Chemistry - Advanced Crux (Sol.)

Advanced Crux_Chemistry
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Advanced Crux- Solution (Chemistry)

1. Answer (C)
2. Answer (A)
3. Answer (B, C)
The colours arise from the absorption of light on promoting an electron from the ground state to higher
state. On descending the group, the energy levels become closer and gap between HOMO – LUMO
decreases.
HOMO is *
LUMO is *
4. Answer (A, D)
A  2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P
Pt  P0
P=
2
Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [23]

 P0  2P0
Kt  ln    ln
P  P0 0  Pt
 P0   t  3P

  2  
Kt  ln 2P0  ln(3P0  Pt )
Rate constant of reaction is independent of initial concentration.

5. Answer (A, D)
A exp erimental
Steric factor =
A calculated
Steric factor = 4.5
It means Aexperimental > Acalculated
[This seems that reaction occurs more quickly than particles collide, thus concept of steric factor was
introduced]
6. Answer (A)
O O
C C
H – CH = O, NaOH, 
(crossed aldol condensation)
CH2
OH
OH O O
H H
C=O C=O
H H
OH–,  H+
HO
CH3
C5H10O is H2C O CH3

7.
CH3 CH3 CH3
+
H
+
C H2O
H2C O CH3 H3C O CH3 H3C + C2H5OH
O
Highly stable carbocation (Q or R)
H3C
+
O
H3C
H3C
P is stabilized by resonance
8. Answer (A, B, D)

(A) [Co(en)(NH3)3(H2O)]3+
(B)
(C) Co3+ = [Ar]3d6

in presence of en and NH3 it form low spin complex
(D) [Co(en)(NH3)4]3+ has larger gap between eg and t2g than [Co(en)(NH3)3(H2O)]3+. So
[Co(en)(NH3)3(H2O)3+ absorb longer wavelength than [Co(en)(NH3)4]3+.
9. Answer (B, C)
(A) Valence shell electrons in iron in compound Fe(CO)5.
Fe(26) – 1s2, 2s2, 2p6, 3s2, 3p6, 3d8 (after pairing of electrons)
Valence = 2 + 6 + 8 = 16
Electrons (3rd shell)
Valence shell electrons in nickel in compound Ni(CO)4
Ni(28) - 1s2, 2s2, 3s2, 3p6 ,3d10
Valence electrons (3rd shell) = 2 + 6 + 10 = 18

(B) Both complexes are formed in low spin condition due to strong field ligand 'CO'.
(C) Metal carbon bond strengthens when complex is formed in lower oxidation number of metal. Since in
lower oxidation number; number of electrons in d-subshell are higher, so it can donate more electrons
in ABMO of ligands and increases the double bond character between metal and carbon
(D) In higher oxidation number, metal may have less number of electrons in d-orbitals, which decreases
the extent of synergic bonding.

10. (a) Answer (D)
G = –nFE = –2 × 96500 × 0.059
= –11387 joule mol–1
 –11.4 kJ mol–1
(b) Answer (B)
0.059 0.001
0.059   log 2 
2 (M )
0.001
log 2
[M 2 ]
0.001
 100 Ksp = 4 × (10–5)3 = 4 × 10–15
[M 2 ]
11. Answer (D)
+3 +2
(P) Fe + e Fe ºG1 = – 1F × 0.77
+2
Fe + 2e Fe ºG2 = + 2F × 0.77
+3
Fe + 3e Fe ºG3 = – 3F × EºFe+3/Fe
ºG 3 = ºG1 + ºG2
– 3F × EºFe+3/Fe = – 0.77 F + 0.88 F
– 3EºFe+3 /Fe = 0.11 (V)
0.11 (V)
EºFe+3 /Fe = – = – 0.036 (V)
3
+
2H2O O2 + 4H + 4e Eº = – 1.23 V
(Q)
–
4e + O2 + 2H2O OH Eº = + 0.40 V
+ –
4 H2O 4H + 4OH Eº = – 0.83 V
2+
Cu + 2e Cu Eº = + 0.34 V
(R)
2+
2Cu Cu + 2eu Eº = – 0.52 V
2+ +
Cu + Cu 2Cu Eº = – 0.18 V
+3
(S) Cr + 3e Cr ºG1 = + 3 × F × 0.74
+2
Cr Cr + 2e ºG2 = + 2 × F ×0.91
+3 +2
Cr + e Cr
EºCr+3 /Cr+2 = – 0.4 V
12. Answer (D)

20  0.1– 10  0.1 1
(P) CH3COOHold  30

30
CH COO–  = 1
 3  old 30
Buffer with [Salt] = [Acid]

pH does not change on dilution (P)  (1)

20  0.1 2
(Q) CH3COO–   
old 40 40
2
CH3COO–  
new 80
CH3 COO –  H2 O   CH3 COOH+ OH–
C x x
– 2 – 2
x2 [OH ]old [OH ]new
Kh = = =
c 2 / 40 2 / 80
2 [OH– ]old
2
 OH–  
new 2
[OH– ]old
 [OH– ]new =
2
 [H+ ]new = 2[H+ ]old
(Q)  5
20×0.1 2
(R) [NH+4 ]old = =
40 40
2
[NH+4 ]new =
80
 NH4 OH +H+

NH+4 +H2O 
c y y
+ 2 + 2
y 2 [H ]old [Hnew ]
Kh = = =
c  2 / 40   2 / 80 
+ [H+old ]2
 [Hnew ]2 =
2
+ [H+ ]old
[Hnew ]=
2
(R)  4
(S) For a saturated solution, [OH– ] = 3 2K sp
irrespective of volume of solution. [H+] remains constant.
(S)  (1)
13. Answer (3)
CH3 CH3 CH3
Br Cl CH3 Br Cl CH3
Br Cl Br Cl Br Cl
CH3 Cl Br
14. Answer (7.00)

Only three streocentre are present.
 Total isomer = 23 = 8
But one is optically inactive.
15. Answer (B, D)
Cis anti Racemic

M and N are meso (identical)
O and P are pair of enantiomers
(B) Bromination proceeds through anti addition.
(D) (M and O) and (N and P) are two pairs of diastereomer.
35.5  2.9
16. % of Cl in X =  100  71.72%
143.5
Empirical formula of (X)
Element % relative no. of atoms Simplest ratio
C 24.24 2.02 1
H 4.04 4.04 2
Cl 71.72 2.02 1
 Empirical formula of (X) is CH2Cl
Since, X has two isomers Y and Z; both react with KOH (aq).

 KOH aq.
Y    dihydroxy compound i.e. 2Cl atoms on adjacent carbon
 KOH aq.
Z    CH 3CHO i.e. Z should have 2Cl atoms on one C atom
Thus Z should be CH3CHCl2 (1, 1-dichlorethane) and Y should be CH2ClCH2Cl (1, 2-dichloroethane)
Reactions:
 
 CH3 CH  OH2 
KOH aq.
CH3 CHCl2  H2 O
 CH3 CHO
 Z Ethanal
  KOH aq.
CH2 ClCH2Cl   CH2 OHCH2OH
ethane-1,2-diol
Y
CH3 CH3 CH3
17. A : C == C B: C == O C : CH2CH3
Ph Ph Ph Ch3
Two isomeric forms of A : C C C C (Ph = C6H5, phenyl)
H3C Ch3 H3C Ph
CH3 CH3
H2 /Pd-C Ph H H2 /Pd-C Ph H
cis ; trans + enantiomer
Ph H H Ph
CH3 CH3
meso
Thus, trans-isomer gives racemic mixture.
18. Answer (C)
Complete
XeF6 Hydrolysis
XeO3 + H2F2
OH–/H2O
–
HXeO4
Slow disproportionation in OH–/H2O
–4
XeO6 + Xe(g) + H2O + O2(g)
19. Answer A(p, s); B(p, q, r, t); C(p, q); D(p)

CH3
CH3
Polymerise Si
(A) (CH3)2SiCl2 + H2O Si—OH O O
OH CH3 CH3
n
(B) 6XeF4  12H2O 

 4Xe  2XeO3  24HF  3O2
(C) Cl2  H2O 

 HCl  HOCl
(D) VCl5  H2O 

 VOCl3  HCl
20. Answer (C)
The first ionisation energy of Be (1s22s2) is greater than that of B(1s22s2p1) because removal of electron
from 2s orbital is tough compare to that from 2p orbital. This is because 2s-orbital is closer to nucleus the
2p-orbital. Reason is incorrect as 2p-orbital is higher in energy
21. Answer (120 – 130)
From POAC,

m moles of MnCl2 = m moles of KMnO4 = x((let)
and, meq of KMnO4 = meq of oxalic acid
 225 
x5   2
 90 
x=1
 m moles of MnCl2 = 1
mg of MnCl2 = (55 + 71) = 126 mg

22. Answer (2.9 – 3.1)
MX has NaCl type structure.
From instructions, it is clear that in MX ionic solid.
Cation M - undergoes CCP
anion X - occupies all octahedral voids
(i) No. of anions left = 1
(ii) No. of anions added = 3
No. of cations left = 1
(iii) No. of cations left = 0
(iv) No. of cations added = 1
No. of anions left = 3
Final no. of cations in an unit cell = 1
Final no. of anions in an unit cell = 3
3
 ratio = = 3.00
1
23. Answer (2)
Given that, Density of surface site = 6.023 × 1014 cm–2
Total surface area = 1000 cm2
Total number of surface sites = density × total surface area
= 6.023 × 1014 × 1000
= 6.023 × 1017
Sites occupied by nitrogen molecule (20%)
20
  6.023  1017  1.2046  1017
100
pV
Number of nitrogen molecule =  NA
RT
Given that
T = 295 K, P = 0.001 atm
V = 2.43 cm3 = 2.46 × 10–3 L
R = 0.0821 L-atm/K/mol
Number of nitrogen molecules

0.001 2.46  103

=  6.023  1023
0.0821 298
= 6.02 × 1016
Therefore, number of sites occupied by each nitrogen molecules
sites occupied by N2 molecules

number of N2 molecules
1.2046  1017
= 2
6.02  1016
24. Answer (0.04 – 0.06)
When NaCl as solute is used
For solvent X For solvent Y
2 = 2Kb m 1 = 2 × Kb m
Kb
 =2
Kb
When solute S is used then molality in both solvent is equal.
For solvent X For solvent Y

a 0.7
i = 1– i = 1– = 0.65
2 2
 a
Tb =  1–  K bm Tb = (0.65)Kbm
 2
 a
1–  × 2
Tb  2
3= =

Tb 0.65
 3
1– = × 0.65
2 2
 3
= 1– × 0.65
2 2
 = 0.05
25. Answer (A, D)
pL
xM = 1 xM  xM = 0
Pure M xL = 1
Pure L
Point Z represents v.p. of pure liquid L
At xL  1, solution is very dilute, L becomes solvent. Very dilute solution of M in L is nearly ideal and obey
Raoults law (pL = xLpL°)

Also, there is positive deviation indicated by graph above dotted line (expected for ideal solution)
 L-M interaction < L - L & M - M Interactions.

26. Answer (9)
0.1 1000
Molality (m) = … (i)
0.9  MWsolvent
0.1 2  1000
Molarity (M) = … (ii)
 0.9  MWsolvent  0.1 MWsolute 
Equating (i) & (ii),

0.1 1000 0.1 2  1000

0.9  MWsolvent  0.9  MWsolvent  0.1 MWsolute 
MWsolute
So, 9
MWsolvent
27. Answer (4)
Diffusion coefficient 
 Here  = mean free path
 = mean speed
T
Since   and   T
P
T T
 Diffusion coefficient 
P
As per question, 'T' is increased four times and 'P' is increased two times.
Hence, diffusion coefficient becomes four times.
28. Answer (A)
Gº = V·P
 2900  2  10–6 P
2900  106
 P  Pa
2
PF – 1 = 14500 bar
 PF = 14501 bar
29. Answer (B, C)
A – C (Isochoric process)  wAC = 0 and UAC = qAC
B – C (Isobaric process)  UBC = qBC + wBC
wBC = –P2(V1 – V2) = P2(V2 – V1)
qBC = HBC
(T)A–C = (T)B–C
 UBC = UAC = qAC

HBC = HAC = qBC
T2 > T1
HCA and UCA are negative
HCA = UCA +
 HCA < UCA

A – B (Isothermal process)
UAB = HAB = 0
V2
wAB = –nRT1 ln
V1
30. Answer (C)
The Fischer projections of P, Q, R and S are
P  2, Q  1, R  1, S  3
31. Answer (B, D)
32. Answer (A, B, D)

HClO 4  HClO3  HOCl

most acidic least acidic
Conjugate ClO 4  ClO3  OCl

most
base least
basic basic
ClO  SO32  Cl  SO42
3ClO  2Cl  ClO3
4ClO3  Cl  3ClO4

33. Answer (0.25)
A B
pA = 1 bar (maintained throughout the experiment)
From diagram:
PB
K eq 1000 K 
PA
 10
 (rG°)1000 K = –RTlnKeq = – 1000Rln10
PB'
(Keq)2000 =  100
PA
(rG°)2000 K = –2000 Rln100
( r G)1000 K 1000 Rln10

 
(r G)2000 K 2000Rln100
1
  0.25
4
34. Answer (13.32)
1
H2 (g)  O (g)  H2 O(l)
2 2
o
Ecell  1.23 V (from given data)
 Go  nFEcell
o
= –2 × 96500 × 1.23 J/mol

Work derived using 70% efficiency and on consumption of 1.0 × 10–3 mol of H2(g)
W = 2 × 96500 × 1.23 × 0.7 × 1 × 10–3
= 166.17 J
This work done = Change in internal energy of monoatomic gas.
 166.17 = nCv,m T
166.17  2
 T 
1  3R

T  13.32 K
35. Answer (A)
Rate  [Substrate]1 (for SN1 reaction)
Rate = k[[P]0 – X]
Order of reaction = 1
For 1st order reaction Q = [P]0(1 – e–kt)
t1/2  Independent of initial concentration.
36. Answer (C, D)

Basicity order: II > I > IV > III
In IV, because of steric effect–N(Me)2 goes out of plane.
That's why resonance of N with the ring decreases and its basic nature increases.
37. Answer (B, C)
X Pd-C/Quinoline/H2
38. Answer (0.2)

Using Raoult's law
PT  x APAo  xB  PBo
 0.3  0.25  PAo  0.75  PBo ... (i)
0.4  0.5  PAo  0.5  PBo ... (ii)
From (i) and (ii)

PAo  0.6 bar
PBo  0.2 bar
 Ans  0.20
39. Answer (18.6)

M.M. = 248
9.3 mL of P  9.3 g of P
9.3
Moles of P =  0.1
93
Moles of Q obtained = 0.1 × 0.75 = 0.075
3
Mass of Q obtained = 248 × 0.1 × = 18.6 g
4
40. Answer (935)
SnO2(s) + C(s)  Sn(s) + CO2(g)
 r Ho  394  581  187 kJ / mol
 r So  52  210  56  6  200 J / K  mol
 r Ho
Tmin (at which reduction will take place) =  935 K
r So
41. Answer (16.28)


X(s)  

 Y(s)  Z(g)
pz
Given K 
po
Hº
lnK  lnA –
RT
pz H
 ln o
 ln A –
p RT
  p 
d ln  oz 
pz 1   p  – Hº
Slope of ln vs is 
po T  1 R
d 
T
–Hº
From the graph, we have  –2  104
R

  H º  2  1 0 4  8.31 4 J
Hº = 166.28 kJ mol–1

42. Answer (141.34)
–RTln K = Gº = Hº – TSº
Hº Sº
lnk  – 
RT R
Sº
 17
R
Sº = 17R = 141.338 J K–1
43. Answer (100.1)
44. Answer (2.5)
Sol. of Q. Nos. 43 and 44
Given molality of AgNO3 solution is 0.1 molal (solution-A)
Tb = ikbm
AgNO3  Ag+ + NO3–
van't Hoff factor (i) for AgNO3 = 2
Tb = 2 × 0.5 × 0.1
(Ts – Tº) = 0.1
(Ts)A = 100.1ºC, so x = 100.1
Now solution-A of equal volume is mixed with 0.1 molal BaCl2 solution to get solution-B. AgNO3 reacts with
BaCl2 to form AgCl(s).
0.1 mole of AgNO3 present in 1000 gram solvent or 1017 gram or 1017 mL solution,
milli moles of AgNO3 in V ml 0.1 molal solution is nearly 0.1 V. Similarly in BaCl2.
2AgNO3 (aq)  BaCl2 (aq)  2AgCl(s)  Ba(NO3 )2 (aq)

0.1V 0.1 V 0 0
0 0.05 V 0.1V 0.05 V
 0.05V  3 0.05V  3 
Tb      0.5  0.075
 2V 2V 
 Ts B  100.075ºC
(Ts)A – (Ts)B = 100.1 – 100.075 = 0.025ºC
= 2.5 × 10–2 ºC
So, x = 100.1 and |y| = 2.5
45. Answer (A, B)
Pb NO3 2 
dil HCl
Room temp.
PbCl2
 white ppt 
Dilute NaOH  aq 
Pb NO 3 2       Pb  OH 2
Room temperature
 white ppt 
Zn NO3 2 
dil HCl
Room temperature
 Zn2  2Cl–
 soluble

dil NaOH aq 
Zn NO 3 2 
Room temperature
Zn  OH 2
 white ppt 
dil HCl aq

Bi NO3 3 
Room temperature
 BiOCl
 White ppt
dil NaOH aq 
Bi NO 3 3       Bi  OH 3
Room temperature
 W hite ppt 
dil HCl
AgNO3 
Room temperature
 AgCl
(White ppt)
dilute NaOH aq 
AgNO3 
Room temperature
Ag2 O
Brownish black ppt 
Hg NO3 2 

dil HCl
Room temperature
 Hg2  2Cl–
 soluble
dilute NaOH aq
Hg NO3 2 
Room temperature
HgO
 Yellow precipitate
46. Answer (12)
The total number of atoms having sp2 hybridisation in the major product (P) = 12
This includes 4 C-atoms, 4 N-atoms and 4 O-atoms.
47. Answer (B, C, D)
d[P]
Rate   k[X]
dt
2X  Y  P
2 mole 1 mole
1 mole 0.5 mole 0.5 mole

d[X]
– = k1[X] = 2k[X]  2k = k1
dt
d[Y]
– = k2[X] = k[X]  k2 = k
dt
1
2k  ln 2
50
1 0.693
k ln2   6.93  10 –3 s –1
100 100
ln 2 ln2  100
 t1/2  x  k1

2  0.693
 50 sec
At 50 sec
d[X] 0.693
–  2k[X]  2   1 = 13.86 × 10–3 mol L–1 s–1
dt 100
At 100 sec
d[Y] 0.693 1 1
–  k 2 [X]  k[X]   ( Concentration of X after 2 half-lives = M)
dt 100 2 2
= 3.46 × 10–3 mol L–1 s–1

48. Answer (0.215)
49. Answer (0.86)
Solution of Q. Nos. 48 & 49
Molar conductivity of HX at infinite dilution

m = 4 × 102 S cm2 mol–1
Molar conductivity of HX at conc. c1 = y × 102 S cm2 mol–1
c
m1 y  102 y
1   

m 4  102 4
On 20 times dilution of the solution of HX
c
m2 3y  102 3y  c1 
2    c2  20 
 2 4
m 4  10  
1 1
  2 = 31
2 3
HX 



 H  X
–
c1(1– 1 ) c11 c11
c112 c 2 c (31)2
Ka   2 2  1
1– 1 1–  2 20(1– 31 )

1 9

1– 1 20(1– 31)
11
20 – 601 = 9 – 91  1   0.215
51
y = 41 = 0.86
50. Answer (A)
H – CH = CH2  CH = CH2

H – C  CH  C  CH
Order of stability of free radical
Q>P>R>S
Stability of free radical 
 Order of bond energy :

S>R>P>Q
51. Answer (D)
(1) Cl2  2Cl (Initiation step) H = 58 kcal/mol
Step (1)  Endothermic (bond breaking)

Step (2)  H = 105 – 103 = 2 kcal/mol (Endothermic)
Step (3)  H = 58 – 85 = –27 kcal/mol (Exothermic)
For complete reaction
light
CH4 (g)  Cl2 (g)  CH3 Cl(g)  HCl(g)
H = 58 + 105 – 85 – 103
= –25 kcal/mol
52. Answer (30)
h 6.6  10 –27
Momentum of photon   gm cm s –1 
 330  10 –7
Momentum of 1 mole of He-atoms = mv

h
 m v  NA 

6  1023  6.6  10 –27

4  v 
330  10 –7

6  6.6  102
v   30 cm s –1
33  4
 Change in velocity of He-atoms = 30 cm s–1
53. Answer (0.77)
(1) MnO 4 (aq)  4H  3e  MnO2 (s)  2H2 O; E  1.68 V
G1o  3F (1.68)  5.04 F
(2) MnO2 (s)  4H  2e  Mn2  2H2O; E  1.21 V
Go2  2F (1.21)  2.42 F
(3) Mn2 (aq)  2e  Mn(s); E  1.03 V
Go3  2F (1.03)  2.06 F

Adding (1), (2) and (3),
MnO 4 (aq)  8H  7e  Mn(s)  4H2O
G  G1o  Go2  G3o

= (–5.04 – 2.42 + 2.06) F
–7F E° = –5.4F
E° = 0.77 V
54. Answer (00.32)
3.74
Number of moles of Cu(NO3)2 =  0.02
187
2Cu(NO3 )2  4KI  Cu2I2   I2  4KNO3
0.02 0.01
I  KI 
2 KI 3
0.01 0.01
(Brown solution)
KI3  H2S  KI  S   2HI

0.01 0.01
( X)
Number of moles of sulphur precipitated (X) = 0.01

Mass of sulphur precipitates (X) = 0.01 × 32
= 0. 32 gm
55. Answer (B, C, D)

  NaBH4 cannot reduce acids
 
  1° amine on reaction with NaNO2/HCl liberates N2 gas.
 
56. Answer (A, B, C)
 P may be H2/Pd, ethanol; Sn/HCl

 R may be NaNO2/HCl; HNO2
 U may be (i) H3PO2, (ii) KMnO4 – KOH,  or (i) CH3 – CH2 – OH, (ii) KMnO4 – KOH, 
57. Answer (A)
k  X
(I) rate 
Xs   X 
Case-1: [X] >> Xs; [X] + Xs  [X]

k  X
rate  k (Zero order w.r.t. X)
 X
I  P, S
Case-2: [X] << Xs; [X] + Xs  Xs
k  X
  rate   k   X (1st order w.r.t. X)
Xs
   I Q, T
Case-3: [X]  Xs
k  X
rate 
Xs   X 
In this case curve-R given in List-II will match.

 I  P, Q, R, S, T (The graph of half-life should start from origin)
k  X
(II) rate 
Xs   X 
 [X] << Xs
 Xs + [X]  Xs
k  X
 rate   k   X (1st order w.r.t. X)
Xs
 II  Q, T
k  X
(III) rate 
Xs   X 
 [X] >> Xs
 Xs + [X]  [X]
k  X
 rate  k (Zero order w.r.t. X)
 X
 III  P, S
k  X
2
(IV) rate 
Xs   X 
 [X] >> Xs
 Xs + [X]  [X]
k  X
2
 rate   k  X (1st order w.r.t. X)
 X
 IV  Q, T
58. Answer (A)
(I) [Cr(CN)6]4–
Cr+2 = [Ar] 3d4 4s0

It is d2sp3 hybridised as CN– is a strong field ligand.

(II) [RuCl6]2–
Ru+4 = [Kr] 4d4 5s0
t2g set contains 4 electron.
(III) [Cr(H2O)6]2+
Cr+2 = [Ar] 3d4 4s0
It has 4 unpaired e– as H2O is weak field ligand.
So, its  = 4.9 B.M.
(IV) [Fe(H2O)6]2+
Fe2+ = [Ar]3d6 4s0
= t2g4 e2g
It has 4 unpaired e–, its  = 4.9 B.M.

59. Answer (6)
H2SO4  H  HSO42 (Ka1 is very large)

1M 1M


HSO 4   2
 H  SO 4 K a2  1.2  10 2
[SO 24  ] coming from Na2SO4 = 1.8 × 10–2
[SO24 ][H ] 1.8  102  1

  K a2
[HSO4 ] 1
 Rather than dissociation of HSO 4 into H+ and SO 24 ions, association between already present H+
and SO 24  will take place.
Assuming ‘x’ mol/L of SO 24 and H+ combines to form HSO 4
 [SO 24  ]  1.8  10 2  x
[H ]  1  x  1 

 (assuming x  1)

[HSO 4 ]  1  x  1
(1.8  10 2  x)1
 1.2  10 2
1
 x = 0.6 × 10–2
[SO 24  ]  1.2  10 2 M


PbSO4 (s)  2 2
 Pb (aq)  SO4 (aq)
If solubility of PbSO4 = s M
 [Pb 2  ]  s
[SO 24  ]  s  1.2  10 2  1.2  10 2 (assuming s << 1.2 × 10–2)
 s  1.2  102  1.6  108

1.6
s  10 6  1.33  10 6
1.2
On comparing with X × 10–Y
Y=6
60. Answer (B, C)
(A) If empirical formula of 3 is P3Q4, then molecular formula is (P3Q4)n
3MP 40 2
  
3MP  4MQ 100 5
15MP = 6MP + 8MQ

9MP = 8MQ
 3MP  8MQ
 For P3Q5, % of P =    100 =  100  34.78%
 3MP  5MQ  23M Q
(B) If empirical formula of compound 3 is P3Q2, we have

3MP 2

3MP  2MQ 5
15MP = 6MP + 4MQ

9MP = 4MQ
If MP = 20
180
MQ   45
4
(C) If empirical formula of 2 is PQ
MP 4 44.44
  
MP  MQ 9 100
9MP = 5MP + 4MQ

5MP = 4MQ
If empirical formula is assumed as P5Q4,
 5MP 
% of P =    100 = 50
5M
 P  4MQ 
Hence P5Q4 is the empirical formula of compound

(D) If empirical formula of I is P2Q, we have
 2MP 
% of P =    100 = 50
 2MP  MQ 
4MP = 2MP + MQ
2MP = MQ
Hence, atomic weight of P and Q cannot be 70 and 35 respectively.
Hence (B, C) are correct
61. Answer (A, C)

O
O
O O
Zn/Hg
AlCl3 HO HCl OH
O O
(P) (Q)
SOCl2
Zn/Hg AlCl3
HCl Cl
O O
[Hydrocarbon] (S) (R)
Compound (S) can not decolorizes bromine water.
R2Cd
Cl R
O O
R2Cd is a less reactive nucleophile so reaction stops at carbonyl group.
62. Answer (B)
Atom X occupies FCC lattice sites as well as alternate tetrahedral voids of FCC.
In FCC, tetrahedral voids are 8 (in a unit cell)
Hence
1 1
Atom X in a unit cell (FCC lattice sites) = 8   6  4
8 2
1
Atom X in a unit cell (in T.V.) = 8  4
2
Total atom X in one unit cell = 8
1
For relation between a and r, since T.V. forms at th of body diagonal,
4
a 3
 2r
4
8r
a=
3
4 3 4
8 r 8   r3
Packing efficiency = 3  100  3  100  35%
a3  8r 
3
 
 3
63. Answer (C)

64. Answer (C, D)
65. Answer (C)

aq NaOH
MnCl2  Mn  OH2 + NaCl
P Q 

Mn  OH2 
PbO
2
H2SO 4
 MnO 4–
P   X
MnO  OH 2 KI
NaCl 
Conc. H2SO4
 Cl2 
starch
 blue
 Y
66. Answer (5)
From the question
Af = 1015, Ab = 1011, f = Forward reaction
log K at 500 K = 6 b = Backward reaction
log kf at 500 K = 9 (from graph)
log kb at 500 K :
k  k
logK  log  f  since  K  f
 kb  kb
6 = log kf – log k b
6 = 9 – log kb
log kb = 3 at 500 K
k 2  Ea  1 1
log   – 
k1 R  T2 T1 
–Eab
kb  A b e RT
 –Eab 
lnk b  ln  A b e RT 
 
 
Eab
lnkb  lnA b –
RT
Eab
2.303logk b  2.303log A b –
500R
Ea
 2.303(log A b – logk b )
500R
Ea
 2.303(log1011 – 3)
500R
Ea
 2.303(11– 3)  2.303  8
500R
Ea = 2.303 × 8 × 500R
 k  –Ea  1 1
ln  2    – 
 k1  R  T2 T1 
k  –Ea  1 1 
ln  250 K   – 
 k 500 K  R  250 500 
 

k   2.303  8  500R  1 
ln  250 K   500 
 k 500 K  R  
 
2.303(log k250 K – log k500 K) = –2.303 × 8

log k250 K – 3 = –8
log k250 K = –5
| log k250 K | = 5
67. Answer (7)
qA  C = RT2ln10
qA  B = 0 ( adiabatic)
qA  C = qA  B + qB  C
qA  C = qB  C
V 
qA  C = nRT2 ln  3  …(1)
 V2 
For B  C
E = q + w
E = 0 (since isothermic)
q =–w
 V 
= –  –nRT2 ln 3 
 V2 
V 
= nRT2 ln  3 
 V2 
V 
q  nRT2 ln  3 
B C  V2 
V 
qBC  RT2 ln  3  [Since n = 1]
 V2 
From A  B
T1V1 –1  T2 V2 –1
600V1 –1  60V2 –1
5
–1
10  10 3  V2 –1
5
–1
105/3  V23
105/3  V22/3
5 3 5

V2  10 3 2
 10 2

5
V2  10 2 ….(2)
From equation (1)
V 
qAC = nRT2 ln  3 
 V2 
Given, qA  C = RT2 ln10
V 
RT2 ln10  RT2 ln  3 
 V2 
V 
ln10  ln  3 
 V2 
 V 
ln10  ln  35 
 2 
 10 
V3
10  5
10 2
5 7
1
V3  10 2
 10 2
2logV3 = 2log107/2
=7
68. Answer (D)
P2O3 + H2O  H3PO3
P4 + NaOH + H2O  PH3 + NaH2PO2
H3PO2 + H2O + AgNO3  H3PO4 + HNO3 + Ag

Hence :-
P2
Q3
R4
S5
69. Answer (A, B, D)
Metal x forms FCC (edge length Lx)

Metal y forms BCC (edge length Ly)
Metal z forms SC (edge length Lz)
3 8
Given rz  ry and ry  rx
2 3
3 8
 rz   rx  4rx
2 3
3
Mz  My Mz = 3Mx
2

 My = 2Mx
Packing efficiency FCC > BCC > SC
Packing efficiency unit cell x > y > z
In FCC unit cell:- atoms along the face diagonals are in contact.
 2 L x  4rx  L x  2 2 rx
In BCC unit cell: atoms along the body diagonal are

4 4 8 32
 3 L y  4ry  L y  ry =  rx  rx
3 3 3 3
32
Ly  rx
3
In SC unit cell, atoms along the edge are in contact
  Lz = 2rz
= 2 × 4rx = 8rx
L x  2 2 rx
32
Ly  rx
3
L z  8rx
 Ly > Lz > Lx
Density of x (Number of atoms of x per unit cell (z) = 4)
zMx 4  Mx
dx  3

(L x ) NA (2 2 rx )3  NA
4Mx Mx
 
16 2rx3NA 4 2rx3NA
Density of y: (Number of atoms of y per unit cell (z) = 2)
zMy 2  2Mx 108Mx
dy   
(L y )3 NA  32 
3
32768rx3 NA
 3 rx  NA
 
 Density of x > density of y.
70. Answer (C, D)

71. Answer (1791)
Mass of S = 0.009 × 199
= 1.791 g
= 1791 mg
72. Answer (0.31)

600
1 (Cp,  Cp, )dT
S600  S300   T
300
 T   T2  600 K 
 1 1  ln 2   
 T1   T1  300 K 
1  S300  1 1 ln 2
S300  1– 0.69
S 300  0.31 J mol1K 1
73. Answer (500)
H600 – H300 = 1 × (Cp, – Cp,) (600 – 300)

Now, at transition temperature,
H600 = TS600
= 600 × (6 – 5)
= 600 J mol–1
 600 – H300 = 1 × 1 × 300
H300 = 600 – 300
= 300 J mol–1


Chemistry - Advanced Crux (Sol.)

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Advanced Crux_Chemistry

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005, Ph.011-47623456

Advanced Crux- Solution (Chemistry)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [23]

Rate constant of reaction is independent of initial concentration.

C5H10O is H2C O CH3

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [24]

(C) Co3+ = [Ar]3d6

(A) Valence shell electrons in iron in compound Fe(CO)5.

Electrons (3rd shell)

Valence shell electrons in nickel in compound Ni(CO)4

Ni(28) - 1s2, 2s2, 3s2, 3p6 ,3d10

Valence electrons (3rd shell) = 2 + 6 + 10 = 18

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [25]

10. (a) Answer (D)

G = –nFE = –2 × 96500 × 0.059

= –11387 joule mol–1

12. Answer (D)

Buffer with [Salt] = [Acid]

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [26]

 [H+ ]new = 2[H+ ]old

 NH4 OH +H+

(S) For a saturated solution, [OH– ] = 3 2K sp

irrespective of volume of solution. [H+] remains constant.

14. Answer (7.00)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [27]

Only three streocentre are present.

15. Answer (B, D)

Cis anti Racemic

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [28]

CH3 CH3 CH3

19. Answer A(p, s); B(p, q, r, t); C(p, q); D(p)

(B) 6XeF4  12H2O 

(C) Cl2  H2O 

(D) VCl5  H2O 

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [29]

m moles of MnCl2 = m moles of KMnO4 = x((let)

and, meq of KMnO4 = meq of oxalic acid

mg of MnCl2 = (55 + 71) = 126 mg

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [30]

0.001 2.46  103

When NaCl as solute is used

For solvent X For solvent Y

When solute S is used then molality in both solvent is equal.

For solvent X For solvent Y

Point Z represents v.p. of pure liquid L

Raoults law (pL = xLpL°)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [31]

 L-M interaction < L - L & M - M Interactions.

Equating (i) & (ii),

Diffusion coefficient 

 Here  = mean free path

B – C (Isobaric process)  UBC = qBC + wBC

wBC = –P2(V1 – V2) = P2(V2 – V1)

 UBC = UAC = qAC

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [32]

HBC = HAC = qBC

HCA and UCA are negative

 HCA < UCA

The Fischer projections of P, Q, R and S are

32. Answer (A, B, D)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 [33]

HClO 4  HClO3  HOCl