IIT-JAM 2016 With Solution

CHEM ACADEMY 1 IIT-JAM 2016
IIT-JAM 2016
SECTION – I
Multiple Choice Type
Section – A contains Multiple Choice Questions (MCQ). Each MCQ type question has four choices out of which
only one choice is the correct answer. Questions 1 – 10 carry 1 mark each and Questions 11 – 30 carry 2 marks each.
1. The correct order of pKa for the following compounds is
OH CO2H
OH
O
(I) (II) (III) (IV)
OH
N NO2
(a) II > I > III > IV (b) II > I > IV > III (c) III > IV > I > II (d) IV > II > I > III
2. The major product formed in the following reaction is
CHEM ACADEMY
OH
OH Ph
H 2SO 4
Ph  
Ph O Ph Ph O
Ph Ph
Ph
(a) Ph (b) (c) (d) Ph
OH
3. The mechanism of the following transformation involves
O HO
O OH
NaOH
+ H H 
H 2O
H (excess) HO
OH
(a) Aldol reaction and Cannizzaro reaction (b) Aldol reaction and Claisen-Schmidt reaction
(c) Knoevenagel condensation and Cannizzaro reaction
(d) Stobbe condensation and Cannizzaro reaction
4. The most basic amino acid among the following is
(a) tyrosine (b) methionine (c) arginine (d) glutamine
5. The crystal field stabilization energy (CFSE) in [Mn(H2O)6]2+ is
(a) 0 0 (b) 2.0 0 – 2P (c) 0.4 0 – 2P (d) 2.0 0
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6. Indicator used in redox titration is
(a) Eriochrome black T (b) Methyl orange
(c) Phenolphthalein (d) Methylene blue
7. Among the following, the compound that has the lowest degree of ionic character is
(a) NaCl (b) MgCl2 (c) AlCl3 (d) CaCl2
8. The correct order of entropy for various states of CO2 is
(a) CO2(s) > CO2(l) > CO2(g) (b) CO2(l) > CO2(s) > CO2(g)
(c) CO2(g) > CO2(l) > CO2(s) (d) CO2(g) > CO2(s) > CO2(l)
9. + –
The coordination numbers of Cs and Cl ions in the CsCl structure, respectively are
(a)4, 4 (b) 4, 8 (c) 6, 6 (d) 8, 8
10. Determinant of a square matrix is always
(a) a square matrix (b) a column matrix (d) a row matrix (d) a number
11. 1
The correct order of H NMR chemical shift () values for the labeled methyl groups in the following
compound is
Me1 O
Me2
O
(a)
CHEM ACADEMY
Me1
<
Me4
Me2
<
Me3
Me3
< Me4 (b) Me3 < Me4 < Me1 < Me2
(c) Me3 < Me1 < Me4 < Me2 (d) Me2 < Me4 < Me3 < Me1
12. Among the following, the most stable conformation of meso-2,3-dibromobutane is
Br Br Br Br
Br Me H Me H Me Me Br
(a) (b) (c) (d)
H Me Me H H Me H Me
H Br Br H
13. The major product X and Y in the following reaction sequence are
Ac O
2 3 Y HNO
 X 
ZnCl 2 H SO 2 4
O 0ºC
O O
NO2
(a) X = O ;Y= O (b) X = ;Y=
O O O2N
O O
O O
O2N
(c) X = ;Y= (d) X = O ; Y = O2N O
O O
O O
14. The major product formed in the reaction of butanenitrile with phenylmagnesium bromide followed
by acdification is
O O NH2 H2N
Ph
(a) (b) (c) (d)
Ph Ph Ph Ph
15. An organic compound on reaction with 2,4-dinitrophenylhydrazine (2, 4-DNP) gives a yellow
precipitate. It also gives silver mirror on reaction with ammoniacal AgNO3. It gives an alcohol and
sodium salt of a carboxylic acid on reaction with concentrated NaOH. It yields benzene-1,2-
dicarboxylic acid on heating with alkaline KMnO4. The structure of the compound among the
following is
(a) (b) (c) (d)

CHO CO2Et
CHO O
16. The major products X and Y in the following reaction sequence are
O
(i) MeMgBr
Cul
ether m CPBA

(ii) Mel
 X  Y
(a) X =
CHEM ACADEMY
MeO
;Y=
MeO
O (b) X =
MeO
;Y=
MeO
O O
O O
O O
(c) X = ;Y= (d) X = ;Y=
17. The true statement about [Cu(H2O)6]2+ is

(a) All Cu–O bond lengths are equal
(b) One Cu–O bond length is shorter than the remaining five
(c) Three Cu–O bond lengths are shorter than the remaining three
(d) Four Cu–O bond lengths are shorter than the remaining two
18. The complexes [Pt(CN)4]2– and [NiCl4]2–, respectively, are
(a) paramagnetic, paramagnetic (b) diamagnetic, diamagnetic
(c) paramagnetic, diamagnetic (d) diamagnetic, paramagnetic
19. The value of ‘x’ in [Cu(CO)x]+ such that it obeys the 18 electron rule is
(a) 6 (b) 5 (c) 4 (d) 3
20. The correct order of NO (cm–1) in the following compound is
(a) NO+ > NO > [NiCp(NO)] > [Cr(Cp)2(NO)4]
(b) [Cr(Cp)2(NO)4] > [NiCp(NO)] > NO+ > NO
(c) NO+ > [Cr(Cp)2(NO)4] > NO > [NiCp(NO)]
(d) [NiCp(NO)] > NO > [Cr(Cp)2(NO)4] > NO+
21. The red colour of ruby is due to
(a) d-d transition of Cr3+ ion in Cr2O3 lattice
(b) d-d transition of Cr3+ ion in Al2O3 lattice
(c) ligand to metal charge transfer transition
(d) metal to metal charge transfer transition
22. The final products in the reaction of BF3 with water are
(a) B(OH)3 and OF2 (b) H3BO3 and HBF4 (c) B2O3 and HBF4 (d) B2H6 and HF
23. The correct order of bond angles in BF3, NH3, NF3 and PH3 is
(a) BF3 > NH3 > NF3 > PH3 (b) PH3 > BF3 > NF3 > NH3
(c) PF3 > PH3 > NH3 > NF3 (d) NH3 > NF3 > BF3 > PH3
24. The maximum of a function Ae  ax 2 (A > 0; a > 0) is at x =
(a) 0 (b) +  (c) – (d) 1/ a

25.
CHEM ACADEMY
At 298 K, 0.1 mol of ammonium acetate and 0.14 mol of acetic acid are dissolved in 1 L of water.
The pH of the resulting solution is
[Given: pKa of acetic acid is 4.75]
(a) 4.9 (b) 4.6 (c) 4.3 (d) 2.3
26. An electrochemical cell consists of two half-cell reactions
AgCl(s) + e–  Ag(s) + Cl–(aq)
Cu(s)  Cu2+(aq) + 2e–
The mass of copper (in grams) dissolved on passing 0.5 A current for 1 hour is
[Given: atomic mass of Cu is 63.6; F = 96500 C mol–1]
(a) 0.88 (b) 1.18 (c) 0.29 (d) 0.59
27. For a zero order reaction, the half-life depends on the initial concentration [C0] of the reactant as
(a) [C0] (b) [C0]0 (c) [C0]–1 (d) [C0]1/2
28. The effective nuclear charge of helium atom is 1.7. The first ionization energy of helium atom in eV
is
(a) 13.6 (b) 23.1 (c) 39.3 (d) 27.2
29. The relationship between the van der Waals ‘b’ coefficient of N2 and O2 is
(a) b(N2) = b(O2) = 0 (b) b(N2) = b(O2)  0
(c) b(N2) > b(O2) (d) b(N2) < b(O2)
30. From the kinetic theory of gases, the ratio of most probable speed (Cmp) to root mean square speed
(Crms) is
(a) 3 (b) 2/ 3 (c) 3/ 2 (d) 3/ 2
SECTION – II
Multiple Select Type
Section – B contains Multiple Select Questions (MSQ). Each MSQ type question is similar to MCQ but with a
difference that there may be one or more than one choice(s) that are correct out of the four given choices. The
candidate gets full credit if he/she selects all the correct choices only and no wrong choices. This section has 10
Questions with a total of 20 marks and each question carry 2 marks.
31. The correct statement(s) about the following species is(are)
O OH Ph N
(I) Ph N (II) Ph N (III)
OH
(a) I and II are resonance structures (b) II and III are resonance structures
(c) II and III are diastereomers (d) III is a tautomer of I
32. Consider the following reaction:
Ph-NH-NH 2
(3 equiv)
(D)-glucose 
 X
cat. H
CHEM ACADEMY
Among the following, the compound(s) whose osazone derivative(s) will have the same melting
point as that of X is(are)
CHO CH2OH CHO CHO
HO H O HO H H OH
H OH HO H HO H H OH
(a) HO H (b) H OH (c) H OH (d) HO H
HO H H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
33. The appropriate reagents required for carrying out the following transformation are
CO2H
OH

(a) (i) PCC, CH2Cl2; (ii) Ph3P = CHCO2Et; (iii) aq. NaOH, heat, then acidify
(b) (i) CrO3, H2SO4, aq. acetone (ii) Ac2O, NaOAc
(c) (i) MnO2; (ii) CH2(CO2H)2, piperidine, pyridine
(d) (i) PCC, CH2Cl2; (ii) BrCH2CO2C(CH3)3, Zn (iii) H3O+, heat
34. The appropriate reagents required for carrying out the following transformation are
O


(a) (i) succinic anhydride, AlCl3; (ii) Zn/Hg, HCl; (iii) polyphosphoric acid
(b) (i) maleic anhydride, AlCl3; (ii) H2N-NH2, KOH; (iii) H2SO4
(c) (i) succinic anhydride, FeCl3; (ii) LiAlH4; (iii) H2SO4
(d) (i) Phthalic anhydride, F3B · OEt2; (ii) HS(CH2)2SH, H+; (iii) Raney Ni; (iv) polyphosphoric
acid
35. The protein(s) that belong to the class of blue copper protein is(are)
(a) ceruloplasmin (b) superoxide dismutase
(c) hemocyanin (d) azurin
36. The ion(s) that exhibit only charge transfer bands in the absorption spectra (UV-visible region)
is(are)
(a) [Cr(C2O4)3]3– (b) [CrO4]2– (c) [ReO4]– (d) [NiO2]2–
37. The type(s) is interaction(s) that hold layers of graphite together is(are)
(a) - stacking (b) van der Waals (c) hydrogen bonding (d) Coulombic
38. True Statement(s) about Langmuir isotherm is(are)
(a) valid for monolayer coverage (b) all adsorption sites are equivalent
(c) there is dynamic equilibrium between free gas and adsorbed gas
(d) adsorption probability is independent of occupancy at the neighboring sites
39. The 3pz orbital has
(a) one radial node (b) two radial nodes (c) one angular node (d) two angular nodes
40.
(a) B2
CHEM ACADEMY
The diatomic molecule(s) that has (have) two -type bonds is(are)
(b) C2 (d) N2 (d) O2
SECTION – III
Numerical Answer Type
Section – C contains Numerical Answer Type (NAT) questions. For these NAT type questions, the answer is a real
number. No choices will be shown for these type of questions. Questions 41 – 50 carry 1 mark each and Questions
51 – 60 carry 2 mark each
41. Among the following, the number of molecules that are aromatic is ____.
H Me
N
Me
42. The number of all possible isomers for the molecular formula C6H14 is ____.
43. Hydrolysis of 15.45 g of benzonitrile produced 10.98 g of benzoic acid. The percentage yield of
acid formed is _____.
44. Acetic acid content in commercial vinegar was analyzed by titrating against 1.5 M NaOH solution.
A 20 mL vinegar sample required 18 mL of titrant to give endpoint. The concentration of acetic acid
in the Vinegar (in mol L–1) is ______.
45. The bond order of Be2 molecule is ____.
46. The number of P-H bonds in hypophosphorus acid is _____.
47. The isotope 214 undergoes one alpha and one beta particle emission sequentially to form an
84 Po
isotope “X”. The number of neutrons in “X” is _____.
48. In a diffrection experiment with X-rays of wavelength 1.54 Å, a diffraction line corresponding to
2 = 20.8º is observed. The inter-planar separation in Å is _____
49. The potential energy of interaction between two ions in an ionic compound is given by
Z Z 
U  1389.4  1 2  kJ mol1 . Assuming that CaCl is linear molecule of length 5.6 Å, the potential
 r/Å  2
energy for CaCl2 molecule in kJ mol–1 is___.

50. The enthalpy of formation for CH4(g), C(g) and H(g) are –75, 717 and 218 kJ mol–1, respectively.
The enthalpy of the C – H bond in kJ mol–1 is ____.
51. Specific rotation of the (R)-enantiomer of a chiral compound is 48. The specific rotation of a
sample of this compound which contains 25% of (S)-enantiomer is ____.
52. Among the following, the number of compounds, which can participate as ‘diene’ component in a
Diels-Alder reaction is ____.
CHEM ACADEMY O
53. Among the following, the number of molecules that possess C2 axis of symmetry is ____.
Me
Me
Cl Cl
H H Me
Me
Cl Cl
BF3 CHCl3 2,5-dimethylthiophene
H H
54. Effective nuclear charge for 3d electron in vanadium (atomic number = 23) according to Slater’s
rule is ____.
55. The total number of isomers possible for the molecule [Co(NH3)4Cl(NO2)]+ is ____.
56. The bond angle in PBr3 is 101º. The percent ‘s’ character of the central atom is ____.
57. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+(aq) + 2H2O(l)
In the above reaction at 1 atm and 298 K, if 6.36 g of copper is used. Assuming ideal gas behavior,
the volume of NO2 produced in liters is ____.
[Given: atomic mass of Cu is 63.6; R = 0.0821 L atm K–1 mol–1]
58. The Hº for the reaction CO(g) + ½O2(g)  CO2(g) at 400 K in kJ mol–1 is ____.
Given at 298 K:
H0f C0p
kJ mol–1 J mol–1 K–1
O2 0 29.4
CO –110 29.1
CO2 –394 37.1
59. The rate constants for a reaction at 300 and 350 K are 8 and 160 L mol–1 s–1, respectively. The
activation energy of the reaction in kJ mol–1 is ____.
[Given R = 8.314 J K–1 mol–1]
60. A 10 L flask containing 10.8 g of N2O5 is heated to 373 K, which leads to its decomposition
according to the equation 2 N2O5(g)  4 NO2(g) + O2(g). If the final pressure in the flask is 0.5
atm, then the partial pressure of O2(g) in atm is ____.
[Given R = 0.0821 L atm K–1 mol–1]
CHEM ACADEMY
SOLUTION
Section A: Multiple Choice Questions (MCQ)
Q.1 - Q.10 Carry One Mark Each.
1.
• Electron withdrawing group increases the acidic character

• Electron donating group decreases the acidic behaviour
• Acid  conjugate Base + H+
1
Higher the ka, lowe will be pKa, higher will be acidity  acidic behaviour  pK
a
• Benzoic acid is more acidic as compared to acetic acid, which in turn is more acidic as
compared to phenol.
CHEM ACADEMY
Thus order of ocidic behaviour will be III > IV > I > II
Hence, correct order of pKa will be III < IV < I < II
Correct Option is (B)
2.
Correct option is (B)
3.
Correct option is (A)
4. If the number of amine (basic) groups are more than carboxylic (acidic) groups then the amino acid
will be basic in nature.
Hence, correct option is (C)
5. Mn 2  3d5 (HS)  t 32g eg2

CFSE = [–0.4 × 3 + 0.6 × 2] 0 = 0 0
Correct option (A)
6.
CHEM ACADEMY
Methylene blue is an indicator used in redox titration.
In oxidised form it is blue and will turn colourless if exposed to reducing agent.
Correct option is (D)
7. More the polaristion, lesser will be ionic character.
NaCl MgCl2 AlCl3
CaCl2


positive charge on cation increases
size of cation decreases
Therefore, polarisation increases (Fajan Rule)
Therefore, co-valent character increases
Therefore, ionic character decreases.
Correct option is (C)
8. Randomness of the gas is more that of liquid, and randomness of liquid is more than that of solid.
9. Cs+ = at body centre
Cl– = At corners
One Cs+ ion surrounded by 8 Cl– ion and vice versa.

10. In the case of square matrix, the determinant of the matrix is always gives out a number i.e.
A  [a ij ]nn then |A| = B where B is any number..
Q.11 - Q.30 carry Two marks each.
11. –O–Me2 protons deshielded by –I effect of oxygen.
Me3 lies in range of  1-2 ppm i.e. alkyl region, highly shielded. Me3 has lower  value.
Me1 and Me4 have similar  value, but due to –R and –I effect of –COMe2 group, Me1 has slightly
more  value than Me4.
Correct order is Me3 < Me4 < Me1 < Me2.
So, correct option is (B)
12. Only (A) and (B) represents meso form
CHEM ACADEMY

13. Electrophilic substitution reactions of Furan occurs at second position and if the second position is
occupied then further electrophilic substitution occurs at fifth position, because the positive charge
is stabilized by the oxygen as well as -system of the ring.
14.
15.
CHEM ACADEMY
16.
17. [Cu(H 2O)6 ]2 

 3d9  t 62g eg 3
The eg orbitals are unsymmetrically filled. Thus, due to John-Teller distortion four Cu-O bond
lengths are shorter than the remaining two.
18. [Pt(CN)4]2– is square planar and diamagnetic, because d8 square planar complexes are diamagnetic.
[NiCl4]2– is tetrahedral and paramagnetic (d8 : e4t24)
19. Value of ‘x’ in [Cu(CO)x]+
Valence electron in Cu = 3d104s1
Cu+ = 3d10. So, 2x + 10 = 18  2x = 8 x=4
20. (Free) NO    N O  2250 cm–1
(Free) NO   N O  1896 cm–1

In NO+ bond order is 3 and in NO bond order is 2.5. Higher the bond order, higher the bond
1 k
strength. So, higher the bond strength higher the frequency,   , where k is bond strength.
2 
CHEM ACADEMY
NO linear  N O  1830 cm–1
Due to back -bonding, the bond order of N-O will decrease and hence N-O stretching frequency
decreases.
NO linear 1672 cm–1

NO bridge 1505 cm–1
Due to more back -bonding in the complex, the N-O bond order will decreases and its N–O
stretching frequency decreases consequently.
21. Due to d-d transition of Cr3+ ion in Al2O3 lattice.
22. BF3 is a Lewis acid.
BF3  3H 2O 
 B(OH)3  3HF
[BF 3  HF   HBF4 ]  3


4BF3  3H 2O   B(OH)3  3H[BF4 ]
23. BF3 is trigonal planar hence
The bond angle decrease, if the electronegativity of the surrounding atom increases (VSEPR theory)
If the electronegativity of central atom decreases, bond angle decreases (VSEPR theory)
CHEM ACADEMY
The correct bond order, BF3 > NH3 > NF3 > PH3.
d 2 2
24. Ae  ax   A2xe  ax  0 ; xe ax 2  0  at x  0
dx
x = 0, x = 
Let at ,  = 0
So, x = 0
0.1
25. 0.1 mole of ammonium acetate in 1L of water, [salt]  = 0.1 mole/L
1
0.14 mol
0.14 mole of acetic acid in 1L of water, [acid] = = 0.14 mol/L
1
As it is an acidic buffer solution.
[salt] [0.1] 10
pH  pK a  log  4.75  log  4.75  log  4.75 + (log 10 – log 14) = 4.60.
[acid] [0.14] 14
26. Method - 1:
Amount of charge passed = i × t = 0.5 × 60 × 60 coulomb.
0.5  60  60
Number of Faraday passed = = 0.01865
96500
Since, two Faraday disolves 1 mole of Cu.
1 0.01865
Therefore, So, 0.01865 Faraday’s will dissolve = moles of Cu
2
0.01865
So, weight of Cu dissolved =  63.6 = 0.59 gm
2
Method-2:
E 3.6
w = z × i × t; Z  ; E Cu 
96500 2
63.6
w × 0.5 × 60 × 60 = 0.59 gm
2  96500
C0
27. For ‘0’ order reaction, t1/ 2 
2k
for nth order:
1
t1/ 2 
CHEM ACADEMY
Cn0 1
for zero order reaction n = 0
1
t1/ 2 
C01  t1/ 2  C0 where C0 is concentration.

2
28.  He   e 
He  E n  13.6 Zeff / n2 where, Zeff is effective nuclear charge
13.6  (1.7)2 eV
= (13.6) × (1.7) × (1.7) = 39.304
1
29. As ‘b’ represents (4 × molecular volume per mole)
b(N2) > b(O2) As molecular of N2 is larger than O2.
2RT 3RT C mp 2
30. Cmp   C rms   
M M C rms 3
Section - B : Multiple Select Questions (MSQ)
Q.31 - Q.40 carry Two Marks each.
31.
In resonating structure there is no shift of atom takes place.

cis and trans stereoisomer are a pair of diastereoisomers.
Hence, III and II are diastereoisomer and III is also a tautomeric form of I.
Hence (C), (D) is correct.
32. All C2 epimers form same osazone moiety. During osazone formation the chirality of C2 carbon is
lost.
For example: D-glucose, D-mannose are C2-epimers and they form same osazone. Fructose also
form the same osazone like that of D-glucose.
CHEM ACADEMY
The osazone formed by D-glucose, L-glucose, D-mannose and D-fractose are structurally similar.
Hence, they have the same melting point.
Correct options are (A), (B) and (C).
33.
Reaction (A):
Reaction (B):
O
OH
All primary alcohols oxidized with Johe’s reagent and give overoxidation product due to formation
of stable hydrate formed after aldehyde formation.
CHEM ACADEMY
However, Benzyl alcohol and allyl alcohols doesn’t form stable hydrates after aldehyde stage
oxidation. Hence, can be selectively.
Oxidized to aldehyde.
Reaction (C):
Mechanism:
Reaction (D)
O Br O CH3
| || |
OH CH 2 C OCCH3
PCC |
  H
DCM CH3
 
Zn
O O ZnBr
H HC C O
Reformatsky reaction
OH
OZnBr O
CHEM ACADEMY O
O
H O
3


O
Hydrolysis of ester
OH
O
O
 H2O OH
OH 
H
Correct options are (A), (C), (D).
34.
Correct option is (A).

35. Ceruloplasmin, hemocyanin and azurin are blue copper proteins. Super oxide dismutase may be
Cu-ZnSOD, MnSOD or FeSOD.
Correct option are (A), (C) and (D)
36. In CrO42– and ReO4–, Cr+6 and Re+7 have vacant orbital and there is only LMCT.
Correct option are (B) and (C).
37. Graphite has van der Waal’s forces that holds layers of it. With - stackings.
Correct options are (A) and (B).
38. According to Langmuir adsorption isotherm
• Adsorption is monolayer
• The gasesous molecules adsorbed at different sites do not interact with each other.
• The phenomenon of adsorption involves a dynamic equilibrium between free gas and adsorbed
gas.
• Each site can hold only one gaseous molecule and involves a constant heat of adsorption. The latter
is identical for all adsorption sites.
39. 3pz CHEM ACADEMY

Threfore, correct option is (A), (B), (C), (D)
n = 3, l = 1
Number of radial node = n – l – 1 = 3 – 1 – 1 = 1
Number of angular node = l = 1
Correct options are (A) and (C).
40. The configuration are
B2  2s 2  * 2s 2 2p1x 2p1y 4 2
Bond order =  1 , 1
(one ) 2
C2  2s 2  * 2s 2 2p 2x 2p 2y 62

Bond order =  2 , 2
(two  ) 2
N2 is N  N 1 and 2
O2 is O = O 1 and 1
hence, correct options are (B) and (C).
Section-C: Numerical Answer Type (NAT)
Q.41 – Q.50 carry One mark each.
41.
Number of aromatic compounds = 3
CHEM ACADEMY
Therefore, hence A and D are not aromatic.
exist in non-planar tub shape
Since compound is not planar. Thus, it is non-aromatic.
Azulene is aromatic [via Craig’s rule also]
The number of aromatic compound = 3

42. C6H14 hexane
CHEM ACADEMY
Correct answer is (5).
43. C6H5CN C6H5COOH
M = 103 gm M = 122 gm
Since, idealy 103 gm of C6H5CN forms 122 gm of CH3COOH
122 15.45
Therefore, 15.4 gm of C6H5CN will form = = 18.3 gm of CH3COOH
103
But actual CH3COOH formed = 10.98 gm
actual wt. formed 10.98
So, percentage yield = theoretical wt. formed  100  18.3  100  60
44. At end point
Millimoles of CH3COOH = millimoles of NaOH
M1V1 = M2V2; M1(20) = 1.5(18)
1.5  18
M1 = , M1 = 1.35 mol L–1
20
Correct answer is (1.35)
45. Be2 = ls2 *1s2 2s2 *2s2
44
 Bond order = 0
2
46. Hypophosphorus acid is H3PO2.
It structure is
Hence, number of P-H bonds is two.

214  210  210
47. 84 P0 82 X 83 X
Therefore, number of neutron = 210 – 83 = 127.
48. According to Bragg’s law, 2d sin  = n
where, d = interplanar distance,  = angle of diffraction, n = order of reflection
2 = 20.8   = 10.4
2dsin 10.4º = 1 × 1.54 Å
1.54Å 1.54
 d   4.266Å
2sin10.4º 0.1805  2
49.
CHEM ACADEMY
U = U1 + U2 + U3
U U U
(Ca 2 Cl  ) Ca 2 Cl (Cl Cl  )
 2  (1)  1  2  (1)  1  (1)  (1)  1

 1389.4   kJmol  1389.4   kJmol  1389.4   kJmol
 2.8   2.8   5.6 
 2 2 1   4 1   7 
 1389.4       1389.4     1389.4  
 2.8 2.8 5.6   2.8 5.6   5.6 
 U = –1736.7 kJ mol–1
50. C(g) + 4H(g)  CH4(g)
H r  H f (P)  Hf (R)  75  (717  4  218)
H r  1664 kJ mol–1 ... (i)
H r  (B.E.)R   (B.E.)P
H r  0  4E (CH) ... (ii)
From equation (i) and (ii),
4E(CH)  1664 kJ mol1
1664
E (C H)   416 kJ mol1
4
Q.51 – Q.60 carry Two marks each
51. Specific rotation of R = 48º
Sample = 25% S with 75% R
R-isomer is in excess. So, specific rotation of mixture will have +ve sign.
Enantiomeric excess (e.e.) = 75% R–25%S = 50%
specific rotation of sample (x)
e.e.   100
specific rotation of pure R  isomer
x 48º 50
50   100 x  24º
48º 100
52. Only cisoid form of Dienes undergoes Diels-Alder reaction.
All these compounds are in cisoid form and they given Diels-Alder reaction.
Furan and anthracene are less aromatic and undergoes Diels-Alder reaction.
CHEM ACADEMY
These two Dienes are in transoid form and they will not give the Diels-Alder reaction.
Hence, correct answer is (6).
53.
Correct answer is (7)

54. z = 23 = 1s22s22p63s23p64s23d3
or (1s2)(2s2p)8(3s3p)8(3d)3(4s)2
 3 n  2 n 1 n
n
S = [18 × 1] + [2 × 0.35] = 18 + 0.7 = 18.7
Therefore, zeff = 23 – 18.7 = 4.3
Correct answer is (4.3)
55. [Co(NH3)4Cl(NO2)]+
there is plane of symmetry optically inactive.
there is plane of symmetry, therefore, optically inactive.
56.
CHEM ACADEMY
Possible isomers = 4
cos  
s
s  100
s
cos101º   0.1908 Or, s = – 0.1908s + 19.08 or 1.1908 s = 19.08
s  100
19.08
Therefore, s % =  16.0228
1.1908
57. Cu(s) + 4H+(aq) + 2NO3– (aq)  2NO2(g) + Cu2+ (aq) + 2H2O (l)
6.36
Wt. of Cu = 6.36 gm. So, moles of Cu =  0.1
63.6
0.1 mole of Cu will produce 0.2 moles of NO2(g).
PV = nRT
nRT (0.2)(0.0821)  (298)
V   4.89L
P 1
Correct answer is 4.89.
58. Hº at 298
 1
Hº  H 0f (products)  H f0(reactants)  (394)kJmol 1   110  0   kJmol 1
 2
= – 394 kJ mol + 110 kJ mol = –284 kJ mol = 284 × 103 J mol–1
–1 –1 –1
H02 T2
0 d(Hº )   CPdT
H1 T1
 1 
C P  CP(products)  CP(reactants)  37.1   29.1   29.4   37.1  (43.8)  6.7 J mol 1K 1
 2 
H 02  H10  CP (T2  T1 ); H 02  H10  6.7(400  298)
H02  H10  6.7(102)  284 103  683.4  (284 103  0.68 103 )kJ mol1 = –284.68kJ mol–1
59. T1 = 300 K, k1 = 8 L mole–1 s–1
T2 = 350 K, k2 = 160 L mole–1 s–1
 k  E  1 1  E T  T 
ln  2   a     a  2 1 
 k1  R  T1 T2  R  T1T2 
RT1T2  k 2  8.314 JK 1mole 1  300K  350K  160 
Ea  ln    ln    52.30368 kJ mole–1
T2  T1  k1  (350  300)K  8 
60. 2N 2O5 (g) 
 4NO 2 (g)  O 2 (g)
10.8 10.8
Number of moles of N2O5 = M M N 2O5  10.5  n N 2 O5   0.1
N 2O5 108
At 373 K temperature, pressure is 0.5 atm
CHEM ACADEMY
V = 10L, So, PV = nRT
Total number of moles (n) =

PV

0.5  10
 0.1632
RT 0.0821 373
After decomposition, let x moles of N2O5 decomposed
2N 2O5 
 4NO 2 (g)  O 2 (g)
x
0.1 – x 2x
2
x x 3x
Total number of moles = 0.1  x  2x   0.1  x   0.1 
2 2 2
3x
0.1   0.1632 (total number of moles)
2
3x x 0.0632
 0.1632  0.1  0.0632    0.0210
2 2 3
x
= number of moles of O2 = 0.021
2
number of moles of O 2 0.021
PO2   total pressure   0.5 = 0.0643 atm
total number of moles 0.1632

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CHEM ACADEMY 1 IIT-JAM 2016

3. The mechanism of the following transformation involves

(a) (b) (c) (d)

17. The true statement about [Cu(H2O)6]2+ is

24. The maximum of a function Ae  ax 2 (A > 0; a > 0) is at x =

(a) 0 (b) +  (c) – (d) 1/ a

energy for CaCl2 molecule in kJ mol–1 is___.

• Electron withdrawing group increases the acidic character

Correct option is (B)

Correct option is (A)

Hence, correct option is (C)

5. Mn 2  3d5 (HS)  t 32g eg2

One Cs+ ion surrounded by 8 Cl– ion and vice versa.

Correct option is (B)

Correct option is (D)

Correct option is (A)

Correct option is (D)

17. [Cu(H 2O)6 ]2 

20. (Free) NO    N O  2250 cm–1

(Free) NO   N O  1896 cm–1

NO linear 1672 cm–1

Correct option is (A)

In resonating structure there is no shift of atom takes place.

Correct options are (A), (C), (D).

Correct option is (A).

39. 3pz CHEM ACADEMY

C2  2s 2  * 2s 2 2p 2x 2p 2y 62

Number of aromatic compounds = 3

exist in non-planar tub shape

Since compound is not planar. Thus, it is non-aromatic.

Azulene is aromatic [via Craig’s rule also]

The number of aromatic compound = 3

Hence, number of P-H bonds is two.

 2  (1)  1  2  (1)  1  (1)  (1)  1

Correct answer is (7)

there is plane of symmetry optically inactive.

there is plane of symmetry, therefore, optically inactive.

Total number of moles (n) =

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