the structure of h aloalkane, and properties ofleaving
OCH3 group, nucleophilic reagent and solvent.
CH3
Influencesor halogen:No matterwhichmechanismthe
nucleophilic substi tution reaction is based the leaving group
(d) CHy-c -CHCH, alwa» leave the central carbon atom with electron pair. This is
loc just the opposite ofthe situation that nucleophilic reagent attacks
H
the central carbonatom with electronpair. Therefore,the
89. X in the following reaction is— weaker the alkalinity of leaving group is. the more stable the
CHy—C -H anion formed is and it will be more easier for the leaving group
c C14
Br2+ to leavethe centralcarbonatom;that is to say,the reactantis
H- CHs more easier to be substituted. The alkalinity order ofhalogen
(a) (+) 2. 3-Dity«nobutane ion is I- < Br- Cl- < F- and the order Oftheir leaving tendency
(b) (—)2, 3-Dibromobutane should 1k Br- > Cl- > F-. Therefore, in four halides with the
(c) Rac. 2, 3-Dibromobutane samealkyl and differenthalogens,the orderof substitution
(d) Meso-2, 3-Dibromobutane reaction rate is RI > RBr > RCI > RE In addition. if the leaving
90. Moleculeswhosemirror image is non —supenmposable group is very easy to leave. many carbocation intermediates
overthemare knownas chiral. Whichof the following
are generated in the reaction and the reaction is based on SNI
moleculeis chiral in nature?
(a) 2 - bromobutane (b) I - bromobutane mechanism.If the leaving groupis not easyto leave, the
(c) 2- bromopropane (d) 2 -2-01 reaction is based SN2mechanism.
Notes 45 —of
moleculeischiral in nature? are generatedin thereactionand the reactionIs basedon S
(a) 2 - bromobutane (b) I - bromobutane mechanism.If the leaving group is not easy to leave, the
(c) 2 - bromcvropane (d) 2 -bromcvrcvan—2-01 reactionis basedon SN2mechanism.

C-40 Chemistry
Influences ofsolvent polarity: In SN1reaction, the polarityof 96. SNI reaction will be fastest in CaseOf:
the systemincreasesfromthe reactantto the transitionstate. (a) I -Chloro-2-methyl propane
becausepolar solventhas a greaterstabilizingeffecton the (b) I -lcxlo-2-methyl propane
transitionstate than the reactant,therebyreduceactivation (c) I -Chlorobutane
(d) I-Iodobutanc
energyandacceleratethe reaction.InSN2reaction.thepolarity
Case}Passage-lI
of the systemgenerallydoesnot changefromthe reactantto
the transitionstateand only chargedispersionoccurs.At this Alkyl halides are insoluble in water but solublein organic
time, polar solvent has a greatstabilizing effect on Nuthan the solvents.
The insolubility in wateris due to their inability to
form hydrogen bonds with water. Alkyl bromides and iodides
transitionstate.therebyincreasingactivationenergyandslow aredenserthan"uter whereasalkylchloridesandfluoridesare
down the reacti(hl rate_ t
example, the decomposition rate (SN ) lighter than water. Alkyl halides have higher boiling points than
of tertiary chlorolnltane in 25cc water (dielectric constant 79) is alkanesofcomparable
molecularueight_Fora givenhalogen
times åster than in ethanol (dielectric constant 24). The atom, the boiling points ofalkyl halides increase vGththe increase
and NaOHin ethanol in the sizeofthe alkylgroup.
reactionrate (SC) of 2-bromopropane
containing w'ateris twice slower than in absolute ethanol. In 97. Which ofthe following is liquid at rc»m temperature (b.p.
a worcLthe level ofsolvent polarity has influenceon both SNI and is shown against it)?
(b) CH.Br(3 0C)
reactions, but Generally speaking, weak
(d) CIV(-78 0C)
polar solvent is favorable SN2 reaction. while strong polar 98. Which o/ the following pcsse-sseshighest melting point?
solvent is mvorable for SN reactim, because only under the action (a) Chlorobenzene (b) m-dichlorobenzene
of polar solvent can halogenated hydrocarbon dissociate into (c) 0-dichlorobenzene (d) "-dichlorobenzene
car%ocationand halogen i-KM1
and solvents with a strong polarity is 99. Readthe followingstatementsand choexse
the correct
favorablefor solvationof cartxwatiKnincreasingits stability. an swer
Generallyspeaking,the reactionoftertianrhaloalkane (i) The boiling points ofisomeric haloalkanes decrease
is based on SNI mechanism in solvents with a strong polarity (for with increasein branching.
example. ethanol containing uater)-
(ii) Among isomericdihalobenzenesthe para-isomers
havehighermeltingpointthantheirorthoandmeta-
(Ding, Y.(2013).A NuclecFhilic Substitution isomers.
Reaction on Saturated Carbon Atom. In Applied Mechanics and (iii) Theisomericdihalobenzenes
havelarge difference
Materials (Vol. 3 12, pp. 433-437). Trans Tech Publications Ltd.) in their IN)ilingandmeltingpoints
IFromCBSEQuestionBank-20211 The isomericdihalobenzenes
havenearlysame
92. S mechanismis favouredin whichof the following boilingpoint.
solvents: (a) (i), (ii) and (iii) are ccrrect
(a) benzene (b) cart»ntetrachloride (b) (i) and (iii) are correct
(c) (ii) and (iv) are Correct
(c) aceticacid (d) carbondisulphide
(d) (ii) and (iv) are correct
93. Nucleophilicsubstitutionwill be fastestin caseof: 100. The decreasing Orderofboilingpoints ofalkyl halides is
(a) I-Chloro-2.2-dimethyl
(b) I-lodo-2.2-dimethyl propane
(c) prcpane
(d) propane Assertion & Reason
94. SNIreactionwill be fastestin whichOfthe following
solvents?
DIRECTIONS: q/'thesequestionscontainsan assertion
(a) Acetone(dielectricconstant21) followedby reason.Read themcare/illlyand ansner the
(b) Ethanol (dielectric constant 24) questionon the basis "[following options. Youhave to select
(c) Methanol(dielectricconstant32) the one rhatbesidescribesthe twoslafements.
(d) Chloroform(dielectric 5) (a) IfbothAssertionandReasonarecorrectandthe Reason
95. polar solventsmakethe reactionåster as they. is a correct explanation of the Assertion.
(a) destabilize transition state and decreasethe activation (b) Ifboth Assertionand Reasonare correctbut Reasonis
energy not a correct explanation of the Assertion.
(b) destabilize transition state and increase the activation (c) If theAssertionis correctbut Reasonis incorrect.
If theAssertionis incorrectbut the Reasonis correct.
energy
(c) stabilize transitionstateand increasethe activation 101. Assertion : Alkylfluoridesare preparedbyheatingAgF
energy alkyl chloride.
(d) stabilizetransitionstateanddecreasethe activation Reason: Becausedirectfluorinationof alkanesoccurs
energy very slowly with rupture ofC C bonds.
 so vents .
(a) Acetone (dielectric constant 21)
(b) Ethanol (dielectric Constant 24)
(c) Methanol (dielectric constant 32)
(d) Chloroform (dielectric constant 5)
95. polar solvents make the reaction faster as they:
(a) destabilize transition state and decrease the activation
energy
(b) destabilize transiticm state and increase the activation
energy
(c) stabilizetransitionstateand increasethe activation 101. Assertion: Alkylfluoridesare preparedby heatingAgF
energy
(d) stabilize transition state and decrease the activation
energy
DIRECT : Each o,'ihese questions contains an ussenion
by reason, Read themearejiill_vand ansuer the
question on the basis of/ollowing options. hu have to select
the one that best describes the two statements%
(g) Ifboth Assertion and Reason are correct and the Reason
is a correct explanation Ofthe Assertion.
(b) If both Assertion and Reason are correct but Reason is
not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) Ifthe Assertionis incorrectbutthe Reasonis correct.
with alkyl chloride.
Reason: Becausedirectfluorinationof alkanesoccurs
very slowly with rupture Ofc C bonds,

Haloalkanes and Haloarenes c-41

102. Assertion Neopentyl chloride is prepared by free radical
chlorination of neopentane. > Matchthe Following
Reason : This is becausefree radicalsnormallydo not
rearran ge. DIRECTIONS : Each question contains statements given in two
103. Assertion : Iodoalkanes are formed byFinkelsteinreaction. columns uiich have to he matched.Statements(A, B, C. D) in
Reason Because Nal is soluble in acetone or methanol. column-I have to be nuarchedwith statements (p, q, s) in column-Il.
104. Assertion : Anti Markovnikov's rule is not applicable for 114. Matchthe columns
HE HUIor HI except HBr. Column - I Coltnnn - Il
Reason : Addition OfHCI, HF or HI to alkenes forms only = CH-CH2C1 (p) gem-Dichloride
Markovnikov's products. (B) CHz-CH.X (q) Vinylichalide
IOS.Assertion : Alkyl iodides cannot be prepared by CH*CHC12 (r) vic-Dichloride
Hunsdiecker reaction. CH2ClCH2C1 (s) Ally-lic halide
Reason: This is becauseiodinereactswith silver salt Of (a)
(b)
carboxylicacidsto give estersand silversalts.
(C)
106. Asserti«m : C-X t»nd length increases from C-F to C-l.
(d)
Reason: Sincethe size of halogenatomincreasesas we
go down the group in the periodic table.
Fill in the Blanks
107. Assertion: HighccMcentration
ofnucleophilefivourSNI
mechanisnl.
DIRECTIONS: Completethefollowingstatementswithan
Reason: 20alkylhalidesare morereactivethan | alkyl
appropriatenord / term to befilled in the blankspace(S).
halides towards SNIreactions.
108. Assertion : Boiling point of isomeric haloalkanesis IIS. A compound is formed by substitution oftwo chlorine for
two hydrogensin propane.The numberof possible
Reason: The boilingpointof isomerichaloalkanes isomericcompoundsis
decreases with increase in branching. 116. Halogenationof alkanesis process.
109. Assertion : Phosphoruschlorides(tri and penta)are 117. The positionofBr in the compound
CH3CH —CHC(Br)
preferred over thionyl chloride for the preparati«l ofalkyl (CH;), can be classified as
chlorides from alcohols. 118. The reaction with CuCl gives
Reason : Phosphorus chlorides giw in pure alkyl halides. 119. Silver benzoate reacts with bromine to form
110. Assertion : tert-butyl bromide undergoes Wurtz reaction
to give 2, 2, 3, A-tetramethylbutane. > True / False
Reason : [n Wurtzreaction, alkyl halides reactwith sodium
in dry etherto gne hydrocart»ncontainingdoublethe DIRECTIONS: Readthefollouingstatementsandwriteyour
number Ofcarlm.n atoms present in the halide. unsweras true orfalse.
Ill. Assertion: Nitrationof chlorobenzene
leadsto the 120. Whenhydrochloricacid gas is treatedwith propenein
formation of m-nitrochlorolrnzene. presence of Irnzoyl peroxide, it gives 2-chloropropane.
Reason (R) : —N02group is a m-directing group.
121. Alkyl halidesreactwith dialkylcopperreagentsto give
112. Assertion : Alkyl iodide can be prepared bytreatingalkyl
alkyl copper halides.
chloride/bromide
withNal in acetone. 122. Benzene reacts with "-propyl chloride in the presence Of
Reason: NaCl/NaBrare solublein acetonewhile Nal is anhydrous AIClg to give Isopropyllxnzene.
123. On sulphonationof C6HsClmixture of o- and p-
113. Assertion : Alkyltknzeneis not prepared byFriedel-Crafts
chIorobenzenesulphonic acids is formed-
alkylation of benzene.
124. The Wurtz-Fittig reaction Involves condensation of one
Reason : Alkyl halides are less reactive than acyl halides.
moleculeOfeachofaryl-halideandalkyl-halide.
 atlOn o nzcnc.
124. The Wurtz-Fittig reaction involves condensation of one
Reason : Alkyl ha lides are less reactive than acyl halides,
moleculeof each of aryl-halide and alkyl-halide.

c-42 Chemistry

ANSWER KEY & SOLUTIONS

benzene< chlorobenzene< dichlorobenzene
1. CH2Cl CHC12
bromochlorbenzene
CH2Cl 12. (c) SNI reactions involve the firmation ofcartxwations.
hencehigher the stability of carbocation,more will
reactivityOfthe parentalkyl halide.Thus tertiary
2. (a) cartx'cation formed from (c) is stabilized by two phenyl
3. (d) 4-Bromobut-l-ene is not an allylic halide groups and one methyl group, hence most stable.
13. (d) Weakerthe C—Xt»nd, greater is the reactivity
4—Bromobut4 ene 14. (a) I e Alkyl halides (having least steric hindranceat
a-carbon atom) are most reactive towards SN2 reaction.
15. (d) Boilingpoint is directlyproportionalto size of the
4. (a) CH*CH2C
- CFI-Cl molecule.All containssamehalogenatombutdifferent
hydrocarbon part. Larger the different hydrcxarl»n part
2•Btomo• I •Chloro but• I •ene
largerthe boilingpoint.
As electrophile Cle attacks on electron rich benzene
ring and substitutes hydrogen on ortho and para position
w.r.to.—CHsgroup.So. the reaction is electrophilic 16.
substitutionreaction.
6, (c)

N-NCV

O IINO.:HCI
O cu2C12
(Diazotksation) Sandmeyer •s reaction
NWether

7. t)) This method is not applicable for the preparation of

aryl halides because the C—Ot»nd in phenol has a partial
doublebondcharacterand is difficultto breakbeing
strongerthan a single t»nd-
8. (c) Ethyl alcohol formsethyl chloridewith thionyl
chloridein presenceofpyridine.
CH3CH20H+SOC12
9. (co Ethylene dichloride can be prepared by adding HCI
to ethylene glycol (CH20H- CH20H).
10. (c) R—OH+SOC12
SO. and HCI being gases escape leaving txhind pure alkyl
halide.
Direct fluorination ofalkane is highly exothermic prcxess.
11. (a) Density is directly related to molecular mass. Higher
the molecularmass,higherwillbe the densityof the
compound. The order of molecular mass is
17. (d) Due to resonance, the electron density increases more
at ortho- and para-positions than at meta-vx»sitions.Further,
the halogen atom becauseof its —I effect has some tendency
to withdraw electrons from the benzene ring. As a result,
the ring gets somewhat deactivated as compared to benzene
and hence the electrophilicsubstitutionreactions in
602 haloarenes occur slowly and require more drastic conditions
as compared to those in benzene.
18. (a) In C6HsCH2Br
carbocationis C6H5C112whichis
+HClt stabledue to resonance.
19. (a) A strongnucleophilefavoursthe SN2reactionanda
weak nucleophile favours the SNI reaction.
First reactionis SNI reactionbecauseC HsOHis usedas
solvent which is a weak nucleophile.
Second reaction is SN2reaction because C2HsO•is strong
nucleophilc.
Haloalkanes and Haloarenes c-43

20. (c) For SN2 reaction polar aprotic solvent is needed. 29. (a) The correct order of increasing bond length is
21. (c) CH3C1+ NH3 -+CH3NH2
Excess Methanamine 30. (b) Alcohols and halogen acids react through I
However,if the two reactantsare presentin the Same mechanism which involves carbocations as intermidate.
amount, then the mixture ofamines (i.e., primary, secondary In such reactions. order of reactivity follows the order of
and tertiary) are obtained. stability ofcarbocaticms; i.e. 3" 20 | 0. Thus the order in
22. (d) Neohexyl chloride is a primary halide asin it Cl-atom is the presente case is C B A.
attached to a primary carbon. 31.

t•CH3
c— CH.—CH2Cl 32. (b) CHECH - C -CH2-CHg

3-chi -dimethy ipentane

23. (b) CHC12 CH2Cl

33. al) C4HICI is a derivative ofC4Hs which itself
&H2Cl exists in three acyclic isomeric forms.
(gem •dihalide) ( Vic•diha Vide) CH3CH2CH CH3CH=CHCH3
24. (a) For a given alkyl group, the order ofreactivityis
(Its four C' s different) (It has 2 types of carbon)

increasingbonden«gy decreasing halogen

reactivity
CHs -C -CH2
This order depends on the carbon-halogen bond energy,
the carbon-fluorine bond energy is maximum and thus has2 Of )
fluorides are least reactive while carb«liodine bond energy
ofacyclic isomers 6± 4+ 2 12
is minimum hence iodides are most reactive.
25. (co 4-Br«nobut-l-ene is an allylic halide 34. (d) Consult Q. I.
35. (a)
€112 36. a») Weaker the base, better the leaving group. Hence

26. (a) Decreasingorder Of basicity

OMCOAc OS02Me OS02CF3
(11) (I) (Ill)
fH3 Decreasing Order Of leaving group
CHA—f + 2Na+ —CH3
CH3 37. (a) Sandmeyer 's r eaction
'-Butyl chloride

CH3CHÄ fH3fH3
Mono
—CH2C1 e- CHs-f—f-CHJ
CHgCH3 CH3CH3
38. (d)

25. (d) The non-reactivity of chlorine atom in vinyl chloride is

39. (d) C13C-CH2C'H3.KOH
due to resonance stabilisatiön. (OH)3C-CH2CH3*3KC1

CH2 CH —CH
CHsCH2?l-0H
28. (a)
 CH2 CH -CH=C.I:
CH3CH -OH
28. (a)

c-44 Chemistry
40. (c) Stability of the three corresponding carbocations Sincetrans- alkeneis morestablethan cis thus trans-
pentene -2 is the main product.
CH2 = CHCHCH3 > C HCH3 > CH2
NaNV1
Anyl 48. (b) CH3 — CH2 —CHC12
41. (a) It is a substitutionreactionwhichinvolvesthe
replacement of | 0 and 2 hydrogens of alkanes by chlorine. CH3 —CH CHCI —CECH
It Occurs in presence ofultraviolet light. Final

10 20 20 10 N-NCI
CH3CH2CH2CH3
HBF
49. (a)
CH3CH2CHCH3 + CH3CH2CH2CH2
42. All givenreactionsgive the vinyl chlorideby
substitution (a), by dehydrohalogenation (b) and by
50. (b) Halidesin whichtwohalogenatomsare presenton
addition (C)
the two adjacentcarbonatoms are knownas vic —
43. t') Reaction (i) is not possible because OH• is a stronger dihalides.
basc than Cl-; hence it can 't replaced by Cl e. However,

in reaction (ii) OH group is firstprot«lated to frm R OH2

in which H20, being a very weak base, is easily replaced
cli ct1H2
I.2-Dichloroethane

44. (b) R - X + Nal v >.'aX

Solublein Insoluble in
(CHAOH.
MezCOi (CHg0H.Me2C0j
El—C—
X —Cl or Br)
C 112 —CH=CH2
45. (c) Greaterthe surfacearea.greaterwill be the boiling
EthyIidenechloride Allyl chloride
point of a comm»und. Surfice area decreases with increase
in branching.
Increasing order of tx'iling point 51. (C)
52. (c) —CH3group is o, p—directing.

—CH <
53. (a) +LiC1

< CH3CH2CH2CH2Br
46. (b)At high temp. i.e., 4000C substitutionoccursin 54. (b) AIC13 C12 €14
preferen ce to addition.

CH3CH—CH2
—HCI
CICH2CH-CH2 O Cl—o
Chlorobenzene
47. (c)Potassiumethoxide is a Strong base, and 2-
bromopentaneis a 20 bromide.so eliminationreaction C6HsN2C1
(d) C 6HsNH2 C'6HsC1
predominates
56. (c)
OC 57. (d)
58. O)) Iftwo halogen a toms are present on the same cartx»n
CH3CH—CHCH2CH3 +CH2 4'HCH2CH2CH3 atom, then they are known as gem—dihalides Oralkyli&ne
pentene• 2(tnator mans Pentene— cis halides
 (b) If twohalogenatomsarepresenton the samecarbon
CH3CH-CHCH2CH3 atom, then they are known as gem—dihalides or alkylidene
Pentaie• 2(ma'oritrans ) Cis halides.

Haloalkanes and Haloarenes c-45

67. (c) If electronreleasinggroupis presentat orthoand
para positionw.r.t-to chlorine, it decreasesthe rate of
nucleophilic substitution reaction.
59.
68. (b) CHECHz-CH:-C1 CH3CH-CH2

CH3 CH3
21
—
ether CH3CH-CHCH3

Ratex C2HsBr C2HsNC

69. (d)
60. (c) Addition of HCI takes place in accordancewith Ethyl is•xyanide
Ethylbromi&
Markownikoffs rule. C2HsNHCHJ
Ethyl methyl amine

(excess) C12
71. (d) —Clis o, p-directing.
72. (c)
61. (a) Peroxideeffect is observedonly in case of HBr.
Therefore, addition ofHCl to prolkne even in the
oflxnzoyl peroxide wcurs to Markmikov 's rule:
Cllcocl COCH3
— CH3 -CHCI -CH3 anhy.AIC'L
Beruoyl
peroxide Chlorobenzene 2•Chloroacetophenone
COCH*
4.ChIoroac
Alc_KOH phenone (M aior)
62. (c) CH -CH2 GH3

CH3-CH GH3 HBr Ortho-Product is minorbecauseofsterichindrance.

73. (a) All those compounds which follow SNI mechanism
The formationOf 2-buteneis in accordanceto
duringnucleophilic subsitution reaction will give racemic
Saytzeff's rule according to which more substituted alkene
is formed in major quantity.
OrderofreactivityofalkylhalidesforSNI-
63. (n) It is an example ofsuthtitution reaction
64. (c) The substitution is faster ifthe electron withdrawing
groupis at orthoandpara positionto —Clgroup. Thus, CHJ —CT-I— Br contains a 20 chiral carbon, so
Compounds(ii) and (iii) both have one electron
C2H5
withdrawinggroup but in compound(ii) electron
withdrawing N02) group is present at orthoposition, it gives a racemic product.
so rate of reaction in compound (ii) is more than that of
(iii), while (i) has no electron withdrawing group. 74. (b) Heavy metal ions, particularly Ag e, catalyse
65. (d) Ifelectron releasing group is present at orthoor para
reaction because of presence of empty orbital.
position it decreases the rate of nucleophilic substitution
reaction.In compound(iii) electronreleasinggroup is 75. (c) R-OH+SOC12 Pyridine RC1+S02t+HC1t
presentat meta position w.l%t.chlorine. so the impact is less SO: and HCI twing gases escape leaving behind pure alkyl
than in compound (ii) wdlereit is present at ortho position. halide.
66. (d) Ifelectron withdrawing group is present at orthoand
ethanolie KOII
para position. then the nucleophilic substitution reaction
rate increases. n bromide
с-46 Chemistry
77. ф) 1twould preferto undergoSN2reaction.
Вт
SN2reactionsоссш ifthere is lesssteric•crowdingоп -
сагЬоп0falkyl ha1ide. case 0fprimary akIyl halides, 86. С —СНЗ
steric crowding is у•сгуIess.So, it wou1dprefer to undergo
SN2reaction. 11.1РАС
пате is 3-bromopentane,
78. (а) Gcmdihalidc•s опtreatmcntwith alcoholicКОН giws 87. Пиеto c«jugation oflonepair0fCl with л bond,partial
а1Кутте
asfollows : dM1blebondcharacterdecreases
bond length thafs
why compound(d) has shortestC—Cltx)nd length.
R —CH2CX2
акКОН 88. (с)
—2H.x

79.
80. (d) 4-ВготоЬиъ1•епсisnot ап a11yIichalide сиз - Н —СПз СНА — —СН —СНз

епе
2' сафоса['ол

ВГ снз вт —Н- shlft снфн

снз-сн юн ен снз --сн енз
ЗАоп»-2-пМЬуЫъ 1-епе снз

вгсщ-сн юн енз юн: ен:вг снз -н

81. (d) АИ Compounds
have tertiary alkyl дгоирbut bond -сн:-сн
betweenсатЬопand iodine(С — 1)is weakest due
to higher ditTcrencein sin• ofcarbonand iodine,
82. (к» Fluoroalkanesаге dit1icu1tto preparedirectlybecause
t10urination0f hydrocarbonswith риге F2 gas оссигк
explosively.Therefore theseаге preparedby treating a[kyl
chlorideог bromidewith saltssuchasHg2F2,АДЕ The снз н
reactionis calledswartsreacti01T.
89.
с н ВГ
СНзВг+Адн-+СНзЕ+АдВг (d) [ + ВГ2
Вт
(transreagent)

83. н снз снз

(trans-2-butene) (Meso)

Nuc1eaTsubstitution will not take р1асе. 90. (а) Сат[юпin yvhich four bonds аге ditTerentis aS
chiralсагЬоп.
84. ate.КОН
не — Гм — сЙ:— ёнз
ВГСН:- СН2Вг—.NCCH2.CH2CN
Вт

85. (С) снз— сн 91. (а) Dehydrohalogenation

(b--elimination)(xcurs аз:

—4СНЗ
КОНЖ, (excess'

[• • me•thylbutatk• апа
тоге •ubq'tutedАспе
 BrCH2—CH2Br —NCCH
KCN
2CH2CN
Br

85. 91. Dehydrohalogenation (b—elimination) occurs as:

CH3 KOH ale. (excess)

t - Bromo- 2 methylbutane Ph
conjugatedand
moresubstitutedAlkene

Haloalkanes and Haloarenes c-47

92. (c) mechanism is favoured by polar protic solvent,
93. (b) Iodine is a better leaving group than Cl. Br and F.
94. (c) Methanolhas higher dielectricconstant(32) than
other given compounds.
95. (d)
96. g') Since lis a better leaving group, and upon leaving, it
will form seconday carbocation (stable) in the compound
I-lodo-2 methyl propane.
97. (a) Boilingpoint ofCH31is 420C which indicates that it is
liquid at temperature. CHgI is larger molecule so it
has strenger vander Waal's force of attraction than others, interactionsandhencethe t»iling points-
98. Para-dichl(rotxnzene
has mestsylllmetricalstructure 109. (d) Thionyl chloride is preferred over PC13and PC15for
than others. It is f«md as crystalline lattice form, theref«e, it
has highe< melting mint (52 0C) due to symmetrical structure.
O
106. (a) bondlength increasesand bonddissociation
enthalpy decreases. therefore. reactivity order is
107. (d) SNImechanism does not depend on the concentration
of nucleophile. 20 alkyl halides are more reactive than I o
alkyl halidestowardsSNImechanism,because29
carbocationis morestablethan Io carbocation.
108. (a) As the tvanchingincreasesin isomericalkylgroups,
contactsurfaceareaofmolecule
decreases; van
der Waalforcesdecreasereducingintermolecular
the preparation of alkyl chlorides from alcohols because
Thionylchloridegives pure alkyl halide as other two
products (S02 + HCI) are escapable gases.
(CH3)3C Br
110. t)) Dryether

- C—C - + 2 NaBr
99. (co (i) (ii) and (iv) are correct.
100. (c) For the same alkyl group, the boiling points ofalkyl CHs CH
halides decrease in the Order 111. (d) Chlorinationof nitrobenzeneleadsto the formation
RI> RBr RF of In-nitrochlorobenzene because —NO
2group deactivates
This is Ixcause with the increase in size and mass thering txcauseit is metadirecting.
atom,themagnitudeofvanderWaal'sforcesincreases. 112. (c) Alkyl iodide can IN prepared by treating alkyl halides
101. (c) alkyl fluorides are obtained by heating alkyl chlcyide with Nal in presenceof acetone.It is calledFinkelstein
bromide in the presence of metallic fluorides like AgF
SbFy the reaction is known as Swartz reaction.
R-X + AgF/Hg:F2 R- F + AgX\Hg2X2 R-X+Na1 —i R-1+NåX
102. (i) Freeradicalsubstitution
reaction Also. Nal is soluble in acvtme Hit NaBr/'NaClarenot soluble.
sunlight 113. 0)) Alkylbenzenecannot be preparedby FriedaI Crafts
(CH3)4C+C12 «H3)3C-CH2 -Cl alkylation oftxnzene as di, tri alkylated benzenes are also
Freeradicalsnexmallydonotrearrange.
103. (a) Nal is solublein acetoneor methanol.gives I which 114. (c) In allylic halides hydrogenatomis bondedto sp3
undergoesSNIreactionwithRBror RCIto form hybridisedcarbonatom. Whereasin vinylichalide,
todoalkanes.
I has lowerreactivityas a nucleophile. hydrogenatom is bondedto sp2hybridisedcarbonatom.
thereforeiodoalkanecannot be preparedby direct
iodination.Finkeisteinreactionis bestmethodfor the CHgCHC12 CH2-CH2
preparationof iodoalkanes.
104. (a) I-I-Fand H-CIbondsare strongerthan H—Br
bond.
or H—CI
bondsare not brokenby the alkoxyfree Ethylidene chloride
radicals obtained from peroxides. while HI is weaker than (gem-dihali&) Ethylenedichloride(vie-dihalide)
HBr as it is troken by the alkoxy frec radicals obtained 115. 5; The compound is C3H6C12and the number ofpossible
fromperoxides.but the iodineatomsso, formedreadily
combinewith eachotherto give iodinemolecules,rather compunds is 5.
than attackthe doublebondof alkenes. 116. Oxidative;RH+C12 RCI
IOS. (n) Iodine forms esters with the silver salts, this is known
Oxidation No. ofCl is decreasing from O (in C12)to —l
as the Birnbaun-Simonini reaction.
(in RCI). So it is an oxidative process,
2RC02Ag + + C02 + 2Ag1
с-48 Chemistry
117. Ally1ic ; Compoundsin %hich thehalogen at0m is bonded
to sp3 hybridisedсатЬопatom next to carbonсатЬоп- З
Веплзу-1 petoxide•
double bond аге known as allyl halides.
СНЗСН = СНС (ВО (СНА 121. False; In Согеу House symthesis 0fa1kanes, a1kyl ha1ide
118. Ch10rotxnzene•, reacts with 1ithium dia1ky4сиргме

сис1 (Sandmeyer reactiM1)

RX+LiR2Cu -R'R КСИ LiX
C6H5N2C1
122.тое;
АIС1,
119. Bromotxnzene;

сен reaction

Si[v
СбЩ-сн -снз

123. Тт•ие
ВготоЬепгеве
124. Тгт; reaction а1КуА
halide. агу1halideands«iitnn
120. Тгие,• Per0xide etTectis 0bservedоп1у in casc 0f НВт.
in presence0fether is knowT1as Wurt7 f1tting reaction
Therefore, addititm ofHCl to cven in the prcsence 0f
txnzoyl voxide tx•curs according to MaTkoynikov's ги1е • СОН,С1+ 2Na + СIСНз—• СЬНЗСНЗ + 2NaC1