Problems 289

PROBLEM 1554 Drawshapesofthefollowing oxyacid ofsulphur andindicate oxidation statesof

sulphur.
(a) HSO
2 3 (b) HSO
2 2 5 (c) HSO
2 2 4 (d) HSO
2 2 3
(e) HSO
2 2 6 (f) HSO
2 5 (g) HS2 O.
2 8

PROBLEM 1555 Howsulphuricacidismanufacturedbycontactprocess?

PROBLEM 1556 Provide twomethodbywhich sodiumthiosulphate issynthesized. Whythiosulphuric
acidcan ’tbemadebyaddingacidtoaqueoussolutionofthiosulphatesalt?
PROBLEM 1557 Completethefollowingchemicalreactions:
(a) F2+HO2 → (b) Cl 2 +CO →
(c) Cl 2 + NH 3(excess) → (d) Cl 2 +NaOH →
(e) Si O2 + HF →
PROBMEL 1558 Completethefollowingreactions:
(a) Cl 2O+ NaOH → (b) HCl O4 + PO4 10 →
(c) Cl O2 + NaOH → (d) KBr O3 + F 2+ KOH →
(e) Cl 2O 6+NaOH → (f) Cl 2O 6+HF →

PROBLEM 1559 Whyitisnot possible toproduce F2 byelectrolysis ofaqueous NaF,aqueous HFor

anhydrousHF?

PROBLEM 1560 (a) Drawstructuresof OF2 , Cl2O, OF2 2 and I 2O.5

(b) Explainbondanglein OF2 andgiveareasonwhyitisdifferentin Cl 2O.
(c) Whyarethe OFbond in OF2 2 longer thanin OF2 while O—Obond in OF2 2 isshort compared
withthatin H 2O.2

PROBLEM 1561 Completethefollowingreactions:

(a) XeF2+HCl → (b) XeF4+KI →
(c) XeF4+SF 4 → (d) XeF2+HO2 →
(e) XeF4+HO2 → (f) XeF6+HO2 →
(g) XeF6+XeO 3 → (h) XeO 3+XeOF 4 →
2+
PROBLEM 1562 Ferric bromide ( FeBr3 ) whendissolved inwater, converted into Fe evolving
Br2 (g ) whilenochlorinegasisevolvedwhen FeCl 3 isdissolvedinwater.Justify.
PROBLEM 1563 When Cl 2 (g ) ismixedwith F2 (g ), ClF3 (g ) isproducednotthe FCl 3 (g ).Explain.
PROBLEM 1564 Explain whynitrogen formsextra-ordinary stable N 2 at room temperature but
phosphorusforms P2 onlyatveryhightemperature.
PROBLEM 1565 Explain sulphur formscompounds such as SF4 , SF6 , etc while oxygen, of the same
groupformsonly OF2 ?
PROBLEM 1566 In laboratory, HF and HCl can be prepared byreacting the metal fluorides and
chlorideswithconcentrated H 2SO 4 butHBrcan ’tbepreparedbythesameprocedure.Explain.
PROBLEM 1567 Discuss the acidic behaviour shown by boric acid in water and explain why it can’t
be titrated satisfactorily byNaOH.Whydoes glycerol or other such synvicinal diols/triols enhances its
acidicproperties?
290 ProblemsinChemistry

PROBLEM 1568 Explain why CCl 4 isunaffected bywaterwhile S iCl4 israpidlyhydrolyzed? In CCl 4
unreactivetowardssuperheatedsteam?
PROBLEM 1569 Explainthedifferencebetweentemporaryandpermanenthardnessinwater.
PROBLEM 1570 Whatis“Boiler-scale”andhowitisformed?
PROBLEM 1571 Describetheroleof Li 2CO 3 and BaSO 4 inmedicinalchemistry.
PROBLEM 1572 Sodiumhydroxide haslowermeltingpoint (322°C) than sodiumchloride (801°C),
electrolysisofNaClistheprimarysourceofNa-metalnotNaOH.Explain.
PROBLEM 1573 Completethediagrambelowindicating thereagents andspecial reaction conditions
neededtoproduceeachsubstance,using MgCO 3 asthestartingmaterial.
[F ] [E ] [D ] [A] [ ] [C ]
Mg( NO)
3 2 ← Mg( OH)2 ← MgO ← MgCO 3 → MgCl 2 →
B
Mg → MgN
3 2

[ G]
MgHPO 4
PROBLEM 1574 Consider thefollowing sequence ofactions andobservations (1)A smallchunk of
dryice is added to an aqueous Ca( OH)2 solution and a white precipitate formsinitially (2). After a short
time,precipitateredissolve.Writechemicalequationstoexplaintheobservations.
PROBLEM 1575 Although, both boric acid and phosphoric acid have three hydroxy groups,
phosphoricacidisaweaktribasicacidwhileboricacidisaweakmonobasicacid.
PROBLEM 1576 Providemissingreagentsbelow:
[A] [B] [C ] [D ]
Na 2BO4 7 ⋅ 10HO
2 → B( OH)3 → BO
2 3 → BCl 3 → B

E[ ]
→ BF3

PROBLEM 1577 Atypicalbaking powdercontain baking sodaandalum NaAl ( SO4 ) 2 asits active
ingredients. During process, baking powderundergoes areaction that yields CO 2 . Write a plausible
equationforthisreaction.
PROBLEM 1578 Whatisthe principle that underlies the factthat thalliumformsboth + 1 and + 3 ions
whilealuminiumformsonly + 3 ion?
PROBLEM 1579 Whycan ’taluminiumcookwarebeusedincookingstronglyacidicfood?
PROBLEM 1580 Inthe use ofaluminiumsulphate in watertreatment,the waterto be treated isusually
keptbetweenpH5andpH8.Whydoyousupposethisisthecase?
PROBLEM 1581 Completethefollowingreactions:
(a) N 2H( 4 aq.) + HCl → (b) NO(g )+ O(2 g ) →
(c) NO 2 (g ) + HO2 ()
l → (d) NH 3 (g ) + O 2 (g ) →
200°C
(e) NH 4NO 3 ()l →
PROBLEM 1582 Writebalancedchemicalequationforthefollowingreactions:
(a) ActionofAlover FeO 2 3 inpresenceofelectricspark.
(b) Actionofwaterover NaO 2 2.
(c) Oxidationof Pb 2+ (aq.)to PbO 2 inacidicmedium,byozone.
Problems 291

PROBLEM 1583 Writeanequationtorepresent:

(a) Theformationofoxygenbytheactionofwaterover KO 2 .
(b) Oxidationof Cl – to ClO –3 byozoneinacidicsolution.

PROBLEM 1584 How BF3 ispreparedfromborax?

PROBLEM 1585 Youhave available withyouelemental sulphur, chlorine gas, sodium metal and
water.Usingthesematerials,prepare(a) Na 2SO 3 (b) Na 2SO 4 (c) Na 2SO2 3 .
PROBLEM 1586 Whyis it that NF3 hasnodonor properties, but PF3 formsmanycomplexes with
metals?Giveoneexampleofsuchcomplexes.
PROBLEM 1587 Substance( A) is a gas with vapour density 8.5. On oxidation at high pressure and
temperature with a platinum catalyst, itgave acolourless gas( B), which rapidly turned brown in air
forming a gas( C). B and C werecondensed together to give substance( D),which reacted with water
forming a compound( E). E turned blue litmuspaper red. On treatment of E with acidified solution ofKI,
gas B was evolved, but when E wastreated with a solution of NH 4Cl ,astable, colourless gas( F) was
evolved. F did not support combustion, but magnesiumcontinued to burn in it. However, F reacted with
calcium-carbide in anelectric furnace, forming a solid( G), which wasslowly hydrolyzed bywater,
formingasolutionofsubstance A.Identify A to G.
PROBLEM 1588 Explain whyP—Obond length in POCl 3 is1.45 Å whereas the sumofthe single
bondcovalentradiiofphosphorusandoxygenis1.83Å?
PROBLEM 1589 Suggestareasonwhy PF5 isknownbut PH 5 isnot.
PROBLEM 1590 HCl( g) can be prepared from NaCl and H 2SO 4 . HBr and HI can ’t be made ina
similarwayfromNaBrandNaI.Explainwhythisisso?
PROBLEM 1591 WriteLewisstructureforeachofthefollowings:
+
(a) HCP (b) PH 4 (c) PH
2 4 (d) PO 3–
4 (e) PF5

PROBLEM 1592 Completeandbalanceeachofthefollowings:

(a) P4+Al → (b) P4+F 2 →
(c) P4+Na → (d) P4+Se →
(e) P4+Cl 2 → (f) P4+O 2 →
PROBLEM 1593 Oxygenformsdoublebondin O 2 ,butsulphurformssinglebondin S 8 .Explain.
PROBLEM 1594 Explain whyatroomtemperaturefluorine and chlorine aregases while bromineis
liquidandiodineissolidatroomtemperature.
PROBLEM 1595 Suggestshapesofthefollowingspecies:
+
(a) XeOF2 2 (b) XeF + (c) XeF3 (d) XeO 4–
6 (e) XeOF3 2

PROBLEM 1596 Sodiumhydroxide ishygroscopic–that isitabsorbs moisturewhenexposed tothe

atmosphere. A student placed a pellet of NaOHon watch glass. A fewdays later, she noticed that the
pelletwascoveredwithawhitesolid.Whatistheidentityofthissolid?
PROBLEM 1597 Discussthereactivityofwhite P4 .
PROBLEM 1598 Completethefollowingreactions:
(a) NH 3 Red
 →
hotCuO
(b) (NH)4 2 CrO
2 7 Heat
→
292 ProblemsinChemistry

PROBLEM 1599 Aqueous Cu(II)sulphate isblue coloured. When aqueous potassiumfluoride is

added to CuSO 4 solution, agreen precipitate isformed.Ifaqueous KClisadded instead, abright green
solutionisformed.Explain,whathappensineachcase.
PROBLEM 1600 Writebalancedchemicalreaction:

3 → (b) Li 4C+ HCl →

(a) HPO Heat
3
(c) HI + HNO 2 → (d) H 2S+ Cl 2 →
PROBLEM 1601 Arrangethefollowingspeciesinincreasingorderofindicatedproperty:
(a) PCl 5 , S iCl4 ,CCl 4 ,BCl 3 :Ioniccharacter
(b) F –,C 4– ,N 3– ,O 2– :Ionicradii
(c) F,Cl,Br,I:Ionisationenergies
(d) H 2O, SiO 2, CO 2 :Acidiccharacter

METALLURGY
PROBLEM 1602 DiscusstheprincipleinvolvedinextractionofMgfromseawater.
PROBLEM 1603 DiscussthemethodofextractionofMgfromitsdolomiteore.
PROBLEM 1604 Whyextractionofmagnesiumisimpracticalbychemicalreductionofitssalt?
2+ + 2+
PROBLEM 1605 Mg ion being smallerthan Na instead, Mg has verylowionic mobilityand
+
electricalconductivitycomparedto Na intheiraqueoussolution.Explain.
PROBLEM 1606 (a) HowEpsomsalt ( MgSO4 ⋅ 7H 2O) isobtained?Whatisitsuse?
(b) WriteabalancedchemicalreactionofMgmetalwithdilutenitricacid.
PROBLEM 1607 How Na 2CO 3 is manufactured bySolvay process? Whythis method fails in
preparationof K 2CO?3
PROBLEM 1608 Discuss the principle of purification of bauxite Al 2O 3 ⋅ 2HO
2 bythe following
processes:(a) Baeyer’sprocess(b)Hall ’sprocess(c)Serpek ’sprocess.

PROBLEM 1609 HowAlisextractedfrombauxiteore?Describethermitewelding.

PROBLEM 1610 Writethe reaction ofAlmetalwith dilute HCl, H 2SO 4 and NaOH.Whyconcentrated
nitricacidrenderAlpassive?

PROBLEM 1611 DiscussthereactionsinvolvedinpolymerizationofetheneusingZeiglercatalyst.

PROBLEM 1612 Discusstheprinciple involved inextraction ofironfromitsoxide ore, by carbon

reductionmethod.

PROBLEM 1613 Discusstheprincipleofrustingofironandmethodsofitsprotection.

Problems 293

PROBLEM 1614 Whathappenswhenironistreatedwith:

(a) Steam (e) Dilute HNO 3
(b) DiluteHCl (f) Concentrated HNO 3
(c) Concentrated H 2SO 4 (g) Boilingsulphur.
(d) Anhydrous Cl 2 (g )
PROBLEM 1615 How ferrous ammoniumsulphate hexahydrate (Mohr’s salt) is prepared in laboratory.
What are the advantages of using Mohr ’s salt as analytical standard of ferrous ion over ferrous sulphate?
PROBLEM 1616 Howanhydrous and hydrated ferricchloride isprepared inlaboratory. Whathappens
whenanhydrousferricchlorideis(a)heatedabove500°C(b)dissolvedinwater.
PROBLEM 1617 Howtinisextractedbycarbonreductionmethod?
PROBLEM 1618 WhathappenswhenSnisreactedwith:
(a) Cl 2 (g ) (b) dilute HNO 3 (c) conc. HNO 3 (d) conc. H 2SO 4 (e) NaOH
PROBLEM 1619 Howcopperisobtainedfromcopperpyrite,byself-reductiontechnique?
PROBLEM 1620 When copper isexposed to atmospherefora longer time,a green massdeposits on its
surface.Discussthechemicalreactioninvolved.
PROBLEM 1621 WhycopperispassiveindiluteHClordilute H 2SO.4
PROBLEM 1622 Discusstheactionofpureoxygengasovercoppermetalathightemperature.
PROBLEM 1623 Whathappenswhencopperisreactedwith:(Writecompletebalancedreaction)
(a) dil HNO 3 ,
(b) warmHClinpresenceofoxygen,
(c) warm H 2SO 4 inpresenceofoxygen,
(d) concentrated HNO 3 ,
(e) withaqueous Fe 2 (S O)4 3 ,
PROBLEM 1624 HowPbisextractedfromgalena(PbS)byself-reductionmethod?

PROBLEM 1625 Discussthereactionsinvolvedinactionof(i)airand(ii)pureoxygenonlead.

PROBLEM 1626 Leadreactwithhotconcentrated sulphuric acidinthebegining butreaction ceases

aftersometime.Explain.

PROBLEM 1627 Whathappenswhenleadisreactedwith:

(a) dilute HNO 3 (b) concentrated HNO 3 (c) NaOH (d) CH 3COOH
PROBLEM 1628 Howsilvermetalisextractedfromitssulphideore?
PROBLEM 1629 Discussthe roleofAgBrinphotography. Howdoes itreact with Na 2SO2 3 solution?
PROBLEM 1630 Silverornamentgetstarnishedwhenexposedtoatmosphereforalongtime,why?
PROBLEM 1631 Completethefollowingchemicalreactions:
Heat
3 →
(a) Ag + Concent r ated HNO (b) Ag + Concentr at ed H 4 →
2 SO

(c) AgBr + NaCN( aq ) → (d) AgCl + NH4OH →

294 ProblemsinChemistry

PROBLEM 1632 Howgoldisobtainedfromitsorebycyanideprocess?

PROBLEM 1633 HowdoesAureactwithaqua-regia?
PROBLEM 1634 Both copper and silver formsmonovalent ion like alkalimetal but alkali metalsare
highly reactive while Cu and Agare almostinert. What are the reasons forthis difference in reactivity?
PROBLEM 1635 How KMnO4 ismanufacturedfrom MnO2 ?
PROBLEM 1636 How K 2CrO2 7 ismanufacturedindustriallyfromchrome-iron?
PROBLEM 1637 Completethefollowingreactions:
Heat
(a) K 2CrO2 7 →
(b) K 2Cr 2O +KOH
7 →
(c) K 2Cr 2O +7 KCl +H SO2 (concentrated)
4 Heat
→

PROBLEM 1638 Writethebalancedchemicalreactionforthefollowings:

2 2 4 + HSO
(a) KMnO4+K CO 2 4 →
(b) KMnO4+O +H
3 SO2 4 →
(c) KMnO4+ FeC O2 +H
4 SO2 4 →
(d) KMnO4+HCl →
PROBLEM 1639 Drawshapeof FeCl 3 in(a)gaseousstate(b)ether(c)water.
PROBLEM 1640 FeCl 3 and FeBr 3 arewellknown,but FeI 3 hasdoubtfulexistence,explain.
PROBLEM 1641 Howpotashalumisprepared?Whatisitsmajorapplication?
Solutions 297

MOLE CONCEPT

1. Empiricalformula: 
Al K S O Elements



10.5 15.1 24.8 49.6 Masspercentage

= K Al SO
2 8  0.388 0.387 0.775 3.1 Moleratio



1 1 2 8 Simpleratio

Empiricalformulaweight = 258
Fromweightlossinformation:54.4ganhydroussalt ≡ 45.6 g HO
2
⇒ 258ganhydroussalt ≡ 238.89 g = 13.27 mol HO
2
⇒ Empiricalformulaofhydratedsalt = K Al SO ⋅
2 8 13HO
2

2. 1.0moleof KClO 3 ≡ 3.0 moleof Zn

5.104 3 × 5.104 3 × 5.104 × 65
mole KClO 3 ≡ moleofZn = = 8.124 g Zn
122.5 122.5 122.5
3. Applyconservationofmolesofsilverbeforeandafterprecipitateexchangereactionas:
1.8 x 2.052 − x
= +
143.5 188 143.5
where, x ismassofAgBrinmixedprecipitate.
⇒ x =1.064
1 1 x
Also, molesof CuBr2 = molesof AgBr= ×
2 2 188
1 x ×
⇒ Massof CuBr2 = × 223.5 =0.6324 (onsubstituting x)
2 188
Mass%of CuBr2 = 34.18
4. MolesofNaClinsample = 0.01= molesofAgClfromNaClinprecipitate.
2
TotalmolesofAgClprecipitate = =0.01393
143.5
⇒ MolesofAgClfrom KCl = 0.00393 = moles of KCl
⇒ MassofKClinsample =0.00393 × 74.5 = 0.2928g
Mass%ofKClinthesample = 29.28
5. ApplyconservationofmolesofAgbeforeandafterprecipitateexchangereaction:
x 1.94– x 2.4
+ = gi vesx = 1.483 g AgCl in mixed precipitate.
143.5 188 188
⇒ x ×
MassofNaCl = 58.5 = 0.6047g
143.5
1 1.94– x
⇒ Massof CaBr 2 = × × 200 = 0.243g
2 188
⇒ Mass% NaCl= 60.47,CaBr 2 = 24.3
298 ProblemsinChemistry

6. Applyconservationofmass: Ifproductcontain x g SO,2 massof SO 3= 22( − x ) g.

x 222( − x)
Computingtotalmassof S: + =10
2 5
⇒ x =12 ⇒ SO 2 = 12 g,SO =10g 3
7. Massof1.0Lsolution = 1025g
Massofethanolin1.0Lsolution = 8 × 46 = 368g
Massofsolventin1.0Lsolution = 657g
8
⇒ Molality (m) = × 1000= 12.17
657
8. 5.0moles(300g )ofaceticacidispresentin1.0kgsolvent.
⇒ 1300 g solution contain 5.0 moles of solute.
⇒ 1300/1.12=1160.7mLsolutioncontain5.0molesofsolute.
5
⇒ Molarity ( M ) = × 1000= 4.3
1160.7
9. Letthecombustionreactionis:
CH8 18 +On 2 → xCO + (8 − x ) CO 2 + 9HO 2
1 2650
n = (25 − x ); mol es of oct ane= = 23.246
2 114
Computingmassofproduct =23.246 × 28 x + (8– x ) × 44 × 23.246 +9 × 23.246 × 18 =11530
⇒ x = 1.125 ⇒ n = 11.9375
Incaseofcompletecombustion:
25
CH
8 18 + O 2 → 8CO 2+9HO2
2
Efficiency = (n/12.5) × 100= 95.5%
1.846
10. Molesof BaS O=
4 =molesof BaCl 2 ⋅ xH 2O= 7.923 × 10 –3
233
⇒ 7.923 × 10 –3 × (208 +18 x) = 1.936 ⇒ x≈2
11. Letthemixturecontain x g CuS O4 ⋅5H 2O.
x × 5−x
⇒ 159 + × 120 = 3 ⇒ x =3.72
249 246
⇒ Masspercentageof CuSO 4 ⋅ 5H 2O= 74.4
12. InthetwosamplemassratioofCato SiO 2 willremainsamesincebotharenon-volatile.
2x
Beforeheating,let x % CaCO3 ispresent ⇒ %Ca ispresent. ⇒ (85 − x )% SiO 2 ispresent.
5
Afterheating, 51.5% SiO2 and 41.15% CaO arepresent.
40
⇒ × 41.15 = 29.39% Ca is present.
56
Solutions 299
Now:massof Ca / SiO2 beforeheating=massof Ca / SiO2 afterheating.
2x 29.39
⇒ = ⇒ x = 49.97%
5 (85– x ) 51.5
13. Inthereaction of ClO 2 with water, products HCl O3 , HCl aswell asreactant ClO 2 contain one
chlorine atomeach, per formulaunit. Hence, total molesof acid produced will be equal to molesof
ClO 2 hydrolysed. Therefore, there isno need ofbalancing the reaction forcomputation ofmolesof
ClO 2 .
Molesofacid=molesofNaOHrequired = 0.18 = moles of ClO2
10
Totalmolesofgasintheflask = =0.406
0.082 × 300
0.18
Molefractionof Cl O=
2 × 100= 44.33
0.406
14. Thebalancedchemicalreactionis:
C 6H CH
5 +2KMnO
3 4 → CH 6 COOK
5 +2MnO 2+KOH+HO 2
11.5 × 100
Forpreparationof 11.5 g C6H 5COOK, theoreticalyieldshouldbe g
71
92 11.5 × 100
Massoftolueneneeded = × = 9.31g
160 71
15. Balancedchemicalreactionis:
2MnI 2 +13F 2 → 2MnF3+4IF 5
2 × 309 g MnI2 ≡ 13 × 38 gF 2
Q
13 × 38
12 g MnI2 ≡ × 12 = 9.59g
2 × 309
Actualrequirementof
100
F2=9.59 × = 12.78g
75
0.16 100
16. Mass%of Ca= × 40 × =25.6
100 0.25
0.344 32 × 100
Mass%of S= × = 41
233 0.115
0.155 14 × 100
Mass%of N= × = 17.9
17 0.712
⇒ Mass%of C =15.48
Now:
Elements Ca S N C
Mass% 25.6 41 17.9 15.48
Molratio 0.64 1.28 1.28 1.29
Simpleratio 1 2 2 2
300 ProblemsinChemistry

Empiricalformula = CaC2NS2 2 , empiricalformulaweight=156

Hence,molecularformula = CaC2NS2 2
17. Workinginbackwarddirection:
Inthelaststepmolesof (AgBr + AgI) = moles of AgI
0.4881– x 0.5868
⇒ + x = ⇒ x = 0.0933g
188 235 235
0.0933 100
Mass%of NaI= × 150 × = 29.77
235 0.2
NowsubtractingmassofAgIfrom1stand2ndprecipitategives:
Massof (AgCl + AgBr) = 0.3187g
and massofAgBr=0.3948g
y 0.3187– y 0.3948
Again + = ⇒ y = 0.245g
143.5 188 188
0.245 100
⇒ Mass%of NaCl= × 58.5 × = 50
143.5 0.2
Mass%of NaBr= 20.23
18. Letusconsider100gmixtureofNaIandNaClcontaining x g NaI.
 x 100 − x  142
Massof Na 2SO=4  150 + 58.5  × 2 =100 ⇒ x = 30.25
 
14 3
19. 5.0g NH 3 contains × 5 = 4.17 gN 2 and × 5 = 0.83 gH 2
17 17
Therefore,initially 9.17 gN 2 and 5.83 gH 2 werepresent.
Since N 2 islimitingreagent,maximummassof NH=3 11.135g
20. Balancethereactionintermsof ‘ n’ as:
4nXeF2 + —
(CH CH
2 )—
2 → —(CFCF
2 )—
2 n + 4nHF +4 nXeF 4
n
XeF2+2F 2 → XeF6
Formulaweightofoneunitoffluorinatedpolymer = 100 ⇒ for 1.0 kg, n =10
⇒ 40molesof XeF6 wouldberequiredandforthis 80.00 molesof F2 wouldbeconsumed.
⇒ m (F2) = 80 × 38 = 3040g= 3.04 kg
21. Weight lossisdue to conversion of NaHCO 3 into Na 2CO 3 : 31 g weight is lost per mole of
NaHCO 3 .
0.3 0.3
⇒ 0.3 g wt lossfrom molof NaHCO 3 producing molesof Na 2CO 3 .
31 62
Totalmolesofcarbonate =15 × 10 –3
3
⇒ Molesofcarbonateinoriginalsample =0.015 − =0.01
620
Massof Na 2CO 3 inoriginalsample =1.06 ⇒ 42.4%Na CO.
2 3
Solutions 301
x + 3 − x = 376
.
⇒ ⇒
2.45
22. x = 245
. m ( NaCl )= × 58.5 = 1.0g m% NaCl = 50%
1435. 188 188 143.5
23. If M ismolarmassof (CH)3 x Al Cly
0.643 x
m(CH 4)= × 16 = 0.222
M
0.643 y
and m ( AgCl )= × 143.5 = 0.996
M
x 355
.x
dividing: = 2, Also M = 15x + 27 + 35.5 y = 15x + 27 + = 32. 75x + 27
y 2
0.643x × 16
⇒ =0.222 ⇒ x = 1.98 ≈ 2 ⇒ y = 1
32.75x +27
24. Element C H N Cl O
Mass% 25 4.2 9.8 49.6 11.4
Mol% 2.08 4.2 0.7 1.39 0.7
Simpleratio 2.9 6 1 2 1
Empiricalformula C 3H NCl
6 2O
25. Massof AgCl = 0.09 × 143.5 = 12.915gwhichis95.77%oftotalppt.
⇒ Totalmassofprecipitate = 13.485g andmassofimpurity = 0.57g
⇒ Massof NaCl + KCl = 5.9g
x 5.9– x
⇒ + =0.09 ⇒ x = 2.94 g NaCl, 2.96 g KCl
58.5 74.5
m (Na 2O) = 1.558g ⇒ m % (Na 2O)= 31.16
m (K 2O) = 1.867g ⇒ m % (K 2O)= 37.34
26. Cl 2 +2KOH → KCl + KClO +HO
2 ...(i)

3KClO → 2KCl + KClO3 ...(ii)

4KClO 3 → 3KCl O4 + KCl ...(iii)
MultiplyEq.(i)by12andEq.(ii)by4andaddEqs.(i),(ii)and(iii)toobtain
12Cl 2 +24KOH → 21KCl + 3KClO 4 +12HO
2
852 415.5
1000g KClO 4 willbeproducedfrom
852
× 1000 = 2050.54g= 2.05 kg
415.5
1
27. 1.598 g TiO2 loses 0.16g oxygen therefore 80 g TiO 2 will lose 8gofoxygen( 2
moleof oxygen
atom).
⇒ Formulaofnewoxide = TiO 1 =Ti 2O 3
2–
2
302 ProblemsinChemistry

28. Since, the compound contain only one copper atomperformulaunit, its formulacan be assumedto
beas:
Cu(NH)3 x SO 4 ⋅ yHO
2 : M = 159.5 + 17x + 18 y
0.195
Molesofcompoundpresentin0.195g =
M
0.195
⇒ MolesofHClrequired = x = 30.63 × 0.1036 × 10
–3
…(i)
M
Also M gofcompoundcontain18 y gofwater
18 y
0.2gofcompoundwillcontain × 0.2g ofwater = 0.015 …(ii)
M
FromEqs(i)and(ii),
18 y 0.015
× 0.2 × M = ⇒ 18 y = 4.6x
M 0.195x 30.63 × 0.1036 × 10 –3
SubstitutinginEq.(ii)
18 y × 0.2
= 0.015 ⇒ 61.33x = 159.5 + 21.6x and x = 4, y =1
159.5 + 17x + 18 y

3 4 ⋅SO 4HO
Formulaofsalt = Cu( NH) ⋅ 2
Percentageyield: Molarityof CuSO 4 solution =1.1M
⇒ molesof Cu( NH)3 4 ⋅SO 4HO
⋅ 2 precipitate(theoretically) = 25 × 1.10 × 10 –3 = 27.50 × 10 –3
⇒ Theoreticalmassofsolid = 27.5 × 10 –3 × 245.5 = 6.751g
6.127 × 100
⇒ Percentageyield = = 90.75%
6.751
29. Massofwaterproducedinthereaction = 0.09912g
0.09912
⇒ massofhydrogen = g = 11 mg
9
1 0.3283 × 28.8
mmolof CO 2 = 2 m molofNaOH = = 4.73 = mmolofcarbon
2
⇒ massofcarboninstartingcompound = 4.73 × 12 = 56.76 mg
65.12 0.225
massofnitrogen = 28 × × × 1000 = 22 mg
760 0.082 × 298
and massofoxygen = 115.2 –( 56.76 + 11 + 22) = 25.44 mg
Now:
Elements Massmg. mmoles SimpleRatio
C 56.76 4.73 3
H 11 11 7
N 22 1.57 1
O 25.44 1.59 1
Solutions 303
Empiricalformula = C 3H NO
7
Empiricalformulawt. = 73
⇒ Molecularformula = C 6H 14NO 2 2
30. In order to obtain maximumyield froma reaction, the reactants mustbe supplied in stoichiometric
amountsothatnoreactantshouldbeleftunreacted.
Thebalancedchemicalreactionis,
Pb( NO)3 2 +2KI → PbI 2 +2KNO 3
Let x gofKIistaken
⇒ x ⇒ x
molesof KI = molesofPb (NO 3 ) 2 present =
166 2 × 166
⇒ x =5– x ⇒ x ×
x = 2.5g ⇒ massof PbI 2 = 460 = 3.464g
2 × 166 330 332
31. Letmixturecontain x g XH 4 then(5.628– x)g X 2 H 6 .
⇒ x x
molesof X H 4 = and, molesof X 2 H 6 =
M +4 2( M + 4)

⇒ x
5.628– x = (2 M + 6) …(i)
2( M + 4)
Mx + 2 Mx =
Also 5 …(ii)
M + 4 2( M + 4)
SolvingEqs.(i)and(ii)weget M = 27.8
32. Let one formulaunit ofArgyrodite contain ‘a’ mol of silver and b mole of Y . Therefore, moles of
a 
sulphideperformulaunitofmineralmustbe  + 2b .
2 

Hence, Ag a Y b S  a  + bH 2 → a AgS2 + bYS + bHS2

 + 2b
2 
2

PV =
Also, molesof H 2 required = 8.87 × 10 –3
RT
8.87 × 10 –3
⇒ molesofmineralpresentinits 10 g =
b
8.87 × 10 –3  a  
⇒ 10 =  108a + bM +  + 2b 32
b  2 
Solving 1127b = 124a + bM ( + 64) …(i)
108a 11.88
Also =11.88 ⇒ a = bM
bM 108
Substituting‘ a’inEq.(i),
124 × 11.88bM a=
1127b = + bM( + 64) ⇒ M = 72.6 g mol–1 and 8
108 b
Empiricalformula = Ag 8YS 6
304 ProblemsinChemistry

1.48
33. Massofuraniuminthesample = × 238 = 0.894g
394
Mass%ofuraniuminthesample = 89.4
Now UO 2(NO)3 2 + Na 2CO2 +4 HOx 2 → UO2(C O) 2 ↓+ 2NaNO 3
2 4 xHO

mmol 3.756 2.985

Here Na 2CO2 4 isthelimitingreagent,therefore,mmolof 2 4 ⋅xHO
UO 2(C O) 2 formedis2.985.

1.23
⇒ M(UO 2(C O 4 ⋅xHO
2 )) 2 = × 1000 = 412 = 238 + 32 + 88 + 18 x
2.985
54
⇒ x= =3
18
35.5
34. Massofchlorinein0.861gAgCl = × 0.861 = 0.231g
143.5
massofiodinein0.467gcompound = 0.254g
⇒ Iodine Chlorine
weight: 0.254g 0.213g
mole: 0.002 0.006
simpleratio, 1 3
⇒ Empiricalformula = ICl 3
35. CHn 2n + 2
+ O 2 → nCO 2 + HO 2

CO 2+2NH 2→ HN 2  CO  NH 2 +HO 2

1000 × 1000
mole = = 16666.67
60
236 × 1000
molesof CO 2 produced = × n = 16666.67 ⇒ n =12.5
14n + 2
Formulaofhydrocarbon = CH
12 26
250
36. Weightof NaHCO 3 dissolvedat 60° C = 164 × = 41 g
1000
Weightof NaHCO 3 dissolvedat0°C = 6.9g
Totalweightof NaHCO 3 dissolved = 47.9g
Weightof NaHCO 3 recovered = 150g
Totalweightof NaHCO 3 presentoriginally = 150 + 47.9 = 197.9g
197.9
%purity = × 100 = 79.16
250
46
37. Moleof CuSO4 insolution =
159 + 18x
46x
massof HO 2 insolution = 54 + × 18
159 + 18x
46x
⇒ 2 insolution = 3 +
molesof HO
159 + 18x
Solutions 305
46
159 + 18x
⇒ 0.05 =
46 46x
+3+
159 + 18x 159 + 18x
46 20 × 46
⇒ (1 + x ) + 3 =
159 + 18x 159 + 18x
46
⇒ 3= (19 – x ) ⇒ x = 3.97 ≈ 4
159 + 18x
38. Theroastingreactionis,
7
2F eS + O 2 → FeO2 3 + 2SO2
2 × 88 = 176 2 2 × 56 + 48 = 160
Fromtheabovereaction,
16gweightislostby176gFeS
176
4gweightwillbelostby × 4 = 44 g FeS
16
⇒ orecontain44%FeSbyweight.
39. Absorbanceofasolutionislinearfunctionofconcentration.
A1 C1 40 0.001
⇒ = or = ⇒ C 2 = 00007
. M
A2 C 2 28 C2
3
⇒ mol.wt.ofpolymer = = 42857 amu
0.0007 × 0.1
3 2 3 33
40. Volumeofonemolecule = ah = (10 –6 ) 2 × 3 × 10 –6 cm 3 = × 10 –18 cm 3
4 4 4
33
Molarmass = × 10 –18 × 6.023 × 10 23 × 1.2 = 939 × 10 3 amu
4
41. Volumeofsmallestcell =π r l = π(60 × 10 cm ) (6000 × 10 cm ) = 6.785 × 10 cm
2 –8 2 –8 –17 3

massofonesmallestcell = 7.6 × 10 –17 g

⇒ Molarmassofmothercell = 7.6 × 10 –17 × 24 × 60 × 6.023 × 10 23 = 6.6 × 10 10 amu
42. Massof CaSO 4= 0.5g
0.5
⇒ massofCaO = × 56 = 0.2058g
136
massof Mg 2P O 2 =7 0.5g
0.5
⇒ massofMgO = × 2 × 40 = 0.18g
222
0.2058
⇒ mass%ofCaOonovendriedbasis = × 100 = 21.8%
0.9437
306 ProblemsinChemistry

0.18
mass%ofMgOonovendriedbasis = × 100 = 19.07%
0.9437
Onairdriedbasis: CaO = 20.58% MgO = 18%, H 2O= 5.63%
43. Letthesamplecontain x gMohr ’ssalt [ FeS O4 ( NH) ⋅ O]
4 2 SO 46H 2

⇒ x × + 0.5 – x = 0.75
2
392 132 233
0.23
Solving x = 0.23g ⇒ Mohr ’ssalt = × 100 = 46% , (NH)4 2 SO 4=54%
0.50
0.2
Also molesofFein0.2gsample = x × = 2.347 × 10 –4
392 0.5
2.347 × 10 –4
⇒ massof FeO 2 3 obtainedonignitionof 0.2g sample = × 160 = 18.77 mg
2
44. Smallestvolume of AgNO3 would berequired whenthe entire massisdue tohighest molecular
weightconstituent.
Hence,forsmallestvolume,thewholemassshouldbeof BaCl 2 ⋅ 2HO
2
0.3
mmolof BaCl 2⋅2H 2O= × 1000 =1.229 m mol
244
mmolof AgNO3 required = 2 × 1.229 = 2.458
2.458
Volumeof AgNO3 required = = 16.38 mL (smallest)
0.15
Largest volume of AgNO3 would be required when entire massisdue to lowest molecularweight
constituent, i.e.,NaCl.
0.3
mmolofNaCl = × 1000 = 5.128 = m molof AgNO3 required.
58.5
5.128
⇒ Volumeof AgNO3 required = = 34.18 mL (largest).
0.15

ACID-BASE TITRATION
0.4305 × 1000
45. Totalm molofAgClfrom20mLsolution = =3
143.5
mmolesofAgClfrom HCl = 0.8 ⇒ mmolesofAgClfrom CaCl 2 =2.2
⇒ 1.1m moleof CaCl 2 wasconsumedforprecipitationofoxalatefrom20mLsolution.
1.1
Hence, total m molofoxalicacidin250mLsolution = × 250 = 13.75
20
−3
13.75 × 10 × 90
m%ofoxalicacid = × 100= 82.5
1.5
46. Thebalanceddisproportionationreactionis:
2P2O 3+6HO 2 → PH 3+3H PO
3 4
Solutions 307
meqofNaOHadded=6
meqof H 2SO 4 requiredforbacktitration =1.1
⇒ 4.9meqofNaOHneutralized4.9meqof H 3PO 4
49
⇒ Totalmeqof H 3PO 4 produced = 49= mmol H 3PO 4
3
2 49
mmolof PO 2 3 presentoriginally = ×
3 3
98 × 10 –3
⇒ Mass%of PO 2 3 = × 110 × 100 = 79.85
9 × 1.5
2–
47. mmolof CO 3 in10mL =10 × 0.05 × 2=1
In presence ofmethyl orange 3.235 mmol H + isconsumed in which 2mmol H + would be
requiredfor CO 2–
3 ,hence1.235m mol H + for HCO –3 ion.
−
10 × 10 3 × 100
⇒ m% CaCO=
3 × 100= 40
2.5
6.175 × 10 –3 × 162
m % Ca( HCO)
3 2 = × 100= 40
2.5
+
48. mmolof H requiredtoreachthephenolphthaleinendpoint =1.12
⇒ 1.12mmol Na 2CO 3 ispresentper10mLofsolution.
Now, V =17 mL and it contain 1.12 m mol of NaHCO 3 produced intitration inassociation with
original NaHCO 3 .
5mLofthissolutionrequired3.53mLacidtoreachthemethylorangeendpoint.
Q
3.53
∴ 17mLwouldrequire = × 17 =12 mL acid =1.92 m molH +
5
⇒ m molof H + consumedforneutralizationoforiginalbicarbonate =0.8
−3
3 li tr e = 112 × 10
m (Na 2CO )/ × 106= 11.872g
m (NaHCO 3)/ li tr e = 80× 10 –3 × 84= 6.72g
49. mmolofHCltaken = 7.5
mmolofHClleftunreacted =5.244
mmolofHClreacted =2.256 ≡ 1.128 m mol K2SO 3= 0.178gK SO2 3
m% K2SO=3 36.6%
50. mmolof NH 3 fromglycine = 2.5 – 1.8342 = 0.6658 = m mol of nitrogen.
massofnitrogen =9.3212 × 10 –3 g= 18.64%
Theoreticalmass%= 18.66
51. Chemicalreactionsinvolvedintheentireprocessare:
2Ca 3 (P O)4 2 +Mg → Ca 3P +Mg(PO)
7
2 3 2 +3CaO+ 2
O2
Ca 3P +6HO
2 2 → 3Ca( OH)2 + 2PH3
2P H3 + 4O 2 → PO
2 +3HO
5 2
308 ProblemsinChemistry

⇒ 2.4 g (0.1 mol)Mgwillproduce0.2mol PH 3 whichwouldrequire0.4molofoxygen.

⇒ Vol.of O 2 needed = 8.96 L, hencevol.ofairneeded = 42.66 L. at S. T. P.
52. Letthemixturecontain x g of Li 2CO,3 y gof NaHCO.3
30x 106 y
⇒ Afterheating + + 9.3 − (x + y) = 7.37
74 168
44x 62 y
+ =1.93 ...(i)
74 168
Fromtitrationinformation:
2x 2 y 9.3 − (x + y)
+ + × 2 = 0.18
74 168 106
32x 62 y
⇒ − = 0.24 ...(ii)
74 168
Solving,Eqs.(i)and(ii)gives x = 2.11 g, y = 1.825g
and Na 2CO 3 = 5.365g ⇒ NaHCO= 3 19.62%, Na 2CO=3 57.7%
4
53. M (acid) = × 1000 = 185.2
8 × 0.27 × 10
Formulaofacid =C HO
n 2n 2 ⇒ M =14 n + 32 = 185.2 ⇒ n =11
5 55
Now5gacidwillproduce × 11 = mol CO2 aftercompletecombustion.
186 186
TotalmolesofNaOHavailable =1.0
2 × 55 76
MolesofNaOHleftunreacted =1 − = in500mL
186 186
⇒ MolarityofNaOHafterprecipitationof Na 2CO =0.817
3
Therefore, 0.817 × 10 = 0.5 × V ⇒ V = 16.34 mL
54. Let10mLsolutioncontain x m mol NaHCO3 and y mmol Na 2CO 3 :
⇒ x + 2 y = 1.24 and x = 1.5 –1.26 ⇒ y = 0.5
⇒ m(NaHCO 3) = 0.24 × 50 × 10 × 84 = 1.008g = 20.16%
–3

–3
m(Na 2CO )3 = 0.5 × 50 × 10 × 106 = 2.65g= 53%
m(NaCl) = 1.342g= 26.84%
2NaOH
55. C xHOy +O
2 2 → xCO 2 → xNa 2CO 3
6.4 6.4 x 6.4 x
M M M
Let10mLsolutioncontain a mmolNaOHand b mmol Na 2CO 3 :
⇒ a + b = 14.5
64
. x
a + 2b = 18 ⇒ b = 3.5 ⇒ = 0.35 ...(i)
M
25 M 0.35 × 128
Also, =32 ⇒ M =128 ⇒ x= =7
100 6.4
Solutions 309
Also, 12x + y + 32 = 128 ⇒ y = 12
⇒ Formula = C 7HO 12 2
M (NaOH) = 1.8
56. Thebalancedchemicalreactionis:
xHCl → xNH 4 +Co +( x +3) Cl
+ 3+ –
Co( NH)
3 x Cl 3 +
1.58 1.58x 1.58( x +3)
165.5 + 17x 165.5 + 17x 165.5 + 17x
1.58 x 23.63 × 1.5
⇒ = ⇒ x=6
165.5 +17 x 1000
m(AgCl) = 0.053 × 143.5= 7.62g
5x 1 8 1 77x 1
57. × + x × + × = 098
. ⇒ x = 45g
100 53 100 50 100 40
58. meqof Na 2CO =0.6132
3 × 40 = 24.528 ⇒ m%NaCO=2 3 3.25
×
meqof NaOH = 23.046 40 = 922 ⇒ m%NaOH= 92.2
59. Letthesamplecontain x mol Na CO
2 3 and y mol NaHCO. 3
−
⇒ 2x + y = 18.1396 × 10 3 ...(i)
mmolofNaOHcombinedwith NaHCO 3 = 4.1
⇒ Totalmolesof NaHCO 3=16.4 × 10 –3 = y ⇒ x = 0.8698 × 10 −3
164. × 10 –3 × 84
⇒ m % NaHCO= 3 × 100= 91.84
1.5
−
0.8698 × 10 3 × 106
m % Na CO=
2 3 × 100= 6.15
1.5
60. Total NaOH = 0.2 mol,NaOHleftunreacted = 0.06 mol
NaOHcombinedwith CO 2= 0.14 mol producing 0.07 molof Na 2CO. 3
Lethydrocarbonis CH n 2 n +2
⇒ M =14 n +2

⇒ n = ⇒
0.07 n = 7, Molecularformula = CH
14n + 2 7 16

61. Formula = C nH O2 n :M2 = 14 n +32

Lethalf-solutioncontain x m mol Na 2CO 3 and y m mol NaOH.
⇒ x + y = 71.72
2x + y = 123.44 ⇒ x = 51.72
⇒ TotalNa CO
2 =103.44mmol
3
2n
⇒ = 103.44 × 10 –3 ⇒ n =6
14n + 32
Hence,acidis C 6HO12 2
–3
m(NaOH) = 123.44 × 2 × 10 × 40= 9.87g
–3 −3
62. Molesof NaHCO 3=19 × 0.25 × 2 × 10 = 9.5 × 10 = m%NaHCO=3 31.92
310 ProblemsinChemistry

10 –3
Molesof Na 2CO =
3 (26.66 − 9.5) × =8.58 × 10 –3
2
⇒ m%Na CO= 2 3 36.38; m% NaCl= 31.7
63. Let N 1 benormalityofHCland N 2 bethenormalityofNaOH
⇒ 20 N=1 96 N 2 ...(i)
2
Also, × 1000 +8 N 2 × 10 = 50 N 1
50
⇒ 4 + 8N =N
2 5 1
N 2 = 0.25, N 1 = 1.2
64. Letthemixturecontain x m mol K 2C 2O, 4 y m mol KHCO 2 4 and z mmolof H 2CO
2 4 ⋅ 2HO
2 .
Then, 2x + y = 20 ...(i)
y + 2 z = 20 ...(ii)
166x 128 y 126 z = 2725
+ + …(iii)
166 126
⇒ (20– y) +128 y + (20– y)= 2725
2 2
Solving, y = 10.83
⇒ x = 4.585
z = 4.585
⇒ m % KHC2O=4 50.87
m %K C2 O=2 4 27.93
m %H CO
2 2 4 ⋅ 2H 2O= 21.2
65. Letsamplecontain x m mol NH 4NO 3 and y m mol (NH)4 3 PO 4
0077
.
⇒ x + 3 y = 15 and y= × 2 × 10000 = 2.56
601
⇒ x =7.32 and m %NHNO= 4 3 58.56
66. Lethalfsolutioncontain a mmol Na 2CO and 3 b m mol NaOH
⇒ a + b = 0.55 and 2a + b = 0.8 ⇒ a = 0.258b = 0.3
Totalm molof Na 2CO = 3 0.5 =m molof CO produced
2
10.38 × 10 –3
Formulaofacid =C HO
x y 4 ⇒ molesof CO 2 produced = ⋅x
M
Also, 0.168 g acid = 16.18 × 0.125 × 10 –3 equi val ent⇒ M =166
10.38 × 10 –3 x
⇒ =0.5 × 10 –3 ⇒ x =8
166
Also, 12x +y + 64 = 166
⇒ y=6 ⇒ Formula= C 8HO6 4
M (NaOH)= 0.016M
67. Molesof Na 2CO =0.1
3 × 10 × 11.32 × 10 –3 =11.32 × 10 –3
Solutions 311
–3
11.32 × 10 × 106
⇒ m % Na 2CO=3 × 100 = 40
3
0.306 × 1000
mmolesof AgCl= =2.13 from10mLstocksolution.
143.5
⇒ MolesofNaClinoriginalsample = 21.3
( − 11.32) × 10 −3 = 9.98 × 10 −3
⇒ Mass%of NaCl= 19.46
TotalNaOHconsumedfor10mLstocksolution =0.05 × 42.64 = 2.132
⇒ NaHCO 3 inoriginalsample = (21.32 – 11.32) × 10 –3 =10 –2 mol.
100
⇒ Mass%of NaHCO 3=10 –2
× 84 × = 28
3
68. mmolof Na 3PO =24.4
4 × 0.1 × 5= 12.2
100
⇒ m % (Na 3PO )=
4 12.2 × 10
–3
× 164 × = 50
4
Also,ifthemixturecontain y mmol Na 2HPO 4 and z mmol NaH 2PO 4

Then 12.2 × 3+2 y + z =23.572 × 0.5 × 5= 58.93

⇒ 2 y + z = 22.33 ...(i)
Also, 142 y + 120 z = 2000 ...(ii)
Solving; y = 6.9 and z = 8.53
100
⇒ m% Na 2HPO =6.9
4 × 142 × 10 −3 × = 24.5
4
m%NaH PO=2 4 25.5
69. Weightloss = 5 × 0.265 = 1.325g
106gweightislostfrom136gof Li HCO3
Q
136
⇒ 1.325g weightwillbelostby × 1.325 = 1.7g ⇒ m% LiHCO 3= 34
106
mmolesof H 2SO 4 usedforneutralizationof Li 2O and Na 2CO 3=4– 0.579= 3.421
⇒ Totalm molof Li 2O+ Na CO 2 =3 34.21
Also, molesof Li 2O= 12.5 × 10 –3
⇒ molesof Na 2CO =21.71
3 × 10 –3
⇒ m% (Na 2CO )=
3 46 ⇒ m% NaCl= 20

70. Letthemixturecontain x g Li HCO,3 y gNaHCO 3

Onheating: 2NaHCO 3 → NaCO

2 +HO+CO
3 2 2
168 106
2Li HCO3 → Li 2O+ H 2O+ 2CO 2
136 30
CaCO 3 → CaO + CO2
100 56
312 ProblemsinChemistry

30x 106 y 56
Massofresidue = + + (5 − x − y) = 2.58
136 168 100
 56 30   56 106 
 −  + −  = 0.22
 100 136  x  100 168  y
⇒ 0.34x –0.07 y =0.22 ...(i)
Also,m molofNaOHreactedwithbicarbonates = 5 –1.53 = 3.47
⇒ Totalm molof Li HCO3 + NaHCO = 3 34.7

⇒ x + y = −
. × 10 3
347 ...(ii)
68 84
Solving,Eqs.(i)and(ii)gives y =1.686g, x =1
⇒ m% Li HCO=3 20, NaHCO= 3 33.7
−3
71. Molesof NaHCO 3 in 1.0g mixture = 2 × 10 ⇒ m% NaHCO= 3 16.8
–3
AlsomolesofHClconsumedby1gmixture =10.53 × 10
–3
×
Outofthis 2 10 molHClwillbeusedupby NaHCO 3
⇒ 8.53 × 10 –3 molHClwillbeusedupby Na 2CO and
3 CaCO 3
−3
⇒ Moles of (Na 2CO +3 CaCO ) 3= 4.265 × 10 /g of mixture.
Also5gmixtureloses0.75gwt.andmixturecontain0.84g NaHCO 3
⇒ 0.31gweightislostby NaHCO 3 andremaining 0.44g by CaCO 3
Therefore,5.0gmixturecontain0.01mol CaCO 3 , m% CaCO 3= 20
Molesof Na 2CO /g
3 ofmixture = (4.265 – 2) × 10 –3 =2.265 × 10 –3
⇒ m%of Na CO=
2 3 24 ⇒ m% of NaCl= 39.2
72. Lettheoriginalsamplecontained‘ a’m molof CaCO 3 and b mmolof NaHCO 3 .Therefore,
CaCO 3 → CaO + CO2
2NaHCO 3 → NaCO
2 +CO
3 +HO
2 2
b
mmolof CO 2 produced = a +
2
CO 2 + NaOH → NaHCO 3
b b
a+ a+
2 2
NaHCO 3+NaOH → Na 2CO 3
b x
a+ – x
2
Tillphenolphthaleinendpointm molofHCl =5= x
b
Afterphenolphthaleinendpointm molof NaHCO 3 presentinsolution = a +
2
⇒ b
a + = 15 …(i)
2
Solutions 313
Also,fromprecipitationinformation:
b = 0.985 × 1000 =
5 ⇒ a = 10, b = 10
2 197
⇒ massof CaCO 3=1g , massof NaHCO 3= 0.84g
m%: CaCO 3=50, NaHCO =342, Im pu rit y = 8%
73. Inpresenceofmethylorange,thewholeNaOHand Na 2CO 3 areneutralized.
⇒ meqofHCl = 16 × 0.25 = 4 = meqof(NaOH + Na 2CO 3 ) = meq.ofNaOHoriginal
⇒ TotalmeqofNaOHinoriginal1.0gsample = 4 × 5 = 20
20 × 40 × 100
⇒ mass%ofNaOH(original) = = 80
1000
Now,letusassumethatin20mL, x mmolofNaOHhasgotconvertedto Na 2CO 3
⇒ In20mL, mmolofNaOH = 4– x
x
mmolof Na 2CO=3
2
In2ndtitration,HClusedintitrationofNaOH + Na 2CO 3 =5 × 0.1 –9 × 0.2 = 3.2

⇒ uptophenolphthaleinendpoint,m molofHClrequired = 4 – x + x = 4 – x = 3.2

2 2
⇒ x = 1.6
x 5x
⇒ Total Na 2CO 3 formed = × 5 = =4
2 2
mmolofNaOHleftunreacted = 20 – 4 × 2 = 12
8 × 40 4 × (106 + 18)
⇒ weightof1.0gofexposedsample =1 – + = 1.176g
1000 1000
4 × 106
⇒ weight%of Na 2CO 3 inexposedsample = × 100 = 36.05%
1000 × 1.176
50 × 0.0452
74. Molarity( M )of NH 4SCN solution =
22.98
50 × 0.0452
⇒ mmolof Cl CH2 COOH presentinbeverage = 50 × 0.0452 – 10.43 × = 1.234
22.98
⇒ massof Cl CH2 COOH = 1.234× 94.5= 116.6 mg
75. Let20mLstocksolutioncontain x mmol Na 2CO2 4 and y mmol H 2CO2 4

⇒ 2x + 2 y = 23.34 × 0.04 × 5 = 4.668

and 2 y = 26.67 × 0.1 = 2.667 ⇒ x = 1 and y = 1.3335
5 × 10 –3 × 134
Therefore, m%of Na 2C O=
2 4 × 100 = 33.5
2
1.3335 × 5 × 10 –3 × 126
4 ⋅ O=
m%of H 2CO2 2H 2 × 100 = 42
2
314 ProblemsinChemistry

76. Letthesamplecontain x mmol (NH)4 2 SO 4 and y mmol NH 4NO 3 .

+ 1
In20mL,m molof NH 4 ion = (2x + y)
5
+ 1 70
mmolofNaOHreactedwith NH 4 = 5 – 9 × × = 3.5
14 30
1
⇒ (2x + y) = 3.5 …(i)
5
466 100
Also x= × = 6.25 ⇒ FromEq.(i) y=5
233 32
6.25 × 10 –3 × 132
⇒ mass%of (NH)4 2 SO 4 = × 100 = 55
1.5
5 × 10 –3 × 80
mass%of NH 4NO=3 × 100 = 26.67
1.5
77. Thereactioninvolvedis:
3 4 ]Cl 2 +4NaOH → Na 2[Zn(OH) 4 ]+ 4NH 3+ 2NaCl
[ Zn( NH)
10
mmolofNaOHconsumed = 15 – = 13.33
6
13.33
⇒ mmolofcomplexpresent = = 3.33
4
⇒ mass% = 3.33 × 10 –3 × 204 × 100 = 68
10
Alsototalm molof Cl – ionspresentinfinalsolution = 3.33 × 2 + = 8.33
6
⇒ massofAgClformed = 8.33 × 10 –3 × 143.5= 1.195g
78. Fromcharge balance: x + y = 2z …(i)
Alsoif M beempiricalformulaweightthen
1.2 1
× × 1000x = 1.1 …(ii)
M 5
1.2 15
× × 1000 y = 4.95 …(iii)
M 50
DividingEq.(iii)by(ii): 3x = y
Now,substituting x = 1, y = 3, z = 2
Empiricalformula: KH 3(C O) 2 4 2
50 × 0.04
79. Normalityoforiginal H 2SO 4 solution = = 0.1
20
In20mL, meq.of H 2SO 4 leftunreacted = 40 × 0.02 = 0.8
⇒ meq.of Ca 3 (P O)4 in20mL = 20 × 0.1 – 0.8 = 1.2
⇒ Totalmeq.of Ca 3 (P O)4 2 =1.2 × 5=6
6 × 10 –3 310
⇒ mass%of Ca 3 (P O)4 2 = × × 100 = 15.5%
2 6
Solutions 315

80. Thechemicalreactioninvolvedis:
6NH 4Cl O4+ 10Al → 5Al 2 O 3+ 3N +2 6HCl + 9HO 2
3 1
moleofAlreacted = =
27 9
1 6 1
moleof NH 4ClO 4 present = × =
9 10 15
117.5 100
⇒ mass%of NH 4ClO 4 = × = 78.33
15 10
1
AlsomolesofHClproduced =
15
molesofNaOHtakeninitially = 0.1
1
⇒ molesofHClrequiredtoneutralizeleftoverNaOH = 0.1 – = 0.033
15
33
Vol.ofHClrequired = = 66 mL
0.5
81. Volumeofroom = 150m = 150 × 10 L
3 3

150 × 10 3
⇒ Totalmoleof CO 2 intheroom = × 0.01 = 60.9756
0.082 × 300
Reaction: 4KO 2+2HO2 → 3O 2+4KOH
KOH +CO 2 → KHCO3
⇒ molesof KO 2 inoriginalsample = 60.9756
Reactionof KO 2 with H 2SO 4 is:
4 → KS
3
2KO 2+H SO
2 2 O +H
4 O+
2 O
2 2

molesof KO 2 requiredtoneutralize H 2SO 4=2 × 100 × 0.1 × 10 –3 =0.02

5000
massof KO 2 required = × 0.02 = 1.64g
60.9756
3.25 × 1000
82. Equivalentweightofacid = = 63.35 ⇒ Molarmass = 190
68.4 × 0.75
Formulaofacid = CH
n 2 n –1 (COOH) 3 ⇒ 14n – 1 + 135 = 190 ⇒ n=4
Formula = C 7HO10 6

REDOX TITRATION
83. (a) 2.525 × 10 mol
–3

(b) meqof VO 2+ =meqof MnO–4 consumedinlaststep =0.86 × 0.02236 × 5 =9.6148 × 10 –2

Totalmeqofpermanganatetakenagainst Fe 2+ and VO 2+ =1.4087
⇒ meqof KMnO4 usedupby Fe 2+ =1.4087 – 9.6148 × 10 –2 =1.3125
⇒ Molesof Fe 2+ titratedwith KMnO=
4 1.3125 × 10
–3
316 ProblemsinChemistry

(c) meqof Fe 2+ consumedwith CrO

2
2–
7 = 2.525 – 9.6148 × 10 –2 =2.428
⇒ Molesof Fe 2+ consumedwith CrO
2
2–
7 = 2.428 × 10 –3
(d) Massof V= 9.6148 × 10 –2 × 51 × 10 –3

9.6148 × 51 × 10 –5
⇒ %
mV = × 100= 0.25
2
2.428 × 10 –3 2428
. × 10 −3
molesof Cr= ⇒ m%of Cr = × 52 × 100 = 2.1
3 3× 2
423.3 × 10 –3
84. In20.00mLsolutionmolesof U 3O=8 =5.027 × 10 –4
842
⇒ Molesof U 4+ in20mL =1.508 × 10 –3
⇒ meqof U 4+ in20mL = 3.016
meqof MnO –4 requirefor20mL =0.024 × 27.23 × 5= 3.2676
⇒ meqof Fe 2+
=3.2676 − 3.016 = 0.2516
0.2516
⇒ Massof Fe 2O=3 × 160 × 10 –3 =20.128 × 10 –3 g
2
20.128 × 10 –3
⇒ Massof FeO
2 3 associatedwith100g UO 3 8 = × 100 = 4.755
423.3 × 10 –3
4.755
⇒ m%of Fe O=
2 3 × 100= 4.54
104.755
85. Letsamplecontain x mmol Pb 3O and
4 y m molof PbO 2
2.7
⇒ 2x +2 y = × 2 × 1000 –8 × 0.02 × 5 × 25 = 20
134
⇒ x + y =10 ...(i)
5 × 4.48
Also, N (KMnO)4 in2ndtitration = =0.4
5.6 × 10
⇒ . × 10 × 10 ⇒
(3x + y) × 2 = 04 3x +y = 20 …(ii)
Solving,Eqs.(i)and(ii)
x = 5 = y ⇒ m(Pb 3O )4 = 3.425 g, m(P bO2 ) = 1.195 g
⇒ m% Pb 3O=4 68.5 m% PbO=2 23.9
86. 2x = 2y+z
1.7225 1.7225 –3
Also, y+ z =10 × 2 × 10 ...(i)
M M
1.7225 1.7225
z =15 × 2 × 10
–3
2y + ...(ii)
M M
SolvingEqs.(i)and(ii)gives =
y z ⇒ x =1.5 y
Now,substituting y =1, gi vesCu 3(CO) 3 2 (O H)2
Solutions 317

87. meq.of KMnO4=0.1 × 22 × 5= 11 = meq.of CaCO

2 4 ⇒ mmolof CaCl 2 =5.5
Massof CaCl 2 pergramofmixture =5.5 × 111 × 10 –3 =0.61g
MassofNaClpergramofmixture = 0.39g
 1000 1000 
⇒ – ∆T f = K f  3 × 5.5 × 5 × 10 –3 × +2 × 6.67 × 5 × 10 –3 ×  =2.92
 95 95 
⇒ T f =– 2.92C°
88. Lethalfsolutioncontain ‘ a’ mmol Na 2CO and 3 ‘b’ mmolNaOH
⇒ a + b =15 and 2a + b = 25 ⇒ a = 10 = m molof Na CO 2 3
⇒ Totalm molof CaC 2O 4= 20
Also, . × 10 ⇒ x = 20 meqof Na CO
20 × 2 + x = 10 × 06 2 2 4
134 100
m% Na 2C O 2 =20
4 × 10 –3 × × = 31.53%
2 4.25
50 × 0.25
89. M(KMnO4)= =0.055
45 × 5
⇒ Normalityof KMnO4 inalkalinemedium = 0.167N
25 × 0.1
⇒ V= = 15.00 mL
0.167
90. I. meqof KMnO4 = 375
. × 0005
. × 5 = 93. 75 × 10 −3
⇒ Totalmeq.of CO
2
2–
4 =93.75 × 10 –3 × 5= 0.46875
⇒ mmolof K 3[Fe( C O)
2 4 3 ] ⋅ 3H 2O= 78.125 × 10 –3
II. meqof MnO–4=17.5 × 0.005 × 5= 0.4375
⇒ Totalmeqof Fe 2+ ion = 0.875 = m molof Fe 2+

⇒ mmolof Fe 2+ from FeCl 3 ⋅ 6H 2O= 0.875 – 78.125 × 10 –3 =0.7968

0.2155
⇒ Mass%of FeCl 3 ⋅ 6H 2O= × 100= 71.84
0.300
91. Letmixturecontain x m mol H 2CO2 4 ⋅ 2HO2 , y m mol Na 2CO
2 4 and z mmol NaHCO
2 4

⇒ 2 y + z = 40 ...(i)
and 2x + z = 60 …(ii)
Also, 126x + 134 y + 112 z = 6100 …(iii)
Solving,Eqs(i),(ii)and(iii),gives z = 20, x = 20 and y = 10
2.52
⇒ 2 4 ⋅ 2H 2O=
m% of H 2CO × 100= 41.31
6.1
1.34
m% of Na 2C O=
2 4 × 100= 21.96 ⇒ m% of NaHCO=
3 36.73
6.1
318 ProblemsinChemistry

92. meqofhypo = 4= meq ofI 2

⇒ 2m molof I 2 isproducedfromunreactedIClas ICl + KI → KCl +I 2
⇒ mmolofIClcombinedwithoil =0.5
Also,0.127goil ≡ 0.5 m mol of ICl.
0.5 0.5 × 100
⇒ 100goil ≡ × 100 m molof IClor m molofI 2
0.127 0.127
100 × 0.5
⇒ Massof I 2 requiredfor100goil = × 254 × 10 –3 = 100g
0.127
93. meqof KMnO4 reactedwithnitritein10mLsolution = 2 −1 = 1
⇒ Totalmeqof NO –2=100 =m molof NaNO 3

100 × 85 × 10 –3
⇒ m%of NaNO=
3 × 100= 56.67
15
m%of Mg( NO) 3 2 = 43.33
Totalm molesof O 2= 100 + 44= 144
mmolof NO 2= 44 × 4= 176
 NO 2 
⇒ Molar ratio   = 1.22
 O2 

2 3 taken = 75 × 0.0125 × 4= 3.75

94. meqof AsO
meqof MnO –4 usedupinbacktitration =0.1862
87 100
⇒ meqof MnO2=3.5638 ⇒ m%of MnO2=3.5638 × × 10 –3 × = 68.9
2 0.225
95. Molarityoforiginal K 2CrO
2 7 solution =0.85 × 10 –3 M
⇒ mmolof K 2CrO
2 7 initially =2.25 × 10 –3
Tinitial = 41.5 ⇒ ( Absor bance) ini t i al=58.5
T fi nal =43.5 ⇒ ( Absor bance)fi nal =56.6
∝
Absorbance [concentration]oramount.
Q
∴ 56.6%absorbancecorrespondto
2.25 × 10 –3
× 56.6 = 2.177 × 10 –3 mmolK CrO 2 2 7
58.5
⇒ mmolof K 2CrO
2 7 reactedwithalcohol = 7.3 × 10
–5

meqofalcoholinair = 7.3 × 10 –5 × 6= 4.38 × 10 –4

meqofalcoholin56.5mLofblood = 4.38 × 10 –4 × 2300 = 1.0074
⇒ meqofalcoholin100mLblood= 1.783
46
m(C 2H OH)
5 = 1.783 × = 20.5 mg alcoholcontentiswithinthelegallimit.
4
Solutions 319

96. mmolesof BaCO

2 4 lostinwashing =1000 1.5 × 10 –8 = 0.1224
mmolesof CaCO
2 4 lostinwashing =1000 2.34 × 10 –9 = 0.0483
meqof MnO –4 usedupforoxidisingoxalate =0.05 × 13.94 × 5= 3.485
3.485
⇒ mmolofoxalatetitrated =
=1.7425
2
⇒ Totalm molesofoxalateproducedduringprecipitation
=1.7425 + 0.1224 + 0.0483 = 1.9132
Letmixturecontain x g Ba( NO)
3 2 :
x + 0.3657– x= −
⇒ 1.9132 × 10 3 ⇒ x = 0.1397 ⇒ m% Ba( NO) 3 2 = 38.2
261 164
97. Thebalancedredoxreactionis: 2KO 2+6HI → 2KOH+ 2H 2O+3I 2
meqofhypo =15 × 0.4=6= meqofI 2 ⇒ Total I 2 liberated=15mmol
⇒ mmolof KO 2 inoriginalsample=10 ⇒ m% =10 × 10 –3 × 71 × 100 = 71%
2Cu + → Cu 2+ +Cu , Cu 2+ +2I – → CuI+
1
98. I
2 2
8.3
mmolofKItakeninitially × 1000 = 50 =
166
meq.of I 2 producedfromexcess KI =10
⇒ mmolof KI reactedwith Cu 2+ =40 ⇒ mmolof Cu 2+ = 20=mmolof CuO 2
−3 100
2 = 20 × 142 × 10
m%Cu O × =94.67
3
99. 3Br 2 +6OH → 5Br + BrO 3+3HO 2
– – –

10
⇒ –
m molof Br O=
3
3
− 10
⇒ meqof Br O=
3 × 6=20= meqof CaCO 2 4
3
⇒ massof CaC2O 4= 20 × 10 –3 × 64 = 1.28g
⇒ m%= 85.33
100. Letsamplecontain x mmolNaCl.
⇒ Initially x m molofAgClformed.
Now, 2AgCl → 2Ag + Cl2
0.6 x 0.3 x
and 3Cl 2 → 5Cl + –
ClO–3 → 5AgCl
0.3 x 0.5 x 0.5 x
⇒ Final AgCl = 0.4 x +0.5 x +0.9 x mmol
⇒ 0.9 x × 143.5 × 10 –3 =1.5 ⇒ x =11.614
−3
⇒ %NaCl = 11.614 × 10 × 58.5 × 100= 67.94
320 ProblemsinChemistry

101. mmolofKItaken = 2
meqofhypo 50 × 10 –3 ⇒ meqof I – leftunreacted =50 × 10 –3 × 10 = 0.5
⇒ mmolof I – usedupwith CuCO3 = 1.5
Reactionof I – with Cu 2+ is:
2Cu 2+ +5I – → 2CuI +I –3
2
⇒ mmolof Cu 2+ = 5
× 1.5 = 0.6
100
⇒ mass%of CuCO3= 0.6 × 10 –3 × 123 × = 18.45
0.4
102. meq.of Fe
2+
requiredforexcess MnO–4=19 × 0.1 × 10 ⇒ mmolofexcess MnO–4=3.8
− −
mmolof MnO4 reactedwith CN = 16.5 − 3.8 = 12.7
−
meqof MnO–4 = 12.7 × 3 = 38.1 = meq of CN
⇒ mmolof NaCN =19.05
⇒ m% NaCN =19.05 × 10 –3 × 49 × 100 = 93.345
103. meqofoxalatereactedwith MnO2= 200 –50.73 × 0.6 = 169.562
169.562
⇒ mmolof MnO 2 produced = =84.781
2
⇒ meqof KMnO4 usedforoxidationoftoluene =84.781 × 3
84.781 × 3
⇒ mmoloftolueneoxidised = =42.39
6
Massoftoluene = 42.39 × 10 –3 × 92 = 3.8998g
⇒ density (ρ)= 0.78 g / mL
100
meqof KMnO4 leftunreacted =38 × 0.2 × = 72.38
10.5
⇒ mmolof KMnO4 leftunreacted =14.476
Hence,totalm molof KMnO4 presentinoriginalsolution =99.257
99.257
⇒ Molarityoforiginal KMnO4 solution = ≈ 1.0M
100
104. Letmixturecontain x m mol CaOCl 2 and y m mol NaOCl
⇒ 2x + 2 y = 015
. × 2 × 10 × 10 ⇒ x + y = 15 …(i)
0.287 × 10 × 10 3
Also, 2x + y = = 20 …(ii)
143.5
Solving,Eqs.(i)and(ii)gives x = 5, y = 10
100
⇒ –3
m% CaOCl 2 =5 × 10 × 127 × = 31.75
2
–3 100
m% NaOCl =10 × 10 × 74.5 × = 37.25
2
Solutions 321

GASEOUS STATE
8RT
105. Averagevelocity = = 4 × 10 2 ⇒ RT = 2 × 10 4 ⇒ RT = 2πM × 10 4
πM πM
6 3 9 9 −
TotalK.E.ofHe = × RT = RT = ⋅ 2π × 4 × 10 3 × 10 4 = 180 π J
4 2 4 4
12 3 9 9
TotalK.E.ofNe = × RT = RT = × 2π × 20 × 10 –3 × 10 4 =360 π J
20 2 10 10
(360 + 180) π
AverageK.E.permol = = 807.84J
1.5 +0.6
− dP – dP
106. ∝ (P − 1) ⇒ = KP( –1)
dt dt
−dP − dp P −1
P t
⇒
P −1
= Kdt ⇒ ∫ P − 1 K ∫dt ⇒ ln P0 − 1 = Kt
= …(i)
P0 0

d  − mRt  =
Also,   KP( − 1)
dt  VM 
RT (– dm/dt ) = 0.0821 × 300 × 1.0
⇒ K= 3
=7 × 10 –7
VMP ( –1) 7.28 × 10 × 28 (171.8 – 1)
171.8 − 1
Now, ln = 7 × 10 −7 × 10 × 24 × 3600
P −1
170.8
Now, ln =1.83 ⇒ P = 94.33 at m.
P –1
nRT − na = 0.5 × 0.082 × 300 − 0.25 × 3.63 =
2
107. P = 22.06 at m osph ere
V − nb V 2 0.5 − 0.5 × 0.04267 0.25
99b
108. V − b = RT = 100( 0.011075V − b) = 1.1075V − 100b ⇒ V= = 921b
0.1075
4
⇒ 920 b = RT ⇒ b = 24.33 cm mol
3 –1
=4 × π r 3 × 6.023 × 10 23
3
−
⇒ . × 10 9 cm = 134 pm
r = 134
1 × 40
109. n ( but ane)= =1.626 ⇒ Massofbutane=94.308g
0.082 × 300
Massof Ar =94.308 × 19= 1791.852g
46.426
n( Ar ) = 44.8 Final P = = 28.55 bar
1.626
110. Cl 2O 7 → Cl 2 +3.5O 2
1 −α α 3.5 α
322 ProblemsinChemistry

Now,let x bethemolefractionof Cl 2 inthegaseousmixturebeinganalyzed.

rO2 71 0.6
⇒ = 3.5 = ⇒ x = 0.115
rCl 2 32 x
⇒ Mole fr action of Cl2O 7=0.285
rCl 2O7 1 − α 71 0.285
Also, = = ⇒= α 0.2
rCl 2 α 183 0.115

 r1   N   M n N 
/2
25 10  22  n
/2

111.   =  1  2 =  1 ⇒ =   S ol vi ngn = 23
 r2   N 2  0  M1   N2  75 90  20 
n =1 n

r = 32
112. (a) 1.33= M = 18 amu.
rO2 M
18
Vm = = 50L
0.36
PV 1 × 50
Z= = = 1.22, r epulsive for ce is dominati
ng.
RT 0.082 × 500
3 3 − −
(b) KET = KT = × 1.38 × 10 23 × 1000 = 2.07 × 10 20 J
2 2
nRT − = 2 × 0.082 × 300 − =
113. (P +K ) (V − nb) = nRT ⇒ K = P 11 1.615 bar
V − nb 4 − 2 × 0.05
Pb ⇒ Pb
114. Z =1 + 0.5=
RT RT
0.5 RT
⇒ b= = 0.5 × 0.082 × 273 = 11.193 L mol –1
P
a ⇒
Also, TB = a = TB ⋅ Rb = 107 × 0.082 × 11.193
Rb
⇒ a =98.2 bar L mol
2 –2

115. He N2 nHe 1 400 2

= × =
nN 2 3 200 3
2mol 6mol

Also, nHe + nN 2 =8 ⇒ n He = 16 , n N = 24
2
5 5
1 P
Also, = ⇒ P = 1.066 atm
300 × 2 200 × 16
5

116. Applyingconceptofuniformpressure:
150 nN 2 nO2
= = ⇒ nN 2 =36.16, nO2 =5.16
(1 − 0.6)
3
(0.6 − 0.3)
3 3
(0.3) 3
Solutions 323
⇒ W = 300 + 36.16 × 28 + 5.16 × 32 = 1477.6g
Afteradding 50 gH 2 :
175 36.16 5.16
= 3 = 3
(1 − rB )
3
( rB − rC )
3
rC
Solving, rB = 57.6 cm and rC = 28.8 cm

rmix 32
117. = = 0.45 ⇒ M = 158
rO2 M
rPCl 3 71 nPCl 3
Also, = = 0.72=
rCl 2 137.5 nCl 2
⇒ 71x + 0.72x × 137.5 + (1 − 1.72x ) × 208.5 = 158 ⇒ x = 0.268
Now, PCl 5 PCl 3 +Cl 2
1–α α α
rPCl 5 1–α 71 0.539
= = ⇒ α = 0.225
rCl 2 α 208.5 0.268
2
na = ⇒ a =0.02 × (22.5) 2 = 10.125 atm L2mol –2
118. 2
002
.
V
V − nb = nRT ⇒= b V − RT = 22.5 − 0.082 × 273 = 114 cm 3mol –1

a = 10.125
TB = = 1083.12K
Rb 0.082 × 0.114
119. 300 × 1= n × 1.072 × R × 473
600 V = n × 1.375 × R × 273 ⇒ V =0.37L
8a a
120. Tc = = 282 and Pc = = 50
27Rb 27b 2
282 8 27b 2 282R
Dividing = a × ⇒= b = 0.0578 L mol −1
50 27Rb a 50 × 8
282 × 27 × 0.082 × 0.0578
Substituting b in Tc : a = = 4.5 at m L2 m ol –2
8
−1
121. ThesecondVirialcoefficient = b =2 × 10 ⇒ b = 0.1414 Lmol
2 –2

nRT = 0.082 × 300 =

Videal = 4.92, V real = Vid + nb = 5.0614L
P 5
−2 −1 −1 4
122. b = 4.42 × 10 Lmol
3
= 44.2cm mol = 4 × πr 3 × 6.023 × 10 23
3
⇒ r = 16.36 × 10 −9 cm ⇒ Distanceofclosestapproach = 2r = 32. 72 × 10 −9 cm = 327.2 pm
44 Vc
123. Vc = = 97. 77 cm 3mol –1 ⇒= b 3
= 32.6cm mol –1
045
. 3
324 ProblemsinChemistry

8a
TC = = 300 ⇒ . at m L2 mol –2
a = 27
27Rb
RT + =
124. V = B 2.058 L. Also,forthegivenequation:
P
PB = + 10(− 0.1814) =
Z =1 + 1 0.918
RT 0.082 × 273
a
FromvanderWaal ’sequation,for Z < 1, Z = 1 −
VRT
⇒ a =
0.082 ⇒ a = 3.77 barL 2mol –2
VRT
rX 62 40
125. = =2 ⇒ M = 60 amu.
rAr 38 M
nRT − na = 100 × 0.082 × 313 −  100  ⋅
2 2

126. P=   3.6 = 11.16 bar

V − nb V 2 44 (5 − 100 × 0.044)  44 × 5 
44
nRT = 100 × 0.082 × 313 =
Pid = 11.666 bar
V 44 5
P − Preal
Percentagedeviation = id × 100 = 4.33%
Pid
∂(PV )
127. Atminimumin PV − P curve, =0
∂P
−
−B 2.879 × 10 2
⇒ B +2 CP = 0 ⇒ P = = = 96 atm
2C 2 × 14.98 × 10 −5
−1
RT − α ⇒ PV = V − α  β α
128. P = = 1 −  −
V − β TV 2 RT V − β RTV2  V 2
RTV
PV = + β + β + − α
2
1  α  β2
⇒ 1 . .. =1 + β −  + 2 + ...
RT V V2 2
RTV V  RT  V
2

ComparingwithVirialequation:
α α
B =β − and TB =
RT
2
Rβ
129. V. P. = 0.6 × 23.76 = 14.256 mm
1
Molesofgasin1.0Ldryair = = 0.0409
0.082 × 298
Molesof N 2=0.0409 × 0.79 = 0.0323 ⇒ massof N 2= 0.904 4g
Molesof O 2=0.0409 × 0.21 = 0.0086 ⇒ massof O 2= 0.2752g
Solutions 325
14.256
Molesof H 2O( v ) in 1.0 L moist ai r= =0.76 × 10 –3
760 × 0.082 × 298
⇒ Massof H 2O( v ) = 0.0138g
Addingmassesofallthegasesgives = 1.1934 g /L
1  na 
2 
130. T=   P + 2  (V − nb) = 623.57K
nR   V  
− dP KP P
− t
131. = ⇒ ∫ dP = K ∫dt
dt M P0
P M 0
P  Kt ⇒ 4K
⇒ ln  0  = ln 4 = = 2K
P M 4
10 K
ln = ⇒ PHe =7.07 atm
P 2
P  P 
Also, ln  0  = Kt and ln  0  = Kt
 P  He 2  P  CH 4
4

 P0   P0 
2
10 100
⇒   =  ⇒ = 2
 P  He  P  CH 7.07 PCH
4 4

⇒ PCH 4 =8.4 atm

132. Pideal (V − b) = RT for1.0 mol
0.082 × 273 600
⇒ Pideal = = 438.9 ⇒ Z = = 1.367 ( Rep u lsive f orce)
0.075 − 0.024 438.9
133. NH(3 g ) + HCl( g ) → NH 4Cl()s
Moles 0.08 0.26 0
0 0.18 0.08
⇒ Q = 0.08 × 4300 = 3440J
3440
Also, Q = nC v ∆T ⇒∆ T = = 955.55
0.18 × 20
T fi nal = 1255.55K
0.18 × 0.082 × 1255.55
Pfi nal = = 10.3 at m osph ere
1.8
134. Let P1 be the pressure in methanechamberand P2 be the pressure in Hechamberat anyinstant t.
Then:
− dP1 KP KP KP KP
= 1 1 − 2 2 = 1 1 − 2 2
dt 16 4 4 2
− dP
Also,atequilibrium, =0
dt
and P1 = P2 = 37
. ⇒ K 1 = 2K 2
326 ProblemsinChemistry
− dP1 K1 K
⇒ = ( P1 − P2 ) = 1 (2P1 − 7) + =7
dt 4 4 Q P1 P2
4
− dP K
t
2 ln 3
⇒ ∫ (2P1 −17) = 41 ∫dt Solving, t=
K1
= 87.88 second
5 0

3RT ds = 3R 1 3R 3R
135. r.m.s. ()s = ⇒ ⋅ = =2 ⇒ S= = 1558.87 ms –1
M dT M 2 T 2 MS 4M
136. 2NH 3 N2 + 3H 2
1.6 –2 x x 3x = 1.6 + 2x
1.6 × 0.082 × 500 32.8 1.6
Pi ni t ial= = 32.8 Also, = ⇒ x = 0.383
2 48.5 1.6 + 2x
n(NH 3 ) = 0.834, n( N 2 ) = 0.383, n(H 2 ) = 1.149
729.9 × 30
137. P (dryoxygen) = 729.9 mm ⇒ V (dr y oxygen)= = 29.15 mL.
751
PV =
Now, applying const ant,V = 25.82 mL
T
138. Let x molgasispresentincoldflaskand y molinhotflask.
3 2
⇒ 2x = 3 y and x + y = 1 Solving: x = , y =
5 5
3 0.082 × 200
P= × = 9.84 atmosphere.
5 1
139. Boyle ’slaw: PV = C ( constant)
C  ∂V  −
⇒ V= ⇒   = C2 =− V
P  ∂P  , P P
nT

1  ∂V  1
⇒ K =−   = = 1.0 atm –1
V  ∂ 
P nT, P

PVM  1 − 1 
140. ∆m = mcold − m hot = [ncold − n hot ] M =  
R  T1 T2 
Solving: ∆T = T2 − T1 = 3
∂(PV )
141. Theminimumincurvewilloccurat =0
∂P
∂(PV ) P
Also, = +V …(i)
∂P ( ∂P / ∂V )
for1.0mole,vanderWaals ’equationcanbewrittenas:
RT − a
P= …(ii)
V −b V2
∂P − RT 2
⇒ = + a
∂V (V − b) 2 V 3
Solutions 327
 ∂P 
Substituting   inEq.(i)andequatingtozerogives
 ∂V 
2
( bR T – aV
) +2 abV – ab 2 =0
Substituting a,bR, and T gives
− 0.647V 2 + 0.087V − 1.38 × 10 −3 = 0 …(iii)
Solving,Eq.(iii)gives
V = 0.0185 L mol
–1
and 0.01158 Lmol –1 .
The firstsolution yields a negative pressure on substitution into Eq. (ii),but usingV = 0.1158 gives
0.082 × 273 1.362
P= − = 165.56 at m osph ere
0.1158 − 0.032 (0.1158) 2

142. Steam :24.06Benzene:5.464

Toluene:18.00Neon :0.2107
(Highertheintermolecularforceofattraction,higherwillbe ‘a’)
143. Toluene: 0.1463 Steam:0.0305
Benzene: 0.1154 Neon:0.0170
(LargerthevanderWaal ’sradius,higherwillbe ‘’b )

THERMOCHEMISTRY
144. Heatconsumedbywater = 450 × 4.18 × 75 = 141.075 kJ
Heatconsumedbycopper =500 × 0.38 × 75= 14.25 kJ
Totalheatrequired = 155.325 kJ
141.075
%heatusedtoraisetemperatureof H 2O= × 100= 90.82
155.325
145. Fe 2O +2Al
3 → Al 2O 3+ 2Fe ; ∆H = – 851.5 kJ /mol
50g 25g
Here, FeO
2 3 islimitingreagent.
–851.5
Hence, Q= × 50= –266.1 kJ
160
146. ∆H = Σ∆ H comb ( r eact ants)
− Σ∆ H comb ( pr oducts)
=− 1300 − 2 × 286 + 1560 =− 312 kJ
147. Writingthereactionsgivenasfollows:
2NH 4Cl ()s → 2NH(3 g ) + 2HCl(g ) ∆H = 352 kJ
2NH 3 → N 2+3H 2 ∆H = 92.22 kJ
N 2+ 4H +Cl
2 2 → 2NH 4Cl()s ∆H =− 628.86 kJ
Nowaddtheaboveequations:
H(2 g )+ Cl 2 (g ) → 2HCl( g ) ∆H =− 184.64 kJ
⇒ ∆H °f H Cl(g )= – 92.32 kJ / mol.
328 ProblemsinChemistry

148. Writingthegivenreactionsasfollows:
NO 2+O 2 → NO +O 3 ∆H =+ 200 kJ
O 3 →
3
2
O2 ∆H =− 1427
. kJ

O 2 → O(g )
1
2
∆H =+ 249 kJ
Addingabovereactionsgives:
NO 2 → NO + O(g ) ∆H = 306.3 kJ
149. Performing a + b – 2c gives:
4H 2+2O 2 → 4HO
2 ∆H =− 1090
→ HO
1
⇒ H+2 O
2 2 2 ∆H =− 2725
. kJ …(i)
Also a + b + c gives:
3CH 4+2O 2 → H 2O+3CO + 5H 2 ∆H =− 349 kJ
O 2 → 5HO
5
and 5H+
2 2 2 ∆H =− 1362.5 kJ
Addingtheabovetwoequationsgives:
→ 6H 2O+3CO
9
3CH+
4 O
2 2
∆H =− 1711.5 kJ

O 2 → 2H 2O+CO
3
⇒ CH+
4 2
∆H =− 570.5 kJ

150. N(2 g )+ 3H(2 g ) 2NH 3

− 92 = 941.3 + 3 × 436 − 6 B. E. (N – H) ⇒ B. E. (N — H)= 390.25 kJ
151. 306 = 314 + 3 × 121 − 3 B. E. (P – Cl) ⇒ B. E. (P—Cl)= 123.67 kJ
8 = 314 + 3 × 216.5 − 3 B. E. (P – H) ⇒ B. E. (P – H)= 318.5 kJ
152. Multiplythe2ndreactionby2andsubtractfrom1st:
Fe( s) + 2H 2O( )l + 2S O(2 g ) → FeS 2 +2H 2+ 3O 2 ∆H = 987
987 = ∆H °f (FeS 2 ) + 2 × 285.83 + 2 × 296.81
⇒ ∆H °f FeS 2 = − 178.28 kJ/ mol
Also, −137 =− 178.28 − 2H °f (HS2 )
⇒ ∆H °f ( H2 S) =− 20.64 kJ/ mol

153. +3H 2 ; ∆H =− 119 × 3 =− 357

– 357= –156– ∆H °f (benzene) ⇒∆ H f ° (benzene) = 201

R. E.= ∆H °f (exp)– ∆H °f ( theor etical)=– 152 kJ/mol
154. trans-2- but ene→ cis-2- butene ∆H =+ 095
. kcal
cis-2- but ene → 1- butene ∆H =+ 1771
. kcal
1-butene + 6 O 2 → 4CO 2+4HO 2 ∆H =− 649.8 kcal
Solutions 329
Addingabovethreeequationgives:
trans-2- butene + 6O2 → 4CO 2+4HO 2 ∆H =− 647.079 kcal
CH 3
HC== CH +6O 2 → 4CO 2+4HO() 2 l
HC3

H 2O()l → HO(
2 v) ∆H °V = +11 kcal
CH 3
CH== CH +6O 2 → 4CO 2+4HO(2 v) ∆H = − 636.079 kcal
CH 3
– 636.079 =8 × 98 +2 × 80 + B. E. (C==C) +6 × 118 –8 × 196 –8 × 110
B. E. (C == C)=159.921 kcal.
155. Let B.E.(C==C) = , xB.E.(C  C)= y ⇒ x − 2 y =− 72 …(i)

2 g ) →
6C(gr ) + 3H( (g )

∆H = 79 = 6 × 715 + 6 × 218 − 3 (x + y) − 6 × 415 − 152

⇒ x + y = 959 …(ii)
From,Eqs.(i)and(ii) x = 615.33, y = 343.67 kJ.

156. (g ) (g)+ 3H(2 g)

∆H = 6 × 415 + 3 × 348 − 3 × 600 − 3 × 436 = 426 kJ

C 6H(6 g ) → CH 6 ()
6 l ∆H =− 30.8 kJ
() l → CH(
C 6H 12 6 12 g ) ∆H = 33.0 kJ
6 l Theo. → CH
C 6H () 6 ()
6 l Exp. ∆H =− 152 kJ
Addingtheaboveequationsyields:
Cyclohexane( l) → C 6H () 6 l+ 3H 2 ∆H = 276.2 kJ
157. Let B. E.of C =C x, C==C = y andC ≡≡C = z
⇒ y − 2x =− 86 …(i)
z − x − y =− 148 …(ii)
y + 436 − x − 2 × 415 =− 132
⇒ y − x = 262 …(iii)
=
FromEqs.(i)and(iii) x 348 kJ, y 610 kJ, =
SubstitutinginEq.(ii)gives, z =810 kJ
158. Heatevolvedoncombustionofoneunitof CH 2=– 158
⇒∆ H comb ( C10H )=
22 ∆H comb (CH 4)+9 × ∆H comb (CH 2)=– 210–9 × 158 =− 1632 kcal
330 ProblemsinChemistry

159. 3C 2H(2 g ) → CH(

6 6 g) ∆H = 3 × 930 − 3615
( + 348) =− 99 kJ
C 6H(6 g ) → CH
6 ()
6 l ∆H = 45 kJ
⇒ 3C 2H(2 g ) → CH6 ()6 l ∆H =− 54 kJ = ∆H °f CH
6 ()
6 –3
l × 75
⇒ ∆H °f C 6H (6 ) l= 171 kJ
⇒ R.E. = 49 − 171 =− 122 kJ/ mol
2+
160. Ca (g ) + C 2–
2 (g )
∆H = 95
∆H = 1733 C(2 g ) U0
∆H =− 614
Ca(g ) 2C(g )
∆H = 179 ∆H = 1436
∆
= – 60 kJ
Ca()s + 2 C(gr) 
H→ CaC 2()s
179 + 1733 + 1436 − 614 + 95 + U 0 =− 60 ⇒ U 0 = – 2889 kJ
161. Requiredcombustionreactionsare:
C 3H +2O
8 2 → C 2H +CO 2 + HO 3 2 ∆H =− 2220 + 1300 + 285 =− 635 kJ
3
CH+ 4 O 2 → CO+ 2HO 2 ∆H =− 890 + 285 =− 605 kJ
2
90 10
For100gL.P.G., Q= (– 635)+ (– 605)= –1676.98 kJ
44 16
162. Total O 2 consumedin1.0hour = 400 × 60= 24000mL = 24L.
1 × 24
n(O 2)= =0.944; CH 6 O 12 + 66O 2 → 6CO 2+6HO2
0.082 × 310
Energyproduced = 453. 12kJ , available ener gy = 113.28 kJ,
di stance tr avel l ed=
1.1328 km.
164. Fromcombustiondata: ∆H °f (1,3-butadiene) =− 4 × 394 − 4 × 285 + 2841 =+ 125
Frombondenthalpies: 2 × 348 − 615 = 81 kJ = ∆H °f (1,3- butadiene) –130
⇒ ∆H °f (1,3-butadiene)=211
R.E.= 125 – 211=− 86 kJ / mol
165. 2NH(3 g ) → NH 2 ()4 +H(
l 2 g) ∆H = 142 kJ
4 l → NH(
N 2H () 2 4 g) ∆H =18 kJ
Addingtheabovetwoequationsyields:
2NH(3 g ) → NH( 2 4 g )+ H(2 g ) ∆H =160
⇒ 160 = 2 × 393 − B. E.(N– N) – 436
⇒ B.E.(N – N) = 190 kJ/mol
Solutions 331
−
166. – 56 =– 285– ∆H °f (OH) ⇒ ∆H °f (OH ) =− 229
–

Alsofor HF + OH– → F – +HO2

∆H =− 320 − 285 + 229 + 329 =− 47 kJ
167. Writingthegivenreactionsasfollows:
2F eO(s )+ 2 O 2 → Fe 2O()3 s
1
∆H =− 284 kJ

2F e(s ) + 4H+ → 2Fe 2+ +2H 2 ∆H = –175.6

F e2O 3()s → 2Fe( s)+

3
2
O2 ∆H = 8214
.

2H 2+O 2 → 2HO
2 ∆H = –570
Addingtheaboveequationsyields:
2F eO(s ) + 4H+ → 2Fe 2+ +2HO
2 ∆H =− 2082
.
⇒ FeO( s)+2H +
→ Fe 2+ +2HO
2 ∆H =− 104.1 kJ
168. Q = 1316.7 × 2.36 = 3107.412J
3107.412
∆H Neut =− × 1000 J= – 51.79 kJ/ mol
60
169. For 2 5 ) 2 S( g )+ S( g ) → (C 2H)5 2 S(2 g )
(CH ∆H =− 202 + 147 − 223 =− 278 kJ
B. E. (S – S)= + 278 kJ / mol
170. LetB.E. C–C = x, C ≡ N = y and C − H = z
N 2 → CH 3CN( g )
1
⇒ 2C(gr) + 2H+
2 2
1
∆H = 88 = 2 × 717 + 2 × 436 + 2 × 946 − ( x + y + 3 z )

or x + y + 3 z = 2691 kJ …(i)
2C( gr) + 3H2 → CH 2 6 ∆H =− 84 = 2 × 717 + 3 × 436 − ( x + 6 z )
or x + 6 z = 2826 kJ
⇒ x = 2826 − 6 × 410 = 366kJ / mol
y 2691 − 366 − 3 × 410 = 1095 kJ/ mol
=
171. CH 3COOH( g )+ 2O 2 → 2CO 2+2HO(2 g )
∆H = 3 × 410 + 348 + 728 + 352 + 463 + 2 × 498 − (4 × 728 + 4 × 463) =− 647 kJ
⇒ CH 3COOH( l)+ 2O → 2CO 2+2HO()
2 2 l ∆H =− 647 + 52 − 82 =− 677 kJ
⇒ ∆H r eact i on=− 677 + 860 = 183 kJ
172. For CH 3OCH(3 g ): – 348 = –2 × 94 –3 × 68– ∆H °f ⇒∆ H °f =− 44 kcal / mol
⇒ For C 2H OH()
5 l → CHOCH(
3 3 g) ∆H =− 44 + 66 =+ 22kcal / mol
173. BH(3 g ) → B(g )+ 3H( g ) ∆H 1°
B2H(6 g ) → 2B(g )+ 6H( g ) ∆H 2°
332 ProblemsinChemistry

∆H 1° = ∆H f° B(g ) + 3∆H f° H(g ) − ∆H f° BH 3 ( g ) = 563 + 3 × 218 − 100 =1117 kJ

∆H 2° = 2∆H f° B(g )+6 ∆H f° H(g ) – ∆H f° BH(

2 6 g )=2 × 563 +6 × 218 – 36= 2398 kJ

⇒ mean B H bondenergyin BH 3
∆H 1°
= = 372.33kJ /mol
3
mean B H bondenergyin BH
2 6

∆H 2°
== 399.67kJ /mol
6
Also, BH
2 6 hasfourterminal B H sigmacovalentbondandtwo3-centered2-electronbond.
⇒ 2398 = 4 × 372.33 + 2x ⇒ x = 454.34 kJ/mol.
Therefore,average B H bondenergyofthebridged B
 H B bond
454.34
= = 227.17kJ /mol
2
1
Also,BE ∝ ;Hence,terminal B H bondsareshorterthanbridged B H bond.
Bond length
174. Given:

∆H ° =− 120 kJ
+H 2

⇒ +3H 2 ∆H ° =− 120 × 3 =− 360 kJ

Usingcombustiondata: ∆H °= ∆H combust
° ion [Benzene+ 3H 2 –Cyclohexane] =− 215 kJ

Resonanceenergy = ∆H ° (frombondenergy)– ∆H ° (combustion) =− 145 kJ

7893
175. molesofethanolin1.0L = = 171.587
46
7025
molesofoctanein1.0L = = 61.62
114
Also: C 2H OH+
5
7
O
2 2
→ 2CO 2+3HO2
∆H =− (2 × 394 + 3 × 286) + 278 =− 1368kJ mol –1
CH
8 18 + 25
2
O 2 → 8CO 2+9HO2
∆H =− (8 × 394 + 9 × 286) + 208.4 =− 5067.6kJ mol –1
⇒ Heatproducedfrom171.587molethanol =− 171.587 × 1368 =− 234.731 × 10 3 kJ
Heatproducedfrom61.62moloctane =− 61.62 × 5067.6 =− 312.26 × 10 3 kJ
Solutions 333
3
312.26 × 10
⇒ factor = = 1.33
234.731 × 10 3
i.e., automobile running on gasoline will gas 1.33 timesfarther than the automobile running in
ethanol,oncombustionof1.0litreoffuel.
176. Thecombustionreactionis:
C 3H +5O
8 2 → 3CO 2+4HO 2
10 50
i.e., for molofpropane, moleof O 2 wouldberequired.
44 44
50
Therefore, volof O 2 required = × 0.082 × 303 = 28.234 L.
44
100
⇒ Vol.ofairrequired = × 28.234 = 134.45 L.
21
10
Heatproducedinthecombustionreaction = ×−( 394 × 3 − 4 × 286 + 104) =− 2222 kJ
44
Since, Q = ms∆T
⇒ 2222 × 10 3 = 8000 × 4.18 ∆T
⇒ ∆T = 66.45 ⇒ T2 = 96.45C
° .

177. MultiplyingbothEqs(i)and(ii)by2andfinallyaddingthemyields
N(2 g )+ 2O(2 g ) → 2NO(2 g ) ∆G °= 103.56 kJ
2NO(2 g ) → NO( 2 4 g) ∆G ° =− 5.77 kJ …(iii)
Adding: N(2 g )+ 2O(2 g ) → NO( 2 4 g) ∆G °= 97.79 kJ
178. Thecombustionreactionis:
1
CO(g )+ O(2 g ) → CO(2 g )
2
1
∆H ° (frombondenthalpies) = 743 + × 498 − 2 × 743 =− 494 kJ
2
∆H ° (fromformationenthalpies) =− 394 + 111 =− 283 kJ
The above values ofenthalpy indicates that incarbonmonoxide, thebond between carbon and
oxygenisstrongerthanthesamein CO 2 .
179. Theformationreactionis:
N 2+3H 2 2NH 3
Forreactionof0.1mol N 2 , 0.3mol H 2 isalsoreactedand0.2mol NH 3 formed.
⇒ BE(entered) = 0.1 × 944 + 0.3 × 436 = 130.8 kJ
Energyreleasedonformationof NH 3
=0.2 × (3 × 388) = 232.8
⇒ Energytransferredtosurrounding = 232.8 − 130.8 = 102 kJ.
334 ProblemsinChemistry

180. Heatproducedonneutralization = 1316.7 × 2.36 = 3107.412J

molesofHClneutralized = 0.15 × 0.4 = 0.06.
3107.412
⇒ ∆H ( neutr ali zat i on)= = 51.8kJ /mol ofHCl.
0.06

181. Given: CuS O4 ( s)+ ( aq ) → CuS O(4 aq ) ∆H ° =− 66.04 kJ

2 )s+( aq ) → CuS O(
CuS O4 ⋅5H O( 4 aq ) ∆H ° =− 11.495 kJ
Subtractingthesecondequationfromfirstequationyields:
CuS O4 ( s) + 5HO2 → CuSO45H⋅ O()2 s ∆H ° =− 54.545J

182. (a) Forthedesiredequation: (i)–(ii)

CaCl 2 +2HO 2 → CaCl 2 ⋅ 2HO
2 ∆H °= 37.628

183. Carryingoutthefollowingoperationsandrewritingtheequations:
(i) × 2 andreversing (ii) reversing (iii) assuch (iv) × 2
2NaCl ()s → 2Na(s)+Cl 2 (g ) ∆H °= 821.2 kJ
4 l → H(2 g )+ S( s)+ 2O( 2 g )
H 2SO () ∆H °= 810.54 kJ
2Na(s) +S ( s) + 2O(2 g ) → Na 2SO () 4 s ∆H ° =− 1381.5 kJ
H(2 g )+ Cl 2 (g )  → 2HCl(g ) ∆H ° =− 184.42 kJ
Addingtheaboveequationsgivesthedesiredequation:
2NaCl (s ) + H2S O4 ()l → Na 2SO ()+2HCl(
4 s g) ∆H °= 65.82 kJ
184. Therequiredreactionis:
Ag(s)+ 12 Cl 2 (g ) → AgCl () s ∆H °= ?
(i)+(ii)+2 × (iii)–(iv)gives
2Ag + Cl2 → 2AgCl
∆H ° =− 324.4 − 30.56 − 2 × 92.21 + 394 =− 145.38 kJ
⇒ Ag(s)+ 2 Cl 2 (g ) → AgCl ()
1
s ∆H °= –72.69 kJ .

185. Addingthetheoryofcovalentbonding,thestructuresof N 6 (g ) canbepredictedas:

N N
N N N N

N N N N
N N
I II

HereIhasdelocalized π-electronsaswellasaromaticity.
N
N N
3N2 ∆H° = 1 0 7 2 kJ mol
–1

N N
N
Solutions 335
∆H ° (frombondenthalpies) = 3 × 944 − 3163
( + 409) = 1116 kJ mol . –1

The observed ∆H °f is44 kJ mol–1 lessthan that calculated from bond enthalpies indicating
presenceofresonance.Hence,Istructureismostprobable.
186. Ifall energy available formuscularactivity isconsumed in jogging, energy available from0.5 kg
fatforjogging = 500 × 38 × 0.7 = 13300 kJ
13300
minimumjogginghour = = 6.65 hr.
2000
3.24
187. Totalenergyabsorbed = 42.6 × = 3 kJ
46
3 1
Energyabsorbedinonesecond = = kJ
×
60 10 200
1
Surfaceareaofbeaker =m 2 = 50 cm 2 .
200
188. Addingthetwogiventhermochemicalequations(i)and(ii)yields

+ 3H2 ∆H° = –2 08 kJ …(a)

Hadthere been no resonance energy in cyclohexadiene, the enthalpy of(ii)reaction would have
been − 170 − 70 =− 240 kJ. This indicates that independent hydrogenation ofone double bond
givesoffonanaverage120kJofheat.Therefore,theoretically.

+H 2 ∆H°T h eo r e t ic=al–120 kJ

⇒ ° − ∆HTheo
∆H exp ° = 82 = R. E. (benzene)− R. E. (cyclohexadiene)

⇒ –1
R. E. (benzene) = 152 kJ mol .

THERMODYNAMICS
V2 − nb 0.5 – 0.5 × 0.02
189. − W = nRT ln = 0.5 × 8.314 × 300 ln =– 1747.8J ⇒ W = 1747.8J
V1 − nb 2 – 0.5 × 0.02

3
190. ∆H = ∆E + PV
∆ + VP
∆ : ∆E = nCV ∆T = 2 × 8.314 × 100 = 1247.1J

P1 = 4.92 at m and P2 = 4.1 atm

⇒ P1 ∆V = 4.92 × 3= 14.76 L atm and V2 ∆P = 8(4.1 − 4.92) = − 6.56 L atm
⇒ P1 ∆V + V2 ∆P = 8.2 L atm =831.48J
⇒ ∆H = 1247.1 + 831.48= 2078.58J
336 ProblemsinChemistry
3
191. ∆H = ∆E + P1 ∆V + V2 ∆P = 2 × 8.314 × 500 + [4.92 × 3 + 8 (8.2 − 4.92)] × 101.4
= 6.236 × 10 3 J

100  T2 V 
192. ∆S =  20.8 ln +8.314 ln 2  …(i)
28  T1 V1 
Forirreversibleadiabaticexpansion:
 CV + (P2 / P1 ) 
T2 =   T1 = 217.76K
 CP 
V2 PT 30 × 217. 76
Also, = 1 2 = = 2.1776
V1 PT 2 1 10 × 300
SubstitutinginEq.(i)gives ∆S =− 0.692 JK –1

T2 V  373 
193. ∆S = nCV ln . 12.6 ln
+ nR ln 2 = 002 +8.314 ln2  = 0.17 JK –1
T1 V1  300 

194. Applyingconservationofheatto:
∆S ∆S ∆
H 2O()s →
1
H 2O()l →
2
H 2O()l ←S3
q3
H 2O()l
q1 q2
°
0C °
0C TK 363K
10 20
[6000 + 75.42 (T − 273)] = × 7542
. 363
( −T)
18 18
⇒ T = 306.48K
10 6000
Also, ∆S 1 = × = 12.21 JK −1
18 273
10 306.48
∆S 2 = × 75.42 ln = 4.85 JK −1
18 273
20 306
∆S 3 = × 75.42 ln =− 14.31 JK −1
18 363
⇒ ∆S syst em = ∆S 1 + ∆S 2 + ∆S 3 = 2.75 JK −1

195. Processinvolvedare:
H 2O()l → H 2O()l 
∆
→ H 2O()s → H 2O()s
∆S1 S2 ∆S 3
°
– 10C °
0C °
0C –10C°
T2 273
∆S 1 = C P ln = 75.42 ln = 2.814 JK–1
T1 263
− 6000 263
∆S 2 = =− 21.98 JK –1 and ∆S 3 = 37.2 ln = –1.388J K –1
273 273
∆S = ∆S 1 + ∆S 2 + ∆S 3 = – 20.554 JK–1
Solutions 337

196. Zn +H SO
2 4 → ZnS O4 +H 2
100
− Wi rr = ∆nRT
g
= × 8.314 × 300 = 3.84 kJ
65
Insealedvessel, ∆V = 0 ⇒− W = 0
197. P ∝ d ⇒ d ( final) = 2.5 m. Al soP = kd ⇒= k 2 at mm
–1

π π
− dWrev = PdV = kd. . d 2 dd = k d 3 dd
2 2
2.5
kπ π 2 at mm –1 × π
⇒− W = ∫ ddd
3
= k [( 2.5)4 − (0.5) 4 ] = × 39m 4
2 0.5 8 8
= 30.63 at m m=
3
3.1 × 10 J
6

198. AP: =10 bar, T = 300 K, B: P=? T = 300K

3
CP: = 2 bar, T = 250 K, CV = R A B
2
Connectingreversibleadiabaticpoints B and C : T C
γ –5
 TC 1−γ  250  2 V
PB = PC   =2 
 300 
= 3.15 bar
 TB 
10
⇒ −W AB
= 8.314 × 300 ln = 2.88 kJ
3.15
− WBC = CV (T1 − T2 ) = 1.5 × 8.314 × 50 = 623.55J
− WAC = 3.50355 kJ
199. Processisirreversible:
 2 × R 2R  4
(a) − W = Pext ∆V = 2 atm  −  × 273 = 2 × × 8.314 × 273 = 3631.55J
 2 10  5
(b) ∆H = ∆ E = 0 ∴∆ T = 0
γ –1
200. Inreversibleadiabaticprocess: TV = const ant
γ −1
 V2 
⇒ T1 = T2   = T2 (2) 25/ ⇒ T2 = 225.84K
 V1 
5
∆E m = 2 × 8.314 × 72.16= 1499.84J
7
∆H m = 2 × 8.314 × 72.16 = 2099.78J
V −b
201. − dW = RT dV ⇒− W = RT ln 2
V −b V1 − b
−
0.2 0.03
− W = 8.314 × 300 ln =− 10.155 kJ
10 − 0.03
⇒ W =+ 10.155 kJ
338 ProblemsinChemistry

 
202. − dW =  RT − a2  dV
 V V 
V 1 1 0.384 × 0.15
⇒ − W = RT ln 2 + a  −  =− 1152.56 + = –1095J
V1  V2 V1  10 –3
⇒ W =+ 1095J
203. Workwillbedoneonlybetween A–B
⇒ −WAB = PV∆ = 0.8 × 20 L atm = 1622.4J
1
0.8 × 20 C
Initialtemperature TA = = 390.25K
0.5 × 0.082 p 0.8 A B

TB =2 T A = 780.5K
TC = 975.625K
⇒ ∆E AB = 0.5 × 1.5 × 8.314 × 390.25 = 2433.4J 20L 40L
V
∆E BC = 0.5 × 1.5 × 8.314 × 195.125 = 1216.7J
⇒ ∆E AC = ∆E AB + ∆E BC = 3650.1J
q = ∆E − WAB = 4461.3J and ∆H = ∆E + P ∆V = q
204. Atconstant n and V , P ∝ T ⇒ T2 = 3030 K
⇒ q = ∆E = CV ∆T = (75.42 − 8.314) × 2727 = 183 kJ
∆H = C P ∆T = 205.67 kJ
205. − =
WAB PV ∆ = 20 L atm = 2028 J A(1.0 atm, 20 L)
B(1.0 atm, 40 L)
WBC = 0
P
0.5
− WCA = 2 × 8.314 ln =− 11.52 C(0.5 atm, 40 L)
1
− WA ↔ A
= 2016.48J
Sinceprocessincyclic, ∆U and V
∆H = 0and q =− W = 2016.48J
206. Inadiabaticirreversibleexpansion:
0 = CV (T2 − T1 ) + Pext (V2 − V1 )
 CV + RP( ext / P1 ) 
Solvingfor T2 : T2 =   T1 = 263.74K
 CV + RP( ext / P2 ) 
− W = nCV (T1 − T2 ) = 3.22 × 20.785= 2293J
10 × 1
207. Processisisothermal n= =0.4
0.082 × 300
∆U = ∆H = 0
− W = 0.4 × 8.314 ln10 = 7.66J
−3
CV (300) = 21.52 + 8.2 × 10 × 300 = 23.98 JK −1
−
⇒ C P (300K ) = CV + R = 32.294 JK 1
Solutions 339
=
208. dG VdP − SdT atconstant P , dG =− SdT
⇒ ∫dG =− 36.36 ∫dT − 20.79 ∫ln TdT
∆G = – 36.36( T2 – T1 ) – 20.79[ T ln T – T ]T 2
T 1

=− 909 − 20.79 (1543.18– 1399.73) =− 3891.33J

CV = 20.266 +1.76 × 10 T
–2
209.
dE = CdT
V
= (20.266 + 1.76 × 10 −2 TdT
)
1.76 P 
⇒ ∆E = 20.266(T2 − T1 ) + × 10 −2 (T22 − T12 ) = PV
2( − V2 ) = R  2 T1 − T2 
2
1
 P1 
1.76
⇒ × 10 −2 T22 +28.58 T2 – 7869.48 =0
2
Solving, T2 = 255.3K
dT − dP = dT − dP
Also, dS = C p R (28.58 + 1.76× 10 –2 T ) R
T P T P
T2 P −
⇒ ∆S = 28.58 ln +1.76 × 10 –2 (T2 – T1) + R ln 1 = 2.22 JK 1
T1 P2
∆U = ∫CdT
V
= ∫(20.266 + 1.76× 10 –2 T ) dT

1.76 × 10 –2
= 20.266 (255.3 – 300)+ [(255.3) 2 –300)
( 2
] =− 1124.32J
2
∆H = ∫C p dT = ∫(28.58 + 1.76× 10 −2 T ) dT
1.76
= 28.58( 255.3 – 300)+ × 10 −2 [(255.3) 2 − (300) 2 ] =− 1496J
2
210. − W = 2 × 30 L atm = 6084 J ⇒∆ E = (20000 − 6084J) = 13.916 kJ
dV = V
211. −W = ∫PdV = ∫10 ⋅ 10 ln 2 = 10 × ln 10 L atm = 23 L atm 2332.2J
=
V V1
q = 420 + 2332.2= 2752.2J
∫ dTV = 3 ∫(30 + 14 × 10 3 TdT
−
212. ∆E = nC )

= 3 × 30 (T2 − T1 ) + 42 × 10 −3 (T22 − T12 )

= 9000 + 2940 = 11.94 kJ
− W = (T2 − T1 ) nR = 3 × 8.314 × 100= 2494.2J
3
q = 11.94 × 10 +2494.2= 14.4342 kJ
213. Applyingadiabaticconditionsbetween C and A.
 500 
–2.5

P =   × 5 = 1.39 atm.
300 
340 ProblemsinChemistry

WAB = 0 ∆ =0
Q V A(500 K, 5atm)
3
WBC =− 8.314 × 300 ln =− 1918.8J
1.39 P
3
WCA = × 8.314 × 200 = 2494.2 B C(300 K, P )
2 (300 K, 3atm)
=
W 575.4J
 500 
–2.5

PC =  
V
214. × 5 = 1.39 atm
300 
5
PB = × 1.39 = 2.32 atm
3 A(500 K, 5atm)
5
⇒ WAB =− 8.314 × 500 ln = − 3192J P
2.32 B(500 K, PB )
WBC =0
WCA = 1.5 × 8.314 × 200= 2494.2J C(300 K, PC )

W =− 697.8J
V
215. Applyingadiabaticconditionbetween A and D
 300 
–2.5

P =   × 5 = 1.82 atm A(300 K, 5 atm)

200  B(600 K, 5atm)

W1 =− PV1 =− nRT1 =− 300 R P

5
W2 =− nR × 600 ln =− 6064
. R C(600 K, P)
1.82 D(200 K, P)
W3 = 1.82( VC − VD ) = 400 R
W4 = CV × 100 = 150 R V
⇒ W =− 3564 . R =− 2.963 kJ
–2.5
216. P = (2) × 5 = 0.88 atm
A(500 K, 5 atm)
5
WAB =− R × 500 ln =− 868.63 R
0.88 P
1
WBC = 0.88 (500R − 250R ) × = 250R B(500 K, P)
0.88 C(250 K, P)

WCA = 1.5R × 250 = 375 R

⇒ W =− 243.63 R =– 2.026 kJ V
217. A(500 K, 10 bar)

 
− Wi rr = PV
2( − V1 ) = P2  RT − RT  = 08
. RT P
2
 P2 P1  2.0

2
− Wrev = RT ln
P
V
Solutions 341
2
Adding: RT ln + 0.8RT =4200
P
⇒ P = 1.62 atm
–2.5
218. (a) PB = (2) × 10 = 177
. atm
A
WAB =− 1.5 R × 250 =− 375 R
1.77
WBC =− 250 R ln =− 142. 75 R T
1
C
W =− 517.75 R =− 4.304 kJ
B

− 25
.
 250 
(b) P =   = 5.65 atm
500 
V

10 A
⇒ W =− 500R ln − 1.5R × 250 T B(500, P)
5.6
=− 664.9 R C(250, 1)
=− 5.528 kJ
V
219. V1 = 0.082 × 300 = 24.6 L,
0.082 × 500
P2 = = 1.138 atm
36
∆H = ∆E + P1 ∆V + V2 ∆P = 1.5 R × 200 + [11.4+ 36 × 0.138] × 101.4
= 4.154 kJ
220. dG = CdT
P
− TdS − SdT = CdT
P
− T (3 × 10 −3 dT ) − (1.5 + 3 × 10 −3 T ) dT
= (C P − 1.5) dT − 6 × 10 −3 TdT
6
⇒ ∆G = (C P − 1.5) (T2 − T1 ) − × 10 −3 (T22 − T12 ) = 3377J
2
T2 P 5 1
221. ∆S = C P ln + R ln 1 = 3.5 R ln + R ln = 9.1J
T1 P2 3 2

∆V = 0 ⇒ dT = − dT = dT + × −3
222. dS = CV (12 + 28 × 10 3 T ) 12 28 10 dT
T T T
T 40 × 1
⇒ ∆S = 12 ln 2 + 28 × 10 −3 (T2 − T1 ), T2 = = 487.8K
T1 0.082
487.8
∆S = 12 ln + 28 × 10 −3 × 187.8 = 11.09 JK –1
300
223. A → B ∆G ° =− 3 × 1000 − T × 20 =− 9000J
A → C ∆G ° =− 3600 − 10T =− 6600J
∆G ° indicatesthat B ismorestablethan C.
224. =
dG VdP − SdT = VdP − (10 + 12 × 10 −3 T ) dT
342 ProblemsinChemistry

⇒ ∆GV= ∆P − 10 ∆T − 6 × 10 −3 (T22 − T12 )

0.082 × 300
V= = 24.6L
1
400 4
P2 = = at m.
300 3
1
⇒ ∆G = 24.6 × × 101.4 − 10 × 100 − 6 × 10 −3 [( 400) 2 − (300 2 )] =− 588.52J
3
dT = − dT
225. dS = nCV 2(19.686 + 31 × 10 3 T )
T T
T2 −3
∆S = 2 × 19.686 ln + 31 × 10 (T2 − T1 ) = 14.43 JK –1
T1
V2
226. ∆S syst em = nR ln = 2 × 8.314 ln 2.5 = 15.236J
V1
4.17 × 10 3
∆S surr =− =− 13.9J
300
∆S univ = 1.336J
3
227. ∆S = R ln 3 + 2R ln = 15.87 JK −1
2
228. T A =122K and TB = 244K A B
P
⇒ nR =−
WAB =− 1(T2 − T1 ) 244 R
1
WBC = 0, WCA = 2R × 122 ln 2 = 169.12 R
C

W =− 74.88 R
V
=− 622.5J

229. ∆E = ∫CV dT = ∫(a + bT ) dT = aT( 2 − T1 ) + b (T22 − T12 ) = 7.4 kJ / mol

2
∆H = ∫C P dT = ∫(33.314 + bT ) dT = 33.314(T2 − T1 ) + b (T22 − T12 ) = 9.063 kJ / mol
2
3 × 0.082 × 300
V1 = = 36.9L
2
3 × 0082
. × 500
V2 = = 41 L
3
Wecanconstructapathas:
W
A (2.0 bar , 36.9 L, 300K) → B (2.0 bar, 41 L,T )
1

W
→2
C (3 bar, 41 L, 500K)
2 × 41 × 300
T= = 333.33K
2 × 36.9
Solutions 343
Then, W1 = P ∆V = 2 × 4.1 × 101.4 = 831.48J and W2 = 0
⇒ q = 7.4 × 10 + 831.48 = 8.23 × 10 3 J
3

 dT + dV  =  + dT + dV 
dS = nC R  n  (a bT ) R 
 V   V 
V
T T
 T V 
∆S = na ln 2 + bT
( 2 − T1 ) + R ln 2  = 59J
 T1 V1 

230. WAB =− 5500

( − 400) R =− 100 R
5
WBC = 0 A B
Connectingadiabaticpoints A and D.
γ γ
Applying P 1− T = K gives TD = 210K = TC P C
⇒ PC = 2.1 atm D
2.1
⇒ WCD =− 210 R ln =− 155.8 R
1 V
WDA = 1.5 R × 190 = 285 R
WW= AB + WCD + WDA = 29.2 R
= 242.76J
231. TD = 388 K, PB = 2 bar, A

5
WAB =− 500 R ln =− 458.14 R D
2 P
WCD = 1.5R × (388 − 250) = 270 R
B

W =− 251.14 R C
=− 2.088 kJ
V
232. Accordingtosecondlawofthermodynamics:
∆H v
∆S v =
Tb
⇒ ∆H v = ∆S v × Tb = 85 × 353 = 30.005kJ mol –1 .
(b) Sincevaporization processisendothermic,heatlostbysurrounding invaporization of100g
benzeneis:
30005
Q= × 100 = 38468J
78
38468
⇒ ∆S sur r oundi ng=− Q =− =− 108.97 JK –1 .
T 353
233. (a) ∆ Hv = ∆ ⋅
S v Tb 85 329 = 2796 5 J mol
= × –1

100 × 27965
(b) Heatgainedbysurrounding = = 48215.5J
58
48215.5
Increasinginentropyofsurrounding = = 146.55J
329
344 ProblemsinChemistry

234. Forareaction:
− Σ∆ G °f (React ants)
∆GR° = Σ∆ Gf° (P r oduct s)
⇒ ∆G ° ( i)=− 2 × 200 + 762 =+ 362 kJ
∆G ° (ii) =− 396 + 762 =+ 366 kJ
Since, both ∆G ° are positive, areaction with lesspositive ∆G ° will be more likely to occur.
Therefore,reductionof TiO 2 willbemorefavourablethroughreaction(i).
235. ∆H r° =− 111 + 242 = 131 kJ

∆S r° = 190 + 131 − (5.7 + 70) = 245.3 JK –1

⇒ ∆G °= ∆H °− TS∆ °= 131 × 10 3 − 300 × 245.3 = 57.41 kJ
Positive value of ∆G ° indicates that reaction isnon spontaneous at 300 K.Increasing temperature
will decrease ∆G ° and after certain value of T , ∆G ° will become negative, i.e., reaction will turn
fromnon-spontaneous to spontaneous. That specific temperatureat which reaction turns from
non-spontaneoustospontaneouscanbedeterminedbyequating ∆G °= 0 as:
131000
0 = 131 × 10 3 − T × 245.3 ⇒ T = = 534 K
245.3
i.e., attemperatureabove534K,reactionwillbecomespontaneous.
236. At300K,
∆G ° (cis-2- but ene→ trans-2- butene) =− 3 kJ mol –1
∆H ° (cis-2- butene→ trans-2- butene)=− 4.2kJ mol –1
∆ °− ∆G °
⇒ ∆S ° (cis-2- but ene→ trans-2- but ene) = H
T
−4.2 + 3
= × 1000 =− 4JK –1
300
⇒ ∆G ° ()1 at 400 K =− 4.2 × 10 3 + 400 × 4 =− 2600 J
∆G ° ()1 3000
Also, ln K ()1 =− =
RT 8.314 × 300
⇒ K ()1 = 3.33 at 300 K
and K ()1 = 2.20 at 400 K
∆G ° (2) =− 8kJ mol –1 at300K
∆G ° (2) 8000
⇒ ln K (2) =− =
RT 8.314 × 300
⇒ K (2) = 24.7 at300K.
Now,letat400K,mixturecontain x % trans-2-buteneand y% 2-methylpropene.
x 18
⇒ At 400 K, K (1) = 2.2 = =
100 − x − y 82 − y
⇒ y = 73.8%
Solutions 345
y 73.8
⇒ K (2) at400K = = =9
100 − x − y 8.2
⇒ ∆G ° (2) at400K =− 8.314 × 400 ln q =− 7.3 kJ
⇒ ∆G ° (2) at300K =− 8000 = ∆H ° (2) − 300 ∆S ° (2)
∆G ° (2) at400K =− 7300 = ∆H ° (2) − 400 ∆S ° (2)
⇒ ∆S ° (2) = – 7JK –1
∆H ° (2) =− 8000 + 300 (−7) = –10.1 × 10 3 J
K (2)
Also, K (3) =
K ()1
24.7
⇒ At300K: K (3) = = 7.41
3.33
⇒ ∆G ° (3) =− 8.314 × 300 ln 7.41 =− 4995 J
9
At400K: K (3) = =4
2.2
⇒ ∆G ° (3) =− 8.314 × 400 ln 4 =− 4610 J
⇒ −4995 = ∆H ° (3) − 300 ∆S ° (3)
−4610 = ∆H ° (3) − 400 ∆S ° (3)
⇒ ∆S ° (3) = – 3.85 JK –1 and ∆H ° (3) = – 6.15 kJ.
237. Forthedecarboxylationreaction:
CH 3COOH CH 4+CO 2 ∆H ° =− 394 − 74.8 + 484.5 = 15.7 kJ
Also,above65K,reactionisspontaneous
⇒ ∆G °= 0 at65K
⇒ 0 = 15.7 × 10 3 − 65 ∆S °
⇒ ∆S °= 241.54 JK–1 .
Foraspontaneousreaction ∆G °< 0.Since, ∆H °> 0, spontaneityofreactionisdueto ∆S °> 0.

238. Since, ∆G = ∆G °+ RT ln Q = RT ln Q − RT ln K
 
⇒ ∆G = RT ln  Q 
K
Inthepresentcondition:
0.66 × 1.2
Q= = 4.06
0.25 × 0.78
 Q  ∆G 2540
⇒ ln   = = = 15.275 × 10 –2
 K  RT 8.314 × 2000

⇒ Q=
1.165 ⇒ K = 3.48
K
Q Q > K ,reactionwillproceedinbackwarddirectionas:
346 ProblemsinChemistry

H2 + CO 2 HO(
2 g) + CO
0.25 + x 0.78 + x 0.66 − x 1.2 − x

(1.2 − x )( 0.66 − x )
K = 3.48 =
(0.25 + x )( 0.78 + x )
Solving: x = 0.02.
⇒ PH 2 = 0.27 atm, PCO2 = 0.80 atm, PHO2 = 0.64 atm. PCO = 1.18 atm.
239. Fortheabovereaction:
K p = pCO2
 K p (2)  ∆H °  T2 − T1 
Also, ln  =  
 K p ()1  R  TT1 2 

1830 ∆H °  250 
⇒ ln =   = 4.394 ⇒ ∆H °= 173.88 kJ mol–1 .
22.6 R  973 × 1223 
22.6
Also, ∆G ° =− RT ln K p° =− 8.314 × 973 ln = 28.43 × 10 3 J
760
∆H °− ∆G ° 173.88 − 28.43
⇒ ∆S °= = × 1000 = 149.5 JK –1mol –1
.
T 973
240. Theminimumvalueof ∆S willoccurat ∆G = 0 forspontaneousreaction.
19000
⇒ 0 = 19000 − 345 ∆S ° ⇒ ∆S °=
= 55.07 JK –1 .
345
Th − Tc 2200 − 760
241. Efficiencyofengine = = = 0.6545
Th 2200
2 × 3.1 × 1000
Totalheatproduced = × 5510 = 299666.67J
114
Heatconvertedintowork = 299666.67 × 0.6545 = 196132 J
⇒ Q = mgh
196132
h= = 16.67m
1200 × 9.8
242. Since,expansionoccurredatconstanttemperature,
V 1 3.0
∆S = nR ln 2 = × 8.314 ln = 0.36 JK –1
V1 32 0.75
Since,thisiscaseoffreeexpansion, Pext = 0. ⇒ − W = Pext ∆V = 0, q =0
Also,since, ∆T = 0, ∆H = ∆E = 0.
T2 V
243. Q ∆S = nC v ln + nR ln 2
T1 V1
−
3 × 550 × 10 3 3.5 × 0.73
n= = 0.067 and T fi nal = × 300 = 464.5K
×
0.082 300 3 × 0.55
Solutions 347
5 464.5 0.73
⇒ ∆S = 0.067 ×R ln + 0.067 R ln = 0.767 JK –1
2 300 0.55
5
∆E = nC v ∆T = 0.067 × R × (464.5 − 300) = 229 J
2
∆H = ∆E + PV ∆ + VP ∆ = 229 + [3(0.73 − 0.55) + 0.73 × 0.5] × 101.4 = 320.767J .
244. Underisothermalcondition,
V 10
∆S = nR ln 2 = 0.133 × 8.314 ln = 1.33 JK –1
V1 3
P2 3
∆G = nRT ln = 5 × 3 × 101.4 ln =− 1831.25J
P1 10

245. (a) Incaseofadiabaticreversibleexpansion, dq rev = 0 ⇒∆ S = 0.

(b) Incaseofirreversibleadiabaticexpansion:
0 = Pext (V2 − V1 ) + nC v (T2 − T1 )
Pext (V1 − V2 ) −×3 8
T2 = + T1 = + 1000 = 805 K
nC v 0.0821 × 1.5
T2 V 805
∆S = C v ln + R ln 2 = 1.5 × 8.314 ln + 8.314 ln 2 = 3.06 JK –1 .
T1 V1 1000
(c) Incaseoffreeadiabaticexpansion Pext = 0
⇒ 0 = Pext ∆V + nC v (T2 − T1 )
⇒ T1 = T2
V2
⇒ ∆S = R ln = 5.76 JK –1
V1
246. Since, the two gases have same heat capacities, equal amounts, final temperature will be
(T1 + T2 ) / 2 = 323 K.
Also,final P =1 atm, i.e., partialpressureofeachgasinthefinalmixturewillbe0.5atm.
323 1
Now, ∆S 1 (for col d gas) = C P ln + R ln
273 0.5
323 1
∆S 2 (for hot gas) = C P ln + R ln
373 0.5
 323 × 323 
⇒ ∆S = ∆S 1 + ∆S 2 = 2R ln 2 + C P ln   = 12.03 JK –1 .
×
 273 373 
dT + dV = dT + dV
247. dS = nC v nR nC( p − R ) nR
T V T V
  
= n  16.6 dT + 14.8 × 10 −2 dT − 9 × 10 −5 TdT  + R dV 
  T  V 
348 ProblemsinChemistry

 T −
−
9 × 10 5 V 
⇒ ∆S = n  166 . × 10 2 (T2 − T1 ) −
. ln 2 + 148 (T22 − T12 ) + R ln 2 
 T1 2 V1 
= n [5.585 + 29.6 − 10.8 +−( 2.965)] = 42.84 JK –1 .
248. dG =− SdT at ∆P = 0
=− (25.1 + 29.3 ln T ) dT , onintegration
∆G =− (25.1 − 29.3) ∆T − 29.3 (T2 ln T2 − T1 ln T1 )
Substituting, T1 = 298, T2 = 348.
∆G =− 9750J .
249. Since,theprocessisirreversibleadiabaticexpansion:
0 = ∆E + Pext ∆V = ∆E + Pext (V2 − V1 ) …(i)
Also, dE = nC vdT = (18.8 + 0.021 T ) dT
0.021 2
∆E = 18.8 (T2 − T1 ) + (T2 − T12 ) …(ii)
2
 T1 
SubstitutinginEq.(i), 18.8 (T2 − T1 ) + 0.0105 (T22 − T12 ) + RT −  =0
 2
2
Substituting, T1 = 400 K,solvingyields T2 = 352.5K .
dT + dV = dT + dV
Now, dS = C v R (18.8 + 0.021 T ) R
T V T V
T V
Integrating: ∆S = 18.8 ln 2 + 0.021 (T2 − T1 ) + R ln 2
T1 V1
352.5 352.5 × 10
= 18.8 ln + 0.021 (352.5 − 400) + R ln
400 400 × 5
= 1.338 JK–1mol –1

0021
.
FromEq.(ii), ∆E = 188
. (352.5 − 400) + [ (352.5) 2 − (400) 2 ] = – 1268.3J
2
= ( +
dH R C v dT ) = (27.114 + 0.021 T ) dT
0.021 2
⇒ ∆H = 27.114 (T2 − T1 ) + (T2 − T12 ) = – 1663.22J
2
250. ∆G = nV ∆P = 5 × 0.089 × 99 L-atm = 4467.18J
251. Forisoentropicprocess:
T P  P2  5 T2
0 = nC P ln 2 + nR ln 1 ⇒ R ln   = R ln
T1 P2  P1  2 T1
Solving, P2 = 1.474 atm.
252. Underisothermalcondition:
∆S = nR ln PP1/ 2 where P1 = initialpressure, P2 = finalpressure
Let, flask A has N 2 at4 barand flask B at 2 bar. Aftermixingfinal pressure in the combined system
= (83/ ) bar.
Solutions 349
12 6
⇒ ∆S A = R ln and ∆S B = R ln
8 8
∆S A + ∆S B = ∆S = 0.98 JK–1 .
∆H vap 349 × 10 3
253. Atboilingpoint, ∆S syst em = = = 111.4 JK –1
Tb 3133
Heatchangeinsurrounding =− 349 kJ
349 × 1000
∆S surr =− =− 99.71 JK–1
3500
⇒ ∆S univ = ∆S sys + ∆S surr = 111.4 − 99.71 = + 11.69 JK–1 .

ATOMIC STRUCTURE
= V = nh
254. Numberofrevolutionspersecond = 6.5 × 10 15 rp s.
2πr 4π 2 r 2 m
 1 1  1 1   4 4
255. (a) ν= KZ  2 − 2  ⇒ K  − 2  = K  2 − 2  ⇒ inHe,required transition in 4 → 2.
2
 n1 n2  1 2  n1 n2 

1 1   9 9 
(b) K  −  = K  − 2 ⇒ n1 = 3, n2 = 12
 1 16   n1 n2 
2

−19  1
1 −  × 6.023 × 10 = 116.71 kJ/ molH
23
256. E ext = 2.18 × 10  9
D. E. = 116.71× 2.67 = 311.62 kJ/molH 2
PV = 1
n= = 0.04
RT 0082. × 300
⇒ T. E. = 0.04× 311.62 + 0.08 × 116.71 = 21.8 kJ
nn( − 1) =
257. 10 ⇒ nB = 5 Hence, n A = 3
2
 1 1 
∆E = KZ 2  2 − 2  = 3.868 eV when n1 = 3, n2 = 5
 n1 n2 

⇒ 2
KZ = 54.4 eV = I. E.
34 −
ν = h = 6.626 × 10 = 7.28 × 10 6 ms –1
258.
m λ ×
9.1 10
−31
× 10
−10

2
λ= h ⇒ h
V= = 150.7V
2meV 2λ 2 me
h =
259. ∆V = 8.78 × 10 ms
–11 –1
4πmx∆
350 ProblemsinChemistry

1 8
260. = RH ⋅ ⇒λ= 105.14 nm
λ 9
−34 −
hc = 6.626 × 10 × 3 × 10 8 6.626 × 10 34 × 3 × 10 8
EThr eshold = , E =
λ 230 × 10 9
− i nci dent −
105.14 × 10 9
−34
6.626 × 10 × 3 × 10 8  1 1 
K. E. =  −  = 1.026 × 10 –18 J
10
−9  105.14 230 
 1 1  1 1 
261. 25.7 = KZ 2  2 − 2  = KZ 2  − 2 …(i)
 n1 n2  4 n 

1 1 
8.7 = KZ 2  − 2  …(ii)
9 n 
Solving,Eqs.(i)and(ii)gives: n =5
KZ = 122.38= I. E.
2
Also,
 1 
262. 13.6 1 − 2  = 10.93 + x
 n 
 1
54.4 1 − 2  = 49.18 + x, where x iswork-function.
 n 
Solving: n = 4, x = 1.82 eV
E ∆
263. ∆H = 248 × 10 J ⇒
3
= H = 4.12 × 10 −19 J = hc ⇒λ= 482.76 nm
mol ecule N A λ
264. ∆H r eact i on(O 3 → O+ O)2 = 249 − 142 = 107 kJ / mol

λ= hc ⋅ N A = 1119 nm
∆H
−
hc = − 4 × 10 17
265. E = 3.313 × 10 19 J ⇒ Numberofphotons = = 121
λ −
3.313 × 10 19
hc = hc + hc λλ2 3
266. ⇒ λ1 =
λ1 λ 2 λ 3 λ2 +λ3
3RT h =
267. r. m. s.(c) = = 1351.67 ms−1 ⇒λ= −
7.38 × 10 11 m.
M mc
hc = −
268. Energyofphoton = 3.313 × 10 19 J
λ
) = n ∆H = 166.67 kJ
E ( r equir ed for melting
Numberofphotons = 5.03 × 10 23 .
6000
Also,averageenergyrequired/molecule = = 9.96 × 10 −21 J
NA
2 moleculesmelted/photon = 33.
Averagenumberof HO
Solutions 351
2
KZ
269. 3rdI.E. = 2 ⋅ N A = 11817 kJ/mol ⇒ IIndI.E. = 19612 − (520 + 11817) = 7275 kJ / mol.
n
h = 19.85 × 10 −6 ms −1 .
270. ∆V =
4πmx∆
2
KZ 3
271. E = 2 = K b ⋅ T ⇒ T = 20.636 × 10 ° C.
6

n 2
272. Maximum number of emission lines = nn( − 12 )/ , where n is orbit number ⇒ nB = 5. Possible
values of n A are2,3 and 4.Since onlyone photon ofenergygreater than 3.066 eVisemitted, nA
mustbe2andonly n = 5 to n = 1 transitionwouldemitphotonofenergygreaterthan3.066V.
Ionizationenergy (KZ 2 ):
1 1 
3.066 = KZ 2  −  ⇒ KZ (I E)= 14.6 eV
2
 4 25 
273. Weknowthataverageenergyofanoscillatoris
hν
E = hν / kt
e −1
−
hν = 6.627 × 10 × 10 =
34 14
4.8 ⇒ e
48
.
= 121.5
Q −
kT 1.38 × 10 23 × 1000
6.627 × 10 –34 × 1014
⇒ E = = 5.5 × 10 −22 J .
120.5
1 1 
274. K.E. = h (ν − ν 0 ) = hc  − 
λ λ0
1 E 1 − −
⇒ = + where E = 1.5 eV =1.5 × 1.6 × 10 19 J = 2.4 × 10 19 J
λ hc λ 0
−
1 . × 10 19
24 1
⇒ = +
λ 6.626 × 10 × 3 × 10
– 34 8
23 × 10 –8
Solving, λ= 1815
. × 10 −7 m = 1815Å
λ
275. λ ′− λ = (1 − cos θ) where λ′= wavelengthofscatteredbeam = 0.22Å .
mc
−
6.626 × 10 34
⇒ λ = λ ′− h (1 − cos θ) = 2.2 × 10 –11 − −
(1 − cos 45° ) = 0.2129Å .
mc 9.1 × 10 31 × 3 × 10 8
276. de-Broglieequationis:
2
λ= h = h ⇒ h
2meV = 2
mv 2meV λ
−34 2
h
2
(6.627 × 10 )
or V= = −31 −19
=1044 volt.
2meλ 2
2 × 9.1 × 10 × 1.6 × 10 × (3.8 × 10 –11 ) 2
352 ProblemsinChemistry

nh
277. Since, mvr =
2π
−
⇒ nh = nh × Z = hZ = 6.626 × 10 34 × 2
v= = 1.457 × 10 6 ms –1
π
2 mr 2πman0 2 π
2 man0 −31 −12
2π × 9.1 × 10 × 53 × 10 × 3
−
h = 6.626 × 10 34
⇒ h = −31
= 5 × 10 −10 m = 5Å .
×
mv 9.1 10 × ×
1.457 10 6

278. TheHeisenberg ’suncertaintyequationis

∆∆ h h
x⋅ p = ∆∆ ⇒
x⋅ v =
4π 4πm
−34
h 6.626 × 10
⇒ ∆v (min ) = = = 0.58 ms –1
π ∆ −31
4 mx (max) 4π × 9.1 × 10 × 10 −4

279. Theuncertaintyinvelocityis ∆v = 0.001 km hr =2.778 × 10 ms .

–1 –4 –1

⇒ Theuncertaintyinposition:
−
h 6.626 × 10 34
∆x = = = 3.796 × 10 –34 m.
4πmv∆ 4π × 500 × 2.778 × 10 –4

−34
The uncertainty inmeasurement of position ( ∆x = 3.796 × 10 m ) iswhollynegligible as
comparedtomassandvelocityofmovingautomobile.
−34
hc = 6.626 × 10 × 3 × 10 =
8
280. Energyofincidentphoton = 9.94 × 10 –16 J
λ 200 × 10 –12

1 1 −31 −
Energyofemittedelectron = mv = × 9.1 × 10
2
(2 × 10 7 ) 2 = 1.82 × 10 16 J
2 2
⇒ Bindingenergyofelectron = Energyofincidentphoton–Energyofemittedelectron
= 8.12 × 10 –16 J = 5075 eV.

281. Stoppingpotentialisthemaximumkineticenergyofphotoelectron:
− −
⇒ K.E.(max) = eV =
0.5 × 1.6 × 10 19 = 8 × 10 20 J
−34 8
hc = 6.626 × 10 × 3 × 10 = −
Energyofphoton = 7.835 × 10 19 J
λ 253.7 × 10
−9

− − −
Work-function = 7.835 × 10 19 − 8 × 10 20 = 7.035 × 10 19 J = 4.4 eV.

282. Themaximumuncertaintyinpositionofelectroninsidethenucleus = 10 −14 m.

⇒ minimumuncertaintyinmomentum
h = −
( ∆ p) = 0.527 × 10 20 kg ms –1 .
4π∆x
3 3 −23
283. Average T.E. = kT = × 1.38 × 10 × 300 = 6.21 × 10 −21 J
2 2
Solutions 353

10 –3
⇒ p (momentum) = 2mE = 2 × × 6.21 × 10 –21 = 4.54 × 10 −24 kgms –1
N0
−
6.626 × 10 34
λ= h = −24
= 1.46 × 10 −10 m = 1.46Å .
p 4.540 × 10
e
2
(1.6 × 10 –19 ) 2
284. Potentialenergy = = = 7.69 × 10 −19 J
4πε 0 r 4πε 0 × 3 × 10 −10
2a0
285. Probability( P )between 0 and 2a 0 = ∫0 ψ12s dτ where dτ= 4πr 2 dr.
2
− r
2a 0 4 2a 0
P = ∫0 ∫0
− −2 r/a 0
∴ (πa 03 ) 1 e 4πr dr = 2
3 e
a0 2
r dr
a0
4  3 a 0 −4 a 0 
3 3  –4 e −4 1 
 =− 43 e + −  = 0.7624
−4 −4
=− 3  ae
2 0 + ae03 + e −
a 0  4 4   4 4

286. Theradialdistributionfunctionfor1 s orbitalis

2 2
2 2
= 4πr 2 ψ12s ⇒ d[Rr ] =
Rr Formaximum, 0
dr
d π 2 π 3 −1 −2r/a 0 = 2r 2
⇒ [4 r ( a 0 ) e ] 0 ⇒ 2r − = 0 or r = a0.
dr a0

Probability = ∫ ψ12s dτ= ∫0 (πa 03 )

r r −1 −2 r/a 0
287. e 4πr 2 dr
0

4
∫0 r 2 e
r −2 r/a 0
P= 3 dr
a0
−12 −
Integratingbypartsandsubstituting r = 10 m and a 0 = 53 × 10 12 m.
−
⇒ P = 9 × 10 6 .
3RT 3 × 8.314 × 298
288. v rms = = −
= 1360 ms –1
M 4 × 10 3
de-Broglieequation:
34 −
λ= h = 6.626 × 10 × 6.023 × 10 23 = 7.34 × 10 –11 m.
−
mv 4 × 10 3 × 1360
−  1 3 − −
289. Transitionenergy = 2.18 × 10 18 1 −  = 2.18 × × 10 18 J = 1.63 × 10 18 J.
 4 4
3 −18
Translationalenergy = kT = 1.63 × 10
2
2 × 1.63 × 10 –18
⇒ T= −
= 78.744 × 10 3 K .
3 × 1.38 × 10 23
354 ProblemsinChemistry

290. Thereducedmassofmovingelectron
mme
⋅ posi t r on m
(µ=
) = e
+
me m posi t r on 2
4πε 0 2
⇒ rn = n
2
h = (1.0589 × 10 −10 m ) n 2
(m/e 2) eZ2
−10
⇒ r1 = 1.0589 × 10 m = 1.0589Å .

CHEMICAL BONDING
291. CO 2 : O == C==OLinear,non-polarmolecule.
COS: S ==C==OLinear,polarmolecule.
Ο
 
CO 2−
3 : C Trigonalplanarionwith 2
sp -hybridizedcarbon.Itexists
O O inthreeresonatingforms.
− −

Cl
SiCl4 : Si
Cl Cl Tetrahedralmoleculewith sp 3 -hybridizedsilicon.
Cl
Cl Cl Pentagonalbipyramidalwith spd3 -hybridizedphosphorus.
Equatorialbondangle = 120°,Axial-equatorialbondangle = 90.°
PCl5 : Cl P

Cl Cl
H +

Tetrahedralionwith sp 3 -hybridizednitrogen.Allbondangles
NH4+ : N areequaland 109°28 ′ .
H
H H
+ +
PH 4 : Similarto NH 4 .
+ +
PCl 4 : Similarto NH 4 .
Cl –
Cl Cl 3 2
Squarepyramidalionwith spd -hybridizedphosphorus.
PCl6– : P
Cl Cl
Cl
−
SF6 : Sameas PCl 6 .
Solutions 355
F
F
F
72°
IF:7 F I Pentagonalbipyramidalwith spd3 3
-hybridizediodine.
F
F
F
••
292. SO 2 : S Angular(V-shaped)with sp 2 -hybridizedsulphur.
O O
N H:
3 N Trigonalpyramidalwith sp 3 -hybridizednitrogen.
H H
H
••
HO
2 : O
••
Angular(V-shaped)with sp 3 -oxygen.
H H
PCl3 : P Trigonalpyramidalwith sp 3 -phosphorus.
Cl Cl
Cl
NCl 3 : Sameas PCl 3 .
293. (a) Ifeverythings aresame,and central atomsareformssamegroup, bond angle decreases on
descendingdownthegroup.
NH 3> P H >3 AsH >3 S bH >3BiH 3
(b) H 2O> H S>
2 H Se
2 >H Te2

294. AsH 3<H Se

2 < PH <H
3 O<2NH. 3

T-shaped with spd3 -hybridized chlorine. (In trigonal

295. ClF:3 F Cl bipyramidal geometry, lone pairs are stable at equatorial
positions).

F
O
 
COCl 2 : C Triangularplanarwith sp 2 -carbon.

Cl Cl
Cl 2O : Twoshapecanbepredictedas:
•• ••
O
••
Cl
••
••
•
Cl Cl Cl O
•• •
V-shaped wi th oxygen at cent re V-shaped with chlor ine at centre
356 ProblemsinChemistry
••
OF2 : O V-shapedwith sp 3 -oxygen.
••
F F
–
Cl Cl
ICl4– : I Squareplanarwith spd3 2
-iodine.
Cl Cl
F
F F
IF:5 I Squarepyramidal spd3 2
-iodine.
F F
O –
Cl Cl
IO Cl4– : I Squarepyramidalwith spd3 2
-iodine.
Cl Cl
Cl +
Cl
IO Cl4+ : O I Trigonalbipyramidalwith spd3 -iodine.
Cl
Cl
•• + •• −
−
296. N 3 : N ≡≡N → N
•
• Linearwith sp-hybridizednitrogen.
••
I –

I3– : Linearwith spd3 -hybridizedcentraliodine.

I

I
F
F F
BrF:5 Br Squarepyramidalwith spd3 2
-bromine.
F F
–
F F
IF4– : I Squareplanarwith spd3 2
-iodine.
F F
–
F
BF4– : B Tetrahedralwith sp 3 -boron.
F F
F
Solutions 357
•• +
+  
ICl 2 :  I  V-shapedwith sp 3 -iodine.
•• 

 Cl Cl 

Cl
–
I
ICl2– : Linearwith spd3 -iodine.

Cl
F
F
P F:5 F P
Trigonalbipyramidalwith spd3 -phosphorus.
F
F
297. Relative electron withdrawing power of nitrogen is morein NCl 3 than inNOCl therefore
homolyticcleavageofN—Clbondwouldbedifficultin NCl 3 .
F
–
F +

A sF2+ : As
298. A sF:5 F As SnCl3– : Sn
F F Cl
F Cl
Cl
F
Trigonal bipyramidal V-shaped with sp2-As Trigonal pyramidal with sp3-Sn
F –
F F F
N OF: O==N SO32– : S TeF5– : Te
O
O F F
O
2
Angular w ithsp -N Tetrahedral Square pyramidal
3 2
with s pd -Te
– Cl –
Cl Cl
GeF3– : Ge SCl2 : S
F Cl Cl SbCl6– : Sb
F
F Cl Cl
3 3 Cl 3 2
Trigonal pyramidal with sp -Ge V-shaped with sp -S Octahedral with s pd -Sb
F F
+

+
299. ClF4 : F Cl FClO:3 Cl
F O O
F O
Sea Saw Tetrahedral with sp3-Cl
358 ProblemsinChemistry
O +

FClO: + SeO32– : Se
2 Cl
F F O O
O
Tetrahedral Trigonal pyramidal

300. (a) BF(3 µ = 0) = PCl 5 (µ = 0) < POCl3 < SCl2 < ICl3
(b) XeF(2 µ = 0) = SnCl4 (µ = 0) < PCl4 F< XeO 3< SF 4

301. Li 3 N< Li 2O < LiF (Fajan ’srule)

302. (a) Al 2 (CO)3 3 < BeCO3< MgCO <CaCO
3 < 3BaCO < Na
3 CO 2 3

(b) CaS O4 < CaSO 3< CaCO 3

(c) Al 2 (S O)4 3 < MgS O4 < Sr SO4< BaSO 4
(d) FeC 2O 4< CaC O2 <4CaCO <K3 CO 2 2 4
303. Symmetricalrepulsion bythe two lone pairs fromaxial positions cancels the effect ofone-another
andbondanglesremainsintact.
304. Al Cl3 <GaCl 3 <MgCl 2 <CaCl 2 <BaCl 2 < NaCl (Fajan ’srule).
305. (a) NH 3 (b) PF3 (c) AsF3 (d) AsCl3 (e) HO
2

306. (a) H 2S< PH <H

3 O<2 NH 3 (b) GeH –3< Si H <
–
3 CH
–
3
F F F
Cl Cl Cl
307. (a) F P (b) Cl P (c) Br P
Cl Cl Cl
F F F

Cl
–
I
(d) [Cl Cl]+ (e) I
3
V-s haped withsp -iodine
Cl
Linear
308. PCl 3 F(2 µ = 0) < PF3 Cl 2 < PBr F2 Cl2
309. CCl 4 <CHCl 3 <CH 2Cl 2 <CH 3Cl
F O
O F F
310. (a) O Cl (b) Xe
F F F
F
Trigonal bipyramidal Square pyramidal
3 2
3 2
with s pd -Cl with s pd -Xe
Solutions 359
O –
+
Cl Cl I
(c) I (d) Cl Cl
Cl Cl V-s haped withsp3-I
Square pyramidal
3 2
with s pd -I

311. Insolidstate, PCl 5 remainsasdipolarionas [P Cl6 ]– [P Cl+4 ]

Cl –
Cl +
Cl Cl
P
P Cl
Cl
Cl Cl Cl
Cl
Cl
Cl
Ingasphase PCl 5 remainsasisolatedgasmolecule: Cl P
Cl
Cl

312. Dueto back bonding ofa lone pair from p-orbital of oxygen to vacant d-orbital of Si( pπ −d π
bonding).
313. (a) Linear(b)Squareplanar(c)Octahedral(d)T -shaped(e)Squarepyramidal
Cl Cl Cl
(f)Sea-saw(g)Trigonalbipyramidal (h) I I
Cl Cl Cl
CH3 CH3
CF3 CF3
314. (a) FC
3 P (b) HC
3 P
CF3 CF3
CH3 CH3
315. Greaterelectronegativitywhenbondingthroughaxialpositions.
−
316. Pπ − Pπ backbondingin BF3 givessomedoublebondcharacter,whichisabsentin BF4 .
317. Pπ − d π backbondingoccursbetweenSiandCl,whichisabsentin CCl 4 .
318. BF3<BCl 3 <BBr 3 <BI 3
319. 3 3 isinvolved in pπ − d π backbonding, notavailable fordonation
Lone pairofnitrogen in N( S iH)
toaLewisacid.
H H Br H
320. C==C C==C
Br Br H Br
µ≠ 0 µ= 0

321. d (µ = 0) = b(µ = 0) < c < a

322. Dueto larger size of 3 p-orbital with Si, there isfewerchance ofsidewise overlap giving π-bonds.
360 ProblemsinChemistry
F F F
323. N==N N==N
F
µ≠ 0 µ =0

324. Due to freerotation about C—C sigmabond, 1,2-dichloro ethane acquire the anti (moststable)
conformationwhichisnon-polar.Indichloroethane,rotationisrestricted.
Cl
H H
Cl Cl
H H C==C
Cl H H
anti conformation of due to res tricted
1,2-dichloro ethane( µ =0) rotation, µ≠ 0

325. In ClHC == C == CHCl, the two C—Cl bonds arein perpendicular plane and hence the molecule is
polar.
In HClC== C== C== CHCl,the two C—Cl bonds are in the sameplane and individual C—Cl
dipolesareat180°,cancellingoneanothergivingzerodipolemoment.
Cl Cl Cl H H Cl
326. C==C C==C C==C
H H H Cl H Cl
I II I II
Dipolemoment: II<III<I.
N N
N N N N
327. (a) (b)
N N N N
N N

328. NaFhashigher lattice energythan NaCl.Lattice energyisinversely proportional tosquare ofthe

interionic distance. Since, fluoride ion is smallerin size than chloride ion, NaFwill have higher
latticeenergy.
329. The NO 2 existintwoequivalentresonanceformas:
✧ ✧ ✧

N N N
O O O O O O
both N—O bonds are
identical, therefore equal
bond energies.

• •
==O Ithasa one sigmaand one pi-bond and bond orderistwowhereasin
•N NO 2 , the N  O
bondorderislessthantwo.Therefore, N  O bondenergyinNOisgreaterthanin NO 2 .
330. Both NO and NO 2 have oneodd (unpaired) electron. Whenthetwomoleculeapproach eachother,
unpairedelectronmaybesharedtoformacovalentbondas:
ON +NO 2 → ON NO 2
bothNhavecompleteoctet.
Solutions 361
O O
Shape of N2O:3 N—N
O
F
+ F
O
331. (a) O ==S (b) S
F
Cl S
Triangular planar F
3 3
One S -iss pd andother is sp hybridized.

332. N hashigher electronegativity than C,therefore, energyoforbitals ofN islessthan that ofcarbon
andenergyleveldiagramwillbeasfollows:

C(2)p
N(2)p

C(2)s
N(2)s

333. (a) SiF4 is tetrahedral, non-polar molecule while PF3 is trigonal pyramidal, polar molecule.
Therefore, PF3 willbemoresolubleinpolarsolvent.
(b) SF6 issquare bipyramidal,non-polar moleculewhile SF4 isa seasawshaped, polar molecule.
Therefore, SF4 willbemoresolubleinpolarsolvent.
(c) IF5 isa square pyramidal,polar moleculewhile AsF5 isa trigonal bipyramidal,non-polar
molecule.Therefore, IF5 willbemoresolubleinapolarsolvent.

334.

δ-b ond
σ-b ond π-b ond

CHEMICAL EQUILIBRIUM
2 0.5 × 0.2
335. K = = ⇒ x = 0.7 mol
9 0.5( 0.2 +)x
362 ProblemsinChemistry

336. H+ B HB
0.1 0.1 0
0. 08 0.08 0.02 Initial
At equilibrium ⇒ K c = 3.125.
337. NH 4Cl ()s NH 3 ( g ) + HCl(g )
3.66 × 10−2 3.66 × 10–2 −
(0.154– x ) (3.66 × 10–2 – x ) molesatequilibrium K c = 134
. × 10 3
after adding 2.0g NH3.

⇒ K c = 1.34 × 10 −3 = (0.154 − x )(3.66 × 10 −2 − x ).

Solving, x = 0.163 and 0.026
−2
x cannotbegreaterthan 3.66 × 10 , henceitis0.026.
Therefore, onadding 0.2g NH 3 , 0.026 moles of both HCl and NH 3 will combine formingequal
amountof NH 4Cl ()s beforeequilibriumwasre-established.
Thus,amountof NH 4Cl ()s atnewequilibrium = 1.431 g;
%dissociation = 28.45.
 0.63 + 2x 
2

338. K = 6.05 =   ⇒ x = 0.134 ⇒ [H 2]= [I 2 ]= 0.366, [HI ] = 0.898.

 0.5 − x 
339. (CH)3 3 CCl (CH)3 2 C== CH2 + HCl
0.2– x x x Molarity
2
KP
KC = = 0.084 = x ⇒ x = 0.094
RT 0.2 − x
340. CO 2 (g ) +C()s 2CO
79.2 − x 56
x
44
56
At1000K x − x = 2.3 ⇒ x = 8.433g
44
PCO( g ) = 6.286 atm, PCO2 ( g ) = 26.38 atm ⇒ K P (1000K ) = 1.49 atm
56
At1100K: x − x = 5.3 ⇒ x =19.43 g.
44
PCO( g ) = 15.93 atm, PCO2 ( g ) = 24.5 atm; ⇒ K P (1100 K)= 10.35 atm
K (2) ∆H  T2 − T1 
Also ln P =   ⇒∆ H = 177.25 kJ
K P ()1 R  TT 1 2 

341. N 2 +3H 2 2NH 3 Tot al

1− x 1 − 3x 2x 2(1 – x )
16x 2 (1 − x ) 16x 2
⇒ KP = ≈
= 64x 2
(1 − 3x )3 p 2 P
2

−3 −
⇒ x = 9.68 × 10 , x NH 3 = 9.78 × 10 3 .
1
342. HO
2 (g ) H 2 (g ) + 2 O 2 (g ) Total moles
0.85 0.15 0.075 1.075
−2
⇒ K P (T ) = 4.66 × 10
Solutions 363
 4.66 × 10 −2  57.8 × 10 3  T − 1000 
⇒ ln  −11 
=   ⇒ T = 3284K
 8.7 × 10  2  1000 T 

343. H2 + I 2 2HI
1− x 3−x x
2 2
3– x 3– x 2x
2
x 4x 2
⇒ = ⇒ x = 1.5, K = 4.
 x  x  (3 − x ) 2
1 −   3 − 
 2  2
344. Iodine inthegaseous state = 0.0386 mole; Iodine in solid state = 0.0114.Minimum H 2 (g ) would
berequired when solid I 2 ()s hasjustbeen exhausted andthefollowing equilibriumismaintained:
H 2 (g ) + I 2 (g ) 2HI(g )
moles at equilibrium x 0.0386 0.0228
2
(0.0228) −3
⇒ 20 = ⇒ x = 0.67 × 10
x (0.0386)
⇒ molesof H 2 required = 0.012
− 0.0492
345. I 2 +I
–
I3 K = −3
= 745.57 L mol −1
1.299 × 10 × 0.0508
Addingwaterwilldrivethereactioninbackwarddirectionandsolubilitywilldecrease.
346. Ag( ) Bg( ) + Cg( )
0.46 − x x x
(0.46 + x )(0.082) × 300
⇒ 3= ⇒ x = 0.15
5
 0.15 
2
 
 0.61 
⇒ K P (300 K) = × 3 = 0.357
 0.31
 
 0.61
Similarly, K P (320 K) = 1.145
1.145 ∆  20  K (350) ∆H  30 
Now, ln = H   and ln P =  
0.357 R  300 × 320  1.145 R  350 × 320 
Solving, K P (350) = 5.12, P0 (350) = 2.64
2
P 1.92
⇒ 5.12 = ⇒ P = 1.92 ⇒ α (350 K) = =0.7272
2.64 − P 2.64
0.15
Also, α (300 K) = =0.326
0.46
0.4012
% incr ease= × 100= 123.06%
0.326
364 ProblemsinChemistry

175
347. P(NH)3 =175 bar ⇒ PN 2 = = 43.75 bar
4
and PH 2 = 3 × 43.75 = 131.25 bar
(175) 2
⇒ KP = 3
= 3.096 × 10 −4 bar −2
(43.75)( 131.25)
348. Let r betheratioof P (Cl 2 ) to P (Br 2 ). Thus, P (Cl 2 ) = rP ( Br2 )
⇒ Pt = P (Cl 2 ) + P ( Br2 ) + P (Br Cl) = rP (Br2 ) + P (Br2 ) + P ( Br Cl)= (1 + rP
) (Br2 ) + P (Br Cl)
Pt − P ( Br Cl)  P − P (Br Cl) 
⇒ PBr2 = , P (Cl 2 ) = r  t 
r +1  r +1 
2 2
⇒ P (Br Cl) P ( Br Cl)
KP = =
  Pt − PBr Cl    Pt − P (Br Cl)  [ − ( Br Cl )]
2
 r     r  Pt P 
 r +1   r +1   (r + 1) 
Takinglogarithmofeachsideanddifferentiatingw.r.t. r:
ln K p = 2 ln[ P (Br Cl)] − ln r − 2 ln[ Pt − P ( Br Cl)]+ 2 ln( r + 1)
1  ∂P ( Br Cl) 1  1   − ∂P ( Br Cl) 1
0=2   − −2    +2
P ( Br Cl) ∂r  r  Pt − P ( Br Cl)  ∂r  r +1
∂P (Br Cl)
Assigning = 0 andsolvingfor ‘ r’ gives r = 1
∂r
Hence,stoichiometricamountsof Cl 2 and Br2 generatemaximumyieldofBrCl.
349. F2 2F
0.06 − x 2x
 2x   0.06 + x 
2
4x 2
KP =   ⋅ P= × 2.07 = 9.5 × 10 −3
 0.06 + x   0.06 − x  −4
36 × 10 − x 2

−3
⇒ x = 2.03 × 10 ⇒ molefraction of F= 0.065, mole fraction of F=
2 0.935
350. N 2 (g ) +O 2 (g ) 2NO(g )
0.8 − x 0.2 − x (2)x
2
4x
K= = 4 × 10 −4 ⇒ x = 3.95 × 10
−3
(0.8 − x )(0.2 − x )
⇒ molefractionof NO( g ) = 0.08, N(2 g ) = 0.796, O(2 g ) = 0.196
351. Br2 +3F 2 2BrF3
0.25 0.75 0.497
1.497 1.497 1.497
(0.497 × 1.497) 2
K= = 5.248
0.25( 0.75)3
After increasing equilibrium pressure = 2 bar, reaction will shift in forward direction and letx mole
of Br2 reactedfurther.
Solutions 365
0.25 − x 0.75 − 3x
Thennewpartialpressure: Br2 = × 2; F2 = × 2
1.497 − 2x 1.497 − 2x
0.497 +2 x
Br F=
3 × 2
1.497 –2 x
Substituting these partial pressureinequilibrium constant expression and solving gives x = 0.061.
Therefore,newcompositionswouldbe:
Br2 = 0.189, F2 = 0.567, Br F= 3 0.619 moles.
352. Ag 2CO 3 (g ) AgO2 ()s + =
CO 2 (g ) K P 0.0095 bar at120°C.
P (CO 2 ) at 120° C = KP = 0.0095 which islessthan 0.01 bar,the partial pressureof CO 2 in air.
Therefore, Ag 2CO 3 ()s willnoteffervessat120°C.
353. Atequilibrium: 2 A + B 3C + 2D
0.4 1.7 0.9 16
. K c = 6.86
P
354. PCl 5 PCl 3 +Cl 2 K P =
3
Let x mole of Cl 2 isadded out ofwhich y mole reacted with PCl 3 , giving y mol PCl 5 . Also, at new
equilibrium n = 12.
⇒ 6 + x − y = 12 ⇒ x − y=6
P = 2P (2 − y) ⇒ 2 20
and y= and x=
3 32( + y) 3 3
355. Inthecombinedsystempartialpressureofthegasesbeforeanyreactionoccurredare:
250 100
NO = 0.46 × = 0.3285; O 2 = 0.86 × = 0.2457
350 350
Here,NOislimitingreagent:Partialpressureafter1ststep:
NO = 0, O 2=0.0814, NO 2 = 0.3285
Now,let p-bethedecreaseinpartialpressureof NO 2 duetoequilibrium.

⇒ p=
0.0814 + 0.3285 − p + 0.37 ⇒ p = 0.0798 ⇒ K P = 0.645 atm –1
2
356. Let usconsider P0 betheinitial partial pressureofeach Cl 2 (g ) and F2 (g ).Then atequilibrium
partialpressureofeachgaswouldbe:
PCl 2 = P0 − 0.12, PF 2 = P0 − 0.16
2
P ( Cl F) = (0.2) 2
⇒ 3.2 =
P (Cl 2 )P (F2 ) (P0 − 0.12)( P0 − 0.16)
Solving,gives P0 = 0.253 and0.026,wherethesecondvalueisnotacceptable.
(0.04) 2
⇒ K p forsecondequilibrium = = 14.95
(0.133) (0.093) 3
357. Cl 2 + F2 2ClF K = 16.12
0. 0665 0.0665 0.267
366 ProblemsinChemistry

When Br2 isadded: Cl 2 +F 2 2ClF

0.075 − x 0.075 0.25
2
(0.25)
16.12 = ⇒ x = 0.023
0.075(0.075 − x )
Cl 2 +Br 2 2Br Cl
0.07 − x 0.1 − x 2x

(0.046) 2
Kc = = 0.528
0.052 × 0077
.

358. 2NO + Br2 2NOBr. Letinitial partial pressureof NO = p0 anddecrease inpartial pressure
beforethe1stequilibriumbe p1 . Then:
p1
p0 − p1 + 1.25 − + p1 + 1 − p0 = 2.12
2
(0.26) 2
⇒ p1 = 0.26 and Kp =
(P0 − 0.26) 2 (1.12)
Similarly, if p2 bethe total decrease inpartial pressureofNObeforethe second equilibrium was
establishedthen
p2
p0 − p2 + 21.75 − + p2 + 1 − p0 = 22.5
2
(0.5) 2
⇒ p2 = 0.5 and KP =
( p0 − 0.5) 2 (21.5)
Equatingthetwo K P ; P0 = 0.69 and K P = 0.326.
K1
359. Beforeadditionof Br2 (v ) : Cl 2 (g ) +I 2 (g ) 2I Cl
0.492 bar − x 0.03 2x
⇒ 0.522 + x = 0.767 ⇒ x = 0.245 and K 1 =32.4
Afteradding Br 2 (v )
K1
Cl 2 ( g ) +I 2 ( g ) 2I Cl(g )
0.247+ q − p 0.03 0.49 − 2q
K2
I 2 (g ) + Br2 (g ) 2I Br(g )
0.03 0.492 – 0.1476 − p 0.2952
Also, P (Br 2 ) = 0.2 ⇒ p = 0.1444
(0.2952) 2
⇒ K2 = = 14.52
0.03 × 02
Solutions 367
K2
Cl 2 (g ) + Br2 (g ) 2Cl Br( g )
0.247+ q − p 0.492 − 0.1476 − p 2p

(0.49 − 2q ) 2
Also, K1 = 32.4 =
(0.03)(0.1026 + q )
(0.2888) 2
⇒ q = 0.05 ⇒ K3 = = 2.73
(0.1526) ( 0.2)
4x 2
360. K = = 50 ⇒ 2x (mol es of AB ) = 1.87
(1 − x )(2 − x )
361. mmolof I 2 reactedwithhypo = 0.785
⇒ Atequilibrium: m molof H 2 = I 2 =0.785, m molof HI =5.93
 0.785 
2

K =   = 17.52 × 10 –3
5.93 
362. Lettheequilibriumpartialpressureof NO 2 = HO2 ( v ) = 2 p1
Equilibriumpressureof N=2 p2 andequilibriumpressureof NH 3 = 2 p3
⇒ Equilibriumpressureof H 2 = 2 p2 − p3 . Then,
NH
2 4 + 3O 2 2NO 2 + 2HO
2 K1 = 3
1 − p1 − p2 − p3 1 − 3 p1 2 p1 2 p1

NH
2 4 N 2 + 2H 2 K p (2) = ?
1 − p1 − p2 − p3 p2 2 p2 − p3

NH
2 4 N2 +2NH 3 K P (3) = ?
1 − p1 − p2 − p3 2 p2 − p3 2 p3
9 1
Given, 2 p1 = bar and 2 p3 = bar
19 38
3 11
⇒ PNH2 = − p2 and PO2 = bar
4
4 38
9
4
 
 19 
⇒ K1 = 3 = Solving p2 = 0.233
 11 
3
  (0.75 − p2 )
 38 
Usingvaluesof p1 , p2 and p3 gives p(N 2H) 4 = 0.517, p(N 2 ) = 0.233
p(H 2 ) = 0.4528 and p( NH3 ) = 0.0263 bar.
−2 −
⇒ = ×
K p (2) 9.24 10 bar 2
and K p (3) = 2.95 × 10 3 .
363. 2NOCl 2NO + Cl 2
0.64 0.24 0.12
P: 15.2 × 10–3 5.7 × 10−3 2.85 × 10−3 −3
mole: Tot al= 23.75 × 10
−3
K P = 16.875 × 10 bar.
368 ProblemsinChemistry

Let atthis stage x mole ofCl 2 isadded, out ofwhich y molereact back. Also volume is increased to
1.5 litre but at same temperature and pressure, therefore new total mole
= 23.75 × 1.5 × 10 –3 =35.625 × 10 –3 .
Anewequilibrium:mole Cl 2 =2.85 × 10 –3 + x − y
− −
NO = 5.7 × 10 3 − 2 y and NOCl = 15.2 × 10 3 + 2 y
−3
Addingmolesandequatingtototalmolesgives x − y = 11.875 × 10
Therefore,atnewequilibrium,mole-fractionsare:
− −
Cl 2 = (2.85 +11.875 ) × 10 3 /35.625 × 10 3 = 0.4133
−3 −3
5.7 × 10 −2y 15.2 × 10 +2y
NO = −3
and NOCl = −3
35.625 × 10 35.625 × 10
−3
Substitutinginexpressionof K p gives y = 1.108 × 10
⇒ x = 12.983 × 10 –3 mol
4α 2 p
364. NO
2 4 2NO 2 Kp =
1−α 2
M = ρRT
At P = 1,ρ= 2.33 :Applying, where M = molarmassof N 2O. 4
1+α P
⇒ α= 0.6 and K p = 2.25.
Let β-bethedegreeofdissociationatnewequilibrium.Then,
M = 2.33RT M = 5.08RT ⇒
and 1 + β = 0.734 P
1.6 1 1+β P
4β 2 P 4β 2
⇒ 2.25 = = ⇒β= 0.468 and P = 2 bar.
(1 − β)(1 + β) 07341
. ( − β)
92 × 1.5
At P = 1.5, using K p ; α= 5.22 and ρ= = 3.685 g/L
1.522RT
2
P
365. HS2 (g ) H 2 ( g ) + S( g ) K p = 0.099 =
21( − P )
where, P ispartialpressureof H 2 (g ) atnewequilibrium.
0.356
⇒ P = 0.356 and α= = 0.21
1.644
PV =
366. (a) n = 0.05, i.e., out of 0.03 moleof PCl 5 , 0.02 mol has decomposed into PCl 3 and Cl 2
RT
giving0.05moleofgaseousmixture.
2
⇒ α= = 0.67
3
Solutions 369
α P
2
(b) Fromtheinformationinpart ‘ a’; K p = = 0.8
1−α 2
PCl 5 PCl 3 +Cl 2
P: 2.73 − p p p
2
⇒ p ⇒ p = 1.13 at m.
0.8 =
2.73 − p
1.13
⇒ α= = 0.42
2.73
367. H 2 (g ) +CO 2 (g ) HO2 ( g ) +CO ( g )
I: 0.07 0.17 0.03 0.03
⇒ K1 = 7.563 × 10 . –2

II: H 2 ( g ) +CO 2 (g ) HO
2 ( g ) +CO ( g )
0.07 − x 0.17 + y 0.03+ x 0.03 − y
K2
CoO()s + H 2 (g ) Co()s + HO
2 (g )
−x +x
K3
CoO()s + CO(g ) Co()s + CO 2 (g )
− y + y
Also 0.03 + x = 0.09 ⇒ x = 0.06
0.09
Hence, n(H 2 ) = 0.01 ⇒ K2 = =;9
0.01
−2 0.09(0.03– y)
Also, K1 = 7.563 × 10 =
0.01( 0.17+ y)
−2
Solving, y = 2.83 × 10
0.17 +2.83 × 10 –2
⇒ K3 = = 116.64
0.03 –2.83 × 10 –2
368. 2NOBr 2NO +Br 2
0.01– x x x/2

x = PV
n = 0.01 +
2 RT

⇒α= x =
Solving, x = 0.0074 0.74
0.01
5
If5g ofNOBristaken,initialmole = = 0.045
110
 α
Molesatequilibrium = 0.045 1 +  = 0.045 × 1.37 = 0.06165
 2
370 ProblemsinChemistry

nRT =
P= 0.753 atmosphere.
V
369. 4HCl+ O 2 2Cl 2 +2HO
2
0.12 0.405 0.19 0.19
Equilibrium 0.905 0.905 0.905 0.905 mole fraction
4
(0.19) (0.905) 1
Kp = ⋅ Also P = P0 (0.905) = 0.905 atm.
(0.12) 4 (0.405) P
 0.19   1 
4
−1
=   =
 0.12   0.405  15.5 atm.

370. NO
2 5 NO
2 +O
3 2
4 −x x− y x+y
Kc
NO
2 3 2 + O2
NO
x− y y x+ y
(x + y)( x − y)
K = 4.5 = and x + y = 4.5
4−x
5 17
⇒ y= and x =
3 6
×
4.5 5 6 ×
Kc = = 6.428.
3× 7
371. Letinitialvolume=1L.
NO
2 4 2NO 2
0.487 0.0475
−3
K c = 4.633 × 10
Aftercompressionmoles: N 2O =
4 0.487+ x; NO 2 = 0.0475 − 2x
(0.0475 − 2x ) 2 × 2
⇒ Kc = = 4.633 × 10 −3
(0.487 + x )
Solving, x = 0.041 and
0.0068
The1stvalueof x isrejectable,therefore [NO 2 ] = 0.0678, [N 2O]4 = 0.9876
372. LettheinitialpartialpressureofNOClbe p0 .
2NOCl 2NO +Cl 2
p0 − p1 p1 p1
2
p1
Total P = 1 + = 1.2 ⇒ p1 = 0.4
2
Atequilibrium,additionalpressureof Cl 2 = 7.8
Solutions 371
Therefore,atnewequilibrium:
2NOCl 2NO + Cl 2
p0 − 0.4 + p2 0.4 − p2 8 − p2
2
p2
Total P = 9 −
= 8.9 ⇒ p2 = 0.2
2
Now,equatingequilibriumconstantfortheabovetwostages:
 p0 − 0.2 
2
0.2( 0.4)2 7.9(0.2) 2 7.9 × 0.04
= ⇒   = ⇒ p0 = 0.493
( p0 − 0.4) 2 ( p0 − 0.2) 2  p0 0.4 
− 0.2 × 0.16

K P = 3.7 bar.
373. Theequilibriumreactionis:
PCl 5 (g ) PCl 3 (g ) + Cl 2
α 2
Kp = P = 1.78 ⇒ P = 4.8 (Pressuredueto PCl 5 , PCl 3 and Cl 2 )
1−α 2
⇒ PS ol vent = 0.7
P ( PCl5 + PCl 3 +Cl 2 ) 0.1(1 + α )
Now, = ⇒ nS ol vent = 0.022, mass = 3.388g.
P ( sol vent) nS ol vent
100
374. Atequilibrium P (Cl 2O)7 = 10, P (O 2 ) = 70, P (Cl 2 ) = 20 ⇒ KP = = 3.035 × 10 −14
(20) 2 (70) 7
Awhengasesaretakeninequimolarratio,mole-fractionsare:
Cl 2O 7=0.06, Cl 2 =0.545, O 2 = 0.395
(0.06) 2 1
⇒ KP = 2 7
⋅ 7
= 3.035 × 10 −14 ⇒ P = 115 bar.
(0.545) (0.395) P
375. Molarratioofthegasescomingoutofflaskinitiallywillbeequaltotheirrateofeffusion.
PCl 5 PCl 3 + Cl 2
1−α α α

Here, α= degreeofdissociation.
r (Cl 2 ) 137.5 0.53
⇒ = =
r (PCl 3 ) 71 x
where x = molefractionof PCl 3 inthegaseousmixturecomingoutinitially ⇒ x = 0.38
Hence,molefractionof PCl 5 outsideofflask = 0.09
r (PCl 5 ) 1 − α 71 0.09
Now, = = ⇒α= 0.77
r (Cl 2 ) α 208.5 0.53
(0.77) 2
Kp = = 2.577 bar.
0.23
372 ProblemsinChemistry
3
376. As() 2Bg( ) + Cg( ) KP = 4 p
CaseI 2p p
CaseII 2 p − 0.2 p p + 1 − 0.1p

K P = (1.8 p) (0.9 p + 1) = 4 p
2 3

⇒ P = 2.988 bar
P (case II) = 2.7 p + 1 = 9.06 bar
377. Theexchangeequilibriumis:
+ − +
[Ca - E DTA]2– + Pb 2 [P b - EDTA]2 + Ca 2
2–
{[ Pb - E DTA] }[ Ca2+ ] 1018
K= = = 2 × 10 7
{[ Ca – E DTA]2– }[ Pb2+ ] 5 × 1010
The very high K value forthe exchange reaction indicate that all Pb 2+ willbeconverted into
− + −
[ Pb – E DTA]2 , but since concentration ofboth Ca 2 and [Cd – E DTA]2 are veryhigh, will
remainunchanged.Therefore:
[P b – EDTA]2– K[Ca – E DTA]2– 1
Ratio 2+
= 2+
= 2 × 10 7 = 8 × 10 6
[Pb ] [Ca ] 2.5

378. Fromthethermodynamicinformations: ∆H °= 90.5 kJ and ∆S °= 285.5 JK

–1

⇒ ∆G °= 4.85 kJ =– RT ln K ⇒ K = 0.143 = p 2
( p = partialpressureof NH 3 )
⇒ p = 0.378 bar and P (eqm) = 2P = 0.756 bar.
379. ∆ G ° ( r eact i =
on)2 × 52 − 98 = 6 kJ =− RT ln K ⇒ K = 0.09
Also,for NO
2 4 2NO 2
4α 2
K= P = 0.09 ⇒α= 0.1483
1−α 2
Also,sincereactionisoccurringatconstantpressureandtemperature:
v ∝ n ⇒ %volumeincreasewouldbe 14.83.
5
380. AB 2 ( g ) + As() 2 ABg( ) K=
9
Letatnewequilibriumpartialpressureof ABg( ) = x andof AB 2 (g ) = y bar.
5 x2
⇒ = …(i)
9 y
Also x + y = 0.4 …(ii)
Solving,Eqs.(i)and(ii)gives x = 0.27; y = 0.13
 0.13 
Volume%of AB 2 ( g ) =   × 100 = 32.5
 0.4 
Volume%of ABg( ) = 67.5.
Solutions 373

381. Since, volumeofcontainer is1.0 litre, concentrations ofeach species willbeequal totheir moles.
Now,settingtheequilibriumtable
N 2 (g ) + 3H 2 (g ) 2NH 3 (g )
1 − x 3 − 3x 2x − y
NH 3 (g ) + HS2 (g ) NH 4HS (g ), K p = 8 × 10 = K c (RT )
–3 –1

2x − y 1− y y ⇒ K c = 0.4592
⇒ y
K c = 0.4592 = also 2x − y = 0.9
(1 − y)( 2x − y)
1− y
⇒ = 2.42 ⇒ y = 0.3 and x = 0.6
y
(2x − y) 2 (0.9) 2
⇒ K c (forthe1streaction) = = = 1.17
271( − x ) 4 27 (0.4) 4
⇒ –2
K p (for1streaction) = K c (RT ) = 3.55 × 10
–4

[HS2 ] = 1 − y = 0.7M
382. Let P0 betheinitialpressureof 2 4 ( g ), then:
NO
NO
2 4 (g ) 2NO 2 ( g )
18
P0 − 0.3 P0 0.6 P0 Kp = P0 …(i)
35
Ondoublingvolume,theinitialpressurewillbehalved.
NO2 4 (g ) 2NO 2 ( g )
P0
–P 2P
2
2 
2
4P 2 1 α2 18
⇒ Kp = =  P  P02 = ⋅ 2P0 = P0 {fromEq.(i)}
P0  P0   2P  P0 1−α 35
−P 1 − 
2  P0  2
⇒ 35 α 2 + 9 α − 9 = 0
− 9 + 81 + 36 × 35
⇒ α= = 0.3945
70
⇒ 39.45% NO
2 4 dissociated.
383. ∆H ° (Reaction) = ∆H °f (NO
2 5) − ∆H °f (O 3 ) − 2∆H °f (NO 2 ) = 11 − 143 − 2 × 33 =− 198 kJ
Reaction turned spontaneous to non-spontaneous at1175 Kimpliesthat atthis temperature
Q
∆G °= 0.
ie. ., − 198 × 10 3 − 1175 ∆S °= 0 ⇒ ∆S ° =− 168.5 JK –1
Nowat500K, ∆G ° =− 198 × 10 3 − 500 (− 168.5) =− 113.75 × 10 3
Also, ∆G ° =− RT ln K =− 113.75 × 10 3
374 ProblemsinChemistry

⇒ ln K = 27.36 and K p = 7.65 × 10

11

= ∆H °f (P r oduct s)
384. (a) ∆H ° ( React i on) − ∆H °f (React ants)

⇒ − 55 = ∆H °f (NO
2 5) − 2 × 33.2 ⇒ ∆H °f ( N2O)5 =+ 11.4 kJ
Also, ∆S ° ( React i on)
= S ° ( P r oduct −s)S ° ( React ant s)
− 227 = S ° (N 2O)5 – 2 × 240 – 12 × 205 ⇒ S ° (N 2O )=
5 355.5

∆G ° =− 55 × 10 + 298 × 227 = 12.646 × 10 J

3 3

(b) ∆ °> 0, reactionisnon-spontaneousat298K.

Q G∆ °> 0, increasingtemperaturewilldrivethereactioninbackwarddirection.
(c)
Q G
CH 3 CH 3 k P1 CH 3 H
385. C==C C==C
∆G °1
H H H CH 3
∆G °2 k P2 ∆G °3 kP3
HC
3 H
C==C
HC
3 H

∆G1° = 62.97 − 65.85 =− 2.88 kJ =− RT ln K P1

2880
⇒ ln K P1 = = 0.693 ⇒ K P1 = 2
8.314 × 500
∆G 2° = 58.07 − 65.85 =− 7.78 kJ =− RT ln K P2
7780
⇒ ln K P2 = ⇒ K P2 = 6.5
8.314 × 500
Now let us consider initially there was 1.0 molof cis-2-butene only and at equilibrium, there are
x-mol trans-2-buteneand y mol2-methylpropene.
⇒ x y
K P1 = = 2, K P2 = = 6.5
1− x − y 1− x − y
Solving, x = 0.21 and y = 0.6842
⇒ At equilibrium, mixture contain 21% trans-2-butene, 68.42% 2-methyl propene and rest
10.58%cis-2-butene.
386. Let x mol PCl 5 ( g ) decomposesinto PCl 3 (g )and Cl 2 (g ) as:
PCl 5 ( g ) PCl 3 (g )+ Cl 2 (g )
0.02 − x x x
Atequilibrium.: Totalmolesofgaseousspecies = 0.02 + x + 0.015 = 0.035 + x
0.02 – x
⇒ Partialpressure: PCl 5 (g )= × 1.843
0.035+ x
Solutions 375
x
Cl 2 (g ) = PCl 3 (g ) = × 1.843
0.035 + x
2
⇒ x × 1.843
K P = 0.4 =
(0.035 + x )( 0.02 − x )
Solving, x = 0.01 ⇒ Totalmolesatequlibrium = 0.035 + 0.01 = 0.045
0.045 × 0.082 × 500
⇒ V= = 1.0 L.
1.843
387. Letinitially,thereare100molesofgaseousmixture.Then
1
S O+2 O
2 2
SO 3
15 20 65
Afterchangingtemperatureto T , let x moleof SO 2 isconsumed.
Nowatnewequilibrium: SO 2 = 15 − x
O 2 = 20 − x/ 2
SO 3 = 65 + x
 x
Fromthegivencondition: 65 + x = 0.8 100 −  ⇒ x =10.7
 2
Therefore,partialpressuresatnewequilibriumare:
75.7 4.3 14.65
SO 3 = at m, SO 2 = , O2 =
94.65 94.65 94.65
75.7 94.65 94.65
⇒ K P (T ) = × × = 44.75
94.65 4.3 14.65
22600 21
Also, ∆G ° =− RT ln K P =− 22600 + 21 T ⇒ ln K P = − = 3.8
RT R
Solving, T = 429.7K .
388. Initially: CO(g )+ H O(
2 g) CO(2 g )+ H(2 g )
1− x 1− x x x
 x 
2
3
K =9=   ⇒ x=
1 − x  4
1 3
At this equilibrium, molesof CO = H 2O= and molesof CO 2=H= 2 . Now,let us assumethat
4 4
CO(2 g ) flaskcontained x moleof CO(2 g ).Then
CO(g ) + HO( 2 g) CO(2 g ) + H(2 g )
1  1  3  3  1
 + y  + y  + x − y  − y Also y =
4  4  4  4  4
−
0.5 (0.5 x )
⇒ K =9= ⇒ x=4
(0.5) ( 0.5)
Hence,volumeof CO 2 (g ) flask = 4.00 li tre.
376 ProblemsinChemistry

389. H2 + I2 2HI
2x
0.5 − x 0.5 − x 2x ⇒ = 0.15 …(i)
V
2y
0.8 − y 0.8 − y 2y ⇒ =?
V
 2x   2y 
2 2

K =  =  ⇒ y =1.6 x
 0.5 − x   0.8 − y
2y 3.2x
⇒ = × 0.15 = 0.24M
V 2x
390. For C()s + CO 2 (g ) 2CO( g )
2
PCO
KP = = 100 PCO2 = 63
PCO2
⇒ PCO2 = 0.63 and PCO = 6.3 atmosphere
⇒ P ( tot al)= 6.3 + 0.63 = 6.93 at m osph ere.

IONIC EQUILIBRIUM
391. Forweakacid HA, theionizationequilibriumis:
+ −
HA H +A
C (1 − α ) Cα Cα
+ −2
Also, [H ] = 10 = Cα = 0.1 α ⇒α= 0.1
Cα =
2
⇒ Ka = 1.1 × 10
–3
1−α
Now,letusassumethat100mL0.1MHClisaddedto V mLoftheaboveweakacid.
mmolofHCladded = 100 × 0.1 = 10
−
mmolof A inthesolution = x
mmolof HA = 0.1V
If,inpresenceofHCl, x mmolof HA isionized,
+
mmolof H inthesolution = x + 10
−
mmolof A inthesolution = x
mmolofunionized HA = 0.1V − x
+ −
[H ][ A ] (x + 10)( x )
⇒ Ka = = = 1.1 × 10 −3
[ HA ] (100 + V )(0.1V − x )
+ − x + 10
and [H ] = 2 × 10 2 =
100 + V
−
2 × 10 2 x
⇒ = 1.1 × 10 −3 ⇒ V = 192 x
(0.1V − x )
Solutions 377
+ 1920
+
Substitutingin [H ] expression: 2 × 10
−2
= V
192(100 + V )
⇒ V = 540 mL
392. Letdibasicacidbe H2 A :
+ −
H2 A H + HA
− + −
HA H + A2
− −
⇒ [ A 2 ] = Ka2 = 3 × 10 6
− − Ka1 [H 2 A ]
and
+
[H ] = [HA ] + [ A 2 ] = +
+ [ A 2− ]
[H ]
1.4 × 10 –6
⇒ +
[H ] = +
+ 3 × 10 −6 ⇒ +
[H ] = 1.18 × 10
−3

[ H]
pH = 2.926
393. Enthalpyofionizationofformicacidis15kJ/mol
K (47° C) = 15 × 10
3
 20 
⇒ ln   = 0.376
K (27° C) 8.314  300 × 320 
−4
⇒ K a (47° C) = 2.47 × 10
+
[H ] = KC
a
= 4.97 × 10 −3 ⇒ pH= 2.3
−15
+ −7 1.35 × 10 −
394. [D ] = 10 + +
⇒ [D]+ = 1.12 × 10 7 ⇒ pD= 6.95
[ D]
395. Thehydrolysisequilibriumis:
−
OCl – +HO2 HOCl + OH
−
Kw 10 14
Kh = = −8
= 3.33 × 10 −7
K a 3 × 10
−7
[HO –][ HOCl] [ HOCl] 3.33 × 10
= = = = 0.528
[OCl – ] [OCl – ] [HO – ]
−
⇒ %(bymole) HOCl = 34.55, OCl = 65.45.
PV = −
396. n( di mer)= 4.64 × 10 4
RT
−
molesofNaOHusedup=molesof CH 3COOH producedfromdecomposition = 7.8 × 10 4
−4 −4
7.8 × 10 3.9 × 10
⇒ Molesofdimerdissociated = = 3.9 × 10 −4 ⇒α= −4
= 0.84
2 4.64 × 10
−3
397. [CO 2 ] = 2.28 × 10 × 3.2 = 7.296 × 10 −3 M
+ −5
[H ] = K1 [CO 2 ] = 5.53 × 10 ⇒ pH= 4.25
378 ProblemsinChemistry
–
398. [OCl ] = 0.67 : OCl – +HO2 HOCl + OH–
−
[OH ] = KC
h
= 4.72 × 10 −4
⇒ pOH = 3.325 and pH= 10.675
[S ]
399. pOH =p K b + log ⇒ [ S ] = 0.5
[B ]
m molof NH 4Cl = 100
m molof NH 3=50
Afteradding7.5mmolKOH; m molof NH 4Cl = 92.5
m molof NH 3=57.5
92.5
⇒ pOH = pK b + log = 4.9
57.5
⇒ pH =
9.1 and ∆ pH = 0.1.
400. molof CH 3COOH = 0.25, molof CH 3COONa = 0.30
0.3
(a) pH =p K a + log = 4.78
0.25
306.25
(b) pH =p K a + log = 4.799
243.75
290
(c) pH =p K a + log = 4.745
260
Cα
2
401. K a = ; Solvinggives α= 0.27
1−α
⇒ van ’tHofffactor ()i = 1 + α = 1.27
0.5
− ∆T f = iKmf = 1.27 × 1.86 × × 1000 = 1.26
935.5
1.99 × 10
−15
∆H  10 
402. ln =   ⇒∆ H =136.2 kJ
3.16 × 10
−16
8.314  293 × 303 

K w (50° C) 136.2 × 10  
3
30
⇒ ln =  
3.16 × 10
−16
8.314  293 × 323 
−14
⇒ K w (50° C) = 5.7 × 10
pD = 6.62
−6
403. MOHhaslowersolubility ( S = 10 ) andwillprecipitatefirstof pH = 8
−14
404. K sp = 1.6 × 10 = [Fe 2+ ][ OH]
– 2

− − + −2
(i) At pH = 8, [OH ] = 10 6 , [Fe 2 ] = S ol ubility = 1.6× 10
− − +
(ii)At pH = 6, [OH ] = 10 8 , [Fe 2 ] = 160 indicatesveryhighsolubility.
Solutions 379
2+ −
405. CaF2 Ca +2F
– +
F +H HF
−
Let ‘α ’ bethefractionoftotalfluorideionproducedin F form
[ F]– [F]– Ka
α= = − +
= +
where S issolubility.
2S [F ] + [H ] K a + [H ]
−
(a) At pH = 7, [H]+ = 10 7 << K a ⇒α≈ 1 and K sp = 4S 3
−
⇒ S = 2.15 × 10 4
−
3.45 × 10 4
(b) At pH = 5, α= − −
= 0.97 and [F − ] = 25α
3.45 × 10 4 + 10 5
−
⇒ K sp = 4S ⋅ α
3 2
⇒ S = 2.2 × 10 4
406. Proceedingasinproblemno.405.
−
(a) α≈ 1 and S = 7.5 × 10 3
−
. × 10 4
345
(b) At pH = 4; α= −4
= 0.775
3.45 × 10 + 10 −4
−
⇒ K sp = 4S α
3 2
and S = 8.9 × 10 3
−
10 2
407. [ S al t]= =6.67 × 10 –5 M
150
−
[OH]– 2
(5.12 × 10 7 ) 2 K
Kh = = −5
= 3.94 × 10 −9 = w
C ×
6.67 10 Ka
−7
−6 5.12 × 10
⇒ K a = 2.53 × 10 , α= −5
= 7.67 × 10 −3
6.67 × 10
⇒ %protonation = 0.76
+ 2
K w [H] −
408. K h = = ⇒ [H + ] = 24
. × 10 –8 = 1.55 × 10 4 ⇒ pH= 3.8
Kb C
409. Atfirstequivalencepoint,5mmolof NaHCO 2 4 willbeformed.
– 2
K w [OH] − −7
Hence, Kh = = ⇒ [OH ] = 1.3 × 10
K a1 C
⇒ pOH = 6.89 pH= 7.11
Atsecondendpoint, m molof Na 2CO2 =5
4
2 −
K w [OH ] − −6
Now, Kh = = ⇒ [OH ] = 3.92 × 10
K a2 C
⇒ pOH =
5.4 pH= 8.6
380 ProblemsinChemistry
+ 2 −
−21 [ H] [S 2 ]
410. For HS2 : K a = K a 1 × K a 2 = 10 =
[ H2 S]
−24
− −8 1.6 × 10
At pH = 7, [S2 ] = 10
+
andsolubility = [ Zn 2 ] = −8
= 1.6 × 10 −16
10
− −2 −
At pH = 10, [S2 ] = 10 andsolubility = 1.6 × 10 22
−
K sp (Ag 2CO)3 [CO 23 ]
411. = −
= 6.75
K sp (Ag 2CrO 4 ) [CrO 24 ]
Also, [Ag + ] = 2[ CO2–
3 ] + 2[ CrO
2–
4 ]

[Ag + ] 2
⇒ −
=2+ = 2.296
[CO 23 ] 6.75
−12 2−
Also, K sp (Ag 2CO 3 ) = 8.1 × 10 = [Ag + ]2 [CO 2– 2– 2
3 ] = (2.296 [CO 3 ]) [CO 3 ]
− −4
⇒ [CO 23 ] = 1.15 × 10 = Solubilityof Ag CO
2 3
− −5
Similarly, [ CrO24 ] = 1.7 × 10 = Solubility of Ag 2CrO 4

412. Inboth case,solution isanacid-buffer. Let xm molof acid be present in the given volume and ym
molofNaOHin20mLsolution.
y 1.5 y
Then 3.7 = pK a + log and 4.18 = pK a + log
x−y x − 1.5 y
−
Solving, pK a = 3.7 ⇒ K a = 2 × 10 4 .
413. Thebufferpairinthiscaseis H 3PO 4 and NaH 2PO. 4
0.15
⇒ pH = pK a 1 + log ⇒ [H 3PO]4 = 0.3M
[ H3 PO]4
Also, m molofHClneeded = 0.3 × 100 = 30 ⇒ V (HCl) = 20 mL.
m molof NaH 2PO =0.15
4 × 100 + 30 = 45
⇒ m(NaH 2PO)4 = 5.4g
+ −4 [H]+ 2
414. [H ] = 1.48 × 10 M ⇒ [CO 2 ] = = 0.052M
K a1
⇒ 0.052 = 2.3 × 10 –2 P = 2.26 at m osph ere
+ 2
K w [H]
415. Fe + HO
2+
2 Fe( OH)+ +H + K= = ⇒ pH = 4.7
K2 C
– 2– −
416. For AgS2 : 2Ag( CN)2 +S Ag 2S+4CN ;
2
Kd [CN]– 4
K= = 1010 =
K sp [Ag( CN)–2 ][S 2– ]
− −10
⇒ [S 2 ] = 4 × 10
Solutions 381
−
Similarly,forCdS: Cd( CN)24 +S 2–
CdS + 4CN ; –

– 4
Kd [CN] − −12
K= = ⇒ [S 2 ] = 7.28 × 10
K sp [Cd( CN)2–
4 ][S
2–
]
Lower [S 2− ] isrequiredforCdS,itwillprecipitatefirst.
Q
2− 2+ –35
417. [S ] (requiredforprecipitationofCuS) = K sp ( CuS ) / [ Cu]=6 × 10
[S 2− ] (requiredforprecipitationofNiS) = 4 × 10 −18
+ −
− [ H ]2 [S 2 ]
Now, K( H2 S)= K1 ⋅ K 2 = 10 21 =
[HS2 ]
−
10 22
+
ForNiS; [H ]2 = −18
= 2.5 × 10 −5 ⇒ +
[H ] = 5 × 10
−3

4 × 10
+ − −18
Hence, if[H ]is greater than5 × 10 3 (pH = 2.3),[S 2− ]will be less than 4 × 10 and NiSwill not
precipitate,onlyCuSwillbeprecipitated.
418. Minimumcarbonateionconcentrationrequiredforprecipitationofcarbonatesare:
− − − −
For CaCO 3 , [CO23 ] = 4.5 × 10 8 andfor Ni CO3 , [CO23 ] = 1.3 × 10 6
−
[H]+ 2 [CO 23 ]
For H 2CO 3 ; K = KK
1 2 = 2 × 10 −16 =
[ H2 CO]3
 2 × 10 −16 × 0.03 
12/
+
[H ] forprecipitationof CaCO 3 
= −8  = 1.15 × 10 −5 ⇒ pH = 4.93
 4.5 × 10 
 2 × 10 −16 × 0.03 
12/
+
[H ] forprecipitationof Ni CO3 =  −6  = 2.1 × 10 −6 ⇒ pH = 5.66
 1.3 10 × 
⇒ At pH 4.93,CaCO 3 willstartprecipitating but Ni CO3 willremaininsolution and at pH = 5.66,
Ni CO3 willstartprecipitating.
419. Forthedissolutionequilibrium:
AgBr + 2NH 3 Ag(NH)3 +
2 + Br −
−x 1 − 2x x x

 x 
2
−6 −3
K = K sp ⋅ K f = 7.5 × 10 =   ⇒ x = 2.7 × 10
 1 − 2x 
−5
420. For MX , solubi lity= K sp = 1.78 × 10
4 −
For MX 3 , K sp = 27S = 2.76 × 10 18

 K sp 
15/

421. For MX2 3 ; S =   = 4.58 × 10 −5 .

 108 

⇒ Solubilityof MX2 = 2S = 9.16 × 10 −5 ⇒ −

K sp = 3 × 10 12
382 ProblemsinChemistry

− K sp
422. When CaSO 4 starttoprecipitate [SO 4 ] =
2
2+
= 1.6 × 10 −4 M
[Ca ]
K sp (S r SO4 )
(a) [Sr 2+ ] when CaSO 4 starttoprecipitate = −
= 2 × 10 −3
[ SO24 ]
−3
0.15 − 2 × 10
(b) % Sr 2+ ionprecipitatedwhen CaSO 4 begintoprecipitate = × 100 = 98.67
0.15
423. Thedissolutionequilibriumis:
− − − −
Fe( OH)3 +6CN Fe( CN)36 + 3OH : K = K sp ⋅ K f = 1.6 × 10 8
−
Lettheinitialconcentrationof CN = x M
3
−8 ( 0.092) ( 0.275)
⇒ 1.6 × 10 = ⇒ x = 7.57M
(x − 0.55) 6
⇒ MolesofNaCNdissolved = 7.57 × 1.2 = 9.084
Massof NaCN= 445 g.
 x 
2

424. AgBr + 2SO

2–
Ag( S2 O)3 3–
+ Br − K = K sp ⋅ K f = 10 =  
x
2
1.2 − 2x
3
x x  1.2 − 2x 
⇒ x = 0.52 M⇒ molofAgBrdissolved = 0.065
massofAgBrdissolved = 12.22g
0.278 −
2+
425. Initialconcentrationof Ca = M= 6.95 × 10 3 M
40
1.06
Molesof Na 2CO 3 added = = 0.01
106
Molesof CO 2−
3 leftunreactedafterprecipitationof
− −
CaCO 3 = 0.01 − 6.95 × 10 3 = 3.05 × 10 3
−9
K sp 4.5 × 10
⇒ [Ca 2+
]= −
= −3
= 1.475 × 10 −6 M = 0.059 ppm Ca 2+ .
[CO 23 ] 3.05 × 10
−6 3
426. 2 × 10 = 4S ,where S = solubi li ty of P bBr
2

⇒ S = 7.93 × 10 −3 M [Pb
= 2+ − −
]; [Br ] = 2S = 1.586 × 10 2 M
−9
8 × 10 = [ Pb2+ ][I − ]2 ⇒ −
[I ] = 10
−3
M.
+ − R
427. HIn H + In pH = pK In + log
Y R Y
pH(yel l ow) = 8.045 − log 30 = 6.57
pH( r ed)= 8.045 + log2 = 8.35 ⇒ pHrange= 6.57 ←→ 8.35.
− −
428. (a) Zn( OH)2 + 2OH Zn( OH)24
−
x − 2 × 10 3 2 × 10−3
Solutions 383
−3
2 × 10
K = K sp ⋅ K f = 6 × 10 =
4
−
(x − 2 × 10 3 ) 2
−3
⇒ x = 2.18 × 10 M.
−16 2+ − 2 − −
(b) 3 × 10 = [Zn ][OH ] ⇒ [OH ] = 5.47 × 10 7 .
+ –
− −3 [ Ag(NH)
3 2 ][ Cl ]
K1 = 2.4 × 10 =
+
429. AgCl + 2NH3 Ag(NH)3 2 +Cl
[ NH 3 ]2
+
+ −9 [Ag(NH)3 2 ][ CN]–
AgCN +2NH 3 Ag(NH)3 2 +CN – K 2 = 3.3 × 10 =
[NH 3 ]2
−
K1 [Cl ] S ol ubi lity of AgCl
⇒ = 7.27 × 10 5 = −
=
K2 [CN ] S ol ubilityof AgCN
TheaboveratioindicatesthatAgClhasveryhighsolubilitythanAgCN.
 S 
2
−3 −
⇒ K1 = 2.4 × 10  1−2  ⇒ S = [Cl ] = 0.045
 S
− −
⇒ [CN ] = 6.13 × 10 8 .
x − 50 ⇒
430. 4.64 = 4.74 + log x = 450 ⇒ [ Aci d]= 0.45M .
x + 50
431. Let x molofHClisadded.Thenmolesof C 3HO6 3 = x andmolesof
NaC 3HO5 3 = 0.1 − x
0.1 − x
⇒ 3.77 = pK a + log
x
Solving, x = 0.55 mol
⇒ 55mLof1.0MHClwillgivethedesiredbuffer.
+ + +
432. Al 3 + HO 2 Al ( OH)2 + H
c−x x y

⇒ xy
Kh = …(i)
c−x
− + −
HSO 4 H + SO 24
x− y y y
2
y
Ka = …(ii)
x−y
⇒ Solvingfor x and y gives pH =− log y = 3.53
433. AgCN Ag + +CN –
− −
CN + HO
2 HCN + OH
384 ProblemsinChemistry

+ − K sp K w K sp
Applyingmaterialbalance = [Ag ] = [CN ] + [HCN] = +
+ +
[Ag ] K a [Ag ]
Also 1st termon the right hand of the materialbalance is negligible in comparison to the second
term.
+ KK
w sp + −
⇒ [Ag ] = +
⇒ [Ag ] = 1.66 × 10 7
K a [Ag ]
Kb α2 C1 C1 V
434. Q α= ⇒ = =2 ⇒ =4= 2 ⇒ V2 = 4V1 = 200 mL
C α 1 C2 C2 V1
2− − − − −
435. Q S hydrolysedcompletelyinto HS : S 2 + HO
2 HS + OH
−
Kw [HS ]2
Kh = =1 = −
K a2 [S 2 ]
− − − −
⇒ [S 2 ] = [HS ]2 = (6.7 × 10 10 ) 2 = 4.489 × 10 19
2+ 2− −
⇒ K sp = [ Pb ][S ] = 3 × 10 28

Cα
2
+ −3
436. (a) K a = ⇒α= 0.19 and [H ] = 3 × 10 α ⇒ pH = 3.235
1−α
−
K a ( HL) 1.4 × 10 4
(b) K = = −
= 311.11
K a 1 (HCO
2 3) 4.5 × 10 7
2 −
− − K w [OH ]
(c) (i) HCO 3 + HO
2 H 2CO 3+OH : Kh = = ⇒ pH = 11.35
K a1 C
−
(ii) HL + HCO 3 HCO
2 3 + L−
− −
0.024 − 3 × 10 3 3 × 10 3

isveryhigh,allHL willbeneutralized.
QK
[H +][HCO] –3
⇒ K a1 = 4.5 × 10 −7 =
[HCO2 3]
+ −
⇒ [H ] = 6.428 × 10 8 and pH= 7.2.
(0.022 − x )
(d) K a1 = 4.5 × 10 −7 = 10 −7 ⇒ x = 4 × 10 −3
x
+ −
(e) CaCO 3 ()s Ca 2 + CO 23
S S
2− − −
+
H 2O CO 3 HCO 3 + OH
S −x x x
2
Kw
Kh = = 2.12 × 10 −4 = x ⇒ S − x = 3.73 × 10
−5

K a2 S −x
Solutions 385
−5
Also, x = 8.91 × 10
−4 − −
⇒ K sp = SS( − x ) = 1.265 × 10 × 373
. × 10 5 = 4.7 × 10 9
− − −
(f) For CO 23 + HO
2 HCO 3 + OH
− −
K w [OH ][ HCO 3 ]
Kh = = 2−
= 2.12 × 10 −4
K a2 [CO 3 ]
− − − −5
Substituting [OH ] and [HCO 3 ], [CO23 ] = 2.6 × 10
−9 2+ 2− −4
⇒ K sp = 4.7 × 10 = [Ca ][CO 3 ] ⇒ [Ca 2+ ] = 1.8 × 10 M
437. Let x mmolacid(H A)ispresentinits1.7g.
⇒ mmolofsalt = x mmolNa A
mmolofNaOHleftunreacted = 10 − x
− −
Now, A + HO
2 HA + OH
m mols x − y y 10 − x + y

Kw (10 − x + y)
Kh = = 5 × 10 −5 = y …(i)
Ka x−y
− −4 10 − (x − y)
Given, [OH ] = 1.58 × 10 = ⇒ x − y = 9.9842
100
SubstitutinginEq.(i)yields y = 3.16 ⇒ x =13.144
1.7
M= −
= 129.33
13.144 × 10 3
3 −11
438. K sp = 4S = 1.58 × 10 . AlsoHClislimitingreagent.
+ 1
⇒ [Mg 2 ] = [ HCl]= 0.05
2
+ − 2 − −5
⇒ K sp = [Mg ][OH ] ⇒ [OH ] = 1.76 × 10

pOH = 4.75 ⇒ pH = 9.25

440 −5
439. [H 2CO 3]= 0.0343 × 6
=1.5 × 10
10
Cα
2
Also, Ka =
1−α
+
Solving; α= 0.154 ⇒ [H ] = Cα ⇒ pH = 5.63

440. (a) m molofHClconsumed = 5 − 2.0265 = 2.9735 = m molof NH 3

−
2.9735 × 14 × 10 3
⇒ m% N = × 100 = 16.55
0.2515
+ 2.0265
(b) 0.00mLNaOH: [H ] = ⇒ pH = 1.39
50
386 ProblemsinChemistry

m molofHClleft = 2.0265 − 9.65 × 0.1050 = 1.01325

9.65mLNaOH:
+ 1.01325
[H ] = ⇒ pH = 1.69
50
19.3mLNaOH:NoHClleft.
Now, NH +4+HO 2 NH 4OH+H +

+ 2
K w [H ]
Kh = =
Kb C
⇒ +
[H ] = KC
h
= 5.8 × 10 −6 ⇒ pH =
5.23
+
Onadding28.95mLNaOH: m molof NH 4 = 2.9735 − 1.01325 = 1.96
m molof NH 4OH = 1.01325
1.96
pOH = pK b + log = 5.04
1.01325
⇒ pH = 8.96
10
8

(c) pH 6
4
2

0 10 20 30
Vol. of NaOH
(d) pHrange = 4.23 − 6.23
(e) m molofN = 32.5 × 0.101 = 3.2825
0.2345
M= × 1000 = 71.44
3.2825
+ −5
441. Atendpoint, [Ag ] = K sp (AgCl) = 1.58 × 10
−12
− 1.8 × 10
[CrO 24 ] = −5 2
= 7.3 × 10 −3 M
(1.58 × 10 )
0.2 − −5
442. pOH = 5 − log 2 + log = 4.4 ⇒ [OH ] = 4 × 10 M
0.4
− −5
Afteradding Ca 3+ , totalvolume =100 mL ⇒ [OH ] = 2 × 10 M
−19
K sp = 10 = [La 3+ ][OH − ]3 ⇒ +
[La 3 ] = 1.25 × 10
−5

⇒ mmolof La 3+ insolution = 1.25 × 10 −3

− − −
mmolof La 3+ precipitated = 50 × 10 4 − 1.25 × 10 3 = 375
. × 10 3 % La 3+ precipitated = 75.
Solutions 387
+
+ + + x[H ]
443. Al 3 + HO Al ( OH)2 + H Ka = …(i)
S −x
2
S −x x
−
− − y [OH]
PO 34 + HO 4 + OH
HPO 2– Kb = …(ii)
S−y
2
S − y
−20
Also, K sp = (S − x )( S − y) = 10 …(iii)
MultiplyingEqs.(i)and(ii)
+ −
xy([ H ][OH ]) = = 5 × 10 −7 ⇒ −13
KK xy = 5 × 10
(S − x )( S − y) a b

−
Now,solvingfor S : S = 7 × 10 7 .
444. (a) Mg + 2OH → Mg( OH)2 ().
2+ − +
s Attheendofreaction, Mg 2 = 0.1 mol
0.2 0.2
−12 − −6
K sp = 1.6 × 10 = [Mg 2+ ][ OH]
– 2
⇒ [OH ] = 4 × 10 ⇒ pH = 8.6
0.04
(b) Mg 2 + 2OH → Mg( OH)2 ()s Attheend, [Mg 2 ] = 0.1 −
+ − +
= 0.08
0.1 0.04 2
−12
⇒ 1.6 × 10 = 0.08 × [OH − ]2 ⇒ −
[OH ] = 4.47 × 10
−6
⇒ pH= 8.65
(c) Mg( OH)2 +2HCl → Mg 2+ +2Cl – +2HO
2
0.02 0.04 0.02
−12
[Mg 2+ ]= 0.1+ 0.02 = 0.12M ⇒ 1.6 × 10 = 0.12[ OH− ]2
− −6
⇒ [OH ] = 3.65 × 10
pH= 8.56
445. Theprecipitateexchangeequilibriumis:
−
2– [SO 24 ]
PbSO 4+S PbS + SO2–
4 K= −
= 6.4 × 1018
[S 2 ]
+ −
− [H ]2 [S 2 ] − −22 − −4
Alsofor HS2 : K a = 10 21 = ⇒ [S 2 ] = 10 ⇒ [SO 24 ] = 6.4 × 10
[HS2 ]
+ −
Hence, [Pb 2 ] pr esent= 2.5 × 10 5 M
−4
+
Initial [Pb 2 ] = 1.26 × 10 M ⇒ molesofPbSprecipitated = 10 −4
m(PbS ) = 23.8 mg.
1060 × 2.3
446. M (ur ea)= = 0.4
6000
KC
and [H 2S—CO—NH ]= +
3
b
−
= 2.68 × 10 −7
[OH ]
+ −
447. Using K sp ( AgCl ),∆G ° of AgCl()s Ag (aq ) + Cl (aq ) =+ 55.33 kJ
+
Now, 55.33 kJ/mol= G °f (Ag ) − 131 + 110
+
⇒ G °f (Ag ) =+ 76.33 kJ
388 ProblemsinChemistry
+ −
For Ag 2SO 4 : Ag 2SO 4 ()s 2Ag + SO 24
∆G ° ( i oni zati on)
= 2 × 76.33 − 742 + 618.5 = 29.16 =− RT ln K sp .
−6
⇒ + 2
K sp = 7.73 × 10 = [Ag ] [SO 4 ]
2–

+ −2
⇒ [Ag ] = S ol ubi li ty
= 8.8 × 10 M
− −6
− (.177 × 10 3 ) 2 3.16 × 10
448. HOCN H ++OCN Ka = =
C C
C + 0.05
Afteradding100mL0.05MHOCN, [HOCN] =
2
−5 −6
×
2 10 ×
3.16 10
⇒ Ka = = ; Solving C = 0.009 M.
C + 0.05 C
10 6 × 2.5
449. Massofsulphur = = 2.5 × 10 4 g
100
Molesof H 2SO 3 produced = 781.25
−5
Volumeofrain-water = 5.2 × 10 7 L. ⇒ [H 2SO ]=
3 1.5 × 10 M
Suchalowconcentrationofacidindicate α≈ 1.
−
⇒ pH =− log( 1.0 × 10 5 ) = 4.8
[OH]– 2
3
450. [NH]3 = = 0.0158 ⇒ molesofMg = × 0.0158 = 0.0237
Kb 2
m = 0.5688g and %purity = 56.88
451. Thebalancedequationforreactionbetween Br 2 and SO 2 is:
Br 2 +S O2+ 2HO2 → 2HBr +H SO
2 4
0.01 0.02 0.01
Now, HSO
2 4 → H+ + HSO 4
−

0.03+ x 0.01– x

HSO –4 H +
+SO 2–
4
0.01– x 0.03+ x x
(0.03 + x )
K a 2 = 10
−2
=x ⇒ x = 2.36 × 10
−3
0.01 − x
+ −2
[H ] = 3.236 × 10 pH= 1.49and
452. (a) Since, Q forms precipitate with both X and Y , it must be K 2CO 3 because Ag 2CO 3 and
BaCO 3 areinsolublesalts.
(b) KCO 2 3 on mixingwith Pb( NO) 3 2 willgive precipitate PbCO 3 butnoprecipitate willbe
formed ifK 2CO 3 iscombinedwithNaClsolution. Therefore, R is Pb( NO)3 2 and S is NaCl.
(c) If X formsa precipitate with S(NaCl) but not with R = [Pb( NO) 3 2 ], it mustbe AgNO 3 . On
theotherhandif Y formsprecipitateonlywith Q butnotwith R and S , itmustbe BaCl 2 .
453. Let x mLof acid is taken, then volume of salt solution taken = 20 − x. Now, applying Henderson ’s
equation:
Solutions 389
[ S al t] 0.1(20 − x )
pH =p K a + log ⇒ 4.7 = 4.7 + log
[ Aci d] 0.15 x
⇒ 2 − 0.1 x = 0.15 x and x = 8 mL, volumeofsaltsolution = 12 mL.
454. Let x mLofaceticacidtaken,volumeofbasetaken = 50 − x
mmolofacid = 0.15 x,m molofbase = −
(50 x ) 0.1
⇒ mmolofsaltformed = 0.1(50 − x ), mmolofacidleftunreacted = 0.15 x − 0.1(50 − x )
ApplyingHenderson ’sequation:
0.1(50 − x ) 5 − 0.1 x
4.7 = 4.7 + log ⇒ =1 ⇒ x = 28.6 mL
0.15 x − 0.1(50 − x ) 0.25 x − 5
Volumeofbaserequired = 21.4 mL.
455. Thebalanced chemicalreaction involved inprecipitation reaction is:
3Ba( NO) 3 2 ( s)+ 2H PO
3 4 → Ba 3 (P O)4 2 ( s)+ 6HNO(3 aq )
mmol(Initial): 6.13 3 0 0
mmol(Final): 1.63 0 1.5 9
pHofsolutionwillbemainlydueto HNO 3 .
9
⇒ [HNO 3]= = 4.5 × 10 –3 ⇒ pH =− log( 4.5 × 10 –3 ) = 2.35
2000
456. Theminimumconcentrationsofsulphideionrequiredforprecipitationofthesemetalsare:
+
MnS: [S 2– ] = K sp / [Mn 2 ] = 2.5 × 10 –8 M
+
CoS: [S 2– ]= K sp / [Co 2 ] = 4 × 10 –19 M
+
AgS2 : [S 2– ]= K sp / [ Ag ]2 = 6.3 × 10 –46 M
Now,for HS2 : HS2 2H ++S 2–

[H]+ 2 [S 2– ]
K a = K a 1 × K a 2 = 10 =
–21
[ H2 S]
⇒ [H]+ 2
[S 2– ]= 10 –22 .
+
Since,minimum S 2– ionisrequiredfor Ag ,corresponding [H]+ :
+
[ H] (tobeginprecipitationof AgS2 = 10 –22 / 6.3 × 10 –46 = 3.98 × 1011
+ 11 +
i.e., toprevent precipitation of AgS2 , minimum [H ]= 3.98 × 10 and ata [H] below tothis
value AgS2 will precipitate. Sucha large concentration of [H]+ is unachievable, AgS2 will
precipitateatanypracticalconcentrationof H+ .
Limiting [H]+ requiredtobeginprecipitationof CoS:
−
[ H+ ]= 10 –22 / 4 × 10 –19 = 1.58 × 10 2 M ⇒ pH =
1.8

i.e., at [H] above 1.58 × 10 M [S ] willbelessthan 4 × 10 –19 MandCoSwillnotprecipitate.

+ –2 2–

Limiting [H]+ requiredtobeginprecipitationofMnS:

390 ProblemsinChemistry
−
10 22
[ H+ ]= = 6.32 × 10 –8 ⇒ pH = 7.2
2.5 × 10 –8
i.e., atpHbelow7.2,MnSwillnotprecipitate.
pHrange: AtpHbelow1.8,only AgS2 willprecipitate.
At pH > 1.8but<7.2,onlyCoSwillprecipitate.
AtpH>7.2,MnSwillstartprecipitating.
457. Thecellreactionsare:
H 2 → 2H ++2 e
2Ag + +2 e → 2Ag E °= 0.8V
H 2+2Ag +
→ 2H ++2Ag E °= 0.8V
+ 2
0.059 [H]
E = 0.589 = 0.8 – log +
⇒ [Ag + ]= 2.65 × 10 –4
2 [Ag ]2
+ 2 2– −
K sp = [Ag ] [CO
2 4 ]= 4S3 and 2 S = 2.65 × 10 4
⇒ S = 1.325 × 10
–4
⇒ K sp = 4 S = 9.3 × 10 .
3 –12

458. Forthedissolutionreaction:
Zn( OH)2 +2OH – Zn( OH)2–
4 K = K sp ⋅K f = 0.588
x 0.1 − 2x x
x x
K = 0.588 = = –2
(0.1 − 2x ) 2
10 − 4x 2 − 0.4 x
Solving: x = 0.0048M , i.e., 0.0048 × 250 = 1.2 mmol Zn( OH)2 dissolved.
150
mmolof Zn( OH)2 takeninitially = = 1.515
99
⇒ mmol Zn( OH)2 leftundissolved = 1.515 − 1.2 = 0.315
⇒ massof Zn( OH)2 leftundissolved = 31.185 mg
459. ReactionfordissolutionofAgClinammoniais:
Ag(NH)3 2+ +Cl – K = K sp ⋅K f = 4 × 10
–3
AgCl +2NH 3
x 0.1 − 2x x 0.1 + x

x (0.1 + x ) = 0.1 x + x 2
⇒ K = 4 × 10 =
–3
−
(0.1 − 2x ) 2 10 2 + 4x 2 − 0.4 x
⇒ 0.1 x + x 2 = 4 × 10 –5 + 1.6 × 10 –2 x 2 − 1.6 x × 10 –3
−
or 0.984 x 2 + 0.1016 x − 4 × 10 5 = 0

−0.1016 + (0.1016) 2 + 16 × 10 −5 (0.984)

⇒ x= = 3.92 × 10 –4 M
2 × 0.984

460. Theorderinwhichhalideionsshouldbeaddedis: Cl – than Br – than I – .

Solutions 391
K sp (AgCl)
When Cl – isaddedto0.1M, [Ag + ]= = 1.8 × 10 −9 M
0.10
K sp ( AgBr)
When Br – isaddedto0.1M, [Ag + ]= = 5 × 10 −12 M
0.10
K sp (AgI)
When I – isaddedto0.1M, [Ag + ]= = 8.4 × 10 −16
0.10
+ − −
The [Ag ] in equilibrium with AgCl in 0.1M Cl is1.8 × 10 –9 M, which is morethan 5 × 10 12 M
+
([Ag ] required toinitiate precipitation of AgBr when [Br – ] = 0.1M). Hence, the solution
containing [Ag + ]= 1.8 × 10 –9 inequilibrium withAgClin0.1M Cl – , will give precipitate of AgBr
when Br – isadded to 0.1 M.Hadweadded Br – to0.1 M before Cl – , [Ag + ] wouldhave been
−12
5 × 10 M and onmakingthissolution 0.1M in Cl – inthe subsequent stepwould not have
yieldedAgClprecipitate.Hencetheorder.
461. Asweknow, a buffersolution showsitsbest buffering action nearto itsionization constant value.
Therefore,theabovebuffercanbestbepreparedbytaking H 2PO –4 and HPO 2–
4 .
[ HPO 24– ] [HPO 24– ] [ HPO2–
4 ]
(a) pH = pK 2 + log =7 ⇒ log =− 0.22 and = 0.6
[ H2 PO]–4 [H 2PO –4 ] [H 2PO –4 ]
–
(b) In50mLbuffer, [H 2PO ]=
4 0.10 M = 5m mol ⇒ [ HPO2–
4 ]= 0.06 M = 3m mol
mmolofNaOHadded = 20 × 0.1 = 2
ThisaddedNaOHwillneutralize2.0m molof H 2PO –4
⇒ –
mmolof H 2PO =5
4 – 2=3
mmolof HPO 24– =3+2=5
5
pH =p K 2 + log 3
= 7.44
462. Fromthe titration curve it isconcluded that the 1st end point correspond to completion ofthe
followingreaction:
NaCO2 +HCl
3 → NaHCO 3+NaCl
⇒ mmolofHClconsumed = 11 × 0.115 = 1.265 = mmolof Na 2CO 3
⇒ massof Na 2CO =1.265
3 × 106 × 10 –3 = 0.134g
Secondendpointcorrespondstothefollowingreaction:
NaHCO 3+HCl → NaCl +H 2O+CO 2
VolumeofHClconsumed = 35 − 11 = 24 mL
Outofthis24mL,11mLHClwouldbeconsumedby NaHCO 3 producedfrom Na 2CO 3 .
⇒ mmoloforiginal NaHCO 3= (24 – 11)0.115 = 1.495
⇒ massof NaHCO 3 = 1.495 × 84 × 10 –3 = 0.1256g
0.134
⇒ m%of Na 2CO=3 × 100 = 26.8
0.5
0.1256
⇒ m%of NaHCO=
3 × 100 = 25.12
0.5
m%of KCl = 48.08%.
392 ProblemsinChemistry
−
−3 10 3
463. K sp = 10 = [Ca ][ H2PO]4
2+ – 2
⇒ –
[H 2PO ]=
4 = 8.165 × 10 −2 M
0.15
– −
i.e., topreventprecipitation, [H 2PO]4 shouldbelessthan 8.165 × 10 2 M.
Also HPO
3 4 H ++H PO
2
–
4

[H +] [H PO] –
K a 1 [ HP3 O]4 7 × 10 –3 × 0.25
K a1 = 2 4
⇒ [H +]= = −2
[ H3 PO]4 [ H2 PO]–4 8.165 × 10
= 2.14 × 10 −2 M
+ –2
i.e., topreventprecipitation, [H ]> 2.14 × 10 , pH = 1.66 .
i.e., atpHbelow1.66,noprecipitationof Ca( H2 PO)4 2 willoccur.
–
464. (a) Addition of HNO 3 will neutralize OH insolution driving solubility equilibriuminforward
direction and thiswillincrease concentration of Fe 3+ insolution. Also,as Fe 3+ comes in
solution due toneutralization of OH – with HNO 3 , it will form complex with SCN – present
insolution due tohigh K f value, but still, theoverall effectwillbeincrease inconcentration
of Fe 3+ insolution.
(b) Addition ofNaOHwilldrive both equilibrium (i)and (iii)inbackward direction and itwill
decreaseconcentrationof Fe 3+ ioninsolution.
(c) Addition ofNaSCNwilldrive equilibrium(ii)inforwarddirection and concentration of
Fe 3+ (aq ) willdecrease.
(d) Addition of Fe( OH)3 ()s willhave noeffecton Fe 3+ (aq ) concentration sinceactive massof
formerisunity.
465. Thedissociationequilibriumofthecomplexis:
[Cu( CN)4 ]2− Cu 2+ (aq ) + 4CN – ( aq )
Asstrongacidisadded,followingequilibriumwillbeestablishedparallely:
1
H ++CN – HCN K = = 1.67 × 10 9
Ka
The above equilibrium will lie predominantly to right, removing mostof the cyanide ion from1st
equilibrium.Thiswillincreaseconcentrationof Cu 2+ insolution.
4 × 1000
466. mmolofNaCladded = = 68.38
58.5
+
mmolof Ag insolution = 25
+
Now: AgCl(s)+2NH( 3 aq ) Ag(NH)3 2 ( aq )+ Cl – (aq )
x − 0.2 0.1 0.2735
−2
−3 2.735 × 10
K = K sp ⋅K f = 2 × 10 =
x − 0.2
⇒ x =13.875M
468. Thesolubilityequilibriumis:
K = K sp ⋅ K f
Solutions 393
– −41
Co( OH)3 + 4S CN Co( S CN)–4 +3OH –
K = 1.6 × 10
Atthegivenconditions: 1 − 0.4 0.1 10 –7

–7 3
(0.1) ( 10 )
Q= = 7.716 × 10 −22 >> K (1.6 × 10 –41 )
(0.6) 4
Therefore,precipitationmustoccur.
− −5
469. [OH ] ofbuffer = 2 × 10 ⇒ [H +]=5 × 10 −10
−
5 × 10 10 x −11
HCO –3 H ++CO K a 2 = 4.7 × 10 =
2–
Now:
0.1 − x
3

−3
0.1 − x 5 × 10
−10
x Solving: x = 8.6 × 10 M
2+ +
Now,on adding equal volumeof 0.1M Ba ion,concentration of Ba 2 ioninfinalsolution will
−
become0.05Mandthatofcarbonateionwillbecome 4.3 × 10 3 M.
⇒ 2+ 2– –4
K IP = [Ba ] [CO3 ]= 2.15 × 10 >> K sp , precipitationwilloccur.
470. Fortheequilibrium: HCO –3 H ++CO 2–
3

−11 [H +][ CO 2–
] [CO 23– ]
K a 2 = 4.7 × 10 = 3
= 10 −8 ⇒ [HCO –3] = 213 [CO 2–
3 ]
[HCO –3 ] [HCO –3 ]
Also [HCO –3]+[CO 2–
3 ]= 0.1 ⇒ [CO 2–
3 ]= 4.67 × 10
–4

−
1.4 × 10 13
⇒ [Co 2+ ]= −4
= 3 × 10 −10 M
×
4.67 10
1.6 × 10 –44
[Co 3+ ] = −4
= 3.4 × 10 −41 M
4.67 × 10
471. Thehydrolysisreactionis:
+ +
C 6H NH
5 +HO
3 2 CH
6 NH
5 OH+H
3

C (1 −α ) Cα Cα
−14
Kw 10
Kh = = −10
= 2 × 10 −5
K b 5 × 10
−
Cα 10 3 α 2
2
−5
Also K h = ⇒ 2 × 10 = ⇒α 2
+ 2 × 10 −2 α − 2 × 10 −2 = 0
1−α 1−α
−2 × 10 −2 + (2 × 10 −2 ) 2 + 8 × 10 −2
α= = 0.13
2
− −
⇒ [H]+ = Cα = 10 3 × 0.13 = 1.3 × 10 4
pH = 3.88
472. As,aceticacidisadded,itwillreactquantitativelywith OI – as:
CH 3COOH + OI – CHCOO
3
–
+HOI
mmoles: 1 2 0 0
0 1 1 1
394 ProblemsinChemistry

K a [acetic acid ]
K= = 10 6 > verylargevalue.
K a (HOI)
Nowtheconjugatebaseofweakeracid(HOI)willhydrolyzepredominantlyas:
Kw
OH –+HO 2 HOI + OH– Kh = = 5 × 10 −4
Ka
Concentrationof OI – leftunreactedafterreactionwith CH 3COOH =5 × 10 –3
ConcentrationofHOIproducedbyreactionof CH 3COOH with IO –=5 × 10 –3
Now,if x MIO – ishydrolyzedthen:
IO – + HO
2 HOI + OH –
−3
5 × 10–3 − x 5 × 10 +x x
−3 −
−4 (5 × 10 + xx) 5 × 10 3 x + x 2
K h = 5 × 10 = −3
= −3
5 × 10 −x 5 × 10 −x
−3 −6
⇒ x + 5.5 × 10 x − 2.5 × 10 = 0
2

−5.5 × 10 –3 + 3.025 × 10 −5 + 10 −5
⇒ x= = 4.22 × 10 −4
2
⇒ pOH =3.37 and pH = 10.63
473. Thehydrolysisreactionis:
Kw
+
Cl C6 H 4NH +
3 HO 2 ClC 6H NH
4 OH+H
3
+
Kh = = 2.5 × 10 −3
Kb
C (1 −α ) Cα Cα
−2
Cα = 10 α
2 2
−3
K h = 2.5 × 10 = ⇒α 2
+ 0.25 α − 0.25 = 0
1−α 1−α
−0.25 + 0.0625 + 1
and α= = 0.39 (notnegligible)
2
⇒ [H]+ = Cα = 3.9 × 10 –3 and pH = 2.4
+
[ H+ ][dnp]– [H +] [25] [H ]
474. Ka = = = ⇒ pH1 = 3.48
[dnp] 75 3
+
[H ][ 75]
when75%ionized = 1.1 × 10 −4
25
−
+ 1.1 × 10 4
⇒ [H ] = ⇒ pH = 4.53
3
475. For Mg( OH)2 Mg 2+ (aq )+ 2OH(– aq )
−11
2+ –
K sp = [Mg ] [OH]
2
⇒ . × 10
15 = 0.1 [OH – ]2
⇒ [OH –]=1.224 × 10 –5
This is the minimumconcentration of OH – requiredtobegin theprecipitation of Mg( OH)2 .
Therefore, [OH]– ≤ 1.224 × 10 –5 M.
Solutions 395

Nowfor NH 3+HO 2 NH +4+OH –

[NH +4]
[OH]– 2 × 10 –5 × 0.1
Kb = ⇒ [NH]+4 = = 0.16M
[NH 3 ] 1.224 × 10 –5
– 5 −
i.e., to maintain [OH] equal to 1.224 × 10 M or less, the concentration of ammoniumion in
solutionmustbegreaterthanorequalto0.16M.
476. Theequilibriaexistingare:
BaS O4 ()s Ba 2+ (aq )+ SO 2–
4 ( aq )
y x+ y
Kw
SO 2–
4 +HO
2 HS O–4 + OH –
Kb = = 8.33 × 10 −13
Ka
Theabove K b valueindicatesthattendencyofhydrolysisof SO 2–
4 isveryless.

Also, HSO –4 H ++SO 2–

4
0.25 − x x x+ y
Here x M HSO –4 isionizedand y M BaSO 4 dissolved.
⇒ K sp = 10 = yx( + y)
–10
…(1)
− xx( + y)
. × 10 2 =
K a = 12 …(2)
0.25 − x
y(0.25 − x )
2
⇒ ⇒ −2 x
. × 10 –9 =
83 x >> y and 1.2 × 10 =
x 0.25 − x
− −
10 10 10 10
Solving x = 4.46 × 10 –3 ⇒ y= ≈ = 2.24 × 10 −8 M
x+ y x
−
− 10 5
Solubilityinwater = K sp = 10 5 ⇒ fact or = −
= 446
2.24 × 10 8
477. Initialmmolof Na 2CO =500
3 × 0.1 = 50
Now,letusassumethat x mmolofHClisaddedtoadjustthedesiredpH.Then
Na 2CO +HCl
3 → NaHCO 3+NaCl
50 − x 0 x x
Theleftover Na 2CO 3 willhydrolyzetogivethedesiredpHas:
CO 2–
3 +HO
2 HCO –3+OH –

– – −
Kw [OH ] [HCO]3 10 4 x
Kh = = 2 × 10 −4 = =
K a2 [CO 23– ] 50 − x
100 1
⇒ x= = ×V
3 3
⇒ V =100 mL
i.e., to prepare the desired solution, 100 mLofthe given HCl will have to be added and finally
solutionwillbedilutedto1000mL.
396 ProblemsinChemistry

478. Ag + +2CN – Ag( CN)–2

Initial(M): 0.03 0.1
Final(M): ≈0 0.1 − 0.06 0.03
−
[Ag( CN)2 ] 0.03
⇒ . × 1018 =
K f = 25 + – 2
= +
[Ag ] [CN] [Ag ] [0.04] 2
⇒ [Ag + ]= 7.5 × 10 –18 M
–11 2+ – 2
479. (a) For CaF2 : 3.4 × 10 = [Ca ][ F] = [Ca 2+ ]( 0.05) 2
⇒ [Ca 2+ ] requiredtobeginprecipitationof CaF2=13.6 × 10 –9 M
For CaCO 3 : 9.5 × 10 –9 = [Ca 2+ ] [CO2–3 ]= [Ca
2+
] [0.02]
+
⇒ [Ca ] requiredtobeginprecipitationof CaCO 3 = 4.75 × 10 –7 N
2

2+
i.e., higher concentration of Ca isrequired tostartprecipitation of CaCO 3 , CaF2 will precipitate
first.
(b) When CaCO 3 start precipitating, the required [Ca 2+ ] is 4.75 × 10 –7 . To commence
simultaneous precipitation of CaF2 and CaCO 3 at this stage, the minimum [F]– can be
evaluatedas:
− −
3.4 × 10 11 = 4.75 × 10 7 [F]– 2
⇒ [F]– = 8.46 × 10 –3 M.
480. (a) For PbI 2 ()s Pb 2+ (aq )+ 2I – (aq )
∆G ° (at 17°C) =− RT ln K sp =− 8.314 × 290 ln( 7.47 × 10 –9 ) = 45.1166 kJ
and ∆G ° (at 27°C) =− RT ln K sp =− 8.314 × 300 ln( 1.4 × 10 −8 ) = 45.1056 kJ
Now ∆G ° (at17 °C) = 45116.6= ∆H ° – 290 ∆S ° …(i)
∆G ° (at 27°C) = 45105.6= ∆H ° – 300 ∆S ° …(ii)
FromEqs.(i)and(ii), 11 = 10 ∆S ° ⇒∆ S ° = 1.1 JK–1
Substituting, ∆S ° =1.1 inEq.(i):
∆H ° = 45116.6 + 290 × 1.1= 45.4356 kJ mol –1
(b) ∆G ° (at 77 °C)= ∆H ° – 350 × 1.1= 45.8206 kJ= − RT ln K sp
−7
⇒ K sp = 1.45 × 10 = 4 S
3
⇒ S = 3.3 × 10 –3 M
2.54 × 2
481. Normalityofsolution = = 0.0318N
159.5
× 1000
Λ eq = K ⇒ k (specificconductance)
Q N
91 × 0.0318
= = 2.89 × 10 –3 Ω –1cm –1
1000
1   1 l 1  1
Also = k  A ⇒ R=  = –3   = 346 Ω.
R  l 
k A  2.89 × 10  1
Solutions 397

482. Foraweakelectrolyte:
Λc 10
=α = = 0.042
Λ∞ 238
For NH 3 : NH 3+HO 2 NH +4+OH –

C (1 −α ) Cα Cα
−2
Cα = 10 (0.042) =
2 2
Kb = 1.8 × 10
–5
1−α 1 − 0.042
483. Theionizationreactionofaceticacidis:
– +
CH 3COOH CHCOO
3 +H
C (1 −α ) Cα Cα
α 2 10 –2 α 2
K a = 2 × 10
–5
=C =
1−α 1−α
⇒ α 2 + 2 × 10 –3 α − 2 × 10 –3 = 0
−2 × 10 −3 + 4 × 10 −6 + 8 × 10 −3
⇒ α= = 0.0437
2
Λc
Now = 0.0437
Λ∞
⇒ Λ c =17.043 cm2 Ω –1eq –1
× 1000
Also Λc = k
C
Λ c C 17.043 × 0.01
⇒ k= = = 1.704 × 10 –4 Ω –1cm –1 .
1000 1000
1   1
484. G = = k  A  = k ⋅ ,where K iscellconstant (l /A).
R  l  K
⇒ K = Rk = 25 × 0.0116 = 0.29 cm
–1

K = 0.29 cm = kR
–1
Foracetic,acidsolution,

0.29 cm –1
⇒ k (CH 3COOH ) = = 1.463 × 10 –4 Ω –1cm –1
1982 Ω
× 1000 1.463 × 10 −4
⇒ Λm = k = 2
× 1000 = 1.463cm mol –1
Ω –1 .
C 0.1
485. Initially,onlyNaOHwaspresentat0.1M.
× 1000 0.022 × 1000
⇒ Λ m (NaOH) = k = = 220 Ω –1cm 2mol –1
.
C 0.1
After adding equal volume of HCl, NaOH will be neutralized completelygiving NaCl of
concentration0.05(sincevolumeisdoubled,concentrationofsaltwillbehalved).
398 ProblemsinChemistry

0.0056 × 1000
⇒ Λ NaCl = =112 Ω –1cm 2mol –1 .
0.05
Onfurtheradding HCl,no neutralization willoccur and conductivity willbedue toNaCland HCl
2 2
together.Nowtheconcentrationsof NaCl = × 0.05 andconcentrationof HCl = × 0.05M .
3 3
C
Now: k = k (NaCl) + k ( HCl) = (Λ NaCl + Λ HCl ) ×
1000
1000 × 0.017
⇒ × 3 = 112 + Λ HCl
2 × 0.05
⇒ Λ HCl = 510 − 112 = 398 Ω –1cm 2mol –1

486. ForNaClsolution:
× 1000
Λm = k = 126.5 …(i)
C
Herethe1stobjectiveistodetermine k (specificconductance)ofNaClandthen C ( NaCl).
1  A k
Also;conductance G = = k   = …(ii)
R l K
× 1000
ForKClsolution: Λm = k
C
138.3 × 0.02
⇒ k ( KCl)= = 2.766 × 10 –3 Ω –1cm –1
1000
NowfromEq.(ii),
−3
K (cellconstant) = kR = 2.766 × 10 × 85 = 0.235 cm
–1

Now;conductanceofwater
1
⇒ G HO2 =
9200
1
Conductanceof NaCl(aq )= G NaCl( aq ) =
7600
1 1
⇒ ConductanceduetoNaClalone = − = 22.88 × 10 –6 Ω –1
7600 9200
−6
⇒ k ( NaCl)= GK = 22.88 × 10 Ω × 0.235 cm = 5.38 × 10 Ω cm
–6 –1 –1 –1 –1

Substituting,inEq.(i):
−6
5.38 × 10 × 1000
126.5 =
C
⇒ C ( NaCl)= 4.25 × 10 M
–5

Number of moles of NaCl 500

⇒ Volumeofswimmingpool = = −
Mol ar i ty 58.5 × 4.25 × 10 5
= 2.011 × 10 5 L
Solutions 399
ΛC 195 × 0.05 −
487. k (specificconductance) = = . × 10 3 Ω –1cm –1
= 97
1000 1000
1  A − 1.5
Conductance (G ) = = k   = 9.7 × 10 3 × = 0.0291 Ω –1
R  l  0.5

⇒ V
R = 34.36 Ω =
I
V 5
⇒ I= = = 0.1455 A.
R 34.36
× 1000 K × 1000
488. Since, Λ eq =k = where K iscellconstant.
N RN
× 1000
⇒ Λ eq (KCl) = K = 138.3
85 × 0.02
× 1000
Λ eq (PbCl 2 ) = K = 106
70 N
138.3 70 N −2
⇒ = ⇒ N = 3.168 × 10
106 85 × 0.02

⇒ Molarityof PbCl 2 initssaturatedsolution = N = 1.58 × 10 −2

2
⇒ K sp = 4 M = 1.6 × 10 −6 .
3

ELECTROCHEMISTRY
0.15 × 8 × 3600
489. (a) Q = It = far aday
96500
Volumeof F2 (g ) produced =11.2 F= 0.5L
(b) Volumeof O 2 (g ) produced = 5.6 F= 0.25L
490. Partialpressureof O 2 = 722 − 19.83 = 702.17 torr.
−
702.17 25 × 10 3
⇒ Molesof O 2 (g ) produced = × = 9.548 × 10 −4
760 0.082 × 295
− I × 30 × 60 ⇒
Gramequivalentsof O 2 = 3.82 × 10 3 = I = 0.2 am p ere
96500
−4
491. Totalsurfacearea = 11.2 cm ⇒ V = 11.2 × 10 cm
2 3

Massof Ag =11.76 × 10 –3 g ⇒ g eq.of Ag =1.088 × 10 –4 = It

96500
⇒ t =105 seconds.
492. Thecellreactionis: 2Sn 2+
→ Sn 4+ +Sn
19
Initialmolesof SnCl 2 = = 0.1
190
400 ProblemsinChemistry

0.119
MolesofSndeposited = = 0.001= molesof SnCl 4 produced.
119
Molesof SnCl 2 leftunelectrolysed = 0.1 − 0.002 = 0.098
m( SnCl2 ) 0.098 × 190
⇒ = = 71.34.
m( SnCl4 ) 0.001 × 261
5 × 10 5
493. Molesof Br2 required =
94
10 6 It 20 × 10 3
Gramequivalentof Br2 required = = = t
94 F 96500
t = 14.258 hr.
494. E ° cell = 0.28, pH(fromHendersonequation) = 4.188
+ −
E = E °− 0.059 log [H ][Cl ] = E °+ 0.059 pH= 0.527V
Cu 2+ +2Br E °= 0.73V
–
495. Thespontaneouscellreactionis Cu +Br 2
0.059
Atthebeginning: E cell = 0.73 − log (0.05) ( 0.1)2 = 0.827V
2
Inordertoreversethecellreaction,minimumvoltagerequirement = 0.827V
Afterdepositionof2.827gCu:
m molof CuBr2 left = 50 − 44.87 = 5.13 ⇒ [CuBr2 ]= 0.01026M
0.059
⇒ E cell = 0.73 − log ( 0.01026) ( 0.02052)= 2
0.888V
2
Thus,atthisstage,minimumvoltagerequiredtoreversethereactionis0.888V.
− − nEF °
496. For I2 + I I 3 E ° =− 0.001V ⇒ ln K = ⇒ K c = 0.925
RT
[I –3 ] x
⇒ 0.925 = ⇒ 0.925 =
0.25I[ ]
−
0.25(0.25 − x )
Solving, x = 0.158 M.
497. Tl → Tl + + e 0.34
Cd 2+
+ 2e → Cd − 0.40
Cellreaction: 2Tl + Cd2+ → 2Tl + +Cd E ° =− 0.06
+ 2
0.059 [Tl ]
E =− 0.06 − log +
=− 0.036V
2 [Cd 2 ]
498. ThecellreactionbeforeaddingKClis:
1
M +H → M +
+ +
H2
2
[M + ]
E =− 0.4 = E °− 0.059 log +
[ H]
Solutions 401
⇒ E ° ( M+/ M) =+ 0.4177V
−
AfteraddingKCl, [Cl ] = 0.1M
M + Cl → MCl + e
−
Cellreaction:
H + e →
+ 1
2
H2

M + Cl + H → MCl + 2 H 2
− + 1

1
⇒ − 0.05 = E °− 0.059 log
[Cl ][ H]+
–

⇒ E °= 0.05 ⇒ E ° ( MCl/ M ,Cl – ) =− 0.05

⇒ E ° for MCl M
+
+Cl – = − 0.05 − 0.4177 =− 0.4677 V= 0.059log K sp
−8
⇒ K sp = 1.18 × 10 .
[H]+
499. 0.987 = 0.8 − 0.059 log
0.8
+ −4
⇒ [H ] = 5.4 × 10 M
+ 2
[ H]
Ka = = 2.09 × 10 −4
[HOCN]
+ −9
500. [Ag ] inasaturatedsolutionof AgCl = 1.4 × 10
+ −10
[Ag ] inasaturatedsolutionof AgBr =3.3 × 10
+
The spontaneous direction ofreaction willincrease concentration of Ag in AgBr/KBrsolution
+
anddecrease Ag inAgCl/KClsolution.
Therefore,spontaneouscellreactionis
Ag → Ag + (R )
Ag + (L) → Ag

Ag (L) → Ag (R )
+ +

[Ag + ]R
E = 0 − 0.059 log +
= 0.037V
[Ag ]L

0.059 [Zn 2+ ]
501. 0.76 =− E ° Zn 2+ /Zn − log +
2 [H ]2
⇒ E ° Zn 2+ /Zn =− 0.76V
0.059 [Ni 2+ ]
0.24 =− E ° Ni 2+ /Ni − log + 2
2 [H ]
⇒ E ° Ni 2+ /Ni =− 0.24V
402 ProblemsinChemistry

⇒ For Zn + Ni 2+ Zn 2+ +Ni
1.5 − x x
2+
2.303RT [Zn ] x =
E °= 0.52 V= log ⇒ 1.99 × 1017
2F [Ni 2+ ] 1.5 − x
+
Such a large value ofequilibrium constant indicate that allNi 2 hasbeenquantitatively reducedto
Ni.
AmountofZnconsumed = 1.5 × 0.75= 1.125 m ol es
0.059 [Mg 2+ ] 0.059
502. (a) E = E °− log + 2
= 3.17 − log = 3.14V
2 [Ag ] 2
+
(b) Asthereactionproceed, [Ag ] willdecreaseand [Mg 2+ ] willincrease.
+
m molof Ag initiallypresent = 34.6
+
m molof Ag presentfinally = 34.6 − 11.11 = 23.48
+
⇒ [Ag ] = 0.0678M
+
m molof Mg produced = 5.55
⇒ [Mg + ]= 0.119M
0.059 0.119
E = 3.17 − log = 3.128V
2 (0.0678) 2
0.059 [Zn 2+ ] 0.059 0.2
503. (a) E = E °− log 2+
= 1.1 − log =1.1 V
2 [Cu ] 2 0.2
+
(i) On adding NH 3 (aq ) to Cu 2+ solution, complex Cu( NH3 ) 24 will be formedreducing [Cu 2+ ],
2+ 2+
E cell will decrease (ii)Onadding NH 3 (aq ) to Zn solution, complex Zn( NH3 ) 4 willbe formed
+
reducing [Zn 2 ], E cell willincrease.
(b) Afteradding NH 3 , followingequilibriumwillestablish:
Cu 2+ +4NH 3 Cu(NH)3 2+
4

0.059 [Zn 2+ ]
Now, 0.68 = 1.1 − log
2 [Cu 2+ ]
+ −15
Solving, [Cu 2 ] = 1.16 × 10 M
Such lowconcentration of Cu indicate that almostall Cu 2+ hasbeen consumedincomplex
2+

formation.
⇒ 2+
3 4 ] = 0.1 M, [NH 3 ] = 1.1M
[ Cu(NH)
0.1
Kf = = 5.88 × 10 13 .
(1.1) × 1.16 × 10 –15
4

∆S ° ∆H °
504. E °= T− Solvingfor E ° at25°Cand20°gives
nF nF
∆S ° =− 30.88 JK −1 and ∆H ° =− 77.23 kJ and ∆G ° =− 68.03 kJ
Solutions 403

505. Forthegivencell,Nernstequationcanbewrittenas:
E = C + 0.059 pH, where C isaconstant
⇒ 0.129 = 0.059( 6.86− pH)1 ⇒ pH1 = 4.68
0.059 + + −
506. 0.348 = 0.13 − log [Pb 2 ] ⇒ [Pb 2 ] = 4.075 × 10 8
2
2+ − 2 −
K sp = [ Pb ][ F ] = 4.075 × 10 8
507. Thespontaneouscellreactionwillbe:
+
Zn 2 (T f =− 2) Zn 2+ (T f =− 0.9)
0.059 0.9
E =0− log = 0.01V
2 2
508. Thedischargingreactionis:
P b + PbO2 + 2H 2SO → 2PbSO 4+ 2HO2
4
23.92
⇒ m( P bSO4 ) pr oduced= × 2 × 302 = 60.7g
238
23.92
geq.of PbO 2 reduced = × 2 = 0.201
238
⇒ 0.201 × 96500 =3 × t ⇒ t = 6465.5 second= 1.8 h our
509. E ° for 2ClO –3 ClO –4+ClO =–2– 0.03V
0.1 − 2x x x
−2
⇒ K = 9.66 × 10
 
2
Therefore, . × 10
966
−2
=  x  ; Solving x = 0.019M
 0.1 − 2x 
[Fe 2+ ]
510. 0.035 = 0.77 − 0.059 log
[ Fe3+ ]
[Fe 2+ ]
⇒ = 2.87 × 10 12
[ Fe3+ ]
511. Ni 2+ +2HO
2 Ni O2 +H4 +
+ 2e E ° =− 1.678V
–
2e + Ni O2 + 2HO2 Ni ( OH)2 +2OH E ° =− 0.49V
−74
Ni 2+ +4HO2 Ni ( OH)2 + 4H ++2OH E ° =− 2.168V K1 = 4.5 × 10
–
Adding
−28
2H ++2OH K 2 = 10
–
2HO
2
−46
Subtracting: Ni 2+ +2HO
2 Ni ( OH)2 +2H + K = K1 / K 2 = 4.5 × 10
dE ° = ∆S ° ⇒∆ −1
512. Q S ° =− 0125
. × 2 × 96500 =− 24.125 kJK
dT nF
∆G ° =− nEF° =− 2 × 0.0372 × 96500 =− 7179.6J ⇒∆ H ° =− 7196.43 kJ
404 ProblemsinChemistry
2+
513. Let x betheconcentrationof Ca ionindilutedseawater.
0.059 1
− 0.053 = E °− log
2 x
0.059 50
and − 0.0422 = E °− log
2 50x + 0.05
0.059 50x + 0.05
⇒ 0.0108 = log ⇒ x = 7.55 × 10 −4
2 50x
−
⇒ [Ca 2+ ] inseawater = 10x = 7.55 × 10 3 M
9.6 × 10 3
514. Molesof Cl 2 (g ) produced = = 82.05
58.5 × 2
2
nRT − na =
P= 21.66 atm.
V − nb V 2
[H]+ 0.22
515. E = E °− 0.059 log +
= 0.8 − 0.059 log −
= 0.26V
[Ag ] 1.6 × 10 10
+
[Ag + ]L [Ag ]L
516. E = 0 − 0.059 log +
⇒ 0.4312 =− 0.059 log
[Ag ]R 0.1
+ − + − −9
[Ag ]L = 4.9 × 10 9 ⇒ K sp = [Ag ][Cl ] = 4.9 × 10 × 0.05
= 2.4 × 10 −10

RT [H]+ 2 + −7
517. E = 0.28 − ln = 0.6885 ⇒ [H ] = 2.57 × 10 or pH = 6.6
2F pH 2

518. Forthegivencell:
E = E °+ 0.059 pH ⇒ 0.112 = E °+ 0.059 × 4 …(i)
0.3865 = E °+ 0.059 pH …(ii)
Solving,Eqs.(i)and(ii)gives pH = 8.65
1
519. E = E °− 0.059 log +
= 0.8 + 0.059 log K sp = 0.51V
[Ag ]
520. Voltagedropduetoresistancebythecircuit = 0.55V
∆V
⇒ I= = 0.055A
R
Q = 055
. × 96500 = 53.075 kJ
− + −
521. Ag( CN)2 Ag + 2CN
0.1 − x x 0.05 + 2x
(0.05 + 2x ) 0.05x
3 × 10
−19
=x ≈ ⇒ x = 6 × 10
−19
0.1 − x 0.1
Solutions 405
1
E = 0.8 − 0.059 log =− 0.27V
[Ag + ]
1 1
522. E ° Au + /Au − 0.059 log +
= E°
Ag + /Ag
− 0.059 log
[Au ] [Ag + ]
+ + −16
Substitutingvaluesof E ° and [Ag ] = 0.1M gives [Au ] = 1.21 × 10
+ −
Now, Au( CN)–2 Au + 2CN
0.1 − x 2x
−16 −
−39 1.21 × 10 [CN ]2 − −12
K = 5 × 10 = ⇒ [CN ] = 2.02 × 10 M.
0.1
523. Thecellreactionis Zn + 2Ag + Zn 2+ +2Ag.
0.059 [Zn 2+ ]
E1 = 1.52 = E °− log
2 [Ag + ]12
0.059 [Zn 2+ ]
E 2 = 1.04 = E °− log
2 [Ag + ]22
0.059 [Ag + ]12 + −
⇒ 0.48 = log ⇒ [Ag ]2 = 7.31 × 10 10
2 [Ag + ]22
− −
[Cl ] = 0.2M ⇒ K sp = 1.46 × 10 10
524. (a) For AgS2 2Ag + +S 2–
0.059
E °= log K sp =− 1.425V …(i)
2
2Ag + + 2e 2Ag
E °= 0.8V …(ii)
Adding,Eqs.(i)and(ii)gives:
−
AgS2 + 2e E ° =− 0.652V
2Ag +S 2
0.059 1
(b) 0.766 = 0.896 − log 2−
2 [S ]
− −5
⇒ [S 2 ] = 3.92 × 10 M
+ −
525. Cellreactionis: H 2 (g ) + I 2 ()s 2H + 2I E °= 0.535
⇒ 0.755 = 0.535 − 0.059 log [H +][I –
] ⇒ pH= 2.72
526. Forthecellreaction:
1 + –
2
H 2+AgCl Ag +H + Cl

0.47 = 0.23 − 0.059 log [H +][ Cl – ] ; pH = 3.07

0.5 = 0.23 − 0.059 log [H +][ Cl – ]; pH = 3.58
406 ProblemsinChemistry

Ifthereis x molofacidand y molofNaOHinits20mL,then

y 2.5 y
3.07 = pK a + log and 3.58 = pK a + log
x−y x − 2.5 y
2.5(x − y)
⇒ 0.51 = log ⇒ x = 7.6 y
x − 2.5 y
y = −
and pK a = 3.07 − log 3.89 ⇒ K a = 1.3 × 10 4
6.6 y
1.25 × 1.1 × 3600
527. Faradayofelectricitypassed = = 0.0513
96500
51.3 1
⇒ meqof KMnO4 required = 51.3 ⇒ M (KMnO4 ) = × = 0.41M
25 5
It I × 3 × 60 −
528. 2I
–
I 2 + 2e F = = =9.3 × 10 3 ⇒ I = 4.98A
96500 96500
−
Totalmeqof I = 9.3 + 36.3 × 0.1 = 19.93 ⇒ M (KI) = 0.16
+
+ −13 [ Ag ]L
529. [Ag ]R = 8 × 10 ⇒ E = 0 − 0.059 log +
=− 0.71V
[ Ag ]R
− +
530. Forthecellreaction 2Hg + 2Cl + 2H Hg 2Cl 2 +H 2
1 + −5
− 0.52 V= − 0.28 − 0.059 log +
⇒ [H ] = 8.5 × 10 M
[ H ][Cl – ]
Kw [H]+ 2 −
Forsalt R 2 NH 2Cl : K h = = ⇒ K b = 1.36 × 10 7
K b [R 2 NH 2Cl ]
531. Since massofSnincreasing, Sn-electrode is working ascathode and X-metal electrode as anode
and electrons areflowing from X-electrode to Sn-electrode in the external circuit. The half cell
reactionsare:
Sn 2+ +2 e Sn E ° =− 0.14V
n+
X + ne X E ° =− 0.78V
Cellreaction: 2+
nS n + 2 X nS n + 2 X n+ ° = 0.64V
E cell
NowapplyingtheNernstequation:
+
E ° –0.0591 [ X n ]2
E= log +
2n [Sn 2 ]n
0.64 − 0.0591  −2 1
⇒ 0.65 =  log 10 − n log 
2n  2
0.0591
⇒ 0.01 = (2 − 0.3 n) Solving:
2n
⇒ n=3
Solutions 407

532. (a) Thespontaneouscellreactionis:

Zn +2Ag + ( aq ) Zn 2+ (aq )+2Ag() s
(b) ° = E cat
E cell ° hode − E ano
° de = 0.8 −−( 0.76) = 1.56V
(c) ApplyingNernst ’sequation:
0.059 [Zn 2+ ]
1.6 = 1.56 − log …(i)
2 [Ag + ]2
[ Zn 2+ ] [Zn 2+ ]
⇒ log + 2
=− 1.356 ⇒ −2
= 4 × 10 −2
[Ag ] 10
−4
⇒ [Zn 2+
]=4 × 10 M
+
(d) AsweaddKItocathodechamber,some Ag willprecipitateoutas:
Ag + +I – → AgI
The above reaction reducing [Ag + ] fromcathode chamber.This will reduce E cell according
toNernst ’sequation(i).
533. Intheaboveconditions,twoGalvaniccellcanbeconstructedas:
(i) Al/Cuand(ii) Fe/Cu.
° Cu =+ 0.34 + 1.76 = 2.1V
E Al and E F°e/ Cu =+ 0.34 + 0.44 =+ 0.78V
/

dependspredominantlyon E cell ° ,cell(i)ismorelikelytoproducehighervoltage.

Q E cell
0.059 [Al 3+ ]2 0.059 10 –6
E cel l ( i) = 2.1 − log = 2.1 − log = 2.1295V
6 [Cu 2+ ]3 6 10 –3
0.059 [Fe 2+ ]2 0.059 1
E cel l ( i i)= 0.78 − log 2+
= 0.78 − log = 0.75V
2 [Cu ] 2 0.1
⇒ Cell: Al Al 3+ (aq )  Cu 2+ (aq ) Cu willproducegreatervoltage.
534. Q = It = 430 × 60 × 60 = 1.548 × 10 C
6

⇒ numberoffaradaypassed = Q = 16.04 = numberofequivalentsofMgdeposited.

96500
24
⇒ massofMgdeposited = 16.04 × = 192.5g
2
10 6
(d) Numberofgramequivalentsof MgCl 2 requiredtobeelectrolyzed = .
47.5
10 6
⇒ Q= × 96500 = It = 500 t
47.5
⇒ 6
t = 4.063 × 10 sec = 1128.6 hours.
535. (a) 2Al 2 +12 e → 4Al ⇒ 12molesofelectronwillproduce4molesofAl.
+6

1250 × 1.25 × 3600

(b) Numberoffaradayspassed = = 58.29
96500
408 ProblemsinChemistry

27
⇒ Massofaluminiummetaldeposited = 58.29 × = 524.6g = 0.5246 kg.
3
° 3– – +
536. (a) E cell = E ° (I rCl6 /Ir , Cl ) – E ° (CO 2,HO3 HCOOH)
/ =+ 0.97 V
(b) Forthermodynamicspontaneityofacellreaction, ∆ °<
G 0.
Also ∆G ° =− nEF ° < 0 since, E °> 0
⇒ Reactionisthermodynamicallyspontaneous.
537. (a) Thecellreactionis:
Al + 3Ce4+ → Al 3+ +3Ce 3+ …(i)
° = E ° ( cat hode)− E ° (anode) =+ 1.443 + 1.76 = 3.203V
E cell
° ° 0.059 [Ce 3+ ]3 [Al 3+ ] 0.059 8
E cell = E cell − log 4 + 3
= 3.203 − log = 3.23V
3 [Ce ] 3 (6) 3
+
(b) Since, Ce 4 isinlimitedquantity.
∆G ° =− nEF° =− (1 mol e per molCe 4+ )( 3.203) × 96500 =− 309 kJ/mol Ce4+
⇒ ∆G ° (tot al) =− 309 × 12 =− 3708 kJ
(c) Initially [Al 3+ ]= 8 M, [Ce 4+ ]= 6M , [Ce 3+ ] =1M
Also totalmoleof Ce 4+ presentinitially = 6 × 2 = 12
totalmoleof Al 3+ presentinitially = 8 × 2 = 16
totalmolof Ce 3+ presentinitially = 2
Astheconcentrationof Ce 4+ droptohalf,6molof Ce 4+ willbeconvertedto Ce 3+ .
8
⇒ [Ce 4+ ]= 3M , [Ce 3+ ]= 2 M= 4M
Also,for3mol Ce 4+ reductiononemol Al 3+ comesinsolution.
⇒ for6mol Ce 4+ reduction,twomol Al 3+ comesinsolution.
⇒ [Al 3+ ] fi nal =9M
0.059 (4) 3 (9)
⇒ E cell = 3.203 − log = 3.177V
3 (3) 3
2+
538. (a) Firstofall,weneedtodetermine E ° for Cu /Cu half-cell.
E° ∆G °
e + Cu (aq ) → Cu()s + 0.522V − 0.522F
+
Given:
Cu 2+ (aq )+ e → Cu + (aq ) +0.158V − 0.158V

Add: Cu 2+ (aq )+ 2e → Cu()s ° =− 0.68F

∆G ° =− 2 E cell

⇒ ° =+ 0.34V
E cell
Note: Here E ° is determined using ∆G ° =− nEF° relationship since, E ° is an intensive
propertyandcan ’tbemanipulatedalgebraically.
Solutions 409
Now,fortheDaniellcell:
2+
Zn +Cu (aq ) Zn 2+ (aq )+Cu() s
° = E cat
E cell ° hode − E anode
° = 0.34 + 0.76 = 1.1V
+
(b) Initialmolesof Cu 2 = 2 × 4 = 8
⇒ molesof Cu 2+ finally = 2 × 0.4 = 0.8
⇒ molesof Cu 2+ deposited = 8 − 0.8 = 7.2
⇒ molesof Zn 2+ producedduringdepositionof Cu 2+ =7.2
⇒ finalmolesof Zn 2+ inanodechamber = 2 × 4 + 7.2 = 15.2
15.2
⇒ finally [Zn 2+ ]= = 7.6M
2
2+
⇒ ° − 0.059 log [Zn ] = 1.1 − 0.059 log 7.6 = 1.062V .
E cell = E cell +
2 [Cu 2 ] 2 0.4
539. (a) Ni ( OH)3 ()s iscathode:
s e → Ni ( OH)2 +OH
–
Ni ( OH)3 ()+ …(i)
Cd( OH)2 +2 e → Cd + 2OH– …(ii)
2(i)–(ii) 2Ni ( OH)3 (s)+ Cd → 2Ni ( OH)2 + Cd( OH)2
(b) E ° (Ni cad) = 0.49 + 0.81 = 1.3V
E ° for MgCl 2 → Mg + Cl2 is − 3.74V , –ve because thereaction is being driven ina
thermodynamicallynon-spontaneous direction. To makethe reaction proceed as written, the nicad
would have to supply atleast 3.74V. The voltage calculated fornicad battery is1.3 V,sothat nicad
battery can ’t drive this electrolysis. It would take 3 nicad batteries in series to have enough voltage
todothis:
3 × 1.3 = 3.9V > 3.74V .
= × ×
(c) Q 0.1 12 3600 C 4320 C =
⇒ numberoffaradays = Q/ 96500 = 0.0447F
⇒ massofMgdeposited = 0.0447 × 12 = 0.54 gram.
0.059
(d) Nernstequationis: E = E °− log Q.
2
Allthe reactant in nicad battery issolid and the products arealso solid and not part ofQ.Therefore,
as the cell approach equilibrium, there isno change in Q and no change in voltage. This isa
fundamentalideaonthedesignofmostmodernbatteries.
540. (a) Thebalancedcellreactionis:
PbO 2+ H SO2 +4CO → PbS O4 + H O 2 + CO 2

E °= E ° ( P bO2 /P bSO)4 – E ° (CO 2CO)

/ = 1.685+ 0.12= 1.905V
(b) Initialmolesof H 2SO 4
40 1
=1.3 × 3000 × × =15.918
100 98
410 ProblemsinChemistry

20 1
Initialmolesof H 2SO =1.2
4 × 3000 × × = 7.347
100 98
⇒ molesof H 2SO 4 consumed = 8.571
Itisevident fromthe given cell reaction that permoleof H 2SO 4 consumedinvolves transferof
Q =17.142.
twomolesofelectrons,totalelectrontransferred
⇒ Q ( withdr awn)= 17.142 × 96500 C
Ampere-hour = Q/ 3600 = 459.5
(c) TheNernstequationtellsusthatvoltagedependson Q(reactionquotient).
PCO2
Inthegivencell Q = .
[ H2 SO]4 PCO

541. (a) Glu → Gl n +2e + 2H ( CH(OH) → C== O + 2H+ +2 e) E ° =− 0.29V …(i)

+

6 + e → Fe( CN)6
Fe( CN)3– E ° =+ 0.69V
4–
…(ii)
Cell-reaction: (i)+2(ii) Glu + 2[ F e( CN)]6
3–
→ Gl n + 2H+ + 2[ F e(CN)]
6
4–
E ° =+ 0.40V
(b) °= 0.40 > 0, ∆G °< 0, cellisspontaneous.
QE
(c) Nernstequationis:
+ 2
0059
. [ Gln] [H] {[ Fe( CN)6 ]4– }2
E = E °− log
2 [ Gl u][Fe(
{ CN) 6 ]3– }2
Increasingconcentrationofglucosewillincreasecell-potential.
° > 0 ⇒ M → Zn and X → Ni andnetcellreactionis:
542. (a) Forspontaneouscellreaction, E cell
Zn +Ni 2+
Zn 2+ +Ni ° =+ 0.51V
E cell
2+
E cell ° − 0.059 log [Zn ] = 0.51 − 0.059 log0.01 =+ 0.569V
= E cell +
2 [Ni 2 ] 2

(b) During use, [Zn 2+ ] increases and [Ni 2+ ] decreases bythe samefactor. Therefore, when
[Zn 2+ ]=1.0 M, [Ni 2+ ] = 0.01M
0.059 1
E cell = 0.51 − log =+ 0.451V
2 0.01
Note: Equalvolumeofelectrolyteshavebeenconsideredinthetwohalf-cells.
(c) Ifsalt bridge isremoved,electrolysis willstop immediatelydue to accumulation of Zn 2+ ion
around Zn-electrode makingsolution positively charged. This will prevent further oxidation
+
ofZninto Zn 2 ion.Hence,cellvoltagewillbecomezero.
° 2 × 0.55 × 96500
543. (a) ∆G ° =− nEF° =− RT ln K ⇒ ln K = nEF = = 42.84
RT 8.314 × 298
⇒ K = 4.046 × 10 .
18
Solutions 411

E° ∆G °
g )+ 2H +2 e → HO − 2 × 1.23F
1 +
(b) Given: O(
2 2 2 +1.23V
1
O(
2 2 g )+ HO2 → HO
2 2 − 0.55V + 0.55F

Adding: O(2 g )+ 2H ++2 e → HO 2 2 ∆G ° =− 2EF

° =− 1.91F
⇒ E °= 1.91/ 2 = 0.955V .
Q = It = 100 × 1.5 × 3600 = 5.4 × 10 C
5
544.
⇒ Q = +
numberof faradays = 5.596 = numberofgramequivalent of Cu 2 deposited massof
96500
+ 63.5
Cu 2 depositedas Cu = 5.596 × =177.673g
2
Also, vol.of O 2 (g ) producedatanodeatSTP = 5.596 × 5.6 = 31.34 L.
+
Also; initialmolesof Cu 2 = 4.0
5.596
finalmolesof Cu 2+ = 4.0 − = 1.2
2
1.2
⇒ molarityof CuSO 4 infinalsolution = = 0.6M
2
545. (a) Cu()s → Cu + (aq )+ e E ° =− 0.52V
Cu 2+ (aq )+ e → Cu + (aq ) E °= 0.16V
E ° =− 0.36V
2+ +
adding Cu(s)+Cu (aq ) 2Cu (aq )
Negative E ° valueindicatesthattheabovereactionisnon-spontaneous.
Also ∆G ° =− nEF° =− RT ln K
nEF° − 0.36 × 96500
⇒ ln K = = =− 14.02 ⇒ K = 8.14 × 10 –7
RT ×
8.314 298
(b) Thereactioniscombinationof:
2+ −7
Cu(s)+ Cu (aq ) 2Cu + (aq ) K = 8.14 × 10
1
2Cu + (aq )+ 2Br – ( aq ) 2CuBr ()
s K=
K 2
sp

8.14 × 10 –7
K=
2+
Adding: Cu(s)+Cu (aq )+ 2Br – (aq ) 2CuBr ()
s
k sp 2

Now, E ° forthegivencellis 0.5147V .

0.5147 × 96500
⇒ EF° = RT ln K ⇒ ln K = = 20.04
8.314 × 298
−7
8.14 × 10 8.14 × 10 –7
⇒ 8
K = 5.086 × 10 = ⇒ K sp = = 4 × 10 –8 .
K sp 2 5.086 × 10 8
412 ProblemsinChemistry

546. (a) ° = 1.36 + 0.76 = 2.12V

E cell
0059
. [Zn 2+ ] 0.059 (0.04)
⇒ . −
E cell = 212 log – 2
= 2.12 − log = 2.025V
2 [Cl ] 2 (5 × 10 –3 ) 2
(b) Onaddingammonia,followingreactionwillgotorightquantitatively:
Zn 2+ (aq )+ 4NH 3 Zn(NH)3 2+
4 K f = 7.8 × 10
8

Initial 0.04 1M 0
Eqn. x 1 − 0.16 0.04
[Zn(NH)3 2+
4 ] (0.04) 2+ −10
⇒ K f = 7.8 × 10 =
8
= ⇒ x = [Zn ] = 10 M
[Zn ] [NH]3 4
2+
x (0.84)
4

−
0.059 [Zn 2+ ] 0.059 10 10
Now: E = E °− log = 2.12– log −
= 2.28V
2 [Cl – ]2 2 (5 × 10 3 ) 2
547. Thegalvaniccellreactionis:
2Ag + + Cu 2Ag(s)+Cu 2+

0.059 [Cu 2+ ] 0.059

and E = E °− log + 2
= E °− log [Cu 2+ ] + 0.059 log [Ag + ]
2 [Ag ] 2
⇒ E = K + 0.059 log [Ag ]
+

0059
.
where K = E °− log [Cu + ] = constantinthegivenproblem.
2
+ +
⇒ 0.382 = K + 0.059 log [Ag ]1 and 0.01 = K + 0.059 log [Ag ]2
[Ag + ]1 0.01
⇒ 0.372 = 0.059 log +
⇒ +
= 2.0187 × 10 6
[Ag ]2 [Ag ]2
⇒ +
× –9 M
[Ag ]2 ( fi nal ) = 4.9510
Also,initialmmolof Cl – (added) = 2 × mmolof Ca 2+ =2 × 0.02 × 250 = 10
+
Initialmmolof Ag = 250 × 0.01 = 2.5
⇒ mmolof Cl – leftafterprecipitation = 7.5 ⇒ [Cl – ] fi nal = 0.03M
⇒ K sp (AgCl) = [Ag ]2 (0.03) = 4.95 × 10 × 0.03= 1.485 × 10 –10 .
+ –9

548. Q = It = 2.5 × 35 × 60 = 5250 C

⇒ Q =
Numberoffaradays = 0.0544 = numberofequivalentofmetaldeposited.
96500
3.06
⇒ Equivalentmassofmetal = = 56.25 ⇒ Molarmass = 112.5 amu.
0.0544
549. (a) Thespontaneouscellreactionis:
2Sn 2+ (aq )+ O 2+ 4H +
2Sn 4+ (aq )+2HO2 ° = 1.08V
E cell
Solutions 413
ApplyingNernstequation:
 0.01   1 
2 4
0059
.
. −
E = 108 log     = 0.8735V
4  0.10   10 –4 
2+
(b) Atanyinstant ofuses, if x M Sn concentration isdecreased, [Sn 4+ ] willincrease bythe
sameamount.
0.059   0.01 +  2 
x × 16 
⇒ 0.8 = 1.08 − log    10
4   0.10 − x  
x = 0.0966M ⇒ [Sn ]= 0.1066 M; [Sn ]= 0.0034M
4+ 2+
Solving
550. E1 = E °+ 0.059 pH1 and E 2 = E °+ 0.059 pH2
⇒ E 2 − E1 = 0.16 = 0.059 (pH2 – pH)1 ⇒ pH 2 = 12.11
551. Theelectrolysisreactionis:
2Cu 2+ +2HO 2 → 2Cu+4H +O +
2
4 × 30 × 60
Numberoffaradaysofelectricitypassed =
96500
= 0.0746 = numberofgramequivalentof H + produced.
+ 0.0746
⇒ molarityof H = = 0.373 ⇒ pH = 0.43
0.20
552. Ironwillbedepositedfirst.Thecellreactionwouldbe:
Fe 2+ +HO2 → Fe+2H++ 12 O 2
E ° =− 0.44 –1.23 =− 1.67V
0.059 [H]+ 2
⇒ E =− 1.67– log =− 1.4V
2 [ Fe2+ ]
⇒ Aminimumof1.4Vwouldberequiredfortheonsetofelectrolysis.
553. Reductionhalf-reactionis:
M ( aq ) + e → M()s
+

1
E1 = E °− 0.059 log +
= E °+ 0059
. log [M]+ 1
[ M] 1
−2
⇒ E 2 = E °+ 0.059 log [M] 2 = E °+ 0.059 log 10 [M]1
+ +

= E1 + 0.059 log 10 –2 = E1 − 0.118V

i.e., loweringappliedpotentialby 0.118V .
554. ° = 1.66 –0.44 = 1.22V
E cell
0.059 [Al 3+ ]2
E cell = 1.2 = 1.22 − log
6 [ Fe2+ ]3
 [Al 3+ ]2 
⇒ log  2+ 3  = 2.033
[ Fe ] 
414 ProblemsinChemistry

[Al 3+ ]2
⇒ = 108 ⇒ [Al 3+ ]= 1.16 × 10 –4 M
1.25 × 10 –10
⇒ molesof Al 3+ insauce = 1.16 × 10 –4 × 0.1 = 1.16× 10 –5
⇒ massofAldissolved =1.16 × 10 –5 × 27 = 3.132 × 10 –4 g
3.132 × 10 –4
⇒ vol.ofofAl-foildissolved = = 1.16 × 10 −4 cm 3
2.7
V 1.16 × 10 –4
⇒ areaofholes = = = 1.16 × 10 −3 cm 2 .
thi ckness 0.1
1500
555. 1500 = n(28.8 − 2) = 26.8 n ⇒ n = mol H 2 required
26.8
⇒ 2n faradayofelectriccurrentwouldberequired
1500
⇒ Q =2× × 96500 = 8.5 t. ⇒ t = 353 hour s.
26.8
556. Theelectrodesreactionare:
Zn → Zn 2+ +2 e 0.76V
2H ++2 e → H 2 0.00V
Cellreaction: Zn + 2H+ → Zn 2+ +H 2 E ° =+ 0.76V
Now,applyingNernstequation:
0.059 0.1
E = 0.72 = 0.76 – log + 2 ⇒ [H +]= 0.0664M
2 [ H]
For HIO 3 : HIO 3 H++ IO –
3

0.1 − x x x
2
x (0.0664) 2
Ka = = = 0.13
. − x 0.1 – 0.0664
01
2+
557. mmolof Cu electrolyzedin30min = (0.1 – 0.0528)100 = 4.72
meqof Cu 2+ deposited = 9.44 = numberofmF. =
Q Q It
⇒ 9.44 × 10 × 96500 =I × 30 × 60 ⇒ I = 0.5A
–3

i.e., meterisshowingonly80%oftheactualcurrent.
558. Thespontaneouscellreactionis:
2Cr 2+ +Ni 2+ 2Cr 3+ +Ni E ° =+ 0.16V
+3 2
0.059 [Cr ] 0.059 2.56 × 10 –4
E = 0.11 V =0.16 − log = 0.16 − log
2 [Cr +2 ]2 [Ni +2 ] 2 [Ni +2 ]
⇒ [Ni 2+ ]= 5.16 × 10 –6 M.
Solutions 415

559. (a) Theelectrodereactionsoccurringare:

2H 2O+2 e → H 2+2OH –
:atcathode
2HO
2 → 4H ++O+42 e :atanode
Since, phenolphthalein iscolourless below a pHvalue of8 and pink above a pHvalues of10.
Atthe start ofelectrolysis, both the solutions will be colourless. Aselectrolysis proceeds,
cathode compartment will become basic and will acquire pink colouration whileanode
compartmentwillbecomemoreandmoreacidicandremainscolourless.
(b) If electrolysis is stopped at any stage, the two compartments, cathode and anode
compartment,will have samenumber of gramequivalent of hydroxide and hydronium ions.
Therefore, if the content of two compartmentsare mixed,the net result will be formationofa
neutralsolutionanditwillbecolourless.
(c) Aselectrolysis proceed, HO – willbeproduced andwillbeneutralized withHCladded from
out side. Atend point when the whole HClisneutralized, solution willacquire alkaline
natureifelectrolysisiscarriedonfurtherandwillbecomepinkcoloured.
−
25 × 10 3 × 8 × 60
⇒ Q = F = 1.24 × 10 –4 = equivalentsofHClin10mL.
96500
1.24 × 10 –4
⇒ MolarityofHCl = = 0.0124M
0.01
560. Given: HgI 2–
4 +2 e Hg + 4I – E ° =− 0.04V
Hg Hg 2+ +2 e E ° =− 0.85V
Adding: HgI 2–
4 Hg 2+
+4I –
E ° =− 0.89V
WritingNernstequation:
0.059 [Hg 2+ ][I – ]4
E =− 0.89 − log
2 [HgI 2–
4 ]
0.059
Atequilibrium E = 0 =− 0.89 − log K d
2
1
⇒ K d = 6.768 × 10 =
–3
⇒ K f =1.47 × 10 .
30
Kf

CHEMICAL KINETICS
WU NU 5 × 206
561. =5 ⇒ = :
WPb N Pb 238
N 0 − N 1030
U
238
→ Pb 206 ⇒ =
N0 − N N N 238

N0
Also, λ t = ln …(i)
N0 − N
416 ProblemsinChemistry

N 235
=
Q N 0 − N 1030
N0 238 + 1030 1268
⇒ = =
N0 − N 1030 1030
1 1268
⇒ t= −10
ln = 1.35 × 10 9 year.
1.54 × 10 1030
7 80
562. P0 = 200 nm After15min: P0 + p = 240 mm ⇒ p = mm
2 7
200 200
⇒ 15 K = ln and 140 K = ln
80 200 − p′
200 −
7
Solving p′= 84.5 mm
7
⇒ PTot al (after 140 min) = 200 + p′= 495.75 mm.
2
563. Letafter30min,partialpressureof1,3-butadienebe p mm.
− 55
⇒ 30 × 60 × 2 × 10 4 = ln ⇒ p =16.63
55 − p
⇒ p( cyclobut ene)= 38.37 mm
−
[ cycl obutene]= 1.45 × 10 3 M
K 2 E a  T2 − T1  E  
−
8.5 × 10 11 10
564. (a) ln =   ⇒ ln = a   ⇒ E a = 108.1 kJ
K1 R  TT
1 2  2.1 × 10
−11
8.314  300 × 310 
E − 108.1 × 10 3
Also, ln K1 = ln A − a ⇒ ln 2.1 × 10 11 = ln A − ⇒ A = 13.97 × 10 7
RT1 8.314 × 300
Ea −10 −1
⇒ ln K ( 47° C) = ln A − ⇒ K (47° C) = 3.155 × 10 S
×
R 320
0.15
(b) Kt = ln −
⇒ t = 6.53 × 10 11 second
1.65 × 10 7
ln 2
565. (a) λ= = 6.32 × 10 −3 min −1
t12/
−3 100
(b) 5.6 × 60 × 6.32 × 10 = ln ⇒ X = 12%
X
−3
(c) 6.32 × 10 t = ln 100 ⇒ t = 12.14 hou rs
3 x = 8 × 10 −18
566. 1 H infresh10g HO
2 :
10
× 2 × 6.023 × 10 23 − x
18
ln 2 5.35 × 10 6
x = 5.35 × 10
6
⇒ × 40 = ln ⇒ N = 5.6 × 10 5 1 H 3
12.3 N
Solutions 417

567. 2NO
2 5 → 4NO 2 + O 2
p
p0 − p 2p 2
3
PT = p0 + p
2
5
Afterinfinitetime p0 = 584.5 mm ⇒ p0 = 233.8 mm
PT =
2
3
After30min: PT = 284.5 = 233.8 + p ⇒ p = 33.8
2
1 233.8
⇒ K= ln = 5.2 × 10 −3 min −1
30 200
− 233.8
After1.0hour; 60 × 5.2 × 10 3 = ln ⇒ p′= 62.71
233.8 − p′
3
PT = p0 + p′= 327.87 mm.
2
568. Massof X decayedin20days = 0.75 g= massofHe (g ) produced.
0.75
⇒ VolumeofHe(S.T.P.) = × 22.4 = 4.2L
4
Kc E − Ec (106 − E c ) × 10 3
569. ln = uc ⇒ ln 500 = ⇒ E c = 90 kJ
K uc RT 8.314 × 310
90 × 10 3 106 × 10 3
ln K c = ln A − and ln K uc = ln A −
8.314 × 400 8.314 × 300
 K (127° C)  106 × 10 3 90 × 10 3 K c (127° C)
⇒ ln  c  = − ⇒ = 5.05 × 10 6
 K uc (27° C)  8.314 × 300 8.314 × 400 K uc (27° C)
570. Let p0 betheinitialpartialpressureof A2 (g ).
A2 (g ) 2 Ag( )
I. at30min p0 − p1 2 p1
II. at60min p0 − p1 2 p2
I. PTot al = p0 − p1 + 2 p1 + 700 − p0 = p1 + 700 = 760 ⇒ p1 = 60
II. PTot al = p2 + 700 = 800 ⇒ p2 = 100
p0 p0
Now, 30 K = ln and 60 K = ln
p0 − 60 p0 − 100
−3 −1
Solving: p0 = 180 mm ⇒ K = 13.5 × 10 min ⇒ t12/ = 51.28 m in.
180
After75min: 75 K = ln ⇒ p3 = 114.68 ⇒ PT = 700 + p3 = 814.68 mm
180 − p3

571. E af = 11420 × 2.303R = 218.66 kJ

−1
⇒ E ab = E af − ∆H = 115.66kJ mol
418 ProblemsinChemistry

1
572. NO
2 5 → 2NO 2 + O 2
2
1−α 2α α
2
Let x bethemolefractionof O2

r (NO)2 32 0.5
=4 = ⇒ x = 0.15
r (O 2 ) 46 x
r ( N2O)5 1−α 46 0.5 − x
= = ⇒α= 0.31
r (NO 2 ) 2α 108 x
1 ln 2 1 1
Now, Kt = ln ⇒ = ln ⇒ t12/ = 27.17 m in.
1−α t12/ 15 0.69

 1
n
573. m = m0   where, n = numberofhalf-lives.
2
 1 1
2
 1
3
1
4
 1 
5
⇒ m = 
51 + +   +   +   +    =
 4  4  4  4  4   6.66 mg

574. Meq I 2 taken=15,meqof I 2 reactedwithhypo = 7

⇒ meqof I 2 consumedby SO 2 = 8 = Meqof SO 2
⇒ mmolof SO 2 produced = 4
⇒ After4.0hours,total mmolofgases =14
−3
14 × 10 × 0.082 × 400
P= = 2.296 atm
0.2
ln 2 1 10
= ln ⇒ t12/ = 5.43 hour
t12/ 4 6
− −
ΣEK 180 × 10 3 × 1.2 × 10 2 + 200 × 10 3 × 3 × 10 2
575. E = = = 194.28 kJ
i i
ΣK i −
1.2 × 10 2 + 3 × 10 2
−

576. Letatequilibriumdegreeofconversionbe x.
⇒ x = 0.16 ⇒ x = 0.138
1− x
K1
Also, = 0.16 ⇒ K 2 = 6.25 K1
K2
dx =
Now, K1 (1 − x ) − Kx2 = K1 (1 − 7.25x )
dt
⇒ dx = Kdt
1 − 7.25x
1

1 1
⇒ ln = Kt1
7.25 1 − 7.25x
Solutions 419
1 1
Forhalfequilibriumreaction: t= ln = 290 second
7.25K1 x
1 − 7.25 ×
2
K (Ca) = t12/ (Ar ) = = n(Ca) =
577. 8 ( ) = 52.64
nK
K ( Ar) t12/ (Ca ) n(Ar)
− −1
( ) = K (Ca ) + K (Ar ) = 5.198 × 10 10 y
KK
1 100
⇒ t = ln = 1.23 × 10 9 years
K 52.64
35
578. α 0 = α (t =∞−) α (t = 0) = 35° ⇒ 10 K = ln
25
35 35
and 20 K = ln = 2 ln ⇒α= 17.85
α 25
0 ⋅ R after20min = 17.85 + 5 = 22.85.°
17.15
mmolofreactantconsumedafter20min = 10 × = 4.9 m mol.
25
mmolofalkene = 2.94 = m molof Br 2 = 0.15V ⇒
V = 19.6 mL
579. ∆H R =− 3.7 kJ and E af − E ab =− 3.7 ⇒ E ab = 53.5 kJ

 (T )  E  5 
580. ln  12/ 1  = a   and E a = 351.13 kJ
 (T12/ ) 2  R  333 × 338 
ΣEK EK
1 1+ EK2 2 + EK 3 3
E= =
i i
581.
ΣK i K1 + K 2 + K 3
K1 10 K1 10
Also, = and =
K 2 25 K 3 15
EK + 2.5KE
1 2 + 1.5KE
⇒ E=
1 1 1 3
= 79 kJ
+ +
K1 2.5K1 1.5 K1
1
582. K (27° C) = ln = 0.223 hr.−1
0.8
0.8
K (37° C) = ln = 0.693 hr.−1
04
.
0.693 E a  10 
⇒ ln =   ⇒ E a = 87.63 kJ
0.223 R  300 × 310 
0.4
KT( ) = ln = 1.386 hr.−1
0.1
1.386 87.63 × 10 3  T − 310 
⇒ ln = =   ⇒ T = 316.45K
0.693 8.314  310T 
420 ProblemsinChemistry

p0 p0
583. 20K = ln and 40K = ln
p0 − p1 p0 − p2
p0 p0
⇒ ln = 2 ln
p0 − (2.875 − p0 ) p0 − (2.5 − p0 )
2
p0 p0
⇒ =
2 p0 − 2.875 (2 p0 − 2.5) 2
Solving, p0 = 1.5625,2
3 2
If p0 = 2 then 60K = ln = 3 ln ⇒ p = 1.156, PT = 3.156 at m.
2− p 1.5
pB 1
584. = ⇒ pC = 15 pB ⇒ p0 = 15 × 40 + 40 = 640
pC 15
640
⇒ 60(K1 + K 2 ) = ln ⇒ P = 546.17 = pB + pC = 16 pB
640 − P
⇒ pB = 34.135 pC = 512.025 mm of Hg.
585. Initialm molofcyclobutene =10
Letafter20min, xm molcyclobuteneisomerized.
m molofcyclobuteneleft = 10 − x and m molofdieneformed = x
m molof Br 2 requiredafter20min = 10 − x + 2x = 10 + x = 16
10
⇒ x =6 ⇒ 20K = ln …(i)
4
If ym molofcyclobuteneisomerizedafter30min.
10
30K = ln …(ii)
10 − y
FromEqs.(i)and(ii) y = 7.47
⇒ m molof Br2 required = 10 + y = 17.47
⇒ Vol.ofbrominesolutionrequired = 17.47 mL
586. A → A ′ α0
α 0 −α1 −α1 ⇒α 0 − 2α 1 = 40 ⇒α 1 = − 20
2
α 0 −α 2 −α 2 α
⇒α 0 − 2α 2 = 24 ⇒α 2 = 0 − 12
2
α0 α0
⇒ 10K = ln and 20K = ln
0.5α 0 + 20 0.5α 0 + 12

Solving, α 0 = 59°
59 59
⇒ 10K = ln and 40K = ln ⇒α = 29.77
59 − α 3
3
49.5

⇒ Optical-rotationafter40min = α 0 − 2α 3 = 59 − 29.77 =− 0.54.°

Solutions 421
14000 20000
− −
587. 10 2 e RT = 10 3 e RT Solving, T = 313.42K
−1
⇒ Rateconstant K1 = K 2 = 0.464 hr.
n0 ( A2 )
⇒ Kt1 = ln ⇒ n1 = 0.37
n0 ( A2 ) − n1
n0 ( B 3 )
Kt2 = ln ⇒ n2 = 0.37
n0 (B 3 ) − n2
⇒ Totalmolesofgasesafter1.0hr. =1.37 +1.74 = 2.11
P = 5.42 at m.
588. Let α bethedegreeofdissociationafter12hr.
⇒ P = Px 0 1 FromRaoult ’slaw.
20.69 10 10  10 
⇒ = = ⇒α= 0.3 ⇒ 12K = ln  
24 10 + 1 + 2α 11 + 2α  7
1
30K = ln
1−β
where β isdegreeofdissociationafter30hr.
⇒ β= 0.6 andmolesofsoluteafter30hr. = 1 + 2β = 2.2
 10 
⇒ P = 24   = 19.67mmof Hg.
12.2 
R2
589. = 4 = (2) z ⇒ Z (orderw.r.t. C ) = 2
R1
 3  3
y 2
R3
= 0.668 =     ⇒ y (orderw.r.t. B) = 1
R1  2  2
R4  4
= 10.65 = (2) x ×   × (2) 2 ⇒ x(orderw.r.t. A) =1
R3  3
RateLaw: R = KA [ BC
][ ][ ]
2

−
dN = 4 0.42 × 10 3
590. KN = 9.88 × 10 = K × × 6.023 × 10 23
dt 347
ln 2
⇒ K= = 1.35 × 10 −13 sec −1
t12/
⇒ t12/ = 5.13 × 1012 sec = 1.628 × 10 5 year
238 235
591. If x molof U and y molof U hasdecayed,thenpresently
U = 100 − (x + y)
−
100 (x y) + 50 − x
Also, = 50 − y ⇒ = 99
100 50 − y
422 ProblemsinChemistry

50 − x
Also, t (K 2 − K1 ) = ln = ln 99
50 − y
l n 99
⇒ t= = 5.5 × 10 9 year.
K 2 − K1
K1 K1 7
592. A B, =
1 −
x K2 x K2 3
dx =  10 
K1 (1 − x ) − Kx2 = K1 1 − x 
dt  7 
7 1
⇒ ln = Kt1 …(i)
10  10 
 1 − x
 7 
−
Solvingat t =1 gives K1 = 0.309 hr. 1
1 10Kt1
After4.0hr, ln = ⇒ x = 0.58 ⇒ mole%of A afterfourhour = 42%
10 7
1− x
7
Kf 5800 ∆S ° ∆H ° −
594. log = 5.457 − = − ⇒∆ S °= 104.48 JK, 1 ∆H °= 111 kJ
Kb T 2.303R 2.303RT
595. Normalityofchromicacid = 1.2N
Normalityof KI =1N
Istflask: meqofKIleft = 10.4 × 1.2 = 12.48
meqof KI ≡ HO
2 =20
2 − 12.48 = 7.52
2.5 11.16
Initialmeqof H 2O 2=25 × =11.16 ⇒ K = ln
5.6 7.52
IIndflask:Letx meqof HO 2 2 leftundecomposed.
11.16
3K = ln ⇒ x = 3.41 = meqofKIconsumed
x
meqofKIreducedwithchromicacid =16.59
Vol.ofchromicacidrequired = 13.825 mL
+ + −4 −1
596. R = K [ H ][ ester] = K ′ [est er] where K ′= K [H ] = 3.478 × 10 s
1 100
⇒ t= ln = 17 minutes
K ′ 70
597. Lettheinitial molepercentage of A is x and that of B is (100 − x ). Let after ‘’t time, p mole of A and
q moleof B areconvertedinto C.

⇒ −2 x ⇒
2 × 10 × 30 = ln x = 2.22 p
−
x p
Solutions 423
−3 100 − x 100 − x
and 5 × 10 × 30 = ln = ln p + q = 25
100 − x − q 75 − x + p Q
100 − x
= ln solving x = 36
75 – 0.55x
−2 36
After50min: 2 × 10 × 50 = ln ⇒ p = 22.74%
36 − p
−3 64
5 × 10 × 50 = ln ⇒ q =14.2%
64 − q
⇒ molepercentageof C after50min = p + q = 36.94
t12/ = 71 sec. 1− x
598. O14  → Requirednucleiratio = 0.25
1− x 1− y

t = 124 sec. ln 2 1
O15 →
12/
t = ln
1− y 71 −
1 x
ln 2 1 1 1  1− y 2 × 71 × 124
t = ln ⇒ ln 2  −  t = ln = ln 4 ⇒ t= = 332.226 sec.
124 1− y  71 124  1− x 124 − 71
Kc E − Ec 80 × 10 3 − E c
599. ln = uc ⇒ ln 10 = ⇒ E c = 74.25 kJ
K uc RT 8.314 × 300
K c (127° C) 74.25 × 10  100 
3
Now, ln =  
K c (27° C ) 8.314  300 × 400 
K c (127° C) t (27° C)
⇒ = 1706.6 = 12/
K c (27° C) t12/ (127° C)
100 ln 2
⇒ t12/ (127° C) = 42.2 sec. ⇒ K t = ln
= t ⇒ t = 84.4 secon ds
25 42.2
600. Xe (CF 3 ) 2 (g ) → Xe (g ) + CF2 4 (g ) + F2 (g )
Total mole: 0.005 − x x x x
PV = 2.63 × 0.1 =
Aftertime t : n = 0.0107 = 0.005 + 2x
RT 0.082 × 300
−3
⇒ x = 2.85 × 10
ln 2 0.005
⇒ t = ln −
⇒ t = 36.53 sec.
30 0.005 − 2.85 × 10 3
K
→
1
β K1 [β]
601. Ac =9=
K2 [α ]
K
→
2
α
424 ProblemsinChemistry

PV = −
Also, nα = 6.5 × 10 3
RT
−3
nβ = 9nα = 58.5 × 10
⇒ MolesofAcdecayedin5.0hours = nα + nβ = 0.065
ln 2 0.44
⇒ × 5 = ln ⇒ t12/ = 21.68 years
t12/ 0.44 − 0.065

t12/ = 1.5
602. NO → After5.0hour x − y + 1.5 − x − z = 0.225
−
x y

t12/= 2.5
NO 2  → ⇒ z = 1.275 − y …(i)
1.5 − x − z
ln 2
Also, × 5 = ln x ⇒ x =
10 …(ii)
1.5 x−y −
x y
ln 2 1.5 − x 1.5 − x
× 5 = ln ⇒ =4 …(iii)
2.5 1.5 − x − z 1.5 − x − z
SolvingEqs.(i),(ii)and(iii)
x = 1.0g and y = 0.5g
 KK1 2
23/
2
603. Q K =  ⇒ E = (E1 + E 2 − E 3 ) = 153.34 kJ
 K3  3
604. Since,absorbanceofsolutionisdirectlyproportionaltotheconcentrationofcolouredspecies
A1 C1
A ( absor bance)∝ C ⇒ =
A2 C 2
0.600 C1
⇒ = −5
⇒ C1 = 1.2 × 10 −4 M
0.200 4.00 × 10
Also,decompositionof X followfirstorderkinetics:
C0 A 0.600
Kt = ln = ln 0 ⇒ K × 35 = ln = ln 3
C A 0.200
0.600
Kt = ln = ln 80
0.0075
ln 80
⇒ t = 35 = 139.6 minutes.
ln 3
605. (a) Thedecompositionreactionisfollowing1storderkinetics,since,fora1storderreaction:
[ A ]0
Kt = ln
[ A]
where [ A ]0 isinitial concentration and [ A ] isconcentration ofreactant leftunreacted atanytime
“”t .
⇒ Kt = l n[ A ]0 − ln[ A ] ⇒ ln[ A ] = ln[ A ]0 − Kt
i.e., Aplotof ln[ A ] vstimeisastraightlinewithnegativeslope.
Solutions 425
Hence,ratelaw: Rate = K [H 2O]2
(b) Fromthegraph,at t =0
ln[ A ]0 = 0 ⇒ [ A ]0 =1.0
At t = 2800 mi n, ln[ A ] =− 3
3
⇒ −3 = 0 − 2800 K ⇒ K = = 1.07 × 10 −3 min −1
2800
3
At2000min, ln[ A ] =− × 2000 =− 2.142 ⇒ [A] = 0.1173M
2800
606. Let P0 bethe partial pressure ofeach Cl 2Oand NO2 5 inthe beginning. Therefore, the total
pressureafterinfinitetimewouldbe 2P0 + P/0 2.
5
⇒ P = 750 and P0 = 300 mmofHg.
3 0
Now,let us consider “ p” bethe decrease inpartial pressureofboth ofthe reactants aftertime “”t ,
then:
2Cl 2O +2NO2 5 → 2NO 3Cl+2NO Cl+O 2 2
300 − p 300 − p p p p/ 2
300 p=
At10min. 10 K = ln and 600 + 650 ⇒ p = 100
300 − p 2
3
⇒ 10 K = ln   …(i)
2
300
At30min. 30 K = ln …(ii)
300 − p
SolvingEqs.(i)and(ii)yields p = 211.
Total P = 600 + p/ 2 = 705 mmofHg.
th
607. Therateexpressionforageneral n orderreactionis:
1  1 1 
Kt =  − 
n − 1  [ A ]n 1 [ A ]n0 1 
− −

1  1  1 1 − 1
⇒ 400 K =  − 1  = (2 n 1 − 1) …(i)
−
n 1  (0.5) n −1
 [ A ]0
n −1 −
n 1 [ A ]n0
−1

1  1  1 1 − 1
964 K =  − 1 = (4 n 1 − 1) …(ii)
n − 1  (.025 )
−
n 1 n −1
 [ A ]0 n − 1 [ A ]n0
−1

−
964 K 4n 1 −1 3
⇒ = 241
. = −1 = 2n − 1 +1 ⇒ 2n
−1
. = (2)12/
= 141 ⇒ n=
400 K 2 n − 1 2
Substituting, n =1.5 inEq.(i)gives
2( 2 − 1)
400 K =
0.6
−3 − 12/
⇒ –1
K = 2.67 × 10 sec (M )
426 ProblemsinChemistry

608. Fromthegivengraph,half-lifeisdeterminedtobe20sec.
ln2
⇒ K=
20
0.4
⇒ At10sec. K × 10 = ln
[ A]
[ A ] = Concentrationofreactantleftunreactedafter10sec.
ln 2 0.4
⇒ × 10 = ln and [ A ] = 0.28M
20 [ A]
ln2
Hence,at10min: Rate = KA[ ] = × 0.28 = 9.7 × 10 −3 molL –1 sec –1 .
20
609. TheArrheniusequationis:
Ea
log K (s –1 ) = log A − ⇒ Fromthegivengraph, log A = 3
2.303 RT
Ea 10 4
andslope = ⇒ E a = 63.82 kJ
2.303 R 3
Therefore,at500K,
63.82 × 10 3
log K (S –1 ) = 3 − =− 3.66
2.303 × 8.314 × 500
−4 –1 1 100
⇒ K = 2.15 × 10 S ⇒ t = ln = 7485.75 sec = 2.08 hrs.
K 20
610. Fora1storderreaction:
R10 [ A ]10 min
R = KA[ ] ⇒ = = 1.27
R 30 [ A ]30 min
[ A ]0 [ A ]0
Also 10 K = ln and 30 K = ln
[ A ]10 [ A ]30
[ A ]10 −2
⇒ 20 K = ln = 0.239 ⇒ –1
K = 1.2 × 10 min .
[ A ]30
[ A ]30 min R 30
similarly, = 2.94 and [ A ]30 min = = 0.6975M
[ A ]2 hrs K
⇒ [ A ]2hr = 0.237M and R 2 hr =2.84 × 10 molL min .
–3 –1 –1

611. Forreaction: A P
a − xe xe
xe 2
K =2= ⇒ xe = a …(i)
a − xe 3
Also,atanyinstant:
[ ] dx
dP = = K f (a − x ) − Kxb = K b (2a − 3x )
dt dt
Solutions 427
dx = 1 2a
∫0 ∫0 dt
x t
⇒ Kb ⇒ Ktb = ln
2a − 3x 3 2a − 3x
x e 2a ln2
Now, at x= = ; Ktb =
2 6 3
ln 2 2 ln 2 2 ln 2
⇒ t= = = × = 18.48 min.
3 Kb 3 K f 3 2.5 × 10 −2
100 5
612. Inabsenceofcatalyst: 60 KUC = ln = ln
80 4
80
Inpresenceof1stcatalyst: 30 KC1 = ln = ln 2
40
40
Inpresenceof2ndcatalyst: 10 KC 2 = ln = ln 4
10
KC 1 2 ln 2 K EUC − EC1
⇒ = = 6.21 ⇒ ln C 1 = ln 6.21 =
KUC ln(54/ ) KUC RT
Solving, EC1 = 70.44 kJ;Similarly, EC 2 = 70.975 kJ.
 −dN 
  = λ N = 12.5count min
–1
613. (a) Activity  dt 
12.5 12.5 t12/ 12.5 × 5730 × 365 × 24 × 60
⇒ N = = = = 54
. × 1010
λ ln 2 l n2
1
TotalnumberofC-atomin1g =
× 6.023 × 10 23 = 502
. × 10 22
12
5.4 × 1010
⇒ % 14 C pergramofcarbon = × 100 = 1.082 × 10 −10
5.02 × 10 22
 −dN 
(b) Initialactivity   = λ N 0 = 12.5
 dt  0
 −dN 
 
−   dt 
Activityafter50,000years =  dN  = λ N ⇒ = N …(i)
 dt  12.5 N0
N0 ln 2 N
Also λ t = ln ⇒ × 50, 000 = ln 0
N 5730 N
N0
⇒ = 423.4 Substitutinginequation(i):
N
−dN 1
= 125. × = 2.95 × 10 −2 countperminutepergram.
dt 423.4
(c) 12.5 =λ N 0
N0 1 N 5730
7 =λ N ⇒ =1.785 ⇒ t = ln 0 = ln 1.785= 4794 years
N λ N ln 2
428 ProblemsinChemistry

COLLIGATIVE PROPERTIES
614. (a) − ∆T f = 0.6 = K f ⋅ m
0.6 K f 1.86
∆Tb = K b ⋅ m ⇒ = = ⇒∆ Tb = 0.167
∆Tb K b 0.52
n2 n2
(b) − ∆T f = 0.6 = Km
f
= 1.86 × × 1000 ⇒ = 5.8 × 10 −3
18n1 n1
n1 1
⇒ x1 = = = 0.9942
n1 + n2 +
n2
1
n1
⇒ P = Px0 1 = 23.75 × 0.9942= 23.61 torr.
0.6
(c) m= =0.32 ≈ Molar ity
1.86
π= M RT = 0.32 × 0.082 × 293= 7.688 bar.
60
78 = 0.638 ⇒ Molefractionoftoluene
615. Molefractionofbenzene = = 0.362
60 40
+
78 92
V. P. = 0.638 × 93.4 + 0.362 × 26.9= 69.327 mm
n
616. + 0.744 =1.86 ⋅ 2 × 1000 ⇒ n2 = 0.1
250
n1
Also, 752.7 = 760 ⋅ ⇒ n1 = 10.31
n1 + 0.1
⇒ Massoficeformed = 250 − 10.31 × 18 = 64.42 g.
0.1
−∆ T f = 1.86 × × 1000 =1 ⇒ T f =− 1C.
°
185.58
0.25 × 0.082 × 300 × 760
617. V.P.ofsolution = = 21.638 mm.
18 × 12
n1 n2
⇒ 21.638 = 23.75⋅ ⇒ = 9.76 × 10 −2
n1 + n2 n1
 n  1000
∆Tb = K b ⋅ m = 0.52 ×  2  × = 2.82
 n1  18

x + 6 + 10 − x
0.77 180 60
618. = ⇒ x = 5.843g
0.58 x + 10 − x
180 60
619. ∆Tb = iKmb
⇒ 0.15 = 3 × 0.5 × m ⇒ m = 0.1
Solutions 429

Now, Pb(NO)3 2 +2NaCl → PbCl 2 +2NaNO 3

0.1 0.2 0 0
0 0 0.1 0.2
Now,thesolutioncontainstwosalts NaNO 3 and PbCl 2 .
− ∆T f = 0.83 = K f (2 × 0.2 + 3S ) where S ismolarsolubilityof PbCl 2 .
−2
S = 1.54 × 10 ⇒ K sp = 4S 3 = 1.46 × 10 −5 .

620. Inmixtureof A and B ifmolefractionof A = x, then:

400x + 5001( − x ) = 470 ⇒ x = 0.3
Infinalmixture,ifcombinedmolefractionof A and B = y, then
470 y + (1 − y)600 = 496 ⇒= y 0.8
Therefore,inthefinalmixture,molefractionsare: A = 0.24, B = 0.56, C = 0.2
⇒ Molefractioninvapourphaseare:
x A ⋅ PA 0.24 × 400
0 0
x B PB 0.56 × 500
A = = = 0.1935, B = = = 0.5645
P 496 P 496
C = 1 − (0.1935+ 0.5645)= 0.242
38.2
621. Molesofsolute =
202 + 18x
38.2 × 18x
2 =
Massof HO + 250
202 + 18x
38.2 × 1000
⇒ 0.582 = 3 × 0.52 ×
 38.2 × 18x 
(202 + 18x )  250 + 
 202 + 18x 
⇒ x =10, formula = Na 2BO4 7 ⋅ 10HO
2
 10.2 − x 
π = π( NaCl)+ π(sucr ose) ⇒ 7.32 =  2 × x × 4 +
342 
622. RT
 58.5
7.32 × 58.5 × 342
⇒ 342 × 8x + 58.2(10.2 − x ) = ⇒ x = 2.03g
0.082 × 296

m% NaCl = 19.9
1.5
623. Inbenzenesolvent: 1.15 = 5.12 × × 1000 ⇒ M = 185.5 amu.
M × 36
0.48 × 1000
Indiethylether: 1.55 = i × 2.02 × ⇒ i =3
185.5 × 10
Hence,permoleculeofcomplex,threeparticlesareproducedondissociationindiethylether.
Also,inonemolecomplex,mass: C =185.5 × 0.6488 ≈ 120
=
H185.5 × 0.0545 ≈ 10 ⇒ M olecu lar f orm u=laM ( CH)10
430 ProblemsinChemistry

n2
624. 0.26 = K b ⋅ × 1000 …(i)
100
n
1 = K b ⋅ 2 × 1000 …(ii)
W1
SolvingEqs.(i)and(ii), W1 = 26g
10

625. Molefractionofurea = 60 = 0.0322

10
+5
60
20
Molefractionofglucose = 180 = 0.01
20
+ 10
180
molefraction ofglucose isless,vapour pressureabove theglucose solution willbehigher than
Q
the vapour pressureabove ureasolution. To establish equilibrium, some HO 2 ( v ) molecule will
migratefromtheglucosesidetoureasideinordertomakethesolutionsofequalmolefraction.
10 20
⇒ 60 = 180
10 20
+5+ x + 10 − x
60 180
Solving, x=4
So,nowinureasolutionmassofwater = 90 + 72 = 162g
100
m% = × 100 = 6.17
162
nHO2
626. Atequilibrium: 23.6 = 24 × ⇒ nHO2 = 9.833 ⇒ m( H2 O) = 177 g.
nHO2 + n ur ea
⇒ Massof HO 2 ( v ) migratedfromtheglucosesolution = 177 − 90 = 87 g.
n1 n2
⇒ 23.6 = 24 × ⇒ = 16.95 × 10 −3 …(i)
+
n1 n2 n1
Also, 18n1 + 180n2 = 113 ⇒ n1 + 10n2 = 6.277 …(ii)
Solving,Eqs.(i)and(ii), n1 = 5.367 and n2 = 0.09 ⇒ massofglucose = 16.2 g.
m%glucoseinoriginalsolution = 8.1
n1
627. 64.6 = 70 ⋅ where n1 = molesof(methanol+ethanol)
n1 + n2

⇒
n2
= 0.0836 ⇒ x + 80 − x ⇒
n1 = 1.9938 = x = 26.78 g CH 3OH
n1 32 46
1 0 1 0
P + P = 80 ⇒ PB + PT = 160
0 0
628. …(i)
2 B 2 T
Solutions 431
Molefractionsofbenzeneandtolueneinthevapourphase:
0 0
PB P
xB =
and xT = T
160 160
Now,these molefractions will be the molefractions of benzene and toluene in the liquid phase of
condensate.
0 0
PB P 02 02
⇒ ⋅ PB0 + T ⋅ PT0 = 100 ⇒ PB + PT = 160 × 100 …(ii)
160 160
Solving,Eqs.(i)and(ii)
0 0
PB = 120 torr and PT = 40 torr.
 25   25 
   
629. V.P.ofmixedsolvents =  32  × 94 +  46  44 = 73.48 mm
 25 + 25   25 + 25 
 32 46   32 46 
n1
Now, 58 = 73.48 where, n1 = molesofsolvent =1.324
n1 + n2
⇒ n2 = molesofsolute = 0.35
2 × x 11.85 − x
n2 = 2 × molesofNaCl+molesofurea = + = 0.35 ⇒ x = 8.7g
58.5 60
P2 ∆H  T2 − T1 
630. ln =   and V.P.of HO
2 at100°Cis760mm
P1 R  TT
1 2 

760 40.6 × 10 3  50 
⇒ ln =   ⇒ P1 = 100.15 mm
P1 8.314  373 × 323 
−2
631. π= CRT ⇒ C = 6.286 × 10 M
55.55
⇒ P = 55.324 × = 55.26 mm
55.55 +6.286 × 10 –2
−3
6.286 × 10 × 1000
Also, 2 = 1.86 × ⇒ w1 = 5.84
w1
Initialamountofwater = 100 − 2.15 = 97.85
Massoficeformed = 97.85 − 5.84 = 92.01g
1 1000
632. 2.3 = 5.1 × × …(i)
MA + 2M B 20
1 1000
1.3 = 5.1 × × …(ii)
MA + 4M B 20
Solving,Eqs.(i)and(ii)
M A = 25.58 and M B = 42.64
432 ProblemsinChemistry

0.2
633. Mol.wt.ofacid: = 15.1 × 0.1 × 10 −3 ⇒ M =132.45
M
1 1000
⇒ 0.168 = (1 + α ) × 1.86 × × ⇒α= 0.196
132.45 100
634. 0.558 = i × 1.86 × 0.1 ⇒ i = 3 ⇒ Formula = [Co( H2 O) 5 Cl ] Cl2
1 1 10 1000
635. Inbenzene i = ⇒− ∆T f = 2.16 = × 5.12 × × ⇒ M = 118.5
2 2 M 100
10 1000
Inwater: − ∆T f = 1.75 = (1 + α ) × 1.86 × × ⇒α= 0.115
118.5 10
636. MCl 2 M
2+
+ 2Cl −
S olubi li ty= S S 2S
55.55 −2
⇒ 31.78 = 31.82 × ⇒ S = 2.33 × 10
55.55 + 3S
−
⇒ K sp = 4S = 5.06 × 10 5
3

−3 0.25 1000
637. 5.93 × 10 = ( x + 1) × 0.52 × × …(i)
M 10
M =
23x …(ii)
100
FromEqs.(i)and(ii) x = 20.3 ≈ 20
Formulaofprotein = H 20 P
Mol.wt. = 2300 × 20 − 23 × 20 + 23 = 45563 amu
100
638. 754.5 = 760 × ⇒ M =123.46
 100 5 
18  + 
 18 M 
100
Also, 754.5 = 760 ×
 100  α  2 
78  + 1 −  × 
 78  2  123.46 
⇒ α= 0.846 ⇒ %dimerization = 84.6
n −
639. 3.31 = 5.12 × 2 × 1000 ⇒ n2 = 12.93 × 10 3
20
Letthemixturecontain x gcyclohexane.
x + 1.32 − x = −
12.93 × 10 3 ⇒ x = 0.64g
84 128
1
640. 0.25 = K f ⋅ × 1000 ⇒ K f = 3
60 × 200
1.5
Also, 0.2 = 3 × × 1000 ⇒ M y =180
M y × 125
Solutions 433
n1 n2 1 1.5
and 99 = 100 × ⇒ = ⇒ n1 = 99n2 = 99 × = 0.825
n1 + n2 n1 99 180
125
⇒ =
M ( S ol vent) = 151.51 amu
0.825
02 −3
MRT
1 f 151.51 × 10 × 8.314 × (285) 2
∴ K f =3= = ⇒∆ H f = 34.1 kJ mol –1
∆H f ∆H f
0.4
641. 0.45 = K b ⋅ × 1000 ⇒ K b = 3.6
128 × 25
0 2 −
1(
MRT f
) 119.5 × 10 3 × 8.314 × (335) 2
Also, K b = 3.6 = =
∆H v ∆H v
⇒ ∆H v = 30.97 kJ mol–1
P2 ∆H v  T2 − T1 
Now, ln =  
P1 R  TT 1 2 

760 30.97 × 10 3  12 
⇒ ln =  
P1 8.314  335 × 323 
⇒ P1 = 502.8 mm of Hg.
 α 2.5 1000
642. − ∆T f = 2 = 1 −  × 14 × × ⇒α= 0.925
 2 94 100

⇒ m
Massofsolution =102.5g V = =116.5 mL
f
2.5 1000
⇒ Initialmolarity = × = 0.228M
94 116.5
α
Kc = = 360.6
2C (1 − α ) 2
n2
643. × 1000 ⇒
0.7 = 5.12 n2 = 0.041
300
Letmixturecontain x ganthracene,then
x +6−x =
0.041 ⇒ x = 2.677 g.
178 128
0.041
Aftercoolingto4.5°C, − ∆T f = 1 = 5.12 × × 1000
w1
⇒ w1 = 209.92g ⇒ massofsolidbenzeneproduced = 90.08g
644. 1.9 = (1 + α ) × 1.86 ⇒α= 0.0215

Cα =
2
−4
Molarity =1.098 ⇒ Ka = 5.18 × 10 .
1−α
434 ProblemsinChemistry

SOLID STATE
645. Numberof A perunitcell =1
1 7
Numberof B perunitcell = 7 × =
8 8
Empiricalformula = AB 78/ = AB 8 7
646. Numberof A perunitcell =1
1
Numberof B perunitcell = 5 × ⇒ empiricalformula = AB 52/ = AB
2 5
2
7 31
647. Numberofatomsperunitcell = +3=
8 8
Also,infacecentredcubiclattice, a = 22 r
31 × 4πr 3
Packingfraction (φ)= = 0.717
8 × 322
( r)
3

4 8π 63 3
648. Volumeoccupiedbyatoms = 2 × π (R − r ) =
3 3
× R
3 3 64
8π × 63R 3 × 33
⇒ Packingfraction (φ)= = 0.669
3 × 64 × 64 × R 3
 1 1  16
649. Numberofatomsperunitcell =6− +  =
 6 2 3
16πr 3 4
Volumeofunitcell = 242 r 3 ⇒ Packingfraction = × = 0.658
3 × 242 r 3 3

nM ⇒ n × 27 ⇒
650. Density ()s = 3
2.7 = − n = 4, FCC
Na 6.023 × 10 × (4.05 × 10 8 ) 3
23

4 × 128
651. 8.27 =
6.023 × 10 23 a 3
−9 − +
⇒ a = 46.8 × 10 cm = 4.68 Å=2 [r (O 2 ) + r (Cd 2 )]
2+
⇒ r (Cd ) = 1.1Å
2M
652. Density = = 7.15 ⇒ M = 468.52
6.023 × 10 23
× (4.47) 2 × 10.89 × 10 −24
Formulaofsaltis Hg 2Cl 2 .
4M
653. 4.269 = −
⇒ M = 212 Formula CoS2 x
6.023 × 10 × (6.93) 2 × 10 24
23

Solving x = 3
96
⇒ Massofsulphurrequired = × 1500 = 672.89g
214
Solutions 435

h= 2 −
654. Given 2 3.35 × 10 8 cm.
r = 3.35 Å =
2 3
 3 1 
3

Volumeofunitcell = 242 r = 242 

3
× × 3.35 × 10 −8  = 2.93 × 10 −22 cm 3
 2 2 
6 × 12
densi ty= = 0.4 g/ cc
6.023 × 10 23
× 2.93 × 10 −22
655. InHCP,numberofatomsperunitcell =6
Volumeofunitcell = 242 r 3
6 × 4πr 3 π
Packingfraction = = = 0.74
3 × 242 r 3
32
656. h = 2r− and A = 63 r−
3
⇒ V = 123 r−
3

3 × 4π(r+3 + r−3 )
Packingfraction = = 0.64( r+ / r− = 0.414)
123 r−3
3
657. Given a − 2r = 60 and forBCC, 4r = 3a ⇒ a− a = 60 ⇒ a = 448 pm
2
2 × 48
Density (ρ=) = 1.77 g /cc
6023
. × 10 × (4.48) 3 × 10 −24
23

2+
658. For Fe 95O100 , ifthereare x Fe ,
(a) 2x + (95 − x )3 = 200 ⇒ x = 85
Fe 2+ 85 17
⇒ 3+
= =
Fe 15 3
(b) 5% ofcationarevacant.
659. (a) 5%ofanionsitesarevacant.
4 × 128
(b) Densi ty(ρ )= = 8.81 g /cc.
6.023 × 10 23
× (4.7) 3 × 10 −24
4 × 127.2
(c) Densi ty(ρ )= −
= 8.136 g /cc.
6.023 × 10 23 (4.7) 3 × 10 24

660. Numberofcylindricalatomsperunitcell =3
3πr 2 l
Packingfraction = = 0.906
63 r 2 l
661. Edgenotcoveredbyatom = a − 2r
alsoinBCC, 4r = 3a
436 ProblemsinChemistry

3 2 − 3 
Therefore,edgenotcovered =a− a =a 
2  2 
2− 3
⇒ Fractionofedgenotcoveredbyatoms = = 0.134
2
662. InFCC 2(r+ + r− ) = a = 4.8Å ⇒ r+ + r− = 2.4Å
π   rB  
3 3 3
4 ( 4rA + rB )
663. Packingfraction = π =  4 +    = 0.753
3 (22 rA ) 3 122   rA  
πR 2 + πr 2 π
664. Packingfraction = 2
= [1 + (0.414) 2 ] = 0.92
(2R ) 4
4
665. Edgelengthofunitcell = r
3
16 16
⇒ Areaofasurfaceofunitcell = r 2 = × (96) 2 × 10 −20 cm 2 = 4.9152 × 10 −16 cm 2
3 3
6
⇒ Numberofunitcellonsurface = −
= 1.22 × 1016
4.9152 × 10 16
64 − −
Volumeofunitcell = a3 = (96) 3 × 10 30 = 1.089 × 10 23 cm 3
33
Volumeofsolid = 6 cm 3
4× 6
⇒ TotalnumberofCapresent = −23
= 2.2 × 10 24
×
1.089 10
NumberofCapresentonsurface = 1.22 × 1016 × 2 = 2.44 × 1016
2.44 × 1016
⇒ FractionofCalyingonthesurface = 24
= 11 × 10 −9
2.2 × 10
2× M
666. 2.32 = −
⇒ M = 1268 ⇒ x = 47
6.023 × 10 (1.22) 3 × 10 21
23

4 × 78
667. 3.18 = ⇒ a = 54.6 × 10 −9 cm= 546 pm
6.023 × 10 23 a 3
668. Letusconsider100ccofsolidAr:mass =159g
159
Volumeof159gliquidAr = = 112 mL
1.42
PackingfractionofsolidAr = 0.74, actualvolumeoccupiedby Ar = 74 mL.
Q
112 − 74
⇒ %emptyspaceinliquidphase = × 100 = 33.92%
112
a a 
669. Ifthesidelengthofunitcellis ‘ a’.Coordinateofcentreofguestatom B willbe  , , 0 .
2 4
Solutions 437

 a2 a 2  12/

⇒ R r    +   
+ = =a 5 …(i)
 2 4  4
3a
Also,inBCC R= …(ii)
4
r 5
⇒ 1+ = ⇒ r = 0.29R
R 3
4  3 r 3  33 3π  1  r 
3
Packingfraction = π  2R +  ⋅ =  2 +    = 0.684
3  2  64R 3 16  2  3  
670. a − 2r = 34 pm …(i)
Also, 4r = 3 a
3 54 × 2
⇒ a− a = 54 ⇒ a= = 395.6 pm
2 2− 3
2 × 23
Density (ρ=) = 1.23 g /cc.
6.023 × 10 23
× (3.956) 3 × 10 −24
240
671. a = 2R and 3a = 2R + 240 ⇒ ( 3 − 1)a = 240 ⇒ a= = 327.84 pm.
3 −1
209
ρ= = 9.83 g / cc
6.023 × 10 23
× (3.28) 3 × 10 −24
672. Volumeofunitcell = 4.6 × 8 × 5.7 × 10 −24 cm 3 = 2.0976 × 10 −22 cm 3

⇒ n × 100 ⇒
2.93 = − n = 3.7 ≈ 4
6.023 × 10 × 2.0976 × 10 22
23

+ −
673. (a) Numberof Na = 3, Numberof Cl = 3
4π 3 1
Packingfraction = (3r+ + 3r−3 ) × = 0.59
3 162 r−3
+ 1 7
(b) Numberof Na = 4 − =
2 2
− 1 7
Numberof Cl = 4 − =
2 2
4π 7 3 1
⇒ Packingfraction = × (r+ + r−3 ) × = 0.64
3 2 162 r−3
+  1 5 −
(c) Numberof Na = 4 − 1 +  = , Numberof Cl = 4
 2 2
4π  5 3 3 1
Packingfraction =  r+ + 4r−  × =
3 2  162 r−3 0.77
438 ProblemsinChemistry

SURFACE CHEMISTRY
1.36
674. Numberofmoleculesof H 2 in 1.36 cc= × N A = 3.65 × 1019
22400
M
Molarvolume (H 2 ) =
ρ

⇒ M = −
Volumeofone H 2 molecule = 4.743 × 10 23 cm 3
ρN A
 3V 
13/
radius =   = 2.246 × 10 −8 cm
 4π 
−
A (H 2 ) = πr = 1.583 × 10 cm
2 15 2

SurfaceareacoveredonCupergram = 3.65 × 1019 × 1.583 × 10 −15 = 5.78 × 10 4 cm 2

675. Let V (mL)ofsolutionisrequired
0.016 V
N ( aci d)= × 6.023 × 10 23 =9.637 × 1018 V
1000
−
Areacovered = 9.637 × 1018 V × 0.2 × 10 14 cm 2 = 19274 V = 500 cm 2
V = 25.94 × 10 –3 mL
2 7 2 −8
676. Total A = 25000 m = 25 × 10 cm, r = 1.5 × 10 cm
−16
A (NH 3 ) = πr = 7.068 × 10 cm
2 2

25 × 10 7
⇒ N = −16
= 3.53 × 10 23
7.068 × 10
molesof NH 3=0.587
⇒ Vol.of NH 3 atSTPrequired = 13153.5 mL
100
677. N = × 6.023 × 10 23 = 2.69 × 10 21
22400
−14 2
A/molecule = 0.16 × 10 cm
−
Totalareacoveredby N 2 (g )/ gramofcatalyst = 1.6 × 10 15 × 2.69 × 10 21 = 43.04 × 10 5 cm 2

REACTION MECHANISM
• • •
682. (a) O 2NCH CH
2 <CH
• 2• <CH 3CH <C
• H6CH5 <(C•• H) 6
•
5 2 C•

(b) ON—
2 + Cl— + + HC—
3 +

+ +
+
(c)

(aromatic)
Solutions 439
+
+
(d)
+ +
O O O O O
+

O
+
O O O O
−   −   −   −  
(e) CH 2—C —NH 2 < CH 2—C —OCH 3 < CH 2—C —CH 3 < CH 2—C —H
O
−  
< CH 2—C —CH 2OCH 3
683. (a) H 2O < 1- butanol < 1- butyne < 1- butene.
(b) Butanamide < aniline < 1- butylamine.
(c) Oxalic acid < 1,3- pr opandioic acid < acetic acid.
(d) P yr idine < N- methyl pyr r ole < pyr r ole.
(e) Cyclohexancar boxylic acid< p- nitrophenol < phenol < cycl
ohexanol.
684. γ-H is acidic and conjugate base is stabilized by resonance
γ −
H —CH —CH
2 == CH—CHO CH 2—CH==CH—CHO +H +
←→
−
O O
−   
CH 2==CH—CH —C —H ←→ CH 2==CH—CH==C

H
685. (a) 2 < 1 < 3 (b) 3 < 1 < 2 (c) 3 < 1 < 2 (d) 1 < 2 < 3
686. Duetohigh hydrocarbon (hydrophobic) proportion, both areinsoluble inpurewater. NH 2 of A is
basic in nature, forms salt with diluteH 2SO 4 , hence soluble. NH 2 of B isneutral due to resonance
delocalization oflone-pair ofelectron ofnitrogen with carbonyl group hence does not formsalt
with acid and insoluble. However, α-proton of amide B is quite acidic, dissolves in aqueous
solutionofstrongbase:
O O O O
H H
NH2 + OH – NH2 +HO2
B H (res onance s tabilized base)
O
OH
NH2 NH
N—H N
6 8 7.(a) (b)

N OH OH
N
( Aro ma tic)
440 ProblemsinChemistry

OH O O OH OH OH

(c) C C C C C C
CH2 CH2 CH3 CH3 CH CH3 CH2 CH CH3
O
–
COOH O
C
6 8 8. H+H +
O
COOH C
P h thalic acid
O
Sta b le co n ju ga te b a se
I
O O

C— OH C—O–
+H +

COOH COOH
I so p h th a lic a c id C o n ju ga te b a se is n o t sta b iliz ed
b y in tramo lecular H-b ond in g.
II

Due to greater stability ofI,phthalic acid has greater K a 1 than isophthalic acid. Removalofsecond
proton is difficult fromI, since H-isbonded to two oxygen atom,while acidic proton of IIis free
fromH-bonding,caneasilybedeprotonated.
689. Conjugate baseofbenzene sulphonic acidhasgreaterresonance stabilization than benzoate ion,
hencebenzenesulphonicacidisstrongeracidthanbenzoicacid.
−
O O O
    
−
P h —S—O ←→ Ph —S ==O ←→ Ph —S ==O
    
O O O−

Threeequivalentresonancestructure,morestable.
−
O O
  − 
P h —C—O ←→ Ph —C ==O
Onlytwoequivalentresonancestructure,lessstable.
••
−
690. Thiophenolisstrongeracidsinceitproducesaweakconjugatebase CH
6 S.
5
691. m-hydroxybenzoicacid>benzoicacid:Inductiveeffect.
o-hydroxyacid>benzoicacid:Orthoeffect.
p-hydroxybenzoicacid<benzoicacid: + R effectfrompara-position.
Solutions 441
O O–
COOH C
H
OH O
692. +H +

Stab le con jugate b ase

(o rtho effect)

O O–
CO OH C
OMe OCH3
+H +

N o o rth o e ffect

693. A is stronger acid than B although electron donating tertiarybutyl groups arecloser to —COOH
functional group. Itisdue to steric inhibition to resonance of —NO 2 group bytwobulky tertiary
butyl groups in B, while —NO 2 isfreeforresonance in A and increases acid strength markedly by
−R effect.
694. B is stronger base than A. Herebasic strength is controlled by −R effect of —NO 2 . In B, due to
steric inhibition toresonance of —NO 2 bytwobulky tertiarybutyl group, itisnot decreasing basic
strengthby −R effect,hence B isstrongerbasethan A.

H+ +
695. (a)
+

–H+

H H
  • dispr opor tiona
ti on
C—CH 2 →
•
(b) CH 3—CH —C
2 + H— CHCH
3 CH
2 3 + CH3CH== CH.2
 
H CH 3
696. (a)Due to resonance in vinyl chloride, C—Cl bond acquire somedouble bond characterwhilein
chloroethane,C—Cl bond ispure,single sigma covalent bond.
•• − +
•
CH 2== CH—Cl • ←→ CH 2—CH==Cl
••
Vinyl chlor ide
442 ProblemsinChemistry

(b) Dueto resonance in methylvinyl ether, bond order ofC—Cisslightly reduced fromtwowhile
inetheneC—Cbondorderisexactly2.
•• − +
3 ←→
CH 2== CH —••O — CH CH 2—CH== O—CH 3
Methyl - vinyl ether
(Bond or der < 2)
(c) Largersizeofsulphurcomparedtooxygengivesgreateracidityto CH 3SH.
(d) Lone-pairofelectron in vinyl amine isinvolved partlyin resonance delocalization and less
available fordonation to a Lewis acid, hence a weakerLewis base.
•• − +
CH 2== CH— NH 2 ←→ CH 2—CH==NH 2
Vi nyl ami ne
697. Inaqueous medium,Lewisbase strength ofan aminedepends on two important factors — number
ofelectron donating groups bonded to nitrogen and hydration ofconjugate acid bywatermolecule.
In general, increase in either of these increases basic strength. In case of trimethylamine,three
methyl group increases electron density at nitrogen by +I effect but itsconjugate acid isnot
sufficiently hydrated bywater due to lack ofH-capable offorminghydrogen bonding with water.
On the other hand , methyl amine has only one electron-donating methyl group bonded to nitrogen
but conjugate acid ishydrated excessively due tothree hydrogen available which arecapable of
forminghydrogen bonding with water. Effectofhydration here exceeds the electron-donating
effectandhence CH 3NH 2 isstrongerbasethan trimethylamine.

H H
O
H H
H—O
+ +
H
CH3—N H2 +H CH3—N—H---O
H
H
H---O (Exces s ive hydration)
H
CH3
+
H
(CH33) N+H CH3—N—H---O
+ H
CH3
698. The compound must be 1,2-cyclobutan-dicarboxylic acid since all other constitutional isomers are
non-resolvable.
CO OH CO OH

Polar but
H OOC H non-res olvable H H non-polar
dueto plane of but res olvable.
symmetry
H CO OH
(cis-is omer) (tr ans-is omer)

699. A is thermodynamicallyfavoured rearrangement since a less stable (highly strained) cyclopropane

ring is converted into a less strained (more stable) cyclobutyl ring. On the other hand, cyclohexane
is morestable ring than cycloheptane hence rearrangement B is thermodynamically not favoured.
Solutions 443

700. Catalytic hydrogenation involve adsorption of unsaturated compounds on the metal surface, which
isrestricted bythe bulky substituent at unsaturated carbons. Inthis regard, an alkyne has only two
substituent, poses lesssteric hindrance during adsorption, undergo easierhydrogenation while
alkene has four substituents, poses greater steric hindrance during adsorption, undergo
hydrogenationwithdifficulty.
On the other hand , electrophilic addition involve formation of a carbocation intermediate, stability
ofwhich control the reactivity. Alkyneproduces alessstable vinyl carbocation on addition of
electrophile, hence less reactive while an alkene produces a more stable alkyl carbocation and it is
morereactive.
– – +
7 01.
– + +

– +
δ– δ+

702. Theorderofacidicstrengthis: B(1)>A(2)>D(3)>C(4) .

,
A B D, are all more acidic than“ C ” because they are all phenols and the conjugate base that is
formedupon deprotonation can be stabilized byresonance. C isincapable to delocalize negative
chargeviaresonance.
B is mostacidic, because in addition to all the resonance formsavailable in A and D,the charge of
anioncanalsobedelocalizedthroughthe  NO 2 groupas:
O– O O O

–
+ +
N N N N
O + +
O – O O
– O O O O
– – –
– (mo st stab le)
O O

N N
+ +
O O O O
– –
444 ProblemsinChemistry

D isless acidic than A because the two OCH 3 groups on ring makethe systemmoreelectron
rich,whichinturndestabilizetheconjugatebaserelativeto A.
O– O O

H3CO OH3C CH3O OCH3 CH3O OCH3

–

– O
O– O

Ot hers
+ CH3O OCH3
CH3O OCH3 CH3O OCH3
–

(d estab lizin g th e co n ju gate b ase)

l l

N
B asic
7 03.
l l
N No n-b asic

H
Lone pair ofthe basic nitrogen isfullyavailable with nitrogen, i.e., not involved indelocalization
whilelonepairofnon-basicnitrogenispartofaromaticdelocalizationas:
N N N – N
–

l l
+ + +
N N N N
–

H H H H
N
–
+
N

704. III<II<IV<I
O–
Negative charge isonelectronegative atomandstabilized byresonance. This
isthemoststableconjugatebaseofthefouracids.
Solutions 445
O–
The negative charge on electronegative atombut not stabilized byresonance.
This anion isthen lessstable than phenoxide ion but more stable than the
anionsproducedfromIIandIII.
CH2–
Negativechargeisonelectropositivecarbonbutstabilizedbyresonance.

CH2CH2–

Negative charge ison electropositive carbon, and not stabilized by

resonance,henceleaststable.

705. (i) Equilibriumfavour left-side since amidenitrogen isnot basic because the lone pairon
nitrogen isdelocalized through carbonyl groups viaresonance. Therefore, thereaction will
notproceedintheforwarddirection.
(ii) Equilibriumfavours left side. Thepositive charge will bebetter stabilized on pyridine
nitrogenas:
+

+ + +
N N N N +
N
H H H H H
(mo re stabilized)

+ +
CH 3—C ≡≡N—H ←→ CH 3—C==NH (lessstabilized)
(iii) Equilibriumfavoursleftsidebecause thepositive charge willbemorestabilized onnitrogen
bonded tothree ethyl groups. Theinductively electron withdrawing nature ofthree trifluoro
methylgroupswilldestabilizetheammoniumsaltontherightsideofreaction.
706. 2,6-ditertiarybutyl pyridine is more basic than pyridine since t-butyl group stabilized the
protonated ammoniumsalt byinductive effect. However, nucleophilic strength depends on its rate
atwhich itattack to an electrophile. Incase ofdi-tertiarybutyl pyridine, the alkyl group adjacent to
the nitrogen, hinder the lone pair ofnitrogen toattack atanelectrophilic center. Therefore, itis
weakernucleophilethanpyridine.

R
N l l O ⇒ P osing ster ic hindr ance to the attack of lone pair.
R
446 ProblemsinChemistry
py
H py H
pz
707 xz-plane C–———C———C xy-plane

Br Cl
pz
Br  C H and Cl  C H aretwoperpendicularplanesofthemolecule.
708. I>III>IV>II
709. Equilibriumfavours leftsidesince onright sidewehave strong conjugate base HO – and strong
acid, they react to produce more stable species HO 2 and a weak conjugate base
O O–
  
3  C CH==C  OCH 3 . K eq = 10 3 alsopredictequilibriumtofavourleftside.
−
CHO
710. Reaction (a)willproceed toright. Fora spontaneous acid-base reaction, a strong acid mustreact
withastrongbasetoproduceweakacidweakbase.
+ s
In (a) PhCH 2NH 3 (pK a = 9.33) isstronger acid than CH 3CH 2NO 2 (pK a =10) and CH 3CHNO 2 is
strongerbasethan C 6H CH
5 NH
2 2 .Theoppositeiscaseinreaction(b).

711. (a) (b) HO— —NO2

N+

H
O O

(d) Conjugate base is resonance stabilized.

(c)
MeO OMe
N+

H
CO OH

(e) (f) (g)

(h) PhCOOH (i) p-nitrophenol.

OH

NH3Cl
(b) (c)
7 12. (a) O2N CO OH
CO OH
Solutions 447

713. (a) p-methoxyaniline,(b) pyridine,(c) CH 3CH 2NH 2 ,(d) 2,4,6-trinitro-N-N-dimethylaniline.

714. (a) CH 3NH 2 , (b) HN2  C— NH 2 , (c) PhNH 2 , (d) N,N-dimethylaniline,
 
NH
(e) m-nitroaniline.
715. (a) IV<II<I<III
+
(b) CH 3CH 2OH +CH
2 CH3 CH 3 CHCHOH+CH
3 2 CH3 CH 3
 
S– SH
and 2HSO 4 – HS2 O +SO
4
2–
4
–
Majorcomponentsatequilibriumare: CH 3CH 2OH, CH CH(SH)CH,
3 3 HSO 4 .
716. (a) isbettersiteofprotonation,sinceitgivesaresonancestabilizedconjugateacid:
CH3 CH3 +
CH3
+
N N—H N N—H N + N—H
CH3 CH3 CH3

CH3
+
N N—H
CH3
(Co mp lete o ctet of all atoms)

717. Oxygen,sinceitgivesresonancestabilizedoxoniumionas:
+ H
O O O OH OH

+
H+ H+
+
N N N N N
+
H
n o reson ance
( R e so n a n c e s ta b iliz a tio n)
s ta b iliz a tion
OH

+
N

Co mp lete o ctet of
a ll th e ato ms.
448 ProblemsinChemistry

718. (a) (i) A>D>B>C (ii) C>A>B

(b) D>C>E>B>F>A
(c) B>E>C>A>D
(d) C>B>A>D
(e) B>C>D>A
(f) A>C>D>B
(g) B>A>E>D>C
(h) (i) C>D>B>A (ii) E>C>D>B>A
(i) B>E>D>C>A
(j) B>C>D>A>E

CH3 CH3 CH3 CH3 CH3

CH3 CH3 CH3 + δ+
l l l l

N N N
N
+
719. ( i)

– δ–
O
– O O
O
(Reso n an ce h ybrid)

δ+ δ– δ+
– +
( ii) B +
B B B

(Reso n an ce h yb rid)

O O– O Oδ–

–
l l – δ–
( ii i) N N N CH2 N δ–
l l
( ma jo r) (Reso n an ce h yb rid)

720. Theresonanceformsof(i),(ii)and(iii)are:
+
H2 N H2 N H2 N

( i)

O O– O–
+
H2 N H2 N H2 N H2N

( ii)
+
– – –
Solutions 449
+
H2N H2 N

–
( ii i)

The resonance formsof three compounds reveal that compound (i) has maximumdouble-bond
character in C—N bond and compound (iii) has minimumdouble bond character in C—N bond.
Therefore,theorderofC—Nbond-lengthsinthreecompoundsis: (i)<(ii)<(iii).
721. Orderofacidstrengthis: III>II>I.
722. I>II>III.
723. For carbocations, morestable the carbocation, weaker will be electrophile. Hence, order of
electrophilicstrengthis: II>I>III(aromatic).
724. (i) Toleftsinceammoniaisweakeracidthanwater.
(ii) Torightsinceinaqueousmedium,secondaryamineisstrongerbasethantertiary.
(iii) Toleftsincehydroxideionisstrongerbasethanmethylamine.
725. (a) B>C>A,(b) A>C>B,(c) A>B>C.
726. Strength of a base depends on stability of its conjugate acid. For all the above bases, their
conjugateacidsformedafterprotonationacquireveryhighstabilityfromresonanceas:
H H
I H+
N N+ N
N N N
+

+
N N N
H+
II
+
N N N
H H
+
NH NH2 NH2

+
III H2N NH2 +H + H2N NH2 H2N NH2

NH2

+
H2 N NH2

Hereallthreeresonancestructuresareequivalent.
450 ProblemsinChemistry

l l + –
7 27. N + N +
N— N—

+ – +
N + N +
N— N—

+ +
N + N +
N— N—
–
–

728. (i) H c > H a > H b . (ii) H a : Conjugatebaseisaromatic.

(iii) H b : Electronwithdrawinggroupincreasesacidity.
(iv) b: Methoxygroupdecreaseselectrophilic character of carbonyl carbon by resonance
effect.
729. (iii)>(ii)>(iv)>(i).
+ + +
NH2 +
NH3 NH2 NH3

730. H2N N COOH H2N N COO–

H H
at pH < 2. 18 p H b etween 2 .1 8 – 9.09
+
NH2 NH2 NH NH2

H2N N COO– H2N N COO–

H H
p H b etween 9.0 9 – 13 .2 pH > 13 .2
H

N
7 3 1. (a) (b) p-nitr o ani line > ani line.

O N

H
Solutions 451

+
CO OH +
COO–
7 32. (a) H3N ( b) H3N

NH3 NH3
+ +

+ COO– COO–
(c) H3N ( d) H2N

NH2 NH2

733. 3<4<1<2.
734. Conjugatebaseisresonancestabilizedas:
O–

CH 3  CH== CH CHO CH2  CH== CH CHO ←→
→ CH 2== CH  CH== CH
735. The relative strengths of ammoniumions as shown above lies in stability of conjugate base.
Stronger acid produce morestable conjugate base and hence lower pK a value. Also, since
aromatic aminesare weaker base than aliphatic amines,conjugate acid of formerwill be stronger
thantheconjugateacidoflater.
⇒ A>B: acidstrength.

STEREOCHEMISTRY
Cl Cl Cl

736. H H H
Cl H H

H Cl Cl
cis-1,3-dichlorocyclopentane (2) (3)
(1) tr ans-1,3-dichlorocyclopentane

Here (2) and (3) are non-superimpossible mirror images of one another, hence they are
enantiomers . Structure (1)is meso isomeranditis diastereomers ofboth(2)and(3).
Br Br Br Br

737. H H H H 1 and 2, 3 and 4 areenantiomers while1 and 3,

Cl Cl H H 1 and 4, 2 and 3, 2 and 4 are dias tereomers.

H H Cl Cl
(1) (2) (3) (4)

738. (a) Enantiomers(b)Identical(c)Diastereomers(d)Identical

739. 13.9x − 13.9(100 − x ) =− 300 ⇒ x = 39.2,
Hence,39.2%ofthemixtureis(+)2-butanoland60.8%is( –)2-butanol.
452 ProblemsinChemistry

H Br H F H Cl
740. (a) C==C C==C C==C
Cl F Cl Br F Br
I II I II

H Br H F H Cl
C==C C==C C==C
F Cl Br Cl Br F
IV V VI
IandII,IIIandIV,VandVIarepairofgeometricalisomers.
Cl Cl Cl

Cl Cl Cl H H Cl
(b) C ==C H C ==C C ==C H C ==C C ==C H C ==C
H HH H H HH Cl Cl HH H
(i) (ii) (iii)

IIandIIIareenantiomerswhileIisopticallyinactive,mesoform.
CH 3 CH 3 Cl CH 3
   
(c) Sixisomer: CH 3—CH— CH 2CH 2Cl, CH 3CH— CH—CH 3 CH 3—C— CH 2CH,3

Cl
(twostereoisomers),
CH 2Cl

CH 3—CHCH 2 CH 3 (twostereoisomers).
CH 3 CH 3
 
741. HC ≡≡C—CH— CH== CH2 CH 3CH 2—CH— CH 2CH 3
A B
Br
742.

A B C
743. CH 3CH CH 2CH 3 CH 3—C — CH2 CH3
  
OH O
( A) ( B)
CH
2 5 CH
2 5
CH3CH 2 CH3 CH3CH 2
C ==N + C ==N C H C
CH3 H CH3
CH3 CH3 CH3 NH CH3
(C )
N HCH3
( D)
Solutions 453

744. Addition of bromine at carbon-carbon double bond proceed via a cyclic bromoniumion
intermediatefollowedbynucleophilicattackofbromideionas:
Br CH3 CH
2 5
+ CH CH Br
Br 3 2 5
Br – + Br
C————C CH
CH3 2 5 CH3 CH 2 5
CH3 CH
2 5 CH3 CH 2 5 Br
Mixtureofenantiomersobtainedinequalamountgivingracemicmixture.
Catalytichydrogenationoccursatmetalsurfacegiving syn hydrogenation.
H
CH
2 5 CH
2 5 H
H2/Pt CH3
C==C
CH3 CH3 CH
2 5
CH
2 5 CH3
COOH

Cl
745.
A B
D
COOH
C

746. CH 3CH 2— CH— CH== CH2 CHCH

3 CHC
2 HCH
2 3 CHCH
3 CHC
2 H 2CH 2Cl
  
CH 3 CH 3 CH 3
A B C
Cl Cl
 
CH 3CH 2CH CH CH 3 CHCH
3 CC
2 H 2 CH 3 CHCH
3 CHCH
2 2 CH 3 CHCH
3 C==
2 CHCH 3
   
CH 3 CH 3 CH 2Cl CH 3
D E F G
CH 3CH 2CCH 2 CH 3
 
CH 2
H
747. A: Achiral, B: Achiral, C: Meso, D: Meso, E: Meso, F: Meso, G: Chiral,
H: Chiral,I: Achiral.
748. (a) Distereomers,(b) Identicalandmeso.
749. CompoundIisopticallyinactivesinceitcontainaplaneofsymmetry.
Compound IIis enantiomeric since it does not contain plane of symmetry, hence chiral. Also
compoundIispolarwhileIIisnonpolar.
454 ProblemsinChemistry
πz
750. In allene, the twopi-bonds arein perpendicular πy
Cl
planes, hence the twoterminal H  C H planes are Cl
also perpendicular. Therefore, ifallene issubstituted xz
propertyitbecomeschiralas: C–———C—–——C xy
The two terminal Cl  C H planes are
perpendicular toone-another and Cland H atone H
H
terminal are equidistant from either Cl or Hfrom
othercarbon.Thisisnonsuperimposableonitsmirrorimage,henceopticallyactive.
751. (a) IIandIVarechiral,henceopticallyactive.
(b) IandIIIareachiral,possessplaneofsymmetry,henceopticallyinactive.
(c) Thereisnoenantiomerpair,bothIIandIVareidenticalstructure.
(d) IandII,IIandIII,IandIIIarepairofdistereomers.
752. (a) Both I and IIareoptically, but they are not mirrorimageof one another, hence, they are
distereomers.
(b) Distereomers.
(c) Enantiomers.
(d) IandVareenantiomers.
(e) IVandVIaredistereomers.
CH3 CH3 CH3
Cl H
753. +HCl +
H H

H Cl
Ch iral Ch iral
(two stereoiso mers) (two stereoiso mers)
Therefore, in the above addition reaction four stereoisomers(twopair ofenantiomers)will be
produced.
CH 3 CH 3 CH3 CH3 CH3
CH H
  3
H CH3
754. HC 3  C 2  C 3  CH 3 60° 60°
  CH3
H H H
H CH3 H CH3 H CH3
2,3- di met hyl but ane CH3 CH3 CH3
I II III

60°

CH3
HC
3
H

60 ° 60 ° 60 °
I ← II ← III ←
H CH3
CH3
IV
Solutions 455

I
I
III III

Energy:I > III > II > IV

E II II

IV

0
60 120 180 240 300 360
Angle

755. I: CH 3 ≡≡
C C  CH 2  COOH and CH 2== CH  CH== CH COOH are functional
isomers.
CH 3 ≡≡
C C  CH 2COOH and HC ≡≡C  CH 2CH 2COOH arepositionalisomers.
H H
HC ≡≡C COOH + HOOC C≡≡CH stereoisomers.
CH 3 CH 3

O O
   
II: CH 3CH 2CH CH
2 2  C  NH 2 and CH 3  CH  CH 2CH 2  C  H

NH 2
functionalisomers.
O O
   
CH 3CH 2CH CH
2 2  C  NH 2 and CH 3CH 2CH 2  C  NHCH 3 arepositionalisomers.
CH 3 CH 3
H NH 2 and HN
2 H arestereoisomers.
CH 2CH 2CHO CH 2CH 2CHO
756. Onlytwo stereoisomers,since HO
2 willattack tothe intermediate carbocation froma sideanti to
themethylgrouponadjacentcarbon.
H3C CH3 H3C CH3 H3C CH3
l l

H+ + OH2
( b o tto m s id e a tta c k) OH
Enantiomeric (two stereomers)
456 ProblemsinChemistry

757. Thestereocentersarelabeledbystars:
H
N

* O
* O

Thedistereomerpairsare:
H H
N N

O O O
O
and
O O

I I

758. In acid catalyzed hydration of alkene, aplanar carbocation isgenerated in the 1st step. The
nucleophile( HO 2 ) attack inthenext subsequent stepfroma sidewherethesterichindrance is
minimum.

I
H+ H2O
OH
+ –H+
CH3 CH3 CH3
( P a ir o f en an tio me rs)

+
H+ H2 O
II OH
–H+
CH3 CH3
CH3 ( P a ir o f en an tio me rs)
Solutions 457

H+ H2 O
I II OH
+ –H+
CH3 CH3 CH3
( P a ir o f en an tio me rs)
⊕

H+
IV

CH3 CH3
( N o ch iral ca rb o n in ge n era te d o n p ro to n a tio n)

•• +
759. CH 2==CH  NHCH 3 ←→
→ CH 2  CH== N HCH3
N -methyl et henami ne

H +
CH 3 H +
H
C==N + C==N
– –
HC H CH 2 CH 3
2

(Thesearegeometricalisomers)
CH
2 5 CH2 5 CH
2 5 CH
2 5
CH3 CH H
H 3
HC
3
H
760. 60° 60° 60°
H CH3
H CH3 H CH3 H CH3 H CH3
CH3 CH3 CH3
CH3
I II III IV
60°
CH
2 5
CH3

H
H CH3
CH3
V
Energy: I>V>III>II>IV
Stability: I<V<III<II<IV
761. (a) Thiscompoundcontainasymmetryplane,henceopticallyinactive.
(b) Thiscompoundcontain ‘one’chiralcarbon,henceenantiomeric.
458 ProblemsinChemistry
C h ir a l c a r b on

E n an tio me rs

(c) Thiscompoundcontainasymmetryplane,hence,opticallyinactive.
(d) Thiscompoundcontain ‘one’chiralcarbon,hence,enantiomeric.
O Ch iral carb on O

OH En an tio me rs HO

H CH 2OH
HOHC
2 OH HO H
HO H HO H
762. ≡≡
HO H HO H
HO H HO H
CHO CHO
CHO CHO
H OH HO H
180° H OH HO H
→
H OH HO H
H OH HO H
CH 2OH CH 2OH
II V
Enantiomers
AlsoII → D-sugar. V → L-sugar.
SugarI,IIIandIVareallL-sugar.
AnypairsoftwostructuresotherthanIIandVaredistereomerpair.
763. This compound has two chiral carbon, and a double bond capable of showing geometrical
isomerismgiving rise to total eight different configurations possible for the molecule as shown
below:
O O

HO H H OH

COOH COOH
H H H H
E n a n tio me r ic En an tio me r ic
Solutions 459
O O

H H
COOH COOH
H H
OH H H OH
En an tio meric En an tio meric

–
O O

7 6 4. (a) +
NH2 NH2
n o stereo -iso merism
O –
O
( b) CH3
N + CH3
N
CH3
CH3 n o stereo iso merism
–
O O

(c) +
N N

H H
(exh ib it geo metrical iso merism)
–
O O

( d) +
H N H N

H H
(exh ib it geo metrical iso merism)

765. (a) Botharesimilarstructures. (b) Theyarepositionalisomers.

(c) Theyareenantiomers. (d) Theyareconstitutionalisomers.
OH O OH

7 6 6. I : All have chiral carbon

I ke to e n ol
460 ProblemsinChemistry

OH O OH

II

II keto en ol
All have chir al car bon.
OH O OH
I II

III keto en ol
All have chir al car bon.
767. (a) IandIIareidentical.
(b) IandIIareidentical.
(c) IandIIaredistereomers.
(d) IandII,IandIIIarepairsofdistereomers.IIandIIIareenantiomerpair.
768. Both hasnitrogen astheir chiral center. IonIIrecemizesinaqueous solution due totheexistence of
followingequilibrium:
H
+ CH CH2 l l

H2O+ N H3O+ + N CH CH2

H3C C2H5 H3C C2H5
(ach iral)

769. Ithasonechiralcenterandcanexhibitenantiomerismas:

C2H5 and C2H5

ar e enantiomer s.
O O O O
H H

770. The cis and trans formsof3-methoxycyclohexanolare:

OH OH
OCH3 H

H H
H OCH3
cis tr a ns
O– OCH3
OCH3 OCH3
b ase CH3I
cis-3 -met hoxycycl o hexanol H SN2 H
H H
meso for m ( opt i cal ly i nact i ve)
Solutions 461
O–
H
base  OCH3
trans-3-met hoxycycl ohexanol H
H 
 H OCH3
OCH3 
CH3I
H  H +
 OCH3
OCH3  OCH3 H

O–  Enantiomer s ( Racemic mixtur e)

771. (a) Tautomers(Isomer),(b) Conformers,(c) Resonancestructures,(d) Positionalisomers.

HYDROCARBONS
O O
   
772. Ph —CH2—C ≡≡C— CH3 PhCHCHC
2 2 CH 3 PhCHC
2 CH 2CH 3
A B C
PhCH 2COOH PhCH 3 PhCH 2Cl
D E F
CH3 CH3 CH3
Cl
Cl2
+
AlCl3

E Cl
OH OH OH
773.
C CH C—CH3 CH —CH3
A O OH
B C
OH (i) KCN
+ O
CO OH (ii) HO
3

D
O
O
CO OH
7 7 4. O
CHO
CO OH
A B C O
D
462 ProblemsinChemistry
CH3

775.
• •
CHCH3
A Labelled carbons are chiral

CH3 H
Et Et

H CH3
Enantiomeric (two structu res) Enantiomeric (two structures)
CH3
CH3
CH C CH2—C—CH3
776. CH3
Br
A B

CH3

CH—CH—CH3 COOH

Br
C D E

7 77. —CH2—C C— —CH2—CH2—CH2—

O O
A B
CH3 CH2Br

—CH2COOH —COOH
O

C D E F

CH3 CH3
778. —CH2OCH 2CH 2CH—CH==CH 2 —CH2OCH 2CH 2CHCH CH
2 OH
2

A B
Solutions 463
CH3

—CH2OH
HO OH O
C D E
•
RO
SO 2Cl 2 →
•
784. ROSO 2Cl + Cl
RH +Cl
•
→ R • + ClH
R + S O2 Cl2 → R  Cl + SO2Cl
• •

Br Br
Br
7 85.
A B C D

E F

Cl

Cl
786.
Cl E
A B C D F G
Cl

7 87.
Cl
A B Cl C D Cl E F G
Cl

CH3 CH3 Br
  
788. (a) CH 3  C  C H  CHI2 (b) CH6 5  C H  C H  CH 3
 
Cl Cl
I CH3 Br
  
6 5  C H  C HCH 3
(c) CH (d) CH6 5  C  C ( C6 H)5 2
 
Br I
464 ProblemsinChemistry
Cl
+
ring exp an sion Cl
789. (a) + H+
+

Cl
ring expansion +
(b) + H+ Cl
+

CH3
C H2SO4 CH3 B2H6 CH3
790. OH H2O2/N a OH

OH

791. (a) (CH 3CH 2CH) 2 3 B (b) CHCH

3 CH
2 OH
2
(c) 2-methyl-3-pentanol (d) 2-methylcyclohexanol.
792. (a) 1-butene + BH 3/H O2 /NaOH
2 → 1-butanol
(b) 1-butene + dil. H 2SO 4 /heat → 2-butanol
(c) 2-bromo-2,4-dimethylpentane + alcoholicKOH → 2,4-dimethyl-2-pentene
2,4-dimethyl-2-pentene + BH 3 /HO2 2 /NaOh → product.

H2- Pt O3 CHO
2 CH3C HO + (E)
Z n-H2O
(A) (D) C HO
H2-Pt

(B) (C)
H+/ KM nO4
CH3CH2CH2C OOH (F) + CH3C OOH

793. Ozonolysisproductsshowsthat A isasymmetricaldiene:

794. Cold,dilute, alkaline KMnO 4 solution adds on C==C producing cis-diols. One of the stereomer A
produces meso cis-diol therefore it is confirmed that the starting compound is a symmetrical
alkene.
Alsooxidative ozonolysis ofthe starting compound gives no acid asproduct, itindicates that there
isno hydrogen attached to doubly bonded carbon. Fromthese finding it isnow concluded that the
startingcompoundhasfollowingstructuralformula-3,4-dimethyl-3-hexene
Also: A + Cold, dil-KMnO 4 → C(Meso) therefore, A is cis isomer and B is thus trans one. Thus
the various compounds are:A: cis-3,4-dimethyl-3-hexene. B: trans-3,4-dimethyl-3-hexene. C:
Meso-3,4-dimethylbutan-3,4-diol.
D:2-Pentanone.
Cl

795. (A) (B) (C)

Solutions 465

H2SO4 B2H6/H2O2
796. (a) OH
heat Na OH
OH

B2H6/H2O2
(b) OH KM nO4
Na OH
+
H

CH3
(c) Br2 KOH Br2
Br KOH
heat Br Alc oh ol
Alc o hol
Br

Ph Ph Ph
+
( d) Br2 Br C Na
hν
Ph

P d/H2/B a SO
4

H H

H H Br
(1) Na /heat Na/liq NH3 NBS
(e)
(2) CH3Br
H H
H D
Mg/e ther
D2O

Na /liq NH3 BrH Br (CH2=C H)2Cu

(f)

KCN H
+ Br2 Br
(g) –H+
OH2 Br+
Br HO OC HO OC O
O
466 ProblemsinChemistry
Br2
( h) P ro du ct
OH2

797. (a)

+
H + +
–H

OH •• O
OH
••
+
–H
••
M e- sh ift +
OH
••
•• OH
OH
•• H2 O
+
–H ••
OH
••
(b) IV < II < II I < V <I
+
798. A: Et 3 NCCl 2
–
B: Et 2 NCHCl 2 C: Et 2 N  CHO

Ph Ph Ph Ph
+ +
7 99. (a) H
+ Cl
Cl
+
(b) H Cl
•• + •• ••
O O O O Cl
••
+ ••
re so na nce sta b ilized
+
(c) HOCl HO– + Cl

+
OH
Cl +
HO–
C6H5CH CHCH3 C6H5CH CHCH3 C6H5CH CHCH3
Cl Cl
sta b ler car b oca tion
Solutions 467
CH2Cl Cl
Cl
800.

A B C D E CH2Cl

Cl CHO

F G H O I OH J

H 3C H CH3 H O
80 1. H 3C CH3 CH3COOH
H3C CH3 H3C CH3
OH OH
A B C D
CH3 H
H 3C CH3
Cl Cl
E F

802.
A:5-methyl-2,4-heptadiene; B:CH 3CHO C:2-butanone; D:Glyoxal
E:2-hydroxyethanoicacid.
803. A:3-methyl-1-butene; B:3-methyl-2-butanol; C:3-methyl-2-butanone

CH3

H H2

8 04. CH3 C C C C C CH3 Pt CH3

CH3
CH3 H H H3C
P d /Ba SO
4
(A) H
Na /liq NH3 H H
H H
( Op tic a lly I nac tive C)

H H
H3C O3
H HOOC C CHO
CH3 CH3 E (O A)
H
H3C
H H
( O A)D
468 ProblemsinChemistry
CH2Cl
8 05.
Cl
A B C D

Cl H H H H

Cl OH OH
E F G

806. C2H5 C2H5 HOOC COOH

A B C D
O

8 0 7.

A B
+ +
Br C u( I) C Cu H
D=A
A B
8 0 8.
Br HO
E=A
C F

809. (A) OH (B) ONa (C) OMe

(D) MgBr (E)

OH
Br
(F) (G)
Br

(H) (I)
Br
Solutions 469
OH
+
(J) CNa (K)

Br

(L)
Br
Br CH2Br
8 1 0.
Br Br B Br C Br Br E H
A D

8 1 1. A B C D Cl E
CH2Cl Cl

OH
Cl
812. (a) (b) (c)
Cl

H CHO
8 13.
A B O C O

8 14.

Br Br OH
B OH Br C Br D O OH
A E

815.

81 6.
A
B
C
OH
+ +
H M e - sh ift
8 1 7. (a) –H+
–H2O +
470 ProblemsinChemistry

Cl
Cl

Br
(b) Br2 Br
+ Br
Br

Br

OH2 Br

OH
CH3 CH3 CH3 CH3

8 1 8. HOOC CHO H3C CHO H3C COOH H3C COOH

H H H I
A B C D E
O
Br OH

8 19.
CO OH
A B C D E

820. (a)

+
(b) (i) + H+
+

+
–H

+
Br H
Bu–
(i i) C
Solutions 471
Cl
Cl
(i i i) Cl
–
N OC (CH3)3 N
H
H
821. (a) A B
H
Br Br

(b) H OCH2 CH2OH

X Y
Br Br
Z

Br
822.
A B C

COOH COOH COOH

O OH
COOH
D O E F

H H
O CH3 CH3 CH3 OH

(b) H Br + Br H (c) H
823. (a) HO H
H OH
CH3 CH3
H

OH
O O
( d) (e) (f)
OH
H

Br OCH3
(g) (h)
H H
Br Cl
472 ProblemsinChemistry

H
CH3 —OCH3 —OCH3
BH3/H2O2 OH
8 2 4. C C
H CH3
Na OH CH3
tra ns syn h yd ration H
CH3

H
CH3 CH3 —OCH3
BH3/H2O2 OH
C C
H —OCH3 Na OH CH3
syn h yd ration H3C
H
O CO OH

825. CH—
3 —C C—CH3 CH3—C—CH 2CH 2—CH—CH COOH
2
B
A
CO O Na CO OH

CH—CH2CO ONa CHCH2COOH

CH2CH 2CO O Na CH2CH 2CO OH
C D
CH 3 CH 3 CH 3 CH 3
H Br Br H H Br H Br
826. (a) Br H H Br (b) H Br Br H
H Br H Br H Br Br H
CH 3 CH 3 CH 3 CH 3
(meso) (enant iomeric) (meso) (enant i omeric
)
CH 3 CH 3 CH 3 CH 3
Br H Br H H Br H Br
H Br Br H H Br Br H
(c) (d)
Br H H Br H Br Br H
Br H Br H H Br H Br
CH 3 CH 3 CH 3 CH 3
(enant i omeric
) (enant iomeric) (meso) (meso)
Solutions 473

OMe
8 27. (CH2)10C O

A B
C

CH3
HO H
H CH3
D Ph
E Br

+
Br
+
Br2 H—O –H+
Pr oduct
828. Star ting compound
HO l
l

829. (a) (i) HgS O4 H/ SO

2 4 (ii) NaBH 4
(b) (i) HS2 O heat
4/ (ii) Br2 /MeOH
(c) (i) C 2H ONa
5 C
/ 2 OH
H 5 (ii) HOOC  CH== CH COOH
CH3
8 3 0. ( a) —CH3 (b) CH3— — — CH
3
CH3

831. Ifthe numberofdouble-bonds aresame,heat ofhydrogenation depends on degree ofsubstitution

at carbon-carbon double bonds. More the numberofalkyl substituents at carbon-carbon double
bond, morestable will be the alkene towards hydrogenation, hence smallerwill be the heat of
hydrogenation.Onthatbasis:
C—leastsubstituted,highestheatofhydrogenation.
A—mostsubstituted,leastheatofhydrogenation.

H+
832.
OH –H2O
+
H2C

H
–H+ +

I
474 ProblemsinChemistry

+
H+ –H+ H+

H +

+
+
–H+ H–- Sh ift

II
OMe

833. (a) (b) (c)

Br ( ra c e mic) OCH3 HO ( ra c e mic) OH

Ph Ph
(d) (e)
+
H H
Br
C2H5ONa RCO3H HC CNa
834. O
C2H5OH

O–
CH3I HgSO4
Pr oduct
H2SO4
C CH

Cl

8 3 5. (a) (b) (c)

D
Solutions 475

+
8 36. +H +

+ II
I

Cl Cl
Cl– Cl–
I + II +

Cl Cl

8 37.
A B
H H

CO OH

H H D
C
CN

E O F OH G

C2H5
838. HOOC COOH

A C2H5 O O C
B

CH 3

839. CH 3 ≡≡
C C  CH 2  COOH H ≡≡
C C CH  COOH
(A) B
O
 
H ≡≡
C C  CH 2  C  OCH 3 3 ≡≡CCH 3
CHC
C D

CH3 CH3 CH3 CH3

Br2 C2H5ONa MCP BA
840. (a) Br O
heat C2H5OH

OH
CH3

( i) CH3COONa
( ii )H3O+ OAc
476 ProblemsinChemistry
Cl

Cl2 C2H5O Na (i ) CH Cl3

( b) Pr od uct
hν C2H5OH ( ii) N a OH

O
CHI3 
Na ∆ Na
(c) H ≡≡
C C  H →
/ →
3 ≡≡CH →
CHC 3 ≡≡CNa
CHC – +
 →
∆
HO +

3
→ Product
CH 2
HBr Na  
(d) CH 3 ≡≡
C CH → CH 3  C== CH2 → CH 3  C  C CH 3
 Heat  
Br CH 2
H H
H CH3 +
O
l l

+
l l + O
O CH3 O CH3

841. (a) H+

–H+

O
O + O
–
NH2
(b) +NH 3 HN
3 HO
H –
H
+ O OH O
N N
HO HO
H
H
+
N N
HO OH HO OH

–
O OH
H
H
OH O
Br2 O+ –H
+ O
(c)
Br Br
Br
+
Solutions 477

H+ + H SO4–
8 42. H H +H 2SO4
+
H
( 3 ° c a rb o c a tio n)
+
H OCH3
l l
O
Cl2 + H CH3 –H+
8 43. (a) Cl Pr od uct
H Cl
H

Br Br
+
( b) Br HO–
+Br 2 H H
O—H l
l
O—H O
H H H
+
H

OH O O O
O

H+ + –H+
(c)
l l

O— O
OH OH H OH OH

H+ + –H+
l l

O O O O
H

OH CH3 OH Br CH3 OH CH3

CH C— CH3 CH— CH— CH3 CH2—C— CH3

8 4 4.
Br
A B C

OH CH3 OH CH3

CH2—C CH2 CH2—C— CH2OH O

H
D E F
478 ProblemsinChemistry

CH3 +

8 45. +H +
+
I
H+
I–

+
I
I–
+

B
+

+H+ Br–
8 4 6.
+
Br
H– sh ift

Br
Br– + + Br–
Br

847. Thiscompound hasa chiral carbon. Therefore can beresolved into enantiomers.Treatmentofthis
compoundwithconcentrated sulphuric acid bring about isomerization into a more stable
compoundbutwithoutanychiralcarbon,henceopticalactivityislostas:
+
H+ H– sh ift + –H +

2 ° carb o cation 3° ca rb oc at ion No ch ir al ca rb on

CH3 CH3 CH3

OH
848.

A B C

+
8 49. +H + +

Protonationatanyothersidewillproducealessresonancestabilizedcarbocation.
Solutions 479

ALKYL HALIDES
850. (a) n-iodoheptanesinceiodideionisabetterleavinggroup.
(b) Sodiumethoxidesinceitisastrongernucleophilethanethanol
(c) 1-butyltosylate,duetolesssterichinderence.
(d) triarylbutoxidewithethylbromide.
(e) with-2-bromopentane.
851. Both the reactions are examples of S N 2 reaction. Since aniline isa weaker nucleophile than
cyclohexylamine,formerundergoesslowersubstitutionreaction.
Cl CH3 CH3
H3C CH3
CH3 CH3
852. H3C H3C CH3
A B C
CH3 CH3

CH3 CH3CH2CH—COOH
H2C
D E

H
Cl H H
CH3 H3C
8 53. CH3
CH3 H3C CH3
C
A B H
H
H H
CH3
CH3
H3C CH3
H E
D

854. (a) Methylbromideundergo halogen exchange withNaIformingmethyliodide. Iodide beinga

betterleavinggroupthenbromide,rateofhydrolysisisincreased.
(b) Thepredominantreaction inthiscaseiselimination (E-2)whichdepends onconcentration of
both alkyl halide and base. Increasing concentration ofbase increases the rateofE-2reaction
decreasingconcentrationofalkylhalide.
−
(c) NaCNisionized completelygiving ambident (CN ) nucleophile. Since carbon isbetter
−
electron donor than nitrogen, bonding occurs fromcarbon side. AgCNbeing covalent, CN is
nottotallyfreeforattackandattackprimarilyoccursfromnitrogensidegivingisocyanide.
480 ProblemsinChemistry
H+ CH2+ Cl–
8 5 5.(a) OH –H2O Cl

CH2+ CH2Cl
Cl–

H+ Cl–
( b) OH +
–H2O Cl
(3 ° carb o catio n)

856. (a) C—Fbondisthestrongestcarbon-halogenbond,undergoverydifficultheterolysis.

(b) Latterformsamorestablecarbocation.
(c) t-butylchlorideformamorestablecarbocation.
857. (a) AgNO3 formsinsolubleAg X drivingreactioninforwarddirection.
(b) Moreacidicsolventincreasestherateofheterolysisfacilitatingformationofcarbocation.
858. (a) CH 3CHC H(3 A ) CH 3CH CH(3 B ) (b) CH2CH2CH2OCH3
 
OTs N3 C
H
CH3S
CH3

859. II I < II <I

860. (a) Ethanol being a very weak nucleophile can’t activateS N 2 reaction, andCH 3Br being veryless
reactive in S N 1reaction, neither S N 1nor S N 2 take place. Adding excess of C 2H ONa
5 involve
S N 2 reactionandetherisformed.
(c) Et 3 P isabetternucleophilethan Et 3 N.
N3
861. (a) OCH2CH CH2
(b)
I

Br

(c)
(d) MeO— N—H (e) Br

862. Tertiary butyl being a bulky base abstract H-fromless hindered β-carbon giving thisalternative
product.
Solutions 481
OTs OMe
863. CH3ONa ;
OTs SN2 OTs

OTs OTs
CH3ONa
OTs E-2

8 6 4. 1 ,5 -hexad i ene, 1,4-pent adi ene

N N

H CH3

2- m et hyl - 1,4- pent adi ene, 3- m et hyl - 1,4- pent adi ene
N N

H H
CH3
H H
CH3
865. (a) HO ——CH3 (b) CH3——OH (c) H
CH H
CH
4 9 4 9
(racemic)

CH3 CH3
CH3——H CH3O——H
(d) (e)
CH3——H H——CH3
CH
2 5 CH
2 5

866. (a) First (b) Second (c) First

Br Heat
+
Br + H2O OH
867. (a)
–H+

CH3 CH3
(b) Heat HO
2
H3C H H3C H
+ 2H
+
+

OH OH
482 ProblemsinChemistry

868. (a) Though neopentylbromide isprimary, bulky tertiary butyl group poses very large steric
−
hindrancetotheattackofbulkynucleophile N3.
Br N3
– S2
N
(b) H——CH3+N 3 CH3——H
D D
(c) Ratewilldouble (d) Ratewilldouble(e) notrelated
(f) Racemizationoccurthroughcarbocationintermediate.
869. (a) n-iodoheptane (b) C 2HONa
5 (c) n-butyltosylate (d) isopropoxidewith C 2H Br.
5

NaOH CHI3
870. (a) HO— —OH Product
Excess

NH3
(b) C 6HCH
5 OH
2 TsCl
→→ P r oduct.
CH CHCH SNa
(c) C 6HOH
5 TsCl
→
3
→
2 2
P r oduct.
BH
2 6 KOH
(d) Cl Product.
H2O 2/OH –

871. Allylbromideproduces a resonance stabilized carbocation justifying itsgreaterreactivity in S N1

reaction. Also carbon β to Br has an empty p-orbital which share some of the shared electron pairs
of pentavalent transition state formedin S N 2 reaction, increasing its stability and hence reactivity.
− −
872. (a) CN beingweakernucleophilethan H .
(b) 3°carbocationismorestablethan1°.
(c) Geminaldiolsareunstable.

+ –H+
873. (a) Pr oduct
+
•• O
OH
••
H
(b) —Br +Br –
O
– O

– – – –
874. (a) CF3 < CH3O <CHS 3 <F (b) CH 3COO –<CH SO –
3 <CF
3 SO 3
–
3

Br
Br
Br Br
875.

A Br D
B C E
Solutions 483
CH2Br CH2Br
H——CH3 H——CH3
H——CH3 HC——H
3
CH2Br CH2Br
F G

COOH

876.
Br
A B HOOC D
C

CH3 H
877. (CH3)2CHOH CH3—CH—CH2CH3 C C
O
B H CH3
A
OH D
CH3 C
CH3
C C
H H
E
Cl

CH3CH C— CH3
8 78.

CH3
A B C

Br O
O

8 79. COOH

A B C D

E
484 ProblemsinChemistry

O I
880. I OH
I I NC
C D
A B

Br Br

8 8 1.
OH
A B C D

CH SNa
882. (a) →→ (b) TsCl
→→NaI
TsCl 2 5

PhCHCHI 2 CHC ≡≡ CNa

(c) NaH
→→2 (d) n-butylbromide 3→
H2N— CH — CH2 OH

NH3 CH == CH2
(e) TsCl
→→ (f) →

O O NaI
883. S I
O CH3 Rate =1
mes ylate
O O NaI
S I
O CF3 Rate = 5000
triflate

In both mesylateand triflate, the leaving group anion is stabilized byresonance. Inthe case of
triflate, thethreefluorides provide additional stabilization totheanion viaelectron withdrawing
inductiveeffect.
O O– O O
–      
Mesylate: O  S  CH 3 ←→ O ==
S CH 3 ←→ O ==S  CH 3 ≡≡ O  S  CH 3
     
O O O–
O

O O– O O F
–       
Triflate: O  S  CF3 ←→
→ ==
O S CF3 ←→
→ S CF3 ≡≡ O  S  C  F
O ==
      
O O O
– O F
( mor e stable)
Solutions 485

O O O
HO CH3 OCH3 +
Ag+
8 8 4. 1. +
–H+
O O O OCH3
Ph Ph Ph
P lan ar carbo cation

O O
O
Ag+ OCH3
2. + HO CH3
O O O –H+
+ O
O
Ph O
Ph Ph
a reso n an ce stab ilized
acyl o xo n iu m ion

885. (a) SN–2, CH 3CH 2Br , (b) S N1, (CH)3 3 CCH 2Br , (c) SN–1, CH 2== CH  CH 2Br .

H n-Bu Cl
886. (a) C==C ( b) (c)
Ph Et CH3— CH — CH
2—

CH3 CH3

iPr Et
CH( CH3)2
CH3
( d) (e) (f) (g)
H H
OH
Et COOCH3

CH3 Et (Reten tio n of co n figu ratio n)

( Ra ce mic mixtu re)

CH3 CH 3CH 2 OH CH3

887. (a) (b) C (c)
HC
3 CH  CH 2CH 3 CH3

CH 3
( E nant i omer s)
SCH ( CH3)2 Ph Ph
( d) (e) Cl CH2 Et (f) CH 2==C
CH3 H C( CH)
3 3
( Retention of configur ation)
486 ProblemsinChemistry

(g)

CH 3 Cl CH 3
  heat  + H – -shi ft
888. CH 2==C  CH 2  CH  CH 3 → CH 2==C  CH 2  CH  CH 3 ←→ →
CH 3 CH 3
 + + 
CH 2==C  CH  CH 2CH 3 ←→ CH 2  C== CH  CH 2CH 3
X Y
CH 3 CH 3
 CH3OH  +
X +CH 3OH → CH 2==C  CH  CH 2CH 3 → CH=
2 =C  CH CH 2CH 3 + CH 3OH 2
 
HC3  O H
+
OCH 3

H CH 3
  CH3OH
Y +CH 3OH → CH 3  O
+
 CH 2 C==CHCH 2CH 3  →

CH 3
 +
CH 3OCH 2  C==CHCHCH
2 +CH
3 OH
3 2

KOH NBS
889. I —Br KOH
EtOH EtOH

NBS KCN(a q)
—Br Pr oduct

890. Since,thetosylateistertiary,E–2and S1N areequallyprobable:

F F
P hNH2
E -2

H3 C OTs
CH3
F PhHN F
SN1
+
: Net result is racemic mixture.

H3 C NHPh
E n an tio me r ic CH3
E n an tio me r ic
Solutions 487
Br
Br H
CH CH
3 7
3 7 H CH
3 7 H
CH
2 OK
5
891. CH C ==C
4 9
H H H CH
4 9
H CH
4 9
H Major alkene
More s table conformer
Br
Br CH
CH
3 7
H 3 7
H H
H Repel each other
CH
2 OK
5
CH C==C
4 9
H H CH
3 7 CH
4 9
H CH
4 9
H Minor alkene
Les s stable conformer
CH2CH3 OCH3 CH3 CH3

8 92. (a) (b) (c) +

C
H CH3
CH3 OCH3 OCH3
CH3CH2CH2O
( Ra ce mic mixtu re)

Br
8 9 3. O

A B C D

OMe

894. (a) (b) no reaction (c) OEt

Cl H

Ph

(d) CH3CH2CH C—CH3 (e) CN (f)

ONa + CH4
( c is + tr an s)

Br
Br –
8 9 5.
+
H
l l N N
H—N
488 ProblemsinChemistry

Br H
H +
N
N l
l

–H +
N

896. Esters are usually water insoluble, ifacetic acid is used, it gives homogeneous mediumdriving
reactioninforwarddirection.
897. (a) 2-chlorobutane,
(b) 2-chloro-2,3-dimethylbutane,
(c) 1-methylchlorocyclopentane,
(d) 1-ethyl-2-methylchlorocyclohexane.
D D D

8 98. (a) C (b) C + C

CH3 H3C CN CH3
NC NC
H H H
Ts Cl KI
8 9 9. (a) OH
Ts Cl CH3CH2NH2
( b) OH
CH3CH2CO OH
(c) OH H+/h eat
Ts Cl Na HS
( d) OH
Ts Cl CH3O Na
( d) OH

900. OnlyIIcan beused forsuccessful synthesis ofGrignard reagent, restall contain acidic proton and
willreactwith R – (fromGrignardreagent)formingalkane.
Cl
O– O
O –
9 01. (a) +OCH 3 O O +Cl –
Cl

( b) Br –
+OCH 3 Br OCH3
O
O–
O
– Br– OCH3
Solutions 489
O O
–
+OH O– O
(c) HO HO O–

O
H2O O O–
P r oduct HO O

—Br
Mg
9 02. (a) —Br +
s ( MgB r) SN2

H H
+
H+ H–- sh ift
( b) —OH +
–H2O

H– – sh ift

+ +
Br– r ing
P r od uct
exp ansi on

–
903. (a) (CH)3 3 CI ismorereactivesince I isabetterleavinggroupthan Cl – .
(b) Iismorereactivesince β H islessstericallyhinderedcomparedtoII.
CH ( CH3 )2 CH ( CH
3 )2 CH ( CH 3 )2
Cl Cl
CH3O– CH3O–
H H
9 0 4.(a) E-2 E-2
H
H
( a c h ir a l)
E n an tio mers

(b) Asshownin(a),thepredominanteliminationproductisachiral.
CH( CH3)2 CH( CH3)2
(CH3)2HC H OCH3 OCH3 H CH( CH3)2
Cl Cl
CH3O– CH3O–
(c) H H
H SN2 H
H H
E n an tio me rs
490 ProblemsinChemistry
CH3
(CH3)3C OK (CH3)3C OK
9 0 5. I ( CH3)3C OH II
( CH3)3C OH

II is morereactive towards elimination reaction since the bulky base will abstract aH fromside of
leaststericcrowdinggivingmorestablealkene.

OCH3 +
OCH3 OCH3
Cl +

Reso n an ce stabilization

906. (a) Firstismorereactivesinceitproducesamorestablecarbocation:

(b) Secondismorereactivesinceitproducesaresonancestabilizedallyliccarbocation.
(c) Firstismorereactivesinceitproducesamorestablebenzyliccarbocation.
(d) Secondismorereactiveduetothesamereasonaswith(b).
(e) Secondismorereactiveduetothesamereasonaswith(a).

Cl–
–I+ + I
907. I
CH3OH
III
–H+
Me– -sh ift

Cl–
II
+

CH3OH
IV
–H+

ALCOHOLS AND ETHERS

908. Ethylene oxide being a three memberedring, suffers fromvery large angle strain and therefore
highlyunstablewhereasTHFisafivememberedring,itisstable.
CH3ONa O H SO
909. Ph —CH—CH 2OCH 3 ← Ph →2 4 Ph — CH—CH 2OH
 CH3OH CH3OH 
OH OCH 3
Solutions 491

O
CH2OH N2H4 CH2OH H2SO4 O3
910. (a) NaOH/Heat Heat Zn -H2O

LiAlH4
P r oduct.

Br OH

H eat aq u eo us
( b) +Br 2
K OH

+
–H+ H+
+ H eat

O O

O3
+
Z n /H2O
Y
X

LiAlH4 Co nc .H2SO4
Y
H eat

O CH2
H2CO O O
N aOH O3
X
H eat Z n -H2O

CH3

—CH2Br —CH2MgBr —CH2D —CH2—C— OH

9 1 1.
CH3
A B C
D

CH3
—CH2 C
CH3
E
492 ProblemsinChemistry

912. Athighertemperature,intramoleculardehydrationisentropyfavoured.

913. 2- butanol 2- butanone 2- bromobutane

A B C OMgBr
D

CH 3 CH 3
 
914. Ph —CH—CH —CH 3 ( A ) Ph —C—CH 2CH(3 B ) Ph —C ==CHCH(3 C ) CH 3COOH( D ).
  
OH OH Br
O

NBS KOH O3
915. (a) Ph—CH2— Ph—CH— + PhCHO
CCl4 Eth an ol Zn –H2O
Br

H3O Ag2O C2H5O Na

( b)
Br2/H e at C2H5OH
O O
CN Br

N a OH K MnO4
Ca O Heat H2SO4
OO O O
H O
COOH
Br
Ag2O COOH
C2H5O Na K MnO4
Br2 He at
C2H5OH H2SO4
O
O

O CH2
O3 N2H4/OH–
(CH3)3COK Ag2O
Z n -H2O H e at
(CH3)3COH Br2 He at
O
Solutions 493

H3O+
(c) CH3COCl
OH
H2O
O O OH
O
O3 H2SO4 NaBH4 OCOMe
Zn -H2O Heat
O OCOCH3
OCOCH3

H H3O+ SOCl2 Zn
CH3CH2CHO+
Heat
O OCOCH3

H
PBr3 NaBH4
Br
O

OH
OH Br
9 16.
O
A B C D E F

OH H
G

OH
H+ + –H+
917. (a)
–H2O

•• O
OH
OH OH + –H+
(b) +H +
+
+
CH2
(c) +
–H2O +
–H
OH +H

H -sh ift
CH3
–H+ + –H+
494 ProblemsinChemistry
OCH3 OH O
(d) H+
H2O +CH 3OH

H2O Na BD4
918. (a) + (CH3COO)2Hg OH
D

SOCl2 Mg
OH Cl
(b) A
Eth er

PCC H A H3O+ CrO3

H2SO4
O O

OH
PhMgBr HO + 
(c) CH 3COCl →→ 3
excess
CH 3—C— CH 6 5

CH6 5

O O
O O
(d) MeMgBr H3 O+ OH SOCl2 C2H5ONa
C2H5OH
OH OH
OH B2H6
CH3MgBr
H2O2/OH– H3O+
OH Cl

Ts Cl N aCl
9 1 9.(a)
SN2

(b) Ethylbromidebeing a primaryhalide undergo predominantly S N 2 reaction whilecyclohexyl

bromidebeingasecondaryhalide,undergoE-2reaction.
OH O O
920. (a)
(b)
OH H H
A A
B
Solutions 495

O
OH COCH3
(c) +CH 2O (d) (i) ( ii)

OH OH

9 2 1.

A Br B C

OH O OH
CH3 H CH3
H H H3O+ H
922. H3O+ CH3
CH3 H H
CH3 H CH3 H
CH3
OH CH3
(Racemic mixtu re) OH
(meso diol)

923. Chlorination of alcohols with HCl proceeds by S1N mechanism, rearranged products are also
obtained. Chlorination of alcohol with SOCl 2 proceed by S N 2 mechanism,no rearranged product
isobtained.

9 2 4.(a) Br
ONa + P r oduct.

( b) ONa + PhCH2Br P r oduct.

(c) —ONa + CH3CH2Br P r oduct.

(d) CH 3CH 2ONa + CH ==CH—CH

2 Br
2 → P r oduct.
925. Themajorproductis2-chloro-2-methylbutane.
926. (a) (CH)3 2 C== CHCH2 Cl givesaresonancestabilizedtertiarycarbocationas:

+
+

Allylchloride gives primarycarbocation and therefore less stable than the above mentioned
carbocation.
496 ProblemsinChemistry

(b) Inacidicmediumalcoholundergoisomerizationviacarbocationintermediateas:
H+ H2O HO
–H2O + + –H+
OH

Ph
Ph
H+ +
927. (a) Ph + Ph Ph
–H2O +
••
OH OH OH Ph O—H
••
Ph
–H+
Ph
O

OH
+
H+ +
( b) –H+
–H2O

H+ + –H+
(c) —— OH O
–H2O + ••
OH OH OH

H+ +
–H+
(d)

O +O HO HO
H

928. PhCH(OH) CH2 Ph PhCOCH 2Ph

X Y
R R R
HBr (CH3)3COK
929. (a)
P ero xide (CH3)3COH
Br

H+ –H+
( b) OH
–H2O +
O O CH2 +
Solutions 497
OH OH
CHO CH3— CH — CH
2SPh
(c) (i) ( ii) ( ii i)
CHO
OH OH OH
A B
C D
OH
( iv)

930. C 6H —CH
5 —
2 CH — CH3 C 6H —
5 CH— CH 2OH
 
OH CH 3
( A)
( B)
CH 3 CH 3 CH 3
  
931. CH 3— CH— CH —CH 3 CH 3—CH CH 2CH 2OH CH 3—C— CH 2CH 3
 ( B) 
OH OH
( A) (C )

CH 3 CH 3 CH 3
  
CH 3—CH CH 2COOH CH 3—C— CH 2CH 3 CH 3—CH— COOH
(D )  (F )
Br
(E )

OH
9 32.

B O
A
C

CH 3 CH 3 CH 3
  
933. CH 3—CH —C— CH 2CH 3 CH 3—CH — CH—CH 2CH 3 CH 3—CH — CH—CH 2CH 3
   
CH 2 CH 2OH COOH
( A) ( B) (C )

CH 3 CH 3
  CH 3
CH 3— CH— C—C 2H; 5 CH 3—CH— CH — CH2 CH3 C==CHCH 2CH 3
   CH 3
O OH (F )
(D ) (E )
498 ProblemsinChemistry

936. 1,3-butandiol( A) 3-ketobutanoicacid( B).

H+ Methyl shift + H2O

934.
+ –H+
OH
(Majo r)
Cl Cl
–
935. * OC2H5 * *
CH2—CH—CH2—OC2H5 CH2—CH—CH2—OC2H5
O
O O
I –

Mg D2O
937. (a) —OH + HCl —Cl —D
eth er

O
H2SO 4
(b) CH 2== CH 2+ Cold, dilute,alkaline KMnO4 → CH 2 —CH 2 →
  Heat
O
OH OH
CH 3

938. (a) CH 3— CH— CH 3+Br 2 Heat
→ (CH)3 3 CBr

CH 3
C H OH 
(b) (CH)3 3 CBr (from a) +C H
2 ONa
5 →
2 5
CH 3—C== CH 2
E -2

(c) (CH)3 2 C== CH2 + HBr 

Peroxide
→ (CH)3 2 CHCH 2Br

CH ONa
(d) (CH)3 2 CHCH 2Br 
3
→ (CH)3 2 CHCH 2OCH 3
S2
N

(e) (CH)3 2 CHCH 2Br +CH COONa

3 → (CH)3 2 CHCH 2OCOCH 3
(f) (CH)3 2 CHCH 2Br + KCN( aq ) → (CH)3 2 CHCH 2CN

O
OH Cl COOH
939. —O—C— COOH

A B C D E
CH2OH
Cl

F G H I
Solutions 499
OH OH

940.
A B C

I
O
941.
O
A I C
B

HO
942. (a) 2-methylpropene + BH
2 6 →
2 2
Pr oduct
NaOH

CH COOT
(b) 2-methylpropene + BD
2 6 
3
→ P r oduct.
CH COOT
(c) 2-methylpropene + BH
2 6 
3
→ P r oduct.
C H Br
(d) 2-methylpropene + B2H 6+HO 2 2 → (CH)3
NaOH
2 CHCH 2OH NaH
→ →
2 5
P r oduct.

OH H+
943. + –H+
–H2O CH2
+

CH3O CH3O

944. HO CH CH—CH2OH HO CH—CH—CH2OH,

Br Br
X
A
CH3O
O O

HO—CH2—CHO C6H5—C—O CH CH—CH2O—C—C6H5,

B
C
500 ProblemsinChemistry

CH3O
I

HO CH CH — CH
2Br, HO CH CH CH2OH

D E
CH3O

CH3O CH CH — CH
2OH

9 45.

O O C
Cl Cl
A B
CH3
CH3 CH3 CH3 H
9 4 6. C— CH2CH3 C C and C C
H CH3
OH
A B
O
OH

— C— CH3 — CH — CH CH CH3
3

C D E

CH 3 CH 3 CH 3
  
947. CH 3CH 2— CH— CH==C — CH—CH 2CH 3 CH 3CH 2—CH— C—CH 3
  
CH 3 O
A B

CH 3 CH 3 CH 3
  
CH 3CH 2— CH— C—H CH 3—CH —CH—
2 COOH CH 3CH 2—CH— CH —CH 3
  
O OH
C D E
Solutions 501

CH 3

CH 3—CH —
2 C== CHCH 3 CH 3CHO CH 3—C — CH2 CH3
 
O
F G H

CH3 CH3 CH3

—CH— CH2OH —CH— COOH C— CH3 O

9 48.

A C
B
D

H H
OH

O O
E F
OH I
CHO
OH
949. (a) (b) (c) (d)
(en an tio mers)

OCH3
HO CH2CH3
OH

(e) (f) (g) H

SCH3

(h) HO (i) OCH2CH3

OH

OH

OH
( j)

( en an tio me r s)
502 ProblemsinChemistry
+ +
950. (a) PCC,(b) NaBH 4,HO3 ,(c) PdC / ,(d) Mg,Ethyleneoxide, H 3O , PBr 3 ,
(e) TsCl, CH 3ONa ,(f) SOCl 2 , Mg/ether, CH 2O, HO3 + ,
(g) Ethyleneglycol/ H +, Li AlH,4 HO
3
+
, (h) CH 3MgBr , HO
3
+
.
Br
Mg
951. C6H5MgBr
A

O O
H OH

H PCC
A
H3O+
CH3MgBr

OH

CH3CH2ONa NaH H3 O+
P r oduct

OCH2 CH3 Br
9 5 2. (a) (b) + Br + CH3 Br

OH

l l CH3
+
S S
Br– O
(c) (d) (e) O

enant i omers
OH
CH3 OH
(f) OCH3 (g) O (h)
OH SCH2 CH3
O
OH
(i) O —S— (j) CH3
CH3
O
Solutions 503

Si
O O
953. +CF 3CO3H Si
F–
O

H3O+
O + (CH3)3SiF O

O–K+
(A ) OH
+ +
954. A : CH 3MgBr /E ther , HO
3 ; B: NaOCH 3,HO,3 NaHCH
/ CH
3 Br
2 ; C : mCP BA;

+ MeO SO2
D : Hg( OAc)2 ,CH 3OH, NaBH 4 ; E : CH 3CH 2SNa HO
/ 3 F:

955. Incaseofreaction1,themechanismisaseriesofprotonationand S N 2 reactionsas:

H
+
O O I
CH3 CH3
H+ +CH 3OH
I–

H+ + I–
CH3—OH2 CH3I +H 2O
In the case of reaction 2, the mechanismis also a series of protonation andS N 2 reaction. However,
phenol is not converted toiodobenzene because ofprotonated phenol can ’t be substituted by
iodideion (I – ) duetostrong C  O bondinphenol:
H

O O+ OH
CH3 CH3
H+ I– +CH 3I

+
O+ –
O
H H
o t hers
–
Ca rb o n -o xyge n b o n d ac q u ire p artia l d o u b le b o n d ch arac te r,
c an ’t b e su b s titu ted u n Nd2erS
co nd it io n s.
504 ProblemsinChemistry

O O

OH K2Cr2O7 OH CH2N2 OCH3

956. (a)
H3 O+

(1 ) CH3CH2MgBr (2 eq)
Pr oduct
(2 )H3O+

OH Ts Cl NaN3 N3 H2/Pd NH2

( b)

Cl
Pr od uct

OH PCC CH2 PPh 3

(c) Pr oduct

OH O OH TsCl
PCC CH C–Na+
(d) C CH
CH2Cl2 H3O+

C CH
N a BH4 Pd mCP BA
Pr oduct
Ba SO4

9 57. (a) —D (b)

OH
H H
(c)
(d)
( e n an tio me r s)
(e) CH2CH3 + OH
SCH3
OH CH2CH3
CH3 CH3
Solutions 505

OH OH
I
(f) (g)

HO HO OH
OCH2CH3
(h)

O
958. (a) (1) PCC, (2) CH 3Li , (3) HO
3
+
; (b) HI /RedP ; (c) (1) SOCl 2 , (2) Mg/ether; (3)  ,
+ +
(4) HO3 ;(d) (1) PCC,(2) NaBH 4 ,(3) HO 3 .

H O
B– O
H CH3 CrO42–
9 59. S low
OH H+ O— Cr — OH

O
C—Hbond cleavage occur in slow rate determing step. Therefore, replacement ofH byD will
slowdowntherateofreaction.
O
D H P CC
C:
OH CH2Cl2 D

C  H bondwillbebrokeninpreferenceto C  D bond.
O
O
+
O l
l O —S— —+ Cl –
9 60. + Cl —S—
H H O
O
H

O +
N Cl–

P yr id ine O —S— —+

O
506 ProblemsinChemistry
Cl– H
O
+
N
O— S— + 60 °C Cl

N
+ O
–
+ + O— S—

Higher temperature promotesSN–2 reaction of tosylate bychloride ion generated in the firststep
ofreaction.

Ot-Bu
O
961. (a) (b)
SCH2CH3
(c)

S
OCH3
O

OCH3
O O
Br
(d) (e) (f) OH
+
N3
O O
OCH3

O
(g) (h) (i)
OH
OPh O OH

O
( j) (k)

O O
Solutions 507
HO Br O HO
N3
NaOH NaN3 NaH CH3I
Pr od uct
9 62. (a) H3 O+

O
HO

CH2 CH Li mCP BA NaH LiAlH4 NaH

( b)
CH3I
CH3I
Pr od uct
fr o ma
O OH

H Br H3O+
9 63. PCC
M g/eth er

O O

H3O+ CH3CH2O Na CH2N2

HO HO OCH2CH3
OCH2CH3
mC P BA

964. I>II>III>IV.
D
OCH2CH3
965. (a) (b) (c)

OH
O
Br
OH
Ph
(d) (e) H
CH3
CH2CH3
508 ProblemsinChemistry

OCH2CH3
OH HO
OH
9 66. (a) (b) (c)

( e n an tio me r s)

( M a jo r) (M aj o r)

OH
O
Br
( d) (e)

OH
CH3Li H3O+ NaH CH3I
PCC Pr oduct
967. (a)
CH2Cl2

(b) OH CH2N2
PCC Pr oduct
CH2Cl2

EtONa NaH CH3I

(c)
O

(d) OH PBr3 Ph SNa mCP BA

Pr oduct

968. Therearetwoproblemswiththe route outlined above. First,because the above alcohol istertiary,
it will be difficult to makethe tosylate, which isa large, sterically demanding group. Ifyou can
makeit, the second step is also difficult as it require SN–2 reaction of a tertiary tosylate byH.This
systemis veryhindered and will not readily undergo susbtitution reaction. Elimination will bea
seriouscompetitionreaction.Abettermethodwouldbeasfollows:
S

OH O — C— SCH
3

N aH CH3I Bu3S nH
CS2
Solutions 509

OH Cl
K2Cr2O7 SO Cl2 NH3
9 69. (a)
H2SO4
O
P OCl3
P r od uct
COOH
Br NaOH K2Cr2O7 Na/ NH3 H3O+
( b)
H2SO4 E t OH

OH CH2N2
Pr od uct

NH2
OH Ts Cl N aCN LiAlH4
( c)
CH3C O Cl
P r o d uct

OCH3 H O CH3

H
970. (a) —Cl (b) (c)
H
CH3
(d) (e)

Br Na OH mCP BA
9 7 1. (a) EtOH
O
Na CN
Pr od uct
H2O
510 ProblemsinChemistry

C.H 2SO4 NBS/hν Mg

(b) —OH —Br —MgBr
CCl4 et her

PCC
—OH O
CH2Cl2
OH
TsCl NaBH4
Pr oduct

CH3 OH Ph OH

9 7 2. (a) (b) CH3—C—CH2CH3 (c) OH (d)

Cl CH3 I OH

9 73. O O PhS– O–
O O H2O O O –
OH O SPh
P ro du ct

O O
OH

C H ONa Hg( OAc)2 NaBH

975. (a) PhCH 2CH 2CH Br
2 2
5
→ PhCH 2  CH== CH2 → →4
C2H 5OH H 2O

OH O
  
Ph  CH 2  CH  CH 3 →
PCC
Ph—CH 2—C —CH 3
CH2Cl 2 I
OH
Na I HO +  Pd
3 ≡≡CH → CHC
3 ≡≡CNa →→ 3 ≡≡C  C  CH 3 →
– + 3
CHC CHC Pr oduct
heat
 CaCO 3/ PbO
CH 2Ph

O
B2H6 PCC
( b) —CH2OH —C—H
H2O2/N a OH CH2Cl2
I
Cl OH
Cl2 Mg I H3O+
—CH—
AlCl3 eth er
OH
Cl2 PCC
—CH— —Cl Pr od uct
Al Cl3 CH2Cl2
Solutions 511
O
SOCl 2 C2H 5ONa
CP BA
(c) CH 3CH 2CH CHOH
2 2 →→→ m CH 2CH 2  CH  CH 2
CH
2 OH
5

OH
NaCN HO  PCC
→→ 2
CH 2CH 2CH  CH 2CN → Pr oduct
CH2Cl 2

/ NBSh ν Mg
976. CH 2== CH  CH 3 → CH 2==CH  CH 2Br → 2 =CH  CH 2MgBr
CH=
CCl 4 THF

OH
P r opanal HO + 
→→ CH 2== CH  CH 2  CHCH 2CH 3
3

CHI3 NaH
Product ← ←

Co n c.H2SO4 mCP BA PhO– H2O

9 7 7.(a) Pr od uct
h eat

O
CH3 OH CH3 H3C

O HO–
( b) OH PBr3 Br Na NH2 C CH
H2O
NH3
I OH Br
OH
Na I PCC
C2H5—C C— CH2—CH—C2H5 Pr od uct
h eat CH2Cl2

+H + HOCH2CH2—CH— CH2—CH3
9 78.
O O+
CH— CH3
+
H– Sh ift
H
Br
Br– +
HOCH2CH2—C— CH2CH3 HOCH2CH2—C— CH2CH3

CH2CH3 CH2CH3
512 ProblemsinChemistry

C H ONa Hg( OAc) NaBH

979. (a) CH 3CH 2CH CH
2 Br
2 2
5
→ CH 3CH 2CH==CH 2 → 2 4
C2H 5OH HO
2

OH O OH
 ( i) C2 H5MgBr   PCC 
CH 3CH 2  C  CH 3 ← 3 H 2  C  CH 3 ←
CHC CH 3CH 2  CH  CH 3
 ( ii) HO
2 CH2Cl 2
CH 2CH 3

Br
NBS/hν  CH
2 ONa CP BA
(b) PhCH 2CH 3 → Ph  CH  CH 3 → Ph  CH== CH2 m→
5
CCl 4 CH
2 5 OH
O
HBr
Ph → Pr oduct
BH H CrO SOCl 2
3 C  CH== CH2 → 3 C  CH 2CH 2OH → →
2 6 2 4
(c) (CH)3 (CH)3
H2O 2NaOH
/

O
Al Cl3   H 2SO 4
→ (CH)3 3 C  CH 2  C  —I → Product
PhI SO 3

PCC
(d) CH 3CH 2OH → CH 3CHO(I)
CH2Cl 2

OH Br
O Na OH PBr3 Na NH2
OH CH3— CH — CH CH3—C C–Na+
2Br
H2O
I H3 O+
Pr od uct
CH 3 CH 3
 O 
Mg  PBr3 C2H 5ONa
(e) CH 3— CH— CH 2Br →→ CH 3—CH— CH 2CHCH
2 2 OH →→
Et 2O CH
2 OH
5

CH 3
 ( i) KCN
CH 3— CH— CH 2—CH== CH 2 mCP
→BA
→
+
Product
(i i) HO
3

CH 3CH 3
 
980. (a) CH 3  C  CH  CH 2CH 3 (b) + CH3C CH
 * –
Br O OMgBr
( Racemi c)
Solutions 513
OH H CH3 SEt
CH 3

(d) CH 3  CH  C  CH 3
CH3 SEt OH H
(c) +  
NHPh CH 3
(Racemic)

S
(e) (f)
Br OCH3
OEt
O OH OH
Br NBS/hν
Mg
981. (a) Et2O H2O CCl4
Br
O Na
Pr oduct
Br

(b) (CH3)3COK NBS/hν KOH

(CH3)3COH CCl4 ∆
Cl

HO N a OH Br NBS/hν
H2O CCl4

OH OTs Cl
Ts Cl N aCl
9 8 2. (a)
SN2

CH3 CH3 CH3

OTs I Cl
NaI N aCl
( b)
SN2 Et2O ,SN2

CH3 CH3 CH3

(fr o m a)
514 ProblemsinChemistry

Cl Cl Cl
NBS/hν CH3ONa
9 83. (a) CCl4
Br OCH3
CH3
O
Mg/Et2O H2O
Pr od uct

Br Br
NBS/hν C2H5OK NBS/hν
( b)
CCl4 C2H5OH CCl4
P hS–
Pr od uct
Cl

(c) C2H5ONa
CHO CHO NBS/hν Br CHO
C2H5OH CCl4
I

NBS/hν Br Mg I KCN
Pr od uct
CCl4 Et2O H3O+
Br OH

CH3 CH3
TsCl EtOK mCP BA H+
( d) O Pr od uct
EtOH EtOH
OH

PCC P hMgBr Ph H3O+ Ph

984. (a) OH O
CH2Cl2 OH
OMgBr
OH
Ph
(b) OH H2SO4 B2H6
OH heat
Ph Ph
HO–,H 2O2
(as in a)

O
O O
O3
(c) —Ph EG/H+
H2O2
Ph–C—CH2CH2CH2—COOH Ph—C—CH2CH2CH2COOH

fro m (b) LiAlH4

O
O OH
H2SO4 H3O+
Ph Ph—C—( CH2)3—CH2OH
Solutions 515

Ph
Ph Ph
H+ –H2O + Ph CH3OH
985. H3C—C OCH3
—CH3 attack from (±)
OH2 b o th sid e giving
OH (a p lanar carbo catio n)
+ racemic p ro du ct
(+)-2 -ph enyl-2-b u tan ol

Br

986. CH 2== CH  CH 2CH 2OH( A ) CH 2  CH  CH 2  CH 2OH( B )

Br
Br

O O O
C D E
OH OTs

9 87. Ts Cl Na OH
H H Pr od uct
SN2

Br P Ph3 Aceto ne mCP BA H3O+

988. Pr oduct
H
Cl O OH
Cl2 Mg
9 8 9.(a)
hν Et2O H3O

CN
Ts Cl KCN

O
CH3 CH3
( b) mC P BA CH3M gBr H3O+ H2SO4
h eat
OH

O
Na 
(c) CH 3CHC2 ≡≡CH → CH 3CHC2 ≡≡CNa
– +
→ CH 3CH 2 ≡≡
C C  CHCH
2 OH
2
heat HO
2
Na liq. NH 3
+
HO
3

Product
516 ProblemsinChemistry

CH3
H
990. HO H HOOC COOH

CH3
O B
A

CHO
OHC CHO

CH3 OH
D
C
CHO
H2/Pt
∆

E
l l

OH
+
H
O—Ts
991. –H+
–H2O
OH OH
+
l l

O O

992. (a) PBr 3 (S N – 2) → C 2H S

5 Na( SN – 2): Twoinversionwillfinallyleadtoretention.
(b) TsCl→ NaCN

H2SO4 B2H6 OH TsCl OTs

993. (a) OH heat H2O2/NaOH
Me3N
Pr oduct

Br
Br2 NaNH2
(b) C C–Na+ Pr oduct
CCl4

9 94. (a) Br + ONa Pr od uct

( b) +CH 3CH2Br Pr od uct

ONa
(1 ° h alid e)
Solutions 517

Br O–
–Br–
(c) Pr od uct

PBr3 mg CH3CH2C HO PCC

9 95. CH3OH CH3MgBr
eth er CH2Cl2
P C C/CH2Cl2 OH O
CH3CH2CH2OH OH
— M gBr

Mg Et2O
OH Br
P Br3

PBr3 Mg/Et2O H3O+

996. Pr oduct

OH PCC/CH2Cl2
MgBr

OH

NH2
9 9 7. (a) HO (b) Br (c) CH3O OH

Br

OH
( d) (e) S (f) HO Cl

OH

(g) D (h) —CH2CH2OH

OH
518 ProblemsinChemistry

O
O OCH3 Br
9 9 8. (a) (b) (c)

Br
N3 OH

O Ph D D
OEt
( d) (e) (f)
O
OH HO OH

999. In acid catalyzed hydrolysis, protonation activate thereaction andstability of carbocation

intermediatedecidesthereactivity:
H

O O HO
–H+
+H + fast
OH
l l 2 OH2
3 °- c a rb o c a tion +

H
OH
O O+
+H + Sl ow
OH
l l 2
+
1 °- c a rb o c a tion OH2

In alkaline medium,the firststep is nucleophilic attack of hydroxide ion,which preferably occur at

lesshinderedcarbon:

O O

mor e hindr ance is less hindrance is offered

offered from adj acent carbon from adj acent carbon.

O O–
l l
– +
CH2 N N N N –N
+ l l 2
HO
1 0 00.HO
O – O
HO– O H2O
O
OH
HO
Solutions 519
OH OH
l l O

H+ O –H2O* +
–H+
* O O
OH OH2
+

O Ph Ph Ph
1001. *
OH OH
O
H HO OH
+
Ph H+ O –H+
l l
O+—H O*
OH * H2O
*

Ph Ph Ph

1 0 0 2.(a)
OTs CN

A B C O D
CN CHO
O O O
O
( b) O O O

H H H H
A B C D

1003. (a) mCP BA → HMeOH

+
/ ,
(b) mCP BA → NaN 3HO/ 2 ,
(c) (CH)3 3 SBr.

–H2O
1 0 0 4.
HO
l
O H—N +
H+
l
l l O +
O O
H2N— NH2 H— NH
NH2
–H+
NH2

H2O

O H—N N N
O
O–
l
l NH2
520 ProblemsinChemistry

Ts Cl Na CN CH3Li H3O+ Ph3P CH2

1 00 5.(a) Pr od uct

OH
H

LiAlH4 PBr3 PPh3 (CH3)2C O

( b) Pr od uct
B u Li
COOH
Cl OH O

CN C— OH
N aOH H3O+ 2I
(c) l
l Pr od uct
H2O H+/h eat
CN C— OH

O
I
OH
OH
+ H3O+
1 0 0 6. O—H +CH 3COOH – +N 2
OAc

N – N
N—H OAc N—H

H
O

+
H+
1 00 7.
OH
O
+

H
H
+
–H+
Pr od uct
OH
Solutions 521

OH OH
OH
CH3 Ph H
1008. (a) H H
and its enantiomer. (b) OH (c) CH3
CH3
CH3 H
Ph
OCOCH3 D
Br OCH3
(d) (e)

OH

CH3
PBr 3 Mg O xi r a ne SO Cl2 C2H5O Na
1 0 09.(a) —OH CH2CH2OH P r o d uct
Et2O H 3 O+ C2H5OH

O O O O
Cr2O72– Me OH C2H5O Na
( b)
OH H+ OH H+ OMe ( 1) OMe

PBr3
HO OH Br Br
( 2)
O O

( 1) M eO
– 2 H3O+
M eOH h eat

COOMe COOMe
O
O O
HO–/h eat
a ld ol

O O
1 0 1 0.Br CHO Br MgBr
A O
B O
C
O
OH O O O

H H
D E
F
522 ProblemsinChemistry

H OH CH3
O
Ph OH OH
Ph
1 01 1.(a) (b) (c) (d)
H
H CH3 OCH3
( R a c e mi c) CH3 CH3
( P h en yl a tta ck fro m b ac k i.side.,e,
fr o m H - sid e to s te r ic r e a so n ).
OCH3
O– –
O O
KH H2O
1 0 12.(a) Pr od uct
–

OCH3 OCH3
OH +
CH2
( b) H+
+ H3CO
–H2O
CH3

H2O
+
OCH3 O
+
CH3
l l
+ H2O
CH3OH2 +

ALDEHYDES AND KETONES

aq  NMgBr
C 2H Br
5 → CH 
2 CN
5   +
NaCN HO
1013.  → C 2H —C
5 —CH2 5 → 3- pentanone.
3

Mg 
C 2H Br
5 → CH 2 MgBr
5 
et her
aq Mg
1014. (a) Br—( CH 2)—5 Br → 2 5 N →
Br—(CH )—C
NaCN E ther
( 1.0 equivalent)

NMgBr O

H3O+
Solutions 523
aq
or Br—( CH 2)—5 Br →→ Sn d ilu te
NaCN HCl NaOH
(E xcess)
CHO CHO (Ald o l)

H2C rO4 H eat

CHO
OH
O

CH3 CH2Br
( b) NBS aq C N Mg
C Cl4
Br N aCN
Br E th er
Br

H3O+

O
CH
2 5 CH
2 5 CH
2 5 CH 3  
1015. C==C and C==C CHCH
3 CHO
2 CHCHC
3 2 CH 3
H CH 3 H CH
2 5 B C
A
OH OH OH
  
CH 3CH 2CH OH
2 CHCH
3 CCH
2 3 CHCH
3 —C—
2 COOH CHCH
3 —C—
2 COOH
D   
H H CH 3
E F G
O
 
1016. (a) Cl 3CCHO (b) CH 3CCl 2 —C —CH 3 (c) C 6HCHO
5

NO2
O O

(d) O2N— —C— —NO2 (e) —C—

NO2
524 ProblemsinChemistry

H
H
1017.
O
CHO CH2OH
A B C D

COOH F
E

OH
1 0 1 8.(a) O
OH

O O
A
B C
OH
(b) CHO
CHO
OH
A B C

O O

(c)

O B
A

1019. (a) CH3CH—COO (b) H2N—

–
—COO– + O2N— —CH2OH

OH

CHO COO–
(c)
CHO CH2OH

A B
Ph CHO

1 02 0.(a) (b)
B OH
A
Solutions 525
O OH OH
O O O
1021. (a) CHO (b)
O C O
O

OH H+
1022. (a) N NH
Be ckma n n ’s
r earr an gement
( Oxi me) O
A (Cap ro lactu m)
B
O
Ph Ph OH
(b) C ==N C ==N CH3—C—NHPh CH3COO –
HC
3 OH HC
3 E F
C D
O
P h—C—N H CH
3 P hCOO– CH3NH 2
G H I
H H O
N C ==N N C ==N N
OH H—C—N H— HCOO–
(c)
M
K L
J
O

N C—NH2 N COO–
+ NH3
P
N O
O
CH3 Ph OH Ph
1023. Ph—C—CH C ==N C ==N
A CH
2 5 C2H 5—CH CH
2 —CH
5 OH
CH3 CH3
B C

O CH 3 CH 3 O CH
2 5
      
P h —C— NH — CH— CH
2 5 C 2H —
5 CH— C — NHPh CH 3—CH— NH 2
D E F
526 ProblemsinChemistry

O
O
HOOC COOH
Cl –
OH– OH– –
1024. H not

COO–

TsCl NaCN
1025. (a) OH CN

SOCl2

Mg
MgCl
Eth er

H3O+

O
Mg
(b) C2H5Br C2H5MgBr
aq KOH H3O+ H2CrO4
PCC
C2H5OH CH3CHO OH O

1 0 26. CHO CH C— CHO CH2CH— CHO

A B CH3 C CH3

O O O
Br
CH3—C C— CH3 C— CH3
1 0 27. CH E tO– –
CH– + C
E t O—C COOEt COOEt

O Br Br Br
Pr od uct
Solutions 527
O
Cl
1028. O

A B C D E
O O OH
    
1029. (a) Ph —CH== CH—C —CH +
3 CH —C
3 —CH —C—
2 CH 3

CH 3

O O
   
(b) C 6H CH==
5 CH—C — C6 H 5+ C H6 —C
5 — CH== C—CH6 5

CH 3
O

(c) C 6H CH==
5 CH— NO 2
( d)

OH
O

H
(e)
(f)
O O O

O O

OH– C6H5C HO
1 0 3 0.(a) CH3 CH CHC6H5
Al d ol

O
O

OH– C6H5C HO C6H5CH

( b)
Al d ol
528 ProblemsinChemistry

NO 2
− C H CHO 
(c) CH 3CH 2NO 2 → CH 3CH—NO
OH
2 →
6 5
C 6H CH==
5 C— CH 3
HO
2

NH 2 NH 2
Li AlH  BH3 CH3COOH 
→4 C 6H —CH==
5 C— CH 3 → → CH
6 5 CH 2CH— CH 3
O

O
C
CH3
OH–
( d) Al d ol Pr od uct
N aBH4
O
O O
CHC6H5
OH– C6H5CHO
(e)
Ald ol

CHC6H5
N2H4
OH–/Heat

CH 3 CH 3 CH 3 CH 3 CH 3
    
1031.CH 3—C== CH— CH—CH 3 CH 3—CH— COOH CH 3—C— COOH CH 3—C— COOH
A B  
Br OH
C D
CH 3 CH 3 CH 3
  
1032.CH 3— CH— C ≡≡CH CH 3—CH— C≡≡C—CH 2CH CH
2 3 CH 3—CH— C—CH 2CH 2CH CH
2 3
A B  
O
C
CH 3

CH 3— CH— COOH CHCH
3 CH
2 COOH
2
D E
Cl

1033. CHO
C D
A
Cl
B
Solutions 529

CH 3OH CH 3
  
1034.CH 3— C— CH —CH 2CH 3 CH 3—C— C—CH 2CH 3
   
CH 3 CH 3O
A B
O O
CH
6 5 OH CH
6 5    
1035.C 6H CHO
5
C ==N C ==N CH
6 —C
5 —NH 2 H—C —NHCH
6 5
A H H OH D E
B C

C 6HCOOH
5 CH
6 NH
5 2
F G
O
O O
O COOH
CHO NNHPh
1036. O

CHO D =E
A B C

OH O
COOH
CHO
O
MgBr
F
G
H J

H CH 3 CH 3 OH CH 3
    
1037.CH 3CH 2— C— CH 2OH CH 3CH 2—CH— CHO CH 3CH 2CH— CH —C— CH 2CH 3
 B 
CH 3 CHO
A C

CH 3 CH 3 CHO
  
CH 3CH 2—C== CH — C—CH 2CH 3 CH 3—C— CH 2CH 3 CHCHC
3 2 CH 3
   
CHO CHO O
D E F
1038. (a) O 3/ Zn - HO
2 followedbyAldolcondensation.
(b) O 3/ Zn - HO
2 followedbyAldolcondensation.
(c) X = KMnO 4/NaOH (dilute) Y = HIO 4 , Z = diluteNaOH(Aldol)
530 ProblemsinChemistry

CH3
Bu Li
( d) X =CH 3OCH2Cl + Ph3P : Y = CH3OCH C— —O Me:

CH3

Z = H — C— CH— —OH

1 03 9.(a) +H + –H +
•O
+ • +
O O O OR O
H R
OR
H
OH O OH
OH OH

( b) H+ + –H+
OH OH

•• O
OH

•• H
O +
•• O —H
+ –H2O –H+
–H+
OH2 Pr od uct
O O

OH
O
LiAlH4 H2SO4
1 0 40.(a) —CH— CH3
H eat CHCH3

O3/Zn-H2O

H3O+ CH3 CH3M gBr

H eat H2O O+CH3CHO
OH
H Br P e r o xi de

a q K CN H3O+

Br COOH
Solutions 531
+
PhMgBr HO MnO
(b) PhCHO →→ 3 Ph —CH — Ph →2 Ph —C— Ph →
   Ph 3P == CH2
OH O
Ph
CH== CH2 .
Ph
O
(c) H3O+ H2SO4
+ CH2 CH CH2CH2M gBr
H eat

HB r( ex ce ss)Pe ro x ide
Br

Br2
Na
H eat H eat
Br

Br

OH OH

Al c . K OH B2H6 H2C rO4

H2O2/OH–

O –
– O
CH
(CH2)9O H2O
O (CH2)9 (CH2)9O O (CH2)9 P r oduct.

– O–
O CH

1042. (a)
C CH
O O C C–MgBr
O O
A B
OH

C C—CH( CH2)5—CH3
O O
C
532 ProblemsinChemistry

H H
C C
O O
(CH 2—
CH— )5 CH3
D
OH

(b) —MgBr —CH2CH2OH —CH2CHO

E F G

O
O O O O
(c)

H OH OH
I J
O O

1 0 43. (a) —CH CH— C— CH3 (b) P h— CH CH— C— CH CH — Ph

O

1041. Viaaldolcondensation:
(c) Ph —CH2—CH ==C— Ph

CHO

O OH O
Mg
—– HO   
1044. (a) PhBr et
→ PhMgBr →→2
her
Ph—CH 2—CH — CH3 PCC
→ PhCH 2—C —CH 3

O HO P d -CaCO
(b) CH 3CHC2 ≡≡CNa+ ——— 2→ CH 3CHC2 ≡≡CCHCH
2 OH
2 → 3 P r oduct.
H2

O
Mg —— HO PBr
(c) PhBr → PhMgBr →→ →3 PhCHCH
2
– PhCHCH
2 OH
2 2 Br
2
et her

O
Mg CH CHCN HO +  
(d) PhBr → PhMgBr 
3
→
2
→ 3
Ph —C— CH2CH 3
et her

N2H 4/OH –
(e) Pr oduct fr om (d) → PhCH 2CH 2CH 3
Heat
Solutions 533

Na
(f) H—C ≡≡C—H →→
Na PhBr
Ph —C≡≡C— Ph →
Heat liq. NH3

O
H Ph
RCO3H
C C
Ph H Ph
H Ph H

O CH 3
  
1045. CH 3CH 2CHC2 — O— CH—CH 2CH 3 CHCH
3 CH
2 CH 3 CHCH
3 CH
2 CHOH
2 2
A  C
OH
B
O O
   
CH 3—C —CH 2CH 3 CHCH
3 —C==
2 CH —C— CH2 CH3 CHCH
3 C==
2 CH — CH2 CH2 CH3
D  
CH 3 CH 3
E F
OH O
   Mcpba
CH 3CH 2CH— CH —CH 2CH CH
2 3 CH 3CH 2CH— C—CH 2CH 2CH 3 → A
  Bayer vi ll ige
r oxi dat ion
CH 3 CH 3
G H
O
OH O
O
1046. OCH3 OCH3
I
A
B
C
O D

COOH

O
E

Heat dil. NaOH O

E reflux
O
534 ProblemsinChemistry
CH2Ph
1047. (a) Ph—C —CH2CH2CH2OTs Ph—C—CH2CH2CH2—N
O O O CH2Ph
O

A B

CH 2Ph
P h —C—CH 2CH CH
2 —N
2
  CH 2Ph
O
C
OH OTs O

( b)
A B C D

(c)

OH O
A B
Ph

( d) — CH — Ph —C— Ph —C NN HPh

A OH O
B C

C H MgBr
(e) H—C ≡≡CNa C 6HCHC 2 ≡≡CH → ≡≡CMgBr
2 5
5 C 2H +C
6 HCHC
6 5 2
D E
NHNH2
KOH
(f)
EG

O OH
  HO + 
1048. (a) Ph —C— OMe + MeMgBr(excess) →
3
Ph —C— CH 3

CH 3

O O
  HO +   Li AlH4
(b) Ph —C—OMe →
3
– Ph —C—OH → PhCH 2OH PCC
→ PhCHO
Solutions 535

CH 3 OH
 HO +  –H2O
(c) Ph —C— OMe 3
→ Ph —C—CH 3 → Ph —C—CH 3
   
Br OH O
Unst able

O O
CHO CH CH
HO CH2CH2OH
O KCN
1 0 4 9.(a) O
H+
CH2Br CH2Br CH2CN
OH
O Sn /H Cl
CHO CH
O H+ LiAlH4
O
CH2CH2OH CH2CHO
( He mia c e ta l)
H +OH
Et Et O 2
O +
O ••
H+ H2O
(b) ••
O O
OH
O OH

–H+

OH

H+ Me-Sh ift –H+

105 0. (a)
–H2O
+ +
•• O
OHOH OH H—O
••

(b) H+
+
O O CH2
•• O +

••
+ CH CH
H—O HO +
•• CH3 O +
CH3
(En o l)
(Keto)
536 ProblemsinChemistry

CH3 CH3
–H+ H+ + H–-Sh ift
+
O O O

–H+

+
O CH2OH O CH2+ O O
H+ +
(c)
–H2O

–H+

COOMe COOMe COOMe

O OH O
CH
– H2O [O]
1051. (a) O + O
–
CH O
O OH O
COOMe COOMe COOMe

COOH COOH COOMe COOMe –

CH—COOMe
OH OH
O
H2O CH—COOMe
–
O O O O

OH OH
COOH COOH COOMe COOMe

∆
O O
Solutions 537

OH
H+
(c) O
+HN—Me –H2O ••
•• –H2O CH—N—OH
CH +
H HO N—Me
Me
OH

–H+ +
P r oduct O—H
N

Me

O
O
O
HOCH2CH2OH
1052. (a) H CH—CH2CH2—C—CH3
H+
O O
O
CH3CH2CH2CH PPh 3
CH—CH2CH2—C CH—( CH2)2—CH3
O
CH3

H3O+
H N2H4 H2/Ni
Pr oduct
OH–/Heat
O
Br
H H
C C
Br2
CH— CH — CH
3
( b) KOH
1 e q u iva le nt Br H eat

H CH3 C C— CH3
N a /liq NH3
C C
H

O
SO Cl2 Mg H2O
(c) PhCH2OH PhCH2MgCl PhCH2CH2CH2OM gCl
E th er

P r od uct
538 ProblemsinChemistry

Cl
H3O+ HBr
(d) + –H+
He at P er o xide
Br

(CH3)2Cu Li

Br
Br2 C2H5ONa
(e)
Heat
X HBr P ero xide

O OH Br
H2CrO4
aq KOH
X
Mg Eth er

MgBr
H+ X
P r oduct

OH OH OH
Br
1053.
CH—CH CH2 C—CH2CH3 C CHCH3
H3C
CH3 CH3
C
A B
HO
OH CH2 O

CH2
CH

CH3 E
D
Solutions 539

O O

C CH
CH3
1 05 4.
CH3
C CH
O
A B C D

1055. (a) N 2H /4 NaOH / Heat (b) RLi → CHI3 → P r oduct.

(c)

O OH OH

H HCN H3O+ CO OH CH3OH CO O CH3

( d)
H+/H eat
NH2

H yd ro lyse CO O CH3 NH3 S O Cl

P r od uct 2

O
O O O O–
O
(e) –
+CH 3–
H

H+ –H2O

1056. (a) (b)

O
Ph
O
540 ProblemsinChemistry

O — BF3 CH 3
+−  
1057. Ph —CH== O + BF3 → Ph —CH== OBF3 →
===
Ph — CH — CH2 —C— CH 3
+

O CH 3
  
→ P h —C— CH2 — CH—CH 3
OH
PhMgBr HO +  H 2CrO 4 PhC ≡≡CNa HO +
1058. CH 3CHO →→ Ph —CH—CH 3 →→  →
3 3

OH OH H
  
P h — C— C≡≡C— Ph  Na
→ Ph —C—– C == C — Ph
 li q. NH3  
CH 3 CH 3 H

1 05 9.(a) +CH 2
+
O O–
O

CH2

+
H O— CH2 O
OCH3 –

(b) H
HO HO
O
X

Zn H2O RCO3H
1060. (a) O+ CH 2—COOEt CH3—C CH—COOEt P r oduct.
Refo rmatsky
reaction CH3
Br

( b) O+ PhCH PPh3 P r oduct.

O
O O
∆
(c) +Cl 2 Cl CN
aq KCN
Solutions 541

CH2—OH
( d) O+ H+
P r oduct.
CH2—OH
O
OH
(e) H3O+ H+
+ P hMgBr P h— C—CH P h—C CH2
3
∆
CH3 CH3
O

Ald ol H+
(f) +OH – ( dil ut e) P r oduct.
∆

O–MgCl
1 0 6 1. OH
MgCl H3O+

R e ve r se

MgCl+

+
N N OH
Ag2O
1 06 2.(a)
+N 2
O O
A
O
CH3OH

O
( b) H2C C O
( Ke te n e)
O
B
C
542 ProblemsinChemistry

O
H2O Li AlH4
(c) O– O NH
+ N–
N—N N NH
–
D

+
(d) H+
+
O HO HO

Me- Sh ift

–H+ +

HO HO

H+ OH HO OH
(e) En o li za ti on
(3 mo lecu le) + OH

HO HO

– 3H2O

(f) H2O
CH2
+ ••
+ CH2 –H+ HO— CH2
O O

+
HO O–
HO O
H
Solutions 543

O
O

CH3 CH2N2 CH3 CH3CH2O Na H3O+

1 0 63.
∆

a ltern a tive ly OH
CH3O H /H Cl
OCH3 NaH CH3I

CH3CH2Br N aH OCH2CH3
OMe
OMe OH

OEt
OEt
O O O

O O CO OH
O
1 06 4.

OH
A B
CH2CH2OH D
C D

Al te r n a tive
O O O — CH — CH
2OH

CO OH
B
A O
COOH
O
1 06 5.
COOH H
HOOC O
A
B C
O
H
O
OH
O
OH
O
D E
544 ProblemsinChemistry

l
OH
l

1 06 6. C N C N
OH
l l
O
A

B C
O

NHCH3
C N NH2

O H
D E F
COOH

G
H
CH3
Ph Ph l
l

1067. (a) C N C N (b)

H l OCH3
H
l
CH3 OCH3

O
N
(c) H (d) (e)
O

O
O O
OH
(f)
+
O O
NNH2 OH
Y Z
X

+
1068. (a) N 2H NaOH
4/ heat,
/ HO,
3 Ph 3P == CH2 ,
+
(b) N 2H NaOH
4/ heat
/ , HO
3 , HNCH 3H/ –P
2 dC/
(c) Ph 3P == CH2 , HN2  OCH 3 ,
(d) CH 3Li /HClHO
/ 2 , Ph 3P == CH2 .
1069. III<II<I.
Solutions 545

1070. The nucleophilic addition of cyanide ion will occur at carbonyl carbon. Therefore, the stable
conformationat α-carbonwillbe:
OH O O
H H OH
OH
H 2
H – CN–
NC H
==R R 1
As shown above, attack fromside 1 will produce B and attack fromside 2 will produce C. Since,
attack ofCN – fromside 2 will sufferless steric hindrance, C will be formedin greater amountthan
B.
H H

CH3CH2MgBr H3O+
1071. (a) PCC

OH O
CH3 CH3 P lanar ar r angement
H H

CH2CH3 + OH

CH3 OH CH3 CH2CH3

Majo r p ro du ct (Min or p ro du ct)
(nu cleophilic ad d ition of
CH3CH2– o ccu r from sid e op po site
to —CH3 gro up)

(b) Inthemoststableconformshownbelow:
O HC CH3 H
HC
3 OH Ph H Ph H
3 H
+
– HO
3 OH + CH3
CH3
CH3 OH
Ph H H CH3 H CH3
H
Ph (M ajor) (M inor)
(attack occur from
les s -hindered side)
CH2I

Ph3P C6H5CH2CHO
1072. P r oducts
Bu Li
546 ProblemsinChemistry
OH
O OH

HCN H3O+
(b) CN H2O COOH
H
H2SO4
COOH
Heat
O
O
O
(c) LiAlH4 TsCl NaCN
H H+
H
OH OH
O O

(1 ) CH3Li
Pr oduct
(2 ) HCl/H2O
CN
O O

O O
K2Cr2O7 CH3Li
(d)
H2SO4 excess
O H O

N2H4
OH–/h eat
O

1073. A will proceed more efficiently. The electronegative chlorine, via inductive effect, increases the
electrophilicityofthecarbonylcarbon,makingitmoresusceptibletoattackbycyanideion.
O
O
O3 (CH3)2NH
EG
1 07 4.(a) O H C l/H
Pr od uct
H+ (CH3)2S 2O

O O
O
( b) EG O3 N2H4
O O
H+ DMS N aO H/∆

H Cl N2H4
Pr od uct
H2O
Solutions 547

O O
(c) CH3Li N aBH4 H+
H O H3O+ H3C O H2O

O O
CH3 OH CHO CH3 O OH
H+ NaH CH3I
Pr od uct

l l
O +
O O O– O OH O OH2
H+
1075.
l l

HO—N—H l
N
HO—N +
l
N H
H HO H HO
H H

H H
+ HO + H
O N O N O N N
HO Cl– O
O

–H2O H+ O
– ✧✧

O N O N
+
Cl–

OCH3 OCH3

10 76. (a) CH3 + CH3

CH3 CH3
(Ma jo r)

H OH H OH
O
(c) + (d)

(Ma jo r)
548 ProblemsinChemistry

O
O O O3 O O
HOCH2CH2OH H
1077. (CH3)2S
H+

O
H
C2H5NH2 O O CH3COCl
N Product
H2/Pd

O O OPh O
OPh l l
CH3O CH3O CH3O +
1078. O–Ph
O
l l
O+ HO

H+ H
H
O l l

O+ O
–H+ H CH3
Product CH3O
CH3

HO OPh
O HO
CN OH
HCN F H2/Pd F
1079. (a) F NH2
O

Pd/H2
Product
OH
HCN SnCl2
(b) O
HCl
CHO
O O
EG B2H6 PCC
(c)
H+ NaOH/H2O2
H O

O O
Pd NH3
H2 ∆
H2N O H O
H3 O+ O
Product
H2O
Solutions 549

1080. Thebondanglerequiredat carbonyl carbonis120°. Inthecaseof cyclohexanone, thesix

memberedringcanaccommodatethisbondangleeasilyandthus, thedrivingforcetowards
hemiacetal formation, where the bond angle is 109° is small. On the other hand, in
cyclopropanone, thesystemishighlystrained, andhemiacetal formationenablessomeofthe
3
straintobealleviatedbyallowingthecarbonylcarbontobe sp hybridized.
H
H+
O+CH 3OH
OCH3
ringislessstrained
thancyclopropanone

1081. (a) CHCOCHBr

3 2 ,(b) CHCHO
3 ,(c) CHCOCF
3 3 ,(d) CHCHO
3 .
+
1082. A : CHONaCHOH
3 / 3 , B : (CH)3 2 NH, C : CHCH==CHMgBr
3 2 ; HO
3 ,
D : CHOHHSO
3 / 2 4.
O CH3
O

(CH3)2CuLi CH3CH PPh3

1083. (a)
H2O
(Conjugateaddition) CH3 CH3

CH3
O
mCPBA

CH3

O
O O O O
O
EG PBr3 Mg
(b)
H+ ether H2O
OH OH OH
PCC H3O+
Product
H2O

Cl Cl
H
H OH– SN2
1084. H
H H O
OH O H
–
trans
[—O– andClareanti,substitutionispreferred]
550 ProblemsinChemistry
Cl

H Tautomerism
OH –OH

H OH O
cis [HandClareanti,eliminationispreferred]

+ H
O O
   
1085. HO  CHCHCH 2  C  H+H → HOCHCHCH 2  C  H →
+
2 2 2 2

H
+
O+ OH O OH O OH2
–H+ H+ CH3OH
Product
–H+

CN

1086. (a) (b) NH2

O
Ph
O O

N
CHCH2
(c) +CH 3CH2—CH C—CHO (d) (e)
O
cis-trans CH3

– O O O–
CH3O H
–
1087.

H H H
A
H O
O
CH3OH
+ H

H H
morestable lessstable
Solutions 551

O O–
– H2 O H2/Pd
1088. (a) + C CCH3 Product
BaSO4
C CCH3

OH
H2SO4 mCPBA CH3MgBr H3O+
(b) O Product
heat

CH2N2 NaCN
(c) Product
H2O
O
O
O
OH

CH3MgBr H2 O NaH CH3CH2I

(d) Product
ether

1089. (a) mCPBA CH3ONa OCH3

O CH3OH
OH

CH3
Ph3P C
PCC OCH3 CH3
Product
O

OH
O

H CH3CH2MgBr H3O+ PCC

(b)
H2O

N N
552 ProblemsinChemistry

OH

1090. CH 3  CH 2  CH  CHO CH 3  CH==CH  CHO CH 3  CH  CHCHO
2
A B 
Cl
C
CH 3  CH  CH  CHO CHCH
3  CH 2  CHOH
2 CHCH
3  CHCHOH
2 2
   
Cl Cl Cl OH
D E F

O
 
NaNH 2 CH 3  C  CH 3 HO +
2  C== CH 2 → 2 ≡≡CNa →  →
3
1091. (a) CHCH
3 CHCHC
3
 NH 3 HO
2
Br

OH
KMnO4  PBr3 KOH
CH 3  CH  CH 3  CHCHC
3 2 ≡≡C  C  CH 3 → → Product
  EtOH
OH CH 3

CH 3
 PBr3 KOH mCPBA
O HBr HNO2
(b) CH 3  C  OH →→→ → → Product
 EtOH
CH 3

CH 3 CH 3
 Hg(OAc)2 NaBH4 H 2CrO4 
(c) CHCHCH
3 2  CH==CH 2 →→→ CH 3  CH 2  CH  C  CH 3
HO
2  
O
HO +
→→
3
Product
HC ≡≡CMgBr
Br2 (i)NaNH 2 /NH3
CH==CH
2 2 → CH 2  CH2 
  (ii)HO3 +
Br Br (iii)MgEt/ 2O

CHCH
2 3 CHCH
2 3
 BH HCrO  SOCl 2
2  C==CH 2 →→ 2  CH  COOH →
2 6 2 4
(d) CHCH
3 CHCH
3
HONaOH
2 2/
PhOH Cl 2
→→ Product
AlCl 3 AlCl 3
Solutions 553

O
O O  
  CHO –   s CH==CH  C  CH3
6 5  CH 2  C  CHCH → CH6 5  CH 2  C  CH  CH 
3 2
1092. CH 2 6 5 6 5

O O
CHO
−
  CHOH  

3
CH—CH—C
6 5 —CH—CH
2 6 5 ←
3
CH—CH—C
6 5 —CH—CH
2 6 5
O O–
  
CH—CH—C—
2 2 CH 3 CH—CH==C—
2 CH 3

O
 
6 5  CH  C  CH  CH
CH 6 5
 s
CH 2  CH 2  C  CH 3
 
O

Ph O Ph O Ph O

CH3OH Ph CH3OH
Ph Ph
H CH3O–

O CH3 CH3 OH CH3

–
O
CH3 O

1093. (a) H3C— —C—SCH2C6H5 (b) —CH CH—C—CH3

O
CH3
O

CHC6H5
(c)

O O O

Br
(CH3)3CO– –
1094. (a)

Br
554 ProblemsinChemistry

O
O O Ph
O O H
KOH Ph—C—C—Ph Ph Ph
(b) Ph Ph Ph Ph Ph
s O O–
O O

Ph Ph Ph Ph
s OH– Ph s EtOH
EtOH
Ph –H2O

Ph O Ph
O

O O

Ph Ph Ph Ph
–H2O
H

HO Ph Ph Ph
Ph

1095. Differenceinreactivitytowardshydrolysisreactionliesinthestabilityofcarbocationintermediate
as:
H H
H
O O H+ O O+

+
H H2C H H
+ +
O O O

OH OH OH
Allylicgroupprovideextrastabilityduetoresonance
H H H
+ H +
O O O O O notstabilizedby
H+ allylicresonance

OH
Solutions 555

O
H
H+ + –H+
1096. H3C H CH3—C OH CH2 CH—OH
– +
CH2—CH—O—H
Product
H—O—–CH—CH2–
+

1097. II<III<I.

H+ OH –H+
1098.
O O O O+ O l l
l l + OH2
H

OH HO OH
H2O

O OH
l l
OH
+
–H+
Product

O
O O
EG Mg CH3CHO H2O CH3
1099. H Br H
H+ Ether

O H l l
OH
OH
H3O+
Product

CH3

O
I O– O
–I– OCH3
I –
1100. H +OCH 3
OCH3 A

HO
H3O+

H O
556 ProblemsinChemistry

–
H2O
1101. Compound+EtO +
– O O– O O
H CH3 H
CH3
CH3 CH3
50% 50%
Planar(achiral)

HO +
MeMgBr PCC
1102. (a) PhCHO →→→ CHCl
3
Product
2 2

OH CH3
mCPBA NaH CH3I
(b) O Product
H+
OH
O
OH OH
O O Mg CH3CHO H3 O+
(c) Product
H+ Et2O H2 O
Br Br
O O

O O
OH
1103. H
OH
A B C D E F
O O

OH O O O
OH
1104.
A B C D

CH 3 CH 3 O CH 3 O CH 3
       
1105. CH 3  C  C==C  CH 3 CH 3  C  CH 3 CH 3  C  C  CH  CH 3
  
CH 3 CH  CH 3 B CH 3
 C
CH 3
A
Solutions 557

CH 3 CH 3 CH 3 CH 3
   
CH 3  C  CH CH  CH 3 CH 3  C  CH==C  CH 3
  
CH 3 OH CH 3
D E
Br

1106. A : CHCHCH
6 5 2 3; B : CHCH
6 5 CH 3 ; C : CHCH==CH
6 5 2;

OH O
  
D : CHCHO
6 5 ; E : CHCH
6 5 CH 3 ; 6 5  C  CH 3 .
F : CH

1107. ClCH 2  H (CH)3 2 CH— Ph

O Ph3P CH2 H3O+

EG Product
1108. (a) CHO
H+
CH H2O
O
O O
O
O

(i)H + H2/Pd N
(b)
H2N H (ii)H 2/Pd NH H+

HO
H
OH
1109. (a) (b)

(Racemic) (CH3)2HC OH
O Ph
(c) H
H CD2OH
OH CH2Ph CH3
CH3
H (e) HO (f) Ph—CH—C(CH3)2 (g)
(d)
H OH
CH3
OH
H
O
N
1110. (a) N (b) NH—C—CH3

H
558 ProblemsinChemistry

(c) PhCHMgBrEt + NH
2 / 2 O,HO,PCCCHCl
3 / 2 2 (d) (e)

O O

MgBr
EG O3 H+
1111. (a) Product
H+ (CH3)2S H3 O+ H2O
O

CH3 CH3
Fe/HCl NaNO2 KI CrO2Cl2
(b)
HCl/0°C Ac2O

NO2 I

CHO
CH3MgBr H3O+ CH2Cl2
Product
H2O PCC

(c) O3 H+
NH2 Product
(CH3)2S BH3

OH TsCl OTs (CH3)3COK

1112.
(CH3)3COH

B2H6 PCC
H2SO4 Product
NaOH/H2O2 CH2Cl2
heat

Majorproduct
(notrequired)
Solutions 559

OH O O OH OH

1113. (a) , ,
, ,
O OH OH O OH
OH OH

OH OH
O O O

D D Br
(b) (i) (ii) (iii)
D D

O O O
D
O
CHO
OMe
1114. (a) (b) (c) Ph—CH2—CH C—Ph
OH NHCH3
O
OH

CHO
(d) (e)

OH
O O
O
D CHO CHO CHO
1115. (a) D D (b) Br (c) CH

OH
OH OH

H
(d)
560 ProblemsinChemistry

1116. Ahasenolizablehydrogenbondedtochiralcarbon,therefore,itacquireplanarityatchiralcarbon
whenconvertedtoitsenolform.Duetoplanarityatchiralcarbonintheenolform,itformsboth
enantiomersinequalamountwhenconvertedbacktoketoform.Nosuchenolizationispossible
with B sinceithasno α –H atchiralcarbonandhence, itsopticalactivityisretainedevenin
aqueousalkalinesolution.

EtO– EtOH
A +
O O– O O
H H H

Planarstructure Racemicmixture

O O –
– O
CH2
O O
CH2—H
1117. – O
+OH

O
H2O
∆

O
O
OH
1118. (a) (b) (c)
CH—COOH
O
O O

OH
(d) (e) (f)

Br

H H
O O
(g) Cl Cl (h) N

OH PCC H HO– CH2 PPh3

1119.
CH2Cl2 ∆ (Aldol) H
O
O
Solutions 561

O
O O O
CHO
1120. (a) (b) H H (c)
D D

N (g)
(d) (e) (f)
OH CN
N
+ H
O OH
O l
l

H –H+
1121. (a) HO +H + l l O
H O
H
+ H +
OH2 O CH3
l l

O
H+ H CH3 –H+
O O Product

+ NO2
O OH
l l

C C H2N—O— —NO2
H H+
(c)
H

NO2 NO2
OH OH
–H+ +
Ph—CH—N—O— —NO2 —CH—N—O— —NO2

H H H
NO2 NO2

H+ + l l

Ph—CH—N—O— —NO2 Ph—HC N—O— —NO2

–H2O
H A
NO2

– – CH3O–
PhCN+O— —NO2 Ph—C N—O— —NO2

NO2
562 ProblemsinChemistry

1122. HighproportionofenolintheequilibriummixtureofcompoundIIcanberationalizedbytwo
factors:
(a) Itisconjugatedsystem.
(b) ItformsasixmemberedcyclicringviaintermolecularH-bondingas:
H
O O

H IntermolecularH-bonding.

O O
OH OH– –
1123. O N C OMe
N

H
–
O
N H N–
H
OMe O
N OMe
O O N

H2O –H2O N H

O N
OMe
OH OH

O3 LiAlH4 PCC
NaOH
1124. (a) Product (b) Product
(CH3)2S heat CH2Cl2

O OH
O
O
OH
RCO3H H3O+
(c) O
COOH
CH3OH
Product
H+
Solutions 563

antito t-butyl,shift
OH H
OH OH
1125. (a) HNO2
H+

+
NH2 OH OH2

l l

+
OH
–H+
Product
H–-Shift

OH OH OH
H+
HNO2

NH2 OH OH2
+

–H+
Product + l l

CH—OH

O
O O

– H2O
MeO– Product
(b)
O
OH O Ph
–
Ph Ph
O O O –
O

MeO– H2O

OH O O
Ph – O
Ph Ph
Ph
564 ProblemsinChemistry

H2O
OH
H+ + H+
1126. (a) O OH OH –H2O OH +
–H+

OH
–H+

O CH3
OH
+

(i)CH 3MgBr H+ HO–

(b)
(ii)H 2O –H2O
O O O CH2–H

HO–

O– – O O O

H
H2O

OH

Br Br
O
LDA SN2
1127. +Br –
O
O OH O O–
Br Br
LDA
+Br –
O CH3 O CH2– O
Solutions 565

1128.
OH
A B C D
O

O NOH

E F G

CH 3 CH2 5 CH 3 CH2 5 CH 3 CH2 5

     
1129. CH 3  CH C==CHCH 3 CH 3  CH  C  CH2 5 CH 3  CH  C  CH  CH 3
A   
OH H OH
B C
CH3 O CH 3 CH 3
    
CH 3  CH C  CHCH
2 3 CHCH
3  CH  CHCH
2 3 CH 3  CH  CH==CH  CH 3
D  F
OH
E
CH 3

CH 3  C== CH  CHCH
2 3
G

CARBOXYLIC ACIDANDITS DERIVATIVES

1130. Extractionofasolutionofcarboxylicacidandphenolin CCl 4 withaqueoussolutionof NaHCO 3
willbringcarboxylicacidinaqueousphaseas R COONaleavingphenolinorganicphase.
1131. A :2-methylmalonicacid, B :Propanoicacid.
OH O
Br2
1132. (a) –H+
O O
• OH
•
Br O
+
Br

+
CH3COOH
(b) +H +
–H+
+

OCOCH3
566 ProblemsinChemistry

OH

+
(c) H+
NHCOCH3 –H2O
NHCOCH3

•• NHCOCH
3
–H+
+ Product

O
O
COOH
1133. (a) PhCONHCH3 (b) (c)
O CH3

O O OH
O

OCH3
(d)
COOH

dilute HBr dilute

1134. (a) →→→ (b) →→→
HBr NaCN NaCN
HSO
2 4 Peroxide HSO
2 4

SOCl2 Cl
COOH
O
(c)
I
Br
Ag2O Mg I H3O+
Br2/Heat ether

COOEt
1135. (a) CHOH+NaCO
3 2 3 (b) (c) Ph—CH— COOEt

COOH COPh
(d) CHCHCH(COOEt)
3 2 2
Solutions 567

(e) (i) H3C— —COOH (ii) H3C— —CH2NH2 (iii)H 3C— —C—Ph

O O
CHOH    
1136. (a) HOOC—
(CH)—COOH
2 4 →
2 5
CHO—C
2 5 — ( CH 2 )—C —OCH2 5
4
H+
O
COOEt
EtO–
EtOH
I

O O
COOEt
COOEt Cl COOEt
LDA COOEt
I –

P HO +
aqueous
(b) CHCOOH
3 →
4
ICHCOOH
2 →→ 3
HOOC—CH—COOH
2
I2 NaCN HO
2
+
CHOH/H/Heat
2 5

tEOOC COOEt
SOCl
1137. (a) PhCHOH
2 →2 PhCHCl
2 → PhCHCN
NaCN
2

CH 3
SOCl CHMgCl HO + 
(b) PhCOOH →2 PhCOCl 3→→ 3
Ph—C— CH 3
Excess

OH

EtONa CH2 CH—CH2Br

(c) COOEt
EtOOC COOEt COOEt
H3O+ H2O

C2H5OH
COOH
SOCl2
Heat
COOH
COOH

COOEt
568 ProblemsinChemistry

O
Cl
Cl
OH O O
Cold,dilute O
1138. (a)
alkaline/KMnO 4
OH O O
Cl OH O O

Cl2 aqueous H2CrO4

(b) RCO3H O
hν NaOH

CH3 CH3 CH3

H2SO4
CH3
(c) CH3Cl CH3Cl
AlCl3 Heat AlCl3

SO3H SO3H
O
COOH
P2O5 KMnO4/H3O+ dilute
O
Heat NaOH/Heat H2SO4
COOH
O
O
O OH
COOH
P2O5 O
(d) O
Heat H+
COOH COOH
O
NH2 NH2

PCl5 NH3 O3 COOH

1139. (a) 6-hepten-1-ol Heat
H2O2 NH

O
NaBH4
(b) PhCHBr
2 →→
NaCN
PhCHCHNH
2 2 2
Solutions 569

HO + HSO HBr
(c) PhCHO+CHMgBr
3 
3
→ PhCH CH 3 → PhCH==CH 2 →→NaCN
2 4
Heat
 Peroxide
OH
PhCHCHCN
2 2

O
COOH
P 4/I2 Na H3O P 2O5
1140. (a)
COOH COOH ∆ Heat O
I COOH

O O
COOEt
Et ONa H 3O +
(b) C2H5O—C—(CH2—
)4 COOC2H5
Et OH Heat
O
CH3
LDA CH 3I

O CH3
1141. (a) HCOOH
H—C—NH—CH—CH2CH3
Heat
NH2

C2H5MgBr H3O+
(b) CH3COOEt
Excess
OH

NH2 NHCOCH3
CH3COOH
(c)
Heat

OMgCl
Br
(d) Mg HCOCl H3O+
Product.
Et2O
570 ProblemsinChemistry
O
COOH COOH
1142. O OH COOH
C
A B O
D
O OH
1143. O O

O COOH
A B COOH COOH
C D E
CH3 CH3

1144. CH3—CH—CH2COOH CH3CH—CH—COOH

A COOH
Br C
B
O O

H H
D E F
CH 3 CH 3 CH 3
  
1145. CHCHCHC
3 2 HCOOH
2 CHCHCH—
3 2 CH—COOH CHCHC==
3 2 CHCOOH
A  C
Br
B
CH 3

CHCH—C==
3 2 CH 2
D

O
O
1146. OH O
NH2 HOOC
NH HOOC
B C
A D
Solutions 571

O CH 3 O O
      
1147. CHCH—C
3 2 —CH— C—OCH
3 7 CHCH—C
3 2 —CH— CH 3 CHCHCHOH
3 2 2
A  C
COOH
B
OH

CHCHCHO
3 2 CHCHCH
3 2 —CH— CH 3
D 
CHO
E

O
COOCH3
COOH
O
1148. COOH
COOH
O
A B C

1149. C2H5OOC—CH—COOC2H5 HOOC COOH

COOC2H5 B

A
O O
O O COOEt
COOEt
EtO OEt
C
D E

CH3

1150. COOC2H5
COOH C2H5OH
A C D
CH3
B
O OH

1151.
A B
572 ProblemsinChemistry
O
CH2COOH
1152. (a) MeO— —NHCOCH3 (b) Ph—C—NHOH (c)
O CH3
C C

O O
COOH
O OH
(d) (e)
O O O OCOCH3
Y
X X Y
OH Cl

1153. (a) OCH3 OCH3

A O B O

CN CN COOH
  
(b) Ph—C— CF3 Ph—C— CF3 Ph—C— CF3
  
OH OCH 3 OCH 3
C D E

2 ≡≡CH
1154. TsO—CHC 2 ≡≡CLi TsOCHC
TsO—CHC 2 ≡≡C—CHCHCl
2 2
A B C
2 ≡≡CCHCHCN
NC—CHC 2 2 HOOC—CH—C
2 ≡≡C—CHCHCOOH
2 2
D E
O– O–

+ +
1155. CH2
O
A
CH3COCl CH3COCl

O O

O O
Cl
Cl
Solutions 573

H H H
NaCN H3O+
1156. (a)
H CH2Cl H CH2CN H CH2COOH

LiAlH4

H
NaBr TsCl
Product.
H
OH
CH3
H H
(CH3—CH—CH2)2AlH
(b)

H COOEt H CHO

O
COOH
H3O+ LiAlH4 OH
(c) O

OH OH

O O O

H3O+ NH3 H2SO4

OH OH
(d)
Heat Heat
COOH CONH2
CONH2

Pd H3O+ Conc.H 2SO4

(e)
BaSO4 Et COOH Heat Et O
OH O

CH2OCOPh
LiAlH4 PhCOCl
COOH
O CD3
1157. CD2OH
CD3 CD2OCOPh
LiAlD4 PhCOCl
H2 O
O CD3 CD3
O
574 ProblemsinChemistry

CH 3 CH 3
 
1158. Ph—CH— CHCOOH
2 Ph—CH— CHCH
2 3 PhCHCH—
2 COOH PhCHCHCH
2 2 3
A  C D
COOH
B
PhCH(CH)3 2
E
O
O O
COOH COOEt COOEt
1159. COOEt
COOH COOEt
A B C D E
O
O O
   
1160. (a) Ph—CH—C
2 —CH—C —OCH 3 (b)

Ph
18
−
1161. (a) HOOC—CHCHCH—OH
2 2 2 (b) HN—CHCOO
2 2 (c) HOOC—CHCHCHCONH
2 2 2 2

O O O
COOCH3 COONa
1162. (a) CH2CH2CH3

X Y Z
(b) CH—(CH)—COOH
3 2 10

O O O

CH2O H2O
1163. (a) +LDA –
CH2 OH
O O
PCC

H
O O
O
—Br
EtONa H3O+
(b) O
COOH
O

Heat
Solutions 575

O O
  Cl 2   CHONa
(c) Ph—C —CHCH
2 3 → Ph—C —CH CH 3 25
→
heat
 CHO
2 5 H
Cl
O O
    +
Ph—C —CH==CH 2 →
HBr
Ph—C —CHCHBr
2 2 H→
CH2 —C H 2
 
OH OH
O O
O O
Ag2O Mg
Product Ph—C—CH2CH2CH2CH2OH Ph—C—CH2CH2Br
H2O H3 O+ ether
O O
O O
LDA LDA CH3I
(d)
OMe
O O
O
O
COOEt
OC2H5 EtONa LDA
(e) C H O
2 5

O
O O

COOEt CH3CH2CH2Br
Heat H3O+

O O
SOCl 2     NH
1164. (a) PhCOOH → Ph——Cl
C ≡≡
PhC →
CNa Ph—C —C ≡≡C— Ph   
2 4
– OH/Heat

Pd
Product ← Ph—CH—C
2 ≡≡C—Ph
BaSO/H
4 2
O OMgBr O

(b) Ph—C—OMe+ H3O+

MgBr Ph—C—OMe Ph—C—
Heat

LiAlH4

H2SO4
Ph—CH
Heat
576 ProblemsinChemistry

C2H5ONa PhCH2CH2CH2Br COOCH3

(c) Ph

COOCH3
+
O OH OH

H H+ H +
1165. (a) –H+
•• O—H Product
OH OH
••

O
HO O
O O EtO O
O
COOEt HCl O
(b)

O
HO

O
+

O O–
O O
EtO– EtOOC
1166. EtO (EtOOC)2CH–
OEt
COOEt
O
H3O+ HOOC
Heat

O O
EtO– CH3CH2COOC2H5 OEt
1167. (a) s
OC2H5 CH3—CH—C—OEt
O O

H3O+ s
CH3CHCOOEt
COOEt
Heat
O O O O
Solutions 577

OEt
(b) CH3MgBr

O O O O
[from(a)]

OEt Ph
(c) PhMgBr

O O O O
O
(d) CH3MgBr HCN H3O+
OC2H5 CN COOH
OH OH
B2H6 H2SO4
COOH CH3COOH Heat

OEt
(e) PhNHNH2
Product.
O O
[from(a)]
O O O
EtO–
1168. (a) OEt OEt

OH OH
O O O O
CH2—CH2 O O O O
(b) CHMgBr
OEt H+ OEt CH2

O
N2H4
O O
H3 O+ OH–/Heat
578 ProblemsinChemistry

l l

H OH2
O
O COOH
H2O O—Cr—OH
1170. K2Cr2O7 +H 2SO4 HO—Cr—OH
heat
O
O
OH H
OH
O
CH C O
OCr—OH H2CrO4 H2O
H OH
O
H2Ol l

+
O O—H OH
+
C C l l C—O—CH3
OH H+ HOCH3
OH OH H

–H+
+
OH2 OH
+ l l
C O C—O—H C—OH
H –H2O H+
OCH3 OCH3 OCH3

H2O
O

OCH3

O O
NaN3 H2/Pd/C HCl N
Br NH2
1171. (a) HCl

CH3COCl H2
Product N—H
Ni
Solutions 579
CHO CHO CHO
NaNO2 CuCN
(b)
HCl/0°C

HCN
NH2 N2+ Cl– CN

CN

H2/Pd OH
Product

CN

PBr Mg
1172. CHOH
3 →3 CHBr
3 → CHMgBr
3
ether
OH
O O
CH3MgBr H3O+ HO
excess OH
O K2Cr2O7
Product
H2SO4

–
O O OLi+

C C C
OH O–Li+ O–Li+
1173. (a) +CH 3Li –
CH3Li+ CH3

OH

C
–H2O OH H3O+
Product
CH3
580 ProblemsinChemistry

H H
+
H O
 +
••
OH  H 2O
(b) R —C ≡≡N+•• R —C ≡≡N—H → R —C==N—H 
2
O+
H H
H
+
OH O O
 HO
2
  H+   Tautomerism
R —C— NH 2 R —C— NH 2 R —C —NH 2 ←→→ R —C== NH
 −H + 
OH OH
+
H

OH OH O
 +  +  
+
R —C— NH 3 R —C== O—H+NH 3 R —C —OH+NH 4

• OH
•

O O O H Cl O H Cl
        −    
R —C —OH+
••
S → R —C —O —S— O → R —C —O—S== O 
+
 +
Cl Cl Cl Cl –

O Cl O Cl
  R −   
Cl – +SO+2 R —C —Cl ←→ C O ←Cl
 R —C —O—S= = O
 
–
O O—S —Cl
−
O O
  − +  + H O
(c) R —C —N—N ≡≡N ←→ R —C== N—N ≡≡N → R —N==C==O+N 2 2
O
 
R C
HO
R —NH 2 ← OH ←
2
HO+CO+
2 2 N

H
Solutions 581

H H Cl–

N CH3 N CH3
l l +
1174. Cl
O O
CH3O Cl CH3O P O
P
Cl Cl Cl
O
+
+ N CH3

N
H3CO CH3O
H

Cl–
Product
O OH
LiAlH4 CH3O NaH
CH3O
1175. (a)
O OH

CH3CH2I
Product
O
COOH
LiAlH4 OH SOCl2 Mg
(b) ether H3O+

H3O+ NaCN TsCl OH

Product

1176. (a) II>III>IV>I, (b) I>II>III>IV, (c) III>II>I.

COOH LiAlH4 PBr3

1177. (a) H2O OH Br

OCH3 H2SO4 H3O+ NaCN

heat,CH 3OH

O
582 ProblemsinChemistry

H3O+ H2SO4 HBr

CH2
(b) CH3 COOH ROOR
O COOH ∆
O
OH
O

O H2SO4 aq.NaOH
COONa
∆
OH

1178. (a) A willhydrolysefirst, (b) Ratewillincrease, (c) Ratewilldecrease,

(d) Ratewilldecrease.
O
O O–
Ph
1179. OCH3 Ph Ph
– OCH3 OCH3
H
–
OCH3 O
O–
O O
Ph
Ph OCH3
CH3O– + Ph OCH3
CH3 O
Ph
Ph
H3O+ OCH3
CH3OH

∆H = (BE) Reactants − (BE) Products = 91 + 99 − (85 + 102) = 3 kcal

O O O O– O O–
+
* * CH3OH * +CH 3OH2
1180. H3C O CF3 CH3 O CF3 CH3 O CF3
+
l l OCH3 OCH3
O H
H CH3
O O O
+
CH3OH2 *
CF3—C—OCH3 + CH3—C—O*– CH3—C—OH
Necleophileattackatmoreelectrophilic.C
Solutions 583

OH O
OH

O
H3C H3C COOH
COOH
1181. H3C OH H
O

A B
C O
O O
O CH3 O
CH3
H3C COOH H3C CH3—C—C—–C—OC2H5
X
CH3 CH3
COOH
D E

1182. A : CHCOOCHCH;
6 5 2 3 B : CHCHOH
3 2 ; C : CHCHO
3 ; D : CHCOOH
6 5 .
1183. CHCH==CH
6 5  COOH CHCHBrCHBrCOOH
6 5 CHCH(OH)CH(OH)COOH
6 5
A B C
CHCOCOCOOH
6 5 CHCOCOCOCl
6 5 CHCOCOCONH
6 5 2
D E F

O HO
O –
O
–O O COOH
1184. (a)
–
HO
O
H2O COOH

O O
HO O–

–
TsCl OH
(b) Product

N H H N
N
HO TsO TsO
584 ProblemsinChemistry

N—OTs
s
BuLi O
(c)

O O

BuLi C –
N O C—N
OTs
O O

H2O
s Product
C
N O

O O O O

2–
1185. (a) +CO 3 OEt
OEt s
CH2CH2Br
H
Br

O O O O
CO32–
Product
– OEt OEt
H CH2CH2Br

Br
Solutions 585
– OEt
COOEt O
COOEt COOEt COOEt

(b) Na s CH2CH2—COOEt

COOEt COOEt EtOOC COOEt

O O

COOEt COOEt
Na/∆

s
EtOOC EtOOC COOEt
O OEt

O O

COOEt COOEt

EtOOC EtOOC
O OEt
–
O
EtOOC EtOOC EtO O
O O
t-BuOK
1186. O
N N –
R CH3 R CH2– N

AcO HO O O O
O
Ac2O Tautomerize

N N
N

R R
R
AcO OH HO OH
MeMgBr H2O NaOH
Me Me
H2O
N N

R R
586 ProblemsinChemistry

O CH3 O OH
–H2O Tautomerize
Me

N N

R R

– COOEt
EtO– COOEt
1187. (a) COOEt COOEt
O
– OEt

EtO– + COOEt

CH3MgBr
EG COOEt
(b) (i) O O
COOEt H+ O O
O
O
(i)N 2H4
(ii)HO –/heat
(iii)H 3O+
O
Br

H2SO4 heat Br2/H+

(ii) COOEt
H2O
O O O
Br

EG
H+ O O

O O H2SO4
Heat
2X +Na Product.
H2O
O O
Solutions 587

H2SO4 Heat KMnO4

(iii) COOEt COOH
H2O H+/heat

O O
CH3Li NaBH4 TsCl NaCN
excess

O OH CN
H2SO4
H2O
COOH

R
O R
N +
(iv) COOEt RNHNH2 N H N—H
N OEt
H+ COOEt
O
–

R H
N+
Product EtO– N
O

1188. EG LiAlH4 PCC N2H4

H+ H2O HO–/heat
O
O
COOCH3 O
COOCH3

H3O+
Product
H2O O
O

H3O+ Br2/P Br
1189. (a) —Br KCN —CN —COOH
H2O (HVZ) COOH
588 ProblemsinChemistry

HO + LiAlH4
(b) CHCH
3  CHCN
2 
3
→→ Product
 HO
2
CH6 5

O O H+/H2O H+
1190. OH OH
H—O
l
O l

COOH H
HO HO
O+
O
H2O

–H2O
OH +
OH
O –H+ O
H
HO OH
O

–
BrMgCH2 CH2MgBr CH2MgBr
1191. (a)
O O O OMgBr
–

CH2MgBr
BrMgO
OMgBr O
BrMg—O

H3O+

OH
HO
S– HS
(b) O–
O
S S O N O
l l
NH2 N
NH2 + +
H H
H
NH2
1192. (a)

(b) CHI3 (excess); AgOheat

2 / ,
Solutions 589
(c) CHONa;
3 CHCHCHBr;
3 2 2 NaOHHO;
/ 2 heat,
+ +
(d) MgEt
/ 2O; COHO
2/ 3 ; CHOHH
3 / .
O
Mg CO2 SOCl 2 NH3   LiAlH4
1193. PhBr →→ +
PhCOOH → → Ph  C  NH 2 →
Et 2O HO
3

O
Product
H+
Br
O
 
Br HOOC  CH 2  C  CH 3 HOOC  CH 2  CH  CH 3
1194. C 
OH
A B D
COOH H
1195 CH COOCH 3 C==C CH
6 5  CH  CH 3
  H COOH 
CH  COOCH CH
6 5 OH
 B
C
CH 3
A
COOH COOCH 3
H Br H Br
H Br H Br
COOH COOCH(CH)CH
3 6 5
D (E and F )
1196. AllthethreereactioninvolvesSN–1reactionoftertiaryhalideas:

CH3 CH3
∆
A : CH3O— —C—Br CH3O— —C+ +Br –

CH3CN
CH3 CH3
HereCH 3O—fromparapositionstabilize
thecarbocationincreasingreactivity. CH3
+
CH3O— —C—N C—CH3

CH3
CH3 CH3
+ –H+ tautomerize
CH3O— —C—N C—CH3 CH3O— —C—N C—CH3 Product
OH2
CH3 l l
CH3 OH
590 ProblemsinChemistry

Theabovemechanismrevealthatelectrondonatinggroupwillincreasethereactivityandelectron
withdrawinggroupwill decreasethereactivity. Therefore, reaction A will bethefastest and
reaction B willbetheslowest.
OH OH

O OH
1197. LiAlH4 NH4Cl
H–
OEt TsCl
H
HO l
l
OTs
+
O O
OH–

O O O OH

N OH
1198. (a) (b) (c) OH
O

O O O
O CH3
I
N—CH3
N
(d) (e) (f)
H
O
O
O O
O O
C C
OH –H+ OH
1199.
l l
O
HN Ph –H+
H2N
l
l

Ph Cl
O
O O
O O

Ph O
Ph –H+ Ph
O O HN l
l
O
N H—N O
+
Ph
Ph Ph
Solutions 591

Cl
SEt O

1200. (a) (b) noreaction (c) OEt

OMe
CCl3
O
OLi
COOH
(d) (e) (f) +
OEt
OHC

1201. (a) AgOHO

2 / 2 ,(b) {(CH)3 3 COAl
}3 ,(c) CHMgCl;PCC
3 ,(d) NaBH 4 .
O O–

OEt OEt O OEt

CH3MgI
1202. (a) O
–
O O
Product

C N C N–Li+ H2O
(b)
+CH 3Li Product

O O
Br
NaOEt Br NaOEt
1203. EtO EtO
Diethylmalonate
O O

EtO OEt
NH3 SOCl2 H3O+
Product
∆

O O O

1204. (a) (b) OEt

592 ProblemsinChemistry

O O
O

(c) (d)

COOEt

O O O OH

Br CN CN
CH3
1205.

A B C D
OH O

OC2H5

E
O O O O

OC2H5 C2H5OK C2H5I OC2H5

C2H5OH
C2H5
F
O

H+
∆

1-Phenyl-1-butanone

AMINES
SOCl H
1206. (a) R —OH → R —Cl aqueous
 → R —CN → RCHNH
2 KCN 2
2 2
Ni
HCrO
2 4 NHOH
2 OH Na
(b) —OH ==O ==N —NH2
Hg

O
CHCOCl   LiAlH4
(c) CHNHCH
6 5 3 →
3
CH—N—
6 5 C—CH 3 → CH—N—
6 5 CHCH
2 3
 
CH 3 CH 3
Solutions 593

NaNO CuCN LiAlH4 CHCOCl

(d) CHNH
6 5 2 →2 CHNCl
6 5 2 →→ CH
6 5 CHNH
2 2 
3
→
HCl0C°
LiAlH
→4 CHCHNHCHCH
6 5 2 2 3

CH 3 CH 3 CH 3
  
1207. CHCH—CH—
3 2 CHNH
2 2 ,CHCHCH—
3 2 CHOH,
2 CHCHCH—
3 2 CHO, CHCHCH(CH)
3 2 3 2
A B C D

1208. HN—
2 —CH3

O O OH
COOH COOH
1209.
—CN

A B C

O O OH
NH2

D E
CH3

N—CH3
1210.
+ +
N N
CH3 I– CH3 CH3 OH– CH3 C
A B
CH3
CH3
+
+ N—CH3
N—CH3
I– OH–
CH3 F
CH3
E
D
N(CH)HBr
32 N(CH)32 N(CH)33 I N(CH)33 OH

1211. (a)

N(CH)HBr
32 N(CH)32 N(CH)33 I N(CH)33 OH E
A B C D
594 ProblemsinChemistry

NOH NH2 N(CH)33 I

Ph Ph Ph Ph
(b) Ph Ph Ph Ph

A B C D
CH3 CH3
+
N –
Br
H
1212. +N(CH)33
H
A N N+ C
H3C CH3 H3C CH3
B CH3
O O O
H H
+
N3 H2 NH2
1213. N
Pb/CaCO3

O O
H H H
– +
N N

1214.Hinsberg’s method: Addbenzenesulphonyl chloridetothemixtureof butylamineand

dibutylamineandfilterofftheprecipitatecontainingsulphonamides.Nowdissolvetheprecipitate
inaqueousKOHsolution.Sulphonamideofbutylaminewillcomeintosolutionastheirpotassium
saltleavingsulphonamideofdi-butylamineinsoluble.Filterthesolutionandtreatbothresidueand
filtrateseparatelywithdiluteacid.
H O 
   
CHCHCHCH—N —S —CH 

3 2 2 2 6 5
 
CHCHCHCHNH  CHSOCl O 
 →  Insoluble
3 2 2 2 2 6 5 2
(CHCHCHCH)
3 2 2 2 2 NH O 
  
(CHCHCHCH)
3 2 2 2 2 N—S —CH 6 5

  
O 
↓ KOH
K+
−
(CHCHCHCH)
3 2 2 2 2 N—SOCH+CHCHCHCH—N—
2 6 5 3 2 2 2 SOCH
2 6 5
Insoluble Soluble
+ +
dilute H dilute H
+ +
(CHCHCHCH)
3 2 2 2 2 NH 2 CHCHCHCHNH
3 2 2 2 3
Solutions 595

H H NO CH3 CH3
+ –
N I
N N N
1215.
–
N+ I
NH2 NH2 OH H3C CH3
CH3
A B C D
O H
CHCHCOOEt
2 2 N
1216. (a) N— (b)
N D
A C
CHCHCOOEt
2 2

(c) HN—CHCHCHCH—NH(E)
2 2 2 2 2 2

O O
HO +   NH3   Br2 CHCl
1217. (a) R —CN → R —C —OH → R —C —NH 2 → R —NH 2 →
3 3
Heat
RNC
HO
2 NaOH KOH

HO + HNO
(b) R — NC 
3
→ R —NH 2 →
2
R —OH →→
TsCl KCN
R —CN
HO
2

O
 
1218. (i) PhCHNH—C
2 —CH==CH 2 (ii) PhCHCOCHCl
2 2 (iii) ClCOOEt(iv) BrCHCHCOOH
2 2

1219. (a) (CHCHCHCH)

3 2 2 2 3B CHCHCHCHNH
3 2 2 2 2
A B
(b) PhNHCOOH PhNH 2 PhNHCONHPh
C D E
(c) CHNHCN
2 5 CHNHCHNH
2 5 2 2
F G
−
O O
 O
  − +
1220. HC—C
3 +CH—N
2 2 → CH—C—
3 CH—N
2 2 → CH—C
3  CH 2 +N 2
  
CHCl2 CHCl
2 CHCl(
2 B)

O– O
 +  
Also, ClCH—C—
2 CH—N
2 2 → ClCH—C
2 —CHCH+N
2 3 2
 A
CH 3
596 ProblemsinChemistry

CH 3 CH 3 CH 3 CH 3
   
+ –
1221. CH—C—
3 NHCHCH
2 3 CH—C—
3 –N— CHCHOH
2 3 CH—C==
3 CH 2
   C
CH 3 CH 3 CH 3
A B
CHCHN(CH)
3 2 3 2 (CH)3 3 COH.
D E
OH
NO 2  CH==CO
1222. (a) MeC ——CHOH
2 (b) RCHNMe
2 2 (c) CH==C—
2 CN 2
→ CH==C—CN
2
CHOH 
2 OCOCH 3
− Br
1223. (CH)3 2 CH—C— NH+OH
2
–
→ (CH)3 2 CH—C— NH →
2
– (CH)3 2 CH—C— NHBr
    –Br  
O O O

− – − ••
OH
→ (CH)3 2 CH—C— N—Br
••
–Br
→ (CH)3 2 CH—C —N •
•
→ (CH)3 2 CH—N==C==O
   
O O

HO
2→ (CH)3 2 CHNH+CO
2 2

O O O

KOH PhCHBr
1224. (a) O+NH 3 N—H 2 N—CHPh
2

O O O
+KBr OH – PhCHNH
2 2
HO
2

KMnO NH PO LiAlH4
(b) PhCHBr
2 →4 PhCOOH →3 PhCONH 2 →
2 5
PhCN → PhCHNH.
2 2
–
OH/Heat Heat

O O O
Heat aqueous PCC
1225. (a) +Cl 2
KOH
Cl O

H
N N
HN—CHCH—NH
2 2 2 2 H2
∆ Ni
N N
H
Solutions 597
O H
O NH N
O H2
(b) +NH(excess)
3
Ni
O NH N
[form(a)]
H

AROMATIC COMPOUNDS

1226. C2H5— —CH—CH3 C2H5— —C—CH3 C2H5— —C—CH3

OH O O
A Cl
B
C
O O

HOOC— —COOH —
[C— —C—OCH2CH2O]—
n

D E
COOH
O Cl
1227. (a) —CH CH—C—CH3 (b)
O
O2N COOH

Br Br COOH

(c) OH (d)
S
O OCH3

(e) (f)

NO2

–
(g) X : HNO/HSO
3 2 4 followedbyreductionwith NH/OH/Heat.
2 4
–
Y :Reductionwith NH/OH/Heat
2 4 followedbynitration.
598 ProblemsinChemistry

Ph –H+ +
1228. –H+
+
OH2 Product
+

Br

1229. NBS aq.KOH

CCl4 OH H+

CH3 CH3 CH3

+
Ph Ph + Ph
–H+ PhCH C—CH3

CH3

1230. CH3O— —C CHCH3 CH3O— —C—CH3 HO— —C—CH3

B O O
A C
Cl O

CH3O— —C—CH3 —O—C—CH3

D O E

O O
Ph Ph
PhCH2COCl Cl2
1231. (a)
AlCl3 AlCl3

Cl
Ph
N2H4
OH–/Heat

Cl
Solutions 599

OH
OH
CHO CH—CH3
H3O+
CH CH3Cl
(b) CH3
CH3MgBr AlCl3

PCC
Product

COOH
H2SO4 KMnO4 H3O+
(c)
Heat NaOH
HO3S
SO3H

AlCl3 HNO3
(d) +CH 3CH2CH2Cl
H2SO4

NO2

1232.
H3C—CH CH2OH H3C—CH CH2I

OC2H5 I
A B

CH3
H3C—CH CH2OH CHO

OH O
C D
Cl

CH3
CHO

O
E
600 ProblemsinChemistry

OH
C2H5ONa (CH3COO)2Hg NaBH4
1233. (a) PhCH2CH2CH2Br PhCH2CH CH2
H2O
PhCH2—CH—CH3
C2H5OH

OH
Pd/BaSO4 H3O+ CH3C CNa
Product Ph—CH2—C—CH3 PCC
PhCH2—C—CH3
H2
C C—CH3 O
Cl Cl
O
HNO3 NBS
(b) Mg
O2N— —CH2CH2OH Product.
H2SO4 ether CCl4

NO2
O

—C—Cl O
AlCl3
(c) +Cl 2 Cl— —C—
AlCl3
Cl

AlCl Mg Oxirane
(d) CH+Cl
6 6 2 →3 CHCl
6 5 → CHMgCl
6 5 → CHCHCHOH
6 5 2 2 PCC
→
ether HO +
3

O OH
  PCC
 HO + CHMgCl
CHCH—C
6 6 2 —CH
6 5 ← CHCHCH
6 5 2 —CH
6 5 ←←
3
← 6 5

I I

HNO3 AlCl3
(e) +I 2
(CH3)3CCH2COCl
C
SOCl2 O CH2

(CH3)3CCH2COOH

H3O+/Na2CrO4
B2H6/H2O2
(CH3)3CCH2CH2OH
NaOH
Solutions 601

O O

1234. (a) Ph Ph
Ph
O
NO2 O
X Y Z
O O O
–
(b) Ph—C—CH2 Ph—C—CH2—CH2—C—Ph Ph Ph
O
Z
O O

(c) Ph
Ph CN CHO Ph
X O
Y
Z

AlCl3 CrO2Cl2
CH3COOMe
1235. (a) —CH3 —CHO
CH3Cl Ac2O C2H5ONa
O O O
Heat
Br2
Product —CH CH—COOMe
AlBr3 O
O O
HOCH2CH2OH
(b) Ph AcOH
+KCN Ph CN H+/Heat O O
Ph CN
O
H3PO4 H3O+ CH3MgBr
Product Ph

O
O2N
HNO3 CH3COCl NaBH4
(c) Product
H2SO4 AlCl3
S S
602 ProblemsinChemistry

NO2 NH2 F

HNO3 Zn-HCl HNO2 HBF4

1236. (a)
H2SO4 0°C ∆

CH3COCl

NHCOCH3 NHOC—CH3 NH2

HNO2 H3O+ HNO3 CH3Cl H3O+

0°C H2SO4 AlCl3

NO2 CH3
F F F

HBF4 KMnO4 HNO2 HBF4

∆ NaOH 0°C ∆

NO2 COOH CH3

– H
O + F
(b) O2N— —F N
O
+
+ •• N—Et
–

Et
(Positivechargeat p-carbonactivate
thenucleophilicattack)
–
O F
+ H Et
N —N
O2N— +HF
O
–
+
N—Et Et

Et

O O O

(c) (i) AlCl3 OH

+ O CH3OH
Product
H+/Heat
O
Solutions 603

R R
(ii) + AlCl3
—COCl
R′ R′
O
O
C—Cl
(iii) AlCl3
+

CH3Cl HNO3
(iv) CH3— CH3—
Zn-HCl
AlCl3 H2SO4 —NO2 CH3— —NH2

COOC2H5 COOH

CH3CH2OH Ag2O
H3O+ CrO2Cl2
OHC— —NH2
H+
Ac2O

NH2 NH2
O

OH O—C—Ph OCOPh

H2SO4 KOH H3O+ PhCOCl HNO3

1237. (a)
∆ ∆ H2SO4

NO2
NO2 N2Cl

HNO3 Br2 Zn-HCl NaNO2 H2O

(b)
H2SO4 AlBr3 HCl/0°C boil
Br Br
O

O—C—Ph

PhCOCl

Br
604 ProblemsinChemistry

CH3 COOH

CH3Cl HNO3 KMnO4 H3O+ PhOH

(c) Product.
AlCl3 H2SO4 NaOH H+/Heat

NO2 NO2

NO2 NHCOCH3

HNO3 HNO3 H3O+

(d) Zn-HCl CH3COCl
H2SO4 H2SO4

NO2

NaNO2 NaNO2
Product
HCl/0°C Heat

NO2 NH2

HNO3 H3O+
(e) Zn-HCl CH3COCl HNO3
H2SO4 H2SO4

OH NO2

aq. KCN NaNO2 Zn-HCl H2O NaNO2

Product
HCl/0°C boil HCl/0°C

NO2
OH OH OH OH
Br Br dilute
Conc.H 2SO4 Br2 Br Br
(f) H2SO4
FeBr3 reflux

SO3H SO3H
NO2 NO2

Cl2 Zn-HCl NaNO2

1238. (a) +HNO 3/H2SO4
FeCl3 HCl/0°C
Cl aq
Product
KI
Solutions 605

Cl Cl

HNO3 Zn-HCl NaNO2 aq

(b) +Cl 2/FeCl3 Product
H2SO4 KI
HCl/0°C

NO2
NO2 NO2

Cl2 Zn-HCl NaNO2 aq

(c) Product
FeCl3(excess) HCl/0°C KI
Cl Cl
NHOAc NHOAc

NO2
Conc.H 2SO4 HNO3
HNO3 Zn-HCl CH3COCl
1239. (a)
H2SO4 Blocking H2SO4

SO3H
N2+Cl– NH2
Ph NO2 NO2 H3O+
PhLi NaNO2
LiCl+N 2 + Reflux
HCl/0°C
NO2
NO2 NH2
Br Br Br Br
Zn-HCl Br2 NaNO2
(b)
aqueous H3PO2
HCl/0°C

Br Br
COOH
NH2 NH2 NH2 NH2
(c) NaOH NaNO2(excess) H2O
CaO/Heat HCl-0°C Boil

NH2 NH2
O O HO OH

O OH
Tautomer
606 ProblemsinChemistry
H NH2 H NH2
+
N: CH3 N
1240. CH3 H2O
C O
_ –H2O
MeO MeO O
CH2CH2COOMe H2C
CH2COOMe
H NH2 H NH2
+
_ N +
N
+ CH
3
CH3
MeO H MeO
H HC
CH2COOMe
CH2COOMe
H H

N N
–H+ + –NH 3
CH3 CH3
MeO MeO H
CH2COOMe CH2COOMe

CHO HO +
Mg PCC
1241. (a) PhBr ether
→→ → →
2 3
PhCHOH
2 Product

CrOCl
(b) PhCH 3 2→
2
Product.
AcO2
Etard’sreaction
OH

NaOH H3O+
(c) +CHCl 3 Product
Reimer-Tieman
reaction
OH OH

ConcH 2SO4 AlCl3(excess) H3O+

(d) Product.
CH3COCl Reflux

SO3H
OH OH O

H2 H2CrO4
(e) Cl2 C2H5ONa
Ni Product
∆ C2H5OH
Solutions 607

O
PhMgBr H3 O+ PCC HCN H 3O +
(f) PhCHO Ph—C—Ph Product
O O

(g) O
AlCl3 H3O+ Zn(Hg)
+
HCl
COOH HOOC
O
HF

O
CH3 CH3 CH3

HNO3 HCl
1242. (a) Zn-HCl NaNO2 H2O
H2SO4
HCl/0°C Boil HCN/AlCl3

NO2 OH
CH3

H3O+

CHO
OH
SO3H SO3H OH OH

HNO3 KOH H3O+ LiAlH4

(b)
H2SO4
NO2 NO2 NH2

OH OH
Br
Br Br
Br2 Zn-powder
(c)
H2O Heat
Br Br
Br
608 ProblemsinChemistry
OH
OCOCH3 OCOCH3 OH

CH3COCl AlCl3 H3O+

(d)
Protection CH3CH2CH2Cl

OH OCH3 OCH3

ConcH 2SO4 KOH H3O+ (i)NaOH

(e) ConcH 2SO4
∆ ∆ (ii)CH 3Cl Blocking

OCH3 SO3H

CH3
KOH NBS H3O+ CH3Cl
Product
aq Reflux AlCl3

1243. PhCHBr+CHCl
2 3.

CH3 CH3 CH3

NO2
ConcH 2SO4 HNO3 H3O+ NaNO2
1244. (a) Zn-HCl
H2SO4
HCl/0°C
H2O
Product
SO3H Boil
CH3 CHO CHO CH3

CrO2Cl2 HNO3 N2H4

(b)
Ac2O H2SO4 OH–
NO2 NO2

H2O NaNO2 Zn-HCl

Product
Boil HCl/0°C
CH3

ConcH 2SO4 KOH H3O+

(c) Product
Heat
Solutions 609
NO2

HNO3 NaNO2 CuCl

(d) Zn-HCl
Product
H2SO4 HCl/0°C
(Excess) NO2

NO2

Zn-HCl NaNO2 CuCN

(e) Product
HCl/0°C
NO2
[from(d)]

NO2 NO2 NO2

Na2S NaNO2 KI Zn-HCl NaNO2

(f)
HCl/0°C HCl/0°C
NO2 NH2 I H2O
[from(d)] Product.
Boil

NO2 NO2

NaNO2 CuBr Zn-HCl NaNO2 KCN

(g) Product.
HCl/0°C HCl/0°C
NH2 Br
[from(f)]

CH3 CH3

HNO3 NO2 Br
Zn-HCl NaNO2
(h) Toluene CuBr
H2SO4
HCl/0°C
(excess)

NO2 Br
CH3Cl
Product.
AlCl3

NO2 NO2

HNO3 Br2(excess)
(i) Zn-HCl
H2SO4 FeBr3 Product
Br Br
610 ProblemsinChemistry
NH2 NHCOCH3

HNO3 Zn-HCl CH3COCl ConcH 2SO4

(j) H3O+ Br2
H2SO4 Protection FeBr3

SO3 H
Br NH2
NH2
Br Br Br Br
Br Br H3O+ KOH
NaNO2 CuBr
fusion
HCl/0°C

OH SO3 H
OH
NH2

HNO3 Zn-HCl CH3COCl HNO3 H3O+ Br2

(k) H2SO4
H2SO4 FeBr3(excess)

NO2
Br NH2
Br Br Br Br
NaNO2 CuBr NaNO2
Zn-HCl
HCl/0°C HCl/0°C

KCN
Product NO2 NO2

CH3 CH3 CH3

ConcH 2SO4 Br Br
Br2(excess) H3O+ KMnO4
(l)
FeBr3 reflux NaOH
H3O+
SO3H Product.
SO3H
NH2 I
Br Br Br Br
H3O+ NaNO2 KI
(m)
Reflux HCl/0°C aq

SO3H
[from(j)]
Solutions 611
CH3
CH3
NO2
Br2 NO2
(n)
FeBr3
[from(a)]
Br
CH3
CH3 CH3
NO2
SnCl2 NO2 NO2
(o) NaNO2 H2O
HCl/0°C Boil

NO2
NH2 OH
[from(h)]

CH3
CH3 CH3
NO2
NO2 CN
(p) NaNO2 CuBr Zn-HCl NaNO2 KCN
HCl/0°C HCl/0°C aq

NH2
Br Br
[from(o)]

HNO 3 Zn-HCl NaNO 2 Phenol

(q) Toluene H3C— —N2+Cl– Product
H2SO4 HCl/0°C

(r) H3C— p-cresol

—N2+Cl– Product.

[from(q)]

NO2 NH2

Na2S NaNO2 H3PO2 Zn-HCl CH3COCl HNO3

1245. (a) H2SO4
HCl/0°C
NO2
NH2

H3O+ CF3CO3H
Product.

NO2
612 ProblemsinChemistry
CHO

N2H4 Cl2 CrO2Cl2

(b) H3C— —Cl Product.
OH–/Heat AlCl3 Ac2O

NO2

Na2S NaNO2 CuCl

(c) Product
HCl/0°C
NO2

KCN H3O+ Zn-HCl NaNO2 KCN

(d) NO2 NO2 Product
∆ HCl/0°C aq

Cl CN

Br

CF3CO3H Br2
(e) H2N— —CH3 O2N— —CH3 O2N— —CH3
FeBr3

Br

Zn-HCl
H2N— —CH3

CH3 CH3

NaNO2 H3PO2
(f)
HCl/0°C
Br Br

NH2

NO2 NO2 O
CHO CH
(g) H+
O Zn-HCl NaNO2 KCN LiAlH4
HOCH2CH2OH
HCl/0°C aq
CH2NH2
CHO
H3O+
Boil
Solutions 613
NO2 NHCOCH3 NHCOCH3

CH3Cl H3 O+
(h) Zn-HCl CH3COCl
AlCl3

CH3
NO2

KMnO4
NaOH/Heat

COOH
CH3 CH3 CH3 CH3

HNO3 Zn-HCl CH3COCl HNO3 H3O+

(i)
H2SO4 H2SO4
NO2

NO2 NHCOCH3 NH2

CH3

CF3CO3H

NO2

NO2

NH2
NH2

Br2-H2O
Br Br Br Br
(k) NaNO2 H3PO2
HCl/0°C

Br Br
614 ProblemsinChemistry
CH3 CH3 COOH

CH3Cl HNO3
NO2 NO2
1246. (a) KMnO4
AlCl3 H2SO4 NaOH/Heat

NO2 NO2
CONH2

NO2
NH3
∆

NO2
NO2 NH2

Br Br
HNO3 Zn-HCl Br2 CF3CO3H
(b)
H2SO4 H2O

NO2
Br
Br Br

Br
NO2 NO2 NH2

HNO3 Zn-Hg
(c) Cl2 CH3COCl
H2SO4 FeCl3
Cl Cl
NH2

Br2 H3O+
FeBr3
Cl
Br
Solutions 615
Cl Cl

(d) AlCl3 NO2

HNO3
+Cl 2
Excess H2SO4

Cl Cl
C2H5 C2H5 C2H5 C2H5 C2H5

SO3H CN COOH
1247.

A B D E
SO3H
C
O
COOH
O
COOH
F
G O

Mg CH2O H3 O+
1248. (a) H3C— —Cl H3C— —CH2OH
Ether

OMe
Br
(b) KNH2
OMe

NH2

CHO CHO CH3

AlCl3 Cl2 N2H4/OH–

(c) +CO+HCl AlCl3 Heat
Cl Cl
616 ProblemsinChemistry
NO2 NH2 NHCOCH3
HNO3
(d) Zn-HCl CH3COCl ConcH 2SO4
H2SO4

NH2

HNO3 H3O+ NO2

H2SO4 Warm

NO2 NH2 NH2 Br

Br Br Br Br
Na2S Br2 NaNO2 CuBr
(e)
FeBr3 HCl/0°C

NO2 NO2 NO2 NO2

NO2
Zn-HCl CH3 COCl HNO3 H3 O+
(f) H3C— —NO2 H3C— —NHCOCH3
H2 SO4

NO2
NaNO2 H3 PO2
H3C—
HCl/0°C

OH
CHO CHO
Zn CO/HCl HNO3
(g)
Heat H2SO4 H2SO4
NO2

CH3 CH3

N2H4 Zn-HCl NaNO2 H2O

OH–/Heat HCl/0°C boil

NO2 OH
Solutions 617

O O O
     
1249. (a) Ph—C —CH
2 5 (b) CH—C
2 5 —OEt (c) CH—C
6 5 —CH 3 (d) CHCH==CH—COOEt
6 5

COCl AlCl3
1250. (a) C6H6 + Zn(Hg)
HCl

O
AlCl3 Zn(Hg)
(b) C6H6 + Cl HCl

O O O

(c) + O+AlCl HF
3

HO—
O
O O
Zn(Hg)
HCl

AlCl3 NBS C2H5ONa

(d) +C 2H5Cl
CCl4 C2H5OH

Cl O OH
AlCl3 Mg H3O+
(e) +Cl 2
Ether

O OH

AlCl3 NaBH4
(f) +CH 3COCl

OMe N NHCOCH3 OMe

Br Cl Br
1251. (a) (b) (c) (d)
COCH3

NO2 Br COOCH3
618 ProblemsinChemistry
CH3 CH3 CH3
CH3
NO2
Conc.H 2SO4 HNO3 NO2
1252. (a) dilute
H2SO4
H2SO4
(Heat)
SO3H SO3H
NO2 NO2 NH2

HNO3 Br2 Zn-HCl

(b)
H2SO4 FeBr3
Br Br
CH2CH3 CH2CH3 Br—CHCH3

C2H5Cl HNO3
(c) Br2
AlCl3 H2SO4 hν

NO2 NO2
COCH3

aq PCC
KOH

NO2
COCH3 COCH3 CH2CH3

CH3COCl N2H4/OH–
(d) HNO3
AlCl3 Heat
H2SO4
NO2 NO2

NO2 NH2

(e) Zn-HCl

[from(d)]
Solutions 619
NO2

HNO3 Cl2
(f)
H2SO4 AlCl3
Cl
CH3 CH3

H+ NO2+
—N —N—CH3 —N—CH3
1253. + +

H O2 N H
(metadirecting)
NH3
Product.
O
O

AlCl3 NaBH4 H2SO4

1254. (a) + Cl
Heat

B2H6 PCC
Product.
OH–/H 2O2

NO2 NO2 NO2

HNO 3 Na2S
(b) FeSO 4
H2SO4 H2O2
Heat NO2 NH2 NO
CH3 COOH

CH3Cl(excess) KMnO4
(c)
AlCl3 NaOH/Heat

CH3 COOH
CHO CHO CH3

O
CO/HCl Cl2 Zn(Hg) Mg
(d)
AlCl3 AlCl3 HCl Ether
Cl Cl
620 ProblemsinChemistry
CH3
O
H3O + Mg SOCl2 H3O +
Ether
CH3 OH

OH
NO2 NH2

HNO3 Br2 Zn-HCl

(e)
H2SO4 FeBr3
Br Br
CH3 CH3 CH2Cl

CH3Cl Br2
(f) Cl2
AlCl3 FeBr3
hν

Br Br
O O

AlCl3 HNO3
(g) +CH 3COCl
H2SO4

NO2
CH2 CH3 CH2 CH3

AlCl3 Conc.H 2SO4 HNO 3

(h) +CH 3 CH2 Cl
H 2SO4

SO3 H
CH2 CH3

NO2
C2H5ONa Cl2 H3O+
Product
C2H5OH hν Heat

SO3 H
Solutions 621
Br Br

(i) FeBr3 Conc.H 2SO4

+Br 2

SO3H

NO2 NH2

HNO 3 CH3COCl CH3Cl H 3O+

(j) Zn-HCl
H2SO4 AlCl3

CH3
N

CH3I

CH3
O O

1255. (a) (b) (c)

X X
N
X
OH O

(d) (e)

X X
O CH3 Br

NO2 Cl CH3
1256. (a) (b) (c) (d) (e)
Br Cl

NO2 OCOPh
622 ProblemsinChemistry
OD OH

H2O
1257.
D D

NO2 NO2
COOH

CH3Cl KMnO4 HNO3

1258. (a)
AlCl3 NaOH/Heat H2SO4
Heat NO2 NO2

HNO 3 Zn-HCl NaNO 2 CuCN

(b) H3 C— H3 C— —CN
H 2SO4 HCl/0°C

H 3O +
Product
CH3

NO2
CH3Cl HNO3
(c)
AlCl3 H2SO4 (Heat)

NO2
O
O
AlCl3
(d) + Cl OH

NaBH 4

CH3 COOH
AlCl3 KMnO 4 HNO 3
(e) +CH 3 Cl
NaOH/Heat H2SO4

COOH
NH 3
Product
Heat

NO2
Solutions 623

AlCl3 H2
(f) + —Cl Product
Pt

O
OH O O OH

OH (b)
1259. (a) (c)

O COCH3

CHO
AlCl3 C2H5C CNa H3O+
1260. (a) +CO/HCl

OH

N2H4 PCC C C—C2H5

C C—C2H5
OH–/Heat

Pd-BaSO4
Product

O
O

AlCl3 Zn(Hg) HF
(b) + O HCl
HOOC HOOC
O O
CH3Cl
AlCl3
CH3
O

O
Cl AlCl CH3MgBr H3O+
(c) PhH+ 3
Ph—C—CH2CH3 Product.
O
624 ProblemsinChemistry

OH OMe O NH2

CH3
1261. (a) (b) (c) (d)

HOOC

Cl SO3H NO2
COOH COOH

CH3Cl KMnO4 Br2

1262. (a) FeBr3
AlCl3 NaOH/Heat
Br

(CH3)2CHOH SOCl2
Product

O O O

AlCl3 HF
(b) + O

HOOC
O O
N2H4
Product
OH –/Heat

CH3

CH3Cl Cl2 Mg
(c) CH3 — —CH2 Cl
AlCl3 hν ether
(excess) O
H3O +
CH3 Product
NO2
O
HNO3 Cl2 Mg
(d)
H2SO4 AlCl3 ether
Cl
NO2 NO2

H3O+ Ag2O

OH CH2COOH
Solutions 625
O

AlCl3 AlCl3 HF Zn(Hg)

(e) +CH 3 Cl
O HCl
HOOC
O

H+ NaBH 4
Product
Heat

+ H
I
1263. +I + I Cl–

OH C6H6 H+
1264. +HF CH2 CH—CH2 +
–H+
Allylalcohol

C6H6 +
Product
–H+

COOH

OH
CH3
1265.
H3C—C

CH3
Cl

AlCl3 HNO3 Zn-HCl NaNO 2 CuCN

1266. (a) +Cl 2 Product.
H2SO4 HCl/0°C

CHO CHO CH3

AlCl3 HNO 3 N2H4

(b) +CO+HCl
H2SO4 OH –/Heat
NO2 NO2
626 ProblemsinChemistry

NO2

HNO 3 Cl2 NaNO 2 CuBr

(c) Zn-HCl Product.
H2SO4 AlCl3 HCl/0°C
Cl
CH3 CH3 COOH

KMnO 4 Sn/HCl NaNO 2

CH 3Cl HNO 3
(d) HCl/0°C
AlCl3 H2SO4 NaOH/Heat
H2O
Product.
NO2 NO2 Boil

CH3

Sn-HCl NaNO2 CuCN H3O+

(e) Product
HCl/0°C

NO2 [from(d)]

NO2 NHCOCH3 NHCOCH3

NO2
HNO 3 CH3COCl HNO 3
Zn-HCl
(f)
H2SO4 H2SO4
Heat

NO2
HBF 4 NaNO 2 H3O+
Product
Heat HCl/0°C

NO2 NH2

HNO3 NaNO2
(g) Na2S
H2SO4 HCl/0°C
Heat NO2 NO2

OMe OH

H2O
LiAlH4 CH3Cl KOH
Boil
NH2 NO2
Solutions 627
I I

(h) HNO 3 HNO 3 Sn-HCl NaNO 2

+I 2
H2SO4 HCl/0°C

NO2 I

H2O
Boil

OH

NO2
NO2
1267. (a) (b)
N
C6H5S
NO2
NO2

NO2 NO2 Ph

NHPh N—Ph
(c) (d)
O2N NO2 O2N NO2

CH2OH CH2OH
OMe
CHO (b)
OMe
1268. (a)

A B O O

OMe OMe OMe OMe OMe

(c)

HO HO O
O OH

E F G H I
628 ProblemsinChemistry

CH2 OH
CH2 O–
OMe
(d) OH OMe
O–

OMe OMe OMe

J K L
NO2

–
(e) CH(COOEt)2 Br CH(COOEt)2
M
NO2
N
(f) NaH/CHI(excess)
3 LiAlH 4 Br2 / FeBr 3
O P Q
OMe OMe OMe OMe

1269. (a)

A
NO2 NH2 N2Cl

B C D

(b) O2N O N

O2N E
I I

(c) H2 N NO2 O2 N I

I I
G H
Br Br Br

(d) CH3 CH2 O NH2 CH3 CH2 O N2 Cl CH3 CH2 O

I K
J
Solutions 629

(e) HO N2Cl HO I

L M

(f) H2N CH3 CH3 N2Cl

CH3 CH3
N O

CH3 CN CH3 COOH

CH3 CH3
P Q
CHO CHO
CHO CHO

1270. (a)
N2Cl Cl
NO2 NH2
C D
A B
N2HSO4 OH

(b)
MeO OMe MeO OMe
E F
CH3 CH3 CH3

H2N NH2 N2Cl N2Cl HO OH

(c)

G H I
COOH
(d) N N N (e) Noreaction(L)
N2Cl
J COOH K
630 ProblemsinChemistry

CH3
(f) N
N N CH3
H3C +
CH3 P
CH3 O
M
Br

CH3 CH3 CH3 COOH

1271.
CH3 Br CH3 CH3 COOH
A C D
B
O

COOH
N

N
Br COOH
E G
O
F

OMe OMe OMe

1272.
Br
A B C
O O OH
O O

OH OH
1273.
O OH OH
A B C
CHO

OH OH
D E
O CH3

1274. H3C— —C—O—CH—CH 2CH3 H3C— —COOH

OH O
A B C D
Solutions 631

COOH
1275. Br

COOH
A B
C
COOH COOCOCH3
COOH
O

1276.
OH O CH3
OMe
B C
A
COOH COOH COOH

Br Br

OH OH OH
D F
Br
E
O

C—OC2H5
CH3CH2OH CH3CHO C6H5COOH
1277. C D
B
A
1278. (a) Aromatic,cyclicandfullyconjugatedwithsix π-electrons.
(b) Antiaromatic,cyclicandfullyconjugatedwith 4π-electrons.
(c) Non-aromatic,cyclicbutnotfullyconjugated.
(d) Antiaromatic,cyclicandfullyconjugatedwith 4π-electrons.
1279. Conjugatebaseof A invokearomaticcharacterinthemiddleringtherefore, deprotonationof
benzylicHin A isfavoured.Ontheotherhandconjugatebaseof B doesnotbringanystabilityby
aromaticitydeprotonationofbenzylicHisnotasfavouredasincaseof A.
CH3
H3C H
s
–H+

A Aromaticanion
632 ProblemsinChemistry
CH3
H CH3
–
–H+

B non-aromaticanion

1280. (a) +
Br Br
OCH3

OCH3 OCH3
(b) + +
NH2

NH2 NH2
O

H H H
(c) + (d)
O O O O

NO2

NO2
(e) (f)

CH3O Cl

NO2
O

O
CH3
(g) (h)

O2N
Solutions 633

CHO

(i) CHO (j)

O
I

1281. Nitrationofbenzeneproceedsbythefollowingmechanism:
O O O
      +
N •• +H—O—S —OH N + +HSO –4 O==N= =O
O OH
O – + O—H   − + 2 nitroniumion
O
–
O—SO3H
O H H
+
H
Slow
+N + NO2 NO2 NO2
Ratedetermining + +
O step
Resonancestabilized σ-complex
NO2
fast

H
NO2
+
Reactionenergydiagram:
Thereactionproceedsat same
rate for both benzene and
Energy

hexadeutrobenzenesinceC—H
bondcleavageisnot occurring CH
6 6 NO2
inratedeterminingstep. HNO3
HSO
2 4

Reactioncoordinate
634 ProblemsinChemistry

1282. Sulphonationofbenzeneproceedsbythefollowingmechanism:
O O O

O S—O– S—OH S+
+ H+
S HO O –H2O O
O + +
O
O O
H
S S
C6H6 HSO4–
O + O
(diphenylsulphone)
O O

C
CH3COCl CH3 Na/NH
3 O3
1283. Products
AlCl3 t-BuOH (CH3)2S

1284. (a) CHCOClAlCl

3 / 3 ,Br 2 /FeBr 3 ,(b) PCCCHCl/ 2 2 , NBSh/ ν,
(c) HRhPressure,NaIO
2/ / 4 ,(d) CHCOClAlCl
3 / 3 ,HNOHSO
3/ 2 4,
(e) (CH)3 2 CHCOClAlCl
/ 3 , NaNHEtOH
/ 3/ , Zn(Hg)HCl
/ ,
(f) NBSh/ ν, Mgether
/ , CHO,PCC(
2 g ) Br2 /FeBr 3 ,HNOHSO
3/ 2 4.
1285. Thereactionwill beslower withacetophenonethanwithbenzeneastheacyl groupisa
deactivatinggroupinelectrophilicaromaticsubstitution.
O O– O– O–

+ +
Acetophenone
Asshownabove,electronwithdrawing (  R) effectofacylgroupdecreasestheelectrondensity
+
fromthearomaticringmakingitlesssusceptibleforattacktoanelectrophile( Br inbromination
reaction).
Also, acyl group, byresonance, bringspositivechargeonorthoandparapositions, hence,
meta-positionsarerelativelyricherinelectronscomparedtotheortho/parapositions. Hence,
electrophile,ifattacksatall,itattacksatmetapositionsonly.
1286. Themechanismofsubstitutionreactionis:

Cl OCH3 +Cl –
– –
N OCH3 N Cl N
l l OCH3
Solutions 635
Onthebasisof abovemechanism, it canbeconcludedthat theorder of reactivitywill be:
<
A C B < .
Thereasonfortheaboveorderare: Forthepyridiniumsalt,oneoftheresonanceformsbearno
charge.Thiswillbeastable,neutralspeciesandtheactivationenergyis,accordingly,lowrelative
toothers A and C.

– –
–
+OCH 3 OCH3 OCH3 Cl
+ +
N+ Cl N Cl N Cl N OCH3
Cl–
CH3 CH3 CH3 CH3
stable,neutral
species

+
N OCH3

CH3
Inthecaseof 3-chloropyridine, thenegativechargeonintermediatecan’t bedelocalized,
therefore,thisreactionwouldbeexpectedtobeslowerthan4-chloropyridinewherethenegative
chargeisdelocalized.

Cl – Cl Cl Cl
–
+OCH 3 OCH3 OCH3 OCH3
+ – –
N N N N
Cl
Cl OCH3 Cl OCH3
– –
OCH3
l l
N N N
–
(morestable)

H
+
C6H6
+ +
1287. O l
l +H O—H OH +
HO
HSO4–

– +
HSO4 H+
–H2O
+

H OH
636 ProblemsinChemistry
O
HO CN

AlCl3 HCN NaH

1288. +CH 3COCl
CH3CH2Br

NH —NH2 CN
O O O
CH3COCl LiAlH4

H
O
CH3O N CH3O
l l
H
1289. C
CH3 H OH
HN
CH3O CH3O
H
CH3
CH3O CH3O

+ + H+
NH HN
l
l OH2
CH3O CH3O
CH3 H H
CH3
CH3O +
–H+
Product
NH
CH3O
H
CH3

1290. (a) Antiaromatic,fullyconjugated,planarwith4 π-electrons.

(b) Aromatic,planar,fullyconjugated,6 π-electrons(twofromringoxygen).
(c) Non-aromatic,planarfullyconjugated, 7π-electrons(onefromradical).
(d) Non-aromatic,notfullyconjugated.

Cl Cl
1291. (a) + (b)

O2N NO2

OCH3
Solutions 637

O
(c) (d)
O
HO3S NO2 O2N

OCH3

(e) (f)

COOH

1292. (a) (b) Br O —NO2

COOH
O2N
O NO2 NO2 NO2

Br NH2
(c) (d) + +

OCH3 NH2

SO3H NH2
NO2

(e) (f)
OCH3
NO2

1293. The σ-complexesformedbyattackatortho,paraandmetapositionsareasfollows:

CH3 CH3 CH3 CH3
+ +
HNO3
H2SO4 NO2 NO2 NO2

+ H H H
2° 2° 3°
638 ProblemsinChemistry
CH3 CH3 CH3
+

para
attack
+ +

H 2° NO2 H 3° NO2 H 2° NO2

CH3 CH3 CH3

+
meta +

attack NO2 NO2 NO2

H H + H
2° 2° 2°

1294. (a) CHClAlCl

3 / / ν
3 ,NBSh,CHONa 3 ,
(b) CHCOClAlCl
3 / 3 , Fe(Hg)HCl,
/ NaNHEtOH
/ 3/ ,
–
(c) HSOHOheat
2 4/ 2 / , KMnONaOHheat
4/ / ,
(d) CH(CH)
3 2 2 COClAlCl/ 3 , / ν
NBSh,CHONa,RhH
3 / 2 /∆.
1295.  B(OH) 2 isametadirectinggroupduetofollowingresonancephenomena:
–
HO OH HO OH HO OH HO OH
– – –
B B B B

+ +

Theaboveresonancestructuresrevealsthat  B(OH) 2 withdrawelectronsfromortho/para

positionsdeactivatingtheringforattackofelectrophile. Even,ifthecompoundissubjectedto
electrophilicattack,itoccursatmetaposition.
CH3 CH2Br

Cl2 CH3Cl NBS NaN3

1296. (a) Product
AlCl3 AlCl3 hν SN2

Cl Cl
Br

SO3H
H2SO4/H2O Br2 CH3COCl
(b) Product
disulphonation FeBr3 AlCl3
Solutions 639
H
–
OH
1297. C6H5—CH2—Br C6H5—C—O—S— C6H5CHO+ S
+ E2
CH3 CH3
S O H

1298. +H +
+

–H+
Product

+
H
CH3 CH3 CH3 CH3

+
–H+
1299. +D +

+
D+
H D H 3° D
D
CH3 CH3 CH3

D H +
H
–H+
D D
+

D D D
D+
CH3 CH3

D D D D
H –H+
+

D D
640 ProblemsinChemistry

1300. Benzoicacid.
Themechanisminvolvesadditionofelectronstoformaradicalanioninthefirststepas:
COOH COOH COOH COOH

l
l

EtOH Na
+e
l

–
l l –
COOH COOH
–
l l

EtOH

Stabilizedby
electronwithdrawinggroup
O O O

Br2
AlCl3 H2O OH AlCl
1301. + O 3

O O
O
O
C
Zn(Hg) OH
OH
HCl
CH3Li(2mol)
H 2O
Br Br

O NH2OH
Product

Br
Br NNH2 Br O

Cl
1302. (a) (b) (c) (d)

Br

CN OH
enantiomers
Solutions 641
Br Br Br

NO2
Br2 CH3COCl HNO3
1303. (a) FeBr3 AlCl3 H2SO4

O O
Br Br Br

OH N2+Cl– NO2
H2O/∆ NaNO2 H+ Fe EG
HCl/0°C H3 O+ HCl H+

O O O

O
O O O O

EG HNO3 H3O+
(b)
H+ H2SO4
O2N
(Alternatively) (o/pdirecting) O
Zn(Hg)/HCl

HNO3 CrO2Cl2
H2SO4 Ac2O O2N
O2N
O

O2N
(Etardsreaction)

1304. (a) (b) + (c) (d)

N
642 ProblemsinChemistry

NO2

Cl

Br
NO2
1305. (a) (b)

O2N

NO2 OCH3

(c) COOH (d) (e)

OH

D NH2
Ph D D
1306. (a) (b)
OH (c)
HO D D
D

OH OH OH

CF3 O
(d) (e) CHO (f)
+CH 3OH OCH3
CHO
N

1307. (a) (CH)3 2 CHCOClAlCl

/ 3 ,PhP==CH
3 2,
(b) OZn–HO,Zn(Hg)HCl
3/ 2 / ,
+
(c) Br2 /FeBr 3 ,HNOHSO,
3/ 2 4 MgetheroxiraneHO,
/ / / 3 PCCCHCl
/ 2 2,
(d) Alternative: CHClAlCl
3 / 3 , HSOHNO,NBSh
2 4/ 3 / ν, MgetherCHO,
/ / 2 PCCCHCl
/ 2 2.
CHOCH==PPh
1308. 3 3 CHCH==CHOCH
6 5 3 CHCHCHO
6 5 2
A B C
1309. Only B, D and G areformed.Inordertorationalize,weneedtoseethesigmacomplexineachcase.
Insigmacomplexleagingto C, E, F, H,oneoftheresonanceformplacesthepositivechargeon C1 ,
whichisthecarbonbearingnitrogroup.Theseproductsarethenalldisfavoured.
Solutions 643
NO2 NO2 NO2 NO2

+
+

O2N + NO2
σ-complexof B σ-complexof D σ-complexof G

Innoneoftheresonanceformsoftheabove σ-complexitispossibletoplacepositivecharge(+)on
carbonbearing  NO 2 group.
SigmacomplexofremainingfourplacespositivechargeonC-bearing  NO 2 inoneoftheir
resonanceform:
NO2 NO2 NO2

+
O2N O2 N O2 N

+
+

σ-complexof C NO2

O2N +

notfavouredresonanceform

O O O
O O
H H NH3 Pd/C
EG
1310. (a) ∆ H2
H+

NH2
O
H
H3O+
Product O

CF3 CF3 CF3

HNO3 Fe/HCl;NaNO 2 C6H5N(CH3)2

(b) Product
H2SO4 HCl/0°C
NO2 N2+Cl–
644 ProblemsinChemistry

1311. Br2 +FeBr 3 → Br +FeBr 4

+ –

OH OH OH

H3C CH3 H3C CH3 H3C CH3

+Br +
+

Br
O S O
SO3H Br
l
l OH +HBr+SO 3
Br–

1312. (a) I,(b) I,(c) I,(d) I,theyareallaromatic.

1313. (a) III<II<I,(b) II<I<III,(c) III<II<I.

NO NO NO NO

+ +
meta
1314. +E + H H H
attack
E E E
+
NO l
l N O +N O

+
para
+E +
attack
+
E H E H E H
σ-complexisstabilizedby+ R effect
of—NOfunctionalgroup.

HNO3 NBS
1315. (a) +CH 3CH2Cl
H2SO4 hν
NO2
C2H5ONa
Product
C2H5OH

Cl AlCl
3
(b) + N2H4
Product
NaOH/∆ H2SO4
O
O
Solutions 645
CH3 CH3 CH3

NO2
AlCl3 Cl2 H2SO4
(c) +CH 3Cl FeCl3 HNO3

Cl Cl
COOH

NO2
KMnO4
NaOH/∆

Cl
OH
CH3 CH3
OH
CN OH
1316. (a) (b) (c)
O
OCH3
(d) (e) OH— N N

CH3Cl H2SO4 NaOH H3O+

1317. (a) Product
AlCl3 SO3/∆ fusion

HNO3 Br2 SnCl2

(b)
H2SO4 FeBr3 HCl

AlCl3 N2H4 Br2

(c) + Cl
NaOH/∆ FeBr3
Br
NBS/hν C2H5ONa
Product
C2H5OH
646 ProblemsinChemistry

3 +
E+ H H H
1318. 2 attackatC-2 +
O O E O E O E
1 Threeresonancestructures +

E E
+
E H H
attackatC-3 +
O O
+
Tworesonancestructures,
lessprobable.

Therefore,electrophileismostlikelytoattackatC–2position.
+
NO2 NHCOCH3 N2Cl–

Zn-HCl CH3COCl CH3Cl H3O+ NaNO 2

1319. (a)
AlCl3 HCl/0°C

CH3
H2O
Product
∆

OCH3 OCH3 O O

Na/NH3 H3O+ HCl CH3Cl

(b)
EtOH Na/∆
Cl
O

CH2 PPh3
Product

OH
NBS Mg CH2O H3O+
(c) PCC
hν ether
CH2Cl2
H
NH2
CH3I(excess) NH3
Product Pd-C/H2
O
Solutions 647

1320. (a) II,(b) I.

1321. (a) III<I<II,(b) I<II<III,(c) I<II<III.

Cl
AlCl3 Zn(Hg) CH3Cl
1322. (a) + Product
HCl AlCl3
O
NHCOCH3

HNO3 Zn CH3COCl H3O+

(b)
H2SO4 HCl H2SO4 H2O

CH3CH2ONa NBS/hν —
Product H2N—
CH3CH2OH

CHO CHO
Cl

CrO3 O EG
1323. Ac2O orAlCl 3 H+

O O O O
CHO CH

H3O+ H2/Pd (CH3)2NH

Zn
Product
HCl

N
N O
CH3 CH3
CH3 CH3

CN CN CN
+
E+
1324. H H
orthoattack
E E
+
648 ProblemsinChemistry

CN CN
+
+
H H
E E
destabilizedbyCN
CN +
CN
+
E
meta +
attack
H E H E

Metaattackof E avoidestheelectronwithdrawingeffectof CN groupaspositivechargecan’t

+

interact directlywithCNgroup. Therefore, metaattackisfavouredoverortho/paraattackof

electrophile.

1325. (a) (b)

N
A
H
B

MeO COOMe OMe

COOMe
O
1326.
l l +
NH N O–
H NH2
NH2

OMe OMe
COOMe
COOMe H+
–H2O
N N OH

NH2 NH2

OMe OMe H
H+ COOMe –NH3 COOMe

+
N N
+
NH3
Solutions 649

OMe OMe
COOMe H+ COOMe –H+
H
N+ N

OMe
COOMe
+
NH3 +NH 4
l l
N

Mg CHO PCC
1327. (a) PhBr →→ →
2
Product
Et 2O CHCl
2 2

NBSh ν aq.NaOH PCC

(b) Ph  CH 3 →
/ →→
Product
CCl 4 CHCl
2 2
CrO
Ph  CH 3 → Ph  CHO
3
or
AcO2
(Etard’sreaction)

OH
CHCl3/NaOH
(c) Ph—OH
Reimer-TiemannReaction
CHO
OH OH

H2SO4 CH3COCl H3O+

(d) HO—
Reflux

O
SO3H
CH3

OCH3 OCH3 OH O
H2/Ni H3O+ PCC
(e)
Heat Reflux CH2Cl2

O
Cl2 EtONa
Product
heat EtOH
Cl
650 ProblemsinChemistry

OH OH
PhMgBr HO +  HSO 
(f) Ph—CHO →→→→
PCC3 HCN
Ph—C— Ph 2→4 Ph—C— Ph
HO
CHCl
2 2  2 
CN COOH

O O

AlCl3 Zn(Hg)
(g) + O
HCl
COOH COOH
O HF

(h) H+ Heat
+
NHNH2 O N

COOH
1328. (a) (b) (c)
Br COOH
Br CN

(d) (e) (f)

Br

(g) (h)

SO3H
Solutions 651
O O
O
AlCl3 Cl2
1329. (a) +
Cl AlCl3
Cl

HNO3,H 2SO4 N2H4

Product
OH–/heat
Cl
OH

Br
Br2 Mg (i)CH 3CH2CHO H2SO4
(b)
FeBr3 Et2O (ii)H 3O+ heat
O

H3O+ NaBr mCPBA

Product

Br
+
NH3
1330. (a) (b) + (c)

Br

NO2
Br

NO2

HNO3 Fe Ac2O HNO3 H3O+ NaNO2

1331. H2SO4 HCl/0°C
H2SO4 HCl

O2N— —N2+Cl–

I
OH OH
H2SO4 NaOH H3O+ CCl4 H3O+
SO3 fusion NaOH
COOH
(I)
Product
652 ProblemsinChemistry
O O

Br2
1332. (a) CrO2Cl2
FeBr3
Ac2O
MeO (Etard’sReaction) MeO MeO

Br
(onlyproduct)

Ph3P CH2

MeO

Br
O

Ph3P CH2
(b) Product
1equiv.

O
OH
N

CH3COCl H2NOH LiAlH4

(c) C6H6 Product
AlCl3

(d) NBS NaOH PCC CH3CH2CH PPh 3

Product
hν CH2Cl2

1333. (a) Non-aromatic,(b) Aromatic,(c) Aromatic, (d) Nonaromatic,(e) Aromatic,(f) Aromatic.

1334. Since,bothringsarearomaticwiththefollowingresonancestructure:

⊕
s

boththeringsarenowaromatichencedoublebondcharacterbetweenthe
ringsareveryless,thereforelessbarriertorotation,

1335. (a) Deactivated,(b) Deactivated,(c) Activated,(d) Activated,(e) Deactivated,(f) Activated.

Cl2 H2SO4
Product
1336. (a) AlCl3 HNO3
Solutions 653
Br O

Br2 Cl Zn(Hg) NBS/hν

(b) Product
FeBr3 AlCl3 HCl CCl4

Cl H2SO4 Zn(Hg)
(c) Product
AlCl3 SO3 HCl

O
O

1337. (a) (b) (c)

O2N

Br O
O

O
COOH

(d) (e) (f)

CH3

NO2 NO2 CHO

NH2 O OH

1338. (a) (b) (c)

O2N NO2

O Br

NHCH2CH3 O
N
O2N NO2 O—C—Ph
(d) (e) (f)
Cl

NO2 CF3
654 ProblemsinChemistry

Cl

HO—
(g) (h)

OCH3

CH3
O
l
NHCH3 O +N O N—CH3
H O–
l

–
1339. O2N + O O2N + O2N + O–
N N –H+ N
O O– O–

NO2 NO2 NO2

O–
N
O2N NO2 H2O
Product

NO2
1340. (a) Non-aromatic,(b) Non-aromatic,(c) Antiaromatic,
(d) Antiaromatic,(e) Antiaromatic,(f) Aromatic,
(g) Aromatic,(h) Aromatic.
1341. Since,doublebondisinresonanceandinvolvedinaromaticityas:

Here,boththeringsarearomatic,therefore,thisresonanceformis
amajorcontributor. Duetothisresonancestructurethedouble
⊕
s bondbetweenthetworingshasacquiredsignificantsinglebond
charactergivinglowenergybarriertorotation.

CH3Cl(excess) KMnO4 H3O+

1342. (a) C6H6 AlCl3
CH3— —CH3 Product
NaOH/Heat
Solutions 655

NO2 NH2 NHCOCH3

HNO3 Zn CH3COCl
(b)
H2SO4/heat HCl excess
NO2 NH2 NHCOCH3

NO2 NHCOCH3

CF3CO3H H3O+ heat NaNO2 Sn HNO3

HBF4 HCl H2SO4
NO2 NHCOCH3

F F
CHO CH3

CO HNO3 Fe/HCl NaNO2 H2O

(c) heat
Product
HCl/AlCl3 H2SO4 HCl
NO2 NH2
NHCOCH3 NHCOCH3

HNO3 Fe CH3COCl H2SO4 HNO3

(d)
H2SO4 HCl SO3 H2SO4

SO3H
OH N2+Cl– NH2 NHCOCH3

NO2 NO2 NO2 NO2

H2 O NaNO2 dil.HCl
boil HCl/0°C

OH
SO3H
NH2
Sn
HCl

NHCOCH3 NHCOCH3

HNO3 Fe/HCl CH3COCl H2SO4 dil.HCl CF3CO3H

(e)
H2SO4 SO3

Product
SO3H
656 ProblemsinChemistry

O O
CHO
CH

(CH3)2C CH2 HNO3 Fe/HCl

(f) CO/HCl EG/H+
H2SO4
AlCl3 HF

O O
C H

N2H4 dil.HCl H2O NaNO2

NaOH/heat boil HCl/0°C

OH OH

SO3H N

1343. (a) (b) (c)

Br O2N O

O O
NO2 Cl NO2
NO2

Cl
(d) (e) (f)
+
CH3 CH3 SO3H O2N

Cl CH3

NHCOCH 3
(g) (h) CH3CO COCH3
Br

CH3
Solutions 657
O O
O

EG
Cl Cl2
1344. H+
AlCl3 AlCl3

Cl
O
O O O O
H3 O+ H3O+ H Mg
Et2O

HO Cl
O

N2H4 PCC
Product
NaOH CH2Cl2
heat

HO
O
Cl

CH3Cl O HNO3 Zn
1345. (a) H2SO4
AlCl3 AlCl3 HCl

NO2 NH2

NaNO2 H2O
HCl/0°C boil

OH
CH3 COOH

CH3Cl HNO3 KMnO4 H3O+ NH4HS

(b) Product
AlCl3 H2SO4 NaOH/heat

NO2 NO2
658 ProblemsinChemistry

O O

COOH
1346. (a)

A B C D
NO2 NO2 NO2

Co(OAc)2
(b) Noreactionsincethereisno α —H
AcOH/HBr/O2
tophenylring.
E
NO2
F

O
Br
FeBr3 Mg H3O+
1347. (a) +Br 2
Et2O

PCC
Product
CH2Cl2
OH
O

(CH3)2CHCOCl HNO3 Zn
(b)
AlCl3 H2SO4 HCl

NH2

LiAlH4 CuCN NaNO2

Product HCl/0°C

CN
Br Br

NO2
Br2 H2SO4 HNO3 dil.HCl Fe/HCl NaNO2
(c)
FeBr3 SO3 H2SO4 HCl/0°C
NaBF4
Product
∆
SO3H SO3
Solutions 659
NHCOCH3 Cl

HNO3 Fe CH3COCl HNO3 O Zn/HCl

(d)
H2SO4 HCl H2SO4 AlCl3

NO2
NO2 NO2 NHCOCH3

Sn/HCl CF3CO3H dil.

HCl

NO2 NO2 NH2

3
1348. (a) Non-aromaticsince,ithasa sp carbon. (b) Aromatic.

OCH3

F NO2
1349. (a) (b) CH3O— —CH3 (c)

C NO2
O CH3
Br

(d) (e) —OH

1350. (a) (b)

O
O
OMe O OMe

OMe OMe
(c) CH2Ph

(Minor)

O
CH2Ph
(Major)
660 ProblemsinChemistry
CH3 CH3

Br
CH3Cl H2SO4 Br2 dil.HCl HNO3
1351. (a) Product
AlCl3 SO3 FeBr3 H2SO4

SO3H SO3H

ONa OCH3

H2SO4 NaOH CH3I Br2

(b) Product
SO3 fusion FeBr3

NHCOCH3

HNO3 Fe/HCl CH3COCl H2SO4

(c) dil.HCl CF3CO3H
H2SO4 SO3 Product

SO3H

SO3 KMnO4 H3O+

1352. (a) Product
H2SO4 NaOH

t-BuCl KMnO4 H3O+

(b) Product
AlCl3 NaOH

t-BuCl CH3COCl
(c) Product
AlCl3 AlCl3

OMe

t-BuCl HNO3
(d) Product
AlCl3 H2SO4
OMe
Cl

NH3 NaNO2 CuCN H2SO4 CH3OH

(e) Product
H2S HCl/0°C H2O H+/heat
NO2
Solutions 661

CH3Br HNO3 Fe/HCl NaNO 2 Heat

(f) Product
AlCl3 H2SO4 HBF4/0°C

Br2 HNO 3 Cl2 NH3 NaNO 2 H2O

(g) Product
FeBr 3 H2SO4 AlCl3 H2S HCl/0°C boil

O
AlCl3 HNO3 N2H4
(h) + Product
Cl H2SO4 NaOH/heat

O
AlCl3 HNO3 Zn-HCl NaNO 2 H2O NaOH
(i) + Cl H2SO4 HCl/0°C boil

CH3I
Product
Br Br O Br O

Br2 H2SO4 Cl
1353. (a) FeBr3 SO3 AlCl3

SO3H SO3H
dilHCl Zn(Hg)
Product
HCl
O

Cl Br2 (excess) Zn(Hg)

(b) Product
AlCl3 FeBr3 HCl

O Cl O

Cl2 SO3 Cl dil.HCl

(c)
AlCl3 H2SO4 AlCl3

Zn(Hg) Mg D2O
Product
HCl Ether

H2SO4 Fe/HCl Ac2O HNO 3 dilHCl NaNO 2 CuCN

(d) Product
HNO 3 H2SO4 HCl/0°C
662 ProblemsinChemistry
NO2

HNO3 Te/HCl Ac2O CH3CH2COCl dilHCl NaNO2

(e)
H2SO4 AlCl3 HCl/0°C
HBF4
Product
Heat
CH3I H2SO4 NaOH CH3I NBS NaOH
(f) CH3— —OCH3 Product
AlCl3 SO3 Heat hν/CCl4 aqueous

Br2 HNO3 H2S Ac2O Cl2 dilHCl CF3CO3H

(g) Product
Fe H2SO4 NH3 FeCl3

CH3I SO3 Br2(excess) HCl(dil)

(h) Product
AlCl3 H2SO4 FeBr3

Cl
CN

1354. (a)
(b) (c)
Br
NO2
NO2

Cl NH2 OEt

(d) (e) (f)

O
(likeFriesrearrangement)

H
Cl
A: O O
1355. and AlCl 3 ;B: MeMgBrHO
/ 2 ;C: HSOHO
2 4/ 2 ;

O O
D: AgOHO;
2 / 2 E: Ph
Solutions 663

NHOAc

CH2CH3
1356. (a)
(b)

O
CH3 C(CH3)3
Cl
OH
(c) (d) (e) O2N—
Br CH3 CH(CH3)2

NO2
Cl Cl COOH

HNO3 Li/Et2O CO2/H2O NH3/H2S NaNO2

1358. (a)
H2SO4 HCl/0°C
CuCN H3O+
H2O
Product
NO2 NO2
Cl

Mg/Et2O CO2 CH3I KMnO4

(b) Product
H2O AlCl3 NaOH/heat

Cl OCH3
HNO3 CH3ONa Fe/HCl NaNO2
(c)
H2SO4 CH3OH HCl/0°C
O2N
OCH3
H2O
boil
F HO

OCH3
HNO3 CH3ONa Fe/HCl NaNO2 CuCN
(d)
H2SO4 CH3OH HCl/0°C
O2N OCH3
NaOH H3O+
H2O H2O
HOOC
664 ProblemsinChemistry

Br Br
O O

1359. (a) —OCH3 (b) —NO2

OCH3

(c) —OCH3

O2 N

Cl F

NH2
1360. (a) (b) (c)
MeO NO2 Br

OMe SO3H NO2

OMe

OMe
(d) (e) O

1362. (a) Aromatic,

(b) Notaromatic,ithasa sp 3 carbonwhichpreventdelocalization,
(c) Aromatic,
(d) Notaromatic.
1363. A: KMnONaOHheat
4/ / ;B: SOCl 2 ;C: Et 2 NCHCHOH;
2 2 D: NaS2 .

OCH3 O OCH3 OCH3 O

1364. O O O
HO HO H3CO
A B C
O
H OH OH
O O
COOH COOH
O
OH
H3CO HO HO COOH
D E F
Solutions 665

1365. (a) Cl— —NO2 (b) O2N—

Cl

(c) H3CO— —CH3 (d) O2N—

Cl NO2

Cl Cl Cl
Cl

Cl2 N2H4/OH–
O
1366. AlCl3 AlCl3

C
O
Cl Cl

HNO3 NH4HS
H2SO4
NO2 NH2
666 ProblemsinChemistry

CARBOHYDRATES,A MINO ACIDSAND POLYMERS

1367. (a) AreducingsugarreducesTollen’sreagent,FehlingsolutionaswellasBenedict’ssolution
whilenon-reducingsugardonotgivepositivetestwithanyoneofthesereagents.
(b) α-D-glucopyranosehashemiacetalstructureandreducesTollen’sreagent,Fehlingsolution,
Benedict solution while methyl-α-D-glucopyranoside has acetal structure and are
non-reducing,thereforefailintheabovetests.

Alkylgroup
—C—O O—H —C—O O—R′
C C
—C R(=HorCHOH)
2 —C R

α -D-glycopyranose If R′ =CH,methyl
3 α -D-glycopyranoside
give+veTollen’stest donotgivesTollen’stest

1368. Maltoseandsucrosearethetwomostcommondisaccharide.
+
Maltose+HO2 
H→
2molesofglucose(CHO)
6 12 6
+
H
Sucrose+HO2 → Glucose+Fructose
1369. Celluloseandstarcharethemostcommonpolysaccharides.Bothonhydrolysisproducesmany
moleculesofglucose, i.e., bothareglucosepolymers.
1370. Lactoseisadisaccharide.LactoseisareducingsugaranditreducesTollen’sreagent,Fehling’s
solutionandBenedictsolution.Lactoseonhydrolysisgives D-glucoseand D-galactose.
1371. Epimersarethediastereomersthatdiffersinconfigurationatonlyonestereocenter.Theabove
twodiastereomersdifferinconfigurationonlyatC-2andthiscanbeconfirmedbytheirreaction
withphenylhydrazine.
CH==NNHPh
C==NNHPh
D-glucose+CHNHNH
6 5 2 HO H CHNHNH+
6 5 2 D-mannose.
H OH
H OH
CHOH
2

SamephenylosazoneformationconfirmthatonlyC-2
hasdifferentconfigurationin D-glucoseand D-mannose.

CHO CHOH
2 CHO
HO H HO H HO H
H2 H2
1372. H OH H OH HO H
Ni Ni
H OH H OH HO H
H OH H OH H OH
CHOH
2 CHOH
2 CHOH
2
Solutions 667

CHNHNH
6 5 2 CHNHNH
6 5 2
CH==NNHCH
6 5 CH==NNHCH
6 5

C==NNHCH
6 5 C==NNHCH
6 5
H OH HO H
H OH Differentosazone HO H
H OH H OH
CHOH
2 CHOH
2

CHO CH==NNHCH
6 5

H OH C==NNHCH
6 5
CHNHNH
HO H 6 5 2
HO H
HO H HO H
H OH H OH
CHOH
2
CHOH
2
C
Sameosazoneasobtainedfrom. B

1373. Aminoacidexistasdipolarionas:
 +
—C— NH 3

COO –
(Dipolarion)
(Zwitterion)
Duetoitsexistenceintheformofdipolarion,thereexistaverystrongintermolecularattraction
whichisresponsibleforitshighmeltingpoint.
1374. (a) pH = 2 indicatehighlyacidsolutionandcationicformwillpredominate:
+
–
HN—CH—COO
2 HN—CH—C
2 OOH HN—CH—COOH
pH=12 pH =2 3
 ←  → 
CH—CH—CH
3 3 HC—CH—CH
3 3 CH—CH—CH
3 3

(b) At pH =12, anionicformpredominate.

1375. (a) Instronglyacidicsolution —NH 2 getsprotonatedandcationicformwillpredominate:

HOOC—CHCH—CH—
2 2 COOH

NH 3
+

(b) Instronglybasicsolution—COOHwillgetdeprotonatedandanionicformwillpredominate:
−
OOC—CHCH—CH—
2 2 COO –

NH 2
668 ProblemsinChemistry

(c) AtisoelectricpH,zwitterionwillpredominate:
HOOC—CHCH—CH—
2 2 COO.–

NH 3
+

1376. IsoelectricpointisthepHatwhichzwitterionhasitsmaximumconcentration.Glutamicacidisa
dicarboxylicacid,itszwitterionundergodeprotonationas:
−
HOOC—CH—CH—CH—
2 2 COO – OOC—CHCH—CH—
2 2
–
COO+ H+
 
NH 3 NH 3
+ +

+
Inordertosuppresstheaboveionizationsothatzwitterionpredominate,higher [H ]willhaveto
bemaintainedandthereforeisoelectricpHwillbelower.Glutamicisamonocarboxylicacidno
+
extra H isrequiredtosuppressabovetypeofionizationandhenceisoelectricpHishigher.
+ + −
–
NH 2 NHCl
3
NHCl
3 NH 2
   
1377. A : H—C— COOH B : H—C— COOCH 3 C : H—C— COOCH 3 D : H—C— COOH
   
CHOH
2 CHOH
2 CHCl
2 CHCl
2

NH2
Na(Hg) 
D →+ H—C— COOH
diluteH 
CH 3

O
  +
HO/Heat
1378. CH—C
3 —H+NH+HCN
3 → CH—CH—
3 CN 
3
→ CH—CH—
3 COO –
 HO
2 
NH 2 NH 3
+
Alanine
1379. (a) Astepgrowthpolymerizationresultsfromreactionoftwofunctionalgroupreleasingout
somesmallmoleculesas HO, 2 HCl, CHOH3 asbiproduct.
O O
(b) CHO—C—
3 —C—OCH3 +HO—CH—CH—OH
2 2

Dimethylterphthalate Ethyleneglycol

O O
Heat
—OCHCHO—C—
2 2 —C— +2CHOH
3

Poly(ethyleneterphthalate)
Decron
Solutions 669

1380. Teflonisapolymeroftetrafluoroethyleneandsynthesizedasfollows:
O O O
    Heat
 
Ph—C —O—O—C —Ph → 2Ph—C —O ( ≡≡RO)
• •

Benzoyl peroxide

Heat
•
RO + CF==CF
2 2 → RO—CF—CF
2
•
2 (Initiation)
ROCF—CF
2
•
2 +CF==CF
n 2 2 → RO—CF—CF
[ 2 2 ]—CF—CF
n 2
•
2 (Propagation)

RO—
[CF—CF]—CF—CF
2 2 n 2
•
2 + RO
•
→ RO—[CF—CF
2 2 ]—CFCF—O
n 2 2 R
RO—[CF—CF]—CF—CF
2 2 n 2
•
2 + ROCF—CF
2
•
2 → RO—[CF—CF]
2 2 —O
n +2 R
2RO—
[CF—CF
2 2 ]—CF—CF
n 2
•
2 → RO—
[ CF—CF]—O
2 2 2 n +2 R

O O
    Heat
1381. (a) n HO—C —(CH)—C
2 4 —OH + nHN—
2 (CH 2 )—N
6 H 2 →
Adipicacid

O O
   
—
[C —(CH 2 )—C
4 —NH—(CH)—NH]—
2 6 n
+ HO
2
Nylon6,6

(b) DuetoextensiveintermolecularH-bondingamongthepolymerchains,nylonpossessvery
highmeltingpoint.

MISCELLANEOUS
O
O
NH2
1382. (a) O (b) H (c) CH3CH2OH+H—C—H

PhNH
OH
OH
(d) (e) (f)
CN

O
Br
O
Cl OH

1383. (a) (b) (c) CH3COCH3 (d) CH3 CH3

O
670 ProblemsinChemistry
O

COOH
N OH
(e) (f) +

O
CH3
H

(g) —N N— —OH (h) H

NH2
O

Br NH2 Br
1384. A : B: C:

—C N
D:

O
O
H—N O
1385. (A)
N

Ph3P CHCH3
(B)

O O O

OH– H+
(C) OH
Aldol Heat
Solutions 671

H3C H 3C H3C
N N N
COOCH3 COOH COOH
1386.
O
C6H5 O
OH
O (C )
Cocaine( A) (B )

O
(i)CHMgBr   CHN
1387. CHCHOH PCC
→ CHCHO 
3
→ PCC
→ CH
6 5  C  CH 3 →
2 2
6 5 2
(benzylalcohol) CCl 4
6 5
(ii)HO3 + CCl 4 ∆

CH3

X
OH

CH3(CH2)3CH2MgBr H3O+
X

O OH

LiAlH4 PCl3 Mg
1388.
H2O ether
MeO MeO

OH —OMe
—OMe (MgCl)+
H3O+ O
MeO
MeO

—OMe
H+/Heat

MeO
(Dimestrol)
672 ProblemsinChemistry

OH O

1389.
A C
O OH
B
O O O

Br

D E F
OH

Br

O
CHO O
O3
O
Zn-H2O +

H I

Mg (i) O
 PCl CHONa
1390. (a) PhCHBr
2 → PhCHMgBr
2 → Ph—CH 2CHCHOH
2 2 →3
2 5
ether (ii)HO3 + CHOH
2 5

NaBH4 (CH3COO)2Hg,CH 3OH

Ph—CH2 —CH CH2
OCH3
Solutions 673

Br HC C–Na+ C CH B2H6
(b)
NaOH/H2O2

OH

CHO
PCC (i)CH 3MgBr
Product
CCl4 (ii)H 3O+

OH

CH2CH3
OH
1391. (a) (b) (c) O
OH
OH
O O

CH3
Br C2H5O OC2H5
1392.
Ph
A B C
D
COOH

Br OH

CN (b)
+
1393. (a) H OH H

(Enantiomeric) H OH
Major Minor
Ph
CH3 CH3
Ph
(c) (d) OEt (e) O
OH
674 ProblemsinChemistry

1394.
OH

H+ / ∆ OH
B2H6/H2O2
–H2O
NaOH
1
Cold,dilute,alkaline 3
KMnO4 Regioselectivehydroboration
followedbyoxidation.

OH
OH

O
O O O O O O

EG/H+ LiAlH4 H2O PBr3

1395.

O OEt O OEt OH Br

O O
HCl
Product PhONa

1396. Enol2isthermodynamicallymorestablethan3becausethealkeneinthistautomerisconjugated
witharomaticringaswellaswithcarbonylgroup.The C==C doublebondinenol3isisolatedand
thestabilityaffordedto2-throughresonanceisnotavailableto3.
Solutions 675

O O H O OH
O O

H3O+ CH3 CH2

H2O
1 2(thermodynamicallymorestable) 3(lessstable)

–H3O
H+ H +
O O OH O

H l l H
O
2
H

OH–
1397. X
O– O–
moststable Thisenolishighlydisfavoured-theindividual2 pz orbitalofthe
doublebondareorthogonalandconsequently,the pπ-bondcan’tform
(Berdt’srule)

OH–
Y
O–
moststableenolateanionbecausethedouble
bondisinconjugationwitharomaticring.

O– O–
OH–
Z

Lessstable Moststable,becausethedoublebondistetrasubstituted
andconsequentlythermodynamicallymorestablethan
thealternative,trisubstitutedenolateanion.

1398. Here,theacidityisdueto COOH groupsandnotdueto α H.Also, COOH isastrong

electronwithdrawingfunctionalgroup, distanceofone COOH groupfromotherdetermine
acidicstrength.Largerthedistance,weakeristheacid.Thus,theorderofacidstrengthis:
C>B>D>A
676 ProblemsinChemistry

COOH COCl
1.KOH,H 2O SOCl2
1399. A : X 2.H 3O+ or(COCl) 2
orPCl 3 orPCl 5

CH3CH2COONa
Product
Br O

EtONa H3O+
B: X + Product (Throughnucleophilic
additionofenolateion)

Heat N
C: X +
N

O O
O O

CH3 CH3O–
1400. +CH 3O– –
CH2
MeOH
O
OH
O O
O O

–
MeOH

–O O
O
OH OH OH
O

Heat
–H2O
O
Solutions 677

CHO CH CH2

O
1401.
OH OH
O CH3
CF3CO3H
O O N
OH C
A CH3
D
B
H2SO4/H2O
E
O
O O O O
Br OH Br CN
OH KCN
1403.
H+/∆
O

CN
H+

O O O O

EtO–
1404. EtO OEt EtO
s
OEt

H H H

O O
lessacidic moreacidic

+ EtO OEt
s
(notformed)
O– O O O
EtO

OEt OEt
–EtO–

B
O

(CH3COO)2Hg NaBH4 PCC

1405. (a) CCl4
H2O
Styrene
678 ProblemsinChemistry

OH H
B2H6–H2O2 PCC
(b)
NaOH CCl4
O
Br
KCN H3O+
(c) HBr
Peroxide H2SO4

OH LiAlH4 OH

O
HgSO4 Br2
1406. (a) —C CH —C—CH3 Product
H2SO4/H2O AlCl3

H2/Pd/BaSO4 B2H6–H2O2
(b) —C CH Product
NaOH

O
PhMgBr H3O+
(c) —C—CH3 Product
ether H2O

(froma)

QUALITATIVE ANALYSIS
1407. A: PbCO 3 , B: PbO, C: PbO, 3 4 D: Pb(NO)3 2 , E: PbO 2 , F: PbCl 2 , G: PbI 2
2+
1408. A: Cu(NO)3 2 ; B: NO 2 , C: Cu(OH) 2 , D: CuO, E: [Cu(NH)3 4 (HO)
2 2]
2–
F: [CuCl 4 ] .
B: 2NO+HO
2 2 → HNO+HNO
3 2

1409. A: ZnCO3 ⋅ Zn(OH) 2 , B: ZnO, C: ZnSO,4 D: Zn(OH) 2 , E: [Zn(NH)3 4 ]2+

1410. A: Fe, B: FeSO 4 , C: FeO,2 3 D: FeO,
3 4 E: FeCl 3 , F: Fe(OH) 2 , G: Fe(OH) 3
1411. SOFCl.
1412. A: BaCO 3 , B: BaO
1413. A: CrCl 3 , B: NaCrO,
2 4 C: NaCrO,
2 2 7 D: NaCl, E: CrOCl 2 2 , F: (NH)4 2 CrO
2 7
G: CrO.
2 3
1414. A: ZnCO3 ⋅ Zn(OH) 2 B: CO 2 , C: ZnO, X: KZn[Fe(CN)
2 3 6 ]2 , D: ZnS,
E: Zn(OH) 2 .
1416. A: CaCO 3 , B: CaO, C: CaCO. 2 4
Solutions 679

1417. A: Bi 2O+PbCrO,
3 4 B: Bi(OH) 3 +Pb(OH) 2 , C: Bi(OH) 3 , D: PbO 2 , E: PbCl 2 , F: BiI 3

1418. A: CuCl2 , CrCl 3 , B: CuS, C: CrO,2– 4 D: CrO 5

1419. A: CrO,
2 3 B: Al 2O,3 C: PbCrO,4 D: Al(OH) 3
1420. A: FeO,
2 3 B: MnCl2 ⋅ 2HO, 2 C: Fe(OH) 3 , D: MnS, E: CrOCl 2 2.
1421. A: PbO,
3 4 B: Fe(CrO)4 2 , C: PbO 2 , D: PbS, E: Fe[Fe(CN) 4 6 ]3 , F: PbCl 2 .
1422. A: HgI 2 , B: AlI 3 , C: K[HgI
2 4 ], D: ⋅
HgOHg(NH)I, 2 E: Al(OH) 3

1423. A: ZnO, B: Ca(NO 3 ) 2 , C: Zn(OH) 2 , D: [Zn(NH)3 4 ]2+ , E: CaCO 3 .

1424. A: Ba(NO 3 ) 2 , B: CaCl 2 ⋅ 6HO, 2 C: CaCO, 2 4 D: BaCrO,4 E: BaCO 3 .
1425. A: AgCrO,
2 4 B: AgCO,
2 3 C: AgO, 2 D: CrO.5
1426. A: Mg, B: MgN, 3 2 C: Mg(OH) 2 , D: ⋅
NH,3 E: HgOHg(NH)I. 2
1427. A: FeSO 4 ⋅ 7HO,2 B: FeO,
2 3 C: SO, 2 D: SO 3 , E: FeCl 3 .
1428. A: HgCl 2 , B: HgCl 2 2 , C: Hg, D: HgI 2
1429. A: Bi 2S,3 B: HS, 2 C: Bi(OH) 3 , D: BiO,–3 E: BiI 3
1430. A: ZnCl 2 , B: MgCl 2 , C: Mg(OH) 2 , D: ZnS, E: HCl.
1431. A: FeO,
2 3 B: MgSO 4 ⋅ 7HO, 2 C: FeS, D: Mg(OH) 2 , E: S, F: BaSO.4
1432. A: CuBr2 , B: ZnSO 3 , C: CuS, D: Zn(OH) 2 , E: BaSO 3 , F: SO 2
1433. A: FeO,
3 4 B: AgI, C: Fe[Fe(CN)4 6 ]3

1434. A: AgCO,
2 3 B: CuCl2 , C: AgCl, D: CuS, E: [Cu(CN) 4 ]3–
1435. A: FeCl 3 , B: ZnSO,4 C: Fe(OH) 3 , D: Zn(OH) 2 , E: HgOHgSO ⋅ 4
1436. A: AlCl 3 , B: BaSO 4 , C: BaCrO 4 , D: Al(OH) 3 , E: CoOAl 2O.3
COORDINATION COMPOUNDS
1437. (i) hexaamminecobalt(III)chloride.
(ii) pentaamminechlorocobalt(III)ion.
(iii) tetraamminesulphatocobalt(III)nitrate.
(iv) potassiumpentachloronitridoosmate(VI).
(v) sodiumdithiosulphatoargentate(I).
(vi) potassiumamminedicyanodioxoperoxochromate(VI).
(vii) pentaamminenitritoirridium(III)chloride.
(viii) potassiumtetrachloroplumbate(II).
(ix) copper(II)potassiumhexacyanocobaltate(III).
(x) potassiumhexacyanoaurate(III).
(xi) lithiumtetrahydridoaluminate(III).
(xii) sodiumtetrahydridoborate(III).
(xiii) sodiumhexafluoroaluminate(III).
(xiv) tetraaquadichlorocobalt(III)chloridedihydrate.
1438. (i) hexaamminechromium(III)hexaisothiocyanatochromate(III).
(ii) tetraamminecopper(II)tetrachloroplatinate(II).
(iii)tetraammineplatinum(II)tetrachloroplatinate(II).
(iv)hexaamminecobalt(III)tetracyanonickelate(II).
(v)tetraamminedichloroplatinum(IV)tetrachloroplatinate(II).
(vi)hexaamminecobalt(III)hexanitrocobaltate(II).
(vii)pentaamminenitrochromium(II)hexanitrochromate(II).
680 ProblemsinChemistry

(viii) tetrapyridylplatinum(II)tetrachloroplatinate(II).
(ix) hexaamminenickel(II)hexanitrocobaltate(III).
(x)hexamminecobalt(II)diamminetetrachlorochromate(II).
(xi)tetraamminedibromocobalt(III)tetrachlorozincate(II).
(xii) pentaamminecarbonatocobalt(III)tetrachlorocuperate(II).
(xiii) diamminesilver(I)hexacyanoferrate(II).
(xiv)dichlorobis(ethylenediamine)chromium(III)tetrachloropalladate(II).
1439. (i) µ-amidobis(pentaamminecobalt(III))nitrate.
(ii) µ-amido-µ-sulphurdioxidebis(tetraamminecobalt(II))nitrate.
(iii)tri- µ-carbonylbis(tricarbonyliron(0)).
(iv) µ-amido-µ-hydroxotetraamminecobalt(III)bis(ethylenediamine)cobalt(III)chloride.
(v) µ-amido-µ-hydroxodibis(ethylenediamine)cobalt(III)bromide.
(vi) µ-amido-µ-nitrodibis(ethylenediamine)(cobalt(III))chloride.
1440. (i) [Co(NH)3 5 Br]SO 4 (ii) [Pt(en) 2 Cl 2 ]SO 4 (iii) [Pt(Py) 4 ][PtCl 4 ]
(iv) K[Fe(CN)
3 5 (CO)] (v) Cs[TeF]5 (vi) [Pt(NH)3 3 Br]NO 3
(vii) [Co(en) 2 Cl 2 ]Cl ⋅ HO 2 (viii) [Cr(HO) 2 6 Br 2 ]Cl (ix) (NH)4 3 [ZrF]7
(x) [Ni(NH)3 6 ]3 [Co(NO)2 6 ]2 (xi) [Cr(en) 2 Cl 2 ]2 [PtCl 4 ] (xii) Al[AuCl4 ]3
(xiii) Fe[Fe(CN)
4 6 ]3
1441. A: [Co(NH) 3 3 (HO)ClBr]Br
2 ⋅ HO;
2 B: [Co(NH)3 3 (HO) 2 2 Br]Cl ⋅ Br
1442. A: [Co(NH)3 5 Br]SO,4 B: [Co(NH)3 5 SO]Br, 4 Ionizationisomerism.
1443. A: [Pt(NH)3 4 Cl 2 ]Br B: [Pt(NH)3 4 Br 2 ]Cl 2
1444. A: [Cr(HO) 2 6 ]Cl 3 , B: [Cr(HO) 2 5 Cl]Cl 2 ⋅ HO,
2 C: [Cr(HO) 2 4 Cl 2 ]Cl ⋅ 2HO.2
1445. [Ti(HO) 2 6 ]Cl 4
4− 3 2
1446. [CoCl 6 ] , octahedral, spd -hybridization,anouterorbitalcomplex.
1447. In case of [Co(NH)3 6 ][Cr(NO)2 6 ], cobalt will be discharged at cathode while with
[Co(NO)2 6 ][Cr(NH)3 6 ], chromiumwillbedischargedatcathode.
1448. [Cr(NH)3 6 ][Cr(NO)2 6 ] willhavelowerconductivityduetolargerhydratedradius.
1449. Conductingreagent:dimer482,non-conductingreagent:monomer241.
1450. [Pt(NH)3 4 ][Pt(NO)2 4 ] and [Pt(NH)3 3 (NO)][Pt(NO) 2 2 3 NH]3 only.
1451. A: [Cr(NH)3 4 BrCl]Cl B: [Cr(NH)3 4 Cl 2 ]Br
1452. A: [Cr(NH)3 4 Br2 ]Cl ⋅ HO 2 B: [Cr(NH)3 4 BrCl] ⋅ Br ⋅ HO 2 C: [Cr(NH)3 4 (HO)Cl]Br 2 2.
1453. A: [Co(NH)3 3 (HO) 2 2 SO]NO4 3 ⋅ HO,2 B: [Co(NH)3 3 (HO) 2 2 NO]SO3 4 ⋅ HO2
C: [Co(NH)3 3 (HO)(NO)(SO)] 2 3 4 ⋅ 2HO 2 D: [Co(NH)3 3 (HO) 2 3 ]SO 4 ⋅ NO 3 .
1454. A: [Pt(NH)3 4 Cl 2 ]Br 2 B: [Pt(NH)3 4 ClBr]BrCl C: [Pt(NH)3 4 Br2 ]Cl 2
1455. A: [Co(NH)3 3 (HO)Br 2 2 ]ClHO, 2 B: [Co(NH)3 3 (HO) 2 2 Cl]Br 2
1456. [Cr(HO) 2 5 Cl]Cl 2 ⋅ HO
2
1457. (a) Rediscomplementcolourofgreenwavelengthand vice-versa.Hence,ligand B isproducing
smallercrystalfieldsplitting.
+
(b) [CoA 6 ]3
2+ 3+
1458. [Cu(NH)3 4 ] 1459. [Cr(en) 3 ]
1460. Duetolackof d-d-electronictransition.
− 8 2+ 2– −
1461. (a) CN isastrongligand, d (Ni ) hasallpairedelectronsin Ni(CN) 4 , while Cl isaweak
ligand Ni 2+ (d 8 ) hastwounpairedelectrons.
Solutions 681
10
(b) Nihas d -configurationin Ni(CO) 4 andcomplexistetrahedral.
(c) Niin [Ni(NH)3 6 ]2+ is spd3 2 -hybridized.
+
1462. Iodideionbeingastrongreducingagent,reduces Cu 2+ to Cu .
3+
1463. Weakligandfieldof HO 2 givesfiveunpairedelectronsin d-orbitalsofFein Fe(HO)2 6 andno
electronictransitionfromone d-orbitaltoother d-orbitalcanoccur.
−
Ontheotherhand, CN beingaverystrongligand,givesaverylargecrystalfieldsplittingand
electronictransitionfromone d-leveltootherrequirephotonsofhighenergyandabsorption
occurinUV-region.
1464. K[Mn(CN)
3 6 ] : µ= 2.82Bm. Octahedral,innerorbitalcomplex.
K[MnBr
2 4 ] : µ= 5.92Bm, tetrahedral.
1465. (a),(b),(d),(e)
−
1466. F isaweakligand,formshighspincomplexand CoF63− hasfourunpairedelectronsin d-orbital.
− 3+ 3–
CN isastrongligandandallsixelectronsinthe d-orbitalof Co in Co(CN) 6 arepaired.
1470. Thetrans-isomerof [CoCl 2 (en) 2 ] possessaplaneofsymmetryandhence,doesnotshowoptical
isomerismwhilecisformisdevoidofanysymmetry,itshowsopticalisomerism.

Cl NH2

HN
2 NH2 Cl NH2

Co Co

HN
2 NH2 Cl NH2

Cl HN
2

trans[CoCl 2(en)]2
(hasplaneofsymmetry) Cis[CoCl 2(en)]2

2+
1471. Complex [ZnAB2 2] willbesuperimposableonitsmirrorimageduetopresenceofplaneof
symmetrywhile [ZnABCD ]2+ isopticallyactive.
A A
2+ 2+

2+
Zn B Zn
D

A B
B C
PossessplaneofSymmetry DevoidofSymmetry
(Opticallyactive)

1472. [Pt(NH)3 2 Cl 2 ] isasquareplanarcomplex,therefore,show cis-trans isomerismasshownbelow:

Cl NH3 Cl NH3

Pt Pt

Cl NH3 H3N Cl
Cis Trans
682 ProblemsinChemistry

Ontheotherhand [Zn(NH)3 2 Cl 2 ] istetrahedralandallthepositionsaroundmetalareequivalent,

therefore,no cis-trans isomerismisobserved.
3+ 3+ 3
1473. Inoctahedralcomplex [CrL]6 ,Cr has 3d configuration.Thesplittingpatternandelectron
fillingin d-orbitalof Cr 3+ canbeshownas:

∆0
3d3
Cr3+

Thenatureofligandwillaffectthe (∆ 0 ) valuebutnottheelectronicconfigurationinthelower
level of d-orbital. Therefore, magneticproperties, whichdepends onnumber of unpaired
electronswithcentralmetal,willnotbeaffectedbyidentityofligand.
1474. “”and“”
a c areidenticalandbothare trans isomers. “”b and “”d arepairofenantiomersandboth
are cis-isomer.
1475. Thecomplexis [CoCl 6 ](CHN)2 10 2 2 anditisoctahedral.
Cl

Cl Cl 4–

Co2+

Cl Cl

Cl

1476. Thecomplexhasformula [Ti(HNCONH)

2 2 4 I 2 ]I.
3+
1477. (a) Cr hydrolysesinwateraccordingtothefollowingreaction:
Cr 3+ +HO2 Cr(OH) 2+ +H +
+
Intheabovereaction, H isproducedwhichimpartacidicnaturetothesolution.
(b) As OH – isadded, agelatinousprecipitateof Cr(OH) 3 isproducedat first instant which
dissolvesonaddingexcessof OH duetoformationofcomplex [Cr(OH) 6 ]3– as:
–

3OH –
Cr 3+ +3OH – → Cr(OH) 3↓→ → [Cr(OH) 6 ]3– (aq )
1478. (a) tetraoxalatozirconate(IV)ion (b) diaquatetrachlorocupperate(II)ion
(c) amminetrichloroplatinate(II)ion (d) tetracyanotetrahydroxomolybedate(IV)ion
1479. ElectronicconfigurationofFe(II)is
2+
Fe :
6 0 0 0
3d 4s 4p 4d
Solutions 683
2+ 3+ 5 2+
Here Fe isreadilyconvertedinto Fe (3d ) duetothereasonthat Fe ,afterlosinganextra
electronyields astableelectronicconfiguration: 3d 5 wherethe 3d-orbital is completely
half-filled.
With Ni(II) (3d 8 )and Co(II) (3d 7 ), nosuchstableelectronicconfigurationisformedafter
removinganextraelectronfromthe 3d-orbitals,therefore,formationofNi(III)andCo(III)from
Ni(II)andCo(II)respectivelyareverydifficult.
1480. (a) Anaqueoussolutionof [Ni(SO)(en) 4 2 ]Cl 2 whichproduceprecipitatewith AgNO3 solution
anditwillnotgiveanyprecipitatewithaqueous BaCl 2 solution.However,aqueoussolution
of [NiCl 2 (en) 2 ]SO 4 willformaprecipitatewith BaCl 2 .
(b) Aqueoussolutionof [Ni(en) 2 I 2 ]Cl 2 will formawhiteprecipitatewithaqueous AgNO3
solutionwhichwillbesolubleinexcessofammoniasolution.However,aqueoussolutionof
[NiCl 2 (en) 2 ]I 2 will formanyellowprecipitate of AgI whichwill be insoluble in
concentratedammoniasolution.
4– 2+ 5 –
1481. (a) In [MnCl 6 ] ,Mn has 3d configuration.Since, Cl isaweakligand,therewillbesmaller
crystal-fieldsplitting. In [Mn(CN) 6 ]4– , Mn 2+ hasagain 3d 5 configuration, butnow CN – isa
strongligand,therewillbelargercrystal-fieldsplittingas:

3d5 3d5
4–
[MnCl6] [Mn(CN)]6 4–

(b) Since, strongligandfieldabsorbshorter wavelengthlight, therefore, [Mn(CN) 6 ]4– will

transmitslongerwavelengths.
1482. (a) Since,thecomplexisemittinglongwavelength(yellow)light,shortwavelengthvisiblelight
wouldhavebeenabsorbed.Thisisalsoevidentfromthehighstrengthligandfieldgivenby
strongligands-cyanideion.
(b) In [Co(CN) 6 ]3– ,Co isin 3d 6 stateandligandisstrong,thereisnounpairedelectronsas:

3d6
Nounpairedelectron,complexisdiamagnetic
Strongligand
field

(c) If NH 3 moleculesaresubstitutedforcyanideions, complexwillabsorblongwavelength

visiblelightandtheshiftinabsorbancewillbetowardsredregionofthespectrum.Thisis
duetothefactthat NH 3 isaweakerligandthan CN – .
684 ProblemsinChemistry
2+ 5
1483. Inhighspincomplexof Mn (3d ),alltheelectronsareoccupyingsinglythefive- d-orbitalsas:

Mn2+

+
Asevidentfromtheaboveorbitalenergydiagramfor Mn 2 , electrontransitionisnotallowed
fromlowerleveltohigherlevelsince,anyelectronictransitionfromlowenergyleveltohigh
energylevelwillviolate“PauliExclusionPrinciple”.Therefore,complexof Mn 2+ isveryfaintly
coloured.
1484. For aspontaneousreaction ∆G °< 0, ie. ., E °> 0. Intheaboveexample, boththereduction
reactions are spontaneous. Also reduction potential of reaction (II) is more positive,
corresponding ∆G ° will bemorenegative, reactionwill bemorespontaneous. Therefore,
[Co(NH)3 6 ]3+ ismorestableand [Co(HO) 2 6 ] 3+
ismorereactive.
1485. (a) [Cr(HO)
2 4 Cl 2 ]Cl (b) [Cr(HO)
2 6 ]Cl 3 .
1486. (a) Coordination,(b) Ionization,(c) Linkage,(d) Hydrate.
O O

OH OH2
OH
N N
OH2

1487. O
Co3+ Co3+
OH O
OH2 O
O H OH

OH2
O O
H
Cisisomer Transisomer
•
Nitrilotriaceticacid [N(CHCOOH)]
• 2 3

NH

HN
2 NH2

1488. (a)
Co3+

HN
2 NH2

HN
Solutions 685

1489. Weakertheligandfieldstrength,smallerwillbethecrystalfieldsplittingandlongerwillbethe
wavelengthofabsorption.Hence:
[Cr(CN) 6 ]3– <[Cr(en) 3 ]3+ <[Cr(NH)3 6]
3+
<[CrCl 6 ]3– <[Cr (HO)
2 6]
3+

1490. Strongertheligandfield,greaterwillbethecrystalfieldsplittingandhence,higherwillbethe
frequencyoflighttobeabsorbed.Hence,orderoffrequencyoflightabsorbedbythesecomplexes
is:
3+
[Cr(HO)
2 6] <[Cr(en) 3 ]3+ <[Cr(CN) 6 ]3–
1491. (a) Stronger theligandfield, greater will becrystal fieldsplitting, smaller will bethe
wavelengthoflightabsorbed.
⇒ λ :[Fe(CN) 6 ]4– <[Fe(HO)
2 6]
2+

(b) Highertheoxidationstateofcentralmetal,greaterwillbethecrystalfieldsplitting.Hence,
therewillbegreatercrystalfieldsplittingof d-orbitalsin Mn(III) complexcomparedtothat
in Mn(II) complex. Hence, [Mn(CN) 6 ]4– will absorbat longerwavelength(lowenergy
photons)than [Mn(CN) 6 ]3– .
HO
2 Br HO
2 Br

1492. (a) Pt Pt

HO
2 Br Br OH2

Cis Trans

Cl Py Cl Br Cl Br

(b) Pt Pt Pt

HN
3 Br HN
3 Py Py NH3
2+
(c) Zn hastetrahedralarrangementofligandsaroundit:
Cl

Zn2+

HN
3 NH3

NH3

Cl Cl

H2O Cl H2O OH2

(d) Ni Ni

H2O OH2 H2O OH2

OH2 Cl
Cis trans
686 ProblemsinChemistry
O

O Cl
O
O O
Cl O O O
(e) Co Co

Cl O O O
O O O
O Cl
trans
O
Cis
(Opticallyactive)
Cl
en
Cl

1493. (a) Co en Co en

NO2
en
NO2
(enantiomeric) (trans)
Cl
en
Cl

(b) Co en Co en

Cl
en

OH2 Cl Cl Cl
(cis) (trans)
H3N OH2 H3N OH2 H3N OH2

(c) Cr Cr Co

H3N Cl H3N OH2 H2O NH3

Cl Cl Cl

NH3 NH3
en
Cl Cl Cl NH3

(d) Pt Pt (e) Cr en

Cl Cl Cl Cl
en
NH3 Cl
Solutions 687

1494. Co(III) = 3d , weakligand,magneticmoment = 4 × 6 = 24BM4.9BM. =

6

3+ 6
(b) Co : 3d , magneticmoment = 0; en isastrongligand.
+
(c) Mn 3 (3d 4 ) and CN – strongligand,twounpairedelectron, µ= 8BM2.82BM
= .
2+ 5 –
(d) Mn (3d ) and Cl isaweakligand, µ= 5 × 7BM5.916BM =
1495. NiCl 2 +(CH)3 3 P → Compound
Fromelementalcomposition,empirical/molecularformula = [NiCl 2 ((CH)3 3 P) 2 ] .Since,ithas
noisomericforms,complexmustbetetrahedral:
Cl

Ni (CH)P
33

Cl P(CH)33
bis(trimethylphosphine)dichloronickel(II)
+
Magneticmoment: Ni 2 (3d 8 ) and sp 3 hybridizationindicatepresenceof twounpaired
electrons,hence, µ= 8 = 3.82BM.
1496. Zeromagneticmomentindicatethatthereisnounpairedelectronandcomplexissquareplanar
(dsp 2 hybridizedNi).
2– 2–
CN Br CN Br

Ni2+ Ni2+

CN Br Br CN
Cis trans
NH3 NH3
– –
Cl Cl Cl NH3

1497. (a) Co3+ Co3+

Cl Cl Cl Cl

NH3 Cl
trans
Cl Cl

Cl NH3 Cl NH3

(b) Co3+ Co3+

Cl NH3 HN
3
NH3

NH3 Cl
(Facial) (Meridional)
688 ProblemsinChemistry

1498. (a) Noisomers(b) Noisomers.

O O
O
O O O
O O O O O
3–
O 3–

(c) Co3+ Enantiomers Co3+

O
O O O O O
O O
O O
O O
2+
1499. Cyanideionisastrongligandandin 3d 8 (Ni ) itgivessquareplanargeometry:

dx–y
2 2
Energy

dxy

dz2

dxz dyz
2–
[Ni(CN)4 ] crystalfieldsplitting.

Thereisnounpairedelectron,complexisdiamagnetic.
+
Chlorideionisweakligand,in 3d 8 ( Ni 2 ), itproducestetrahedralligandfield.
Energy

[NiCl 4 ]2– crystalfieldsplitting.

Therearetwounpairedelectronsandcomplexisparamagnetic.
µ= 8BM2.82BM
= .
Solutions 689

1500. Whenasubstanceabsorbsaparticularcolourwhenbathedinwhitelight,theperceivedcolourof
thereflectedortransmittedlightisthecomplementarycolour.Also,wavelengthsofabsorbedand
transmittedlightsareinverselyrelated.
Cyanideionbeingstrongerligandthan HO 2 ,formerabsorbslightofshorterwavelengththanlater
andwavelengthsoftransmittedlightislongerforcyanideion(yellow)andshorterfor HO
2 (blue
orgreen).
1501. Thecrystalfieldsplittingenergyisequaltotheenergyofphotoncausingabsorptionmaximum.
6.625 × 10 –34 × 3 × 10 8
⇒ ∆= hc = = 4.23 × 10 –19 J
λ ×
470 10 –9

1502. Strongertheligandfield,shorterthewavelengthsofphotonabsorbed.
3+
(a) [Co(HO)2 6] (b) [FeF]6 3– (c) [CuCl 4 ]2–
0.875 1000
1503. − ∆T f = 0.56 = i × 1.86 × × ; i = vantHoff’sfactor
233.5 25
⇒ i = 2.Hence,formulaofcomplexis [Co(NH)3 4 Cl 2 ]Cl.
1504. Rustconsistsofmixtureof Fe(OH) 3 and FeO 2 3 ⋅nHO
2 .Oxalicacid,beingabidentate,chelating,
strongligand,formsstablecomplexwithiron,removingrustas:
Fe 3+ +3CO 2–
2 4 → [Fe(CO) 2 4 3]
3–

CN –
1505. Cu +2CN → Cu(CN) 2 ↓→→
2+ –
excess Cu(CN) 2–
4
White Soluble
Thecomplex Cu(CN) 2– 4 ishighlystableanditionizesveryfeeblyas:
2–
Cu(CN) 4 Cu +4CN: – K d isverysmallandequilibriumliespredominantlytoleftside.
2+

If HS2 gasisbubbledatthistime,noprecipitateofCuSisformedduetopresenceofverysmall
amountof Cu 2+ ioninthesolution(lessthanrequiredtoexceedthesolubilitylimit).
1506. Theinitial greencolourationisduetopresenceof [CuCl 4 ]2– inconcentratedsolution. On
dilution,solutionturnedblueduetoconversionof [CuCl 4 ]2– into [Cu(HO)
2
2+
6] .
1507. K f (Formationconstant)
2+
[Fe(HO)
2 5 NCS] 7.3 × 10 –5
= = = 0.393
[Fe(HO)
2 6]
3+
[SCN]– (0.2) (10 –3 − 7.3 × 10 –5 )
1508. Electricalconductanceofelectrolytedependsonnumberofionsavailable.Bycomparisonwith
theconductanceofstandardelectrolyte,natureofunknownelectrolytecanbeestablished.Inthe
givenexperiment,conductanceofunknownwillmatchas:
[Co(NH)3 6 ]Cl 3 =FeCl 3 , [Co(NH)3 5 Cl]Cl 2 =MgCl 2 and
[Co(NH)3 4 Cl 2 ] Cl=NaCl .
1509. CoCl 2 atlowconcentrationappearpinkcolouredduetoitsexistenceas [Co(HO)2 6 ]Cl 2 . On
addingHCl,followingreactionoccurs:
6 ]Cl 2 +HCl → [Co(Cl) 6 ]
4–
[Co(HO)2
blue-coloured
Adding HgCl 2 , pinkcolourisrestoredduetothefollowingreaction:
690 ProblemsinChemistry

[CoCl 6 ]4– +HgCl 2 +HO2 → [Co(HO)

2 6]
2+
+[HgCl 4]
2–

pink colourless

1510. Thecomplexissquareplanarandexhibit cis-transisomerisminwhich cis-formispolarwhile

trans-formisnon-polar.Dipolemomentmeasurementcanallowdistinctionbetweenthesetwo
forms:
Polar

Cl Cl Cl NH3

Pt Pt

HN
3
NH3 HN
3 Cl

Cis trans-Non-polar
2+ 3 +
1511. Bothsolutionscontainhydratediron [Fe(HO) 2 6] and [Fe(HO)
2 6] ions.Highertheoxidation
stateoftransitionmetal,greaterwillbethecrystalfieldsplittingandshorterwillbetheabsorption
wavelength.Thewavelengthofemittedlightisinverselyrelatedtoabsorptionwavelength.On
3+
thisbasis,transmittedlightfrom [Fe(HO) 2 6] willhavelongerwavelength-willappearyellow,
2+
while [Fe(HO) 2 6] solutionwillbebrown.Thiscanalsobeexplainedonthebasisofelectronic
configurations:
+
Fe 3 (3d 5 ) andweakligandfield,completelyhalf-filled d-orbital.Difficult d-d-transitions.
2+ 6
Fe (3d ) andweakligandfield,lessthanfull-filled d-orbital,easier d-d-transition.

REPRESENTATIVE ELEMENTS
1512. (a) BO+3Mg
2 3 → 3MgO+2B
(b) Al 2O 3 willcomeinsolutionas Na[AlO].
2
(c) CO+2Na[Al(OH)
2 4 ] → 2Al(OH) 3 +NaCO+HO
2 3 2
H H H
1513. B B
H H H
H
 s
1514. (a) BF+EtOH
3  → Et—O → BF3
⊕
+
• → s
(b) BCl 3 +PhNH 2 → PhHN 2 • BCl 3
(c) BF+KF
3 → K[BF]4
1515. (a) HFisaweakelectrolyte,butwhenmixedwithKF,formsastrongelectrolyte KHF2 which
ionizesas:
KHF2 → K+H+2F+ + –

−
Fluorideionsmakesacomplex AlF4 with AlF3 , makingitsoluble.Adding BF3 , causes AlF3 to
reprecipitateas:
4 → BF4 +AlF.3
– –
BF+AlF
3
Solutions 691

1516. (a) Intrisilylamine, pπ- dπ backbondingoccursmakingnitrogen

2
sp -hybridized.

HSi—N—SiH
3 3 Nosuchbackbondingis possibleintrimethylamineandnitrogenis in
3
sp -state.
SiH3
(b) Duetopresenceofvacant d-orbitalwithsilicon,itformsanetworkstructureas:
O
O==Si==O Si==O

O==Si==O
Nosuchbondinginpossiblewith CO 2 sincecarbondoesnotpossessvacant d-orbital.Therefore,
CO 2 remainsasisolatedgaseousmolecule.
1517. (a) 6NaOH+SiCl 4 → NaSiO+4NaCl+3HO
2 3 2

(b) HSiCl+HO
3 2 → HSi(OH)
3 → HSi—O—SiH+HO
3 3 2
(c) SiF+4HO
4 2  → Si(OH) 4 +4HF
1518. (a) Sn+2NaOH  → NaSnO+H
2 2 2

(b) 2SO+PbO
2 2 → Pb+2SO 3
(c) SiHCl
2 2 +2HO
2 → 2HCl+SiH(OH)
2 2 → —
(SiHO)—
2 n
Polymer
(d) 4ClCHSiCl
2 3 +3Li[AlH]4 → 4ClCHSiH+3Li[AlCl
2 3 4]
H H H H
1519. Be Be Be
H H H H
Apartofthechainstructureofpolymeric BeH2
HereeachBeistetrahedrallycoordinatedandeachhydrogenbridgingtwoBeatoms. The
Be—H—Bebondisa3centred2electronbond.
1520. (a) NaH+HO2 → NaOH+H 2
(b) 2NaN+Heat
3 → 2Na+3N 2
(c) 4KO+HO
2 2 2 → 4KOH+3O 2
(d) NaF+BF 3 → Na[BF]4
∆
1521. (a) [NH]4 2 [BeF]4 → BeF+2NHF
2 4

(b) 2NaCl+BeCl 2 → 2Na[BeCl

2 4]
Water
(c) BeF2 ()s → 2+ −
[Be(HO)
2 4] +2F
1522. (a) BeCl 2 monomerislinearandBeatomhastwovacant 2 p-orbitals,followingdiagramshows
oneofthesevacantorbitals:
Cl—Be—Cl
Cl—Be—Cl Cl
Cl—Be Cl—Be
Vacant2- p-orbital Cl—Be—Cl Cl
Dimer
692 ProblemsinChemistry

DimerizationoccursbyCllonepairdonationintovacant 2 p-orbitalofBe.Hybridizationof
2
Beindimeris sp andeachBeatomstillhasonevacant 2 p-orbital.
(b) DiethyletherisaLewisbaseand BeCl 2 isaLewisacid,adductformationoccurs.
OEt2

Be Beistetrahedrallycoordinatedand 3
sp -hybridized.
EtO
2 Cl
Cl
1523. Anhydrous CaCl 2 ishygroscopicandformsahydrate,probably CaCl 2 ⋅ 2HO. 2 Inthepresenceof
alotofwater,hydratebecomesliquidsinceitisdeliquescent.Therefore,actionasadryingagent
dependsonhygroscopicnatureof CaCl 2 .
Ontheotherhand, CaH 2 reactswith HO 2 liberating H 2 :
CaH+2HO
2 2 → Ca(OH) 2 +2H 2
Therefore, CaH 2 isusedtoremove HO 2 fromasolvent.
1524. NaFandNaClareionicspecies.Thelatticeenergyandhence,meltingtemperature,ofNaFisthe
greater of thetwobecauseof itssmaller internuclear distance. CF4 and CCl 4 arecovalent
compounds,andsodonotadheretotheionicmodelandtheirmeltingtemperaturearedetermined
byvanderWaal’sforcewhichdependsonmolarmasses.
7 11
1525. np/ ratiofor 4 Be and 6 C are0.75and0.83, lessthanone, i.e., theirnucleicontainfewer
neutronsthanprotons,thereforepositronemittedas:
4 Be
7
→ 3 Li 7 + +1 e 0

6C
11
→ 5B
11
+ +1 e
0

14
np/ ratiofor 6 C is1.33,greaterthanone, i.e., itsnucleuscontainlargenumberofneutronsand
thereforesomeneutronsareconvertedintoprotons.
0n
1
→ 1 H1 + −1 e 0 , i.e., 6 C14 → 7 N 14 + −1 e 0
1526. Heconsistsoftwoprotons, twoneutronsandtwoelectronsandsumofthemassesofthese
nucleonsis4.033amu.Therefore, ∆m = 0.304 amuperatom.
∆E = ∆mc 2 = 2.736 × 1012 J/mol=2.835 × 10 7 eV.
1527. Ionicmobilityandconductivityinsolutiondependsonhydratedradiusoftheion. Largerthe
hydratedradius,lowerwillbetheionicmobilityandconductivityinaqueoussolution.Sizeof
hydratediondependsonextent ofhydrationwhichconsequentlydependsonpositivecharge
densityofcation.Smallersizeandhigherchargegivesagreaterchargedensityandcationsare
+
heavilyhydrated. Li ismosthydratedinitsgroupandhence, haslowestionicmobilityand
conductivity.
1528. Li hasmost negativereductionpotential suggest that ∆G ° shouldbemost negativeforthe
reaction:
Li → Li + + e E °=+ 3.05V, greaterthan E ° forCs.
Onthebasisofaboveobservation, Li shouldbemost reactive. Theactual reasonforhigher
reactivityofCsliesonkinetics.Ondescendingdownthegroup,meltingpointofmetal(GroupI)
decreasesandtheenergyproducedbyreactionissufficienttomeltthemetal,whichspreadmetals
Solutions 693
throughoutthesolutionallowinglargersurfaceareaforreaction.Hence,kineticsfavourgreater
reactivityofalkalimetalsdownthegroup.
1529. Dilutesolutionofalkalimetalsinliquidammoniaaredarkblueduetopresenceofsolvatedmetal
ionsandsolvatedelectrons:
M +NH 3 → M NH+3 e NH 3
+ −

Ifthesolutionisallowedtostand, thecolourslowlyfadesuntil it disappearsowingtothe

formationofmetal amide. At concentrationabove3M, solutionsarecopper-bronzecoloured
becauseofformationofmetalionsclusters.
1530. A: Li, B: Li 2O, C: LiH, D: H 2 , E: LiOH.
+ +
1531. Mg 2 ismoreheavilyhydratedthan Li duetogreatercharge/sizeratiointheformercase.
+
1532. Insalt,Beisdivalention Be 2 .SinceBebelongstoIIndperiodofperiodictabletheonlyavailable
orbitalsforcoordinationwith HO 2 are 2s and 2 p andamaximumoffourlonepairofelectronscan
beaccommodated.
1533. A:Ca, B: Ca(OH) 2 , C: CaCO 3 , D:CaO, E: CaC 2 .
1534. A: BaCO 3 , B: CO 2 , C: CaCO 3 , D:BaO.
1535. Duetoinertpaireffect,thestableoxidationstateis+2andnot+4whileforSnboth Sn 2+ and Sn 4+
arepossibleanditactsasareducingagent.
Sn 2+ → Sn 4+ + 2e.
1536. Innon-polarsolvent, dimericstructureisretainedwhileinaqueousmedium, highhydration
3+ −
energyissufficienttobreakthecovalentdimerinto [Al(HO)
2 6] and Cl as:

Cl Cl •• Cl
Al Al → Al(HO)
2
3+
6 +Cl –
Cl • Cl Inpolar(aqueous)solvent
• Cl
Innon-polarsolvent

1537. (a) BH+NH(excess)

2 6 3 Low
→ BH
2 6 ⋅ 2NH 3
T
High
(b) BH+NH(excess)
2 6 3 → (BN) x [Boronnitride].
T

(c) BH+NH
2 6 3 1:2
→ BNH(Borazine).
3 3 6
High T

1538. (a) BNH+HCl

3 3 6 3 → BNHCl
3 3 9 3

(b) BH+HO
2 6 6 2 → 2HBO+6H
3 3 2

(c) BNH+HO
3 3 6 9 2 → 3NH+3HBO+3H
3 3 3 2

(d) BH+EtOH
2 6 6 → 2B(OEt) 3 +6H 2
(e) BH+LiH
2 6 2 → 2Li[BH]4
(f) BH+HCl
2 6 → BHCl+H
2 5 2

(g) BH+Cl
2 6 3 2→ 2BCl 3 +6HCl
−
1539. A: Al 2Cl 6 , B: Al (aq ) + Cl ( aq ), C:AgCl,
3+
D: Al(OH) 3 , E: Li[AlH]4
694 ProblemsinChemistry

1540. (a) SiO+2C

2 Heat
→ Si+CO
Si+2Cl 2 → SiCl 4
(b) SiO+2C
2 → Si+2CO
2200°C
Si+C → SiC
1541. (a) Al 4C+3 12HO
2 → 3CH+4Al(OH)
4 3

(b) CaC+HO
2 2 2 → CH+Ca(OH)
2 2 2
°
(c) CaC+N
2 2 1100C
→ CaNCN+C
(Nitrolium)
O
(d) SiC+NaOHO
2 + 2 →
2
NaSiO+CO+HO
2 3 2 2

(e) MgC+HO
2 3 4 2 → 2Mg(OH) 2 +CHC3 ≡≡CH
1542. 2CHMgCl+SiCl
2 5 4 → (CH)
2 5 2 SiCl 2 +2MgCl 2

CH
2 5 CH2 5
 
(CH)
2 5 2 SiCl 2 +2HO
2 → HO—Si— OH Heat
→ (—Si— O)—n
 
CH2 5
CH2 5

1543. R 3SiCl ismonofunctional andact aschainterminator, hencestopthegrowthofpropagating

polymerchainas:
R R R R
   
(—Si—O)—H+HO—Si—
n R  → (—Si—O) n —O—Si— R
   
R R R R
(growingchain) (From R3SiCl) Chainterminated

CH3 CH3
Si
O O –

1544. (a) (b)

HC
3 CH3
Si Si – –
HC
3 O CH3
_ _ _
_ _
_ . . .
_ _ (d)
_.
_
. . _.
(c)
_ _ _
_
. .
_ _ _
.

_
Solutions 695

_ _

_
. _.
_ _
. _. .
(e)
_ _
. . .
_
_ _
. .

_ _

HO
1545. (a) P4 + 3NaOH → PH+3NaHPO
2
3 2 2

(b) CaNCN+HO 3 2 → 2NH+CaCO 3 3

(c) NH+I
2 4 2 2 → N+4HI 2
(d) NO+NaNH
2 2 2 → NaN+NH+NaOH
3 3

1546. Superphosphate:
3[Ca 3 (PO)4 2 ⋅ CaF]+7HSO
2 2 4 → 3Ca(HPO)
2 4 2 +7CaSO 4 +2HF
14444 244443
Superphosphate
Triplesuperphosphate:
[Ca 3 (PO)4 2 ⋅ CaF]+6HPO
2 3 4 → 4Ca(HPO)
2 4 2 +2HF
(Triplesuperph osphate)

1547. (a) NO+NaCl

2 5 → NaNO+NOCl
3 2

(b) NO+Na
2 5 → NaNO+NO 3 2
(c) NO+HO
2 4 2 → HNO+HNO 2 3
(d) 2NO+Cl2 2  → 2NOCl
2
(e) 2NO+HCl
2  → 2NOCl+Cl 2 +2HO 2

1548. In N 2 ,duetosmallersizeof 2 p-orbital,effective pπ- pπ overlaptakesplacegivingveryhigh

“bond-energy”to N 2 molecule.In P2 , bondenergyisjusthalfoftheN—Nbondenergyin N2
duetopoor pπ- pπ overlapbetweenthelarger 3 p-orbitals. Ontheother handin P4 , each
phosphorusistetrahedrallybondedtothreeotherphosphorusatomsgivingthree σ-bondtoeach
phosphorus,greaterbondenergythan P2 , hencemorestable P4 isformed.
P
N N P P P P
better pπ-pπ overlap poor pπ-pπ overlap P
morestablestructure

1549. In NF3 , N—Fbondisstrongestanditbehaveslikeotherinertmolecules CF4 , etc.

696 ProblemsinChemistry
O
..
P P
O O O O
O O
1550. : P P: O P P O
O O
O .. O O O
P P
P4O6 P4O10
O

1551. (a) Ostwaldmethod: InOstwaldprocess, NH 3 isoxidisedfirst intoNOinpresenceof

platinum,rhodiumcatalystathightemperatureandpressure.NOisthenfurtheroxidisedinto
NO 2 andabsorbedinwater.
Platinum/Rhodium
4NH 3 (g ) + 5O 2 (g ) → 4NO(g ) + 6HO
2 (g )
5atmosphere,850C°
→ 2NO(g ) + O 2 ( g ) 2NO 2 (g )
2 ()l → HNO+HNO
2NO 2 (g ) + HO 3 2
2HNO 2 → HO+NO+NO
2 2

3NO+HO
2 2 → 2HNO+NO
3

(b) 2HNO+2FeO
2 → 2NO+HO+FeO 2 2 3 Oxidisingaction
5HNO+2KMnO+3HSO
2 4 2 4  → 2KSO+2MnSO+3HO
2 4 4 2 Reducingaction
1552. (a) Ligandoxygenhastwounpairedelectronsinitsmolecularorbitals, givingparamagnetic
characterwhile N 2 hasallpairedelectronsinmolecularorbital,anddiamagnetic.
+
(b) NO hasbondorderofthreewhilebondorderofNOis2.5.
4 → 2H+2HSO
+ –
1553. Preparation: 2HSO
2 4

atanode
2HSO –4 → HSO
2 2 8 + 2e −
HSO+2HO
2 2 8 2 → 2HSO+HO.
2 4 2 2

H
O
Structure: 97°
Openbooklikestructure.
O
H 94°

(a) 2KMnO+3HSO+5HO
4 2 4 2 2 → KSO+2MnSO+8HO+5O
2 4 4 2 2
(b) KCrO+4HO+HSO
2 2 7 2 2 2 4  → 2CrO+KSO+5HO
5 2 4 2
(c) 2KI+HO2 2 → I 2 +2HO 2
(d) 2K[Fe(CN)
4 6 ]+HO+HSO
2 2 2 4 → 2K[Fe(CN)
3 6 ]+KSO+2HO
2 4 2
Solutions 697

O O O O O O
           
1554. (a) HO—S —OH (b) HO—S —S —OH (c) HO—S —S —OH (d) HO—S —OH
+IV   +III  
O S
+Vand+III +IVand–II
O O O O O
         
(e) HO—S —S —OH (f) HO—S —O—OH (g) HO—S —O—O—S —OH
         
O O O O O
(+V) (+VI) (+VI)

1555. Incontactprocess, SO 2 isoxidizedbyairinto SO 3 inpresenceof VO 2 5 catalyst:

1 VO
O 2 → SO 3
2 5
SO+2
2
SO 3 isthenpassedthrough98% HSO, 2 4 forming HSO
2 2 7 (oleum).Thissolutionisthendiluted
toobtainsulphuricacidofdesiredstrength.
boiling
1556. NaSO+S
2 3 → NaSO
2 2 3
water

Heatin
2NaS2 3 +3O 2 → 2NaSO+2S
2 2 3
air
Thiosulphuricacidcan’tbepreparedbyaddingacidtotheaqueoussolutionofthiosulphatesalt,
sincethefreeaciddecomposesinwaterintomixtureofS, HS,
2 SO 2 , etc.Itcanbemadeinthe
absenceofwaterandatlowtemperature.
1557. (a) 2F+HO
2 2 2 → 4HF+O 2
(b) Cl 2 +CO → COCl 2
(c) 3Cl 2 +NH
8 3 → N+6NHCl
2 4
(d) 3Cl 2 +NaOH
6 → 5NaCl+NaClO+3HO 3 2
(e) SiO+HF
2 6  → HSiF+2HO
2 6 2

1558. (a) Cl 2 O+NaOH

2 → 2NaOCl+HO 2

(b) 4HClO+PO 4 4 10 → 2Cl 2 O+4HPO

7 3
(c) 2ClO+NaOH
2 2 → NaClO+NaClO+HO
2 3 2
(d) KBrO+F+KOH
3 2 2  → KBrO+2KF+HO
4 2
(e) Cl 2O+NaOH
6 2 → NaClO+NaClO+HO
3 4 2
(f) Cl 2O+HF
6 → FClO+HClO
2 4

1559. First,watermustbeabsentinpreparationof F2 byanymethod,otherwise F2 , beingthestrongest

oxidisingagent, oxidiseswaterinto O 2 convertingitselfintoHF. Secondly, HFinanhydrous
state, isonlyslightlyionizedandisthereforeapoor conductor of electricity. Therefore,
anhydrousHFisdifficulttoelectrolyse.Forthepurposeofproducing F2 byelectrolyticmethod,a
mixtureofHFandKFiselectrolysed.HFfirstcombineswithKFformingaconducting K[HF2 ],
enablingelectrolysiseasier.
698 ProblemsinChemistry
F
O O O—O O==I—O—I==O
1560. (a) F 103° F Cl 111° Cl F
O O
(b) Repulsionbetweenthelonepairreducesthebondanglein OF2 whilein Cl 2O,bondangleis
greaterthantetrahedralbondangleduetostericcrowdingofthelargerhalogenatoms.
1561. (a) XeF+HCl
2 2 → Xe+2HF+Cl 2
(b) XeF+KI
4 4 → Xe+4KF+2I 2
(c) XeF+SF
4 2 4 → Xe+2SF 6
(d) 2XeF+HO
2 2 2 → 2Xe+4HF+O 2
6 2 → 2Xe+XeO+12HF+
3
(e) 3XeF+HO
4 3 2
O2
(f) XeF+HO6 3 2 → XeO+6HF 3
XeF+HO
6 2 → XeOF+2HF 4
(g) 2XeF+XeO6 3 → 3XeOF4
(h) XeO+XeOF3 4 → 2XeOF 2 2
3+
1562. Fe ( aq .) isastrongeroxidisingagentthan Br 2 butweakerthan Cl 2 .
1563. In ClF3 ,Clhastenelectronsinitsvalenceshell,sevenofitsownandthreesharedelectronsfrom
threefluorine. Since, chlorinehasvacant d-orbitals (3s 2 3 p 5 3d 0 ), it canextenditsvalency
beyondeight, i.e.,itcanviolateoctetrule.Ontheotherhand,in FCl 3 ,thecentralfluorineatom
hasten-valenceelectronswhichisnotpossiblesince, fluorinehasnovacant d-orbitalsandit
cannotviolateoctetrule (2s 2 2 p 5 ).
1564. Duetoverysmall sizeofnitrogen, their p-orbitalsmakeseffectiveoverlapformingstrong
pi-bondsandnitrogenacquireoctetconfigurationbyformingasigmaandtwopi-bondsbetween
twonitrogenatomsas:

N N hascompleteoctetatbothnitrogen.

Ontheother hand, duetolargesizeof phosphorusatom, their p-orbitalsdonot overlaps

efficientlytoformpi-bonds.Duetothisreasons,phosphorusatomsformspreferablysigmabonds
andat roomtemperatureit exist as P4 containingsigma-bondsonly. Ifheatedat veryhigh
temperature,itdecomposespartiallyintolessstable P2 molecules.
1565. Sulphurcontainsvacant d-orbitals, canextenditsvalencybeyondeight whileoxygenlacks
vacant d-orbital,can’tviolateoctetrule
1566. CuF+HSO
2 2 4 → CuSO+2HF4

2NaCl+HSO 2 4 → NaSO+2HCl
2 4
HBrandHIcannotbepreparedbytheabovemethodbecausetheyareoxidisedintoelemental
bromineandiodineas:
2NaBr+2HSO 2 4 → NaSO+SO+2HO+Br
2 4 2 2 2.
Solutions 699
+ –
1567. Boricacid B(OH) 3 ,onlypartiallyreactwithwatertoform HO
3 and B(OH) 4 ,itbehavesasa
weakmonobasicacid
–
B(OH) 3 +2HO
2 B(OH) 4 + HO
3
+

Thus,boricacidcan’tbetitratedsatisfactorilywithNaOHasasharpendpointisnotobtained.
Adding cis-diol ortriol (glycerol)enhancesacidicstrengthofboricacidbyformingastable
complexas:

B(OH) 3 +2HO
2 B(OH) –4 +HO3 +
…(i)
 
–

    OH
 C O 
 C  OH –2HO
B(OH) 4 +
–
→
2
   diol
→
 B
 C  OH    –2HO
2
   C O OH
  
   s

  C O  
 O  C 
  B  
   
  C O O  C 
   
(X )
Theformationof complexof B(OH) –4 withdiols, asshownabove, removes B(OH) –4 from
solution,drivingreaction(i)inforwarddirectionandall B(OH) 3 reactsquantitativelywithwater
forming B(OH) –4 requiredforformationofstablecomplex( X).Thisincreasesacidstrengthand
boricacidbecomesstrongacidinpresenceofsuchorganiccompounds.
1568. In CCl 4 , carbonhasnovacantorbitalwherewatercanattackandtherefore,itisinerttowards
water.Ontheotherhand,Siin SiCl 4 hasvacant 3d-orbitals,availableforattackbywater,which
makesithighlyreactivewithwater.
Cl

Cl Si Cl OH2

vacant d-orbitalsarethesiteof
Cl
attackbywatermolecule

Ifsufficientenergyissuppliedbyusingsuperheatedsteam, CCl 4 hydrolysesformingphosgene

gas:
Superheated
CCl 4 +HO(
2 g ) → COCl 2 +2HCl
1574. Initially CaCO 3 isformedaswhiteprecipitateas:
CO+Ca(OH)
2 2 → CaCO 3 ↓ +HO
2
700 ProblemsinChemistry

Onfurtherpassageof CO 2 ,solid CaCO 3 comesinsolutionbyformingsolublebicarbonateas:

CaCO+HO+CO
3 2 2 → Ca(HCO)3 2 ( aq )

1575. Phosphoricacidisprotondonorandgivesthreeprotononcompleteionisation, exhibitingits

tribasiccharacter:
O==P(OH) 3 PO 3–
4 +3H
+

Ontheotherhand, boricacidiselectrondeficientandboronhasonlysixsharedelectronsin
valenceshell, ie. ., twoelectronsshortofstableoctetconfiguration.Hence, HBO
3 3 behavesas
Lewisacid.Also,itcanacceptonlyonelonepair,itismonobasic:
s ⊕
(HO) 3 B (avacantorbital)+ •
• NH 3 → (HO) 3 B ← NH 3
1577. 3NaHCO+NaAl(SO)
3 4 2 → 3CO+2NaSO+Al(OH)
2 2 4 3
1578. Inertpaireffect.Aswedescenddownagroupintheperiodictable,inertpaireffectbecomesmore
andmorepronauncedandoxidationnumberdecreasesbytwounit.
1579. Aluminiumbeingstronglyelectropositive,reactswithacidcomponentsoffood.
3+
1580. Inbetween pH=5 to pH=8,Al precipitateas Al(OH) 3 .Asitsettles,thegelatinous Al(OH) 3
trapsandremovessuspendedsolidsfromthewater.
1581. (a) NH(
2 4 aq )+HCl → NHCl
2 5
3
(b) 2NO(g )+ 2 O(2 g )  → NO(
2 5 g)
(c) 2NO(2 g )+HO()2 l → HNO+HNO
2 3
(d) 2NH 3 (g ) + 4O 2 ( g ) → NO+3HO
2 5 2
°
200C
(e) NHNO
4 3 ()l → NO+2HO
2 2
Electricspark
1582. (a) 2Al+FeO2 3 → Al 2O+2Fe
3 ∆H <0
(b) NaO+HO
2 2 2 → 2NaOH+ 12 O 2 (g )
(c) Pb 2+ +O+HO
3 2 → PbO+O+2H
2 2
+

1583. (a) 2KO+HO

2 2 → 2KOH+ 32 O 2
(b) 3O+Cl
3
–
→ 3O+ClO
2
–
3
1584. Boraxontreatmentwith CaF2 inconcentratedsulphuricacidsolutiongives BF3 as:
NaBO+6CaF+8HSO
2 4 7 2 2 4  → 6CaSO+4BF+7HO+2NaHSO
4 3 2 4

1585. S+O 2  → SO 2 …(i)

Na+HO2 → NaOH(aq ) + 12 H 2 (g ) …(ii)
FromEqs.(i)and(ii),
2NaOH+SO 2 → NaSO+HO
2 3 2 …(iii)
SO 2–
+HO+Cl
32 2 → 2Cl +SO 4 +2H +
– 2–

{fromEq.(iii)}
Boilingelementalsulphurinalkalinesolutionof NaSO
2 3 givesthiosulphateas:

3 ( aq ) + S ()s →
SO 2– 2–
SO
2 3
(thiosulphateion)

1586. The NF3 haslittletendencytoactasdonormolecule.ThehighlyelectronegativeFatomsattract

electronsandthesemomentspartiallycancelthemomentfromthelonepairwhichreducesits
Solutions 701
donorpower.Ontheotherhand,in PF3 ,P  F bondlengthislargercomparedto N  F, bond,
electronwithdrawingeffect of fluorinedoesnot transmit effectivelyontothelonepair on
phosphorusin PF3 .Hence, PF3 actasagooddonormolecule.
Ni[CO] 4 +4PF 3 → Ni(PF)3 4 +4CO
1587. A:NH;B:NO;C:NO;D:NO;E:HNO;F:N;G:CaNCN
3 2 2 3 2 2 .
1588. In POCl 3 ,thereis pπ − d π backbondingbetweenoxygenandphosphorusas:
O

pπ – dπ Duetothis pπ − d π backbonding,P—Obondacquiredouble
backbonding P bondcharacter andhence, P—Obondis shorter thanthe
expectedbond-length.
Cl
Cl Cl

1589. Toattain the pentavalent state, d-orbitals must be used. Hydrogen is not sufficiently
electronegativetomakethe d-orbitalscontractsufficiently,hence, PH 5 isnotformed.
1590. HCl( g ) ispreparedfromNaCland HSO2 4 as:

∆
2NaCl+HSO
2 4 → NaSO+2HCl
2 4 (g )
HCl( g ) doesnot possesssufficient reducingpowerrequiredforreducing HSO
2 4 , hence, the
abovereactionissuccessfulinpreparing HCl( g ).
ContrarytoHCl,HBrandHIareoxidisedby HSO 2 4 as:
2HBr+HSO 2 4 → Br 2 +SO+2HO 2 2
2HI+HSO 2 4 → I 2 +SO+2HO2 2
Hence,HBrandHIcan’tbepreparedbythereactionofNaBrandNaIwith HSO
2 4.
+
 H  O
   •• ••  
1591. (a) H ≡≡
C P •• (b)  P  (c) H  P  P  H (d) P
H H   –
O O–
  H H
 H  O –

F
F

(e) F P

F
F

1592. (a) P+4Al

4 → 4AlP
(b) P+10F
4 2 → 4PF5
(c) P+12Na
4 → 4NaP3
(d) P+Se
4 → PSe
4 6 +PSe
4 10
(e) P+Cl
4 2 → PCl 3 +PCl 5
2O
(f) P+3O
4 2 → PO
4 6 →2 PO
4 10
702 ProblemsinChemistry

1593. Doublebondisformedbyside-wise(lateral) overlapingof p-orbitalsholdingelectronsof

oppositespin.Forefficientpi-bonding(lateraloverlap),the p-orbitalsmustbeclose-enoughin
ordertoallowthemtooverlapuptosomeextentandthiswillbepossibleifatomsaresmall
enoughinsize. Oxygen, beingthesmallest initsgroup, its p-orbitalsarecloseenoughand
formationofpi-bondbecomepossible.Ontheotherhand,sulphuristoolargeinsizethattheir
p-orbitalsdon’tcomecloserenoughtoallowtheformationofpi-bonds,hence,sulphurexistas S8
inwhichallbondsaresigmacovalentbonds:

S S

O-molecule
2 S-atomsare Swith
8
showing π-bond muchdistantand allsingle,sigma
formation noeffective π-bond covalentbonds
areformed

1594. Aswedescenddowntohologengroupinperiodictable,molarmassincreasesrapidlyandhence,
intermolecularforceofattraction(vanderWaalsforceofattraction).Duetothisincreaseinforce
ofattraction,volatilitydecreasesfromtoptobottomandtheirboiling/meltingpointincreases.
3
1595. (a) Xein XeOF 2 2 is spd hybridizedandshapeofthemoleculeis
F
O

Xe

O
F
•• +
+
(b) Xein XeF is sp 3 hybridized: •
• Xe  F
••
Linear
+
(c) Xein XeF3 is sp 3 hybridized: F

+
Xe

F
F
(d) Xein XeO 4– 3
6 is spd
2
hybridized:
O

O O 4–

Xe

O O