Most Difficult Chemistry Questions 2009-2018

Most Diﬃcult Questions
Previous Years 2009-2018

Chemistry
CHEMISTRY
1. Assuming 2s-2p mixing is NOT operative, the paramagnetic species among the following is
[JEE (Adv)-2014 (Paper-2)]
(A) Be2 (B) B2
(C) C2 (D) N2
2. The standard state Gibbs free energies of formation of C(graphite) and C(diamond) at T = 298 K are
fG°[C(graphite)] = 0 kJ mol–1
fG°[C(diamond)] = 2.9 kJ mol–1
The standard state means that the pressure should be 1 bar, and substance should be pure at a given
temperature. The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces its volume by 2 × 10–
6 m 3 mol–1. If C(graphite) is converted to C(diamond) isothermally at T = 298 K, the pressure at which
C(graphite) is in equilibrium with C(diamond), is

[Useful information : 1 J = 1 kg m 2s–2; 1 Pa = 1 kg m –1 s–2; 1 bar = 105 Pa]
(A) 14501 bar (B) 29001 bar
(C) 1450 bar (D) 58001 bar
3. Pure water freezes at 273 K and 1 bar. The addition of 34.5 g of ethanol to 500 g of water changes the freezing
point of the solution. Use the freezing point depression constant of water as 2 K kg mol–1. The figures shown
below represent plots of vapour pressure (V.P.) versus temperature (T). [molecular weight of ethanol is 46 g
mol–1]
Among the following, the option representing change in the freezing point is
1
Wate ter
r Wa
Ice l
V.P./bar
V.P./bar
1
ano
(A) (B) Et h
Ice ter
+
Wa
Water + Et
h anol
270 273 271 273
T/K T/K
1
ter Wate
Wa r
nol Ice
V.P./bar
V.P./bar
1
tha
(C) Ice +E (D)
ter
Wa
Water + Et
h anol
270 273 271 273
T/K T/K
Chemistry MOST DIFFICULT QUESTION
4. The qualitative sketches I, II and III given below show the variation of surface tension with molar concentration
of three different aqueous solutions of KCl, CH3OH and CH3(CH2)11OSO3–Na+ at room temperature. The correct
assignment of the sketches is [JEE (Adv)-2016 (Paper-2)]
Surface tension
I.
Concentration
Surface tension
II.
Concentration
Surface tension
III.
Concentration
(A) I : KCl
II : CH3OH
III : CH3(CH2)11OSO3–Na+
(B) I : CH3(CH2)11OSO3–Na+
II : CH3OH
III : KCl
(C) I : KCl
II : CH3(CH2)11OSO3–Na+
III : CH3OH
(D) I : CH3OH
II : KCl
III : CH3(CH2)11OSO3–Na+
5. Among the following complexes (K – P), K 3 [Fe(CN) 6 ](K), [Co(NH 3) 6]Cl3 (L), Na 3 [Co(oxalate) 3] –3(M),
[Ni(H2O)6]Cl2(N), K2[Pt(CN)4](O) and [Zn(H2O)6](NO3)2(P), the diamagnetic complexes are
[IIT-JEE-2011 (Paper-2)]
(A) K, L, M, N (B) K, M, O, P
(C) L, M, O, P (D) L, M, N, O
6. The compounds P, Q and S
O
COOH OCH3
C
O
HO H3 C
P Q S
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MOST DIFFICULT QUESTION Chemistry
were separately subjected to nitration using HNO3/H2SO4 mixture. The major product formed in each case
respectively, is [IIT-JEE-2010 (Paper-2)]
COOH OCH3 C
O
(A)
HO H3C O2N
NO2 NO2
COOH OCH3 C
O
(B)
HO NO2 H3C NO2
NO2
O NO2
COOH OCH3 C
O
(C)
HO H3C NO2
NO2
COOH OCH3 C
O NO2
(D)
HO H3C NO2
NO2
7. The acidic hydrolysis of ether (X) shown below is fastest when [JEE (Adv)-2014 (Paper-2)]
Acid
OR OH + ROH
(A) One phenyl group is replaced by a methyl group

(B) One phenyl group is replaced by a para-methoxyphenyl group
(C) Two phenyl groups are replaced by two para-methoxyphenyl groups
(D) No structural change is made to X
8. In the following reaction sequence, the correct structures of E, F and G are
O O
Heat I2
[E] [F] + [G]
Ph OH NaOH
*
(  implies 13C labelled carbon) [IIT-JEE-2008 (Paper-2)]
O O
(A) E = Ph * CH3 F = Ph * O Na G = CHI3
O O
(B) E =
CH3 F = Ph G = CHI3
*
Ph O Na
O O
*
(C) E = Ph CH3 F = Ph
*
O Na G = CHI3
O O
*
(D) E =
CH3 F = Ph G = CH3I
*
Ph O Na
9. The major product in the following reaction is
O 1. CH3MgBr, dry ether, 0 °C

Cl 2. aq. acid
CH3
OH
O
(A) H3C (B) H2C CH3
CH3 CH3
CH3
(C) (D)
CH2 O
O CH3
10. The major product of the following reaction sequence is
O
(i) HCHO (excess)/NaOH, heat
+
(ii) HCHO/H (catalytic amount)
O O O O OH
(A) (B)
HO O O O OH
(C) (D)
OH
11. In the reaction,
O
(1) NaOH/Br2
H3C C O
T,
NH2 (2) C
Cl
the structure of the product T is [IIT-JEE-2010 (Paper-2)]
O
H3C C O
(A) O C
NH
(B) C CH3
O
H3C NH
(C)
C
O
O
H3C C O
(D) NH C
12. The order of basicity among the following compounds is [JEE (Adv)-2017 (Paper-2)]
NH
I. II. N NH
H3 C NH2
NH2
III. HN N IV.
H2 N NH
(A) IV > I > II > III (B) IV > II > III > I
(C) I > IV > III > II (D) II > I > IV > III
13. Cellulose upon acetylation with excess acetic anhydride / H2SO4 (catalytic) gives cellulose triacetate whose
structure is [IIT-JEE-2008 (Paper-2)]
AcO
AcO O O–
H H
AcO O OAc H
H H O H
H O O OAc H H H OAc
H
(A) OAc H
–O H H OAc
H OAc
AcO
AcO O O–
H H
AcO O OH H
H H O H
H O O OH H H H OH
H
(B) OH H
H H OH
–O
H OH
AcO AcO AcO
H O H H O H H O O–
H H H
(C) OAc H
O
OAc H OAc H
–O O H
H OAc H OAc H OAc
AcO AcO AcO
H O H H O H H O O–
H H H
(D) H H H H H H
–O O O H
OAc OAc OAc OAc OAc OAc
14. The correct statement about the following disaccharide is [IIT-JEE-2010 (Paper-1)]
CH2OH
O
H H CH2OH H
H O
OH H H OH
OCH2 CH2 O CH2OH
OH
H OH OH H
(a) (b)
(A) Ring (a) is pyranose with -glycosidic link
(B) Ring (a) is furanose with -glycosidic link
(C) Ring (b) is furanose with -glycosidic link
(D) Ring (b) is pyranose with -glycosidic link
15. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) under different conditions. The correct statement(s)
among the following is(are) [JEE (Adv)-2017 (Paper-1)]
(A) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic
(B) The work done by the gas is less when it is expanded reversibly from V1 to V2 under adiabatic conditions
as compared to that when expanded reversibly from V1 to V2 under isothermal conditions
(C) The work done on the gas is maximum when it is compressed irreversibly from (p2, V2) to (p1, V1) against
constant pressure p1
(D) The change in internal energy of the gas is (i) zero, if it is expanded reversibly with T1 = T2, and (ii) positive,
if it is expanded reversibly under adiabatic conditions with T1  T2
16. A reversible cyclic process for an ideal gas is shown below. Here, P, V, and T are pressure, volume and
temperature, respectively. The thermodynamic parameters q, w, H and U are heat, work, enthalpy and internal
energy, respectively [JEE (Adv)-2018 (Paper-1)]
A(P1, V1, T1) C(P2, V1, T2)
Volume (V)
B(P2, V2, T1)
Temperature (T)
The correct option(s) is (are)

(A) qAC = UBC and wAB = P2(V2 – V1) (B) wBC = P2(V2 – V1) and qBC = HAC
(C) HCA < UCA and qAC = UBC (D) qBC = HAC and HCA > UCA
17. The %yield of ammonia as a function of time in the reaction N 2 g + 3H 2 (g)  2NH 3 (g), H < 0 at (P, T1)
is given below
T1
%yield
time
If this reaction is conducted at (P, T 2), with T2 > T1, the %yield of ammonia as a function of time is represented
by [JEE (Adv)-2015 (Paper-1)]
T2
%yield
T1
(A) (B)
time
T2
T1
T1
%yield
%yield
(C) T2 (D)
time time
18. For a reaction, A  P , the plots of [A] and [P] with time at temperatures T1 and T2 are given below.
[A] / (mol L–1) 10 10
[P] / (mol L–1)

T1
T2
5 5
T2
T1
Time Time
If T2 > T1, the correct statement(s) is (are)
(Assume H and S are independent of temperature and ratio of lnK at T 1 to lnK at T2 is greater than T2/T1.
Here H, S, G and K are enthalpy, entropy, Gibbs energy and equilibrium constant, respectively)
(A) H < 0, S < 0 (B) G < 0, H > 0
(C) G < 0, S < 0 (D) G < 0, S > 0

19. The given graphs/data I, II, III and IV represent general trends observed for different physisorption and
chemisorption processes under mild conditions of temperature and pressure. Which of the following choice(s)
about, I, II, III and IV is (are) correct? [IIT-JEE-2012 (Paper-2)]
I P constant II P constant
Amount of gas adsorbed
T T
III IV
200 K
Potential Energy
250 K Eads
0 Distance of molecule
from the surface
–1
Hads = 150 kJ mol
(A) I is physisorption and II is chemisorption

(B) I is physisorption and III is chemisorption
(C) IV is chemisorption and II is chemisorption
(D) IV is chemisorption and III is chemisorption
20. The correct statement(s) regarding, (i) HClO, (ii) HClO2, (iii) HClO3 and (iv) HClO4, is(are)
(A) The number of Cl=O bonds in (ii) and (iii) together is two
(B) The number of lone pairs of electrons on Cl in (ii) and (iii) together is three
(C) The hybridization of Cl in (iv) is sp3
(D) Amongst (i) to (iv), the strongest acid is (i)
21. The colour of the X2 molecules of group 17 elements changes gradually from yellow to violet down the group.
This is due to [JEE (Adv)-2017 (Paper-1)]
(A) The physical state of X2 at room temperature changes from gas to solid down the group
(B) Decrease in HOMO-LUMO gap down the group
(C) Decrease in *-* gap down the group
(D) Decrease in ionization energy down the group
22. Among the following, the correct statement(s) is(are) [JEE (Adv)-2017 (Paper-2)]
(A) AlCl3 has the three-centre two-electron bonds in its dimeric structure
(B) BH3 has the three-centre two-electron bonds in its dimeric structure
(C) Al(CH3)3 has the three-centre two-electron bonds in its dimeric structure
(D) The Lewis acidity of BCl3 is greater than that of AlCl3
23. Addition of excess aqueous ammonia to a pink coloured aqueous solution of MCl26H2O(X) and NH4Cl gives
an octahedral complex Y in the presence of air. In aqueous solution, complex Y behaves as 1:3 electrolyte.
The reaction of X with excess HCl at room temperature results in the formation of a blue coloured complex
Z. The calculated spin only magnetic moment of X and Z is 3.87 B.M., whereas it is zero for complex Y. Among
the following options, which statement(s) is(are) correct? [JEE (Adv)-2017 (Paper-1)]
(A) The hybridization of the central metal ion in Y is d2sp3
(B) When X and Z are in equilibrium at 0°C, the colour of the solution is pink
(C) Z is a tetrahedral complex
(D) Addition of silver nitrate to Y gives only two equivalents of silver chloride
24. Among the following, reactions(s) which gives (give) tert-butyl benzene as the major product is(are)
Br
Cl
(A) (B)
NaOC2H5 AlCl3
OH
(C) (D)
H2SO4 BF3OEt2
25. In the following reaction sequence, the correct structure(s) of X is (are) [JEE (Adv)-2018 (Paper-1)]
(1) PBr3, Et2O Me N3

X
(2) Nal, Me2CO
(3) NaN3, HCONMe2
enantiomerically
pure
Me OH Me OH
(A) (B)
(C) Me (D)
OH Me OH
26. The correct functional group X and the reagent/reaction conditions Y in the following scheme are
(i) Y
X – (CH2)4 – X
O O
(ii) C – (CH2)4 – C
HO OH
Heat
condensation polymer
(A) X = COOCH3, Y = H2/Ni/Heat (B) X = CONH2, Y = H2/Ni/Heat

(C) X = CONH2, Y = Br2/NaOH (D) X = CN, Y = H2/Ni/Heat
27. The major product of the following reaction is
O i. KOH, H2O
ii. H+, heat
CH3
O
CH3 CH3
O O
(A) (B)
O CH3
O
CH3
(C) (D)
28. The reaction(s) leading to the formation of 1,3,5-trimethylbenzene is (are) [JEE (Adv)-2018 (Paper-1)]
O
Conc. H2SO4 heated iron tube
(A) (B) Me H
 873 K
O CHO
(1) Br2, NaOH

(2) H3O+ Zn/Hg, HCl
(C) (D)
(3) sodalime, 
OHC CHO
O O
29. In the reaction shown below, the major product(s) formed is/are [JEE (Adv)-2014 (Paper-1)]
NH2
acetic anhydride
Product(s)
NH2 CH2Cl2
H
N CH3 NH2
O
(A) + CH3COOH (B) H + CH3COOH
NH2 N CH3
O O O
H
N CH3 NH3CH3COO
O
(C) H + H2O (D) H
N CH3 N CH3
O O O O
30. Aniline reacts with mixed acid (conc. HNO3 and conc. H2SO4) at 288 K to give P (51 %), Q (47%) and R
(2%). The major product(s) of the following reaction sequence is (are)
1) Ac2O, pyridine 1) Sn/HCl

2) Br2, CH3CO2H 2) Br2/H2O (excess)
R S Major
3) H3O+ 3) NaNO2, product(s)
4) NaNO2, HCl/273-278K
HCl/273-278K 4) H3PO2
5) EtOH,
Br Br
Br Br
(A) (B)
Br
Br
Br Br
Br Br
(C) (D)
Br Br
Br Br
Br
31. For "invert sugar", the correct statement(s) is/are (Given : Specific rotations of (+)-sucrose,
(+)-maltose, L-(–)-glucose and L-(+)-fructose in aqueous solution are +66°, +140°, –52° and +92°, respectively)
(A) "Invert sugar" is prepared by acid catalyzed hydrolysis of maltose
(B) "Invert sugar" is an equimolar mixture of D-(+)-glucose and D-(–)-fructose
(C) Specific rotation of "invert sugar" is –20°
(D) On reaction with Br2 water, "invert sugar" forms saccharic acid as one of the products
Paragraph for Q. 32. & 33.
Thermal decomposition of gaseous X2 to gaseous X at 298 K takes place according to the following equation:


X2(g) 
 2X(g)
The standard reaction Gibbs energy, rG°, of this reaction is positive. At the start of the reaction, there is one mole
of X2 and no X. As the reaction proceeds, the number of moles of X formed is given by . Thus,  equilibrium is the
number of moles of X formed at equilibrium. The reaction is carried out at a constant total pressure of 2 bar. Consider
the gases to behave ideally. (Given : R = 0.083 L bar K–1 mol–1) [JEE (Adv)-2016 (Paper-2)]
Choose the correct answer :
32. The equilibrium constant Kp for this reaction at 298 K, in terms of equilibrium, is
82equilibrium 82equilibrium
(A) (B)
2   equilibrium 4  2equilibrium
42equilibrium 42equilibrium
(C) (D)
2   equilibrium 4  2equilibrium
33. The INCORRECT statement among the following, for this reaction, is
(A) Decrease in the total pressure will result in formation of more moles of gaseous X
(B) At the start of the reaction, dissociation of gaseous X2 takes place spontaneously
(C)  equilibrium = 0.7
(D) KC < 1
The reactions of Cl2 gas with cold-dilute and hot-concentrated NaOH in water give sodium salts of two (different)
oxoacids of chlorine, P and Q, respectively. The Cl2 gas reacts with SO2 gas, in presence of charcoal, to give a
product R. R reacts with white phosphorus to give a compound S. On hydrolysis, S gives an oxoacid of phosphorus, T.
34. P and Q, respectively, are the sodium salts of
(A) Hypochlorus and chloric acids (B) Hypochlorus and chlorus acids
(C) Chloric and perchloric acids (D) Chloric and hypochlorus acids
35. R, S and T respectively, are
(A) SO2Cl2, PCl5 and H3PO4 (B) SO2Cl2, PCl3 and H3PO3
(C) SOCl2, PCl3 and H3PO2 (D) SOCl2, PCl5 and H3PO4
Paragraph for Q. 36. to 38.
Copper is the most noble of the first row transition metals and occurs in small deposits in several countries. Ores
of copper include chalcanthite (CuSO4·5H2O), atacamite (Cu2Cl(OH)3), cuprite (Cu2O), copper glance (Cu2S) and
malachite (Cu2(OH)2CO3). However, 80% of the world copper production comes from the ore chalcopyrite (CuFeS2).
The extraction of copper from chalcopyrite involves partial roasting, removal of iron and self-reduction.
36. Partial roasting of chalcopyrite produces
(A) Cu2S and FeO (B) Cu2O and FeO
(C) CuS and Fe2O3 (D) Cu2O and Fe2O3
37. Iron is removed from chalcopyrite as

(A) FeO (B) FeS
(C) Fe2O3 (D) FeSiO3
38. In self-reduction, the reducing species is
(A) S (B) O2–
(C) S2– (D) SO2
An aqueous solution of metal ion M1 reacts separately with reagents Q and R in excess to give tetrahedral and
square planar complexes, respectively. An aqueous solution of another metal ion M2 always forms tetrahedral
complexes with these reagents. Aqueous solution of M2 on reaction with reagent S gives white precipitate which
dissolves in excess of S. The reactions are summarized in the scheme given below :
Scheme :
Q R
Tetrahedral M1 Square planar
Excess Excess
Q R
Tetrahedral M2 Tetrahedral
Excess Excess
S, stoichiometric amount
R
White precipitate Precipitate dissolves
Excess

39. M1, Q and R, respectively are
(A) Zn2+, KCN and HCl (B) Ni2+, HCl and KCN
(C) Cd2+, KCN and HCl (D) Co2+, HCl and KCN
40. Reagent S is
(A) K4[Fe(CN)6] (B) Na2HPO4
(C) K2CrO4 (D) KOH
In the following reactions
Pd-BaSO4 i. B2H6
C8H6 C8H8 X
H2 ii. H2O2, NaOH, H2O
H2O
HgSO4, H2SO4
i. EtMgBr, H2O
C8H8O +
Y
ii. H , heat
41. Compound X is
O OH
CH3 CH3
(A) (B)
OH
CHO
(C) (D)
42. The major compound Y is
CH3 CH3
(A) (B)
CH3
CH2
CH3 CH3
(C) (D)

P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating, P forms the cyclic
anhydride. Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S,
T and U.
COOH COOH COOH

H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
S T U

43. Compounds formed from P and Q are, respectively
(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U)) and optically inactive S
H /Ni
44. In the following reaction sequences V and W are respectively Q 
2

V
AlCl3(anhydrous) 1. Zn-Hg/HCl
+V W
2. H3PO4
O
CH2OH
(A) O and (B) and
CH2OH
O O V W
V W
O
HOH2C
(C) O and (D) and
CH2OH CH2OH
O V W
V W

The reaction of compound P with CH3MgBr (excess) in (C2H5)2O followed by addition of H2O gives Q. The compound
Q on treatment with H2SO4 at 0ºC gives R. The reaction of R with CH3COCl in the presence of anhydrous AlCl3 in
CH2Cl2 followed by treatment with H2O produces compound S. [Et in compound P is ethyl group]
(H3 C)3C
CO2Et
Q R S

45. The reactions, Q to R and R to S, are
(A) Dehydration and Friedel-Crafts acylation
(B) Friedel-Crafts alkylation, dehydration and Friedel-Crafts acylation
(C) Friedel-Crafts alkylation and Friedel-Crafts acylation
(D) Aromatic sulfonation and Friedel-Crafts acylation
46. The product S is
HO3S
O CH3 H3COC
(H3C)3C
(H3C)3C H3C CH3
(A) (B)
COCH3
H3C
CH3
(H3C)3C COCH3
(H3 C)3C CH3
(C) (D)
COCH3

Treatment of benzene with CO/HCI in the presence of anhydrous AlCl3/CuCl followed by reaction with Ac2O/NaOAc
gives compound X as the major product. Compound X upon reaction with Br2/Na2CO3, followed by heating at 473
K with moist KOH furnishes Y as the major product. Reaction of X with H2/Pd-C, followed by H3PO4 treatment gives
Z as the major product. [JEE (Adv)-2018 (Paper-1)]
47. The compound Y is
OH
COBr Br
(A) (B)
HO O
Br
COBr
(C) (D)
Br
48. The compound Z is
(A) (B)
O O
OH
(C) (D)
49. Match the entries in Column I with the correctly related quantum number(s) in Column II. Indicate your answer
by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS. [IIT-JEE-2008 (Paper-2)]
Column I Column II
(A) Oribital angular momentum of the electron (p) Principal quantum number
in a hydrogen-like atomic orbital
(B) A hydrogen-like one-electron wave function (q) Azimuthal quantum number
obeying Pauli principle
(C) Shape, size and orientation of hydrogen-like (r) Magnetic quantum number
atomic orbitals
(D) Probability density of electron at the nucleus (s) Electron spin quantum number
in hydrogen-like atom
50. Dilution processes of different aqueous solutions, with water, are given in LIST-I. The effects of dilution of the
solutions on [H+] are given in LIST-II. [JEE (Adv)-2018 (Paper-2)]
(Note: Degree of dissociation () of weak acid and weak base is << 1; degree of hydrolysis of salt <<1; [H+]
represents the concentration of H+ ions)
List-I List-II
P. (10 mL of 0.1 M NaOH + 20 mL of 1. the value of [H+] does not change on dilution
0.1 M acetic acid) diluted to 60 mL
Q. (20 mL of 0.1 M NaOH + 20 mL of 0.1 M 2. the value of [H+] changes to half of its initial
acetic acid) diluted to 80 mL value on dilution
R. (20 mL of 0.1 M HCl + 20 mL of 0.1 M 3. the value of [H+] changes to two times of its
ammonia solution) diluted to 80 mL initial value on dilution
1
S. 10 mL saturated solution of Ni(OH)2 in 4. the value of [H+] changes to times of its
2
equilibrium with excess solid Ni(OH)2 is initial value on dilution
diluted to 20 mL (solid Ni(OH)2 is still
present after dilution).
5. the value of [H+] changes to 2 times of its
initial value on dilution
Match each process given in LIST-I with one or more effect(s) in LIST-II. The correct option is
(A) P  4; Q  2; R  3; S  1
(B) P  4; Q  3; R  2; S  3
(C) P  1; Q  4; R  5; S  3
(D) P  1; Q  5; R  4; S  1
51. An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List I. The variation
in conductivity of these reactions is given in List II. Match list I with List II and select the correct an-
swer using the code given below the lists : [JEE (Adv)-2013 (Paper-2)]
List I List II
P. (C2H5)3N + CH3COOH 1. Conductivity decreases and then increases
X Y
Q. KI (0.1M) + AgNO3 (0.01M) 2. Conductivity decreases and then does not
X Y change much
R. CH3COOH + KOH 3. Conductivity increases and then does not

X Y change much
S. NaOH + HI 4. Conductivity does not change much and
X Y then increases
Codes :
P Q R S
(A) 3 4 2 1
(B) 4 3 2 1
(C) 2 3 4 1
(D) 1 4 3 2
52. The standard reduction potential data at 25ºC is given below.
Eº(Fe3+, Fe2+) = + 0.77 V;
E°(Fe2+, Fe) = – 0.44 V
Eº(Cu2+, Cu) = + 0.34 V;
Eº(Cu+, Cu) = + 0.52 V
Eº[O2(g) + 4H+ + 4e–  2H2O] = + 1.23 V;
Eº[O2(g) + 2 H2O + 4e–  4OH–] = + 0.40 V
Eº(Cr3+, Cr) = – 0.74 V;
Eº(Cr2+, Cr) = – 0.91 V
Match Eº of the redox pair in List I with the values given in List II and select the correct answer using the
code given below the lists : [JEE (Adv)-2013 (Paper-2)]
List I List II
P. Eº(Fe3+, Fe) 1. –0.18 V


Q. Eº(4H2O 
 4H+ + 4OH–) 2. –0.4 V
R. Eº(Cu2+ + Cu  2Cu+) 3. –0.04 V
S. Eº(Cr3+, Cr2+) 4. –0.83 V
Codes :
P Q R S
(A) 4 1 2 3
(B) 2 3 4 1
(C) 1 2 3 4
(D) 3 4 1 2
53. Match the reactions in Column-I with appropriate types of steps/reactive intermediate involved in these reactions
as given in Column-II [IIT-JEE-2011 (Paper-2)]
Column I Column II
O O
H3C
O
aq NaOH
(A) (p) Nucleophilic substitution
O O
CH3Mgl
(B) CH2CH2CH2Cl (q) Electrophilic substitution
CH3
O 18
O
18 H2SO4
(C)
CH2CH2CH2 OH (r) Dehydration
H2SO4
CH2CH2CH2C(CH3)2
(D) OH (s) Nucleophilic addition

H3C CH3
(t) Carbanion
54. Different possible thermal decomposition pathways for peroxyesters are shown below. Match each pathway
from List I with an appropriate structure from List II and select the correct answer using the code given below
the lists. [JEE (Adv)-2014 (Paper-2)]
P
R + RO
 
–CO2
O Q
R + RO
   
O R + X + carbonyl compound
R O R –CO2
(Peroxyester) R
RCO2 + RO R + X + carbonyl compound
   
–CO2
S
RCO2 + RO R + RO
   
–CO2
List-I List-II
O
O
P. Pathway P 1. C 6H 5CH 2 O CH3
O
O
Q. Pathway Q 2. C 6H 5 O CH3
O
O CH3
R. Pathway R 3. C6H5CH2 O CH3
CH2C6H5
O
O CH3
S. Pathway S 4. C6H5 O CH3
C6H5
Code :
P Q R S
(A) 1 3 4 2
(B) 2 4 3 1
(C) 4 1 2 3
(D) 3 2 1 4
Answer Q.53, Q.54 and Q.55 by appropriately matching the information given in the three columns
of the following table. [JEE (Adv)-2017 (Paper-1)]
Columns 1, 2 and 3 contain starting materials, reaction conditions, and type of reactions, respectively.
Column 1 Column 2 Column 3
(I) Toluene (i) NaOH/Br2 (P) Condensation

(II) Acetophenone (ii) Br2/h (Q) Carboxylation
(III) Benzaldehyde (iii) (CH3CO)2O/CH3COOK (R) Substitution
(IV) Phenol (iv) NaOH/CO2 (S) Haloform
55. The only CORRECT combination in which the reaction proceeds through radical mechanism is
(A) (II) (iii) (R) (B) (III) (ii) (P)
(C) (IV) (i) (Q) (D) (I) (ii) (R)
56. For the synthesis of benzoic acid, the only CORRECT combination is
(A) (III) (iv) (R) (B) (IV) (ii) (P)
(C) (II) (i) (S) (D) (I) (iv) (Q)
57. The only CORRECT combination that gives two different carboxylic acids is
(A) (IV) (iii) (Q) (B) (I) (i) (S)
(C) (III) (iii) (P) (D) (II) (iv) (R)
58. Match the four starting materials (P, Q, R, S) given in List I with the corresponding reaction schemes
(I, II, III, IV) provided in List II and select the correct answer using the code given below the lists.
List-I List-II
P. H H 1. Scheme I
(i) KMnO4, HO, heat (ii) H, H2O
(iii) SOCl2 (iv) NH3
? C7H6N2O3
OH
Q. 2. Scheme II
OH (i) Sn/HCl (ii) CH3COCl (iii) conc. H2SO4
(iv) HNO3 (v) dil. H2SO4, heat (vi) HO
? C6H6N2O2
NO2
R. 3. Scheme III
(i) red hot iron, 873 K (ii) fuming HNO3, H2SO4, heat
(iii) H2S.NH3 (iv) NaNO2, H2SO4 (v) hydrolysis
? C6H5NO3
NO2
S. 4. Scheme IV
(i) conc. H2SO4, 60ºC
CH3 (ii) conc. HNO3, conc. H2SO4 (iii) dil. H2SO4, heat
? C6H5NO4
Code :
P Q R S
(A) 1 4 2 3
(B) 3 1 4 2
(C) 3 4 2 1
(D) 4 1 3 2
59. The sum of the number of lone pairs of electrons on each central atom in the following species is
[TeBr6]2–, [BrF2]+, SNF3 and [XeF3]–
(Atomic numbers: N = 7, F = 9, S = 16, Br = 35, Te = 52, Xe = 54) [JEE (Adv)-2017 (Paper-1)]
60. A closed tank has two compartments A and B, both filled with oxygen (assumed to be ideal gas). The partition
separating the two compartments is fixed and is a perfect heat insulator (Figure 1). If the old partition is replaced
by a new partition which can slide and conduct heat but does NOT allow the gas to leak across (Figure 2), the
volume (in m3) of the compartment A after the system attains equilibrium is ____. [JEE (Adv)-2018 (Paper-1)]
1 m3 , 5 bar,
400 K 3 m3, 1 bar, 300 K A B
A B
Figure 1 Figure 2
61. The surface of copper gets tarnished by the formation of copper oxide. N2 gas was passed to prevent the
oxide formation during heating of copper at 1250 K. However, the N2 gas contains 1 mole % of water vapour
as impurity. The water vapour oxidises copper as per the reaction given below: [JEE (Adv)-2018 (Paper-2)]
2Cu(s) + H2O(g)  Cu2O(s) + H2(g)
p H 2 is the minimum partial pressure of H2 (in bar) needed to prevent the oxidation at 1250 K. The value of
ln( p H 2 ) is _________.
(Given: total pressure = 1 bar, R (universal gas constant) = 8 J K–1 mol–1, ln(10) = 2.3. Cu(s) and Cu2O(s)
are mutually immiscible.
1
At 1250 K: 2Cu(s) + O (g)  Cu2O(s); G = –78,000 J mol–1
2 2
1
H2(g) + O (g)  H2O(g); G = –1,78,000 J mol–1; G is the Gibbs energy)
2 2
62. The plot given below shows P – T curves (where P is the pressure and T is the temperature) for two solvents
X and Y and isomolal solutions of NaCl in these solvents. NaCl completely dissociates in both the solvents.
12
3 4
Pressure (mmHg)
760
1. solvent X
2. solution of NaCl in solvent X
3. solvent Y
4. solution of NaCl in solvent Y
360
362
367
368
Temperature (K)
On addition of equal number of moles of a non-volatile solute S in equal amount (in kg) of these solvents, the
elevation of boiling point of solvent X is three times that of solvent Y. Solute S is known to undergo dimerization
in these solvents. If the degree of dimerization is 0.7 in solvent Y, the degree of dimerization in solvent X is
_____. [JEE (Adv)-2018 (Paper-1)]
63. Consider an electrochemical cell: A(s) | An+ (aq, 2 M) || B2n+ (aq, 1 M) | B(s). The value of H for the cell
reaction is twice that of G at 300 K. If the emf of the cell is zero, the S (in J K–1 mol–1) of the cell
reaction per mole of B formed at 300 K is .
(Given: ln(2) = 0.7, R (universal gas constant) = 8.3 J K–1 mol–1. H, S and G are enthalpy, entropy and Gibbs
energy, respectively.) [JEE (Adv)-2018 (Paper-2)]
64. Consider the following reversible reaction,
A(g)  B(g)  AB(g)
The activation energy of the backward reaction exceeds that of the forward reaction by 2RT
(in J mol–1). If the pre-exponential factor of the forward reaction is 4 times that of the reverse reaction, the
absolute value of G (in J mol–1) for the reaction at 300 K is __________.
(Given; ln(2) = 0.7, RT = 2500 J mol–1 at 300 K and G is the Gibbs energy) [JEE (Adv)-2018 (Paper-2)]
65. Among the complex ions, [Co(NH2–CH2–CH2–NH2)2Cl2]+, [CrCl2(C2O4)2]3–, [Fe(H2O)4(OH)2]+, [Fe(NH3)2(CN)4]–,
[Co(NH2–CH2–CH2–NH2)2(NH3)Cl]2+ and [Co(NH3)4(H2O)Cl]2+, the number of complex ion(s) that show(s)
cis-trans isomerism is [JEE (Adv)-2015 (Paper-2)]
66. For the given compound X, the total number of optically active stereoisomers is _________.
HO HO
This type of bond indicates that the configuration at the
specific carbon and the geometry of the double bond is fixed
This type of bond indicates that the configuration at the

specific carbon and the geometry of the double bond is NOT fixed
HO HO
X
67. The substituents R1 and R2 for nine peptides are listed in the table given below. How many of these peptides
are positively charged at pH = 7.0? [IIT-JEE-2012 (Paper-1)]
H3N CH CO NH CH CO NH CH CO NH CH COO
H R1 R2 H
Peptide R1 R2
I H H
II H CH3
III CH2COOH H
IV CH2CONH2 (CH2)4NH2
V CH2CONH2 CH2CONH2
VI (CH2)4NH2 (CH2)4NH2
VII CH2COOH CH2CONH2
VIII CH2OH (CH2)4NH2
IX (CH2)4NH2 CH3
68. The total number of distinct naturally occurring amino acids obtained by complete acidic hydrolysis of the
peptide shown below is [JEE (Adv)-2014 (Paper-1)]
O O H O H O H
N
N N N
N N N
N O
H CH2 O H O H CH2
Solution
1. Answer (C)
Be2 = 1s2*1s22s2*2s2
B2 = 1s2*1s22s2*2s22pz2
C2 = 1s2*1s22s2*2s22pz22px12py1
N2 = 1s2*1s22s2*2s22pz22px22py2
2. Answer (A)
Gº = V·P
 2900  2  10 –6 P
2900  106
 P  Pa
2
PF–1 = 14500 bar

 PF = 14501 bar
3. Answer (C)
 W  1000 
Tf = iK f  2 
 M2  W1 
 34.5  1000 
= 1 2 
 46  500 
=3K
273 (K) – Tf = 3 (K)
 Tf = 270 K
Also, with decrease in temperature, V.P. decreases.
 Graph (C) is correct.
4. Answer (D)
 A solution of CH 3OH and water shows positive deviation from Raoult's law, it means by adding
intermolecular force of attraction decreases and hence surface tension decreases.
 By adding KCl in water, intermolecular force of attraction bit increases, so surface tension increases by
small value.
 By adding surfactant like CH3(CH2)11OSO3–Na+, surface tension decreases rapidly and after forming micelle
it slightly increases.
5. Answer (C)
[Co(NH3)6]Cl3 d 2sp3 diamagnetic
Na3[Co(OX)3] d 2sp3 diamagnetic
K2[Pt(CN)4] dsp2 diamagnetic
[Zn(H2O)6](NO3)2 sp3d2 diamagnetic
6. Answer (C)
COOH COOH
HNO3/H2SO4
HO HO
NO2
OCH3 HNO3/H2SO4 OCH3
H3C H3C NO2
O O NO2
C HNO3/H2SO4
C
O O
7. Answer (C)
–OCH3 group has +R effect. It increases the stability of the carbocation.
8. Answer (C)
O O O O
 I2 + NaOH
–CO2 C  C 
iodoform reaction
Ph  OH Ph CH3 Ph ONa + CHI3
-keto acid E G
9. Answer (D)
O O– CH3
Cl Cl
CH3
CH3
O
CH3 – MgI
10. 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
11. Answer (C)
O
O C
O C
NaOH + Br2 Cl NH
H3C C H3C NH2
NH2
H 3C
12. Answer (A)
NH2
H2N NH
IV
Resonance with two NH2 groups increases electron density on 'N' of NH
NH
Lesser increase of electron density on = NH due to
only one resonance with one –NH2
CH3 NH2
2
sp
N
N This LPe– is not available as it is involve in aromatic Sextet.

2
H 'N' is bonded to sp C on both sides.
III
N This LPe– is not involve in aromaticity. So more available

H
Also, 'N' is bonded to sp3 C on one side.
II
 IV > I > II > III

13. Answer (C)
Cellulose is polymer of -D glucose. Hence structure (C) is correct.
14. Answer (A)
CH2OH
5 O
H CH2OH H
H O
H
4 1
OH H H OH
O—CH2—CH2—O CH2OH
OH
3 2
H OH -linkage OH H
(a) (b)
Ring (a) is six membered oxygen containing ring.

 Pyranose ring and CH2OH of C—5 and —OR of C—1 are across of one another hence, it is -glycosidic
linkage.
15. Answer (A, B, C)
(A) In free expansion, Pex = 0  w = 0
For isothermal free expansion of an ideal gas,
U = 0 q=0
 Adiabatic also
(B)
WIsothermal > WAdiabatic

Isothermal
P
Adiabatic
V1 V V2
(C) Area under irreversible P v/s V graph in compression is more than that under P-V graph of reversible
compression.
(P1, V1)
P1 (P1, V2)
Irreversible
P
Reversible
P2 (P2, V2)
V1 V V2
16. 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 > T 1
HCA and UCA are negative
HCA = UCA + VP
(–ve)
 HCA < UCA
A – B (Isothermal process)
UAB = HAB = 0
V2
wAB = –nRT1 ln
V1
17. Answer (B)

On increasing temperature forward as well as backward reaction rate increases due to which initially %yield of
NH3 is higher at T2 K but equilibrium attain at lower time at T2 K hence its yield at equilibrium is low at T2 K.
18. Answer (A, C)
ln K1 T2
ln K 2 T1
 On increasing temperature, K decreases.

 H° < 0
From graph K > 1  G° < 0
– H S
ln K1 T1R R T2
ln K 2 H S T1
T2R R
( H T1 S ) T2 T2
( H T2 S ) T1 T1
–H° + T1S° > –H° + T2S°

 S° < 0
19. Answer (A, C)
Under mild conditions of temperatures extent of physisorption decreases with increasing temperature so
graph (I) is correct. As initial temperature provided meets the necessary activation energy needed for chemical
bond formation for chemisorption so graph (II) is also correct. Finally graph (IV) is correct for chemisorption
as plot is now of potential energy vs distance of molecule from surface. Hence, answer is (A, C).
20. Answer (B, C)
HClO HClO2 HClO3 HClO4
Cl O 0 1 2 3
lone pair on Cl 3 2 1 0
Hybridization sp3 sp3 sp3 sp3
HClO4 is strongest acid
21. 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 *
22. Answer (B, C, D)
H e– H e
– H
B – B It has two 3c-2e bonds.
e– e
H H H
Cl Cl Cl
2AlCl3  Al Al No 3c-2e bond
Cl Cl Cl
CH3 CH3 CH3

Al Al Has two 3c-2e bonds.
CH3 CH3 CH3
Also, BCl3 is stronger lewis acid than AlCl3.

23. Answer (A, B, C)
(X) = CoCl26H2O, or, [Co(H2O)6]Cl2 (Pink)
2+
Co = [Ar]
3d
H2O is weak field ligand, therefore No pairing of electron
 Number of unpaired electron, n = 3
 s  n(n  2) B.M.
= 15 B.M.
= 3.87 B.M.


[Co(H2O)6 ]2   6NH3(aq)  2
 [Co(NH3 )6 ]  6H2O
O2 will oxidise [Co(NH3)6]2+ to [Co(NH3)6]3+, therefore shift in forward.
 Y = [Co(NH3)6]3+Cl3 [1 : 3 complex]
Co(III) = [Ar]
3d
NH3 is strong field ligand
 Forces electrons to pair up.
 n=0
 = 0 B.M.
[Co(NH3)6]3+ = [Ar]
3d 4s 4p
2 3
d sp
+ 6H2O; H = +ve
2+ – 2–
Also, [Co(H2O)6] + 4Cl [CoCl4] (aq)
( X) (Z)
(Pink) Blue
At 0°C, equilibrium shifts in backward, therefore pink colour.

24. Answer (B, C, D)
Br
+
NaOEt
–
AlCl3 + 1, 2 H +
Shift
Cl
+
H +
BF3 1, 2 H– +
+
O–H Shift
H
25. Answer (B)
Me OH
The correct structure of X is
Me OH Me Br Me I
PBr3 NaI
Et2O(SN2) acetone(SN2 ) NaN3, HCONMe2
(SN2)
Me N3
enantiomerically pure
Enantiomerically pure product after several substitution reactions, is only possible when each reaction must
stereospecific in nature which confirms pathway used is SN2 in nature.
26. Answer (A, B, C, D)
X (CH2)4 X
When x = –COO Me and Y = H2/Ni will give diol. Diol will form polyester with dicarboxylic acid.
In B, C and D diamine is obtained which will give polyamide with dicarboxylic acid.
27. Answer (A)
CH3 CH3
CH3 O OH
O H O O O +
O
KOH, H2O H
CH3
O
O O

+
(Minor) (Major)
28. Answer (A, B, D)
H
H
C
H O Me Me
(A) Me C C Me Conc.H2SO4
+ 3H2O
O C H 
H H H
H Me
C O
H C
Me
Me
|
C H Me Me
H C
C Heated iron tube
(B) 873K
C C
Me C Me
Me
|
H
O
||
C—Me
|
Br2/NaOH
(Haloform reaction)
Me
(C) Me—C C
|| ||
O O
O
O Na
C
|
C C—O Na
Na O || ||
O O
3H3O+
COOH
Soda lime

(decarboxylation)
COOH
COOH
CHO CH3
Zn/Hg,HCl
(D) (Clemmensen reduction)
OHC CHO CH3 CH3
29. Answer (A)
H
+
NH2 N
O O
H O
O
+ CH3COO–
NH2 CH2Cl2
O
H
N
O
+ CH3COOH
30. Answer (D)
NH2 NH 2 NH 2 NH 2
Conc. HNO3 NO 2
+ +
Conc. H2SO 4
NO 2
NO 2
51% 47% 2%
(P) (Q) (R)
O O
NH2 NH – C – CH 3 NH – C – CH 3
NO2 Ac 2O, Pyridine NO2 Br2 NO 2
CH3COOH
(R) Br
+
H3 O
+ –
N2 Cl NH2
NO2 EtOH
NO 2 NaNO2, HCl
NO 2
 273-278 K
Br Br Br
(S)
Br
NO2 Sn/HCl
NH2 Br 2
NH2
H2 O (excess) Br Br
Br Br Br
(S)
NaNO2 , HCl
Br Br
+ –
H 3PO 2 N2 Cl
Br Br Br Br
Br Br
31. Answer (B, C)

Invert sugar is an equimolar mixture of D-(+) glucose and D(–) glucose.
+
H +
C12H22O11 + H2O C6H12O6 + H2O C6H12O6
(+) sucrose D(+)-glucose D(+)-glucose
(+52°) (–92°)
Invert sugar
92  52
 Specific rotation of invert sugar =  20
2
 D-glucose on oxidation with Br2-water produces gluconic acid and not saccharic acid
32. Answer (B)

X2(g) 


 2X(g)
Initial mole: 1 0
  eqbm 
Moles at equilibrium : 1   eqbm
2 
eqbm
1 eqbm
2 P P
Partial pressure :
 eqbm   eqbm 
1   1  
2  2 
(Px )2 2eqbmP
 Kp = 
Px2   2eqbm 
1  
4 
42eqbm × P
 Kp =
4   2
eqbm 
Since P = 2 bar
82eqbm
So, K p 
4   2
eqbm 
33. Answer (C)
Since, G°, is positive
It means Kp < 1.
Kp = –2.303 RT log Kp
So,  eqbm = 0.7
8  (0.7)2
Kp = 1
4  (0.7)2
Hence, eqbm  0.7

34. Answer (A)
cold
Cl2  2NaOH(dil.)   NaOCl NaCl  H2O
(P)
hot
3Cl2  6NaOH(conc.)   NaClO3  5NaCl  3H2O
(Q)
(P) and (Q) are salts of HOCl and HClO3 respectively.

35. Answer (A)
Charcoal
SO2  Cl2 
Catalyst
SO2Cl2
(R)
10SO2 Cl2  P4  4PCl5  10SO2

(R) (S)
PCl5  4H2 O  H3PO 4  5HCl

(S) (T)
36. Answer (A)

Partial roasting of chalcopyrite
O2 / 
CuFeS2   Cu2 S  FeO
37. Answer (D)
FeO  SiO2  FeSiO3

gauge flux slag
38. Answer (C)

Cu2S + Cu2O  6Cu + SO2
39. Answer (B)
Ni+2 + HCl  [NiCl4]–2
Ni+2 + KCN  [Ni(CN)4]–2
40. Answer (D)

Zn2   OH  Zn(OH)2 
OH
 [Zn(OH)4 ]2 
white ppt Soluble
41. Answer (C)
OH
Pd-BaSO4 i. B2H6
C8H6
H2 ii. H2O 2, NaOH, H2O
42. Answer (D)
H2O
C8H6
HgSO4
H2SO4
i. Et MgBr, H2O
+
ii. H , Heat
43. Answer (B)
H COOH COOH
dil. alk. KMnO4 H OH
C
H OH
C
COOH
H COOH
(S)
(P)
H COOH
COOH COOH
C dil. alk. KMnO4 H OH HO H
C HO H + H OH
HOOC H COOH COOH
(Q) (T) (U)
44. Answer (A)
O
H COOH
C H2/Ni
O

C
HOOC H
(Q) O
(V)
O O
Zn(Hg)
O+ AlCl3 H3PO3
anhydrous HCl
HO HO
O O O O
(V) (W)
45. Answer (B)
46. Answer (C)
Solution of Q. 45 & Q. 46
– +
O OMgBr
C(CH3)3 C – OEt CH3MgBr (excess)/(C2H5)2O C(CH3)3 CH3–C–CH3
(P)
H2O
H H
O O–H
C(CH3)3 C(CH3)2 H2SO4/ C(CH3)3 CH3–C–CH3
0°C
(Q)
–H2O (dehydration)
CH3
CH3
C(CH3)3 C(CH3)2 C(CH3)3
(alkylation)
(R)
O
CH3–C–Cl/AlCl3
(Acylation)
CH3
CH3
C(CH3)3
COCH3
(S)
47. Answer (C)
CHO O—H
COOH
Br Moist
CO/HCl Ac2O Br2/Na 2 CO3
AlCl3 AcONa COOH KOH
(anhy.) D
CuCl (X) (473 K) (Y)
48. Answer (A)
O
CO/HCl – C– H AC2O/NaOAC – CH = CH – COOH
AlCl3/CuCl
(X)
H2/Pd–C
– CH2 – CH 2 – COOH
H3PO4
O
(Z)
49. Answer A(q); B(s); C(p, q, r), D(p, q, r)

50. Answer (D)
20  0.1– 10  0.1 1
(P) CH3 COOH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) [ CH 3COO– ] old = =
40 40
2
[ CH 3COO– ] new = 80
–
 CH3 COOH+ OH–
CH3COO + H2O 
c x x
x 2 [OH– ]old
2
[OH– ]new
2
Kh = = =
c 2 / 40 2 / 80
– 2
[OH ] new = [OH ]old
– 2

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 + H2 O 
c y y
y 2 [H+ ]old
2
[H+ ]2
Kh = = = new
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)
51. Answer (A)
Conductivity
(P)
(C2H 5)3 N
+
Firstly it decreases due to nutrilization of CH3COOH and replacement of H+ by (C2 H5)3NH but thereafter buffer
+
formation takes place and [H+] becomes constant and (C2 H5)3NH increases hence conductivity increases but
+
after equivalence point (C2H5)3N is not ionized due to much higher concentration of (C2 H5)3N in solution.
(Q)
Conductivity
VKI
AgNO 3 + KI 
 AgI(S) + KNO 3
Initially only Ag+ is replaced by K+ hence conductivity remain the same thereafter equivalence point [K+]
increases hence conducitity increases.
(R)
Conductivity
VCH3COOH
Initially conducitity decreases due to replacement of OH– by CH3COO– and then almost constant due to
buffer formation
(S)
Conductivity
VNaOH
Decreases due to removal of H+ by Na+ then increases due to OH–.
52. 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
+
(Q) 2H2O O2 + 4H + 4e Eº = – 1.23 V
–
4e + O2 + 2H2O OH Eº = + 0.40 V
+ –
4 H2O 4H + 4OH Eº = – 0.83 V
2+
(R) Cu + 2e Cu Eº = + 0.34 V
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
53. Answer : A(r, s, t), B(p, s, t), C(r, s), D(q, r)
O O
H CH2 H2C
O O O O
OH Nucleophilic addition
A.
Carbanion
O OH O
Dehydration HO – H
–H2O
O Cl
Cl O O
B. CH3MgBr Nucleophilic
CH3 substitution CH3
Carbanion
Nucleophilic
addition
H
..
.O
. O H H
18 18
H–O H–O O  H–O O
–H
Nucleophilic +H
C.
addition H
Dehydration
18
O
+H Electrophilic
D. OH Dehydration substitution
H
Me Me
54. Answer (A)
O O
(1) C6H5CH2 – C – O CH3 C6H5CH2 + CO2 + CH3 – O
O CH3 CH3
O
(3) C6H5CH2 – C – O C CH3 CO2 + C6H5CH2 + CH3 – C – O
CH2 – C6H5 CH2 – C6H5
O
C O CH3 O CH3
(4) C6H5 O C – CH3 C6H5 – C – O + O – C – CH3

CH3 CH3
O O
C O C
(2) C6H5 O CH3 C6H5 O + CH3 – O
55. Answer (D)
h
Br2 Br + Br
CH3 CH2
+ Br + HBr
CH2 CH2 – Br
+ Br2 + Br
56. Answer (C)
COO–Na+
NaOH
C CH3 Br2 + CHBr3
O
H2O/H+
COOH
It is haloform reaction
57. Answer (C)
O
CH3 – C
O
CH3 – C
CH = O CH = CH – COOH
O
CH3 COOK
Cinnamic acid
It exists in two geometrical forms.
C –H C –H
H – C – COOH HOC – C – H
Trans O
isomer Cis isomer
It is basic example of Perkin's reaction.
58. Answer (C)
NO2
Scheme I (S)
CH3
NO2
Scheme II (R)
Scheme III H – C  C – H (P)
OH
Scheme IV
OH
59. Answer (6)
Br
Br Br
Te It has one lone pair
Br Br
Br
Br It has two lone pairs

F
F
F
SN It has no lone pair
F
F
F
F
Xe It has three lone pairs
F
60. Answer (2.22)

From figure - 1,
51 5
nA = 
R  400 400 R
1 3 3 1
nB =  
R  300 300 R 100 R
From figure. 2,
After the system attains equilibrium,
PA = PB and TA = TB = T
n A RT nBRT
 
VA VB
5 1
 
400 R.VA 100 R.VB
VA 5 4
   VB  VA
VB 4 5
4
 VA + VB = 4 m3  VA + VA  4
5
20
 VA = = 2.22 m3
9
61. Answer (–14.60)
1
(i) 2Cu(s)  O2 (g)  Cu2O(s), G  –78 kJ / mole
2
1
(ii) H2 (g)  O2 (g)  H2O(g), G  –178 kJ / mole
2
(i) – (ii)
2Cu(s)  H2O(g)  Cu2O(s)  H2 (g), G  100 kJ
G  G  RT ln K  0
 pH 
 105  8  1250 ln  2 0
 pH O 
 2 
 pH 
10 4 ln  2   105  0
 pH O 
 2 
ln pH2 – ln pH2O  –10
–2
Now, pH2O  XH2O  PTotal  0.01 1  10
 ln pH2  2 ln10  –10
ln pH2  4.6  –10
ln pH2  –14.60
62. Answer (0.05)

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 b m 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
63. Answer (–11.62)
A  A n  ne –
B2n  2ne –  B
2A  B2n  2A n  B
H° = 2G°, Ecell = 0

G° = H° – TS°
G
 G° = TS°  S 
T
– RT ln K [A n ]2 22
S   – R ln 2n  – 8.3  ln
T [B ] 1
 S° = – 11.62 JK–1 mol–1
64. Answer (8500.00)

A(g) + B(g)  AB(g)
Eab – Eaf = 2RT
Af
=4
Ab
Kf
K=
Kb
–E a f /RT
Kf = Afe
K b = A b e –Eab /RT
Kf A (E –E )/RT
= f e ab af
Kb Ab
 K = 4e2RT/RT
K = 4e2
G° = – RT In K
= – RT (2 + ln 4)
= – 2500 (2 + 2 × 0.7)
= – 8500 J mol–1
Absolute value is 8500.00.
65. Answer (6)
Cl N
N N N Cl
Co Co
N N N Cl
Cl N
Cl O
O O O Cl
Cr Cr
O O O Cl
Cl O
NH3 NH3
NC CN NC NH3
Fe Fe
NC CN NC CN
NH3 CN
NH3 NH3
NH2 NH2 NH2 Cl
Co Co
NH2 NH2 NH2 NH2
Cl NH2
OH2 OH2
H3N NH3 H3N Cl
Co Co
H3N NH3 H3N NH3
Cl NH3
H2O OH
H2O OH H2O OH2
Fe Fe
H2O OH H2O OH2
H2O OH
(All the six complexes will show cis-trans isomerism)

66. Answer (7.00)
HO OH
HO OH
Only three streocentre are present.

 Total isomer = 23 = 8
But one is optically inactive.
OH
OH
HO
OH
67. Answer (4)

W hen any group in R 1 and R 2 is basic group then amino acid is positively charged at pH = 7.0.
So, answers are peptide IV, VI, VIII and IX.
68. Answer (1)
On hydrolysis only glycine is formed as natural amino acid.
  

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Most Difficult Chemistry Questions 2009-2018

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Most Diﬃcult Questions

Previous Years 2009-2018

C(graphite) is in equilibrium with C(diamond), is

(A) One phenyl group is replaced by a methyl group

(  implies 13C labelled carbon) [IIT-JEE-2008 (Paper-2)]

9. The major product in the following reaction is

O 1. CH3MgBr, dry ether, 0 °C

10. The major product of the following reaction sequence is

AcO AcO AcO

AcO AcO AcO

(A) Ring (a) is pyranose with -glycosidic link

(B) Ring (a) is furanose with -glycosidic link

(C) Ring (b) is furanose with -glycosidic link

(D) Ring (b) is pyranose with -glycosidic link

A(P1, V1, T1) C(P2, V1, T2)

The correct option(s) is (are)

[A] / (mol L–1) 10 10

[P] / (mol L–1)

If T2 > T1, the correct statement(s) is (are)

(A) H < 0, S < 0 (B) G < 0, H > 0

(C) G < 0, S < 0 (D) G < 0, S > 0

(A) I is physisorption and II is chemisorption

(1) PBr3, Et2O Me N3

(A) X = COOCH3, Y = H2/Ni/Heat (B) X = CONH2, Y = H2/Ni/Heat

(1) Br2, NaOH

1) Ac2O, pyridine 1) Sn/HCl

[JEE (Adv)-2018 (Paper-2)]

37. Iron is removed from chalcopyrite as

[JEE (Adv)-2014 (Paper-2)]

[JEE (Adv)-2015 (Paper-2)]

42. The major compound Y is

Paragraph for Q. 43. & 44.

COOH COOH COOH

[JEE (Adv)-2013 (Paper-2)]

Paragraph for Q. 45. & 46.

[JEE (Adv)-2017 (Paper-2)]

Paragraph for Q. 47. & 48.

48. The compound Z is

R. CH3COOH + KOH 3. Conductivity increases and then does not

(D) OH (s) Nucleophilic addition

Column 1 Column 2 Column 3

(I) Toluene (i) NaOH/Br2 (P) Condensation

64. Consider the following reversible reaction,

A(g)  B(g)  AB(g)

This type of bond indicates that the configuration at the

PF–1 = 14500 bar

OCH3 HNO3/H2SO4 OCH3

H3C H3C NO2

10. Answer (A)

11. Answer (C)

12. Answer (A)

Resonance with two NH2 groups increases electron density on 'N' of NH

N This LPe– is not available as it is involve in aromatic Sextet.

N This LPe– is not involve in aromaticity. So more available

 IV > I > II > III

Ring (a) is six membered oxygen containing ring.

WIsothermal > WAdiabatic

16. Answer (B, C)

17. Answer (B)

 On increasing temperature, K decreases.

–H° + T1S° > –H° + T2S°

CH3 CH3 CH3