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1.

[Sol.

2.

[Sol.

WhatisthepKbofaweakbasewhose0.1MsolutionhaspH=9.5?
(A)7.5
(B*)8
(C)9
(D)10
1
pOH= [pKblogC]
2
9=pKblog(0.1)
pKb=8
Ans.

Theenthalpychangeforthereaction,
CH3CHO(g)CH4(g)+CO(g)at300Kis17.0kJ/mol
CalculatethetemperatureatwhichrHforthereactionwillbezero.
[Given:Cp,m(CH4,g)=38J/Kmol;Cp,m(CO,g)=31J/Kmol&Cp,m(CH3CHO,g)=52J/Kmol]
(A)1300C
(B*)1027C
(C)700C
(D)Noneofthese
AsperKirchoff'slaw
r H T2 r H T1 r C p ,m (T2 T1 )

rCp,m=38+3152=17
0(171000)=17(T2300)
T2=1300K or
T2=1027C Ans.]
3.

Theequilibriumbetween,gaseousisomersA,BandCcanberepresentedas
Reaction
Equilibrium constant
A(g) B(g)

K1=?

B(g) C(g)

K2=0.4

C(g) A(g)
:
K3=0.6
IfonemoleofAistakeninaclosedvesselofvolume1litre,then
(A*)[A]+[B]+[C]=1Matanytimeofthereactions
(B)ConcentrationofCis4.1Mattheattainmentequilibriuminallthereactions
1
0.24
(D*)Isomer[A]isleaststableasperthermodynamics.
(a)
[A]+[B]+[C]=1mole/L
sinceforeveryreactionng=0

(C*)ThevalueofK1is
[Sol.

(b)

[ C]
=0.4[C]=0.4[B]
[B]
[ A]
=0.6
[C]

[A]=0.6[C]

[A]+[B]+[C]=1
0.6[C]+

[ C]
+[C]=1
[0.4]

1 =1
[C] 0.6
0 .4

[C]=

4
1

16.4 4.1

[B] 1

=K1]
[A ] 0.24

4.

Whichofthefollowingarrangementwillproduceoxygenatanodeduringelectrolysis?
(A)DiluteH2SO4solutionwithCuelectrodes.
(B*)DiluteH2SO4solutionwithinertelectrodes.
(C*)FusedNaOHwithinertelectrodes.
(D*)DiluteNaClsolutionwithinertelectrodes.

5.

CalculatetheEMF(inmilliVolt)ofthecell
Pt|H2(g)|RNH3Cl(aq)||HA(aq)|H2(g)|Pt
1bar0.1M0.01M0.5bar
[Given:Ka(HA)=4106, K b ( RNH 2 ) =105,2.303

[Sol.

RT
=0.06; log2=0.3]
F
[Ans.0087.00]

[H ]2RHS ( PH 2 ) LHS
0.06
Ecell=
log 2
[H ]LHS (PH 2 ) RHS
2
K w 10 14

Kh=
=109
K b 10 5

ForRNH3Cl
=

Kh
10 9

=104
C
0 .1

RNH3+(aq)+H2O(l) RNH2(aq)+H3O+(aq)
Ateqm
C(1)

C
C
+
[H3O ]LHS=C
=0.1104=105
ForHA

Ka
4 10 6

=2102
C
0.01
[H3O+]RHS=C=0.0121022104

(2 10 4 ) 1
0.06
0.06

log (8 10 2 )
Ecell=
log
=
5 2
0 .5
(10 )
2
2

0.06
0.06
log 8
2
2
2
=0.030.9+0.06=0.087V
or
Ecell=87mV Ans. ]

6.

AsolutionofNa2S2O3istobestandardisedbytitrationagainstiodineliberatedfromstandardKIO3
solution.Thelaterispreparedbydissolving4.28gmofKIO3inwaterandmakingupto500ml.20ml
ofthissolutionarethenmixedwithexcessKIsolutionandthefollowingreactionoccurs.

IO3 +5I+6H+3I2+3H2O
TheresultingiodineistitratedwiththeNa2S2O3solutionaccordingto
I2+ 2S2O32 2I+ S4 O 62
anditisfoundthat48mlareneeded.
Calculatetheconcentration(inmillimoles/L)ofNa2S2O3solution.
[Sol.

MolarityofKIO3solution=

[Ans.0100.00Ans.]

4.28 / 214
=0.04moles/L
0.5

0.04 20
3
1000
=2.4103

MolesofI2produced=

Molesof S2 O32 req.=2 n I 2


=22.4103
=4.8103
Concentrationof S2 O32 =
7.

[Sol.

4.8 10 3
=100millimoles/L
48 103

Whatvolumeof0.2MRNH3Clsolutionshouldbeaddedto100mlof0.1MRNH2solutionto
produceabuffersolutionofpH=8.7?
Given:pKbofRNH2=5;log2=0.3
(A)50ml
(B*)100ml
(C)200ml
(D)Noneofthese
LetVmlofRNH3CladdedintoRNH2solution
[RNH3Cl]inresultantsolution=

0 .2 V
;
100 V

2=

0 .2 V
10

[RNH2]=

100 0.1
100 V

0.2 V
100 V

5.3=5+log
100

0
.
1

100 V

[RNH 3 ]
pOH=pKb+log
;
[ RNH 2 ]

8.

V=100ml

ForthereactionA(g)+2B(g)lC(g)+D(g); Kc=1012.
3

[Sol.

IftheinitialmolesofA,B,CandDare0.5,1,0.5and3.5molesrespectivelyinaonelitrevessel.What
istheequilibriumconcentrationofB?
(A)104
(B*)2104
(C)4104
(D)8104
A(g)+2B(g) C(g)+D(g)
n
Ateq 0.5x12x0.5+x3.5+x
~
y ~
2y ~
1 ~
4
(duetoveryhighvalueofequilibriumconstant)
1 4
;y=104
y (2 y) 2
[B(g)]=2y2104

1012=

9.

Ans.]

Selectcorrectstatement(s).
(A*)Anelectron'senergyincreaseswithincreasingdistancefromnucleus.
R
4
(C)ThesecondorbitinHe+hasradiusasthefirstorbitinhydrogenatom.
(D*)Thenumberofd-electronsretainedinFe2+ionis6(AtomicnumberofFe=26)

(B)TheshortestwavelengthintheBrackettseriesofHe+ionis

10.[MATCH THE COLUMN]


Column I
Column II
(A)

ln2

(P)

Ifinitialmoleistwothenmoleofradioactiveelement
leftaftertimet.

(B)

1et

(Q)

Fractionofnucleithatdecayintimet.

(C)

et

(R)

Ratioofactivityofnucleusattimettoinitialactivity.

(S)

Ratioofhalflifetomean(average)lifeforradioactive
element.

(D)

t
1
t
1
/2

[Ans.(A)S,(B)Q,(C)R,(D)P]
11.

At300K,thevapourpressureofanidealsolutioncontaining3moleofAand2moleofBis600torr.
Atthesametemperature,if1.5moleofA&0.5moleofC(non-volatile)areaddedtothissolutionthe
vapourpressureofsolutionincreasesby30torr.Whatisthevalueof PBo ?
(A)940

[Sol.

(B)405

(C*)90

(D)noneofthese

P= PAo x A PBo x B
4

o 3
o 2
PB
; 3P o 2P o 3000
600= PA
A
B
3 2
23

&

4 .5
2

o
o
PB
; 4.5P o 2P o 4410
630= PA
A
B
4.5 2 0.5
4.5 2 0.5
1.5 PAo 1410 ; PAo 940 & PBo 90

12.

[Sol.

ThefH(N2O5,g)inkJ/molonthebasicofthefollowingdatais:
2NO(g)+O2(g)2NO2(g)
rH=114kJ/mol
4NO2(g)+O2(g)2N2O5(g)
rH=102.6kJ/mol
fH(NO,g)=90.2kJ/mol
(A*)15.1
(B)30.2
(C)36.2
(D)noneofthese
1
1
N2(g)+ O2(g)NO(g)
2
2
N2(g)+O2(g)2NO(g)
2NO(g)+O2(g)2NO2(g)
1
O (g)N2O5(g)
2 2
(1)+(2)+(3)

13.

Ans.]

fH=90.2
rH=90.22
rH=114

...(1)
...(2)

102.6
=51.3
2

2NO2(g)+

rH=

...(3)

5
N2(g)+ O2(g)N2O5(g)
2

fH(N2O5,g)=15.1kJ/mol]

d[A ]
ForthereactionAB,theratelawexpressionis d t =k[A]1/2.Ifinitialconcentrationof[A]is

[A]0,then
2 1/ 2
1/ 2
(A*)Theintegeratedrateexpressionisk= ( A 0 A )
t

(B*)Thegraphof A Vstwillbe

(C)Thehalflifeperiod t1 / 2 =

K
2[A]10/ 2

(D*)Thetimetakenfor75%completionofreaction t 3 / 4 =
[Sol.
t=0
t

[A]0
k

AB
a

ax
x
5

dx
=k(ax)1/2
dt

dx
(a x )1 / 2 k dt
0
0

2 (a x )1 / 2

1
1

(a x ) 2
(1)
kt
1

2 0

2 a 1 / 2 (a x )1 / 2 kt

= 2 a

1
1

1/ 2

= 2a

2 1

14.

0
x

kt

1 / 2 a 1 / 2
2 a
2

kt1 / 2

2 1

= 2 a

t1 / 2

2 1/ 2 1
= a 1
k
2

1/ 2

2 1/ 2 a
t75%= k a 4

2[A]0 2 1
k

a1 / 2 [A ]0

]
k
k
A2.5gmimpuresamplecontainingweakmonoacidicbase(Mol.wt.=45)isdissolvedin100ml
th

1
waterandtitratedwith0.5MHClwhen ofthebasewasneutralisedthepHwasfoundtobe9
5

andatequivalentpointpHofsolutionis4.5.Given:Alldataat25C&log2=0.3.
Selectcorrectstatement(s).
(A)Kbofbaseislessthan106
(B*)Concentrationofsalt(C)atequivalentpointis0.25M
(C*)VolumeofHClisusedatequivalentpointis100ml
(D)Weightpercentageofbaseingivensampleis80%.
th

[Sol.

1
Whenbaseis neutralised
5

(a / 5)

pOH=pKb+log
4a 5

RNH2+HClRNH3Cl

1
5=pKb+log
4
pKb=5.6

ax
4

a
5

a
5

1
pH= [pKwpKblogC]
2
logC=0.6
C=0.25
LetVmlofHClisused

4.52=(145.6logC)

0 .5 V
=0.25
V 100
V=100ml
M.Molesofacid=M.Molesofbase
=0.510050

Wt.%ofbaseinsample=

50 10 3 45
10090 ]
2 .5

Paragraph for question nos. 15 to 17


W.H.Nernstderivedamathematicalrelationshipbetweentheemfofacell(Ecell)andtheconcentration
ofreactantsandproductsinaredoxreactionundernon-standardconditions.Thenernstequationfor
aredoxreactionofthetype
aA+bBcC+dD
is

Ecell= E ocell

RT
lnQ
nF

0.0591
logQ
n
whereQisthereactionquotient.Atequilibrium,thereisanonettransferofelectron,soE=0andQ
=K,whereKistheequilibriumconstant.Wecanalsoapplynernstequationforahalfcelltocalculate
oxidationorreductingpotential.

Ecell= E ocell

at298K

15.

WhatistheEMFofrepresentedcellat298
Ag|Ag+(aq,0.1M)||H+(aq,0.1M)|H2(g,0.1bar)|Pt
Given : E o

Ag / Ag

[Sol.

(A)0.77V
Cellreactionis

0.8V
(B)0.829V
(C*)0.77V
(D)Noneofthese
+
+
2Ag(s)+2H (aq)2Ag (aq)+H2(g)
0.0591
(0.1) 2 0.1
log
Ecell=0.80
2
(0.1) 2

Ecell=0.80+0.02955
=0.77V
Ans. ]
16.

FindthesolubilityproductofasaturatedaqueoussolutionofAg3PO4at298Kiftheemfofthecell
Ag|Ag+(saturatedAg3PO4)||Ag+(aq,0.01M)|Agis0.1182Vat298K.
(A)1016
(B)2.71015
(C*)3.331017
(D)Noneofthese

[Sol.

0.0591 [Ag ]RHS


log
Ecell=
1
[Ag ]LHS
0.0591 0.01 0.01
log
10 2
;
1
x
x
+
4
[Ag ]LHS=x=10 M

0.1182=

Ag3PO4(s)l3Ag+(aq)+ PO 34 (aq)
1
10 4
3

104

17.

1
4
Ksp=[Ag+]3[PO43]=(104)3 10
3

17
Ksp=3.3310 ]
Whatwouldbethereductionpotentialofanelectrodeat298K,whichoriginallycontained1M
K2Cr2O7solutioninacidicbuffersolutionofpH=1.0andwhichwastreatedwith50%oftheSn

necessarytoreduceall Cr2 O 72 toCr3+.AssumepHofsolutionremainsconstant.


2.303 RT
0.06
F
(C*)1.187V

Given : E oCr O 2 / Cr3 ,H 1.33 V ;log2=0.3;


2 7

(A)1.285V

(B)1.193V

(D)Noneofthese

Cr2 O 72 +14H++6e2Cr3++7H2O
Initialconn
1
0.1
0
Afterreaction 0.5
0.1M
1M
[Sol.

ERP= E oRP

[Cr 3 ]2
0.06
log
[Cr2 O 72 ][H ]14
6

ERP=1.33

1
0.06
log
(0.5) (0.1)14
6

0.06
log(21014)
6
=1.187V]

=1.33

18.

Atcertaintemperature(T)ifconductivityofpurewateris5.5107Scm1thencalculatepOHof
purewaterattemperatureT.

Given : H =350Scm2eq1; OH =200Scm2eq1


(A)5
[Sol.

(B*)6

(C)7

(D)8

k 1000
5.5 10 7 1000
; N
=106
N
550
Kw=N2orM2 ;
pH=pOH=6 ]
H 2O

19.

CalculatethemillimolesofSeO32 insolutiononthebasisoffollowingdata:
70mlof

M
solutionofKBrO3wasaddedtoSeO32 solution.Thebromineevolvedwasremovedby
60

boilingandexcessofKBrO3wasbacktitratedwith12.5mlof

M
solutionofNaAsO2.
25

Thereactionsaregivenbelow.
(a) SeO32 + BrO3 +H+ SeO 24 +Br2+H2O(b) BrO3 + AsO 2 +H2OBr+ AsO 34 +H+
[Sol.

(A)1.6103
(B)1.25
+4+5

(C*)2.5
+60

(D)Noneofthese

SeO32 + BrO3 +H+ SeO 24 +Br2+H2O

(a)

+5+31+5

BrO3 + AsO 2 +H2OBr+ AsO 34 +H+

(b)

Inreaction(b)
gmeq.of BrO3 =gm.eq.of AsO 2
n BrO 6 n AsO 2
3

n BrO
3

12.5 1
2 =103
1000 25

10 3

Inreaction(a)
molesof BrO3 consumed=

70
1 10 3

=103
1000 60
6

gmeq.of SeO32 =gm.eq.of BrO3


n SeO 2 2 10 3 5
3

n SeO 2 2.5 10 3
3

20.

[Sol.

Ans.

HowmanytimessolubilityofCaF2isdecreasedin4103MKF(aq.)solutionascomparetopure
waterat25C.GivenKsp(CaF2)=3.21011
(A)50
(B*)100
(C)500
(D)1000
3
11
4S =3.210
S=2104
9

LetsolubilityofCaF2isxinKFsolution
K sp=x(2x+4103)2;3.21011=x10616;x=2106]
21.

Statement-1 :
pHof107MNaOHsolutionisexistbetween7to7.3at25C.
Statement-2 :
Duetocommonioneffectionizationofwaterisreduced.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.

22.

Statement-1

Ingeneralphenolphthaleinisusedasanindicatorforthetitrationofweakacid
(HA)againststrongbase(NaOH).
Statement-2 :
Atequivalentpointsolutionisbasic.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.
Paragraph for question nos. 23 to 25
Afactory,producingmethanol,isbasedonthereaction:
CO+2H2lCH3OH
Hydrogen&carbonmonoxideareobtainedbythereaction
CH4+H2OlCO+3H2
Threeunitsoffactorynamely,the"reformer"fortheH2andCOproduction,the"methanolreactor"for
productionofmethanolanda"separator"toseparateCH3OHfromCOandH2areschematically
showninfigure.

CH4
+
H2O

Reformer

CO
+
H2

()

Methanol
Reactor

CO
+
H2
+
CH3OH
()

CH3OH

()

Separator

()

Fourpositionsareindicatedas,,and.Theflowofmethanolatpositionis103mol/sec.The
2
factoryissodesignedthat oftheCOisconvertedtoCH3OH.ExcessofCOandH2atposition
3
areusedtoheatthefirstreaction.Assumethatthereformerreactiongoestocompletion.Atthe

1
position()moleratioofCOtoH2is .
3
CO+2H2lCH3OH

23.

Hr=100R

WhatistheflowofCOandH2atposition()?
(A)CO:1500mol/sec.;H2:2000mol/sec.
10

[Sol.

(B)CO:1500mol/sec.;H2:3000mol/sec.
(C)CO:1000mol/sec.;H2:2000mol/sec.
(D*)CO:1500mol/sec.;H2:4500mol/sec.
x
3x
0
CO+2H2lCH3OH
xy 3x2y
y
y 2

x 3
2
y= x=103mol/sec.
3

24.

[Sol.

25.
[Sol.

26.

[Sol.

3
x= 103mol/sec.
2
x=1500mol/sec.
(CO,)=1500mol/sec.
(H2,)=4500mol/sec.
]
WhatistheflowofCOandH2atposition()?
(A)CO:500mol/sec.;H2:1000mol/sec. (B*)CO:500mol/sec.;H2:2500mol/sec.
(C)CO:500mol/sec.;H2:2000mol/sec. (D)CO:500mol/sec.;H2:1500mol/sec.

(CO,)=15001000500mol/sec.
(H2,)=450020002500mol/sec.

Amountofenergyreleasedinmethanolreactorin1minute?
(A)1200kcal
(B*)12000kcal
(C)6000kcal
CO+2H2lCH3OH
q=H100060
=61041002
=12106cal
q=12000kcal
]

(D)Noneofthese

Thefreezingpointdepressionofa0.10Msolutionofformicacidis0.2046C.Whatistheequilibrium
constantforthereactionat298K?
HCOO(aq)+H2O(l)
HCOOH(aq)+OH(aq)
(Given:Kf(H2O)=1.86Kkgmol1,Molarity=molality)
(A)1.1103
(B*)91012
(C)91013
(D)1.11011
Tf=Kf.m.i
0.2046=1.860.1(1+)
=0.1
HCOOH(aq)
H+(aq)+OH(aq)
C 2
1
0.1 (0.1) 2
Ka=
=
= 102
(1 )
9
0 .9

11

KW
10 14
Kh= K = 1
91012Ans.]

2
a
10
9

27.

Determinetheamountofheat(inkcal)givenoffatconstantvolumewhen0.5molofN2&1.5molof
H2reactedaccordingtoequationat300K.
N2(g)+3H2(g)2NH3(g)
(Given:R=2cal/mol/K)
(A)378.8kcal
(B)190kcal

[Sol.

190=E+

r H300 =380kcal/mol

(C)1888.8kcal

(D*)189.4kcal

(1) 2 300
1000

E=189.4kcal/mol]
28.

WhatmassofH2(g)isneededtoreduce192gmofMoO3tometal?[At.wt.ofMo=96]
(A*)8gm
(B)16gm
(C)32gm
(D)Noneofthese

[Sol.

EquivalentsofMoO3=

M
144

24
6
6

=equivalentsofH2
WH 2
192
=
; WH 2 =8gm
24
1

29.

Theyieldofproductinthereaction
2A(g)+B(g)
2C(g)+QkJ
wouldbelowerat:
(A)lowtemperatureandlowpressure
(B)hightemperature&highpressure
(C)lowtemperatureandtohighpressure
(D*)hightemperature&lowpressure

30.

GivethecorrectorderofinitialsT(ture)orF(false)forfollowingstatements
I:
Lyophobicsolsareirreversiblesols.
II:
Micellesformationtakesplaceonlyabovekrafttemperature
III:
PO43ionshavemorecoagulationvaluethanSO42ionsforcongulationofpositivesols.
IV:
Thevaluesofthecolligativepropertiesobservedexperimentallyareverysmallofcolloidalsols
(A)FTTF
(B)TFTF
(C)TTTT
(D*)TTFT

31.

Thesolubilityofcommonsaltis36.0gmin100gmofwaterat20C.IfsystemsI,IIandIIIcontain
20.0,18.0and15.0gofthesaltaddedto50.0gmofwaterineachcase,thevapourpressureswould
beintheorder.
(A)I<II<III
(B)I>II>III
(C)I=II>III
(D*)I=II<III

12

32.

Readthefollowingstatements.
Statement-1 :Higherthecriticaltempofagas,morereadilyitwillbeadsorbedonthesolidadsorbent,
Statement-2

TC
:Theexcludedvolumeofagaswillbesmaller,if P issmall
C

(A)Statement-1istrue&statement-2isfalse
(B)Statement-1isfalse&statement-2istrue
(C*)Botharecorrect
(D)Bothareincorrect.
[Sol.

TC
8a / 27 Rb 8b
=
= ]
PC
a / 27 b 2
R

33.

TheconductivityofasaturatedsolutionofAg3PO4is9106Sm1anditsequivalentconductivityis
1.50104Sm2equivalent1.TheKspofAg3PO4is
(A*)4.321018
(B)1.8109
(C)8.641013
(D)Noneofthese

[Sol

=K

1000
N

1.50104104=9105102

1000
N

N=6105
N
6 10 5
S=M= n =
=2105mol/L
3
f
Ag3PO4=3Ag++PO4
3S S
Ksp=(3S)3.S =27.S4
=27(2105)4=4.321018 ]

34.

[Sol.

96.5gmofAoxidizedasAA3++3e,when2Fchargeispassedthroughsolutionwithcurrent
efficiencyof90%.WhatiselectrochemicalequivalentofA?
(A)53.61
(B)48.25
(C*`)5.55104
(D)5.55103
w=Znq
Z=

35.

96.5
=5.55104
0.9 2 96500

Whichgraphrepresentszeroorderreaction[A(g)B(g)]:

13

(A)

d[B]
(B) dt

[B]
t

[Sol.

k=

(D*)

t3/4

[A]0

[A]0

x
t

t=x.

1
k

t 3 / 4 =
36.

t1/2

(C)

3
.a ]
4k

Statement-1

n
ratioincreasesduetoemissionofapositron
p

Statement-2

Positronformsinthenucleusbytheconversionofneutronintoaproton.

e
0
1

(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C*)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.
37.

80.0gmsaltofweakbase&strongacidXYisdissolvedinwaterandformed2litreofaqueous
solution.ThepHoftheresultantsolutionwasfoundtobe5at298K.IfXYformsCsCltypecrystal
having

rX (radiusofX+)=1.6& rY (radiusofY)=1.864thenselectwritestatement(s).

[Sol.

(Given:Kb(XOH)=4105;NA=61023)
(A*)Molarmassofsaltis100g/mol
(B)%Degreeofdissociationofsaltis0.25
(C*)EdgelengthofABis4
(D)DensityofsolidsaltXYis2ingm/cc
XY(aq)X+(aq)+Y(aq)
X+(aq)+H2O(l)
XOH(aq)+H+(aq)
Atequation
C(1) C
C
[H+]=C=

Kw
10 14
80
1
C ;(105)2=

5
Kb
4 10
M
2

14

M=100gm/mol

Kh
1002.5103
C

3 a=2(r++r)

aforXY:

1.732a=2(1.6+1.864)
a=4=4108cm
EffectiveformulaunitofXY=1
d=

Z. M
1 100
1 1000
=
=2.6gm/cc]
8 3
23 =
a NA
(4 10 ) 6 10
384
3

38.

Selectwritestatement(s)
(A)8Cs+ionsoccupythesecondnearestneighbourlocationsofaCs+ion
(B*)Eachsphereissurroundedbysixvoidsintwodimensionalhexagonalclosepackedlayer
(C)Iftheradiusofcationsandamionsare0.3and0.4thencoordinatenumberofcationinthe
crystalis6.
(D*)InAgCl,thesilverionisdisplacedfromitslatticepositiontoaninterstitialpositionsuchadefect
is
calledafrenkeldefect

39.

Theenthalpyofneutralizationof1MsolutionofHClwith1MNaOHis57.3kJ/mol.Theenthalpyof
solutionofaweakbaseXOH(1M)withsameHClsolutionis54.6kJ/mole.Ifmolarconductivityof
1MsolutionofXOHis200104Sm2mol1&molarconductivityofXOHatinfinitedilutionis
0.20Sm2mol1thenselectcorrect statement(s)[Assumeallstatementsat298K]
(A*)HionizationofXOHis3.0kJ/mol
(B)pHof1MXOHsolutionis12
(C)pKaofX+is1
(D*)AtequivalentpointresultantsolutionofHCl&XOHisacidic

[Sol.

m
200 10 4
= =
=0.1;
m
0.2

acidis10%ionisedsoenthalpyofionisationofXOH=

XOH(aq)
CX

2 .7
=3kJ/mol
0 .9

X+(aq)+OH(aq)
X
X

( 0 .1 C ) 2
Kb=
=0.0111
0 .9 C

10 14
Ka=
=9.11013
0.011

Duetocationichydrolysisresultantsolutionisacidic

]
15

40.

MatchtheColumn.

(P)

Column II
Numberofradialnode=1

(B)

(A)

Column I
2s

(Q)

Numberofmaximainradialprobability
distributioncurve=2

(R)

Numberofangularnode=0

(S)

angulardependsupon

(C)
r

(D)

4d

[Ans.(A)P,Q,R(B)P,Q,S(C)R(D)P,Q,R]
41.

[Sol.
42.

[Sol.

43.

[Sol.

Thetotalnumberofneutronspresentin10gD2O(Dis12 H )are:
(A)2.5
(B)5.0
(C)10.0
10
10=5NA
20

(D*)Noneofthese

Ethylchloride(C2H5Cl),ispreparedbyreactionofethylenewithhydrogenchloride:
C2H4(g)+HCl(g)C2H5Cl(g)
H=72.3kJ
WhatisthevalueofE(inkJ),if70gofethyleneand73gofHClareallowedtoreactat300K.
(A)69.8
(B)180.75
(C)174.5
(D*)139.6
70
73
No.ofmolesofC2H4= =2.5,
No.ofmolesofHCl(LimitingReagent)=
=2
28
36.5
H=E+ngRT; 72.3=E+(18.314300)/1000
E=69.80;fortwomolesE=69.802
139.6kJ Ans.]
IfHvaporisationofsubstanceX(l)(molarmass:30g/mol)is300J/gatit'sboilingpoint300K,then
molarentropychangeforreversiblecondensationprocessis
(A)30J/mol.K
(B)300J/mol.K
(C*)30J/mol.K
(D)Noneofthese
Hvaporisation=30030J/mol
Scondensation=

H vaporisati on
Tboiling po int

16

300 30
J/mol.K
300
=30J/mol.K Ans.

44.

Statement-1: Thereisnochangeinenthalpyofanidealgasduringcompressionatconstant
temperature.
Statement-2: Enthalpyofanidealgasisafunctionoftemperatureandpressure.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D*)Statement-1istrue,statement-2isfalse.

45.

ChlorinegascanbeproducedbythereactionofHCl(aq)withMnO2(s).OnlyMnCl2(s)andH2O()
arethebyproducts.WhatvolumeofCl2(g)(in litre)ofdensity2.84g/Lwillbeproducedfromthe
reactionof400mLof0.1MHCl(aq)withanexcessofMnO2?
[Ans.0.25
L]

[Sol.

MnO2(s)+4HCl(aq.)MnCl2(s)+Cl2(g)+H2O(l)
No.ofmolesofHCl=0.10.4=0.04
No.ofmolesofCl2produced=
VolumeofCl2produced

46.

[Sol.

0.04
71
4

0.71
2.84

0.71g

0.25litre

5
7
3molesofidealgasX(Cp,m= R)and2molesofidealgasY(Cp,m= R)aretakeninavesseland
2
2
compressedreversiblyandadabatically,duringthisprocesstemperatureofgaseousmixtureincreased
from300Kto400K.Calculatechangeininternalenergy(U) in calofgaseousmixture
(GivenR=2cal/mol.K)
[Ans.1900cal]

= (n1C v ,m1 n 2 C v ,m 2 ) T
5
3
= 3 R 2 R 100=1900cal]
2
2

47.

[Sol.

TheentropiesofH2(g)andH(g)are130.6and114.6Jmol1K1respectivelyat298K.Usingthe
datagivenbelowcalculatethebondenergyofH2(in kJ/mol) :
2H(g);G=406.62kJ/mol
H2(g)
[Ans.436kJ/mol]
2H(g);G=406.62kJ/mol
H2(g)
G=HTS
2 114.6 130.6

406.62=H298
;
1000

406.62=H29.38 ;
H=436kJ/mol

298(98.6)

406.62=H
1000
]

17

48.

Thefollowingsequenceofreactionoccursincommercialproductionofaqueousnitricacid.
4 NH 3 (g ) 5O 2 (g ) 4 NO (g ) 6H 2O(l ) H 904kJ ...(1)
2 NO(g ) O 2 (g ) 2 NO 2 (g )
H 112kJ ...( 2)
3NO 2 (g ) H 2O(l ) 2HNO 3 (aq ) NO(g ) H 140kJ ...(3)

Determinethetotalheatliberated (in kJ) atconstantpressurefortheproductionofexactly1moleof


aqueousnitricacidbythisprocess.
[Ans.493kJ]
[Sol.

1 mole of HNO3=

3
3
3
molesofNO2 moleofNO moleofNH3
2
2
2

3 1
3 1
1
(904) (112) (140) =493kJ/molheatliberated
2 4
2 2
2

49.

Statement-1: fHofN2(g)iszero.
Statement-2: fHofN(g)iszero.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D*)Statement-1istrue,statement-2isfalse.

50.

Assumeidealgasbehaviourforallthegasesconsidered&vibrationaldegreesoffreedomtobeactive.
SeparateequimolarsamplesofNe,O2,SO2&CH4weresubjectedtoatwostepprocessasmentioned.
Initiallyallareatsamestateoftemperature&pressure.
Step I Allundergoreversibleadiabaticexpansiontoattainsamefinalvolume,whichis
doubletheoriginalvolumetherebycausingthedecreasesintheirtemperature.
Step II AfterstepIallaregivenappropriateamountofheatisochoricallytorestorethe
originaltemperature

stepI
noheatonlywork

stepII

noworkonlyheat
CH4
SO2
O2 Ne O2 SO2 CH 4
Ne

V
Markthecorrectoption(s).
(A)DuetostepIonly,thedecreaseintemperaturewillbemaximumforCH4.
(B)DuringstepII,heatgivenwillbeminimumforCH4
(C*)Therewillbenonetchangeininternalenergyforanyofthegasafterboththestepsofprocess
18

[Sol.

51.

arecompleted.
(D)ThePVgraphofCH4&SO2willbesameforoverallprocess.
Idealgas&initial&finaltemperaturearesame
E=0forall
(C)iscorrect
Also|w|ismaximumforCH4isstepI&overall
E=0|q|forCH4willbemaximum
option(B)isincorrect
SinceafterstepI,allhavesamevolume,samemoles&pressureofCH4ishighestTemperatureof
CH4willbehighest&sinceinitialitissame
decreaseintemperaturewillbeleast
option(A)isincorrect
forSO2&CH4isdifferent(duetovibrationaldegreesoffreedom)
graphisdifferent
option(D)isincorrect;
option(C) ]
Whichofthefollowingstatement(s)is/arefalse:
1
(A)rSfor N2(g)N(g)ispositive
2
(B*)Gsystemisalwayszeroforareversibleprocessinaclosedsystem
(C*)Gforanidealgasisafunctionoftemperatureandpressure
(D*)entropyofaclosedsystemisalwaysmaximizedatequilibrium

52.
(a)
(b)
(c)

[Sol.
53.

Twomolesofanidealgas(notnecessarilymonoatomic)issubjectedtothefollowingsequenceof
steps.
Itisheatedatconstantvolumefrom298Kto348K
Itisexpandedfreelyintoavacuumtodoublevolume.
Itiscooledreversiblyatconstantpressureto298K.
Calculatetotalworkdone (|w|) in kJ fortheoverallprocess.
Given : R = 8.3 JK1 mol1
[Ans.w=0.83kJ]
w=nRT=28.350=0.83kJ]
Acylindricalcontainerofvolume44.8litresiscontainingequalno.ofmoles(inintegerno.)ofanideal
monoatomicgasintwosectionsAandBseparatedbyanadiabaticfrictionlesspistonasshownin
figure.Theinitialtemperatureandpressureofgasinbothsectionis27.3Kand1atm.Nowgasin
section'A'isslowlyheatedtillthevolumeofsectionBbecomes(1/8)thofinitialvolume.
Findchangeinenthalpy(H)forsectionAin kcal.

19

Given : R = 2 cal/mol-K, Cv,m of monoatomic gas =


[Sol.

3
R,
2

[Ans.80.53kcal]

At 1 atm & 0C ideal gas occupy 22.4 litre.


Initialvolumeinbothsection=22.4litre
ThegasinsecBiscompressedreversibly&adiabatically
T1V1 1 = T2 V2 1

V1
T2=T1
V2

27.3(8)2/3
4T1

V1 T2
Finalpressure P2=P1 V T 18432atm
2 1
FinalpressureinsectionA=finalpressureinsecB32atm

P2 V2
FinaltemperatureinsectionA T1 P V
1 1

32
27.3 (1.875)
1

1638K

54.

55.

[Sol.

5
HA=nCp,mT 10 R(163827.3)=
80.53kcal
Ans.]
2
WhatisthepKbofaweakbasewhose0.1MsolutionhaspH=9.5?
(A)7.5
(B*)8
(C)9
(D)10

Theequilibriumconstantforthereaction
A(g)+2B(g)lC(g)
is0.25dm6mol2.Inavolumeof5dm3,whatamountofAmustbemixedwith4molofBtoyield1
molofCatequilibrium.
(A)3moles
(B)24moles
(C*)26moles
(D)Noneofthese
A(g)+2B(g)lC
n
4
0
t=0

20

n1

42

KC=0.25=

1equilibrium
[ C]
[C]
2 [A]=
2
[A ][B]
[B] (0.25)

1
n 1
=
=25n=26molesAns.]
5
5 0.25 2 2
56.

[Sol.

ThemolarheatcapacityofanidealgasaregivenbyCp,m=a+bT&Cv,m=c+bT,wherea,b&
careconstantandtemperatureinK.Whichofthefollowingistrueforisoentropicprocess.
(A)TabVbecT=constant
(B*)TcVacebT=constant
(C)TabVcTeb=constant
(D)Noneofthese
Cp,mCv,m=R
(a+bT)(c+bT)=R
ac=R

dS=

Cv
R
dT+ dV
T
V

1
(c bT)
dT+(ac) dV=0
V
T
clnT+bT+(ac)lnV+c'=0
lnTc+lnVac=bTc'
Tc.VacebT=constant
]

S=

57.

Forthereaction

[Sol.

CH3COCH3+Br2 H
CH3COCH2Br+H++Br
thefollowingdatawascollected
[Acetone]
[Br2]
[H+]
Rate of reaction (Ms1)
0.15
0.025
0.025
6104
0.15
0.050
0.025
6104
0.15
0.025
0.050
12104
0.20
0.025
0.025
8.0104
Theorderofthereactionw.r.t.CH3COCH3andBr2respectivelyare:
(A)0,1
(B*)1,0
(C)1,1
(D)1,2
Rate=k.[Acetone]x.[Br2]y.[H]z
6104=k.(0.15)x(0.025)y(0.025)z
...(i)
4
x
y
z
610 =k.(0.15) (0.050) (0.025)
...(ii)
4
x
y
z
1210 =k.(0.15) (0.025) (0.050)
...(iii)
4
x
y
z
810 =k.(0.20) (0.025) (0.025)
...(iv)
0.025

(i) (ii),1=
0.050

y=0,henceratedoesnotdependupontheconcentrationofBr2.
21

6 0.025
1 1
; =
(i) (iii), =
12 0.050
2 2

z=1

3 3
(i) (iv), =
4 4

58.

x=1

ConsiderthereactionAB,graphbetweenhalflife(t1/2)andinitialconcentration(a)ofthe
reactantis

t1/2
a

Hencegraphbetween

(A)

d[A ]
andtimewillbe
dt

d[A ]

dt

(B)

d[A ]

dt

(C*)

d[A ]
dt

(D)

d[A ]
dt

t
d[A ]
isnotdependonconcentrationofreactant]
dt

[Sol.

Zeroorderreactiont1/2a&rateofreaction

59.

Considerthereaction:
AB+C
InitialconcentrationofAis1M.20minutestimeisrequiredforcompletionof20%reaction.
d[B]
=k[A],thenhalflife(t1/2)is
dt
(A)55.44min.
(B)50min

If

[Sol.

(C*)62.13min

(D)Noneofthese

0.693 1
C0
1
1
k= .ln

= .ln
t 1/ 2
t
C
20
0 .8

t1/2=62.13min.Ans.

]
22

60.

TheenthalpyofneutralisationofHClandNaOHis57kJmol1.Theheatevolvedatconstant
pressure(inkJ)when0.5moleofH2SO4reactwith0.75moleofNaOHisequalto
3
(B)570.5
4
H++OHH2O+57kJmol1

(A*)57
[Sol.

(C)57

(D)570.25

n H =2 n H 2SO 4 =20.5=1.0
n OH =nNaOH=0.75

61.

[Sol.

3
Heatevolved=0.7557= 57kJ
Ans. ]
4
Howmuchheatwillberequiredatconstantpressuretoform1.28kgofCaC2fromCaO(s)&C(s)?
Given: fH(CaO,s)
=
152kcal/mol.
fH(CaC2,s)
=
14kcal/mol
fH(CO,g)
=
26kcal/mol
(A)+112kcal
(B)224kcal
(C)3840kcal
(D*)2240kcal
CaO(s)+3C(s)CaC2(s)+CO(g)
fH=(1426)(152)=+112kcal/mol

Totalheatrequired

62.

[Sol.

1280
112
=
64

2240kcal ]

Whatistheratiooftheenergyyieldoncombustionofhydrogenatomstosteamtotheyieldon
combustionofanequalmassofhydrogenmoleculestosteam?
1
Given: H2(g)+ O2(g)H2O(g)H=242kJ
2
B.E.(HH)=436kJ
(A)0.80:1
(B)1:0.80
(C)1.80:1
H2(g)2H(g)
H1=436kJ

(D*)2.80:1

1
H2(g)+ O2(g)H2O(g) H2=242
2

678
=2.8:1
]
242
A(g)2B(g);rH=20kJ/moleat300K
IfCP,m(A)=20J/KmolandCP,m(B)=5J/Kmol.Whichofthefollowingstatementiscorrect?
(A)Hwillbeincreaseonincreasingtemperature
(B*)Hwilldecreaseonincreasingtemperature.
(C)Hwillbeunaffectedbytemperaturechange.

63.

1
2H(g)+ O2(g)H2O(g)H3=678kJ
2

Desiredratiois

23

[Sol.

(D)Hwilldecreaseondecreasingtemperature.
rCp,m=10J/Kmole

rH2=rH1+rCp,mT

rH2<rH1
d

( H )
=rCp,m=ve
dT

64.

Inasystem,theequilibriumreaction:
2NH3(g)
N2(g)+3H2(g)
wasstudiedstartingwithNH3andNe(inertgas).Itisfoundthatat10atmand700K,theequilibrium
gaseousmixturecontains10mole%eachofNH3(g)andNe(g).CalculateKP(inatm2)
(A*)432
(B)420
(C)864
(D)Noneofthese

[Sol.

X N 2 + X H 2 =10.101=0.8
X N 2 =

1
0.8
4

0.2

X H 2 =

3
0.8
4

0.6

PNH3 =0.110=1atm
PN 2 =0.210=2atm
PH 2 =0.610

6atm

KP=2216
KP=432(atm)2

Ans.]

Paragraph for Question Nos.65 to 67


Whenthereactantsaremixedinachemicalsystem,thesystemwillproceedspontaneouslytoa
positionoflowerfreeenergy,andthesystemwilleventuallyachieveequilibrium.Atanypointalongthe
wayfromthepurereactantstoequilibrium,thereactantsarenotatstandardstates.Thechangein
Gibbsfreeenergyforareversiblereactionunderthesenonstandardconditions,rGisrelatedtorG
bytheequation
rG=rG+RTlnQ
WhenQisthereactionquotient.Furthermore,aslongasGisnegativethatisthereactionis
"descending"fromthefreeenergyofthereactantstotheequilibriumpositionthereactionisspontaneous.
Eventuallythesystemreachesequilibriumbecausenofurtherchangeinconcentrationofreactantsand
productsisseenatthispoint.Gmustbezero;thatisthereisnofurtherchangeinfreeenergyinthe
system. SubstitutingG=0andQ=K intoequation.
0=G+RTlnK
or
G=RTlnK
65.

ThestandardfreeenergyofformationofNaBr(s)is347kJ/mol.CalculateGforthereaction
2NaBr(s)2Na(s)+Br2(l)
24

(A)347kJ
(B)694kJ
(C*)694kJ
[Sol. Na(s)+1/2Br2(l)NaBr(s)G=-347
Thegivenreactionis2{G}=+694kJ/Mole
66.

[Sol.

At300K,thestandardfreeenergyofformationofN2O5(g)is43kJ/mol.CalculateGforthe
followingreaction.
2N2(g,2bar)+5O2(g,1bar) l 2N2O5(g,2bar)
Given : ln 2 = 0.7, R = 8 J/K mol
(A)94.4kJ/mol
(B)57.4kJ/mol
(C)77.6kJ/mol
(D*)Noneofthese
G=G+RTlnQ;whereQ=Reactionquotient
Q=

PN2 2O5

22
=1
1 .2

= 5 2
P 2 .P 5
N2

O2

G=432=86kJ/mol
67.

(D)347kJ

Ans.

WhatisthepartialpressureofHCl(g)aboveanaqueoussolutionthatis2MinH+and1.5MinClat
2000
K.ReactionisH+(aq)+Cl(aq)lHCl(g)
7
Given :R=8.0J/mol.KfG(HCl,g)=95kJ/mol.,fG(Cl,aq)=131.848kJ/mol.,
2000
K.
7
(A)0.03bar
(B)107bar
(C*)3107bar
H+(aq)+Cl(aq)lHCl(g)
fG=fG(HCl)fG(H+,aq)fG(Cl,aq)
fG=95(131.848)=36.848kJ/molor36848J/mol
fG=2.303RTlogK

alldataat
[Sol.

136.848=2.3038

2000
logK
7

2000=

(D)3.33108bar

2000
logK
7

K=107
K=

68.

PHCl
P (in bar )
= 2 1.5 ;

[H ] [Cl ]

P=3107bar

Whichofthefollowingstatement(s)aretrueaboutZvsPgraphforarealgasataparticulartemperature.

25

behaviourofmost
realgases

X
dZ 0
dP =

(A*)Z1asP0formostrealgases
(B*) dZ dP isveasP0formostrealgases
(C) dZ dP 0atapressurewhererepulsiveandattractiveforcesarecomparable.
(D*)AtpointX,intermolecularattractiveforcesdominatingoverrepulsiveforces.
69.

ArealgasobeystheequationP Vm b =RT,where(b=0.1L/mol),if2molesofgasisslowly
compressedfrom1.2litreto0.6litreat300Kthenworkdoneintheprocessis:
(A)1.99kJ
(B*)4.59kJ
(C)7.69kJ
(D)3.93kJ
V2

[Sol.

w= P dV
V1

n RT
2RT
P(Vn0.1)=nRTor P= V 0.2 n = V 0.2

V2

1
=2RT (V 0.2) dV
V
1

V2 0.2
V2 0.2
=2RT ln V 0.2 =2.3032RTlog V 0.2
1
1

=2.30328.314103300log
70.

0.4
1

+4.59kJ

Ans.

SO3gasisenteringtheenvironmentataconstantrateof6.93106gm/L/dayduetotheemissionof
pollutinggasesfromthermalpowerplant,butatthesametimeitisdecomposing&followingfirstorder
kineticswithhalflifeof100days.
Basedonaboveinformationselectthetruestatement(s).
(A*)ConcentrationofSO3inKotais1.25105M(AssumeSO3presentinKotawithconstant
concentrationmeansrateofformationanddissociationofSO3areequal)
(B*)IfSO3emissionisstoppedthenafter1000daysitsconcentrationswillreduceto ~
1.2108M.
(C)If103Lofairispassedthrough1Lpurewater(assumingallSO3tobedissolvedinit)&resulting
solutionistitratedagainst1N,NaOHsolutionofwhich15mlisconsumed.
(D)AnindustryismanufacturingH2SO4attherateof980kgperdaywiththeuseofSO3inairit
26

[Sol.

should use8105Litreair/day.
AssumingSO3conc.tobexM
(A)

dx
6.93 10 6
=
kx
dt
80

whenSO3concentrationwillreachsteadystateorconstantconcentration
dx
=0
dt
6 . 93 10 6
6 . 93 10 6
x=
=
=1.25105M
80 k
80 0.693 10 2

(B)
M
(C)

(D)

[SO 3 ]0
1
;[SO ] =1.25108
Totaltime=10t1/2=10100=1000days; k= ln
3 t
[
SO
]
t
3 t

Eq.ofSO3=Eq.ofNaOH
1031.251052=1V
V=2.5102litre
MolofSO3=MolofH2SO4

980 103
;
V=8108litre
98
WhatistheequivalentweightofH2SO4inthereaction?
H2SO4+NaINa2SO4+I2+H2S+H2O
(A)12.25
(B)49
(C*)61.25
5H2SO4+8NaI4Na2SO4+4I2+H2S+4H2O
n-factorofH2SO4=8/5

V1.25105=

71.

[Sol.

Eq.wt.=
72.

[Sol.

(D)Noneofthese

mol.wt. 98 5
=
61.25 Ans. ]
n
8

Pressureof10molesofanidealgasischangedfrom2atmto1atmagainstconstantexternalpressure
withoutchangeintemperature.Ifsurroundingtemperature(300K)andpressure(1atm)always
remainsconstantthencalculatetotalentropychange(Ssystem+Ssurrounding)forgivenprocess.
[Given:n2=0.70andR=8.0J/mol/K]
(A)56J/K
(B)14J/K
(C*)16J/K
(D)Noneofthese
p1
2
Ssystem=nRln p =108ln =56J/K
1
2

Ssurrounding=

q
T

U=q+w=0or

q=w=Pext(V2V1)

nRT nRT
P
P
1
=nRT ext ext =108T 1

q=Pext
P1
P1
2
P2
P2
q=40T
27

q
40J ;
Ssystem+Ssurr=564016J/KAns. ]
T
TheenthalpyoftetramerizationofXingasphase(4X(g)X4(g))is100kJ/molat300K.
TheenthalpyofvaporisationforliquidXandX4arerespectively30kJ/moland72kJ/molrespectively.
SfortetramerizationofXinliquidphaseis125J/Kmolat300K.
WhatistheGat300KfortetramerizationofXinliquidphase?
(A)52kJ/mol
(B)89.5kJ/mol
(C*)14.5kJ/mol
(D)Noneofthese
4X(l)4X(g)X4(g)X4(l)
fortetramerizationofliquid
H=30410072
H=52kJ/mol
S=125J/mol/K
G=HT.S
G=52300(125)/1000=52+37.5
G=14.5kJ/mol
Ans.]

Ssurrounding=
73.

[Sol.

74.

[Sol.

75.

WhatisthevalueoffH(C2H6,g)?
Given: fH(CH4,g)=66kJ/mol;subH(C,S)=718kJ/mol
B.E.(CC)=345kJ/mol,B.E.(HH)=436kJ/mol
(A*)85kJ/mol
(B)633kJ/mol
(C)185kJ/mol
LetB.E.ofCHisx
C(s)+2H2(g)CH4(g)
66=718+24364x ;
B.E.(CH)=414kJ/mol
2C(s)+3H2(g)C2H6(g)
fH(C2H6,g) =2718+34363456414
=85kJ/molAns. ]

(D)Noneofthese

Statement -1 : Totalnumberofmolesinaclosedsystematnewequilibriumislessthantheold
equilibriumifsomeamountofasubstanceisremovedfromasystem
(considerareactionA(g)
B(g) )atequilibrium.
Statement -2 : Thenumberofmolesofthesubstancewhichisremoved,ispartiallycompensatedas
thesystemreachedtonewequilibrium.
(A*)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.
Paragraph for Question Nos. 76 to 78
If we know the equilibrium constant for a particular reaction, we can calculate the
concentrations in the equilibrium mixture from the initial concentrations. Commonly only the
initial concentration of reactants are given.

76.

Inastudyofequilibrium
H2(g)+I2(g)l2HI(g)
1molofH2and3molofI2gaveriseatequilibriumtoxmolofHI.
28

Additionofafurther2molofH2gaveanadditionalxmolofHI.Whatisx?
(A)0.5
(B)1
(C*)1.5
(D)Noneofthese
Q.77 Inaboveproblem,whatisKpatthetemperatureoftheexperiment.
(A)1
(B)2
(C*)4
[Sol.1&2
H2(g) +
I2(g)
l
2HI(g)
m
IEq 1x/2
3x/2
x
x x

IIEqm 3
2 2

or
(3x)

x x

3
2 2

3x

(2x ) 2
x2
=
x
(3 x ) 2
x
1 3
2
2

(D)Noneofthese

x+x
2x

x=1.5 Ans.

(x )2
(1.5) 2
Kc= 1 x 3 x =
=4Ans.
(
1

0
.
75
)

(
3

0
.
75
)
2
2

Q.78 Inastudyofequilibrium
2SO2(g)+O2(g)l 2SO3(g).
Startingwith2moleSO2and1.5moleO2in5litreflask.Equilibriummixturerequired0.4mole
KMnO4inacidicmedium.HenceKCis:
(A)0.2
(B*)5.0
(C)675.0
(D)Noneofthese
[Sol.
2SO2(g)+O2(g)l 2SO3(g)
Initial
2
1.5
0
Atequilibrium 22x 1.5x
2x
(22x)2=0.45
x=0.5
[SO 3 ]2
(1 / 5) 2
KC=
=
=5 Ans.]
[SO 2 ]2 [O 2 ] (1 / 5) 2 (1 / 5)

Q.79 Selectincorrectstatement(s):
(A*)Entropyofanisolatedsystemalwaysremainsconstantduringphasetransitionprocess
(B*)Ssurrounding<0forreversiblecondensationofvapour
(C*)fG>0forBr2(g)athightemperature.
(D*)A2(g)+B2(g)2AB(g)+200kJ.
OnthebasisofaboveinformationHf(AB,g)is100kJ/mole.
Q.80 Selectcorrectstatement(s):
(A)
Workisanintensiveproperty
(B*) IfenthalpyofsolvationofionsA+(g)andB+(g)isgreaterthan|Latticeenergy|thenHsolution
of
AB(s)isnegative.
(C*) Inirreversibleadiabaticcompressionofanidealgas,increaseintemperatureismoreascompare
29

final
(D)

toreversibleadiabaticcompressionifprocessiscarriedoutfromsameinitialstatetosame
pressure.
TheequivalentweightofMnSO4ishalfofit'smolecularweightwhenitisconvertedtoMn2O3

Q.81MATCH THE COLUMN


Column-I

Column-II

2HCl(g)H2(g)+Cl2(g)

(P)

H=+ve;S=+ve

(B)

2O3(g)3O2(g)

(Q)

H=ve;S=+ve

(C)

MgCO3(s)MgO(s)+CO2(g)

(R)

H=ve;S=ve

(D)

2NO2(g)N2O4(g)

(S)

H=+ve;S ~
0

(A)

[Ans. (A)S,(B)Q,(C)P,(D)R]

Paragraph for Question Nos. 82 to 84


Areactionissaidtobefirstorderifit'srateisproportionaltotheconcentrationofreactant.Letus
considerareaction
A(g)B(g)+C(g)
Att=0
a
0
0
Attimet
ax
x
x
Therateofreactionisgivenbytheexpression

dx
=k(ax)andintegratedrateequationforagiven
dt

1 a
wherea=initialconcentrationand(ax)=concentration
reactionisrepresentedask= ln
t ax

ofAaftertimet.
Q.82 ThermaldecompositionofcompoundXisafirstorderreaction.If75%ofXisdecomposedin100
min.Howlongwillittakefor90%ofthecompoundtodecompose?
Given : log 2 = 0.30
(A)190min
(B)176.66min
(C*)166.66min
(D)156.66min
[Sol.

1
1

k= ln
t
1 1 / 4
k=

1
ln(4)
100

ln ( 4)
100

30

100

ln(10)
t= ln(10)
k
ln 4
100
166.66min.
Ans. ]
0.6
ConsiderareactionA(g)3B(g)+2C(g)withrateconstant1.386102min1.Startingwith
2molesofAin12.5litrevessel,ifreactionisallowedtotakesplaceatconstantpressure&at298K
thenfindtheconcentrationofBafter100min.
(A)0.04M
(B)0.36M
(C*)0.09M
(D)Noneofthese

Q.83

[Sol.

0.693
k= t
1/ 2

t1/2=

after100min
(molesremaining)

A(g)3B(g)+2C(g)
2x
3x
2x
=0.5
4.5
3

Vf
nf
=
Vi
ni

0.693
50min
1.3860 10 2

8
12.5 50litre
2

concentrationofBafter100min=

4 .5
=0.09M
50

Ans.

Q.84 DecompositionofH2O2isafirstorderreaction.AsolutionofH2O2labelledas"16.8V"wasleft
open. Due to this, some H2O2 decomposed. To determine the new volume strength after
2.303hours,20mLofthissolutionwasdilutedto100mL.25mLofthisdilutedsolutionwastitrated
against37.5mLof0.02MKMnO4solutionunderacidicconditions[Given: STPis1atmand273K]
Therateconstant(inhr1)fordecompositionofH2O2is:
(A)0.15
(B)0.30
(C*)0.60
(D)Noneofthese
[Sol.

16.8
=3
5.6
Initialm.equivalentofH2O2=320=60

Normality(N)=

m.equivalentofH2O2remainingafter2.303hrs=37.50.025

100
=15
25

Initial m.eqivalent of H 2 O 2
1

k= ln
t
m.equivalent of H 2 O 2 after time t
k=

2.303
60
log
2.303
15

k=0.60hr1 Ans. ]

31

Q.85 WhatisthemassofH2Opresentinairin10litreclosedvesselwith80%relativehumidityat1atmand
300K?
Given : Vapour pressure of H2O is 30 torr at 300 K.
(A*)0.23gm
(B)0.36gm
(C)2.3gm
(D)3.6gm
[Sol.

P . Pressure of H 2 O
%R.H.= Vapour Pressure of H O 100
2

80=

PH 2O
30

100

PH 2O =24torr

PV=

w H 2O
M

RT

w H 2O
24
10=
0.0821300
760
18

w H 2O =0.23gm

Ans. ]

Q.86 Theheatcapacityofliquidwateris75.6J/mol.K,whiletheenthalpyoffusionoficeis6.0kJ/mol.
Whatisthesmallestnumberoficecubesat0C,eachcontaining9.0gofwater,neededtocool500
gofliquidwaterfrom20Cto0C?
(A)1
(B)7
(C*)14
(D)Noneofthese
[Sol.

500
75.620
18
Letnnumberofcubesarerequired

Heatreleasedbywater=

9
500
6000=
75.620
18
18
n=14
Ans.]

so,

Q.87 IntwodifferentvesselsXandYcontainingH2O(l)atthesametemperature,thevacantspaceleftover
thesurfaceofH2O(l)isVand3V.Whatistheweightratio( WH 2O in X / WH 2O in Y ) ofvapoursin

[Sol.

twovessels?
(A*)1:3
(B)3:1
Atconstantpressure&temperature
Vn

(C)1:4

(D)1:1

V1
n1
=
V2
n2
w1 1
w 3
2

Ans.]

32

Q.88 Gforthedissociationofthedimer(A2l2A)inbenzenesolutionat27Cis6.909kcal/mol.
If8molesofAisdissolvedin10dm3ofbenzeneat27C.Whatistheratioofequilibriumconcentration
ofmonomertodimer [A] [A 2 ] ?Given:R=2Cal/mol.K
[Sol.

(A*)1:200
(B)1:100
G=RTlnKeq
6.9091000=23002.303logKC
5=logKCorKC=105

(C)200:1

(D)800:1

K 'C =1/KC=105forreaction
2A
l A2
0.82xx
K 'C isveryhigh

so2x ~
0.8

~ y
0.82x
105=

0 .4
( y) 2

y=(0.4105)1/2

[A ] y 2 10 3
5
1

[A 2 ] = x
0 .4
1000 200

Ans.

2103

Q.89 2gmofanimpuremixtureofMgCO3wasdissolvedin50mlof0.8MHCl.Theexcessofacid
r
e
q
u
i
r
e
d
20mlof0.2MNaOHforcompleteneutralization.ThepercentageofMgCO3inthesamplewillbe
(A)7.56%
(B)37.8%
(C*)75.6%
(D)Noneofthese
[Sol. LetweightofMgCO3isxgm

x
50
20
2=
0.8
0.2
84
1000
1000

x=(0.040.004)

%ofCaCO3=

84
=1.512
2

1.512
100=75.6 ]
2

Q.90 Followingtwoequilibriumissimultaneouslyestablishedinacontainer
PCl5(g)
PCl3(g)+Cl2(g)
CO(g)+Cl2(g)
COCl2(g)
IfsomeNi(s)isintroducedinthecontainerformingNi(CO)4(g)thenatnewequilibrium
(A)PCl3concentrationwillincrease
(B*)PCl3concentrationwilldecrease
(C)Cl2concentrationwillremainsame
(D)COconcentrationwillremainsame
Q.91 PhasediagramofCO2isshownasfollowing

33

73
Liquid

Solid

67
P(atm)

5
Gas

1
195 217

298 304
T(K)

Basedonabovefindthecorrectstatement(s)
(A)298KisthenormalboilingpointofliquidCO2
(B)At1atm&190KCO2willexistasgas.
(C*)CO2(s)willsublimeabove195Kundernormalatmosphericpressure
(D*)Meltingpoint&boilingpointofCO2willincreaseonincreasingpressure
Q.92 100ml0.5NH2SO4(strongacid)isneutralisedwith200ml0.2MNH4OHinaconstantpressure
calorimeterwhichresultsintemperatureriseof1.4C.Ifheatcapacityofcalorimetercontentis
1.5kJ/C.Whichstatementis/arecorrect
Given :
HCl+NaOHNaCl+H2O+57kJ
CH3COOH+NH4OHCH3COONH4+H2O+48.1kJ
(A*)EnthalpyofneutralisationofHClv/sNH4OHis52.5kJ/mol
(B*)Enthalpyofdissociation(ionization)ofNH4OHis4.5kJ/mol
(C)EnthalpyofdissociationofCH3COOHis4.6kJ/mol
(D*)Hfor2H2O(l)2H+(aq.)+2OH(aq.)is114kJ
[Sol.
H2SO4
+
2NH4OH
(NH4)2SO4
+
2H2O
Initialm.moles

100 0.5
2
=25

Hneutralisation=

2000.2
=40(limitingreagent)

1.5 1.4
=52.5kJ/mol
40 103

HneutralisationofNH4OHwithstrongacid=52.5kJ/mol
Hneutralisation=Hionisation+rH(H++OHH2O)
52.5=x57
Hionisation(NH4OH)=x4.5kJ/mol
forNH4OHandCH3COOH:
Hneutralisation=Hionisation(NH4OH)+Hionisation(CH3COOH)+rH(H++OHH2O)
=48.1=4.5+y57
HionisationofCH3COOH=y4.4kJ/mol
34

for2H2O(l)2H++2OH
H=+257=114kJ
Ans.]

Q.93 CalculatetheenthalpyofsublimationofC(s)inkJ/molfromthefollowingdata
Given:
ResonanceenergyofCH3COOH(g)is110kJ/mol
fH(CH3COOH,g)=415kJ/mol,Hf(H,g)=220kJ/mol
Bondenergy(inkJ/mole)
CH
=
410kJ/mol
;
CC =
345kJ/mol
C=O
=
730kJ/mol
;
CO =
350kJ/mol
OH
=
460kJ/mol
;
O=O=
500kJ/mol
[Ans.715]

[Sol.

H O
| ||
2C(s)+2H2(g)+O2(g) H C C O H(g )
|
H

LetenthalpyofsublimationofC(s)isx
Hf(CH3COOH,g)=415kJ/mol
=2x+4220+5001103410345730350460
enthalpyofsublimationofC(s)=715kJ/mol
Ans. ]
Q.94 A1litrereactionvesselwhichisequippedwithamovablepistonisfilledcompletelywitha2M
aqueoussolutionofH2O2.TheH2O2decomposestoH2O(l)andO2(g)isafirstorderprocesswith
half
life
5hrsat300K.Asgasformed,thepistonmovesupagainstconstantexternalpressureof1atm.
Calculatethemagnitudeofworkdone(in Cal)bythegasfromthestartofsixthhourtilltheend
of15hrs?Given : R=2Cal/mol.K
[Ans.225]
[Sol. Attheendof5hours
MolesofH2O2remaining=

21
1
2

attheendof15thhours
2 1 1

4
23
MolesofH2O2decayedingiventimeinterval=10.250.75
molesofO2formed=0.375
W=PV=nRT=(0.375)3002cal=225cal

225
Ans.
]
Statement-1 :
Ingeneralphenolphthaleinisusedasanindicatorforthetitrationofweakacid

MolesofH2O2remaining=

Q.95

35

(HA)againststrongbase(NaOH).
Statement-2 :
Atequivalentpointsolutionisbasic.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationforstatement-1.
(C)Statement-1istrue,statement-2isfalse.
(D)Statement-1isfalse,statement-2istrue.
Q.96 ThemassofP4O10producedif440gmofP4S3ismixedwith384gmofO2is
P4S3+O2P4O10+SO2
(A)568gm
(B*)426gm
(C)284gm
(D)396gm
Q.97 Volumeofwaterwhichmustbeaddedto8MHCltomake2lit.of7.3%w/vHClsolutionis
(A*)1.5lit.
(B)0.5lit.
(C)1lit.
(D)2lit.
Q.98 MolarityofaqueousNaOHsolutionwillbe,ifmolefractionofNaOHinthesolutionis0.5.
[Given : density of pure NaOH = 4 gm/ml]
(A)76.92
(B*)35.71
(C)68.96
(D)26.46
Q.99 ThemolarityofOHioninthefinalsolution,if200mlof8MHClsolutionismixedwith800mlof2M
Ca(OH)2solution,is
(A)0.08M
(B*)1.6M
(C)3.2M
(D)0.16M
Q.100 CalculatepercentagechangeinMavgofthemixture,ifPCl5undergo50%decomposition.
PCl5PCl3+Cl2
(A)50%
(B)66.66%
(C*)33.33%
(D)Zero
Q.101 Forwhichofthefollowingsolution,minimumamountofNaOHisrequiredforcompleteneutralisation.
[Assume complete dissociation of acid ]
(A)50mlH2SO4solution[basicity=2](dsolution=2gm/ml),%w/w=98
(B)50mlH3PO4solution[basicity=3](dsolution=2gm/ml),%w/w=98
(C)100mlHClsolution[basicity=1](dsolution=1.5gm/ml),%w/w=36.5
(D*)100mlHNO3solution[basicity=1](dsolution=1.5gm/ml),%w/w=36.5
Q.102 Statement-1: Foraverydilutesolutionmolality&molarityarealwaysapproximatelyequal
Statement-2: Massofsolutionisalwaysapproximatelyequaltomassofsolventforaverydilute
solution.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C*)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.
Q.8

Statement-1: Molalityofpureethanolislesserthanpurewater.
Statement-2: Asdensityofethanolislesserthandensityofwater.
[Given : dethanol = 0.789 gm/ml; dwater = 1 gm/ml]
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
36

(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.
Q.9

'2V'mlof1MNa2SO4ismixedwith'V'mlof2MBa(NO3)2solution.
(A)MolarityofNa+ioninfinalsolutioncan'tbecalculatedasVisnotknown.
2
(B)MolarityofBaSO4infinalsolutionis M .
3
4
(C*)Molarityof NO3 infinalsolutionis M.
3
2
(D)Molarityof NO3 isfinalsolutionis M .
3

Q.10 Selecttheoption(s)whichhaveequalnumberof'O'atom.
(A)10mlH2O(l)
(B*)0.15moleofV2O5
(C*)12gmO3(g)
(D)12.0441022moleculesofCO2
Q.11 Theincorrectoption(s)is/are:
Forthereaction,
aA(g)+bB(g)cC(g)+dD(g)
[Given : a + b c + d]
(A)Vapourdensityofmixtureincreaseswiththeprogressofreactionif(a+b)>(c+d).
(B)Percentagechangeinvapourdensity,withprogressofreactiondependsuponextentofreaction.
(C*)Variationofvapourdensityofthemixture,withprogressofreactiondoesn'tdependon
stoichiometric coefficientsofthespecies.
(D*)Vapourdensityofmixturedecreaseswiththeprogressofreactionif(a+b)>(c+d).
Q.12 [ItisknownthattheformationofCOorCO2dependsupontherelativeamountofO2andcarbon.
WhenO2islimiteditgivesCO,wheninexcessgivesCO2.COcanbeconvertedtoCO2when
reactedwithO2.]
1
When1molofCOisformedfrom1molofcarbonand molofO2,25Kcalheatisevolved.
2
When1molofCO2isformedfrom1molofcarbonand1molofO2,75Kcalheatisevolved.

Selecttheoption(s)inwhichheatevolvedismorethan100Kcal.
(A)10molofcarbonand1.5molofO2

(B*)36gmofcarbonand96gmofO2

(C*)6molofcarbonand3molofO2

(D)72gmofcarbonand32gmofO2

Q.13 10mlsampleofH2SO4solution(sp.gr.ofsolution=1.47)istreatedwith10gmimpureKIsolution.
Thefinalmixtureisneutralisedby20ml of 8 % (w/v)NaOHsolutionforleftH2SO4.TheliberatedI2
isdividedintotwoparts
37

Evolved I2
Part-II

Part-I
Passedthrough20mlNa2S2O3solution
yielded0.3gNaI

PassedthroughexcessKCl
Gives0.497gofCl2

Reactions :
8KI+5H2SO44K2SO4+4I2+H2S+4H2O
H2SO4+2NaOHNa2SO4+2H2O
I2+2Na2S2O32NaI+Na2S4O6
I2+2KCl2KI+Cl2
Column I

Column II

(A)

M Na 2S2O3

(P)

26.56

(B)

%(w/W)ofH2SO4

(Q)

0.1

(C)

%purityofKI

(R)

0.008

(D)

TotalmolesofI2evolved

(S)

20
[Ans.(A)Q,(B)S,(C)P,(D)R]

Q.1

H3PO4undergoesdissociationas
H3PO4 3H++ PO 34
if

8
n cation n anion
=
3
(n H3PO 4 ) undissociated

Calculate%dissociationofH3PO4.

[Ans.40%]

Q.2

Thaactionofbacteriaonmeatandfishproducesapoisonouscompoundcalledcadaverine.Asits
nameandoriginimply,itstinks!Itisobservedthat510gmofitcontains300gmcarbon,70gm
hydrogen&restisnitrogen.Giventhatitsmolarmassis102g/mol.Determinethemolecularformula
ofcadaverine.
[Ans.C5H14N2]

Q.3

AsampleofMgCO3containsimpuritieswhichdonotreactwithaacid.When10gramsofthesample
werereactedwiththeacid,2463mlofcarbondioxidewereobtainedat27Cand1atmpressure.
Calculatethe%puritybymassofthesample?[R=0.0821atm.L/mole/K]
[Ans.84%]

Q.4

CalculatetheamountofZnOproduced (in gm)when195gmofZnSreactswith89.6lO2at1atm


and273K.
ZnS+O2ZnO+SO2
[Ans.163gm]
38

Q.5

OnceTom&Jerryenteredachemistrylabwhereachemistwaspreparing3lH2SO4solution.He
labelled the solution as 10 m (dsolution = 3.3 gm/ml).Asthechemistleftthelab,amischiefcamein
Tom'smind.HetriedtothrowthesolutiononJerrybutfailed.IndoingsosomeoftheH2SO4solution
fellonthefloor,soheaddedwatertomakeitagainto3l.Thechemistreturnedback&gotastonished
whenhesawtheresultofanalysis,thatwered = 1.5 gm/mland % w/w = 98.Findoutthemolesof
H2SO4whichfelldownonthefloor.
[Ans. 5
mol]

Q.6

Twoliquids'A'(Molecularmass=40)and'B'(Molecularmass=20)arepartiallymiscible.When1
molofAand3molofBareshakentogetherandallowedtosettle,twolayer'L1'and'L2'areformed
asshownindiagram.

L1
L2
Layer'L1'contains0.1molefractionof'A'andlayer'L2'contains0.4molefractionofAcalculatethe
ratioofmassesoflayerL1tolayerL2.
[Ans.
Q.7

11
]
14

PreparationofcobaltMetaborateinvolvesthefollowingstepsofreactions:
(i)

Ca2B6O11+Na2CO3(aq) Boiled
CaCO3(insoluble)+Na2B4O7+2NaBO2

(ii)

Na2B4O7
NaBO2+B2O3

(iii)

CoO+B2O3
Co(BO2)2.

(a)

MassofCa2B6O11in kgrequiredtoproduce14.5kgofCo(BO2)2,assuming100%yieldofeach
reaction.

(b)

Iftheyieldofreaction(i),(ii)&(iii)is60%,

200
%&32.2%respectively.Calculatemassof
3

Ca2B6O11inkgrequiredtoproduce14.5kgofCo(BO2)2.
[Ans.(a)32.2kg,(b)250kg]
Q.8

(a)
(b)
(c)

Waterisaddedto3.52gramsofUF6.Theproductsare3.08gramsofasolid[containingonlyU,Oand
F]and0.8gramofagasonly.Thegas[containingfluorineandhydrogenonly],contains95%bymass
fluorine.
Determinetheempiricalformulaofthegas.
Whatfractionoffluorineoftheoriginalcompoundisconvertedintogaseouscompound.
Whatistheempiricalformulaofthesolidproduct?
39

(d)

WriteabalancedequationforthereactionofUF6andH2O.
[Assume that the empirical formula is same as molecular formula.]
[Ans. (a)HF;(b)66.66%Fingas,33.33%Finsolid;(c)UF2O2;
(d)UF6+2H2OUF2O2+4HF]

Q.1

Amixtureconsistingof0.010moleeachofC2H2andO2isconfinedtoonelitervesselandcausedto
reacttoitsmaximumextentinordertogiveCO2andH2O.Ifallsubstancesremaininthegaseousstate
at110oC,whatwillbethefinalpressureofthegasesinthevessel?
(A*)0.566atm
(B)0.498atm
(C)0.460atm
(D)0.440atm

Q.2

Theionizationenthalpyofhydrogenatomis1.312106Jmol1.Theenergyrequiredtoexcitethe
electronintheatomfromn=1ton=2is
(A*)9.84105Jmol1
(B)8.51105Jmol1
5
1
(C)6.5610 Jmol
(D)7.56105Jmol1

Q.3

Forthegivenreaction:
H2(g)+Cl2(g)2H+(aq)+2Cl(aq)

G=262.4kJ

ThevalueGibbsfreeenergyofformation( G of )fortheionCl(aq)is:
(A*)131.2kJmol1 (B)+131.2kJmol1 (C)262.4kJmol1

(D)+262.4kJmol1

Q.4

Areactionthatisspontaneouscanbedescribedas:
(A)releasingheattothesurroundings
(B)havingthesamerateinboththeforwardandreversedirections
(C)proceedinginboththeforwardandreversedirections
(D*)proceedingwithoutexternalinfluenceonceithasbegun.

Q.5

Oxidisingpowerofchlorineinaqueoussolutioncanbedeterminedbytheparametersindicatedbelow:
1
Calculatetheenergyinvolvedintheconversionof Cl2(g)toCl(aq)
2

Usingthedata,diss H Cl2 =240kJmol1,eg H Cl =349kJmol1,hyd H Cl =381kJmol1.


(A)+120kJmol1
Q.6

(C*)610kJmol1

(D)850kJmol1

Forthefollowingthreereactionsa,b,andc,equilibriumconstantsaregiven:
(a)
CO(g)+H2O(g)lCO2(g)+H2(g)
;
K1
(b)
CH4(g)+H2O(g)lCO(g)+3H2(g) ;
K2
(c)
CH4(g)+2H2O(g)lCO2(g)+4H2(g)
;
K3
Whichofthefollowingrelationsiscorrect?
(A)K3. K 3 .K 32 K12
(C)K2K3=K1

Q.7

(B)+152kJmol1

(B) K1 K 2 K 3
(D*)K3=K1K2

StandardentropyofformationofX2,Y2andXY3are60,40and50JK1mol1respectively.Forthe
1
3
reaction, X2+ Y2XY3,H=30kJtobeatequilibriumthetemperaturewillbe
2
2

40

(A)1000K
Q.8

(B)1250K

(C)500K

(D*)750K

Q.9

CalculateGforthefollowingreactionifthehydrogenissuppliedat4.00atmandtheoxygenis
suppliedat3.00atm,whilethewaterproducedisat1.0atmpressure.
2H2(g)+O2(g)2H2O(g)G298=229kJ/mol
(A*)239kJ
(B)9819kJ
(C)453kJ
(D)10148kJ
ForwhichofthefollowingprocesseswouldSbeexpectedtobemostpositive?
(A*)C6H12O6(s)+6O2(g)6CO2(g)+6H2O(g)
(B)CO2(g)CO2(s)
(C)Na+(aq)+Cl(aq)NaCl(s)
(D)Cl2(g)+H2(g)2HCl(g)

Q.10
(a)
(b)
(c)

Calculatethestandardmolarentropychangeforthefollowingreactionsat298K.
4Fe(s)+3O2(g)2Fe2O3(s)
Ca(s)+2H2O(l)Ca(OH)2(aq)+H2(g)
Na2CO3(s)+2HCl(aq)2NaCl(aq)+H2O(l)+CO2(g)
S
J/K mole

Fe
(s)

O2
(g)

27.28 205.14

Fe2O3
(s)

Ca
(s)

H2O
(l )

87.40 41.42 69.91

Ca(OH)2
(aq)

H2
(g)

-74.5 130.68

Na2CO3
(s)
136

HCl
(aq)
56.5

NaCl
(aq)

CO2
(g)

115.5 213.74

[Ans. (a)549.74J/K(b)125.06J/K(c)+265.65J/K]
Q.11

Inafuelcell(adeviceforproducingelectricitydirectlyfromchemicalreaction),methanolisusedas
fuelandoxygengasisusedasoxidiser.Thereactionis
3
CH3OH(l)+ O2(g)CO2(g)+2H2O(l)
2
TheGibbsfreeenergyofformationforCH3OH(l),CO2(g)andH2O(l)arerespectively166.2,
394.36and237.13KJ/molerespectively.Thestandardenthalpyofcombustionofmethanolis
726KJ/mol.CalculateefficiencyofconversionofGibbsenergyintousefulwork(thatiswhat
percentageofheatobtainedatconstantpressureinthisreactioncanbeobtainedaselectricalwork).
[Ans.96.7%]

Q.1
(a)
(b)
(c)
(d)
(e)
(f)
Q.2

TrueorFalse.
Molarinternalenergyisanintensiveproperty.
[T]
Heatcapacityatconstantpressureisanextensiveproperty
[T]
Reversibleprocesscanbereversedatanypointintheprocessbymakinginfiniterimalchange. [T]
Lessheatisabsorbedbythegasinthereversibleisothermalexpansionascomparedtoirreversible.
[F]
TheentropyofaclosedsystemwithPVworkonlyisalwaysmaximizedatequilibrium.
[F]
Whenasubstanceisinitsthermodynamicsstandardstate,thesubstancemustbeat25C.
[F]
Forthereactiontakingplaceunderstandardstatecondition(AssumeHandSdonotvarywith
temperature)
2A(g)+B(g)C(g)
:
H=+20KJ/mole
IfSofreactionis20J/Kmole

41

Then
(A)Thereactionwillattainequilibriumatveryhightemperature
(B)Theequilibirumwillbeattainedat100K
(C)Equilibriumwillbeattainedatverylowtemperature
(D*)Equilibriumcannotbeattainedatstandardstatecondition
Q.3

1.00gofwaterisintroducedintoa5.00Levacuatedflaskat50C.Whatmassofwaterispresentas
liquidwhenequilibriumisestablished?
Vapour Pressure , 50C
H2O
92.5mmHg
(A)0.083g
(B)0.41g
(C*)0.59g
(D)0.91g

Q.4

WhatarethesignsofHandSforthisreaction?
2C(s)+O2(g)2CO(g)
H
S
(A)

(B*)
+
(C)
+
+
(D)
+

Q.5

Whatisthemostprobabledistanceofa1selectroninaHe+ion.Thewavefunctionfor1sorbitalis
Z3 Zr / a
0

givenby
wherea0=radiusoffirstBohr'sorbitalinHatom(52.9pm)
a 3
0

(A)52.9pm
Q.6

(B)13.25pm

(C)6.61pm

(D*)26.45pm

Show that ratio of wavelengths of x th and y th line of Balmer series is given by

2
y ( x 2) y 4

y = x (x 4) ( y 2) 2

.Calculate 4 forBalmerseries.

405
]
392
Heycongrats!youhavebeenselectedbytheNASAforits"MissiontoMars".Youaresupposedto
bringasampleofairfromMarsina8.21lit.rigidcontainer.Whichcanbear60atmpressure.Youfilled
airat40atmpressureand50K,butthenrealisedthattemperatureincreasesgraduallyfromMarsto
Earth.Thencalculatetheminimumrate(no.ofmoles/day)atwhichmolesmustbeleakedsothat
containerdidnotexplodeiftimetakenforreturntripwas4days.
Given:TMars=50K,PEarthsurface=1atm,TEarthsurface=300K.
[Ans.15mol/day]

[Ans.

Q.7

Q.8

AgaseousmixturecontaininggasA,gasBandgasCwasallowedtoeffusethroughanaperture(orifice)
thencalculatemolarratioofgases(nA:nB:nC)comingoutinitially.IfmixturecontaingasA,gasBand
gasCin1:2:3moleratio.
Given: MolecularmassofgasA=2gm/mol
42

MolecularmassofgasB=32gm/mol
MolecularmassofgasC=128gm/mol
Q.9

Thefigureshows initial conditionsofauniformcylinderwithfrictionlesspistonsAandBheldin


shownpositionbymechanicalstoppers.
Mechanicalstoppers
A

25m

35m

40m

He(g)
P=10atm

Ar(g)
P=30/7atm

Ne(g)
P=5/2atm

T=300K

III

II

(a)
(b)
(c)

[Ans.8:4:3]

IfthemechanicalstoppersholdingpistonAandBasshowninfigureareremoved
[Assumethattemperatureremainsconstant.]
Pressuredevelopedineachcompartmentinfinalstate.
WhatwillbethefinalpositionofpistonA(withrespecttofarleftendofcontainer)
WhatwillbethefinalpositionofpistonB(withrespecttofarleftendofcontainer)
[Ans.5atm,(a)50m,(b)30m]

Q.10 Atubeofuniformcross-sectionof1cm2andlength3344cmisdividedintothreecompartmentsby
usingtwofrictionlesspistonseachofmass202.64gm.ThecompartmentsI,II&IIIarefilledbyequal
massesofSO2,O2andHegasesrespectivelyandplacedatanangle30withhorizontalasshown.If
pressureinSO2compartmentwas1atmfindvolumesofcompartmentsI,IIandIII.Assumevolume
ofpistonisnegligibleandtemperatureisconstant.[Useg=10m/s2,1atm=101.32103Pa]

Piston
II
I

III
He

O2
SO2

30
[Ans.144ml,320ml,2880ml]

43

Q.1

Accordingtothisphasediagram,whichphasescanexistatpressureslowerthanthetriplepoint
pressure?
(A)gasonly
(B*)solidandgasonly
(C)liquidonly
(D)solidandliquidonly

Q.2

24gmofcarboniscompletelyreactedwith48gmofO2.TheCO2producedispassedin1L1.5M
NaOHsolution.Theresultingsolutionwhentitratedwith1MHClinpresenceofphenolpthaleinas
indicatorwillconsume
(A*)500ml
(B)1000ml
(C)250ml
(D)300ml

Q.3

Whichofthefollowingthermodynamicconditionatconstantpressureandtemperatureisnecessaryfor
thespontaneityofaprocess?
(A)d(ETS+PV)>0 (B*)d(ETS+PV)<0 (C)d(ETS+PV)=0 (D)d(E+TS+PV)<0

Q.4

Calculateenthalpychangewhen50mlof0.01MCa(OH)2reactswith25mlof0.01MHCl.Given
theHneutralisationofstrongacidandstrongbaseis57.3(aq)kJ/mole
(A)28.6Joule

(B*)14.3Joule

(C)7.15Joule

(D)6Joule

Q.5

ForthereactionA+BlC+D,equilibriumconcentrationsof[C]=[D]=0.5Mifwestartwith
1MeachofAandB.PercentageofAconvertedintoCifwestartwith2MofAand1MofBis
(A)25%
(B)40%
(C)66.66%
(D*)33.33%

Q.6

CH3COCH3(g)lCH3CH3(g)+CO(g)
1
InitialpressureofCH3COCH3is100mmwhenequilibriumissetup,molefractionofCO(g)is henceKp
3
is
(A)100mm
(B*)50mm
(C)25mm
(D)150mm

Q.7

Forwhichofthefollowingreactions,thedegreeofdissociationcannotbecalculatedfromthevapour
densitydata.
(i)2HI(g)lH2(g)+I2(g)
(ii)2NH3(g)lN2+3H2(g)
(iii)2NO(g)lN2(g)+O2(g)
(iv)PCl5(g)lPCl3(g)+Cl2(g)
(A*)(i)and(iii)
(B)(ii)and(iv)
(C)(i)and(ii)
(D)(iii)and(iv)

Q.8

ThevaluesofKCforthefollowingreactionsaregivenasbelow
AlB,KC=1,BlC,KC=3andClD,KC=5
EvaluatethevalueofKCforAlD
(A*)15
(B)5
(C)3

Q.9

(D)1

Statement -1:TimetakenfortheeffusionofsamemolesofH2(g)isgreaterthan thatof He(g),


if(rHe rH 2 ) 2

44

[where rH 2 andrHearerateofeffusionofH2(g)andHe(g)respectively]
Statement -2: MolecularmassofHe(g)isgreaterthanthatofmolecularmassofH2(g).
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.
Q.10 Column-Iandcolumn-IIcontainsfourentrieseach.Entryofcolumn-Iaretobematchedwithoneor
morethanoneentriesofcolumn-II.
Giventhatinallcasestheparametersbeforev/stobeony-axisandtheparameterafterv/stobeon
x-axis.AlltheparameteraretakenandplottedinSI system.

(A)

Column I

Column II
y

PT v/s T 2
[n & V are Constant]

(P)
x

y
(B)

(C)

P V v/s T
1

n 10 mol

P
1
v/s 2
V
V
[n 1molandT 298K]

(Q)
45

x
(R)
y
x

(D)

V v/s T
[n & P constant]

(S)
y

[Ans.(A)Q,S;(B)Q;(C)S;(D)P,R]
Q.1

Whichofthefollowingstatementsistrue?
(A)Foraprocesstobespontaneous,thenumberofmolesofproductmustexceedthenumberof
molesofreactant
(B)Exothermicreactionsarealwaysspontaneous
(C*)Theentropyoftheuniverseisincreasing
(D)Inaspontaneousprocess,Ghasapositivevalue

Q.2

Forthereaction
CaCO3(s)lCaO(s)+CO2(g)
EquilibriumconstantKpis1.642atmat1000K,if40gmofCaCO3wasputintoa10Lflask,
percentageofcalciumcarbonatewouldremainunreactedattheequilibrium.
(A)66%
(B)34%
(C*)50%
(D)25%

45

Q.3

Astudentfoundthat310kJofenergywasreleasedonburning10gofpropan-1-ol,
CH3CH2CH2OH.
Fromthisexperiment,whatistheenthalpyofcombustion,inkJmol1,ofpropan-1-ol?
(A)310
(B)1296
(C*)1860
(D)3100

Q.4

Whichoccurswhenasubstanceisconvertedfromliquidtogasatthenormalboilingpoint?
I.
Potentialenergyofthesystemincreases
II.
Thedistancebetweenmoleculesincreases
III.
Theaveragekineticenergyofthemoleculesincreases
(A)IIonly
(B*)IandIIonly
(C)IIandIIIonly
(D)I,IIandIII

Q.5

10litresampleofanidealgasisexpandedreversiblyandisothermallyat300Kfrominitialpressureof
10atmtofinalpressureof1atm.Theheatabsorbedbygasduringtheprocessisapproximately
(A)15kJ
(B*)23kJ
(C)32kJ
(D)50kJ

Q.6

Theenthalpyofneutralizationofoxalicacid(H2C2O4)byastrongbasein25.4Kcal/mol.
The enthalpy of neutralization of the reaction between a strong acid and strong base is
13.7Kcal/equivalent.Theenthaplychangeoftheprocess H2C2O4l2H++C2O42is
(A*)2.0Kcal
(B)11.8Kcal
(C)1.0Kcal
(D)2.0Kcal

Q.7

Theequilibriumconstantforthefollowingreactionshavebeenmeasuredat823C.
CoO(s)+H2(g)lCo(s)+H2O(g);
K=67
CoO(s)+CO(g)lCo(s)+CO2(g); K=490
Thevalueofequilibriumconstantofthereactionfollowingreactionis
2CO2(g)+2H2(g)l2CO(g)+2H2O(g)
490
(A)
67

Q.8

67
(B)
490

(C)49067

67
(D*)

490

Thefollowingequilibriumaregiven:
N2+3H2l2NH3
...K1
N2+O2l2NO
...K2
1
O lH2O
...K3
2 2
Theequilibriumconstantofthereaction

H2+

5
2NH3+ O2l2NO+3H2O,intermsofK1,K2andK3is
2

(A) K1K 2 K 3
Q.9

(B) K1K 32 K 2

(C*) K 2 K 33 K1

(D)K1K2K3

Agivensysteminequilibriumcanliveoneoftheinfiniteequilibriumstate
accessibletoit.ForexampleforequilibriaAgCl(s)lAg+(aq)+Cl(aq),the
possible
equilibrimstateareshownbyfollowingcurve.
MatchtheentriesincolumnXwithY.

46

X
Reactions

Y
EquilibriumStates

(a)

(g)

(d)

(b)I2(s)

I2(aq)

(e)

(c)N2O4(g)

2NO(g)

(f)

(g)
(A)ad,bg,cf

(B*)ae,bg,cd

(C)ad,bf,ce

(D)ad,bf,cd

Q.10 2moleofidealmonoatomicgaswassubjectedtoreversibleadiabaticcompressionfrominitialstateof
P=1atmandT=300Ktillthepressureis 4 2 atmandtemperatureisTK.Thegasisthen
subjectedtoreversibleisothermalexpansionatTKtilltheinternalpressureisoneatm.Thegasisnow
isobaricallycooledtoattaininitialstate.FindWNet(incalorie)forwholeprocess.[Use ln 2 = 0.7]
[A ns. 1.2 1003or1.191003(takingR
=1.98)]
Q.1

Thenumberofcarbonatomspresentinasignature,ifasignaturewrittenbycarbonpencilweights
1.2103gis
(A)12.041020
(B*)6.021019
(C)3.011019
(D)6.021020

Q.2

Concentrationof2MNaOHsolution[dsolution=1.2gm/ml]canalsobewrittenas
(A*)8%w/vNaOH
(B*)6.66%w/wNaOH
(C)1.3mNaOHsolution
(D*)6.66107ppbNaOH

Q.3

Forthereactionat298K:A(g)+B(g)lC(g)+D(g)
H=29.8kcal;S=0.10kcalK1.Valueofequilibriumconstantis
(A)0
(B*)1
(C)
(D)Noneofthese

Q.4

Inthefollowingreaction:3A(g)+B(g)l2C(g)+D(g)initialmolofBisdoubleofA.Atequilibrium
molofAandCareequal.Hence%dissociationofBis
(A*)10%
(B)20%
(C)40%
(D)5%
47

Q.5

Considerthereactionatequilibrium:A(s)+B(g)+Heatl2C(s)+2D(g)
IfthepressureofBisdoubledthencalculatethefactorbywhichpressureofDischangedtore-establish
theequilibrium.
(A)2
(B)3
(C*) 2
(D) 3

Q.6

OndecompositionofNH4HS;thefollowingequilibriumisestablished.
NH4HS(s)lNH3(g)+H2S(g)
ifthetotalpressureisPatm,thentheequilibriumconstantKPisequalto
(A)Patm
(B)P2atm2
(C*) P 2 4 atm2
(D)4P2atm2

Q.7

Statement -1: Additionofanon-reactinggasatconstantvolume&constanttemperaturetoacontainer


containinggasA,doesnotchangethepartialpressureofgasA.
Statement -2: Additionofnon-reactinggastoacontaineratconstantvolume&constanttemperature
resultsinincreaseintotalpressureofthecontainer.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B*)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D)Statement-1istrue,statement-2isfalse.

Q.8

Statement -1: Massofasolutionof1litreof2MH2SO4[dsolution=1.5gm/ml]isgreaterthanthe


massofsolutioncontaining400gmMgOwhichislabelledas40%(w/w)MgO.
Statement -2: MassofH2SO4in1litre2MH2SO4[dsolution=1.5gm/ml]isgreaterthanthemassof
MgOin1litre40%(w/w)MgO[dsolution=2gm/ml]solution.
(A)Statement-1istrue,statement-2istrueandstatement-2iscorrectexplanationforstatement-1.
(B)Statement-1istrue,statement-2istrueandstatement-2isNOTthecorrectexplanationfor
statement-1.
(C)Statement-1isfalse,statement-2istrue.
(D*)Statement-1istrue,statement-2isfalse.
Question No. 9 to 12
QuestionsgivenbelowconsistoftwostatementseachprintedasAssertion(A)andReason(R);
whileansweringthesequestionsyouarerequiredtochooseanyoneofthefollowingfourresponses:
(A)ifboth(A)and(R)aretrueand(R)isthecorrectexplanationof(A)
(B)ifboth(A)and(R)aretruebut(R)isnotcorrectexplanationof(A)
(C)if(A)istruebut(R)isfalse
(D)if(A)isfalseand(R)istrue

Q.9

Assertion:
Reason:

Inaclosesystem,numberofreactingspeciesmaynotbeinstateofequilibrium(Material,
thermalandMechanical)
Eitherofthetworateofreaction(forwardorbackward)isveryslow. [Ans.A]

Q.10 Assertion :
We can not write equilibrium constant of a condensed phase (in pure state)
transformation
48

Q.11

Reason:

Positionofequilibriumisdependentonamountofspeciesrepresentingequilibria.
[Ans.C]

Assertion:
spontaneous.
Reason:

The approachtowards equilibrium in aclosed system at constant T andP is

Q.12 Assertion:
Reason:

(G)T,Phasminimumvalueatthestateofequilibrium.

[Ans.A]

Whenamultiphasesystemreachesequilibriumatconstanttemperatureandpressure
Gibbsfunctionsofallthephasesbecomesame.
Forverysmalltransferofmaterialfromonephasetoother,changeinGibbsfunction
willbezero.
[Ans.D]

Q.1

Thesample(s)containingsameno.of'Na'atomasthereare'Na'atomsin5.3gmofNa2CO3,is/are
(A*)4gmofNaOH
(B*)5.85gmofNaCl
(C)0.25moleofNa2SO4
(D)5.6gmofNa3PO4

Q.2

Forthereactionat1000C
CaCO3(s)lCaO(s)+CO2(g),

G=27kJ, p CO 2 =0.0033atm

Hence,Gatthistemperatureis:
(A)60.5kJ
(B*)87.5kJ
Q.3

(D)+33.5kJ

Aradioactivenuclideisproducedataconstantrateof-persecond.Itdecayconstantis.IfN0be
theno.ofnulceiattimet=0,thenmaximumno.ofnucleipossibleare
(A*)

Q.4

(C)33.5kJ

(B)N0

(C)/

(D)

+N0

The radioisotope 15 P32isusedinbiochemicalstudies.Asampleofthisisotopehasanactivity1000

timesthedetectablelimit.Howlongcouldanexperimentberunwiththesamplebeforetheradioactivity
couldnolongerbedetected( t1 / 2 =14.2days)
(A)~28days
Q.5

(B)~102days

(C*)~142days

(D)~50days

Forwhichofthefollowingreaction,doesvalueofequilibriumconstantindependentofchoiceof
standardstate.
(I)
CO(g)+H2O(g)lCO2(g)+H2(g)
(II)
COCl2(g)lCO(g)+Cl2(g)
(III)

1
1
NO(g)l N2(g)+ O2(g)
2
2

(A)I,II

(B)I,II,III

(C*)II

(D)I,III

49

Q.6

Baseduponthefollowinghypotheticalequilibriumat273K
XCl2.6H2O(s)lXCl2.2H2O(s)+4H2O(g);KP=8.11011atm4
Y2HPO4.12H2O(s)lY2HPO4.7H2O(s)+5H2O(g);KP=3.2109atm5
Z2SO4.10H2O(s)lZ2SO4(s)+10H2O(g);KP=1.01030atm10
Whichisthemosteffectivedehydratingagentat273K(Aqueoustensionat273K=6.0103atm)
(A)XCl2.6H2O(s) (B)Y2HPO4.7H2O(s) (C*)Z2SO4(s)
(D)Z2SO4.10H2O(s)

Q.7

ForthesynthesisofNH3fromtheHaberprocessstartingwithstoichiometricamountofN2andH2,
theattainmentofequilibriumispredictedbywhichcurve:
N2(g)+3H2(g)2NH3(g)

(A*)

(B)

(C)

(D)

Q.8

Ifwhichofthefollowingreactionat25Cyouexpectequilibriumconstanttoincreasewithtemperature.
(I)
2O3(g)l3O2(g)
(II)
I2(g)l2I(g)
(III) CaCO3(s)lCaO(s)+CO2(g)
(IV) X(g)lX(aq)
(A*)II,III
(B)II,III,IV
(C)III,IV
(D)all

Q.9

224mlofDryCO2(g)atSTPwaspassedinILofNaOHsolutionofunknownmolarity.10mlof
resultingsolutionwhentitratedwith0.01MHClrequired30mlforphenolphthaleinendpoint.Findthe
molarityoforiginalNaOHsolution.
(A)0.03M
(B*)0.04M
(C)0.05M
(D)0.06M

[Sol.

10

10
=0.1,0.04M]
1000

Q.10 Fluorocarbon polymers can be made by fluorinating polyethylene according to the reaction
(CH2)n+4nCoF3(CF2)n+2nHF+4nCoF2,wherenisalargeinteger.TheCoF3canbe
regeneratedbythereaction2CoF2+F22CoF3.
IfHFformedinthefirstreactioncannotbereused,thencalculateweightoffluorine(inkg)areconsumed
perkgoffluorocarbonproduced,(CF2)n?
[Ans.1.52]

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70