INDIAN ASSOCIATION OF CHEMISTRY TEACHERS

NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) 2017-18

Examination Date : 26-11-2017 Time: 2 Hrs. Max. Marks : 240

Q. PAPER CODE : C321 HBCSE Olympiad (STAGE - 1)

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1
1. At constant T and P, 5.0 L of SO2 are reacted with 3.0 L of O2 according to the following equation
2SO2 (g) + O2 (g)  2SO3 (g)
The volume of the reaction mixture at the completion of the reaction is
(A) 0.5 L (B) 8.0 L (C) 5.5 L (D) 5 L
Ans. (C)
2SO2 (g) + O2 (g)  2SO3 (g)
Sol. Initial volume 5 L 3L 0
Volume after 0 + (3 – 2.5) + 5 = 5.5 L
reaction = 0.5

2. The following disaccharide is made up of

O
CH2OH
OH O O OH
OH OH
CH2OH

OH OH

(A) D-aldose and D-ketose (B) L-aldose and L-ketose

(C) D-aldose and L-ketose (D) L-aldose and D-ketose
Ans. (D)
H
HO–CH2 O OH
H O H
Sol. CH2OH
H H H H
HO OH H CH2–OH

OH OH OH OH
L Aldose D Ketose

3. One mode of 4-nitrocatechol (4-nitro-1,2-dhydroxybenzene) on treatment with an excess of NaH

followed by one mole of methyl iodide gives-
(A) 4-nitro-1, 2-diamethox ybenzene (B) 4-nitro-5methy-1, 2-dimethox ybenzene
(C) 2-methox y-5 nitrophenol (D) 2-methoxy-4nitrophenol
Ans. (D)
OH OH
O Na
–

OH
O Na OCH3
–

Sol. 
NaH
Excess
 More nucleophilic 
CH3 –I
1mol

NO2 NO2
NO2
(1 Mol)

2
4. The colour changes of an indicator HIn in acid base titrations is given below
+ –
HIn (aq) H (aq) + In (aq)
Colour X Colour Y
Which of the following statements is correct?
(A) In a strong alkaline solution colour Y will be observed
(B) In a strong acidic solution colour Y will be observed
–
(C) Concentration of in is higher than that of HIn at the equivalence point
(D) In a strong alkaline solution colour X is observed
Ans. (A)
Sol. It is an acidic indicator therefore will remain in ionized form in strong alkaline solution (opposite ion
effect).

5. The table below gives the results of three titrations carried out with 0.200 M HCl to determine the
molarity of a given NaOH solution using phenolphthalein as indicator. NaOH was taken in the
burette and HCl was taken in a conical flask for the titrations

Titration No. V HCl(mL) VNaOH (mL) MNaOH moldm–3

I 21.4 19.3 0.222

II 18.6 16.8 0.221
III 22.2 21.1 0.210

–3
The actual molarity of the prepared NaOH solution was 0.220 mol dm . Which among the
following could be the reason for the wrong value obtained in titration III?
(A) Number of drops of phenolphthalein added to the titration flask was more in this titration
(B) The concentration of HCl was wrongly used as 0.250 M for the calculation of M NaOH
(C) A few drops of NaOH solution were spilled outside the titration flask during titration
(D) A few drops of the neutralized solution from titration II were left behind in the flask
Ans. (C)
NaOH

Sol. HCl

– nOH– nacid [HCl] VHCl

[OH ] = = = = 0.21 M < 0.220
VOH– VNaOH VNaOH

6 The solution with pH value close to 1 is

(A) 10 mL of 0.1 M HCl + 90 mL of 0.1 M NaOH
(B) 55 mL of 0.1 M HCl + 45 mL of 0.1 M NaOH
(C) 75 mL of 0.2 M HCl + 25 mL of 0.2 M NaOH
(D) 75 mL of 0.2 M HCl + 25 mL of 0.1 M NaOH
Ans. (C)

3
 + 15 – 5 –1
Sol. [H ] = = 10 M
75  25
or pH = 1

7. The most basic nitrogen in the following compound is

H2N O I
II HN

IV
(H3C)2N
N O
O III O
(A) I (B) II (C) III (D) IV
Ans. (C)
H2N O I
II HN

IV
Sol. (H3C)2N
N O
O III O
Lone pair of III is localised therefore it is most basic.

8. For the reaction N2 + 3H2  the rate expression is –d[NH3] /dt = k[H2] [N2]
The correct statement is
I. The reaction is not elementary
II. The reaction is of second order
III. –d[H2]/dt = –d[NH3]/dt
(A) II only (B) I and II (C) II and III (D) I, II and III
Ans. (B)
d[N2 ] 1 d[H2 ] 1 d[NH3 ]
Sol. r=– =– =
dt 3 dt 2 dt

9. Which of the following is correct ?

A liquid with
(A) low vapour pressure will have a low surface tension and high boiling point
(B) high vapour pressure will have high intermolecular forces and high boiling point
(C) low vapour pressure will have high surface tension and high boiling point
(D) low vapour pressure will have low surface tension and low boiling point
Ans. (C)
Sol. A liquid with low vapour pressure (less volatile) will have a high surface tension and high boiling
point

4
10. At 25°C, nitrogen exists as N2 and phosphorous exists as P4 because
(A) N2 has valence electrons only in bonding and nonbonding orbitals, while P has valence
electrons in both bonding and antibonding orbitals
(B) higher electronegativity of N favours formation of multiple bonds
(C) bigger size of P does not favour multiple bonds
(D) P has preference to adapt structures with small bond angles
Ans. (C)
Sol. Nitrogen forms multiple bonds due to small size.

11. The product of the following reaction is

NH2 (i) HNO2. 0.5°C

(ii) dil. H2SO4, heat
(iii) HI, heat

NH2

OH

OH I

OH
(A) (B)
I
I

I I

(C) OH (D) I

Ans. (A)
  
NH2 NN NN NN
Sol. 
HNO2
  H2O
CH2 CH2 CH2–OH

NH2 NN


OH OH OH
I–
 dil
H2 SO4 heat
 

HI  heat 


CH2–OH CH2–OH2 CH2–I

5
12. Three samples of 100 g of water (samples I, II and III), initially kept at 1 atm pressure and 298 K
were given the following treatments.
Sample I was heated to 320 K and cooled to 298 K
Sample II was heated to 300 K, cooled to 273 K and heated to 298 K
Sample III was heated to 373 K and cooled to 298 K
At the end of these processes, the internal energy of
(A) III is the highest
(B) II is the highest
(C) I and III are the same, II is lower than that of I and III
(D) I, II and III are the same
Ans. (D)
Sol. Internal energy change is a state function.

13. For the reaction

5 Br (aq) + BrO3 (aq) + 6H (aq)  3Br2(aq) + 3H2O (I)
– – +

– – + 2
the rate expression was found to be –d[BrO3 ] / dt = k [Br ] [H ] [ BrO3– ]

Which of the following statements is /are correct?

I. Doubling the initial concentration of all the reactants will increase the reaction rate by a factor of
8
–1
II. Unit of rate constant of the reaction in a buffer solution is min
III. Doubling the concentration of all the reactants at the same time will increase the reaction rate
by a factor of 16
– –
IV. rate of conversion of BrO3 and rate of formation of Br are the same
(A) I and II (B) II and III (C) II and IV (D) III only
Ans. (D)
d[BrO3– ] 1 d[Br2 ]
Sol. r=– =
dt 3 dt
– + 2
r' = K[2Br ] [2H ] [ 2BrO3– ]

= 16 r

14. In the Lewis structure of ozone (O3), the formal charge on the central oxygen atom is
(A) +1 (B) –1 (C) 0 (D) –2
Ans. (A)
+1
–1 O
Sol.
O O

6
15. Which of the following on treatment with hot concentrated acidified KMnO4 will give
2-methylhexane -1,6-dioic acid as the only organic product?

(A) (B) (C) (D)

Ans. (C)
O
C–OH

Sol. 
H / KMnO4

C–OH
O
2–Methylhexane–1,6 –dioic acid

16. For the following spontaneous process

H2O(I) H2O(s) at 268 K, which of the following is true?
(A) Ssys < 0 (B) Ssys > 0 (C) Ssurr < 0 (D) Ssys = –Ssurr
Ans. (A)
Sol. Liquid is converting into solid also in the process heat is released therefore Ssys < 0
also Stotal > 0

–1
17. Lithium oxide (Li2O; molar mass = 30 g mol ) is used in space shuttles to remove water vapour
according to the following reaction
Li2O(s) + H2O(g)  2LiOH(s)
If 60 kg of water and 45 kg of Li2O are present in a shuttle
I. water will be removed completely
II. Li2O will be the limiting reagent
III. 100 kg of Li2O will be required to completely remove the water present
IV. 27 kg of water will remain in the shuttle at the end of the reaction
(A) II only (B) II and IV (C) III and IV (D) II, III
Ans. (D)
Sol. LR ER
Li2O(s) + H2O(g)  2LiOH(s)
45  103 60  103
initially 0
30 18
3 3
or = 1.5 × 10 mol = 3.33 × 10 mol
3
after reaction 0 (3.33 – 1.5) × 10
3
= 1.83 × 10 mol

7
18. The order of enol content in the following molecule is
O
O O O O

O CH3CH2CCH2 CH3 CH3CH=CHCCH3 CH3CCH2CCH3

(a) (b) (c) (d)
(A) a > d > c > b (B) a > c > d > b (C) a > c > b > d (D) a > b > c > d
Ans. (A)
O O–H

Sol. (a)
O OH
Aromatic
H
O O O O
(d) Active methylene group

OH
O
(c)
Conjugated
O OH

(b)

19. The product of the following reaction is

(i) C6H5MgBr, dry ether
+
(ii) H3O
O
(iii) PCl5
(iv) NaOC2H5/C2H5OH
CH3 CH3 CH3
(A) (B) (C) (D)
C6H5 C6H5 C6H5 C6H5
Ans. (C)
CH3 CH3 Tertiary alcohols are converted to
PhMg Br –
tertiary chlorides under mild
Sol. O O MgBr H3O OH conditions with retention of
SN2
Ph Ph configuration, presumably through
an SN1, tight ion-pair mechanism.
CH3 CH3
PCl5 EtONa
Cl EtOH
E2
Ph Ph

8
20. At constant volume, 6.0 mol of H2 gas at 0ºC and 100 kPa was heated to 250 kPa. The molar heat
–1
of H2 at constant pressure (CP) = 28.9 J mol . (assume that the heat capacity values do not
change with temperature). The final temperature of the H2 gas and the change in entropy of the
process are
–1 –1 –1 –1
(A) 273ºC and 113 kJ mol K (B) 410ºC and 158.8 J mol K
–1 –1 –1 –1
(C) 682.5ºC and 113 J mol K (D) 682.5 K and 113 J mol K
Ans. (D)
P1 P
Sol. = 2
T1 T2

100 250
= or T2 = 682.5 K
273 T2

T2
S = nCV ln
T1

T2
= 2.303 n(CP – R) log
T1

682.5
= 2.303 × 6 × (28.9 – 8.314) log
273
 113 J mol mol
–1 –1

21. The cubic unit cell of an oxide of metals A and B is as given below, in which oxygen.
A and B are represented by open circles, crossed circles and dark circle respectively.

O
A

The formula of the oxide can be deduced as

(A) AB8O12 (B) ABO (C) ABO6 (D) ABO3
Ans. (D)
Sol. Number of atoms of A/unit cell = 1
1
Number of atoms of B/unit cell = 8 × =1
8
1
Number of atom of 0/unit cell = 12 × =3
4
So, the formula of the oxide is ABO3.

9
22. When a medal is electroplated with silver (Ag)
(A) The medal is the anode
(B) Ag metal is the cathode
+
(C) The solution contains Ag ions

(D) The reaction at the anode is Ag + e  Ag

+ –

Ans. (C)
Sol. For electroplating of metal with silver
Cathode  Metal
Anode  Ag
Solution  Electrolyte containing Ag
+

23. The energy of an electron in Bohr's orbit of hydrogen atom is –13.6eV. The total electronic energy
of a hypothetical' He atom is which there are no electron– electron repulsions is
(A) 27.2 eV (B) –27.2 eV (C) –108.8 eV (D) 108.eV
Ans. (C)
Sol. Electronic energy per electron = –13.6 × 4 eV
Total Electronic energy = –13.6 × 4 × 2 = – 108.8 eV

24. Iodine is a solid and sublimes at ordinary temperature. This is because of :

(A) weak - bonds
(B) strong - bonds
(C) lone pair-bond pair repulsions
(D) weak van der Waals forces between 2 molecules

Ans. (D)
Sol. I2 is solid & sublimes at ordinary temperature because of weak vander waal’s force between I2

molecules.

25. The equilibrium constant of the following isomerisation reaction at 400K and 298 K are 2.07 and
3.42 respectively.
k1
cis-butene trans-butene
k–1

Which of the following is/are correct ?

I. The reaction is exothermic
II. The reaction is endothermic
III. At 400K 50% of cis-butene and 50% of trans-butene are present of equilibrium
IV. Both at 298K and 400K, k1 =k–1
(A) I and IV (B) II and IV (C) I and III (D) I only
Ans. (D)
Sol. As on T increase, Keq is increasing, Reaction is exothermic.

10
26. Which of the following will not give a straight line plot for an ideal gas ?
(A) V vs T (B) T vs P (C) V vs I/P (D) V vs I/T
Ans. (D)
Sol. PV = nRT
nRT
V=
P
1
V v/s will not be a straight line.
T

27. Levonorgestrel is a commonly used contraceptive. The number of chiral centres present in this
molecule is :

CH
OH
C

O
Levonorgestrel

(A) 4 (B) 5 (C) 6 (D) 7

Ans. (C)
Sol. Number of chiral centres are 6.

CH
OH
C
* *
*
* *
*
O
Levonorgestrel

28. Which of the following ethers cannot be prepared by Williamson Synthesis ?

OC(CH3)3 OCH3
OCH3
(A) (B) (C) (D)
O
Ans. (B)
PhO + (CH3)3C—X  No Reaction
–
Sol.
(CH3)3CO + Ph—X  No Reaction
–
Or
2
Hint : (CH3)3C—X and Ph—X do not react by SN reaction.

3–
29. IUPAC name of complex ion [CrCl2(ox)2] is
(A) dichlorodioxalatochromium (III) (B) dioxalatodichlorochromate(III)
(C) dichlorodioxalatochromate(III) (D) bisoxalaeodichlorochromate(III)

11
Ans. (C)
Sol. IUPAC name is dichlorodioxalatochromate (III)

30. Sodium azide (NaN3) is used in airbag of cars. This is safety device with inflates on an impact
according to the reaction 2NaN3  2Na + 3N2
An air bag of a particular car can be filled with 44.8 L of gas at STP. The mass (g) of NaN3
required to fill this airbag completely at 298K and 1 atm. pressure is :
(A) 87 (B) 130 (C) 84 (D) 100
Ans. (A)
Sol. As the maximum volume of airbag will remain same irrespective of temperature hence to fill me
bag at 298 K.
V = 44.8 L
T = 298 K
P = 1 atm
n (of N2) = 1.83
2
moles of NaN3 required =
mass of NaN3 required = 1.22 × 65 = 79.4 g
 So it should be bonus.
Comment : If we consider that airbag will contain same mole at both temperature (273 K & 298 K)
(i.e. assuming volume expansion at bag with temperature)
So moles of N2 at STP = 2 (T = 273 K)
Moles of N2 at 298 K & 1 atm = 2
2 4
Moles of NaN3 reqd. = ×2=
3 3
4
Mass of NaN3 required = × 65 _~ 84 g.
3
So (A) can be considered with the above unjustified assumptions.
31. Which of the following mixtures of water and H2SO4 would have mass percentage of H2SO4 close
to 30?
(A) 30 g H2SO4 + 100 g H2O (B) 1 mol of H2SO4 + 2 mol of H2O
(C) 1 mol of H2SO4 + 200g of H2O (D) 0.30 mol H2SO4 + 0.70 mol H2O

Ans. (C)
98
Sol. Mass percentage of H2SO4 = × 100 = 32.88
298
Closest to 30.

32. In chlorides, the common oxidation states of aluminium and thallium are +3 and +1 respectively
because.
(A) Tl-Cl bond is ionic and Al-Cl bond is covalent
(B) 6s electrons of Tl are bound more strongly than the 3s electron of Al
(C) Tl-Cl bond is stronger than Al-Cl bond
(D) 3s electrons of Al are bond strongly than the 6s electrons of Tl
Ans. (B)
Sol. 6s electrones of Tl are bond more strongly than 3s electrons of Al. (inert pair effect)
Also Ionisation energy of Tl > Ionisation energy of Al.

12
33. In the given compound the order of case with which hydrogen atom can be abstracted from
carbons I to VI is :
IV
II H VI
O C CH3
I H
H3C C C
H
V
CH3
III
(A) I > VI > IV = V > I > III (B) II > I > VI > III > IV = V
(C) II > I > III > VI > IV = V (D) IV > II > I > III > IV = V
Ans. (B)
Sol. Breaking of C–H bond is inversely related to stability of intermediate free radical.
O O O O O O
> > > > =

(Stability order of free radical)

Use the table given below to answer questions 34 and 35

Reaction E0/V
Ag Ag + e
+ –
–0.80
Cr + 3e 3Cr
3+ –
–0.74
Zn + 2e Zn
2+ –
–0.76
2(s) + 2e 2 
– –
0.54
+ 2e Co
2+ –
Co –0.28
+ 2e Ni
2+ –
Ni –0.26

34. The best reducing agent among the following is

(D) 
+ 2+ 3+ –
(A) Ag (B) Zn (C) Cr
Ans. (D)
+ 2+ 3+
Sol. Ag , Zn , Cr are not reducing agents.
–
I Is a reducing agent.

35. Eº of the given cell is :

NI (Ni2 ,1.0M) (Co 2 ,1.0M) Co

(A) +0.02V (B) –0.02V (C) –0.54V (D) +0.54V

Ans. (B)
Sol. Eºcell = Eºcathode (RP) – Eºanode(RP)
+2 +2
= EºCo /Co – EºNi /Ni
= –0.28 – (–0.26) = –0.02 V

13
36. Which of the following is not a pair of a Lewis acid and a Lewis base ?
+
(A) H , (C2H5)2O (B) H2O, AlCl3
3+
(C) Fe , CO (D) SiF4, BF3
Ans. (D)
Sol. Both SiF4 & BF3 are both lewis acids.

37. The type of isomerism that Co(NH3)4Br2Cl can exhibit is/are

(A) geometric and ionisation
(B) ionisation
(C) Optical and ionisation
(D) Optical, ionisation and geometric
Ans. (A)
Sol. It can exhibit geometric & ionisation.

38. Pyrethrins are produced in chrysanthemum flowers and used as insecticides.

Structure of pyrethrin I is given below

O O

Pyrethrin I (molar mass = 32.8g/mol)

3
The volume of 0.05 mol dm bromine water that would with 500 mg sample of Pyrethrin I is
3 3 3 3 3
(A) 12.2 cm (B) 122 dm (C) 122 cm (D) 1.31×10 cm
Ans. (C)
Sol. Total position where Bromine water can attack is four.

39. Coniferyl alcohol is isolated from pine trees. The following observations were made about this
alcohol.
I. It forms methylated product with Mel in presence of base
II. One equivalent of coniferyl alcohol reacts with two equivalents of benzoyl chloride
III. Upon ozonolysis, coniferyl alcohol gives a product 'Y' (M.F C2H4O2).
OH
OH OH OH OH

(A) (B) (C) (D)

OMe OMe OH OMe
OMe OH OH OH
Ans. (D)

14
 OH OCH3
CH3I
Sol. Base
OMe OCH3
OH OCH3
O
O O–C–Ph
2Ph–C–Cl

OCH3
O–C–Ph

CH=O
Ozonolysis O=CH–CH2–OH
(M.P.) C2H4O2
OMe
OH

40. Which of the following represents a polymer of prop-2-en-l-ol ?

(A) CH2–CH2–CH (B) ––CH2–CH–– (C) CH2 C–– (D) ––CH2–CH2–CH2–O––
n n n
OH CH2OH HOH2C
Ans. (B)
Sol.
CH2–CH
nCH2=CH

Polymerisation

CH2–OH
CH2–OH n

41. A 500 mL glass flask is filled at 298 K and 1 atm, pressure with three diatomic gases X, Y and Z.
The initial volume ratio of the gases before mixing was 5:3:1. The density of the heaviest gas in the
mixture is not more than 25 times that of the lightest gas. When the mixture was heated, vigorous
reactions take place between X and Y and X and Z in which all the three gases were completely
used up.
The gases X, Y, Z respectively are
(A) H2, O2, N2 (B) H2, O2, Cl2 (C) H2, F2, O2 (D) O2, H2, F2
Ans. (C)
Sol. According to given data.
Mole ratio of gas x,y,z are 5 : 3 : 1
 As given in the question that the density of heaviest gas in the mixture is not more then 25
times that of lightest gas. Hence gas mix should be H2, F2, O2
 x = H2 , y = F2, z = O2
1
H2 + F2  2HF H2 + O2  H2O
2
5a 3a – 2a a 2a
2a – 6a – – 2a

15
42. The reaction X + Y  Z is first oder with respect to X and second order with respect to Y. The
3 –1 –3
initial rate of formation of Z = R mol dm sec when [X]0 and [Y]0 are 0.40 mol dm and 0. mol
3
dm respectively. If [X]0 is halved and [Y]0 is doubled, the value of the initial rate would become
(A) 4R (B) R/4 (C) R (D) 2R
Ans. (D)
Sol. X + Y  Z
2
(Rate)1 = K[X] [Y]
X 2
(Rate)2 = K[ ] [2Y]
2
(Rate)1 1
= (Rate)2 = 2(Rate)1 = 2R
(Rate)2 2

43. Which one of the following statements is not correct about glucose ?
–1
(molar mass of glucose = 180 g mol )
(A) An aqueous 0.25 M solution of glucose is prepared by dissolving 45 g of glucose in water to
3
give 1000 cm of solution
(B) 1.00 mmol glucose has a mass of 180 mg
22
(C) 90.0 g glucose contain 1.8 × 10 atoms of carbon
3
(D) 100 cm of a 0.10 M solution contains 18 g of glucose
Ans. (C) & (D)
Sol. (A) W glucose = 0.25 × 10 × 180 = 45 g
(B) W glucose = 1 mmole × 180 = 180 mg
90 23
(C) No. of C–atoms = × NA × 6 = 18 × 10
180

44. The van der Waals equation for one mole of a real gas can be written as
2 –2 –2
(P + a/V ) (V – b) = RT. For the gases H2, NH3, and CH4, the value of 'a' (bar L mol ) are
0.2453, 4.170 and 2.253 respectively.
Which of the following can be inferred from the 'a' values ?
(A) NH3 can be most easily liquified
(B) H2 can be most easily liquified
(C) value of 'a' for CH4 is less than that of NH3 because it has the lower molar mass
(D) intermolecular forces are the strongest in hydrogen
Ans. (A)
Sol. van der Wall's constant 'a' gives information about force of attraction between gaseous molecules..
Higher the value of 'a' higher will be force of attraction, and easier the liquefaction of gas.
Order of intermolecular force of attraction = H2 < CH4 < NH3

16
45. Terpinen-4-ol is an active ingredient in tea tree oil has the following structure

HO

The correct observations for terpinen-4-ol is/are

I. It rotates the plane of plane polarized light.
II. It reacts with Baeyer's reagent to form form a triol
III. On reaction with NaBr and H2SO4, it gives form a diobromo compound
IV. On ozonolysis it gives a compound with molecular formula C10H18O3
(A) I, II, III and IV (B) I, III and IV (C) II and III (D) III and IV
Ans. (A)
Sol. (I) Terpinen-4-ol is an optically active molecule because it is chiral molecule
OH
OH
(II) 
Baeyers's reagent

HO HO

Br
NaBr  H2SO4
(III)  
HO Br

O
O
(IV) 
Ozonolysis
C10H18O3
HO

46. The correct order of the ability of the leaving group is

(A) OCOC2H5 > OC2H5 > OSO2Et > OSO2CF3
(B) OC2H5 > OCOC2H5 > OSO2CF3 > OSO2Me
(C) OSO2CF3 > OSO2Me > OCOC2H5 > OC2H5
(D) OCOC2H5 > OSO3CF3 > OC2H5 > OSO2Me
Ans. (C)
Sol. Weaker bases are better leaving group.
– – – –
 order of Kb: OSO2CF3 > OSO2Me > OCOC2H5 > OC2H5

17
47. Metal 'M' forms a carbonly compound in which it is present in its lower valance state. Which of the
following bonding is possible in this metal carbonyl ?

*(M)  CO (M)  *(CO

(A)  (B) 
M C O M C O
 
(M)  *(CO (M)  *(CO
(C)  (D) 
M C O M C O
 
Ans. (B)
Sol. Bonding in metal carbonyl

-bond

M CO
-bond

-bond  filled d-orbitel of metal and empty * molecular orbital of CO take part.
-bond  Empty hybrid orbital of metal and filled molecular orbital of carbon mono oxide.

48. Acetic acid (CH3COOH) is partially dimerised to (CH3COOH)2 in the vapour phase. At a total
pressure of 0.200 atm, acetic acid is 92.0% dimerized at 298 K.
The value of equilibrium constant of dimerisation under these conditions is
(A) 57.5 (B) 9.7 (C) 97 (D) 194
Ans. (D)
Sol. 2CH3COOH  (CH3COOH)2
a —
a-0.92a 0.46 a
0.08 a 0.46 a
0.46a
 0.02
Kp = 0.54a 2
_
~ 194.
 0.08a 
 0.54a  0.02 
 
49. Silanes are silicon hydrides of general formula SinH2n+2 and have several applications. From the
data given below, the bond dissociation enthalpy of Si-Si bond can be deduced as

H of the reaction 2Si(s) + 3H2(g)  Si2H6(g) is 80.3 kJ mol

–1

Bond dissociation enthalpy for H – H = 436 kJ/mol

Bond dissociation enthalpy for Si – H = 304 kJ/mol
fH [Si(g)] 450 kJ mol
–1

(A) – 304 kJ mol–1 (B) 384.3 kJ mol–1 (C) 304 kJ mol–1 (D) – 384.3 kJ mol–1

Ans. BONUS

18
Sol. 2Si(s) + 3H2 Si2H6 H = 80.3 kJ/mole
2×405 3×436

2Sig 6Hg [(Si – Si) + 6(Si–H)]

80.3 = 2 × 405 + 3 × 436 – [(Si – Si) + 6(304)]

(Si – Si)Bond energy = 304 kJ/mole

50. In the following reaction, three products a, b, c are obtained.

CH3 H3C CH3
CH3
H2C—C—CH—CH3 
H3PO4 /heat
 H3C—C—CH = CH2 + C C +
CH3 OH H3C CH3
CH3 (b)
(a)
CH2

H3C—C—CH—CH3
(c) CH
2
The approximates experimental yields of the three compounds were 64%, 33% and 3%.
Which of the following is the correct with respect to yield and the corresponding product ?
(A) (a)-33% ; (b)-64% ; (c)-3% (B) (a)-3% ; (b)-64% ; (c)-33%
(C) (a)- 3% ; (b)-33% ; (c)-64% (D) (a)-64% ; (b)-3% ; (c)-33%
Ans. (B)
Sol. % yield  stability of Alkene
Decreasing order of stability
H3C CH3 CH2
CH3
C C
H3C—C—CH—CH3 H3C—C—CH = CH2
H3C CH3 > >
(b) (c) CH CH3
2
64% 33% (a)
3%
51. Which of the following represents the correct order of dipole moment?
(A) NH3 > NF3 > H3O (B) NH3 > H2O > NF3
(C) H2O > NH3 > NF3 (D) H2O > NF3 > NH3
Ans. (C)
Sol.

N N
H H F F
H F
Directions of Bond Directions of Bond
dipole and l. p. dipole dipole and l. p. dipole
are same are opposite

Hence H2O > NH3 > NF3

19
52. The best reaction sequence for the synthesis of 2-pentanone would be -

CH3Mg / ether
(A) CH3CH2CH2CHO   X 
H ,H2 O


CH3Mg / ether
(B) CH3CH2CH2CN   X 
H ,H2 O


CH3Mg / ether
(C) CH3CH2CH2CHO   X 
H ,H2 O


(D) CH3CH2CH2Mg + CH2O 
ether
 X 
H ,H2 O

Ans. (B)
O


Sol. CH3CH2CH2CN     CH3–CH2–CH2–C=NMgI 

CH3MgI / Ether

H ,H2O CH3–CH2–CH2–C–CH3
+
CH3 NH3
+
Mg(OH)I

53. Haemoglobin is a Fe containing protein responsible for oxygen transport in the blood. The curves
given below indicate the percentage saturation of haemoglobin by O2 as a function of partial
pressure of O2.
% saturation

I
II

pO
2

Which of the following statement/s is /are correct for the given curves?

I. In presence of CO2, higher PO2 is needed for a given percentage saturation

II. In presence of CO2, lower PO2 is needed for a given percentage saturation

III. The maximum percentage saturation is not affected by the presence of CO2

IV. In the absence of CO2, maximum saturation of haemoglobin occurs at lower pO2

(A) I and IV (B) II and IV (C) I, III and IV (D) II and III

Ans. (C)
Sol. According to given information graph I would be in presence of CO2 and II would be in absence of
CO2.
Now we can conclude from graph that
(i) In presence of CO2 higher PO2 in needed for a given percentage saturation.
(ii) The maximum percentage saturation is not affected by presence of CO2.
(ii) In the absence of CO2, maximum saturation of haemoglobin occurs at lower PO2 .

20
54. An appropriate reagent for the conversion of 1-propanol to 1-propanal is

(A) acidified potassium dichromate

(B) alkaline potassium permanganate

(C) pyridinium chlorochromate

(D) acidified CrO3

Ans. (C)
Sol. Mild oxidising agent pyridinium chlorochromate (PCC) will oxidise primary alcohol into aldehyde.

55. A student performed an experiment to determine the molecular formula of a given sample of
hydrated copper(II) sulphate by weighing the sample before and after heating. The formula
obtained experimentally was CuSO4.5H2O while the actual formula of the given sample is CuSO4.
5H2O. Which experimental error would account for the wrongly obtained result ?

(A) During heating, some of the hydrated copper(II) sulphate was lost

(B) The hydrated sample was not heated long enough to remove all the water present

(C) Weight of the hydrated sample recorded was less than the actual weight taken

(D) The balance used in the study showed all weights consistently high by 0.10g.

Ans. (A)
Sol. W i = m(ini) = m(CuSO4 . x H2O)
wf = m(final) = m(CuSO4) *(possibly dehydrated)
mwater = W i – W f
Wi  Wf
nwater =
18
Wf
nCuSO4 
MCuSO4

nw Wi  Wf MCuSO 4
x  
nCuSO 4 18 Wf

W 
x   i  1
 Wf 
Correct value of x is 5
Experimental value of x is 5.5
Now, Option (A) is absurd, since CuSO4 cannot evaprate.
(C) is wrong If W i is less than correct value Xexperi should be < 5.
Wicorrect  0.1
X exp 
Wfcorrect  0.1

21
 Wicorrect
 1 ; adding same no to numerator & denominator will decrease the fraction.
Wfcorrect
Now, look at (B)
W i = m(CuSO4.xH2O)
W f = m(CuSO4.yH2O) ; y < x
Mass of water evaporated = W i – W f'
Wi  Wf'
Moles of water evaporated =
18
nw MCuSO 4 Wi  Wf'
x  
nCuSO 18 W'  Since we (wrongly) believe it to be anhydrous.
4 f

W 
x   i'  1
W 
 f 
If some water of crystallization is left, W f' must be < W f (the correct value).
Thus, the incorrect value must be < 5. But it is claimed as 5.5.
Hence, none of the options (A), (B), (C) or (D) are correct. In true spirit of chemical science, this
question is ought to be a bonus. However if we assume spillage/any other loss (A) may be taken
as the answer.

56. Malic acid is a dicarboxylic acid present in apples and it has the following structure

OH

H—C—CH2—COOH

COOH
Which of the following synthetic routes will give (±) malic acid ?
(i) HBr
(ii) KOH (aq.)
(i) H2C=CH—COOH +
(iii) HCN/H3O
(i) KOH (aq.)
(ii) PCC
(ii) H2C—CH—COOH +
(iii) HCN/H3O
Br
(i) Red P/I2
(ii) NaOH(aq.)
(iii) H3C—CH2—COOH
(iii) [O]
+
(iv) HCN/H3O
(i) B2H6/H2O2
(ii) [O]
(iv) H2C=CH—COOH +
(iii) HCN/H3O
(A) i an d ii (B) ii (C) ii and iii (D) i and iii
Ans. (B)
Sol. CH2–CH2–COOH 
KOH aq.
 CH2–CH2–COOH 
PCC
 O=CH–CH2–COOH
Br OH
HCN H3O

HOOC–CH–CH2–COOH
OH

22
57. Which of the following cannot act as an oxidising agent ?

(C) HSO4 (D) SO32

2–
(A) S (B) Br2

Ans. (A)
2–
Sol. As sulphide (S ) is in its lowest oxidation state. Hence it cannot act as a oxidising agent.

58. Ellingham diagrams are plots of Gº vs temperature which have applications in metallurgy.

2H2 + O2 = 2H2O G(J) = –247500 +55.85 T ...................... (I)

2CO + O2 = 2CO2 G(J) = –282400 +86.81 T ....................... (II)

The Ellingham diagrams for the oxidation of H2(I) and CO (II) are given below.

The two lines intersect (TE) at 1125 K.

GºkJmol O2

I
–1

II


0 TE Temperature(T)

Which of the following is correct ?

I. Gº for reaction (i) is more negative at T < 1125K

II. G for the reduction of CO is more negative at T < 1125 K

0

III. H2 is a better reducing agent at T > 1125 K

IV. H2 is a better reducing agent at T < 1125 K

(A) I and II (B) I and III (C) III only (D) I and IV

Ans. (C)
Sol. According to the given data, Plot I is for CO as it has more negative G value Plot II is for H2. And
as we know in the Ellingham diagram, compound for which, the Plot lies below acts as a better
reducing agent. So, at T > 1125 K, H2 is a better reducing agent.
Note: The given graph in the question is not according to given data in the question.

23
59. Hydrazine used in rocket fuels can be obtained by the reaction of ammonia and hydrogen peroxide
according to the following equations

2NH3(g) + H2O2(l)  N2H4(l) + 2H2O(l) (Hºreaction = -241kJ/mol)

If Hº (formation) of NH3, H2O2 and H2O are -46.1, -187.8 and –285.8kJ/mol respectively, Hº for
the decomposition of hydrazine into N2 and H2 is
(A) 50.6 kJ/mol (B) 241 kJ/mol (C) -50.6 kJ/mol (D) 120.5 kJ/mol
Ans. (C)
Sol. 2NH3(g) + H2O2()  N2H4() + 2H2O()


reaction   
= HfN2H4  2x Hf H2 O – 2xHf NH3    f H2O2  
– 241 = Hf N2H2   2x  –285.8  – 2x (–46.1) + 187.8

Hf N2H2  = –241 + 2 × 285.8 – 2 × 46.1 – 187.8

  2 2 

2+
60. Sn compounds like SnO and SnCl2 are well known reducing agents, while PbO2 acts as an
oxidizing agent. Which of the following statements support these reactivities?
I. SnO is more stable than SnO2
4+ 2+
II. Sn is more stable than Sn
4+ 2+
III. Pb is more stable than Pb
2+ 4+
IV. Pb is more stable than Pb
(A) I and III (B) I, III and IV (C) II and IV (D) I, II and IV
Ans. (C)
2 4 4 2
Sol. Sno  Sno2 PbO2  Pb O
2 4
SnCl2  SnCl4
+4 +2 +2 +4
Sn is more stable than Sn & Pb is more stable than Pb .
+2 +4
So, Sn acts as reducing agents & Pb acts as oxidising agents.
Above fact can also be explain by inert pair effect.

61. A fuel/ oxidant system consisting of N,N-dimethylhydrazine (CH3)2NNH2 and N2O4 (both liquids) is
used in space vehicle propulsion. The liquid components are mixed stichiometrically so that N2,
CO2 and H2O are the only products. If all gases are under the same reaction conditions, number of
moles of gases produced from 1 mole of (CH3)2NNH2 is
(A) 3 (B) 6 (C) 9 (D) 4.5
Ans. (C)
Sol. (CH3)2N NH2 + 2N2O4  3N2 + 2CO2 + 4H2O(g)
One mole of (CH3)2N NH2 will produce (3 + 2 + 4 = 9) moles of gases.

24
62. An ether (X) with molecular formula C5H10O reacts with excess of hot aq. HI to give a product
which on further reaction with hot NaOH in ethanol forms 1,3 pentadiene. Structure of X is
CH3 O O
(A) (B) (C) (D)
O
O

Ans. (B)
O I
Sol. I NaOH  C2H5 OH

HI
  

63. Compound 'Y' with molecular formula C8H9Br gives a precipitate on heating with alcoholic AgNO3.
Oxidation of 'Y' gives products 'Z' (C8H6O4) which gives an anhydride upon heating.
Compound 'Y' is
Br
(A) (B) (C) (D) Br
Br
Br
Ans. (C)
Alc. AgNO3

C8H9Br
(Y) Oxidation 
Sol. C8H6O4 Anhydride
AgNO3
Precipitate
O
Br COOH C
Oxidation 
O
COOH C
O

64. The observed effective magnetic moment of two octahedral complexes,

K4[Mn(CN)6].3H2O(X) and K4[Mn(SCN)6] (Y) are 2.18 BM and 6.06 BM, respectively. Which of the
following is correct?
I. X is low spin complex with two unpaired electrons
II. Y is high spin complex with 5 unpaired electrons
III. X is a high spin complex with two unpaired electrons
IV. Y is a low spin complex with 5 unpaired electrons
(A) I and III (B) I, II (C) I, II and IV (D) I, II and III
Ans. Bonus
K4[Mn(CN)6].3H2O  Mn with CN = 6 & SFL
2+
Sol.
 Pairing will take place ( t 221 00
2g e g )

25
  Low spin complex with one unpaired electron.
K4[Mn(SCN)6]  Mn with CN = 6 & WFL
2+

 Pairing will not take place ( t111 11

2g e g )

  High spin complex with five unpaired electrons.

So, only II statements is correct, which matches with none of given options. So, question should be
BONUS.
However, from the available options, (B) seem best.

65. The increasing reactivity of the sites (a-d) in the following compound is SN1 reaction is
Cl
d
Cl
c

a CHClCH3

Cl
(A) d > b > c > a (B) d > c > a > b (C) d > c > b > a (D) c > d > b > a
Ans. (C)
Sol. Rate of SN1 reaction  Stability of carbocation
Stability of carbocation
Cl Cl Cl

Cl  Cl Cl

> > >

CH–CH3 CH–CH3 CH–CH3 CH–CH3
 
Cl Cl Cl Cl Cl Cl

66. Which of the following has the shortest bond length ?

(A) O2 (B) O2 (C) O2 (D) O22

Ans. (D)
+
Sol. O2 (BO = 2.5; maximum in available options)
So, it will have shortest bond length.

67. Which of the following statement/s is/are correct about weak acids in aqueous solutions?
I. When pH = pKa of a monoprotic acid, 50% of the acid is ionised
II. If pH = pKa2 of a diprotic acid, the average charge of all the ionised species is 0.5
III. When pH = pKa + 1, 10% of the acid is ionised
IV. When pH = 7, 50% of a monibasic acid is ionised
(A) I and IV (B) I, II and IV (C) I, II and IV (D) I only
Ans. (D)
–
Sol. When pH = pKa of a monoprotic acid, [A ]eq = [HA]eq.
So, 50 % of acid is ionised.

26
 -1
68. 'Iodine number' is the grams of iodine atoms (atomic mass = 127 g mol ) that can react completely
with 100 g of a vegetable oil. Iodine monochloride (ICI) is a reagent used to determine iodine
3 –3
number. In an experiment, 25.00 cm of 0.100 mol dm ICI was added to 127g of the oil. The
3 -3
unreacted ICI was found to be equivalent to 40.00 cm of 0.10 mol dm of Na2S2O3.
The iodine number of the oil can be deduced as
(A) 127 (B) 100 (C) 200 (D) 50
Ans. Bonus
Sol. I-Cl used = 25 mL × 0.1 M = 2.5 mmol
meq of I-Cl left = meq of hypo reacted
= 40 mL × 0.1N
= 4 meq
4
 mmol of I-Cl left = = 2 mmol
2
Thus, mmol of I-Cl reacted with 127g vegetable oil = 2.5 – 2 = 0.5 mmol
100
Thus, mmol of ICl with 100g of oil = 0.5 mmol ×
127
Now, each mol of I-Cl contains 127 g of Iodine atoms.
50
Thus, mass of iodine atom that combines from I-Cl on vegetable oil = × 127 mg = 50 mg. =
127
0.05g
Note: (i) There seems to be an error in the printed paper.
I-Cl will add across C = C as follows :

C=C + I-Cl  I – C – C – Cl

As per the 'definition' offered in the paper, '50' may be the answer. However, going by the correct
standard definition of iodine number : instead of 1 mol of I-Cl, 1 mol of I2 can be added. Thus,
iodine number will be 100.
Final verdict : 68 : Bonus
3
Assuming the error of 10 is neglected,
(B) should be the answer (by standard definition).
(D) may be offered as answer, if the definition given in paper is taken as such.
Comment:
It is a potentially good but improperly worded question.

69. When NiO is doped with a small quantity of Li2O

(A) both cation and anion vacancies are generated
(B) Shottky defects are generated
(C) NiO becomes an n-type semiconductor
(D) NiO becomes a p-type semiconductor
Ans. (D)
2+ +
Sol. When NiO is doped with a small quantity of Li2O, a Ni can be expected to be replaced by 2Li . A
decrease in unpaired electrons would make NiO a p-type semiconductor.

27
70. When a sample of gas kept at 20ºC and 4.0 atm is heated to 40ºC at constant volume
(A) average speed of the gas molecules will decrease.
(B) number of collisions between the gas molecules per second will remain the same.
(C) average kinetic energy of the gas will increase.
(D) pressure of the gas will become 8 atm.
Ans. (C)
f
Sol. KE avg.  nRT
2
As T, KEavg. 

71. Addition of bromine to cis-3-hexene gives

(A) racemic dibromide
(B) a mixture of diastereomeric dibromides
(C) optically active dibromide
(D) meso dibromide
Ans. (A)

H5C2 Br H
H5C2 H5C2 H
C2H5  H C H  Br 
Br2
Sol. 2

CCl 5 2 ( anti addition )

4

H5C2 Br H

H H
Br C2H5 H5C2 Br
H5C2 Br Br C2H5
H H

Racemic mixture

72. An organic compound "X" forms an orange-yellow precipitate with 2,4-DNP reagent. It does not
react with aqueous [Ag(NH3)2] NO3. X on reduction with NaBH4 gives a secondary alcohol and on
oxidation with nitric acid yields a dicarboxylic acid containing the same number of carbon atoms.
On bromination, X gives a monobromo product. On the basis of these reactions, it can be
concluded that X
I. contains aldehydic carbonyl group.
II. contains ketonic carbonyl group.
III. contains ester carbonyl group.
IV. does not contain C=C bonds.
(A) I only (B) III and IV (C) III only (D) II and IV
Ans. (D)
Sol. An organic compounds 'X' forms and orange yellow precipitate with 2, 4-DNP reagent but does not
react with aqueous [Ag(NH3)2] NO3 confirms presence of C=O group in form of ketone.
'X' on reduction with NaBH4 gives secondary alcohol again suggests presence of ketone.
'X' on bromination gives mono bromo product which suggests absence of C=C bond because
in presence of C=C dibromo product would have been formed.

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73. The undissociated form of a weak organic acid HA can be extracted from the aqueous phase into
an organic phase using a water-immiscible organic solvent according to the following scheme
HA Organic phase
KD

Ka + – Aqueous phase
HA H +A
Which of the following is/are correct for this extraction?
I. [HA]org/[HA]aq depends on the pH of the aqueous phase
II. HA can be efficiently extracted from basic aqueous solutions
III. [HA]org/[HA]aq depends on the initial concentration of HA
–
IV. [HA]org/[HA]aq + [A ] depends on the pH of the aqueous phase
(A) II and IV (B) IV only (C) I only (D) III and IV
Ans. (B)

HA (org)

+ –
HA(aq) H +A
Sol. aqueous

Even if HA reacts / dissociates in any medium ;

HA ORG
= KD will be always a constant. .........(i)
HA  aq
Thus, I and III are wrong.
Now, consider (II). Adding more base will pull the aqueous equilibrium towards right side. Thus,
organic HA will be pulled towards aqueous phase. Hence, its extraction by organic phase will be
hampered.
Thus (ii) is wrong.
Obviously, only (iv) remains as the correct option. Hence (B) is the answer.
Comment :
H   A – 
Ka =
HA aq
Ka  A – 
=
H  HA aq
K a  H   A –   HA aq
 = ..................(ii)
H  HA aq
Dividing (i) by (ii) :
HA ORG K D H 
= = function of pH.
 A –   HA aq K a  H 

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74. The correct order of reactivity in nucleophilic substitution reaction of the following compounds a, b,
and c would be
CH3 CH2CONH2 CH3 CH2COOCH3 CH3 CH2COCl
(a) (b) (c)
(A) a > c > b (B) a > b > c (C) c > b > a (D) c > a > b
Ans. (C)
Sol. Correct order of reactivity in nucleophilic substitution at acid derivative depends on following
factors.
1.  + charge on C=O carbon
2. Inversely related to hinderance.
O O O
CH3–CH2–C–Cl > CH3–CH2–C–O–CH3 > CH3–C–NH2 (Order of + on C=O)
(–I) (+m) (+m)

75. The complex ion that does not have d electrons in the metal atom is
– 3+ 3– 3+
(A) [MnO4] (B) [Co(NH3)6] (C) [Fe(CN)6] (D) Cr(H2O)6]
Ans. (A)
MnO4 Mn (3d0)
– 7+
Sol.

76. The order in which the compounds a, b and c react with CH3l would be

N N
N N
(a) (b) (c)
(A) a > c > b (B) b > c > a (C) c > b > a (D) b > a > c
Ans. (B)
Sol. Order in which compounds a, b, c react with CH3–I would depend upon nucleophilicity.

N
> N
> N
undergoes amine inversion (flipping)
No flipping
so hinderance increases
nucleophilicity decreases.
77. An organic compound 'P' with molecular formula C9H8O2 on oxidation gives benzoic acid as one of
the products. the possible structure/s of 'P' is/are
COOH
COOH (CH2)2COOH

COOH

(I) (II) (III) (IV)

(A) I and III (B) II and IV (C) I and II (D) II only
Ans. (C)
Sol. Organic compound 'P' C9H8O2 degree of unsaturation 06 and on oxidation gives benzoic acid.
The possible structure/s of 'P' is/are.
CH2
C CH=CH–COOH
COOH

(I) (II)

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78. The energy of an electron in the ground state of H atom is -13 6eV.
The negative sign indicates that
(A) electrons are negatively charged.
(B) H atom is more stable than a free electron.
(C) energy of the electron in the H atom is lower than that of a free electron.
(D) work must be done to make a H atom from a free electron and proton.
Ans. (C)
Sol. The negative sign in energy of an electron indicates that energy of the electron in the H-atom is
lower than that of a free electron.

79. Radius of Ar atom is 145 pm. The percentage volume occupied by an Ar atom at STP is
(A) 0.03 (B) 3.0 (C) 0.30 (D) 0.06
Ans. (A)
4 22
  (1.45  10 8 )3  6.022  10 23
Sol. % 3 7  100
22400
= 0.034
 0.03

80. The reduction of O2 to H2O in acidic solution has a standard reduction potential of 1.23 V. If the pH
of the acid solution is increased by one unit, half cell potential will

O2(g) + 4H (aq) + 4e  2H2O(l)

+ –

(A) decrease by 59 mV
(B) increase by 59 mv
(C) decrease by 236 mV
(D) increase by 236 mV
Ans. (A)
0.059
Sol. E  E  log10 Qpc (at 25°C)
n
0.059 1
Ei  1.23  log10
4 (10  x )4
&
0.059 1
E f  1.23  log10  x 1 4
4 (10 )
 10  x 1 
E f  Ei  0.059 log10   = –0.059 V
 (10  x ) 
 
 E decreases by 59 mV

31