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Volume 26 No.

3 March 2017
Managing Editor Corporate Offi ce:
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CONTENTS Chemistry Musing Problem Set 44


JEE Main Practice Paper
NEET Practice Paper
8
10
17
BITSAT Practice Paper 24
JEE Advanced Practice Paper 31
AIIMS Practice Paper 40
Chemistry Musing Solution Set 43 51
Crossword 89
Class 11
Concept Map 52
NEET | JEE Essentials 54
Monthly Practice Paper (MPP) 65
Class 12
Concept Map 53
NEET | JEE Essentials 68
Ace Your Way CBSE (Practice Paper) 77
Monthly Practice Paper (MPP) 85

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CHEMISTRY TODAY | MARCH 17 7


CHEMISTRY MUSING
problem
seT 44

C hem istry M using w as started f rom A ugust ' 1 3 issue of C hem istry T oday. T he aim of C hem istry M using is to augm ent the
chances of bright students preparing f or J E E ( M ain and A dvanced) / N E E T / A I I M S / P M T s w ith additional study m aterial .
I n every issue of C hem istry T oday, 1 0 chal l enging probl em s are proposed in various topics of J E E ( M ain and A dvanced) /
N E E T . T he detail ed sol utions of these probl em s w il l be publ ished in next issue of C hem istry T oday.
The readers who have solved five or more problems may send their solutions. The names of those who send atleast five correct
sol utions w il l be publ ished in the next issue. We hope that our readers w il l enrich their probl em sol ving ski l l s through " C hem istry
M using" and stand in better stead w hil e f acing the com petitive exa m s.

jee main/neeT jee advanced


1. The iodine molecule dissociates into atoms after 6. An element crystallises in fcc lattice having edge
absorbing light of 4500 if one quantum of length 400 pm. The maximum diameter which can
radiation is absorbed by each molecule. The kinetic be placed in interstitial sites without disturbing the
energy of iodine atoms is structure is
(Bond energy of I2 = 240 kJ mol1) (a) 1.171 pm (b) 11.71 pm
(a) 21.6 1010 J (b) 21.6 1020 J (c) 117.1 pm (d) 0.117 pm
10
(c) 2.16 10 J (d) 2.16 1020 J comprehension
2. The major product in the following reaction is The process of settling of colloidal particles is known
O (i) CH3MgBr, dry ether, 0C as coagulation of the sol. The particles in any colloidal
Cl (ii) Aqueous acid sol carry a particular charge and can be coagulated by
CH3 adding suitable electrolytes. Generally, it is observed
OH
O that, greater the valency of the flocculating ion added,
(a) H3C (b) H2C CH greater is its power to coagulate. Lyophobic sols are
CH3 CH3 3 generally less stable but can be protected by lyophilic
CH3 colloids, called protective colloids. Their protective
(c) CH2 (d) powers are usually expressed in terms of gold number.
O O CH3
3. A colourless inorganic salt (A) decomposes 7. SnO2 is shaken with a small amount of NaOH
completely at about 523 K to give only two products solution to form a colloidal sol of sodium stannate.
(B) and (C) leaving no residue. The product (B) The sol thus obtained can be coagulated most easily
is a neutral gas while the product (C) is liquid at by
room temperature and is neutral to litmus. White (a) Na3PO4 (b) AlCl3
phosphorus burns in excess of (B) to produce a (c) K4[Fe(CN)6] (d) HCl
strong dehydrating agent, P4O10. The compounds 8. 50 mL of standard gold sol requires 0.1 g of potato
(A), (B) and (C) are respectively starch for its protection from coagulation. The gold
(a) NH4NO2, N2, H2O (b) NH4NO3, N2O, H2O number of potato starch is
(c) NH4Cl, NH3, NCl (d) NaNO3, O2, NaNO2 (a) 5 (b) 10 (c) 20 (d) 25
CO Br /KOH inTeger value
4. NH NaOH (I) 2 (II)
CO 9. The vapour pressure of pure benzene at a certain
In the above reaction sequence, II is temperature is 640 mm Hg. A non-volatile,
(a) b-alanine (b) a-alanine non-electrolyte solid weighing 2.175 g is added to
(c) ethylenediamine (d) g-aminobutyric acid. 39 g of benzene. The vapour pressure of the solution
5. An aqueous solution of a substance gives a white ppt. is 600 mm Hg. The molecular weight of the solid
on treatment with dilute hydrochloric acid which substance is 60 + 1.05 x. The value of x is
dissolves on heating. When hydrogen sulphide is 10. Consider the following list of reagents :
passed through the hot acidic solution, a black ppt. acidified K2Cr2O7, alkaline KMnO4, CuSO4, H2O2,
is obtained. The substance is a Cl2, O3, FeCl3, HNO3 and Na2S2O3
(a) Hg22+ salt (b) Cu2+ salt The total number of reagents that can oxidise
+
(c) Ag salt (d) Pb2+ salt. aqueous iodide to iodine is

8 CHEMISTRY TODAY | MARCH 17


CHEMISTRY TODAY | MARCH 17 9
ex a m da t e s
oF F line : 2 n d
ap r i l
th th
online : 8 & 9 ap r i l

1. A white solid (1) on heating evolves CO2 and gives (a) OA (b) OB (c) OC (d) OD
a white residue (2) which is soluble in water. (2) also
7. H2C2O4 gas (A) + gas (B) + liquid (C)

gives CO2 when treated with dilute acid. (1) and (2)
are respectively (Oxalic acid)
(a) Na2CO3 and NaHCO3 Gas (A) burns with a blue flame and is oxidised to
(b) NaHCO3 and Na2CO3 gas (B). Gas (B) turns lime water milky.
(c) CaCO3 and CaHCO3 Gas (A) + Cl2 (D)
 
(E)
(d) CaHCO3 and CaCO3 A, B, C, D and E are respectively
2. Aldol condensation will not be observed in (a) CO2, CO, H2O, HCOONH2, COCl2
(a) chloral (b) phenylacetaldehyde (b) CO, CO2, COCl2, H2O, HCOONH2
(c) hexanal (d) ethanal. (c) CO, CO2, H2O, COCl2, NH2CONH2
3. In a fcc lattice, atom A occupies the corner positions (d) CO, CO2, H2O, NH2CONH2, COCl2
and atom B occupies the face centred position. If
8. Square planar complexes of the type MABXL (where
one atom of B is missing from one of the face
A, B, X and L are unidentate ligands) shows
centred points, the formula of the compound is
(a) A2B (b) AB2 (c) A2B3 (d) A2B5 (a) two cis and one trans isomers
(b) two trans and one cis isomers
4. In acidic medium, KMnO4 oxidises FeSO4 solution.
(c) two cis and two trans isomers
Which of the following statements is correct?
(a) 10 mL of 1 N KMnO4 solution oxidises 10 mL (d) one cis and one trans isomers.
of 5 N FeSO4 solution. 9. One mole of an organic compound consumes
(b) 10 mL of 1 M KMnO4 solution oxidises 10 mL 4 moles of periodic acid to form HCHO, HCOOH
of 5 M FeSO4 solution. and CHOCOOH. Th e organic compound is
(c) 10 mL of 1 M KMnO4 solution oxidises 10 mL (a) glucose (b) fructose
of 1 M FeSO4 solution. (c) gluconic acid (d) sorbitol.
(d) 10 mL of 1 N KMnO4 solution oxidises 10 mL
of 0.1 M FeSO4 solution. 10. At constant temperature, the equilibrium constant
5. Th e polymer in which the intermolecular force of (Kp) for the decomposition reaction,
attraction is weakest, is N2O4 2NO2
(a) nylon (b) polyvinyl chloride is expressed by Kp = 4x2P/(1 x2), where P = pressure
(c) cellulose (d) natural rubber. and x = extent of decomposition. Which of the
6. Given, G = nFEcell and G = RT ln K. Th e following statements is true?
value of n = 2 will be given by the slope of which (a) Kp increases with increase in P.
line in the figure ? (b) Kp increases with increase in x.
(c) Kp increases with decrease in x.

1.0

0.5
 (d) Kp remains constant with change in P and x.
cell


 ln 

11. P

 
0.5  
 
 
1.0
Here P is


10 CHEMISTRY TODAY | MARCH 17


CHEMISTRY TODAY | MARCH 17 11
OD OD 18. n-Butylamine(I), diethylamine(II) and
HOOC D DOOC D N, N-dimethylethylamine(III) have the same molar
(a) (b) mass. The increasing order of their boiling points
is
OH OH
(a) III < II < I (b) I < II < III
DOOC D OOC D
(c) (d) (c) II < III < I (d) II < I < III
19. An organic compound (A) reacts with methyl
12. Ksp of Mg(OH)2 is 1 1012, 0.01 M MgCl2 will be magnesium iodide to form an addition product which
precipitating at the limiting pH on hydrolysis forms the compound (B). Compound
(a) 8 (b) 9 (c) 10 (d) 12
(B) gives blue colour salt in Victor Meyers test. The
13. A white crystalline solid (A) on boiling with caustic compound (A) and (B) are respectively
soda solution gave a gas (B) which when passed (a) acetaldehyde, tertiary butyl alcohol
through an alkaline solution of potassium mercuric (b) acetaldehyde, ethyl alcohol
iodide gave a brown ppt. The substance (A) on (c) acetaldehyde, isopropyl alcohol
heating gave a gas (C) which rekindled a glowing (d) acetone, isopropyl alcohol.
splinter but did not give brown fumes with nitric
oxide. The gases (B), (C) and the substance (A) 20. Aluminium chloride exists as dimer, Al2Cl6 in solid
respectively are state as well as in solution of non-polar solvents
(a) H2S, NO2, NaCl (b) NH3, N2O, NH4NO3 such as benzene. When dissolved in water, it gives
(c) HCl, NO, NH4Cl (d) CO2, SO2, Na2SO3 (a) [Al(OH)6]3 + HCl (b) [Al(H2O)6]3+ + Cl
14. One mole of magnesium in the vapour state (c) Al3+ + Cl (d) Al2O3 + HCl
absorbed 1200 kJ mol1 of energy. If the first and 21. The time required for 10% completion of a first
second ionisation energies of Mg are 750 and order reaction at 298 K is equal to that required for
1450 kJ mol1 respectively, the final composition of its 25% completion at 308 K. If the pre-exponential
the mixture is factor for the reaction is 3.56 109 s1, calculate its
(a) 31% Mg+ + 69% Mg2+ rate constant at 318 K.
(b) 69% Mg+ + 31% Mg2+
(a) 0.92 104 sec1 (b) 9.22 104 sec1
(c) 86% Mg+ + 14% Mg2+
(c) 92.2 104 sec1 (d) 92 104 sec1
(d) 14% Mg+ + 86% Mg2+
22. Match the lists I and II and pick the correct matching
15. If the molecular weight of Na2S2O3 and I2 are M1
and M2 respectively then what will be the equivalent from the codes given below.
weights of Na2S2O3 and I2 in the following reaction ? List I List II
(A) [Ag(CN)2] 1. Square planar and
2S2O32 + I2 S4O62 + 2I
1.73 B.M.
(a) M1, M2 (b) M1, M2/2 (B) [Cu(CN)4]3 2. Linear and zero
(c) 2M1, M2 (d) M1, 2M2
(C) [Cu(CN)6]4 3. Octahedral and zero
16. The ionisation energy of hydrogen atom (in the (D) [Cu(NH3)4]2+ 4. Tetrahedral and zero
ground state) is x kJ. The energy required for an (E) [Fe(CN)6] 4
5. Octahedral and
electron to jump from 2nd orbit to the 3rd orbit will 1.73 B.M.
be
(a) A 2, B 4, C 5, D 1, E 3
(a) x/6 (b) 5x (c) 7.2x (d) 5x/36
(b) A 5, B 4, C 1, D 3, E 2
17. 1 mole of a non ideal gas undergoes a change of state (c) A 1, B 3, C 4, D 2, E 5
(2.0 atm, 3.0 L, 95 K) (4.0 atm, 5.0 L, 245 K) (d) A 4, B 5, C 2, D 1, E 3.
with a change in internal energy, U = 30.0 L atm. The
change in enthalpy ( H) of the process (in L atm) is 23. 10 g atoms of an a-active radioactive isotope are
(a) 40.0 disintegrating in a sealed container. In one hour,
(b) 42.3 helium gas collected at STP is 11.2 cm3. The half-
(c) 44.0 life of the radioactive isotope is
(d) not defined because the pressure is not (a) 138.6 hr (b) 1386 hr
constant. (c) 13860 hr (d) 138600 hr

12 CHEMISTRY TODAY | MARCH 17


24. Match the column I with column II and mark the (a) CaCO3 CaO + CO2
appropriate choice. (b) 2C + O2 2CO
Column I Column II (c) C + O2 CO2
A. Self reduction P. Lead (d) Fe2O3 + 3CO 2Fe + 3CO2
B. Carbon reduction Q. Nickel 30. In the following reaction,
C. Thermal R. Copper Br
decomposition of + KOH(aq)
H
its carbonyl H
D. Decomposition of S. Titanium CH3
its iodide the product formed is
A B C D (a) (1R, 3R)-cis-3-methylcyclohexanol
(a) P, R P, S Q S (b) (1R, 3S)-cis-3-methylcyclohexanol
(b) P, S P, R Q S (c) (1S, 3R)-trans-3-methylcyclohexanol
(c) P, R P, R Q S (d) (1S, 3S)-trans-3-methylcyclohexanol.
(d) P, Q P, R Q S SOLUTIONS
25. Work done in expansion of an ideal gas from 1. (b) : 2NaHCO3

Na2CO3 + CO2 + H2O
4 L to 6 L against a constant external pressure of (1) (2) White residue,
2.5 atm was used to heat up 1 mole of water at soluble in water
293 K. If specific heat of water is 4.184 J g1 K1, Na2CO3 + 2HCl 2NaCl + CO2 + H2O
then the final temperature of water is (2) (dil.)
(a) 288 K (b) 299 K (c) 279 K (d) 267 K
2. (a) : Chloral (CCl3CHO) has no a-hydrogen atom
26. Arrange the following gem-diols in decreasing and hence, does not undergo aldol condensation.
order of their stability. 3. (d) : Atom A Atom B
OH OH 1 1 5
I. II. OH Z=8 =1 Z=5
OH
8 2 2
OH 5
III. A:B=1: 2:5
OH 2
(a) I > II > III (b) III > II > I So, formula of compound will be A2B5.
(c) I > III > II (d) III > I > II 4. (b) : 10 mL of 1 M KMnO4 oxidises 10 mL of 5 M
27. Aniline is treated with bromine water to give an FeSO4 in acidic medium.
organic compound X which when treated with 2KMnO4 + 8H2SO4 + 10FeSO4 K2SO4
NaNO2 and HCl at 0C gives a water soluble + 2MnSO4 + 5Fe2(SO4)3 + 8H2O
compound Y. Compound Y on treatment with 5. (d) : Natural rubber has the weakest intermolecular
Cu2Cl2 and HCl gives compound Z. Compound forces among the given i.e., van der Waals forces of
Z is attraction and is an example of an elastomer.
(a) o-bromochlorobenzene RT
(b) p-bromochlorobenzene 6. (b) : nFEcell = RT ln K or Ecell = ln K
nF
(c) 2, 4, 6-tribromophenol 1 RT
(d) 2, 4, 6-tribromochlorobenzene. Plot of ln K vs Ecell will have slope = (n = 2).
2 F
28. On addition of 1 mL solution of 10% NaCl to This will only be possible when Ecell = 0.5 which is
10 mL gold sol in the presence of 0.25 g of starch, for the line OB.
the coagulation is just prevented. Starch has the 7. (c) : H2C2O4

CO + CO2 + H2O
gold number ________. (A) (B) (C)
(a) 0.025 (b) 0.25 (c) 0.5 (d) 250 CO2 + Ca(OH)2 CaCO3 + H2O
(B) Lime water Milkiness
29. Which of the following reactions taking place
2NH3/
in the blast furnace during extraction of iron is CO + Cl2 COCl2 NH2CONH2
2 HCl
endothermic? (A) (D) (E)

CHEMISTRY TODAY | MARCH 17 13


A X A B A B 14. (b) : Energy absorbed in the ionisation of 1 mole of
8. (a) : M M M Mg(g) to Mg+(g) = 750 kJ
Energy unconsumed = 1200 750 = 450 kJ mol1
L B L X X L
trans cis cis This energy is required to convert Mg+(g) to Mg2+
(g).
Thus, square planar complex MABXL shows two cis 2+ 450 100
Thus, % of Mg (g) = = 31% and % of
and one trans isomers. 1450 1
9. (c) : CH CH CH CH CH COOH 4HIO4 Mg+(g) = 100 31 = 69%
2
OH OH OH OH OH 2 2 0 2. 5 2 1
HCHO + 3HCOOH + CHCOOH 15. (b) : 2 S2 O23 I2 S4 O26 2I
2
O.N. of S in S2O3 = 2x 6 = 2 or x = + 2
O
10. (d) : The equilibrium constant does not change at all O.N. of S in S4O62 = 4x 12 = 2 or x = + 2.5
with change in concentration, volume, pressure and Change in O.N. of S per mole = 0.5 2 = 1
presence of a catalyst. It changes only with change Similarly, change in O.N. of I per mole = 1 2 = 2
in temperature of the system. M
Therefore, eq. mass of Na2S2O3 = 1 = M1, and
OD O M 1
D NaOH D eq. mass of I2 = 2 .
11. (c) :
H H 2
16. (d) : (I.E)H = E E1 = E1 = x
intermediate K K
Put E1 = = K; K=x
2
O O n 12
H D CO H D K K 5 5
2 tautomerisation E = E3 E2 = K x
OOC 2 2 36 36
3 2
OH OH 17. (c) : H = U + PV
DOOC D

OOC D H1 = U1 + (2 3) = U1 + 6
D+
H2 = U2 + (4 5) = U2 + 20
(H2 H1) = (U2 U1) + (20 6)
(P)
H = U + 14 = 30 + 14 = 44 L atm
12. (b) : Mg(OH)2 Mg2+ + 2OH 18. (a) : H3CCH2CH2CH2NH2
S 2S
n-Butylamine (Primary amine)
Let S1 is the solubility in 0.01 M MgCl2 (common ion CH3CH2NHCH2CH3
Mg2+). [Mg2+] = (S1 + 0.01) 0.01; [OH] = 2S1 Diethylamine (Secondary amine)
1/2 1/2 (CH3)2NC2H5
K sp 10 12
Ksp = (0.01)(2S1)2 ; S1 = N, N-Dimethylethyl amine (Tertiary amine)
4 0.01 4 10 2 Primary amines have two hydrogen atoms available
= 0.5 105 M
for hydrogen bond formation, while 2 amines
[OH] = 2S1 = 2 0.5 105 = 105 M have only one hydrogen atom. 3 amines do not
pOH = 5, pH = 14 5 = 9 have intermolecular association due to absence
boiling of hydrogen atom. Thus, order of boiling points of
13. (b) : NH4NO3 + NaOH NaNO3 + NH3 + H2O
(A) (B) isomeric amines is as follows : 3 < 2 < 1 or III < II < I.
+
NH3 gives brown ppt. with Nesslers reagent (K2HgI4). OMgI
2K2[HgI4] + NH3 + 3KOH H2N HgO HgI 19. (c) : CH3CHO
CH3MgI
CH3 C CH3
Brown ppt. H+ /
Acetaldehyde H2O
+ 7KI + 2H2O H
(A) Adduct
(A) on heating gives N2O gas (C) which rekindles OH
a glowing splinter but is not converted into NO2 by Mg(OH)I + CH3 C CH3
air oxidation.
NH4NO3

N2O + 2H2O H
Isopropyl alcohol (2)
(A) (C)
(B)

14 CHEMISTRY TODAY | MARCH 17


2 alcohols give blue coloured salt in Victor Meyer NH2 NH2
test. Br2/H2O Br Br
20. (b) : Al2Cl6 + 12H2O 2[Al(H2O)6]3+ + 6Cl 27. (d) :
NaNO2/
2.303 100 2.303 100 Aniline 05C
21. (b) : Given, t = log10 = log10 Br HCl
k298 90 k308 75 (X) +
k308 Cl N2Cl

= 2.73
k298 Br Br Br Br
Cu2Cl2
k Ea [T2 T1 ]
Also, 2.303 log10 308 HCl
k298 R T1T2
Ea 10 Br Br
2.303 log10 2.73 = (Z) (Y)
8.314 298 308 2, 4, 6-Tribromo
Ea = 76.6227 kJ mol1 chlorobenzene
Now, k = AeEa/RT 28. (d) : By definition, gold number of starch is the
k318 = 3.56 109 e76622.7/(8.314 318) amount of starch in mg added to 10 mL standard
= 3.56 109 2.59 1013 = 9.22 104 sec1 gold sol which prevents the coagulation of gold
22. (a) on adding 1 mL of 10% NaCl solution. And, the
23. (c) : Gram atoms of helium gas formed in 1 hour amount of starch is 0.25 g = 250 mg. Hence, gold
11.2 number is 250.
= = 5 104
22400 29. (b) : 2C + O2 2CO; H = +ve,
i.e., Gram atoms of radioactive isotope disintegrated It is an endothermic reaction.
in one hour = 5 104
30. (d) : In SN2 reaction, inversion of configuration
Rate of disintegration = N
occurs.
5 104 = 10 or = 5 105 hr1
Br S 2 OH
0.693 0.693 1 + KOH(aq) N 1
t1/2 = hr = 13860 hr 3 H 3 H
5 10 5 H H
24. (c) : A P, R; B P, R; C Q; D S CH3 CH3
Self reduction and carbon reduction are carried out (1 , 3 )- -1-Bromo- (1 , 3 )- a -
3-methylcyclohexane 3-methylcyclohexanol
in case of Pb and Cu. Ni is purified by the thermal
decomposition of its carbonyl and Ti is purified
by the decomposition of its iodide at higher EXAM DATES 2017
temperature. SRMJEEE 1st April to 30th April (Online)
25. (b) : Since work is done against a constant pressure 2nd April (Offline)
JEE MAIN
thus, irreversible. 8th & 9th April (Online)

Given, V = (6 4) = 2 L, Pext = 2.5 atm VITEEE 5th April to 16th April (Online)

W = Pext V = 2.5 2 = 5 L atm NATA 16th April


WBJEE 23rd April
5 1.987 5 1.987 4.184
= cal = J = 506.31 J 24th April (Physics & Chemistry)
0.0821 0.0821 Kerala PET
25th April (Mathematics)
Now, this work is used in heating 1 mole of water. AMU (Engg.) 30th April
w=nC T C 4.184 J g K
1 1 2nd May (Biology & Mathematics)
Karnataka CET
506.31 = 1 4.184 18 T 1 3rd May (Physics & Chemistry)
4.184 18 J mol
T = 6.723 NEET 7th May
So, final temperature = T1 + T = 293 + 6.723 COMEDK (Engg.) 14th May
= 299.723 K BITSAT 16th May to 30th May (Online)
26. (a) : As the internal angle increases, steric hindrance JEE Advanced 21st May
increases and hence, the stability of the gem-diol J & K CET 27th May to 28th May

decreases. AIIMS 28th May

CHEMISTRY TODAY | MARCH 17 15


16 CHEMISTRY TODAY | MARCH 17
ex a m o n
7 t h ma y

1. The IUPAC name of the compound


(c) (d)
CONH2
N N
CHO is (CH3)2 (CH3)2
(a) 5-carbamoylhex-1-enal 6. Which of the following curves represents the curve
(b) 2-carbamoylhex-3-enal
of an ideal gas?
(c) 2-methyl-6-oxohex-3-enamide F
E D
(d) 6-keto-2-methylhexanamide.
2. The following two reactions of HNO3 with Zn are C
A
given as : B
PV

Zn + conc. HNO3 Zn(NO3)2 + X + H2O


Zn + dil. HNO3 Zn(NO3)2 + Y + H2O
The compounds X and Y respectively are O P
(a) NO2 and NO (b) NO2 and NO2
(a) B only (b) C and D only
(c) NO and NO2 (d) NO2 and NH4NO3
(c) E and F only (d) A and B only
3. Which of the following has highest molar
7. Which of the following species is the strongest
conductivity? base?
(a) Diamminedichloroplatinum(II)
(a) OH (b) OR
(b) Tetraamminedichlorocobalt(III) chloride
(c) Potassium hexacyanoferrate(II) (c) OC6H5 (d)
(d) Pentacarbonyliron(0) NO2
4. Sangers reagent is used for the identification of 8. We have three aqueous solutions of NaCl labelled
(a) N-terminal of a peptide chain as A, B and C with concentrations 0.1 M, 0.01 M
(b) C-terminal of a peptide chain and 0.001 M, respectively. The value of vant Hoff
(c) side chain of amino acids factor for these solutions will be in the order
(d) molecular mass of the peptide chain. (a) iA < iB < iC (b) iA > iB > iC
5. In the following reaction, (c) iA = iB = iC (d) iA < iB > iC

OH

X 9. For the reaction,
+
N 1
CH3 CH3 H2(g) + O2(g) H2O(l)
2
The organic product X is B.E.(H H) = x1; B.E.(O O) = x2 and B.E.(OH) = x3.
If the latent heat of vaporisation of water liquid into
(a) (b)
N water vapour = x4, then f H (heat of formation of
(CH3)2 liquid water) is

CHEMISTRY TODAY | MARCH 17 17


x 17. Identify the product of the following reaction.
(a) x1 + 2 x3 + x4 i. PhLi, Et2O
2 F
x * ii. H3O+
(b) 2x3 x1 2 x4
2 *
x2 Ph Ph
(c) x1 + 2x3 x4 (a) * (b)
2
x Ph * Ph
(d) x1 + 2 2x3 + x4 *
2 (c)
10. In the given reactions sequence,
NH4OH NH4OH H2S Ph
MSO4 X Y Z (d)
W hi t e Excess *
M and Z are respectively 18. The successive ionisation enthalpy values for an
(a) Zn, ZnS (b) Al, Al2 S3 element X are given as :
(c) Cu, ZnS (d) Fe, FeS 1st ionisation enthalpy = 410 kJ mol1
2nd ionisation enthalpy = 820 kJ mol1
11. If the equilibrium constant of BOH B+ + OH 3rd ionisation enthalpy = 1100 kJ mol1
at 25C is 2.5 106, then equilibrium constant for 4th ionisation enthalpy = 1500 kJ mol1
BOH + H+ B+ + H2O at the same temperature 5th ionisation enthalpy = 3200 kJ mol1
is Find out the number of valence electrons for the
(a) 4.0 109 (b) 4.0 105 atom X.
8
(c) 2.5 10 (d) 2.5 106 (a) 4 (b) 3 (c) 5 (d) 2
12. The product obtained when, 19. Phenol is distilled with Zn dust followed by
O FriedelCrafts alkylation with propyl chloride
is oxidised with HIO4 is
in the presence of AlCl3 to give a compound B.
OH
B is oxidised in the presence of air to form the
CHO COOH
(a) (b) compound C. The structural formula of C is
CHO CHO COOH
COOH CHO OH
(c) (d)
COOH CH2OH (a)
13. Which is finally produced when acetylene reacts H3 C
with HCl? C O O H
(a) CH2 CHCl (b) CH3CHCl2 H3 C
(c) ClCH CHCl (d) N one of t he s e (b)
14. An unknown element forms an oxide. What will be CH3
the equivalent weight of the element if the oxygen
content is 20% by weight? H3C C O O H
(a) 16 g (b) 32 g OH
(c) 8 g (d) 64 g (c)
15. The ligand called -acid is COOH
(a) CO (b) NH3
(c) C2O42 (d) ethylenediamine. (d)
16. Which of the following is an anti-aromatic 20. m(NH4OH) is equal to
compound? (a) m(NH4OH) + m(NH4Cl) m(HCl)
CH3
(a) (b) (b) m(NH4Cl) + m(NaOH) m(NaCl)
N
:

H (c) m(NH4Cl) + m(NaCl) m(NaOH)


(d) m(NaOH) + m(NaCl) m(NH4Cl)
(c) (d)

18 CHEMISTRY TODAY | MARCH 17


21. At the equilibrium position in the process of 28. Match the options given in column I with
adsorption column II.
(a) H > 0 (b) H = T S Column I Column II
(c) H > T S (d) H < T S P. Mathematical 1. rate constant
expression for rate
22. Distinction between primary, secondary and
of reaction
tertiary alcohols is done by
Q. Rate of reaction 2. rate law
(a) oxidation method for zero order
(b) Lucas test reaction is equal to
(c) Victor Meyer method R. Units of rate 3. order of
(d) all of these. constant for zero slowest step
23. The frequency of radiation emitted when the order reaction is
electron falls from n = 4 to n = 1 in a hydrogen atom same as that of
will be S. Order of a 4. rate of the reaction
(a) 3.08 1015 s1 (b) 2.00 1015 s1 complex reaction
(c) 1.54 1015 s1 (d) 1.03 1015 s1 is determined by
P Q R S
24. The packing efficiency of the two (a) 1 2 4 3
dimensional square unit cell shown (b) 3 4 1 2
is (c) 2 1 4 3
(a) 39.27% (b) 68.02% (d) 2 1 3 4
(c) 74.05% (d) 78.54%
29. The thermal stability of the hydrides of O, S, Se and
25. In Ramsay and Rayleighs isolation of noble gases Te varies in the order
from air, the nitrogen of the air is finally converted (a) H2Te > H2Se > H2S > H2O
into (b) H2O > H2S > H2Se > H2Te
(a) NaNO2 only (b) NO and NO2 (c) H2O > H2Se > H2Te > H2S
(c) NaNO3 only (d) NaNO2 and NaNO3 (d) H2S > H2O > H2Se > H2Te
26. The gold number of some colloidal solutions are 30. Which of the following amino acids can be used to
given as : synthesise the given tripeptide ?
Colloidal solution Gold number Me H
H O O
A 0.01 H2N
N N OH
B 2.5
C 20 H H O
The protective nature of these colloidal solutions (a) Glycine, leucine and alanine
follows the order (b) Alanine, isoleucine and glycine
(a) C > B > A (b) A > B > C (c) Valine, alanine and glycine
(c) A = B = C (d) B > A > C (d) Alanine, serine and glycine
27. CH3CH2NH2 contains a basic NH2 group, but 31. In the anion HCOO the two carbon-oxygen bonds
CH3CONH2 does not are found to be of equal length because
(a) acetamide is amphoteric in character (a) the C O bond is weaker than the CO bond
(b) in ethyl amine the electron pair on N-atom is (b) the anion HCOO shows resonance
delocalised by resonance (c) the anion is obtained by removal of a proton
(c) in ethyl amine there is no resonance while from the acid molecule
in acetamide the lone pair of electrons on (d) the electronic orbitals of carbon atom are
N-atom is delocalised and is less available for hybridised.
protonation 32. In chromic acid anhydride (CrO3), Cr has d0
(d) all of these. configuration but it is bright orange coloured solid,
the colour is due to

CHEMISTRY TODAY | MARCH 17 19


(a) d-d transition (a) (i), (ii), (iii) and (iv)
(b) charge transfer (L M) transition (b) (ii), (iv) and (v)
(c) charge transfer (M L) transition (c) (i) and (iii)
(d) p-d transition. (d) (ii), (iii) and (iv)
33. A cylinder filled with a movable piston contains 39. When excess of KI is added to aqueous CuSO4, the
liquid water in equilibrium with water vapours at solution acquires dark brown colouration. This is
25C. Which one of the following operations results due to the formation of
in a decrease in the equilibrium vapour pressure? (a) CuI2(s) (b) Cu2I2(s)
(a) Moving the piston downward a short distance
(c) I 3(aq) (d) I2(s)
(b) Removing a small amount of vapour
(c) Removing a small amount of the liquid water 40. Reaction by which benzaldehyde cannot be
(d) Dissolving salt in the water prepared is
34. The carbohydrate that yields glucose and galactose (a) + CO + HCl in presence of anhydrous AlCl3
on acid hydrolysis is
(a) sucrose (b) lactose (b) + Zn/Hg and conc. HCl
(c) maltose (d) starch.
35. During enolisation of the following compound, (c) + CrO2Cl2 in CS2 followed by H3O+
which of the labelled hydrogen is involved?
O
H (d) + H2 in presence of Pd-BaSO4

H 41. Hydrazine reacts with KIO3 in presence of HCl as


H N2H4 + IO3 + 2H+ + Cl ICl + N2 + 3H2O
The equivalent masses of N2H4 and KIO3
(a) Ha (b) Hb
respectively are
(c) Hg (d) Any of the three
(a) 16 and 87 (b) 16 and 53.5
36. The correct order of the ligands, OH , NO3 , PPh3 , (c) 8 and 53.5 (d) 8 and 87
pyridine, according to their increasing field strength
is 42. Match the polymers given in column I with their
(a) NO3 < OH < pyridine < PPh3 chemical names given in column II.
(b) OH < NO3 < PPh3 < pyridine Column I Column II
(c) OH < NO3 < pyridine < PPh3 P. Nylon 6 1. Polyvinyl chloride
(d) NO3 < OH < PPh3 < pyridine Q. PVC 2. Polyacrylonitrile
37. A scarlet compound (A) Pb3O4 gives a chocolate R. Acrilan 3. Polycaprolactum
brown ppt. (B) and a colourless solution (C) with S. Natural rubber 4. cis-Polyisoprene
HNO3. The brown ppt. (B) is of P Q R S
(a) PbO2 (b) 2Pb(NO3)2 (a) 1 2 3 4
(c) PbO (d) none of these. (b) 4 3 1 2
(c) 3 1 4 2
38. Consider the following sets of quantum numbers :
(d) 3 1 2 4
n l m s
(i) 3 0 0 +1/2 43. Which of the following will not show geometrical
(ii) 2 2 1 +1/2 isomerism?
F
(iii) 4 3 2 1/2 (a) C C
(iv) 1 0 1 1/2 Cl
(v) 3 2 3 +1/2 F F
Which of the following sets of quantum number is (b) C C
not possible? Cl Cl

20 CHEMISTRY TODAY | MARCH 17


H3 C C2H5 9. (c) : f H = (B.E.)reactants (B.E.)products
(c) C C But all the species must be in gaseous state, so in product
H5C2 CH3 [H2O(l) H2O(g)] Hvap must be added.
H3C CH3 1
Hence for the reaction, H2(g) + O2(g) H2O(l)
(d) C C 2
H3C C2H5 1
f H = ( B.E.)H H (B.E.)O == O
44. Following data is given at 25C, 2
Ag + I AgI + e ; E = 0.152 V [ Hvap + 2(B.E.)OH]
Ag Ag + e ; E = 0.800 V
+
x2 x
What is the value of log Ksp for AgI? = x1 + [x4 + 2x3] x1 + 2 x4 2x3
2 2
(a) 37.83 (b) 16.13 NH4OH
10. (a) : ZnSO4 Zn(OH)2
(c) 8.12 (d) + 8.612
(X)
45. Antiseptic action of dettol is due to
H2S
(a) 4-chloro-3, 5-dimethylphenol ZnS Clear solution
(b) 3-chloro-4, 5-dimethylphenol Thus, M is Zn.
(Z) (Y)
(c) 4-chloro-2, 5-dimethylphenol
11. (c) : BOH B+ + OH; (Kb = 2.5 106)
(d) 5-chloro-3, 4-dimethylphenol.
1
SOLUTIONS H+ + OH H2O; K
Kw
1
CONH2 6
4 BOH + H+ B+ + H2O; K = ?
1. (c) : 2
CHO
3 5 1 2.5 10 6
2-Methyl-6-oxohex-3-enamide
K = Kb = 2.5 108
Kw 14
10
2. (d) : Zn + 4HNO3 (conc.) Zn(NO3)2 + 2NO2 O HIO4 COOH
+ 2H2O 12. (b) :
oxidation CHO
4Zn + 10HNO3(dil.) 4Zn(NO3)2 + NH4NO3 OH
+ 3H2O HCl
13. (b) : CH CH + HCl CH2 CHCl
+ 4
3. (c) : K4[Fe(CN)6] 4K + [Fe(CN)6] CH3CHCl2
Potassium hexacyanoferrate(II) gives a total of 14. (b) : Given that oxygen content is 20% by weight,
5 ions in aqueous solution thus, it has the highest then
molar conductivity whereas other complexes will 80
give lesser number of ions. eq. wt. of unknown element = 8 g = 32 g
20
4. (a) : Sangers reagent is used for the identification of 15. (a)
N-terminal residue of a polypeptide. 16. (c) : Planar conjugated cyclic compounds
H
5. (c) : containing 4n electrons are anti-aromatic, e.g.,
OH (Hofmann cyclooctatetraene (8 es).
+
N elimination) N(CH3)2
H3 C CH3 17. (c) :
6. (a) : For curve B, the value of PV is constant and for
an ideal gas, plot of PV vs P is a straight line, parallel
to x-axis.
7. (b) : OR is the strongest base since R (alkyl) group
is an electron releasing group which increases
electron density on oxygen.
8. (c) : The value of vant Hoff factor for the given
solutions will be the same, i.e., iA = iB = iC due to
complete dissociation of NaCl (strong electrolyte) 18. (a) : Removal of 5th electron requires almost more
in dilute solutions. On complete dissociation value than double the energy required for removing 4th
of i for NaCl is 2. electron. Therefore, the valence electrons should be 4.

CHEMISTRY TODAY | MARCH 17 21


OH CH3 CH CH3 29. (b) : Thermal stability decreases as the size of atom
Zn AlCl3 increases (down the group). Thus, H2O is most
19. (b) : stable and H2Te is least stable.
 CH3CH2CH2Cl
Phenol H3C (B) 30. (c) :
C O O H
H3C
O2

(C)
20. (b) : NH4Cl NH4+ + Cl ...(i)
+
NaCl Na + Cl ...(ii)
NaOH Na+ + OH ...(iii)
+
NH4OH NH4 + OH ...(iv)
Applying (i) + (iii) (ii) to get the equation (iv),

m(NH 4Cl)
+ m(NaOH)
m(NaCl)
= m(NH
4OH)
21. (b) : At equilibrium during adsorption, G = 0
and H becomes equal to T S. 31. (b) : As the anion HCOO has two resonating
22. (d) structures, so the carbon-oxygen bonds are found
to be of equal length.
2.18 10 18
23. (a) : En = J atom1 O O O
n2
18 1 1 H C O H C O H C O
E = E4 E1 = 2.18 10 1.27
42 12
32. (b) : The colour of CrO3 (d0 configuration) is due
= 2.18 1018 ( 0.9375) 2.043 1018 J atom1
to charge transfer from ligand (oxygen) to metal
Also, E = hv
(chromium) and not due to d-d transition.
E 2.043 10 18
v= = 3.08 1015 s1 33. (d) : Dissolving salt in a solvent or liquid lowers the
h 34
6.625 10 vapour pressure.
34. (b) : Lactose on hydrolysis with acetic acid gives
24. (d) : 4R = L 2
R glucose and galactose.
so, L = 2 2R
35. (c) : Hg being located on a saturated carbon is more
Area of square unit cell = (2 2R)2
labile than Ha and Hb and hence, is involved in
= 8R2 L
enolisation.
Area of atoms present in one unit cell
H O O H
R2
= R2 + 4 = 2 R2
4 H H H H
2 R2
So, packing efficiency = 100 100 36. (a) : N O 3< O H < P y< P P h 3
2 4
8R W e a k S t r ong
78.54% field field
ligand ligand
25. (d) : Nitrogen is finally converted into NaNO2 and
NaNO3 in Ramsay and Rayleighs method. 37. (a) : P b 3O 4 + 4H N O 3 PbO2 + 2Pb(NO3)2
N2 + O2 2NO Scarlet Brown Colourless
compound ppt. solution
2NO + O2 2NO2 (A) (B) (C)
2NO2 + 2NaOH NaNO2 + NaNO3 + H2O + 2H2O
26. (b) : Higher the gold number, lower will be the 38. (b) : (i) represents an electron in 3s orbital.
protective power of a colloidal solution. (ii) is not possible as value of l varies from 0 to (n 1).
27. (c) 28. (c) (iii) represents an electron in 4f orbital.

22 CHEMISTRY TODAY | MARCH 17


( iv ) is n o t p o s s ib le a s v a lu e o f mv a r ie s f r o m l t o + l.
43. (d) : will not show geometrical
( v) i s not pos s i bl e a s va l ue fo m av r i e s f r om l t o + l,
i t c a ne ev r be rg e a t e r t ah n l. isomerism due to the presence of similar alkyl
39. (c) : 2CuSO4 + 4KI Cu2I2 + 2K2SO4 + I2 ; groups on the same carbon atom of double bond.
I2(s) + I(aq) I3(aq) 44. (b) : Ag + I AgI + e, E1 = 0.152 V
(dark Ag+ + e Ag, E2 = 0.800 V
brown)
Ag+ + I AgI, E = 0.952 V
40. (b) : Zn-Hg and conc. HCl reduces aldehydes 2.303RT
and ketones but carboxylic acid group remains At equilibrium, E = log Kc
F
unaffected. [AgI] 1
41. (c) : O.N. of N in N2H4 is 2 which changes to 0 in But Kc =
[Ag ][I ] K sp
N2.
2.303RT
molar mass 32 0.952 = log Ksp = 0.059 log Ksp
Hence, eq. mass of N2H4 = =8 F
2 2 4 or log Ksp = 16.13
O.N. of iodine changes from +5 in IO3 to +1 in ICl.
molar mass 214 45. (a) : 4-Chloro-3,5-dimethylphenol, also called
Hence, eq. mass of KIO3 = = 53.5 chloroxylenol has antiseptic properties.
4 4
42. (d)

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CHEMISTRY TODAY | MARCH 17 23


1. Which of the following reactions show the reducing 6. Which of the following complexes formed by Cu2+
property of hydrochloric acid? ions is most stable?
(a) ZnCO3 + 2HCl ZnCl2 + H2O + CO2 (a) Cu2+ 4 NH3 [Cu(NH3 )4 ]2 ; log K = 11.6
(b) Mg + 2HCl MgCl2 + H2 (b) Cu2 4CN [Cu(CN)4 ]2 ; log K = 27.3
(c) MnO2 + 4HCl MnCl2 + 2H2O + Cl2 (c) Cu2 2en [Cu(en)2 ]2 ; log K = 15.4
(d) NH4OH + HCl NH4Cl + H2O
(d) Cu2 4 H2 O [Cu(H2O)4 ]2 ; log K = 8.9
2. Reduction potentials of some ions are given below.
7. The correct decreasing order of acidic character is
Arrange them in decreasing order of oxidising (a) HClO > HBrO > HIO
power. (b) HIO > HBrO > HClO
Ion ClO4 IO4 BrO4 (c) HBrO > HIO > HClO
(d) HClO > HIO > HBrO
Reduction potential (E) 1.19 V 1.65 V 1.74 V
8. Cellulose, the most important constituent of plant
(a) ClO4 > IO4 > BrO4 (b) IO4 > BrO4 > ClO4 cell wall, is made up of
(c) BrO4 > IO4 > ClO4 (d) BrO4 > ClO4 > IO4 (a) branched chain of glucose molecules linked
3. Which of the following will not give iodoform test? by a (1 6) glycosidic bonds at the site of
branching
(a) n-Butyl alcohol (b) sec-Butyl alcohol
(b) unbranched chain of glucose molecules linked
(c) Acetophenone (d) Acetaldehyde
by a (1 4) glycosidic bonds
4. Energy of an electron in hydrogen atom is given (c) branched chain of glucose molecules linked by
13.6
by E eV. Which one of the following b (1 4) glycosidic bond in straight chain
n2 and a (1 6) glycosidic bond at the site of
statements is true if n is changed from 1 to 3? branching
Energy will (d) unbranched chain of glucose molecules linked
(a) decrease three times (b) increase three times by b (1 4) glycosidic bonds.
(c) increase nine times (d) decrease nine times.
9. 1.020 g of metallic oxide contains 0.540 g of
5. In the coagulation of a positive sol, the flocculation the metal. If the specific heat of the metal, M is
powers of Cl, SO42, PO43 and [Fe(CN)6]4 are in 0.216 cal deg1g1, the molecular formula of its
the order oxide is
(a) Cl SO24 [Fe(CN)6 ]4 PO34 (a) MO (b) M2O3 (c) M2O4 (d) M2O

PO34 SO24 [Fe(CN)6 ]4 10. The most stable conformation of chlorocyclohexane


(b) Cl
at room temperature is
(c) [Fe(CN)6 ]4 PO34 SO24 Cl Cl H
H Cl
(d) Cl SO24 PO34 [Fe(CN)6 ]4
(a) (b)

24 CHEMISTRY TODAY | MARCH 17


17. Polarity in a molecule and hence, the dipole moment
(c) (d) depends primarily on electronegativity of the
H Cl constituent atoms and shape of a molecule. Which
Cl H of the following has the highest dipole moment?
11. Identify the correct statement for change in (a) CO2 (b) HI (c) H2O (d) SO2
Gibbs energy for a system ( Gsystem) at constant 18. The rapid change of pH near the stoichiometric
temperature and pressure. point of an acid-base titration is the basis of
(a) If Gsystem = 0, the system has attained indicator detection. pH of the solution is related
equilibrium. to the ratio of the concentration of conjugate acid
(b) If Gsystem = 0, the system is still moving in a (HIn) and base (In) forms of the indicator by the
particular direction. expression
(c) If Gsystem = 0, the process is not spontaneous. [In ]
(a) log pK a pH
(d) If Gsystem = 0, the process is spontaneous. [HIn]
12. The emf of the three galvanic cells given below are [HIn]
(b) log K a pH
represented by E1, E2 and E3. [In ]
I. Zn | Zn2+ (1 M) || Cu2+ (1 M) | Cu [HIn]
II. Zn | Zn2+ (0.1 M) || Cu2+ (1 M) | Cu (c) log pH pK a
[In ]
III. Zn | Zn2+ (1 M) || Cu2+ (0.1 M) | Cu
[In ]
Which of the following is true? (d) log pH pK a
(a) E1 > E2 > E3 (b) E3 > E2 > E1 [HIn]
(c) E3 > E1 > E2 (d) E2 > E1 > E3 19. Correct set of four quantum numbers for the
valence (outermost) electron of rubidium (Z = 37)
13. 1500 mL flask contains 400 mg O2 and 60 mg H2 at is
100C. What is the total pressure in the flask? 1 1
(a) 0.66 atm (b) 0.867 atm (a) 5, 0, 0, (b) 5, 1, 0,
2 2
(c) 8.67 atm (d) 13.47 atm 1 1
(c) 5, 1, 1, (d) 6, 0, 0,
14. Which of the following does not represent the 2 2
correct order of the property indicated? 20. If Ksp[AgCNS] = 1 10 and Ksp[AgBr] = 5 1013
12
(a) Sc3+ > Cr3+ > Fe3+ > Mn3+ : Ionic radii then the value of simultaneous solubility of AgCNS
(b) Sc < Ti < Cr < Mn : Density and AgBr in a solution of water will be
2+ 2+ 2+ 2+
(c) Mn > Ni < Co < Fe : Ionic radii (a) 8.16 107, 4.08 107
(d) FeO < CaO > MnO > CuO : Basic nature (b) 4.08 107, 8.16 107
15. A red coloured oxide (X) on treatment with (c) 8.16, 4.08
conc. HNO3 gives a compound (Y). (Y) with HCl (d) 1 1012, 5 1013
produces a chloride (Z) which is insoluble in cold 21. Which of the following reactions depicts the
water but soluble in hot water. (Z) can also be oxidising property of SO2?
formed by treating (X) with conc. HCl. Compounds (a) SO2 + H2O H2SO3
X, Y and Z are (b) 2H2S + SO2 3S + 2H2O
(a) Pb3O4, PbO2, PbCl2 (c) Cl2 + SO2 SO2Cl2
(b) Mn3O4, MnO2, MnCl2 (d) 2MnO4 5SO2 + 2H2O 5SO42 + 2Mn2+ + 4H+
(c) Fe3O4, Fe2O3, FeCl3 22. 500 mL of a hydrocarbon gas burnt in excess of
(d) Fe3O4, FeO, FeCl2 oxygen yielded 2500 mL of CO2 and 3.0 L of water
16. Which is not true about the coordination compound vapour. The formula of the hydrocarbon is
[Co(en)2Cl2]Cl? (a) C5H12 (b) CH4 (c) C2H4 (d) C3H6
(a) It exhibits geometrical isomerism. 23. The compound in which carbon uses only sp3-hybrid
(b) It exhibits optical isomerism. orbitals for bond formation is
(c) It exhibits ionisation isomerism. (a) (CH3)3C CHO (b) (CH3)3C OH
(d) It is an octahedral complex. (c) NH2CONH2 (d) HCOOH

CHEMISTRY TODAY | MARCH 17 25


24. Which among the following is aromatic? 31. The vapour pressure of benzene at a certain
temperature is 640 mm of Hg. A non-volatile and
(a) (b) non-electrolyte solid weighing 2.175 g is added
to 39.08 g of benzene. The vapour pressure of the

solution is 600 mm of Hg. What is the molecular
(c) (d) weight of solid substance?
(a) 59.5 g mol1 (b) 69.5 g mol1
25. RCH2CH2OH can be converted to RCH2CH2COOH (c) 79.6 g mol1 (d) 79.9 g mol1
by the following sequence of reagents. 32. The two isomers X and Y with the formula
(a) PBr3, KCN, H3O+ (b) PBr3, KCN, H2/Pt Cr(H2O)5ClBr2 were taken for experiment on
(c) KCN, H3O+ (d) HCN, PBr3, H3O+ depression in freezing point. It was found that one
26. Which of the following statements is not true? mole of X gave depression corresponding to 2 moles
(a) London smog is a mixture of smoke and fog. of particles and one mole of Y gave depression due
(b) London smog is oxidising in nature. to 3 moles of particles. The structural formulae of X
and Y respectively are
(c) Photochemical smog causes irritation in eyes.
(a) [Cr(H2O)5Cl]Br2; [Cr(H2O)4Br2]Cl. H2O
(d) Photochemical smog results in the formation of
(b) [Cr(H2O)5Cl]Br2; [Cr(H2O)3ClBr2] . 2 H2O
PAN. (c) [Cr(H2O)5Br]BrCl; [Cr(H2O)4ClBr]Br. H2O
27. An element with molar mass 2.7 102 kg mol1 (d) [Cr(H2O)4Br2]Cl.H2O; [Cr(H2O)5Cl]Br2
forms a cubic unit cell with edge length 405 pm. If 33. The correct order of basicities of the following
its density is 2.7 103 kg m3, what is the nature of compounds is
the cubic unit cell?
(a) Simple cubic (b) Face-centred CH3CH2NH2
(c) Body-centred (d) End-centred (II)
O
28. The ease of dehydrohalogenation with alcoholic KOH
in case of 1-Chloroethane (I), 2-Chloropropane (II) CH3 C NH2
and 2-Chloro-2-methylpropane (III) is of the order (IV)
(a) III > II > I (b) I > II > III (a) II > I > III > IV (b) I > III > II > IV
(c) II > I > III (d) I > III > II (c) III > I > II > IV (d) I > II > III > IV
29. The correct order of reactivity towards electrophilic 34. In complex hydrides, hydride ions act as ligand
substitution is and are coordinated to metal ions. These hydrides
(a) benzene > phenol > benzoic acid > are good reducing agents. Which of the following
chlorobenzene hydrides is not a complex hydride?
(b) phenol > benzene > chlorobenzene > benzoic (a) LiAlH4 (b) NaBH4
acid (c) (AlH3)n (d) LiBH4
(c) chlorobenzene > benzoic acid > phenol > 35. Match the column I with column II and mark the
benzene appropriate choice.
(d) benzoic acid > chlorobenzene > benzene > Column II
phenol. Column I (Property)
(Metal)
30. For a reaction, 2K(g) + L(g) 2M(g) ; U = 10.5 kJ (A) Element with highest second (i) Cr
and S = 44.1 J K1. Calculate G for the ionisation enthalpy
reaction and predict whether the reaction will be (B) Element with highest third (ii) Cu
spontaneous or non-spontaneous? ionisation enthalpy
(a) G = + 0.16 kJ, non-spontaneous
(C) M in M(CO)6 is (iii) Zn
(b) G = 0.16 kJ, spontaneous
(c) G = + 26.12 kJ, non-spontaneous (D) Element with highest heat of (iv) Ni
(d) G = 26.12 kJ, spontaneous atomisation

26 CHEMISTRY TODAY | MARCH 17


(a) (A) (ii), (B) (iii), (C) (i), (D) (iv) species, greater is its tendency to undergo reduction
(b) (A) (iv), (B) (iii), (C) (i), (D) (ii) and stronger is the oxidising power.
(c) (A) (iii), (B) (i), (C) (ii), (D) (iv) BrO4 > IO4 > ClO4
(d) (A) (i), (B) (ii), (C) (iii), (D) (iv) E/V 1.74 1.65 1.19

36. The DielsAlder reaction between 1,3-cyclohexa- 3. (a) : Iodoform test is given by the compounds
containing CH3CO group or CH3CH(OH)
diene and acrylonitrile gives the adduct,
group (which is oxidised to CH3CO group).
Sample is heated with I2 and NaOH, the
existence of yellow ppt. indicates the presence of
CH3CO group or CH3CH(OH) group.
CN
e.g., CH3CHO + 3I2 + 4NaOH
Its IUPAC name is
CHI3 + HCOONa + 3NaI + 3H2O
(a) bicyclo [2.2.2] oct-2-en-5-nitrile Iodoform
(b) bicyclo [2.2.2] oct-5-en-2-carbonitrile (yellow ppt.)
(c) 3-cyano bicyclo [2.2.2] oct-5-ene [O] I2
CH3CH2OH CH3CHO NaOH CHI3
(d) 2-cyano bicyclo [2.2.2] oct-5-ene.
n-Butyl alcohol (CH3CH2CH2CH2OH) does
37. Give the decreasing order of reactivities of the
not give iodoform test as it does not possess the
following monomers towards cationic addition
CH3CO or CH3CH(OH) group.
polymerisation. 1
I. MeCH CH2 II. PhCH CH2 4. (d) : E i.e., when n = 3; E decreases nine
n2
III. CH2 CHCOOMe IV. CH2 CHCl times.
(a) I > II > III > IV (b) II > I > IV > III 5. (c) : According to HardySchulze rule, the
(c) II > I > III > IV (d) I > II > IV > III flocculation power is directly proportional to the
38. For which of the following amino acids, van-Slyke charge. Thus, correct order is :
estimation method is not applicable? [Fe(CN)6 ]4 PO34 SO24 Cl
(a) Alanine (b) Aspartic acid 6. (b) : Stability of a complex depends upon the value
(c) Serine (d) Proline of stability constant. Higher the value of K, more
39. The appropriate reagent for the transformation stable is the complex. Since, K is highest when log K
is 27.3.
Thus, [Cu(CN)4]2 is the most stable complex
among the given complexes.
7. (a) : Acidity decreases as the electronegativity of
the central halogen decreases from Cl to I in HXO
(a) Zn-Hg, HCl (b) NH2NH2, OH
(c) H2/Ni (d) NaBH4 (oxoacids).
8. (d)
40. Which of the following sets of reactants is used for
the preparation of paracetamol from phenol? 9. (b) : Mass of oxygen in the oxide
(a) HNO3, H2/Pd, (CH3CO)2O = (1.020 0.540) = 0.480 g
(b) H2SO4, H2/Pd, (CH3CO)2O 0.540
Equivalent mass of the metal 8 9. 0
(c) C6H5N2Cl, SnCl2/HCl, (CH3CO)2O 0.480
(d) Br2/H2O,Zn/HCl, (CH3CO)2O According to Dulong and Petits law,
6. 4 6. 4
SOLUTIONS Approx. atomic mass 29.63
sp. heat 0.216
1. (c) : HCl is oxidised by strong oxidising agents
like manganese dioxide, lead dioxide, potassium at. mass 29.63
Valency of the metal 3
permanganate, potassium dichromate, etc. hence, eq. mass 9. 0
acts as a reducing agent. Hence, the formula of the oxide is M2O3.
MnO2 + 4HCl MnCl2 + 2H2O + Cl2 10. (d) : In this conformer Cl is at equatorial position
2. (c) : Higher the reduction potential value of a and is least hindered.

CHEMISTRY TODAY | MARCH 17 27


11. (a) : When Gsys = 0, the system is in equilibrium.
RT [Zn2 ]
12. (d) : Ecell E cell ln
nF [Cu2 ]
[Zn2+ ]
For I, 1, Ecell = Ecell
[Cu2 ]
[Zn2+ ]0. 1
For II,
2
[Cu ] 1
0.0591 0.0591
Ecell Ecell log 10 1 Ecell
n n
2+
[Zn ] 1
For III, 10
[Cu2 ] 0.1
0.0591 0.0591
Ecell Ecell log 10 Ecell
n n
E2 > E1 > E3 17. (c) : CO2 being symmetrical has zero dipole
w 400 10 3 moment. Among HI, SO2 and H2O, dipole moment
13. (b) : Number of moles of 2 is highest for H2O as the central atom in it contains
M 32
= 0.0125 2 lone pairs.
w 60 10 3
Number of moles of H2 0.03
M 2
From, pV = nRT,
0.0125 0.0821 373 18. (d) : For HIn H+ + In
Partial pressure of O2
1500 10 3 [H ][In ]
Ka
= 0.255 atm [HIn]
0.03 0.0821 373 [In ]
Partial pressure of H2 pH pK a log
1500 10 3 [HIn]
= 0.612 atm [In ]
or pH pK a log
Total pressure = 0.255 + 0.612 = 0.867 atm [HIn]
14. (a) : Ionic radius of Fe3+ (0.64 ) is less than that of 19. (a) : The electronic configuration of Rb is [Kr] 5s1
Mn3+ (0.66 ). Other properties vary as indicated. Thus, its valence electron enters in 5s-orbital.
15. (a) : Compound X, Y and Z are Pb3O4, PbO2 and For 5s orbital, n = 5
PbCl2. l = 0 (as orbital is s)
Pb3O4 4HNO3 2Pb(NO3 )2 + PbO2 + 2H2O 1
m = l to +l including zero, m = 0 ; s
(X) (Y ) 2
PbO2 + 4HCl PbCl2 + 2H2O + Cl2 Thus, the correct set of quantum numbers for the
(Z) 1
PbCl2 is insoluble in cold water but soluble in hot valence electron of rubidium is 5, 0, 0,
2
water.
Pb3O4 + 8HCl 3PbCl2 + 4H2O + Cl2 20. (a) : Let the solubility of AgCNS and AgBr in water
(X) (Z) be x and y respectively.
AgCNS Ag+ + CNS
16. (c) : Ionisation isomerism arises when the x x
coordination compounds give different ions AgBr Ag+ + Br
in solution, this condition is not satisfied with y y
[Co(en)2Cl2]Cl. [Ag ] = (x + y), [CNS] = x, [Br] = y
+

It is an octahedral complex. Ksp[AgCNS] = [Ag+][CNS] = x(x + y)

28 CHEMISTRY TODAY | MARCH 17


1 1012 = x(x + y) ...(i)
and Ksp[AgBr] = [Ag+][Br] = y(x + y) 24. (d) : Compound has 8 + 2 = 10 -electrons,
5 1013 = y(x + y) ...(ii)
hence it is aromatic.
On solving Eq. (i) and (ii), we get
x = 8.16 107 mol/L has 4 eand has 8 e then, these

y = 4.08 107 mol/L are antiaromatic compounds while has
21. (b) : 2H2S + SO2 3S + 2H2O
8 + 1 = 9 e, hence, it is non-aromatic.
Here SO2 acts as an oxidising agent and thus
PBr3 KCN
oxidises H2S(2) to S(0). 25. (a) : RCH2CH2OH RCH2CH2Br
H3O+
y y RCH2CH2CN RCH2CH2COOH
22. (a) : C x H y x O2 x CO2 O
4 2 2 (v ) 26. (b) : London or photochemical smog are the
Initial vol. 500 mL 0 0 mixture of smoke and fog. London smog is formed
y in cool humid climate when carbon soot particles
After reaction 0 500x mL 500 mL
2
is complete combine with gaseous oxides of sulphur. Since in
Now, 500x = 2500 this type of smog, carbon and SO2 are present, it
x=5 is reducing in nature. Photochemical smog, on
500y the other hand occurs in warm, dry and sunny
3000 climate. It results in the formation of PAN. Since in
2
y = 12 photochemical smog, O3 is present, it irritates the
Thus, the formula of alkane is C5H12. eyes, nose, lungs, etc.
23. (b) : The complete structures of the given 27. (b) : Number of atoms present in the unit cell
compounds are as follows : d a3 N A
(Z )
M
Given, M = 2.7 102 kg mol1
a = 405 pm = 405 1012 m = 4.05 1010 m
(a) d = 2.7 103 kg m3
NA = 6.022 1023 mol1
Hence,
(2.7 103 kg m 3 )(4.05 10 10 m)3 (6.022 1023 mol 1 )
Z
(2.7 10 2 kgg mol 1 )
=4
Since, there are four atoms per unit cell, the cubic
(b) unit cell must be face-centred.
28. (a) : Dehydrohalogenation reaction is also called
b-elimination reaction and the reactivity of
haloalkanes towards elimination reaction is:
3 > 2 > 1.
H O H
(c) H N C N H

sp2

(d) H C O
(sp2 hybridised)
O H 29. (b) : In general, electron releasing groups activate
Thus, (CH3)3C OH uses only its sp -hybrid 3 and electron withdrawing groups deactivate the
orbitals for bond formation. benzene ring towards electrophilic substitution.

CHEMISTRY TODAY | MARCH 17 29


Hence, the correct order is : 34. (c) : (AlH3)n is a polymeric hydride like (BeH2)n,
(MgH2)n, etc.
35. (a)

30. (a) : 2K(g) + L (g) 2M(g)


ng = 2 3 = 1 36. (b) :
H = U + ngRT CN
= 10.5 103 + (1 8.314 298)
= 10500 + (2477.572) = 12977.57 J = 12.98 kJ
37. (b) : Cationic polymerisation is favoured by the
G = H T S
presence of electron donating group (e.g., Me
= 12.98 298 ( 44.1 103)
group). The more the electron donating group, the
= 12.98 + 13.14 = 0.16 kJ
Since G is +ve hence it is a non-spontaneous more stable is the intermediate carbocation, and as a
reaction. result more favoured is the cationic polymerisation.
w Stability of ( C ) is

P Ps m
31. (b) :
P w W II.
m M (+R and I effects of Ph)
H+ +
w/m can be neglected in the denominator as I. Me CH CH2 Me CH CH3
compared to W/M. (+I effect of Me)
H+ +
w M 640 600 IV. :Cl CH CH2 Cl CH CH3
: :

m W 640 (I and + R effect of Cl)


w M 40 2.175 78 40 O
H+
m W 640 m 39.08 640 III. CH2 CH C OMe
+
2.175 78 640 CH3 CH COOMe
m 69.46 g mol 1
39.08 40 (I effect of COOMe)
32. (d) : The structural formula of the complex X is The decreasing reactivity order towards cation
[Cr(H2O)4Br2]Cl H2O, one mole of which gives polymerisation is (II) > (I) > (IV) > (III).
2 moles of particles, i.e., [Cr(H 2O) 4Br 2] + + Cl
38. (d) : Proline has a 2 amino group. Hence, it is not
and the formula of the complex Y is [Cr(H2O)5Cl]Br2,
estimated by this method.
one mole of which gives 3 moles of particles, i.e.,
[Cr(H2O)5Cl]2+ + 2Br. 39. (b) : COCH3 group can be reduced to CH2CH3
by either Zn-Hg, HCl or NH2NH2, OH but with
33. (b) : In , lone pair on NH2 remains Zn-Hg, HCl, dehydration of alcohol takes place.
more available for donation and its conjugate acid is 40. (a) :
resonance stabilised thus, it is most basic. Between
CH3CH2NH2 and (CH3)2NH, the later is more basic
because of the presence of two alkyl groups which
facilitate the donation of lone pair of electrons.
O
CH3 C NH2 is least basic as the lone pair of N
is involve in resonance.

Thus, the correct order of basicity is I > III > II > IV.

30 CHEMISTRY TODAY | MARCH 17


PAPER-I
SECTION 1 (Maximum Marks : 15) 4. In which of the following arrangements, the order
This section contains FIVE questions. is not according to the property indicated against
Each question has FOUR options (A), (B), (C) and (D). ONLY it?
ONE of these four options is correct.
(a) Al3+ < Mg2+ < Na+ < F (increasing ionic size)
For each question, darken the bubble corresponding to the
correct option in the ORS. (b) B < C < N < O
For each question, marks will be awarded in one of the following (increasing first ionisation enthalpy)
categories : (c) I < Br < F < Cl (increasing electron gain enthalpy
Full Marks : +3 If only the bubble corresponding to the correct with negative sign)
option is darkened. (d) Li < Na < K < Rb (increasing metallic radius)
Zero Marks : 0 If none of the bubbles is darkened.
Negative Marks : 1 In all other cases. 5. In a polymer sample, 30% of molecules have a
molecular mass of 20,000, 40% have 30,000 and the
1. What transition in the hydrogen spectrum would rest 60,000. What is the weight average molecular
have the same wavelength as the Balmer transition mass of the polymer?
n = 4 to n = 2 of He+ spectrum? (a) 40,300 (b) 30,600
(a) n1 = 1 to n2 = 2 (b) n1 = 2 to n2 = 4 (c) 43,333 (d) 33,353
(c) n1 = 1 to n2 = 3 (d) n1 = 2 to n2 = 3
SECTION 2 (Maximum Marks : 32)
2. An ideal gas has a specific heat at constant presssure This section contains EIGHT questions.
5 Each question has FOUR options (A), (B), (C) and (D). ONE OR
Cp = R. The gas is kept in a closed vessel of volume MORE THAN ONE of these four option(s) is(are) correct.
2 For each question, darken the bubble(s) corresponding to all
0.0083 m3, at a temperature of 300 K and pressure the correct option(s) in the ORS.
1.6 106 N/m2. An amount of 2.49 104 J of energy For each question, marks will be awarded in one of the following
is supplied to the gas. The final temperature of the categories :
gas is Full Marks : +4 If only the bubble(s) corresponding to the
correct option(s) is(are) darkened.
(a) 375 K (b) 575 K
Partial Marks : +1 For darkening a bubble corresponding
(c) 675 K (d) 475 K to each correct option, provided NO incorrect option is
2 2 3 darkened.
3. In [Ni(CN)4] , [MnBr4] and [CoF6] ions, the
Zero Marks : 0 If none of the bubbles is darkened.
geometry, hybridisation and magnetic moment,
Negative Marks : 2 In all other cases.
respectively are For example, if (A), (C) and (D) are all the correct options for
(a) tetrahedral, square planar, octahedral ; a question, darkening all these three will result in +4 marks;
sp3, dsp2, sp3d2 ; 5.9, 0, 4.9 darkening only (A) and (D) will result in +2 marks; and darkening
(A) and (B) will result in 2 marks, as a wrong option is also
(b) tetrahedral, square planar, octahedral ; darkened.
dsp2, sp3, sp3d2 ; 0, 5.9, 4.9
6. Treatment of cyclobutylmethylamine with nitrous
(c) square planar, tetrahedral, octahedral ;
acid does not give
dsp2, sp3, d2sp3 ; 5.9, 4.9, 0
CH2OH
(d) square planar, tetrahedral, octahedral ;
dsp2, sp3, sp3d2 ; 0, 5.9, 4.9 (a) (b)

CHEMISTRY TODAY | MARCH 17 31


CH2 OH 13. For the given equilibrium;
CH3
(c) (d)
CH3 CH2 CH2 CH3(g) CH3 C CH3(g)
7. The reagent(s) required for the conversion;
RCH CHR RCOOH + HOOCR is/are H
(a) O3 followed by treatment with H2O2 equilibrium constant is found to be 1.732 at 298 K.
(b) hot KMnO4/KOH followed by acidification Now, if in a vessel at 298 K, a mixture of these two
(c) Lemieux reagent gases be taken as represented by the point P in the
(d) Baeyers reagent. figure, predict what will happen?
8. The pairs of compounds which cannot exist together

-butane
P
in aqueous solution are
(a) NaH2PO4 and Na2HPO4

conc. of
(b) NaOH and NaH2PO4
(c) Na2CO3 and NaHCO3 75
(d) NaHCO3 and NaOH conc. of -butane
(a) Immediately above equilibrium will be setup.
9. Which of the following options is/are correct
regarding XeF6? (b) Above reaction will go in the forward direction
(a) It acts as a Lewis acid when it reacts with RbF. till it attains equilibrium.
(b) It undergoes complete hydrolysis to give XeO3. (c) Above reaction will go in the backward direction
(c) It fluorinates silica (SiO2) to give XeOF4. till it attains equilibrium.
(d) Hybridisation of XeF6 is sp3d2 with octahedral (d) Nothing can be said.
geometry. SECTION 3 (Maximum Marks : 15)
10. Two radioisotopes P and Q with atomic masses This section contains FIVE questions.
100 u and 200 u respectively are mixed in equal The answer to each question is a SINGLE DIGIT INTEGER
ranging from 0 to 9, both inclusive.
amount by mass. After 20 days, their mass ratio is
For each question, darken the bubble corresponding to the
found to be 1 : 4. If t1/2 for P is 10 days, then t1/2 for Q correct integer in the ORS.
is For each question, marks will be awarded in one of the following
(a) days (b) 10 days categories :
(c) 5 days (d) 20 days. Full Marks : +3 If only the bubble corresponding to the correct
answer is darkened.
11. With reference to the scheme given, which of the Zero Marks : 0 In all other cases.
given statement(s) about T, U, V and W is (are)
correct? 14. Tropic acid (obtained from the alkaloid atropine),
O (CH3CO)2O C9H10O3, gives a positive CrO3/H2SO4 test at 273 K
W and is oxidised by hot KMnO4 to benzoic acid.
O LiAlH4
U Tropic acid is converted by the following sequence
CrO3/H+
H3C (T) V of reactions into hydratropic acid :
T > 298 K HBr
Tropic acid C 9 H9O2 Br
(a) T is soluble in hot aqueous NaOH.
(b) U is optically active. OH
(C 9 H8O2 )(Atropic acid)
(c) Molecular formula of W is C10H18O4.
(d) V gives effervescence on treatment with aqueous Atropic acid
H2 ,Ni
Hydratropic acid(C 9 H10 O2 )
NaHCO3.
Number of carbon atoms in the ring in tropic acid is
12. A solution of colourless salt H on boiling with
excess NaOH produces a non-flammable gas. The 15. Two aqueous solutions as shown, are put in an
gas evolution ceases after sometime. Upon addition evacuated chamber. When equilibrium is attained,
of Zn dust to the same solution, the gas evolution it is found that one solution contains 0.01% of X
restarts. The colourless salt(s) H is (are) and other 0.02% of urea by weight. If the molecular
(a) NH4NO3 (b) NH4NO2 weight of X is (n 10) amu, then what is n (X is
(c) NH4Cl (d) (NH4)2SO4 non-electrolyte and non-volatile solute)?

32 CHEMISTRY TODAY | MARCH 17


17. How many electrons are transferred when KMnO4
Evacuated
chamber acts as oxidising agent to give Mn(OH)3?
18. The compressibility factor for 1 mole of a van der
X in water Urea in water Waals gas at 0C and 100 atm pressure is found to
be 0.5. Assuming that the volume of a gas molecule
16. Total number of geometrical isomers for the
complex [RhCl(CO)(PPh3)(NH3)] is is negligible, the van der Waals constant, a is x.25.
The value of x is
PAPER-II
SECTION 1 (Maximum Marks : 18) The iodine liberated required 24.5 cm3 of a
This section contains SIX questions. 0.100 mole dm3 solution of sodium thiosulphate.
2
Each question has FOUR options (A), (B), (C) and (D). ONLY ONE 2S2O3(aq) + I2(aq) 2I(aq) + S4O2
6(aq)
of these four options is correct.
For each question, darken the bubble corresponding to the The percentage of copper, by mass in the copper(II)
correct option in the ORS. salt is [Atomic mass of copper = 63.5]
For each question, marks will be awarded in one of the following (a) 64.2 (b) 51.0
categories :
Full Marks : +3 If only the bubble corresponding to the correct
(c) 48.4 (d) 25.5
option is darkened. 4. AgNO3(aq) was added to an aqueous KCl solution
Zero Marks : 0 If none of the bubbles is darkened.
gradually and the conductivity of the solution was
Negative Marks : 1 In all other cases.
measured. The plot of conductance ( ) versus the
1. In the following sequence of reactions, the final volume of AgNO3 is
product (B) is
CH3 (i) Dil. KMnO Dil. NaOH



4
(A) (B)

(ii) HIO4 heat


CH3


O
volume volume
CH2COCH3 (P) (Q)
(a) H2C (b)
CH2COCH3 CH3

O O
CH3

(c) OH (d)

CH3 volume volume


2. The correct acidity order of the following is (R) (S)
OH OH COOH COOH (a) P (b) Q
(c) R (d) S
5. A red solid is insoluble in water. However, it becomes
soluble if some KI is added to water. Heating the red
C CH3 solid in a test tube results in liberation of some violet
coloured fumes and droplets of a metal appear on
(a) III > IV > II > I (b) IV > III > I > II the cooler part of the test tube. The red solid is
(c) III > II > I > IV (d) II > III > IV > I (a) HgI2 (b) HgO
3. The percentage of copper in a copper(II) salt can (c) Pb3O4 (d) (NH4)2Cr2O7
be determined by using a thiosulphate titration. 6. Zinc granules are added in excess to 500 mL of 1 M
0.305 g of a copper(II) salt was dissolved in water nickel nitrate solution at 25C until the equilibrium
and added to an excess of potassium iodide solution is reached. If the standard reduction potentials of
liberating iodine according to the following Zn2+ Zn and Ni2+ Ni are 0.75 V and 0.24 V
equation : respectively. The concentration of Ni2+ in solution
2Cu2+
(aq) + 4I(aq) 2CuI(s) + I2(aq) at equilibrium is

CHEMISTRY TODAY | MARCH 17 33


(a) 0.05 108 M (b) 5.5 1018 M (b) II is more basic than I and III.
(c) 55 108 M (d) 0.75 108 M (c) III is more basic than II.
(d) I is weakly acidic.
SECTION 2 (Maximum Marks : 32)
This section contains EIGHT questions.
Residue
Each question has FOUR options (A), (B), (C) and (D). ONE OR 10. Impure ore Excess of
NaOH(aq.) CO2
MORE THAN ONE of these four option(s) is(are) correct. Soln.
Excess
Precipitate
For each question, darken the bubble(s) corresponding to all the
correct option(s) in the ORS.
Pure ore

For each question, marks will be awarded in one of the following
categories : Above method is applicable for
Full Marks : +4 If only the bubble(s) corresponding to all the (a) red bauxite (b) haematite
correct option(s) is(are) darkened. (c) galena (d) cuprite.
Partial Marks : +1 For darkening a bubble corresponding
to each correct option, provided NO incorrect option is 11. Consider the following sequence of reactions :
darkened. Ba(OH)2/ H2SO4
Zero Marks : 0 If none of the bubbles is darkened. P4 X (oxyacid)


Negative Marks : 2 In all other cases. salt (oxyacid)


For example, if (A), (C) and (D) are all the correct options for (oxyacid)

a question, darkening all these three will result in +4 marks;
darkening only (A) and (D) will result in +2 marks; and darkening A 
(A) and (B) will result in 2 marks, as a wrong option is also (oxyacid)
(oxyacid)

darkened.
In the above sequence of reactions Y and A are
7. Which of the following species have the same shape
respectively
and same bond order?
(a) H3PO2 and H3PO4 (b) H3PO4 and H4P2O7
(i) CO2 (ii) N3
(c) H3PO4 and HPO3 (d) H3PO3 and H3PO4
(iii) O3 (iv) NO2
(a) (i) and (ii) (b) (iii) and (iv) 12. Consider the following solutions :
(c) (i) and (iii) (d) (ii) and (iv) (i) C6H12O6/H2O (1 M)
(ii) NaCl/H2O (1 M)
8. A metal has cubic close packing (ccp) arrangement, (iii) C6H5COOH/C6H6 (1 M)
the layer sequence of which is shown as : (iv) (NH4)3PO4/H2O (1 M)
1 2 6
With respect to these solutions select the correct
5 9 7 statement(s).
(a) All are isotonic solutions.
4 3 8 (b) (iii) is hypotonic of (ii) and (iv).
Z=0 Z = a/2 (c) (ii) and (iv) are hypertonic of (i).
Z (d) (iv) is hypertonic of (i), (ii) and (iii).
10 11
13. The correct statement(s) about the following sugars
14 X and Y is (are)
X CH2OH
13 12 O
Z=a Y H H H HOH2C O
H
A face diagonal passes through the centre of atom 4 HO OH H O CH2OH
H HO
and the centre(s) of which other atom(s)? H OH OH H
(a) 1 (b) 2, 5 (X)
(c) 8, 12 (d) 9, 10 CH2OH
O
9. Consider the following compounds : CH2OH H
O H H
H O H HO OH
H
N N HO H
H OH H OH H
Pyrrole (I) Pyridine (II) NH2
H OH
Aniline (III) (Y)
Which of the following statement(s) is/are correct? (a) X is a reducing sugar and Y is a non-reducing
(a) I is more basic than II. sugar

34 CHEMISTRY TODAY | MARCH 17


CHEMISTRY TODAY | MARCH 17 35
(b) X is a non-reducing sugar and Y is a reducing other hand, when heated with chloroform and then
sugar acidified gave a mixture of two isomeric compounds D
(c) the glycosidic linkages in X and Y are a and b, and E of molecular formula C7H6O2.
respectively 17. Compounds A and B respectively are
(d) the glycosidic linkages in X and Y are b and a, (a) C6H5OH, C6H5OCH3
respectively. (b) C6H5NH2, C6H5OH
14. 4, 4 -Dinitrodiphenyl is obtained when (c) C6H5OH, C6H5NH2
(a) 4-nitrochlorobenzene is heated with Na/ether (d) C6H5CH2OH, C6H5CH2NH2
(b) 4-nitroiodobenzene is heated with copper 18. The compounds D and E respectively are
powder in a sealed tube (a) C6H5CHO, o-HOC6H4CHO
(c) diphenyl is heated with a mixture of conc. (b) C6H5CHO, m-HOC6H4CHO
HNO3 + conc. H2SO4 (c) C6H5CHO, p-HOC6H4CHO
(d) nitrobenzene is treated with 4-nitro- (d) o-HOC6H4CHO, p-HOC6H4CHO
chlorobenzene in presence of anhyd. AlCl3.
SOLUTIONS
SECTION 3 (Maximum Marks : 12) PAPER-I
This section contains TWO paragraphs.
Based on each paragraph, there are TWO questions. 1 1 1
Each question has FOUR options (A), (B), (C) and (D). ONLY ONE 1. (a) : vH R ...(i)
of these four options is correct. H n12 n22
For each question, darken the bubble corresponding to the
correct option in the ORS. 1 1 1
For each question, marks will be awarded in one of the following
vHe RZ 2
categories : He 22 42
Full Marks : +3 If only the bubble corresponding to the correct 1 1 4 4
option is darkened. =R4 =R
4 16 4 16
Zero Marks : 0 In all other cases.
1
PARAGRAPH 1 =R 1 ...(ii)
4
Decomposition of ammonium chloride is an
Comparing equations (i) and (ii), we get
endothermic reaction. The equilibrium may be
n1 = 1 and n2 = 2
represented as :
NH4Cl(s) NH3(g) + HCl(g) 2. (c) : Suppose n moles of gas are present.
A 6.250 g sample of NH4Cl is placed in an evacuated PV 1.6 106 0.0083
n= = 5.33
4.0 L container at 27C. After equilibrium the total RT 8.3 300
pressure inside the container is 0.820 bar and some solid 5 3 3
Cv = R R = R = 8.3 = 12.45 J mol1 K1
remains in the container. 2 2 2
15. The value of Kp for the reaction at 300 K is Heat supplied at constant volume (qv) = n Cv T
(a) 16.2 (b) 0.168 2.49 104 = 5.33 12.45 T
(c) 1.68 (d) 32.4 2.49 104
T= T 375 K
16. The amount of solid NH4Cl left behind in the 5.33 12.45
container at equilibrium is Final temperature, Tf = 300 + 375 = 675 K
(a) 2.996 (b) 28.56 3. (d) : In [Ni(CN)4]2, Ni2+ = 3d8, dsp2 hybridisation
(c) 0.2856 (d) 1.320 (square planar geometry), no unpaired electron is
PARAGRAPH 2 present and magnetic moment is zero.
A mixture of two compounds A and B was separated by In [MnBr4]2, Mn2+ = 3d5, sp3 hybridisation
dissolving in chloroform followed by extraction with (tetrahedral geometry), n = 5,
aqueous KOH solution. The organic layer containing = 5(5 2) B.M. = 35 B.M. = 5.9 B.M.
compound A, when heated with alcoholic solution of In [CoF6]3, Co3+ = 3d6, sp3d2 hybridisation
KOH produced a compound C(C7H5N) associated with (octahedral geometry),
an unpleasant odour. The alkaline aqueous layer on the n = 4, = 4(4 2) B.M. 24 B.M. = 4.9 B.M.

36 CHEMISTRY TODAY | MARCH 17


4. (b) 11. (a, c, d) :
O ONa
N i Mi2 CH2OH
5. (c) : M w O Aq. NaOH O LiAlH4
OH
OH
N i Mi Hot
2 2 2 CH3 CH3 CH3
30(20000) 40(30000) 30(60000)
Mw (T) (U)
(30 20000) (40 30000) (330 60000) Dissolves in No chiral
carbon, optically
hot aq. NaOH
= 43,333.33 43,333 inactive
+ CH2OCOCH3
(CH3CO)2O
CH2NH2 CH2 N N OCOCH3
excess
HONO H3 C
6. (b) :
(W)
Cyclobutylmethylamine M.F. C10H18O4
+
CH2 OH
+ H2O
N2 H+
Cyclobutylmethyl H H
carbocation
H
H+ V gives effervescence with NaHCO3 due to evolution
2O
of CO2.
H+ CH2OH
12. (a, b) : All ammonium salts on reaction with alkali
CH2
produce ammonia, but nitrates and nitrites salts
produce ammonia along with nitrates and nitrites
(i) KMnO4 which on further reduction with Zn dust again
7. (a, b) : RCH CHR RCHO + R CHO produces ammonia.
(ii) NaIO4
A solution of NaIO4 containing a trace of KMnO4 is NH4NO2 + NaOH NaNO2 + NH3 + H2O
called Lemieux reagent. NH4NO3 + NaOH NaNO3 + NH3 + H2O
+6 [H]
8. (b, d) : 2NaOH + NaH2PO4 Na3PO4 + 2H2O NaNO2 NaOH + NH3 + H2O
Zn/NaOH
NaHCO3 + NaOH Na2CO3 + H2O Zn
NaNO3 + 8[H] NaOH + NH3 + 2H2O
9. (a, b, c) : NaOH
RbF + XeF6 Rb+[XeF7] conc. of iso-butane
13. (c) : Qc = tan 75 = 3.732 = Kc
XeF6 + 3H2O XeO3 + 6HF conc. of n-butane
2XeF6 + SiO2 2XeOF4 + SiF4 As Qc > Kc, thus backward reaction takes place till
XeF6 is sp3d3 hybridised with pentagonal bipyramidal equilibrium is attained.
geometry. 14. (6) : (a) Since tropic acid is oxidised by
10. (a) : Let w g of each be taken.
w w CrO3/H2SO4, it suggests the presence of CH OH
Initial mole of P = ; Final mole of P = or CH2OH group in it.
100 5 100
w 4w (b) Tropic acid is also oxidised by hot alkaline
Initial mole of Q = ; Final mole of Q = KMnO4 into benzoic acid, indicating the presence
200 5 200
N0 w 5 100 of a benzene nucleus and atleast one a H-atom
For P : = e 1t or = e 1 20 ...(i) in the side chain of tropic acid. Thus, tropic acid
N P 100 w
should have the following structure :
N0 2t
w 5 200 2 20
CH2 OH
For Q : =e or =e ...(ii) KMnO4
N Q 200 w 4 COOH CH COOH

By eqs. (i) and (ii), 4= e( 1 2) 20 Benzoic acid Tropic acid(C9H10O3)
log e 4 CrO3/H+ (Oxidation)
or 1 2= (273 K)
20
0.693 0.693 log e 4 CHO
or t=
10 t 20 CH COOH

CHEMISTRY TODAY | MARCH 17 37


CH2 OH CH2 Br O O
Dil.
CH COOH
HBr
CH COOH NaOH CH2 C H
H2O A CH2 CH2 H
Tropic acid (C9H9O2Br) CH2 C O CH3
CH2 O
CH3 H2O
OH
(dehydro- C COOH
bromination O O
Atropic acid
H
Heat H
CH3 H2O
H2/Ni CH3 CH3
CH COOH (B) OH
reduction
Hydratropic acid 2. (a)
15. (3) : At equilibrium, lowering in vapour pressure of 3. (b) : Millimoles of hypo millimoles of iodine 2
both the solutions is same. millimoles of Cu2+ ions
0.01 0.02 = 24.5 0.1 millimoles
Then, MX = 30 amu n = 3
MX 60 Mass of copper = 24.5 0.1 103 63.5 g
16. (3) : [RhCl(CO)(PPh3)(NH3)] is a square planar 24.5 0.1 10 3 63.5
So, % of copper = 100%
complex of the type MABCD. Hence, it has three 0.305
geometrical isomers as follows : = 51.0%
Cl PPh3 Cl NH3 Cl PPh3 4. (d) : AgNO3(aq) + KCl(aq) AgCl(s) + KNO3(aq)
Rh Rh Rh Conductivity of the solution is almost compensated
OC NH3 OC PPh3 H3N CO due to formation of KNO3(aq) as Cl and NO3 both
cis trans cis
have almost same ionic conductivity. However, after
17. (4)
the end point, conductivity increases more rapidly
18. (1) : Z = PV ; 0.5 = 100 V ; V = 0.112 L
RT 0.0821 273 due to addition of excess AgNO3 solution.
Neglecting b, van der Waals equation reduces to 5. (a) : When KI is added to mercuric iodide it
a a dissolves in it and forms complex.
P
2
V = RT or PV + = RT
HgI2 + 2KI K2[HgI4]
V V
red solid (soluble)
a
or 100 0.112 + = 0.0821 273 (insoluble)
0.112
On heating, HgI2 decomposes as :
a = 1.25 L2 atm mol2
HgI2 Hg + I2
Comparing 1.25 with x.25, we get x = 1
(droplets (violet
Paper-II of mercury) vapours)
OH 6. (b) : The cell reaction is
CH3 Dil. KMnO CH3 HIO4
Zn + Ni2+ Zn2+ + Ni
4
1. (b) :
CH3 CH3
HO 0.0591 [Zn2 ]
CH3 Ecell = Ecell log
2 [Ni2 ]
CH2 C O At equilibrium, Ecell = 0
CH2
CH2 C O 0.0591 [Zn2 ]
Ecell = log
CH3
2 [Ni2 ]
(A) 0.0591 [Zn2 ]
ENi2+/Ni EZn2+/ Zn = log
2 [Ni2 ]

38 CHEMISTRY TODAY | MARCH 17


12. (b, c, d) 13. (b, c) 14. (a, b, c)
0.0591 [Zn2 ]
0.24 ( 0.75) = log 0.820
2 [Ni2 ] 15. (b) : PNH3 = PHCl = bar
2
[Zn ] 2
= 1.816 1017 Kp = PNH3 PHCl = 0.41 0.41 = 0.168
[Ni2 ]
PV 0.820 4
This concentration ratio shows that almost whole 16. (a) : Moles of gases, n =
of the Ni2+ ions are reduced to Ni and therefore, the RT 0.083 300
concentration of Zn2+ produced from Zn would be = 0.132 mol
nearly 1 M [ Ni(NO3)2 = 1 M]. Thus, 0.132
Moles of NH3 = Moles of HCl = = 0.066
1 2
2
= 1.816 1017 [Ni2+] = 5.5 1018 M Moles of NH4Cl decomposed = Moles of NH3 = 0.066
[Ni ]
6.250
7. (a, b) : CO2 and N3 are linear with bond order 2. O3 Moles of NH4Cl initially present = = 0.117
and NO2 are V-shaped and bond order 1.5. 53.5
Moles of NH4Cl left = 0.117 0.066 = 0.051
8. (b, c, d) : Z = 0 forms the bottom layer, Z = a/2
forms second layer above it and Z = a forms the Mass of NH4Cl left behind = 0.051 53.5 = 2.73 g
third layer. Atoms 5, 6, 7, 8, 9 and 14 are present 17. (b)
at the face centres. Atoms 1, 2, 3, 4, 10, 11, 12 and CHC 3
Mixture of (A) + (B) Organic layer (A)
13 are present at the corners. 4, 5, 2 form one face H
diagonal 4, 9, 10 form another face diagonal; 4, 8, 12 + Aqueous alkaline layer (B).
form one more face diagonal. Since compound (A) does not dissolve in alkali,
10 11 therefore, it may be an amine. Further, since on
14
Z = a 13 treatment with CHCl3 and alcoholic KOH, it
12
6 produces C(C7H5N) having unpleasant smell,
9
Z=
a
8
7 therefore, (A) may be C6H5NH2 and (C) must be
2
C6H5NC and the name of the reaction is carbylamine
1
5
2 reaction.
Z=0 4 Warm
3 C6H5NH2 + CHCl3 + 3KOH
(Carbylamine
9. (b, d) : Due to delocalisation of electrons of the Aniline(A) (alc.) reaction)
N-atom over the benzene ring in aniline (III) and C6H5NC + 3KCl + 3H2O
involvement of these electrons in aromatic sextet Phenyl isocyanide (C)
formation in pyrrole (I), both these amines are (unpleasant smell)
weaker bases than pyridine (II) in which such a Since aqueous alkaline layer (B) on heating with
delocalisation does not exist since the lone pair CHCl3 followed by acidification gives two isomeric
of electrons is present in a sp2-hybridised orbital compounds having molecular formula (C7H6O2).
which lies outside the plane of the ring. Hence, II is Therefore, (B) must be phenol, C6H5OH. It
more basic than I and III. Further, I is so much less undergoes ReimerTiemann reaction to give a
basic that with strong bases, it behaves as a weak mixture of two isomeric compounds with molecular
acid. formula C7H6O2. Thus, (D)and (E) are o- and
10. (a) p-hydroxybenzaldehyde.
11. (a) : P4
OH
PH3 + H2PO2
H+
H3PO2 CHCl3 OH
C6H5OH + HO CHO
Salt (Y) KOH
( ) Phenol CHO
(B) o-Hydroxy- p-Hydroxy-
H4P2O7 benzaldehyde benzaldehyde

250 
600C C H3PO4 + PH3 (D) + (E)
( ) 18. (d)
HPO3

CHEMISTRY TODAY | MARCH 17 39


PRACTICE PAPER

AIIMS
Exam on
28th May

1. Th e order of reactivity of following alkyl halides (a) X + Y (b) X Y +


towards SN1 reaction is (c) X Y (d) X Y
(i) (CH3)3CBr (ii) (C6H5)2CHBr 6. In the reaction,
(iii) (C6H5)2C(CH3)Br (iv) (CH3)2CHBr BrO3(aq) + 5Br(aq) + 6H+(aq) 3Br2(aq) + 3H2O(l)
(v) C2H5Br the expression of rate of appearance of bromine
(a) (v) > (iv) > (i) > (ii) > (iii) [Br2] to rate of disappearance of bromide ion [Br]
(b) (ii) > (i) > (iii) > (v) > (iv) is
(c) (i) > (iii) > (v) > (ii) > (iv)
d [Br2 ] 3 d [Br ]
(d) (iii) > (ii) > (i) > (iv) > (v) (a)
dt 5 dt
2. In the titration of HCl vs NH4OH, the pH at the
d [Br2 ] 5 d [Br ]
equivalence point will be (b)
(a) less than 7 (b) greater than 7 dt 3 dt
(c) equal to 7 (d) none of these. d [Br 2 ] 5 d [Br ]
(c)
3. When current is passed through two cells connected dt 3 dt
in series, the first cell contains X(NO3)3(aq) and d [Br2 ] 3 d [Br ]
the second cell contains Y(NO3)2(aq). Th e relative (d)
dt 5 dt
atomic masses of X and Y are in the ratio 1 : 2. What
7. Consider the following reaction :
is the ratio of the liberated mass of X to that of Y? 
(a) 3 : 2 (b) 1 : 2

   

  

(c) 1 : 3 (d) 3 : 1

4. Consider the following reaction, Th e product,Z is

 (a) toluene (b) benzaldehyde
A (c) benzoic acid (d) benzene.


8. A solid (A) which has photographic effect, reacts

Th e structure of the major productA
is
with the solution of a sodium salt (B) to give a pale
O
yellow ppt. (C). Sodium salt (B) on heating gives
(a) (b) CH2CHO brown vapours. A, B and C are respectively
(a) AgNO3, NaBr, AgBr (b) AgNO3, NaCl, AgCl
(c) AgNO3, NaBr, AgCl (d) AgCl, NaBr, AgBr
(c) (d) 9. Th e number of molecules liberated at anode from
5. An element X is strongly electropositive and molten sodium chloride in one minute by a current
element Y is strongly electronegative. Both are of 300 milliamperes is
univalent. Th e compound formed would be (a) 5.616 1018 (b) 5.616 1019
(c) 5.616 1020 (d) 5.616 1021

40 CHEMISTRY TODAY | MARCH 17


10. Consider the following sequence of reactions : 16. Consider the following set of reactions :

The product (B) is The final product, C is


(a) o-bromophenol (b) p-bromophenol
(a) (c) m-bromophenol (d) 2, 4, 6-tribromophenol.
17. Vapour pressures of chloroform (CHCl3) and
(b) dichloromethane (CH2Cl2) at 25C are 200 mm Hg
and 41.5 mm Hg respectively. Vapour pressure of
the solution obtained by mixing 25.5 g of CHCl3
(c) and 40 g of CH2Cl2 at the same temperature will be
(Molecular mass of CHCl3 = 119.5 u and molecular
mass of CH2Cl2 = 85 u)
(d) (a) 90.9 mm Hg (b) 615.0 mm Hg
(c) 347.9 mm Hg (d) 285.5 mm Hg
11. The true statement for the oxyacids of phosphorus
H3PO2, H3PO3 and H3PO4 is 18. In the following reaction sequence, X is
Br2, H2O NaNO2 + HCl Boiling
(a) the order of their acidity is,
C2H5OH
  
H3PO4 > H3PO3 > H3PO2
(b) all of them are reducing in nature Tribromobenzene
(c) all of them are tribasic acids (a) benzoic acid (b) salicylic acid
(d) the geometry of phosphorus is tetrahedral in all (c) phenol (d) aniline.
the three. 19. A p-type material is electrically
(a) positive (b) negative
12. In vulcanization of rubber,
(c) neutral
(a) sulphur reacts to form a new compound
(d) It depends upon the concentration of p-impurities.
(b) sulphur cross-links are introduced
(c) sulphur forms a very thin protective layer over 20. A plot of volume (V) vs temperature (T ) for a gas at
rubber constant pressure is a straight line passing through
(d) all statements are correct. the origin. The plots at different values of pressure
are shown in the figure. Which of the following
13. In which of the following arrangements of XeF2, orders of pressure is correct for the gas?
XeF4 and XeF6, the decreasing order of XeF bond
length is correct?
(a) XeF2 > XeF4 > XeF6 (b) XeF6 > XeF4 > XeF2
(c) XeF4 > XeF6 > XeF2 (d) XeF2 > XeF6 > XeF4
14. 2.8 g of a pure alkene containing only one double
bond per molecule, reacts completely with 8 g of
bromine (in an inert solvent). What is the molecular
formula of the alkene?
(a) C2H4 (b) C4H8
(c) C3H6 (d) C6H12 (a) p1 > p2 > p3 > p4 (b) p1 = p2 = p3 = p4
(c) p1 < p2 < p3 < p4 (d) p1 < p2 = p3 < p4
15. The reaction, A Product, follows first order
kinetics. In 40 minutes, the concentration of A 21. Which of the following reactions is an example of
changes from 0.1 M to 0.025 M. The rate of reaction, auto-reduction?
when concentration of A is 0.01 M is (a) Fe3O4 + 4CO 3Fe + 4CO2
(a) 1.73 104 M min1 (b) Cu2O + C 2Cu + CO
(b) 3.47 105 M min1 2+
(c) Cu + Fe Cu + Fe2+
(c) 3.47 104 M min1 1 1
(d) 1.73 105 M min1 (d) Cu2 O Cu S 3Cu + SO2
2 2 2

CHEMISTRY TODAY | MARCH 17 41


22. Which of the following reactions is not associated (a) 150 K (b) 300 K
with the Solvay process of manufacture of sodium (c) 600 K (d) 131.25 K
carbonate? 29. Which of the following equations depicts reducing
(a) CO2 + H2O H2CO3 nature of H2O2?
(b) NH3 + H2CO3 NH4HCO3 (a) 2[Fe(CN)6]4+ 2H+ + H2O2 2[Fe(CN)6]3 + 2H2O
(c) NaCl + NH4HCO3 NaHCO3 + NH4Cl (b) I2 + H2O2 + 2OH 2I + 2H2O + O2
(d) 2NaOH + CO2 Na2CO3 + H2O (c) Mn2+ + H2O2 Mn4+ + 2OH
23. Consider the following reactions, (d) PbS + 4H2O2 PbSO4 + 4H2O
PBr3 alc. KOH 30. Consider the reactions given below. On the basis
Ethanol   of these reactions find out which of the algebraic
relations given is correct?
(i) C(g) + 4H(g) CH4(g) ; rH = x kJ mol1
product Z is
(ii) C(graphite, s) + 2H2(g) CH4(g) ; rH = y kJ mol1
(a) CH2 CH2
(a) x = y (b) x = 2y
(b) CH3CH2 O CH2CH3
(c) x > y (d) x < y
(c) CH3 CH2 O SO3H
(d) CH3CH2OH 31. Which of the following pairs of solutions are
expected to be isotonic, temperature being the
24. Glycerol was distilled with oxalic acid crystals and
same?
the products were led into Fehlings solution and
(a) 0.1 M Glucose and 0.1 M C6H5NH3Cl
warmed. Cuprous oxide was precipitated, which is
(b) 0.1 M NaCl and 0.05 M BaCl2
due to (c) 0.1 M Na2SO4 and 0.1 M KNO3
(a) CO (b) HCHO (d) 0.1 M BaCl2 and 0.075 M FeCl3
(c) CH3CHO (d) HCOOH
32. Which of the following has maximum lattice
25. The order of screening effect of electrons of s, p, d energy?
and f orbitals of a given shell of an atom on its outer (a) Li2O (b) Na2O
shell electrons is (c) MgO (d) BaO
(a) s > p > d > f (b) f > d > p > s
(c) p < d < s > f (d) f > p > s > d 33. Tautomerism is not exhibited by
26. Which of the following statements is false? (a) (b)
(a) The lower the concentration of D.O., the more
polluted is the water sample.
(b) The tolerable limit of lead in drinking water is
(c) (d)
50 ppb.
(c) Water is considered pure if it has BOD less than
5 ppm. 34. Extraction of gold and silver involves leaching the
(d) In COD determination, the pollutants resistant metal with CN ion. The metal is recovered by
to microbial oxidation are not oxidised by (a) displacement of metal by some other metal
oxidising agents like K2Cr2O7. from the complex ion
(b) roasting of metal complex
27. The two compounds A and B obtained from
(c) calcination followed by roasting
1-butyne can be distinguished by
(d) thermal decomposition of metal complex.
(i) BH3 H+/Hg2+
B CH3CH2C CH A 35. Which of the following statements about DNA is
(ii) H2O2/OH
not correct?
(a) NaHSO3 (b) litmus solution (a) It has a double helix structure.
(c) iodoform test (d) 2, 4-DNP. (b) It undergoes replication.
28. At what temperature, the translational kinetic (c) The two strands in a DNA molecule are exactly
energy of 14 g of nitrogen will be the same as that of similar.
32 g of oxygen at 300 K? (d) It contains the pentose sugar, 2-deoxyribose.

42 CHEMISTRY TODAY | MARCH 17


36. Which of the following actinoids shows oxidation 46. Assertion : HNO3 makes iron passive.
states upto +7? Reason : HNO3 forms a protective layer of ferric
(a) Th (b) Pu (c) U (d) Ce nitrate on the surface of iron.
37. In the reaction, 47. Assertion : Benzonitrile is prepared by the reaction
NaOH + Al(OH)3 NaAlO2 + 2H2O of chlorobenzene with potassium cyanide.
the equivalent mass of Al(OH)3 is Reason : Cyanide ion (CN) is a weak nucleophile.
(a) 78 (b) 26 48. Assertion : At constant temperature, PV vs V plot
(c) 52 (d) unpredictable. for real gases is not a straight line.
38. To detect nitrogen in hydrazine (NH2NH2) by Reason : At high pressure, all gases have Z > 1 but at
Lassaignes extract, it is fused with sodium in intermediate pressure, most gases have Z < 1.
presence of 49. Assertion : A spectral line will be seen for 2px to 2py
(a) starch (b) charcoal transition.
(c) sugar (d) any of these. Reason : Energy is released in the form of wave
39. The percentage of nitrogen in urea is about of light when the electrons drop from 2px to 2py
(a) 46 (b) 85 (c) 18 (d) 28 orbital.
40. A solution of ammonia in water contains 50. Assertion : Hydrolysis of ()-2-bromooctane
(a) H+ (b) OH proceeds with inversion of configuration.
(c) NH4 + Reason : This reaction proceeds through the
(d) OH, NH4+ and NH4OH. formation of a carbocation.
51. Assertion : Colloidal solutions show colligative
ASSERTION AND REASON
properties.
Directions : In the following questions (41-60), a statement Reason : Colloidal particles are large in size than
of assertion is followed by a statement of reason. Mark the particles of true solution.
correct choice as :
(a) If both assertion and reason are true and reason is the 52. Assertion : Both H3PO3 and H3PO4 have the same
correct explanation of assertion. number of hydrogen atoms but H3PO4 is a tribasic
(b) If both assertion and reason are true but reason is not the acid and H3PO3 is a dibasic acid.
correct explanation of assertion.
Form IV
(c) If assertion is true but reason is false. 1. Place of Publication : New Delhi
(d) If both assertion and reason are false. 2. Periodicity of its Publication : Monthly
3. Printers Name : HT Media Ltd.
41. Assertion : An ionic product is used for any type of 3a. Publishers Name : MTG Learning Media Pvt. Ltd.
electrolytes whereas solubility product is applicable Nationality : Indian
only to sparingly soluble salts. Address : 406, Taj Apartment,
Reason : Ionic product is defined at any state of New Delhi - 110029
4. Editors Name : Anil Ahlawat
the reaction whereas solubility product is only Nationality : Indian
applicable to the saturation stage. Address : 19, National Media
42. Assertion : NO3 is trigonal planar while NH3 is Centre, Gurgaon,
Haryana - 122002
pyramidal. 5. Name and address of individuals who : Mahabir Singh Ahlawat
Reason : N in NO3 is sp2 and in NH3, it is sp3 own the newspapers and partners or 64, National Media Centre,
hybridised. shareholders holding more than one Nathupur, Gurgaon
percent of the total capital : Krishna Devi
43. Assertion : Deep electric shock causes death of an 64, National Media Centre,
animal. Nathupur, Gurgaon
Reason : Electric shock coagulates the blood. : Anil Ahlawat & Sons
19, National Media Centre,
44. Assertion : Aldol condensation can be catalysed Nathupur, Gurgaon
both by acids and bases. : Anil Ahlawat
Reason : b-Hydroxyaldehydes or ketones readily 19, National Media Centre,
Nathupur, Gurgaon
undergo acid-catalysed dehydration. I, Mahabir Singh, authorised signatory for MTG Learning Media Pvt. Ltd. hereby
45. Assertion : Due to Frenkel defect, there is no effect declare that particulars given above are true to the best of my knowledge and
belief.
on the density of the crystalline solid. For MTG Learning Media Pvt. Ltd.
Reason : In Frenkel defect, no cation or anion leaves Mahabir Singh
the crystal. Director

CHEMISTRY TODAY | MARCH 17 43


Reason : One mole of each H3PO3 and H3PO4 2. (a) : At the equivalence point, equal number of
is neutralized by 2 moles and 3 moles of NaOH moles of acid and base added and the pH will reflect
respectively. which species are present.
53. Assertion : The enthalpy of reaction remains 3. (c) : If atomic mass of X = a, then that of Y = 2a
constant in the presence of a catalyst. As Eq. wt. = Atomic mass/Valency
Reason : A catalyst participating in the reaction, 2a
a
forms different activated complex and lowers down Eq. wt. of X , Eq. wt. of Y a
the activation energy but the difference in energy of 3 2
reactant and product remains the same. According to Faradays second law;
54. Assertion : Reducing character of hydrides of Liberated Mass of X Eq . wt . of X
oxygen family increases from H2S to H2Te. Liberated Mass of Y Eq . wt . of Y
Reason : Thermal stability decreases from H2S to a/3 1
H2Te. 1: 3
a 3
55. Assertion : For the Daniell cell : Zn | Zn2+ || Cu2+ | Cu 4. (b) : Due to electron withdrawing nature of the keto
with Ecell =1.1 V, the application of opposite potential group, the C1-atom becomes electron deficient.
greater than 1.1 V results into the flow of electrons
Hence, it is attacked by the nucleophile H2O as
from cathode to anode.
shown :
Reason : Zinc is deposited at anode and copper is
dissolved at cathode. O O
2 1 Addn. of H2O
56. Assertion : Lattice energy in TiO2 will be much C CH HgSO + H SO CH CH
larger than in NaCl. 4 2 4

Reason : The higher value of lattice energy for TiO2 OH


as compared to that of NaCl is due to increased O
ionic charge. Tautomerises
CH2CHO
57. Assertion : One molal aqueous solution of glucose
contains 180 g of glucose in 1 kg water. (A)
Reason : Solution containing one mole of solute in 5. (a) : Strongly electropositive, univalent, X will
1000 g of solvent is called one molal solution. form an 1 : 1 ionic compound with strongly
58. Assertion : [Ti(H2O)6]3+ is coloured while electronegative, univalent Y.
[Sc(H2O)6]3+ is colourless. X+Y X+ Y
Reason : d-d transition is not possible in [Sc(H2O)6]3+.
59. Assertion : The non-fusible impurities present in 1 d [Br2 ] 1 d [Br ]
6. (a) :
iron ore are removed by CaCO3. 3 dt 5 dt
Reason : CaCO3 decomposes to CaO which reacts
with SiO2 to form CaSiO3 slag. d [Br2 ] 3 d [Br ]
60. Assertion : As a lead storage battery gets discharged, dt 5 dt
density of electrolyte present in it, decreases.
Reason : Lead and lead dioxide both react with
sulphuric acid to form lead sulphate. 7. (c) :
SOLUTIONS
1. (d) : More stable the carbocation, more reactive is COOH
the alkyl halide in SN1 reaction. Since the stability alk.
of the carbocations decreases in the order : KMnO4
+ + +
(C6H5)2C(CH3) > (C6H5)2CH > (CH3)3C Benzoic acid
+ +
> (CH3)2CH > C2H5,
8. (a) : Solid (A) is silver nitrate which has
therefore, reactivity of the alkyl halides decreases in
photographic effect, reacts with the solution of
the same order :
NaBr(B) to give a pale yellow ppt. of AgBr. NaBr(B)
(iii) > (ii) > (i) > (iv) > (v).

44 CHEMISTRY TODAY | MARCH 17


on heating gives brown vapours of bromine.

16. (d) :

9. (b) : Quantity of electricity passed


300
60 18 coulombs
1000
At anode : 2Cl Cl2 + 2e
2F = 2 96500 coulombs liberate 1 mole of Cl2
18 coulombs will liberate
1 25.5
18 mole of Cl 2 17. (a) : nCHCl 0.213
2 96500
3 119.5
40
1 nCH Cl 0.47
18 6.022 1023 molecules
2 2 85
0.213 0.47
2 96500 PT = PA xA + PB xB 200 41.5
0.683 0.683
= 5.616 1019 molecules of Cl2 = 62.37 + 28.55 = 90.92 mm Hg
10. (a) :

18. (d) :

11. (d) : The geometry of P in H3PO2, H3PO3 and


H3PO4 is tetrahedral.
12. (b) : Sulphur cross-links are introduced. 19. (c) : A p-type material is electrically neutral as there
13. (a) : The correct decreasing order of XeF bond are only holes and no extra electrons.
1
length is 20. (c) : Since pV T and p hence, volume
XeF2 > XeF4 > XeF6 V
decreases with pressure. Hence, the order of pressure
200 pm 195 pm 189 pm
is p1 < p2 < p3 < p4.
Bond shortening with increase in highly
electronegative F atoms attached to Xe can be 21. (d) : Here cuprous ions reduce itself to Cu.
explained in terms of increase in charge on Xe atom. 22. (d)
14. (b) : 8 g Br2 reacts with 2.8 g of alkene, therefore, 23. (d) :
2.8
mol. wt. of alkene 160 56
8
Thus, the alkene is C4H8 (4 12 + 8 1 = 56)
15. (c) : For first order reaction,
2.303 [ A] 2.303 0. 1
k= log 0 log
t [ A] 40 0.025 24. (d) :
2.303 0.603 HCOOH + CO2
k= k = 0.0347 min1 HCOOH + Fehlings solution
40
Cu2O CO2 H 2O
Rate = k[A] = 0.0347 0.01 = 3.47 104 M min1 red ppt.

CHEMISTRY TODAY | MARCH 17 45


25. (a) : The screening effect of the orbitals is of the 39. (a) :
order : s > p > d > f.
26. (d) : In COD determination, the pollutants resistant
to microbial oxidation are also oxidised by oxidising 28
Percentage of N 100 46%
agents like K2Cr2O7. 60
27. (c) : 40. (d) : NH3 when dissolved in water forms,
NH3 + H2O NH+4 + OH NH4OH
41. (b) 42. (a) 43. (a)
44. (b) : Both carbanion (formed in presence of a base)
and enol form (formed in presence of an acid) act
as nucleophiles and hence, react with the carbonyl
3 14 group of aldehydes and ketones to give aldols. These,
28. (c) : K .E. nRT ; nN 0.5 mol ; TN ? aldols are further dehydrated in presence of an acid
2 2 28 2
32 to give a, b-unsaturated aldehydes or ketones.
nO 1 mol ; TO 300 K 45. (a) : In a Frenkel defect, an ion leaves its position in
2 32 2
the lattice and occupies normally vacant interstitial
Given, K.E. (N2) = K.E.(O2), so nN TN nO TO position. Hence, density remains the same.
2 2 2 2
or 0.5 TN 1 300 or TN 600 K 46. (c) : Passivity is attained by formation of a thin film
2 2
29. (b) : I2 H2O2 2OH 2I 2H2O O2 of oxide on iron.
I2 is reduced to I. Thus, H2O2 acts as a reducing 47. (d) : Aryl halides (chlorobenzene) do not undergo
agent. nucleophilic substitution with KCN because of
the low reactivity of the Cl atom, which is because
30. (c) : x > y because same bonds are formed in of resonance in chlorobenzene. CN is a strong
reactions (i) and (ii) but bonds between reactant nucleophile.
molecules are broken only in reaction (ii). As
energy is absorbed when bonds are broken so, 48. (b) : At constant temperature, plot of PV vs V for
energy released in reaction (i) is greater than that in real gases is not linear because real gases have
reaction (ii). intermolecular forces of attraction.
31. (d) : Effective molarity of BaCl2 = 3 0.1 = 0.3 ; 49. (d) : 2px and 2py have same energy, so neither energy
effective molarity of FeCl3 = 4 0.075 = 0.3. will be released nor spectral line will be seen.
32. (c) : In MgO, Mg2+ ion is smallest in size and double 50. (c) : Reaction follows SN2 mechanism which does
the charge in comparison to Li+ and Na+ ions. not proceed through a carbocation formation.
33. (a) : Quinone has an a-hydrogen, however, it is a 51. (b) 52. (b) 53. (a) 54. (a)
vinylic hydrogen, so it is very difficult to abstract such a 55. (c) : The application of opposite potential greater
hydrogen and hence, it does not show tautomerism. than 1.1 V result into the flow of electron from
34. (a) : The metal in cyanide process is recovered by cathode to anode and zinc is deposited at zinc
displacement of metal by some more reactive metal electrode (cathode) and copper is dissolved at
from the complex. copper electrode (anode).
4M + 8CN + 2H2O + O2 4[M(CN)2] + 4OH 56. (a)
2[M(CN)2] + Zn [Zn(CN)4]2 + 2M Number of moles of solute
57. (a) : Molality
35. (c) : The two strands in a DNA molecule are not Weight of solvent (in kg )
exactly similar but are complementary. If number of moles of solute = 1
36. (b) : Pu shows +7 oxidation state. Weight of solvent = 1 kg
37. (c) : 1 equivalent of NaOH 1 equivalent of Al(OH)3 then, molality = 1, i.e., one molal solution
40 g of NaOH 78 g of Al(OH)3 For glucose (C6H12O6), molecular weight = 180
Hence, equivalent mass of Al(OH)3 = 78. number of moles = 180/180 = 1
38. (d) : Since NH2NH2 does not contain carbon, Weight of water = 1 kg
therefore, during fusion NaCN which is essential Hence, molality of the solution is one.
for positive Lassaignes test for N, cannot be formed. 58. (a) 59. (a)
Therefore, to form NaCN, NH2NH2 is fused with a 60. (a) : Sulphuric acid is consumed due to formation
carbon containing compound such as starch, sugar of lead sulphate and hence, density decreases.
or even charcoal.

46 CHEMISTRY TODAY | MARCH 17


6. (a) : We know, Ksp(PbS) = [Pb2+][S2]
CHEMISTRY MUSING Since, the lead salt is completely dissociated, [Pb2+]
is equal to the concentration of the lead salt, i.e.,
SOLUTION SET 43 [Pb2+] = 0.001 M. If [S2] is the concentration of S2
1. (d) : pV = nRT
required to just start the precipitation of PbS,
w w w 3.4 10 28
pV RT ; pO2V RT ; pN2 V RT [S2 ] 3.4 10 25 M
M 32 28 0.001
pO2 28 Now, the addition of HCl will suppress the dissociation
; pO2 0.875 pN2 of H2S to that extent that is [S2] = 3.4 1025 M.
pN2 32 As, HCl is completely ionised. [H+] = [HCl]
2. (a) : No. of atoms in unit cell = 1 + 2 = 3 +
Let [HCl] be x, therefore, [H ] = x
Volume of unit cell = 24 1024 cm3 H2S 2H+ + S2
Density = 7.2 g cm3 At equilibrium, [H2S] = 0.1 3.4 1025 0.1
Now, density
n At.wt. [H+] = 2 3.4 1025 + x x
V NA [S2] = 3.4 1025
3 At.wt. [H ]2[S2 ]
7. 2 At. wt. = 34.69 g Ka
24 10 24 6.023 1023 [H2 S]
As, 34.69 g of element contains 6.023 1023 atoms
23 x 2 (3.4 10 25
)
6.023 1023 200 1.1 10
200 g has atoms 0. 1
34.69 23
= 3.4724 1024 atoms 3.5 1024 atoms 0.1 1.1 10
x2 x2 = 3.2356
3. (b) : 3.4 10 25
x = 1.80 [HCl] = 1.80 M
Thus, any concentration of HCl greater than 1.80 M
will just prevent the precipitation of PbS.
7. (d) : AlH4 = sp3, tetrahedral = 18e
BH4 = sp3, tetrahedral = 10e
AlCl4 = sp3, tetrahedral = 82e
8. (a) : In Al(BH4)3, each BH4 forms two hydrogen
bridges.
9. (3) : Compounds containing carbonyl group will
exhibit both nucleophilic addition reaction as well as
WolffKishner reduction reaction.
10. (2) : Bn+ B(n + 4)+
Due to the presence of a-hydrogen it can participate millimoles at t = 0 : a 0 Bn+ B(n + 2)+ + 2e

in aldol reaction but will not give Cannizzaro reaction.
t = 10 : (a x) x 5e + B(n + 4)+ B(n 1)+
Also, carbonyl group undergoes Clemmensen reduction Let normality be N for reducing agent.
in presence of Zn/HCl. 25
Thus, at t = 0, a 2 = N 25; N a
4. (c) : (I) Four unpaired electrons. 2
(II) Three unpaired electrons. At t = 10, (a x) 2 + x 5 = N 32
(III) Five unpaired electrons. for Bn+ for B(n+4)+
(IV) One unpaired electron. 7
3x = 7N or x N
Br 3
(i) Br2, h 2.303 25 / 2N 2.303 25 6
5. (c) : (ii) NaOCH3
Now, k log log
10 25 7 10 2 61
N
Br
(iii) Br2
2 3
(iv) (CH3)3CO
k = 2.07 103 min1 2 103 min1 x=2
Br

CHEMISTRY TODAY | MARCH 17 51


SALT ANALYSIS Odour of the salt :
The qualitative salt analysis deals with the identification Ammoniacal Vinegar Rotten egg
of acidic radicals (anions) and basic radicals (cations) in NH4+ CH3COO S2
an inorganic salt or in a mixture of salts.
Odour
AxBy
Salt
Ay+ Bx Flame test :
Cation Anion
(Basic radical) (Acidic radical)

PRELIMINARY TESTS
Note the state (amorphous or crystalline) and
colour of the salt.
Colour of the salt :
Borax bead test :
White
Borax is heated on a loop of Pt wire, colourless
NH4+, Pb2+, Al3+, Zn2+,
Ba2+, Ca2+, Sr2+, Mg2+ glassy bead of sodium metaborate and boric
Colour
anhydride is formed.
Blue Green Brown Na2B4O7 10H2O

Na2B4O7

Cu2+ Ni2+, Cr3+ Fe3+ 2NaBO2 + B2O3


Glassy bead
Coloured salts are then heated on the glassy
Light green Pink Light pink bead, coloured metaborate is formed in the
Fe2+ Co2+ Mn2+ oxidising flame.

54 CHEMISTRY TODAY | MARCH 17


Colour of bead in oxidising flame Ion indicated ANIONS OR ACIDIC RADICALS
Green in hot, light brown in cold Copper
Anions
Pinkish violet in both hot and cold Manganese
First group : CO32, S2, SO32, CH3COO,
Yellowish brown in hot and pale Iron S2O32, NO2
yellow in cold
Brown in hot and pale brown in cold Nickel Second group : Br, Cl, I, NO3, C2O42

Third group : SO42, PO43


First group :
Group reagent : dil. HCl
Salt + dil. HCl

Effervescence or evolution of gas shows presence of 1st group

Colourless gas with suffocating smell with yellow Colourless gas with rotten egg smell (H2S gas)
Pass through K2Cr2O7 Lead acetate
ppt. of sulphur PbS S2 confirmed
Blackish green solution S2O32 confirmed Black ppt.

Starch iodide paper Lime water


zzColourless and odourless gas (CO2 gas)
Brown gas (NO2) Blue
NO2 confirmed CaCO3(CO32 or HCO3 may be present)
milky
Colourless gas with vinegar smell (CH3COO may zzConfirmation test for HCO3 & CO2
3
be present) Salt solution + FeCl3 (neutral) Salt + water boil and pass through lime water
(CH3COO)3Fe CH3COO confirmed
Blood red colour solution

Colourless gas with suffocating smell (SO2) Lime water Lime water does
Heat and pass turns milky not turn milky
through K2Cr2O7
Solution turns green due to
Cr2(SO4)3 SO32 confirmed HCO3 confirmed CO32 confirmed

Second group :
Group reagent : Conc. H2SO4

CHEMISTRY TODAY | MARCH 17 55


Confirmatory tests of acid radicals :
Nitrate (NO3) Oxalate (C2O42) Chloride (Cl)
Brown ring test : On treating On acidifying sodium carbonate extract Chromyl chloride test : On heating
with acetic acid and on adding cadmium
aqueous solution of salt with freshly salt with concentrated sulphuric acid in
chloride solution gives white precipitate.
prepared solution of ferrous sulphate the presence of potassium dichromate,
Filter and dissolve the precipitate in
and concentrated sulphuric acid, gives deep red vapours of chromyl chloride
a brown ring at the junction of twodilute sulphuric acid and add few drops are evolved.
liquids. of potassium permanganate solution. NaCl + H2SO4 NaHSO4 + HCl
The colour of potassium permanganate Salt
NaNO3 + H2SO4 NaHSO4 + HNO3 K2Cr2O7 + 2H2SO4 2KHSO4
Salt is discharged, indicates the presence of
oxalate. + 2CrO3 + H2O
6FeSO4 + 2HNO3 + 3H2SO4
Na2C2O4 + CaCl2 CaC2O4 + CrO3 + 2HCl CrO2Cl2 + H2O
3Fe2(SO4)3 + 4H2O + 2NO Chromyl chloride
Sodium carbonate White ppt.
[Fe(H2O)6]SO4 + NO extract (Red vapours)
2NaCl
[Fe(H2O)5NO]SO4 + H2O CaC O + H SO These vapours on passing through
2 4 2H C O + CaSO
4 2 2 4 4
Brown ring sodium hydroxide solution give yellow
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4
solution of sodium chromate.
+ 3H2O + 5[O]
CrO2Cl2 + 4NaOH Na2CrO4 +
COOH Yellow colour
+ [O] 2CO2 + H2O
COOH 2NaCl + 2H2O
Iodide (I) The yellow solution on neutralising
Layer test : On treating salt with dilute with acetic acid and on addition of lead
sulphuric acid, chloroform or carbon acetate gives yellow precipitate of lead
Confirmatory tests chromate.
tetrachloride and chlorine water, gives
violet coloured layer. for acid radicals of Na2CrO4 + (CH3COO)2Pb
Chlorine replaces iodine that dissolves group II PbCrO4 + 2CH3COONa
Yellow ppt.
in chloroform.
2NaI + Cl2 2NaCl + I2 Bromide (Br)
Salt
Layer test : On treating salt with dilute sulphuric acid, chloroform or
I2 + Chloroform Violet coloured carbon tetrachloride and chlorine water gives brown coloured layer.
layer Chlorine replaces bromine that dissolves in chloroform.
Starch paper test : Violet vapours with 2NaBr + Cl2 2NaCl + Br2
starch paper give blue colour. Salt
I2 + Starch I2-starch complex Br2 + Chloroform Brown coloured layer
Blue colour

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A
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by University of Adelaide researchers. The researchers team has engineered a nanoporous material called nanoporous
anodic alumina to make a special structure called a rugate filter. The surface of the filter has been modified to make
it selective to mercury ions. As water flows through the pores of the filter, the mercury ions become attached to the surface.
An optical systemreflection spectroscopymeasures the amount of mercury present. A range of tests have shown the sensor can
detect mercury at levels of 200 parts per billion in a complex mixture of other metal ions and environmental samples. Continued
work will seek to enhance the optical signals for even higher sensitivity. The promising sensing performance of this system
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This technique could provide the basis for future point-of-analysis systems for monitoring water quality on site and may help
implement better monitoring processes around the world.

56 CHEMISTRY TODAY | MARCH 17


Third group : These radicals cannot be detected by either dil. H2SO4 or conc. H2SO4. For detection of these
acidic radicals we need some specific tests.

CATIONS OR BASIC RADICALS


Group Group reagent Cations Form of ppt.
2+ +
I dil. HCl Pb , Ag , Hg 2+
2 Chlorides
II dil. HCl + H2S gas Pb2+, Hg , Cu , Cd2+, Bi3+,
2+ 2+
Sulphides
Sb3+, As3+, Sn2+/Sn4+
III NH4Cl + NH4OH Fe3+, Al3+, Cr3+ Hydroxides
IV NH4Cl + NH4OH + H2S gas Zn2+, Mn2+, Co2+, Ni2+ Sulphides
V (NH4)2CO3 + NH4OH Ca2+, Sr2+, Ba2+ Carbonates
VI Na2HPO4 + NH4OH Mg2+
Identification of basic radicals :

CHEMISTRY TODAY | MARCH 17 57


Confirmatory tests of basic radicals :
Precipitates Confirmatory Tests
Group I
AgCl Dissolves in NH4OH, white ppt. of AgCl is again obtained on adding dil. HNO3. Yellow ppt. of
AgI is formed on adding KI.
PbCl2 Dissolves in hot water, gives yellow ppt. of PbCrO4 with K2CrO4 and yellow ppt. of PbI2 with KI.
Hg2Cl2 Turns black with NH4OH. Black residue {Hg + Hg(NH2)Cl} dissolves in aquaregia forming
mercuric chloride (HgCl2). On addition of stannous chloride solution to HgCl2 white ppt.
(Hg2Cl2) is formed which turns grey (Hg).
Group II A Precipitates do not dissolve in yellow ammonium sulphide.
HgS Dissolves in aquaregia, grey ppt. of Hg is obtained with SnCl2 or Cu turnings.
PbS Dissolves in dil. HNO3, white ppt. of PbSO4 is obtained on adding dil. H2SO4.
Bi2S3 Dissolves in dil. HCl, white ppt. of BiOCl is obtained on adding excess of water. Black ppt. of Bi
is obtained on adding Na2SnO2 solution.
CuS Blue coloured solution is obtained on adding dil. HNO3 and excess of NH4OH which gives
chocolate brown ppt. of Cu2[Fe(CN)6] with K4[Fe(CN)6].
CdS Colourless solution is obtained on adding dil. HNO3 and excess of NH4OH, which gives yellow
ppt. of CdS again on adding H2S.
Group II B Precipitates dissolve in yellow ammonium sulphide.
As2S3 Insoluble sulphide, As2S5 is obtained by treating with conc. HCl, which gives yellow ppt. of
ammonium arsenomolybdate on adding conc. HNO3 and heating with ammonium molybdate.
SnS2 or SnS Filtrate of sulphide in conc. HCl is reduced to SnCl2 by treating with Fe or Zn
which on adding HgCl2 solution initially gives white ppt. of Hg2Cl2 and finally
turns to grey Hg.
Sb2S3 Filtrate of sulphide in conc. HCl gives white ppt. of SbOCl on adding excess of water and orange
ppt. of Sb2S3 on passing H2S gas.
Group III
Fe(OH)3 Dissolves in dil. HCl, gives prussian blue solution or ppt. of Fe4[Fe(CN)6]3 on adding K4[Fe(CN)6]
and blood red coloured Fe(CNS)3 on adding KCNS.
Cr(OH)3 The solution obtained on heating precipitate with NaOH and Br2 water contains Na2CrO4 which
gives yellow ppt. of PbCrO4 on treating with acidified lead acetate solution.
Al(OH)3 Dissolves in NaOH and is again precipitated out on boiling with NH4Cl.
Group IV Soluble in conc. HCl.
ZnS Solution (ZnCl2) is treated with NaOH, a white ppt. of Zn(OH)2 appears which dissolves in
excess of NaOH and on passing H2S, white ppt. of ZnS is obtained.
MnS Precipitate of MnO2 is obtained on heating the solution with NaOH and Br2 water. HMnO4
imparts pink colour to the supernatant liquid on treating the ppt. with excess of HNO3 and red
lead (Pb3O4).
Group IV Insoluble in conc. HCl
CoS Dissolves in aqua-regia. Yellow ppt. of potassium cobaltinitrite K3[Co(NO2)6] is obtained on
adding CH3COOH (in excess) and KNO2.
NiS Dissolves in aqua-regia. Red ppt. of Ni-dmg complex is obtained on adding NH4OH in excess
and dimethyl glyoxime.

58 CHEMISTRY TODAY | MARCH 17


Group V Soluble in acetic acid.
BaCO3 Yellow ppt. of BaCrO4 is obtained on adding K2CrO4 to solution.
SrCO3 White ppt. of SrSO4 is obtained on adding (NH4)2SO4 to solution.
CaCO3 White ppt. of CaC2O4 is obtained on adding (NH4)2C2O4 to solution.
Group VI
Mg2+ White ppt. of Mg(NH4)PO4 is formed on adding Na2HPO4 and NH4OH to solution.
Zero
NH4+ Salt evolves NH3 gas on heating with NaOH which gives dense white fumes of
NH4Cl with HCl and a brown ppt. of H2N HgO HgI on adding Nesslers reagent, K2HgI4.

DETECTION OF N, S, CI IN ORGANIC sodium metal. The ionic compounds formed during


the fusion are extracted in aqueous solution and can
COMPOUNDS be detected by simple chemical tests.
LASSAIGNES TEST Lassaignes extract : A small pellet of metallic
sodium together with a little amount of the substance
It is a general test for the detection of halogen,
nitrogen and sulphur in organic compounds. is heated to red hot in an ignition tube. It is then
These elements are covalently bonded to the suddenly plunged into about 10 mL of distilled
organic compounds. In order to detect them, water in a China dish. The mixture is boiled well
these have to be converted into their ionic forms. and filtred. Filtrate is known as Lassaignes extract
This is done by fusing the organic compound with (L.E.).

When sodium fusion is carried out with excess of Na + C + N + S NaCNS


Sodium thiocyanate
sodium, thiocyanate decomposes to cyanide and
NaCNS + 2Na NaCN + Na2S
sulphide ions which give their usual tests. Thus,
Lassaignes test fails in case of compounds which
we do not get blood red colour with ferric chloride contain nitrogen but no carbon e.g., hydrazine
even though N and S both are present. (NH2NH2) and hydroxylamine (NH2OH).

CHEMISTRY TODAY | MARCH 17 59


TITRATION HPh + H2O H3O+ + Ph
Colourless Pink
One of the important methods in quantitative analysis Some common examples of acid-base indicators :
is volumetric analysis, a commonly used laboratory
technique. It is used to determine the unknown Indicators pH Range Acid Base
concentration of a sample by measuring its volume. Phenolphthalein 8.0 - 10.0 Colourless Pink
ACID BASE TITRATION Methyl orange 3.1 - 4.4 Red Orange

It is a method used to determine the strength of an Methyl red 4.4 - 6.2 Red Yellow
acid or alkali and this type of titration is based on Phenol red 6.4 - 8.0 Yellow Red
the neutralisation reaction.
Thymol blue 1.2 - 2.8 Red Yellow
AH + BOH AB + H2O
(Acid) (Base) (Salt) Thymol blue 8.0 - 9.6 Yellow Blue
INDICATOR Methyl yellow 2.9 - 4.0 Red Yellow

An indicator is a chemical substance that undergoes TITRIMETRIC CALCULATIONS


a colour change at the end point. The end point
of an acid-base titration can be determined using Strength of a solution : It is the amount of solute in
acid-base indicators. Acid base indicators are either grams present per litre of the solution.
weak organic acids or weak organic bases. The Strength (g/L) = Normality Eq. wt.
colour change of an indicator depends on the pH of Strength (g/L) = Molarity Mol. mass
the medium. The un-ionized form of an indicator Normality equation : N1V1 = N2V2
has one colour, but its ionized form has a different (Solution 1) (Solution 2)
colour. Molarity equation : M1V1n1 = M2V2n2
For example, consider the indicator phenol- (Solution 1) (Solution 2)
phthalein, whose ionization can be written as : [ N = M n, where n = valency factor]

60 CHEMISTRY TODAY | MARCH 17


1. To a solution of an acid radical, MgSO4 solution is 8. In the separation of Cu2+ and Cd2+ in 2nd group
added and white ppt. appears only on heating. The qualitative analysis of cations, tetrammine
acid radical may be copper(II) sulphate and tetramminecadmium(II)
(a) CO32 (b) SO32 (c) HCO3 (d) C2O42 sulphate react with KCN to form the corresponding
2. In second group, H2S is passed in the presence of cyano complexes. Which one of the following pairs
dil. HCl because of the complexes and their relative stability enable
(a) HCl checks incomplete precipitation of higher the separation of Cu2+ and Cd2+?
group radicals (a) K3[Cu(CN)4] more stable and K2[Cd(CN)4]
(b) HCl checks precipitation of sulphur less stable.
(c) both (a) and (b) (b) K2[Cu(CN)4] less stable and K2[Cd(CN)4]
(d) none of the above. more stable.
(c) K2[Cu(CN)4] more stable and K2[Cd(CN)4]
3. During the titration of CH3COOH with NaOH, the less stable.
pH at the end point is likely to be (d) K3[Cu(CN)4] less stable and K2[Cd(CN)4]
(a) less than 7 (b) more than 7 more stable.
(c) equal to 7
(d) depends upon molarity of NaOH. 9. 0.45 g of acid (molecular weight 90) is neutralised by
20 mL of 0.5 N caustic potash. The basicity of acid is
4. An aqueous solution of a salt gave white precipitate (a) 1 (b) 2 (c) 3 (d) 4
on treatment with dilute HCl. The precipitate
dissolved in boiling water. Both the solutions give 10. 35.4 mL of HCl is required for the neutralisation of
white precipitate with dilute H2SO4 and yellow a solution containing 0.275 g of sodium hydroxide.
precipitate with K2CrO4 and KI separately. The The normality of hydrochloric acid is
metal ion present in the solution is (a) 0.97 N (b) 0.142 N
(a) Hg(II) (b) Hg(I) (c) Pb(II) (d)Cu (II) (c) 0.194 N (d) 0.244 N
5. Potassium chromate solution is added to an aqueous 11. The reagent(s) that can selectively precipitate S2
2
solution of a metal chloride. The precipitate thus from a mixture of S2 and SO4 in aqueous solution
obtained is insoluble in acetic acid. This is subjected is (are)
to flame test, the colour of the flame is (a) CuCl2 (b) BaCl2
(a) lilac (b) apple green (c) Pb(OOCCH3)2 (d) Na2[Fe(CN)5NO]
(c) crimson red (d) golden yellow. (JEE Advanced 2016)
6. An aqueous solution of 6.3 g oxalic acid dihydrate 12. Two solutions of HCl, A and B have concentrations
is made up to 250 mL. The volume of 0.1 N NaOH of 0.5 N and 0.1 N respectively. The volume of
required to completely neutralise 10 mL of this solutions A and B required to make 2 litre of 0.2 N
solution is HCl are
(a) 40 mL (b) 20 mL (c) 10 mL (d) 4 mL (a) 0.5 L of A and 1.5 L of B
(b) 1.5 L of A and 0.5 L of B
7. Which one of the following statements is correct
(c) 1.0 L of A and 1.0 L of B
when SO2 is passed through acidified K2Cr2O7
(d) 0.75 L of A and 1.25 L of B.
solution?
(a) SO2 is reduced. 13. In group IV analysis NH4OH is added before passing
(b) Green Cr2(SO4)3 is formed. H2S gas because
(c) The solution turns blue. (a) the sulphides of group IV are insoluble in NH4OH
(d) The solution is decolourised. (b) the sulphides of other metals are soluble in
(NEET Phase-I 2016) NH4OH

CHEMISTRY TODAY | MARCH 17 61


(c) the concentration of S2 ions is high enough to (a) region 1 (b) region 2
precipitate the sulphides of group IV (c) region 3 (d) region 4.
(d) the sulphides of second group are soluble in (JEE Main 2016)
NH4OH. 21. Cl2 gas is continuously passed with constant shaking
14. A solution of a metal ion when treated with KI gives a through Lassaignes extract containing CS2. If the
red precipitate which dissolves in excess of KI to give a extract contains both NaBr and NaI, first a violet
colourless solution. Moreover, the solution of metal ion colour is produced, then the organic layer turns
on treatment with a solution of cobalt(II) thiocyanate colourless and finally orange colour is seen in the
gives rise to deep blue crystalline precipitate. The metal CS2 layer. The CS2 turns colourless between violet
ion is and orange colour due to the formation of
(a) Pb2+ (b) Hg2+ (c) Cu2+ (d) Co2+ (a) IBr (b) ICl (c) BrCl3 (d) NaI3
15. In the following reaction sequence in aqueous 22. A solution containing Na2CO3 and NaHCO3
solution, the species X, Y and Z, respectively are is titrated against HCl. The volume of the acid
Ag+ Ag+ With time
S2O32 used when methyl orange is added as indicator
is x mL and the volume of the acid used when
  
Clear White Black
solution precipitate precipitate
phenolphthalein is added as indicator separately is
(a) [Ag(S2O3)2]3, Ag2S2O3, Ag2S y mL. The volume of HCl used for the neutralisation
(b) [Ag(S2O3)3]5, Ag2SO3, Ag2S of NaHCO3 will be
(c) [Ag(SO3)2]3, Ag2S2O3, Ag (a) (x y) mL (b) (x 2y) mL
(d) [Ag(SO3)3]3, Ag2SO4, Ag (c) (x + y) mL (d) (x + 2y) mL
(JEE Advanced 2016)
23. In the titration of sodium carbonate with
16. Lassaignes test for nitrogen is positive for which hydrochloric acid taken in burette the indicator
compound? used is
(a) NH2OH (b) NH2NH2 (a) phenolphthalein for first equivalence point and
(c) H2NCONH2 (d) All of these methyl orange for second equivalence point
17. When intimate mixture of potassium dichromate (b) methyl orange for first equivalence point and
and KCl is heated with conc. H2SO4 , which of the phenolphthalein for second equivalence point
following is produced in the form of red vapours? (c) either methyl orange or phenolphthalein for
(a) CrO3 (b) Cr2O3 both equivalence points
(c) CrO2Cl2 (d) CrCl3 (d) thymol blue for both equivalence points.
18. A laboratory reagent on strongly heating gives two 24. A blue colouration is not obtained when
oxides of sulphur. On addition of aq. NaOH solution (a) ammonium hydroxide dissolves in copper
to its aqueous solution a dirty green precipitate is sulphate
obtained. Identify the reagent. (b) copper sulphate solution reacts with
(a) FeSO4 (b) CuSO4 K4[Fe(CN)6]
(c) Al2(SO4)3 (d) None of these (c) ferric chloride reacts with sodium ferrocyanide
19. 25 mL of a solution of barium hydroxide on titration (d) anhydrous white CuSO4 is dissolved in water.
with a 0.1 molar solution of hydrochloric acid gave 25. Sodium extract is heated with concentrated HNO3
a titre value of 35 mL. The molarity of barium before testing for halogens because
hydroxide solution was (a) Ag2S and AgCN are soluble in acidic medium
(a) 0.14 M (b) 0.28 M (c) 0.35 M (d) 0.07 M (b) silver halides are totally insoluble in nitric acid
20. The hottest region of Bunsen flame shown in the (c) S2 and CN, if present, are decomposed by
figure below is conc. HNO3 and hence, do not interfere in the
test
(d) Ag reacts faster with halides in acidic medium.
(JEE Main 2016 online)
26. Which of the following statements is wrong?
(a) Using Lassaignes test, nitrogen and sulphur
present in an organic compound can be tested.

62 CHEMISTRY TODAY | MARCH 17


(b) Using Beilsteins test, the presence of halogens pink colour in NaOH when the pH is more than 7.
in a compound can be tested. 4. (c) : Pb2+ + 2Cl PbCl2
(c) In Lassaignes filtrate, the nitrogen in an organic
compound is converted to NaCN. PbCl2(s) + H2O PbCl2(aq)
(d) In the estimation of carbon, an organic
compound is heated with CaO in a combustion
tube.
PbI2
27. The brown ring test for nitrates depends on
(a) the reduction of nitrate to nitric oxide
(b) oxidation of nitric oxide to nitrogen dioxide 5. (b) : BaCl2 + K2CrO4 BaCrO4 + 2KCl
(c) reduction of ferrous sulphate to iron BaCrO4 is insoluble in acetic acid and Ba gives
(d) oxidising action of sulphuric acid. apple green colour in flame test.
6.3 1000
28. The following four solutions are kept in separate 6. (a) : Normality of oxalic acid 0. 4 N
63 250
beakers and copper metal is put in each of them.
N1V1 = N2V2
Which solution will become blue after sometime ?
V1 0.1 = 10 0.4 V1 = 40 mL
(a) AgNO3 solution (b) Zn(NO3)2 solution
(c) Ba(NO3)2 solution (d) NaNO3 solution 7. (b) : K2Cr2O7 + H2SO4 + 3SO2 K2SO4 +
29. An aqueous solution of FeSO4, Al2(SO4)3 and Cr2(SO4)3 + H2O
(Green)
chrome alum is heated with excess of Na2O2 and
filtered. The materials obtained are 8. (a) : K3[Cu(CN)4] is more stable whereas
(a) a colourless filtrate and a green residue K2[Cd(CN)4] is less stable.
(b) a yellow filtrate and a green residue 9. (b) : Eq. of acid = Eq. of base,
(c) a yellow filtrate and a brown residue 0.45 20 0.5
(d) a green filtrate and a brown residue. Eq. wt 45
Eq. wt. 1000
30. Which of the following plots represents the graph Mol. wt. 90
of pH against volume of alkali added in titration of Basicity 2
NaOH and HCl ? Eq. wt. 45
10. (c) : Number of equivalents of NaOH
Mass 0.275
(a) (b) 6.875 10 3
Equivalent mass 40
Number of equivalents of HCl = Number of
equivalents of NaOH
NV 3
(c) (d) 6.875 10
1000
N 35.4
6.875 10 3 or N = 0.194 N
SOLUTIONS
1000
1. (c) : 2NaHCO3 + MgSO4 Mg(HCO3)2 + Na2SO4 11. (a) : (a) Cu2+ will give black precipitate of CuS while
Soluble CuSO4 is soluble.
2 2
Cu2+ + S CuS Cu2+ + SO4 CuSO4
Black precipitate Soluble
(b) Ba2+ will give white precipitate of BaSO4 while
2. (a) : Due to common ion effect, the ionisation of BaS is soluble.
H2S is suppressed by HCl and only group II basic Ba2+ + S2 BaS Ba2+ + SO4
2
BaSO4
radicals are precipitated. Higher groups are not Soluble White precipitate
precipitated. (c) Pb2+ will give precipitate with both S2 and SO4 .
2

3. (b) : In the titration of CH3COOH with NaOH, Pb2+ + S2 PbS Pb2+ + SO4
2
PbSO4
phenolphthalein is used as an indicator. It gives Black precipitate White precipitate

CHEMISTRY TODAY | MARCH 17 63


(d) 2Na+ + S2 Na2S

2 22. (b) : Methyl orange (M) indicates the neutralisation


2Na+ + SO4 Na2SO4 of both Na2CO3 and NaHCO3 in a mixture with
Soluble
HCl solution and the volume used is x mL.
12. (a) : x L of 0.5 N HCl + (2 x) L of 0.1 N HCl M
Na2CO3 + 2HCl 2NaCl + H2O + CO2
= 2 L of 0.2 N HCl M
NaHCO3 + HCl NaCl + H2O + CO2
i.e., 0.5 x + 0.2 0.1 x = 0.4
0.2 Phenolphthalein (P) indicates the neutralisation of
0.4 x = 0.4 0.2 = 0.2 or x 0.5 Na2CO3 only upto single stage, i.e., upto NaHCO3
0.4
13. (c) stage with HCl and the volume used is y mL.
P
14. (b) : Hg2+ + 2I HgI2 Na2CO3 + HCl NaHCO3 + NaCl
Red ppt . For complete neutralisation of Na2CO3, the
volume of HCl used will be 2y mL. Hence, the
HgI2 + 2KI 2HgI4
Soluble volume of HCl used for neutralisation of NaHCO3
only = (x 2y) mL.
23. (a) : In the titration of sodium carbonate with
Ag+ hydrochloric acid first equivalence point appears
15. (a) : Ag+ + 2S2O32 [Ag(S2O3)2]3 at pH of about 8.3, hence, phenolphthalein is used
(Excess) Argentothiosulphate
as indicator for first equivalence point. Whereas,
(X) (Soluble)
second equivalence point appears at pH of about
With time
Ag2S2O3 Ag2S 3.9, hence, methyl orange is used as indicator for
(due to hydrolysis)
(Y) (Z) second equivalence point.
(White ppt.) (Black ppt.)
24. (b) : 2CuSO4 + K4[Fe(CN)6] Cu2[Fe(CN)6]
16. (c) : Hydroxylamine and hydrazine, both do not Chocolate ppt.
have carbon, hence, NaCN will not be formed + 2K2SO4
in Lassaignes extract leading to negative test for 2
25. (c) : S and CN ions if present may interfere by
nitrogen. giving white ppt. of AgCN and black ppt. of Ag2S
17. (c) : K2Cr2O7 + 4KCl + 6H2SO4 2CrO2Cl2 + with AgNO3. Thus, before testing for halogens
Chromyl chloride they are decomposed by conc. HNO3, so that they
(red vapours) do not interfere in the test.
6KHSO4 + 3H2O
26. (d) : In the estimation of carbon, organic compound
18. (a) : The reagent is FeSO4 which gives SO2 and SO3 is heated with CuO in a combustion tube.
on heating. CuO + C Cu + CO
2FeSO4 Fe2O3 + SO2 + SO3 27. (a) : The brown ring is appeared due to the
Ferrous
sulphate formation of a brown complex between nitric oxide
Ferrous sulphate gives dirty green coloured Fe(OH)2 (formed as a result of reduction of the nitrate ion by
with aqueous NaOH. Fe2+ ions) and Fe2+ ions.
FeSO4 + 2NaOH Fe(OH)2 + Na2SO4 NO3(aq) + 3Fe2+ +
(aq) + 4H (aq) NO(g) + 3Fe3+(aq) +
(Dirty green) 2H2O(l)
19. (d) : Ba(OH)2 + 2HCl BaCl2 + 2H2O Fe2+(aq) + NO(g) + 5H2O(l) [Fe(H2O)5NO]2+ aq
M1 V1 M2 V2 M1 25 0.1 35 Pentaaquanitrosonium ion (I)
(Brown complex)
1 2 1 2
M1 = 0.07 M 28. (a) : Cu + 2AgNO3 Cu(NO3)2 + 2Ag
Blue
20. (b) : Region-2 is the region of the blue flame which
is the hottest region of Bunsen flame. 29. (b) : Yellow filtrate is due to chromate ion (CrO42)
and green residue is due to Fe(OH)2.
21. (b) : I2 first liberated combines with Cl2 to form
colourless iodine monochloride. 30. (c)

64 CHEMISTRY TODAY | MARCH 17


Class XI

T his specially designed column enables students to self analyse their


extent of understanding of complete syllabus. Give yourself four
marks for correct answer and deduct one mark for wrong answer.
Self check table given at the end will help you to check your
readiness.

Total Marks : 120 Time Taken : 60 Min.

NEET / AIIMS 1/ 2
x Kp x Kp P
Only One Option Correct Type (a) (b)
a Kp P a Kp
1. 1.12 mL of a gas X is produced at STP by the action 1/ 2 1/2
x Kp x Kp
of 2.3 mg of an alcohol with methyl magnesium (c) (d)
iodide. The molecular mass of alcohol and the gas a P a Kp P
X are respectively 6. In a polar molecule, the ionic charge is
(a) 32 ; CH4 (b) 46 ; CH4
4.8 1010 e.s.u. If the interionic distance is 1 ,
(c) 46 ; C2H6 (d) none of these.
then the dipole moment is
2. The wave number of electromagnetic radiations (a) 41.8 debye (b) 4.18 debye
emitted during the transition in between two energy (c) 4.8 debye (d) 0.48 debye
levels of Li2+ ion whose principal quantum number
7. If the collision frequency of a gas at 1 atm pressure
sum is 4 and difference is 2, is
8 is Z, then its collision frequency at 0.5 atm is
(a) 3.5 RH (b) 4 RH (c) 8 RH (d) RH (a) 1.0 Z (b) 0.25 Z (c) 2 Z (d) 0.50 Z
9
3. The root mean square velocity of a gas molecule at 8. If M is the molecular weight of FeC2O4, then its
100 K and 0.5 atm pressure is 106.4 m s1. If the equivalent weight in the conversion,
temperature is raised to 400 K and the pressure FeC2O4 Fe3+ + CO2 is
is raised to 2 atm, the root mean square velocity
M M
becomes (a) (b)
(a) 106.4 m s1 (b) 425.6 m s1 3 6
(c) 212.8 m s 1
(d) 851.2 m s1 M
(c) (d) equal to M.
2
4. What will be the heat of formation of methane if 9. The volume of 0.05 M KMnO4 solution required to
the heat of combustion of carbon is x kJ, heat of oxidise completely 2.70 g of oxalic acid (H2C2O4) in
formation of water is y kJ and heat of combustion acidic medium will be
of methane is z kJ?
(a) 120 cm3 (b) 240 cm3
(a) (x y + z) kJ (b) ( z x + 2y) kJ 3
(c) 360 cm (d) 480 cm3
(c) ( x 2y z) kJ (d) ( x 2y + z) kJ
10. Which one of the following is present as an active
5. a moles of PCl5 is heated in a closed container
ingredient in bleaching powder for bleaching
to equilibriate PCl5(g) PCl3(g) + Cl2(g) at a
action?
pressure of P atm. If x moles of PCl5 dissociate at (a) CaOCl2 (b) Ca(OCl)2
equilibrium, then (c) CaO2Cl (d) CaCl2

CHEMISTRY TODAY | MARCH 17 65


11. The correct order of decreasing ionic character of energies required to convert all the atoms present in
lead dihalides is : 7 mg of lithium vapours and 23 mg of sodium
(a) PbF2 > PbCl2 > PbBr2 > PbI2 vapours to their respective gaseous cations
(b) PbF2 > PbBr2 > PbCl2 > PbI2 respectively are
(c) PbF2 > PbI2 > PbCl2 > PbBr2 (a) 52 J, 49.5 J (b) 520 J, 495 J
(d) PbCl2 > PbBr2 > PbF2 > PbI2 (c) 49.5 J, 52 J (d) 495 J, 520 J
12. The compound which will not show tautomerism 19. An ideal gas has a volume V at temperature T.
is During a change, it follows an additional law
(a) PhCH CHOH (b) PhCH CHOCH3 VP2 = constant. The final temperature of the gas
when it expands to a volume 2V will be
(c) (d) PhCH NOH
(a) 2T (b) 2 T (c) 1.5T (d) 2.5T
More than One Options Correct Type
Assertion and Reason Type
20. The reversible expansion of an ideal gas under
Directions : In the following questions, a statement of
adiabatic and isothermal conditions is shown in the
assertion is followed by a statement of reason. Mark the correct
figure. Which of the following statement(s) is (are)
choice as :
(a) If both assertion and reason are true and reason is the
correct?
correct explanation of assertion.
(b) If both assertion and reason are true but reason is not the
correct explanation of assertion.
(c) If assertion is true but reason is false.
(d) If both assertion and reason are false.
13. Assertion : CH4 does not react with Cl2 in dark.
Reason : Chlorination of CH4 takes place in
sunlight. (a) T1 = T2
(b) T3 > T1
14. Assertion : Suspended particulate matter (SPM) is (c) wisothermal > wadiabatic
an important pollutant released by diesel vehicles. (d) Uisothermal > Uadiabatic
Reason : Catalytic converters greatly reduce
pollution caused by automobiles. 21. Which of the following statements are not correct?
(a) Kw is always constant and equal to 1014.
15. Assertion : Absolute ethanol cannot be obtained by (b) pH + pOH = pKw at all temperatures.
simple fractional distillation of a mixture of alcohol (c) Salts of weak acid and weak base do not undergo
and water. hydrolysis.
Reason : The absolute alcohol boils at 78.3C. (d) Addition of sodium acetate to acetic acid
JEE MAIN / JEE ADVANCED / PETs increases the pH of acetic acid.
Only One Option Correct Type 22. In an exothermic reaction, heat is evolved, and
1
16. The electron affinity values (in kJ mol ) of three system loses heat to the surroundings. For such
halogens X, Y and Z are respectively 349, 333 and system
325. Then X, Y and Z are respectively (a) qp will be negative (b) rH will be negative
(a) F2, Cl2 and Br2 (b) Cl2, F2 and Br2 (c) qp will be positive (d) rH will be positive.
(c) Cl2, Br2 and F2 (d) Br2, Cl2 and F2. 23. Examine the following two structures for the
17. The number of nodal planes present in anilinium ion and choose the incorrect statements.
*s-orbital is NH3
(a) 0 (b) 3 (c) 1 (d) 2 +
I. II.
18. The ionisation enthalpies of lithium and sodium are
520 kJ mol1 and 495 kJ mol1 respectively. The

66 CHEMISTRY TODAY | MARCH 17


(a) II is not an acceptable canonical structure 28. Addition of HCl to 3, 3, 3-trichloropropene gives
because carbonium ions are less stable than (a) Cl3CCH2CH2Cl (b) Cl3CCHClCH3
ammonium ions. (c) Cl2CHCHClCH2Cl (d) Cl2CHCH2CHCl2
(b) II is not an acceptable canonical structure Matrix Match Type
because it is non-aromatic. 29. Match the terms given in Column I with the
(c) II is not an acceptable canonical structure compounds given in Column II.
because nitrogen has 10 valence electrons. Column I Column II
(d) II is an acceptable canonical structure. (A) Acid rain (P) CHCl2CHF2
(B) Photochemical smog (Q) CO
Integer Answer Type
(C) Combination with (R) CO2
24. How many of the following compounds are used as haemoglobin
stabilizers for H2O2 to check its decomposition? (D) Depletion of ozone layer (S) NO2
(T) Unsaturated
K2O, H3PO4, glycerol, Na2O, alcohol, acetanilide
hydrocarbons
25. The number of alkali metals existing as liquid at A B C D
303 K is (a) Q P R, S S, T
Li, Na, K, Rb, Cs, Fr (b) R, S S, T Q P
26. When Sn (IV) chloride is treated with excess of (c) R, S Q P S, T
conc. HCl, the complex [SnCl6]2 is formed. The (d) S, T R, S Q P
oxidation state of Sn in the complex is 30. Match the terms given in Column I with the
Comprehension Type compounds given in Column II.
Column I Column II
Alkenes and alkynes undergo electrophilic addition (A) Entropy of vapourisation (P) decreases
reactions but alkynes are less reactive than alkenes in (B) K for spontaneous (Q) is always
these reactions even though they contain two -bonds. process positive
Although the addition of unsymmetrical reagents to (C) Crystalline (R) Lowest entropy
solid state
unsymmetrical alkenes and alkynes generally occurs in H vap
accordance with Markovnikovs rule, yet there are many (D) U in adiabatic (S) of ideal
Tb
exceptions. expansion gas
27. Propene on reaction with chlorine water gives A B C D
(a) P Q R Q, S
(a) (b)
(b) P R Q Q, S
(c) Q, S Q P R
(c) (d) (d) Q, S Q R P

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CHEMISTRY TODAY | MARCH 17 67


NEET JEE
Class
XII

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Unit P RINCIPLES R ELATED TO


9 PR ACTICAL C HEMISTRY
ORGANIC COMPOUNDS
PREPARATION
< 10C

Acetanilide : It is an acetyl derivative of aniline.


It is prepared by acetylation of aniline.

It is an electrophilic substitution reaction in


which acetanilide acts as nucleophile and
nitronium ion acts as an electrophile.
Aniline yellow : It is an azo dye also known as
p-aminoazobenzene.
It is prepared by coupling of benzenediazonium
chloride with aniline in acidic medium.

It is a nucleophilic acyl substitution reaction in


which aniline acts as a nucleophile and acetic
anhydride acts as an electrophile. Iodoform : It is triiodomethane and is an iodine
analogue of chloroform. It is used as a mild
p-Nitroacetanilide : It is a nitro derivative of
antiseptic and disinfectant.
acetanilide.
It is prepared by treating an organic compound
It is prepared by nitration of acetanilide with
nitrating mixture. containing group (ethanol,

68 CHEMISTRY TODAY | MARCH 17


DETECTION OF FUNCTIONAL GROUPS
propan-2-ol, butan-2-ol) or Detection of unsaturation :
group (acetaldehyde, acetone, butan-2-one,
acetophenone) with iodine in presence of
sodium or potassium hydroxide.

With acetone no initial oxidation takes place.

Detection of alcohol :
CHI3 +
Alcohol
CH3COONa
Dibenzalacetone : Dibenzalacetone is prepared by Xanthate Test CAN Test Ester Test
aldol condensation of acetone with two equivalents
of benzaldehyde. It is a base catalysed aldol ROH + KOH Sample + Ceric Sample +
condensation. ammonium Acetic acid
O O ROK nitrate
H O 2H 2 O CS2 Fruity smell
2 + Appearance of
+ of ester
S K
Benzaldehyde
Acetone
Dibenzalacetone
R O C pink or red colour of
(1,5-Diphenyl-1,4-pentadien-3-one)
S Ce(NO3)4(ROH)2
(Yellow ppt.)

Detection of phenol :
Formation Sample + Sample + Violet Phenolic
of orange NaNO2 + HCl colour group
or red dye C6H5NH2 FeCl3 (C6H5O)3Fe present
Phenol

Phthalein test Liebermanns nitroso test

conc. 4
p-Nitrosophenol

NaOH
, H2O

Indophenol sodium salt


(Blue)

(Colourless)
Phenol (two molecules)

(Pink colour solution)


Note : These tests of phenol, can be used to distinguish between alcohols and phenols, as these tests cannot be given
by alcohols.

CHEMISTRY TODAY | MARCH 17 69


Detection of
carbonyl groups
For ketones only For both aldehydes/ketones

Iodoform test (for methyl Sodium NaHSO3 test Bradys reagent test
ketones) nitroprusside test (2, 4-DNP)
R CO CH3 + 3I2 Sodium nitroprusside
+ 4NaOH 3NaI solution + NaOH + RCOR
+ CHI3 + RCOONa Appearance of (White ppt.)
Yellow ppt. + 3H2O wine-red colour.

(Orange or red ppt.)

For aldehydes only

Schiff s test Benedicts test (Cu2+ ions Fehlings test (Cu2+ Tollens test
Schiff s reagent + R CHO complexed with citrate ions) ions complexed RCHO + 2[Ag(NH3)2]OH
(Colourless) RCHO + 2Cu(OH)2 + NaOH with tartarate ions)
Deep red or violet colour RCOONa + Cu2O + RCHO + 2Cu2+ + RCOONH4
complex Red ppt. 3OH 2Cu+ + + 3NH3 + H2O + 2Ag(s)
3H2O Red ppt. Silver mirror
RCOO + 2H2O
Detection of amino group :
Amino group

Nitrous acid test Isocyanide test Azo dye test

Sample + HNO2 Sample + Sample


CHCl3 + KOH OH
NaNO2 + HCl
Evolution of N2 gas Formation of yellow oily
compound indicates Oensive smell of
indicates 1 amine
2 amine group isocyanide con rms the OH
group
presence of 1 aliphatic or
aromatic amine N N
Formation of water
soluble nitrite salts Orange azo dye
(1 Aromatic amine group present)
indicates 3 amine group

Detection of carboxylic acid group :


Test Experiment Inference
Litmus test Few drops of sample on blue litmus Blue litmus paper turns red.
NaHCO3 test Sample + NaHCO3 solution Brisk effervescence of CO2 indicates presence of COOH
group.
Ester test Sample + Alcohol + conc. H2SO4 Fruity smell of ester inferes the presence of COOH group.

70 CHEMISTRY TODAY | MARCH 17


FeCl3 test 3RCOOH + FeCl3 (RCOO)3Fe Wine red ppt. : acetic acid
(Coloured ppt.) Red colour changes to brown ppt. : formic acid
+ 3HCl No colour change or light yellow colour : oxalic acid
Violet coloured ppt. : salicylic acid
Buff coloured ppt. : benzoic acid
Detection of nitro group :
Mulliken Barker test Zn + NH4Cl Appearance of greyish black
RNO2 + 4[H] RNHOH + H2O
ppt. indicates the presence of
RNHOH + 2[Ag(NH3)2]OH RNO + 2H2O + 4NH3
NO2 group.
+ 2Ag
Grey black ppt.
Ferrous hydroxide test RNO2 + 6Fe(OH)2 + 4H2O RNH2 + 6Fe(OH)3 Appearance of brown ppt.
Light green Red brown ppt. indicates the presence of NO2
group.
CHARACTERISTICS TESTS OF CARBOHYDRATES, FATS Test for proteins :
AND PROTEINS
Biuret test :
Biuret solution Purple or For peptides with
Tests for carbohydrates : chain length of at
(Blue) + Sample pink solution
least 3-amino acids
Tests for carbohydrates
PHYSICAL CHEMISTRY
Simple carbohydrates Complex sugar TITRIMETRIC EXERCISES
Monosaccharides or Starch + I2 solution Strength of a solution : It is the amount of solute in
disaccharides + (Lugols reagent) grams present per litre of the solution.
Benedicts solution (Yellowish-brown) Strength (g/L) = Normality Eq. wt.
(Blue coloured) Strength (g/L) = Molarity Mol. mass
Changes to orange red
Changes to dark Normality equation : N1V1 = N2V2
purple/black (Solution 1) (Solution 2)
or brick red
Molarity equation : M1V1n1 = M2V2n2
Tests for lipids : (Solution 1) (Solution 2)
Grease spot test : Lipid leaves translucent spot [ N = M n, where n = valency factor]
on unglazed brown paper bags. Percentage purity of a given salt
Sudan red test : Sudan red is a fat soluble dye Strength of pure sample
100
that stains lipids red. Strength of given sample
Titration of oxalic acid vs KMnO4
COOH
Titration of Mohrs salt vs KMnO4 zz 2KMnO4 + 3H2SO4 + 5 2H2O
zz 2KMnO4 + 8H2SO4 + 10FeSO4(NH4)2SO46H2O K2SO4 + COOH
2MnSO4 + 5Fe2(SO4)3 + 10(NH4)2SO4 + 68H2O K2SO4 + 2MnSO4 + 18H2O + 10CO2
zz Calculation : zz Calculation:
MKMnO VKMnO 1 MKMnO VKMnO 2
4 4 4 4
MMohrs salt VMohrs salt 5 MOxalic acid VOxalic acid 5

Redox titrations

Proceed with transfer of electrons

CHEMISTRY TODAY | MARCH 17 71


THERMOCHEMISTRY Kinetic study of reaction of iodide ion with
hydrogen peroxide at room temperature :
Enthalpy of dissolution of copper sulphate : It is
the heat change involved during the dissolution of Overall reaction(Clock reaction)
one mole of a solute in such a large excess of solvent
so that no further heat change occurs on dilution. Main reaction
Slow
CuSO4(s) + H2O CuSO4(aq) H2O2(aq) + 2I(aq) + 2H+(aq) I2(aq) +
Dissolution of CuSO 4 in water is exothermic.
2H2O(l)
The enthalpy of solution of CuSO4(s) is calculated
from the highest temperature attained during Monitor reaction
Fast
its dissolution. 2S2O2
3(aq) I2(aq)
+ S4O2
6(aq) + 2I (aq)

Calculation : If dissolution of w g of CuSO4 in


200 g solvent (water) causes tC change in Indicator reaction
temperature, then I2(aq) + starch(aq) Blue colour
Heat evolved (q) = Mass Specific heat As the concentration of thiosulphate ion is
Change in temperature
kept constant, the different time taken (tc) for
q = (200 + W) 4.2 t J
the appearance of blue colour with change in
where, W is water equivalent of calorimeter
concentration of either reactant indicates the
(given).
Enthalpy of dissolution of CuSO4 in water relative rate of reaction.
1
q 159.5 10 3 Initial rate
kJ tc
w The rate of reaction decreases with decrease in the
[ Molar mass of CuSO4 = 159.5 g]
concentration of KI.
Enthalpy of neutralisation of strong acid and The graph of 1/tc versus volume of KI solution is a
strong base : It is the enthalpy change accompanying
straight line.
the neutralisation of one gram equivalent of a base by
an acid in dilute solution at a given temperature. 0.10
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) 0.09
It is an exothermic reaction. 0.08

The heat of neutralisation of a strong acid by a


0.07
1/tc(s1)

0.06
strong base in their dilute solutions is generally 0.05
57.3 kJ. The reaction may be represented as : 0.04
H+(aq) + OH(aq) H2O; H = 57.3 kJ 0.03
Calculation : Heat evolved during neutrali- 0.02
sation of 100 mL of 0.5 N HCl, 0.01

q = (200 + W) t 4.2 J where, W is water 0


4 8 12 16 20
equivalent of calorimeter (given). Volume of KI solution (mL)
Thus, enthalpy of neutralisation of 1000 mL of
q Rate of reaction Concentration of KI
1 N HCl and NaOH = kJ
0.5 100 Similarly, by keeping I ion concentration constant
and taking different concentrations of H2O2, the
MPP CLASS XI ANSWER KEY rate w.r.t. H2O2 can be found out.
1. (b) 2. (c) 3. (c) 4. (d) 5. (d)
6. (c) 7. (b) 8. (a) 9. (b) 10. (a) ELECTROCHEMISTRY
11. (a) 12. (b) 13. (b) 14. (b) 15. (b)
16. (b) 17. (c) 18. (b) 19. (b) 20. (a,c,d)
Variation of cell potential in Zn|Zn2+||Cu2+|Cu
with change in concentration of electrolytes
21. (a,c) 22. (a,b) 23. (a,b,d) 24. (4) 25. (2)
(CuSO4 and ZnSO4) at room temperature :
26. (4) 27. (a) 28. (a) 29. (b) 30. (d)

72 CHEMISTRY TODAY | MARCH 17


Theory 0.001 M 1M 1.1886 V
Nernst equation : 1M 0.1 M 1.0705 V
2.303RT [Zn2+ ] 1M 0.01 M 1.0409 V
Ecell Ecell log ...(i)
nF [Cu2+ ] 1M 0.001 M 1.0114 V
R = 8.314 J K1 mol1, T = 298 K and F = 96500 C Result :
At anode : Ecell decreases with increase in concentration of
Zn(s) Zn2+ (aq) + 2e

Zn2+ in ZnSO4.
At cathode : Ecell increases with increase in concentration of
Cu2+
(aq) + 2e

Cu(s)
Cu2+ in CuSO4.
Thus, n = 2,
Ecell = ECu2+/Cu EZn2+/Zn = +0.34 (0.76) INORGANIC COMPOUNDS
= 1.10 V PREPARATION
Substituting Ecell, n, R, T and F in eq. (i)
0.059 [Zn2+ ] Mohrs salt (Ferrous ammonium sulphate) :
Ecell 1.10 log
2 [Cu2+ ] It is a double salt containing ferrous sulphate
Procedure : and ammonium sulphate in equimolar
Clean the electrodes of copper and zinc using amounts.
a sand paper. It is prepared by dissolving an equimolar mixture
Put the solution of copper sulphate in beaker of hydrated ferrous sulphate and ammonium
and the solution of zinc sulphate in a porous sulphate in water containing a little amount of
pot. sulphuric acid to prevent the hydrolysis.
Connect the voltmeter with electrodes, close FeSO4 7H2O + (NH4)2SO4
the circuit and note down the cell potentials. FeSO4 (NH4)2SO4 6H2O + H2O
(Mohrs salt)
Repeat the experiment by taking the solutions of
CuSO4 and ZnSO4 at different concentrations. Potash alum (Phitkari) :
Observation : It is a double salt containing potassium sulphate
and aluminium sulphate in equimolar amounts.
Concentration Concentration Theoretical
of [Zn2+] of [Cu2+] Ecell It is prepared by dissolving an equimolar mixture
of hydrated aluminium sulphate and potassium
1M 1M 1.10 V
sulphate in water containing a little amount of
0.1 M 1M 1.1295 V
sulphuric acid to prevent the hydrolysis.
0.01 M 1M 1.1591 V
K2SO4 + Al2(SO4)3 18H2O + 6H2O
K2SO4 Al2(SO4)3 24H2O
(Potash alum)

Fluorescent sensor provides low-cost diagnosis of cystic fibrosis!

S
cientists have developed a new diagnostic test for cystic fibrosis. The new device provides a cheaper, easier way
to detect levels of chloride in sweat, which are elevated in cystic fibrosis patients. Cystic fibrosis is caused by
two faulty copies of a gene that affects the flow of chloride in and out of cells, leading to damage to the lungs
and digestive system. Testing chloride levels in sweat is done by manual titrationa labour-intensive technique that
is subject to human error and can miss cases. But a new system is based on a fluorescent dye that decreases in the
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based dye that emits fluorescent light. In the presence of chloride, however, the amount of light given off by the
molecule diminishes: the more chloride, the less fluorescence. The new test can detect chloride over a wider range of
concentrations and, because its automated, it avoids the problem of human error. Besides detecting chloride, the new
fluorescence-based system can also tell the difference between three ions: chloride, bromide, and iodide.

CHEMISTRY TODAY | MARCH 17 73


1. The volume of 0.05 M KMnO4 solution required to (d) reduces permanganate to Mn2+ ion.
completely oxidise 2.70 g of oxalic acid (H2C2O4) in 8. In a protein molecule various amino acids are
acidic medium is linked together by
(a) 120 cm3 (b) 240 cm3 (a) peptide bonds (b) dative bonds
(c) 360 cm3 (d) 480 cm3
(c) a-glycosidic bonds (d) b-glycosidic bonds.
2. Which of the following can be used to distinguish (NEET Phase-I 2016)
between pentan-2-one and pentan-3-one?
9. Two aromatic compounds having formula, C7H8O
(a) NaHSO3 (b) Bradys reagent
which are easily identifiable by FeCl3 solution test
(c) Tollens reagent (d) Iodoform test
(violet colouration) are
3. The product formed by the reaction of an aldehyde (a) o-cresol and benzyl alcohol
with a primary amine is (b) m-cresol and p-cresol
(a) carboxylic acid (b) aromatic acid (c) o-cresol and p-cresol
(c) Schiff s base (d) ketone. (d) methylphenyl ether and benzyl alcohol.
(NEET Phase-I 2016)
10. Formic acid can be distinguished from acetic acid
4. In the preparation of p-nitroacetanilide from by reaction with
aniline, titration is not done by nitrating mixture (a) NaHCO3
because (b) dilute, acidified KMnO4 solution
(a) on nitration it gives o-nitroacetanilide
(c) 2, 4-dinitrophenylhydrazine
(b) it gives a mixture of o- and p-nitroaniline
(d) Na metal.
(c) NH2 group gets oxidised
(d) it forms a mixture of o-and p-nitroacetanilide. 11. The carboxyl functional group (COOH) is present
in
5. During experiment to calculate heat of neutralisation
(a) picric acid (b) barbituric acid
of strong acid and strong base, temperature should
(c) ascorbic acid (d) aspirin.
be recorded till
(a) constant temperature is achieved 12. The volume of 0.1 M oxalic acid that can be
(b) maximum temperature is achieved completely oxidised by 20 mL of 0.025 M KMnO4
(c) minimum temperature is achieved solution is
(d) none of these. (a) 125 mL (b) 25 mL
6. When 3.92 g L1 of sample of Mohrs salt reacts (c) 12.5 mL (d) 37.5 mL
completely with 50 mL N/10 KMnO4 solution. The 13. The most appropriate method of making egg-albumin
percentage purity of the sample of Mohrs salt is sol is
(a) 50 (b) 70 (c) 37 (d) 40 (a) break an egg carefully and transfer the
7. Amount of oxalic acid present in solution can be transparent part of the content to 100 mL of
determined by its titration with KMnO4 solution 5% w/V saline solution and stir well
in the presence of H2SO4. The titration gives (b) keep the egg in boiling water for 10 minutes.
unsatisfactory result when carried out in the After removing the shell, transfer the yellow
presence of HCl, because HCl part of the content to 100 mL of 5% w/V saline
(a) oxidises oxalic acid to CO2 and H2O solution and homogenise with a mechanical
(b) gets oxidised by oxalic acid to chlorine shaker
(c) furnishes H+ ions in addition to those from (c) keep the egg in boiling water for 10 minutes.
oxalic acid After removing the shell, transfer the white

74 CHEMISTRY TODAY | MARCH 17


part of the content to 100 mL of 5% w/V saline (b) cathode to anode and anode to cathode
solution and homogenise with a mechanical (c) cathode to anode in both the cases
shaker (d) anode to cathode in both the cases.
(d) break an egg carefully and transfer only the (JEE Main 2015 online)
yellow part of the content to 100 mL of 5% w/V
18. A salt made of bivalent ions, each of which is capable
saline solution and stir well.
of decolourising acidified KMnO4 solution. The salt
(JEE Main 2016 online)
is likely to be
14. Which of the following discharges colour of bromine (a) stannic chloride (b) ferric sulphate
in carbon tetrachloride? (c) ferrous sulphate (d) ferrous oxalate.
19. In the cell ;
(i) CH3CH CH2 (ii) Zn |Zn2+ (C1)||Cu2+ (C2)| Cu,
Ecell Ecell = 0.0591 V. The ratio C1/C2 at 298 K will
be
(iii) (iv) CH3C CH (a) 2 (b) 100 (c) 102 (d) 1
(a) (i) and (iv) (b) (i), (iii) and (iv) 20. Which of the following statements about aniline
(c) (i), (ii) and (iv) (d) All of these yellow is not correct?
(a) It is an azo dye.
15. A mixture of two aromatic compounds A and B is
(b) It is a basic dye.
separated by dissolving in chloroform followed by
extraction with aqueous KOH solution. The alkaline (c) It can be prepared by heating diazoamino-
aqueous layer gives a mixture of two isomeric benzene with aniline and aniline hydrochloride.
compounds on treatment with carbon tetrachloride. (d) It can be prepared by coupling benzene-
The organic layer containing compound A gives diazonium chloride with phenol in the basic
an unpleasant odour on treatment with alcoholic medium.
solution of KOH. Compounds A and B respectively 21. The purpose of adding dilute sulphuric acid in the
are preparation of Mohrs salt is
(a) to prevent the hydrolysis of ferrous sulphate
(b) to increase the solubility of the salts used
(a) (b)
(c) to prevent the precipitation of carbonates of
metals
(d) to neutralise ammonium salt.
(c) (d) 22. Complete hydrolysis of starch gives
(a) glucose and fructose in equimolar amount
16. The product of acid hydrolysis of P and Q can be (b) galactose and fructose in equimolar amount
distinguished by (c) glucose only
OCOCH3 (d) glucose and galactose in equimolar amount.
(JEE Main 2015 online)
CH3 OCOCH3
(P) (Q) 23. Dilute sulphuric acid is most suitable for carrying
(a) Lucas reagent (b) 2, 4-DNP out KMnO4 titrations. This is because
(c) Fehling solution (d) NaHSO3 (a) it reacts with KMnO4 to liberate nascent
17. A variable, opposite external potential (Eext) is oxygen
applied to the cell : Zn|Zn2+(1 M)||Cu2+(1 M)|Cu, (b) it reacts with the reducing agents used in the
of potential 1.1 V. When Eext < 1.1 V and Eext > 1.1 V titration
respectively, electrons flow from (c) the end point in the titration is sharp
(a) anode to cathode and cathode to anode (d) it does not react with KMnO4 or the reducing
agents used.

CHEMISTRY TODAY | MARCH 17 75


24. The sign for enthalpy of solution of CuSO4.5H2O 28. If the concentration of iodide ions in the following
and CuSO4 (anhydrous) respectively are reaction is increased,
(a) +, + (b) , H2O2 + 2I + 2H+ I2 + 2H2O
(c) +, (d) , + then rate of reaction
25. Enthalpy of neutralisation of ammonium hydroxide (a) will increase (b) will decrease
with HCl is 51.3 kJ. Hence, enthalpy of dissociation (c) may increase or decrease (d) remains same.
of NH4OH is 29. Which of the following substances is not used for
(a) 2.3 kJ (b) 3.5 kJ preparing lyophilic sol?
(c) 4.7 kJ (d) 6.0 kJ (a) Starch (b) Gum
26. The structure of diazoaminobenzene formed during (c) Gelatin (d) Metal sulphide
the preparation of aniline yellow is
30. Alums can be represented by general formula
(a) M2SO4M 2(SO4)3 24H2O in which
(a) M is bivalent metal and M is trivalent metal
(b) (b) M is trivalent metal and M is monovalent
metal
(c) M is monovalent metal and M is trivalent
(c)
metal
(d) M and M both are bivalent metals.
(d)
ANSWER KEY
27. For the identification of b-naphthol using dye test,
it is necessary to use 1. (b) 2. (d) 3. (c) 4. (c) 5. (a)
(a) dichloromethane solution of b-naphthol 6. (a) 7. (d) 8. (a) 9. (a) 10. (b)
(b) acidic solution of b-naphthol 11. (d) 12. (c) 13. (a) 14. (b) 15. (c)
(c) neutral solution of b-naphthol 16. (c) 17. (d) 18. (d) 19. (c) 20. (d)
(d) alkaline solution of b-naphthol. 21. (a) 22. (c) 23. (d) 24. (c) 25. (d)
(JEE Advanced 2014) 26. (c) 27. (d) 28. (a) 29. (d) 30. (c)

76 CHEMISTRY TODAY | MARCH 17


CLASS XII

CBSE
Practice Paper 2017 Time Allowed : 3 hours
Maximum Marks : 70
GENERAL INSTRUCTIONS
(i) A l l q u es t i o n s ar e c o m p u l s o r y .
(ii) Q .n o .1t o 5 ar ev er y s h o r t an s w er q u es t i o n s an d c ar r y 1 m ar k eac h .
(iii) Q .n o .6t o 10 ar e s h o r t an s w er q u es t i o n s an d c ar r y 2 m ar k s eac h . Exam on
(iv ) Q .n o .1t o 2 ar e al s o s h o r t an s w er q u es t i o n s an d c ar r y 3 m ar k s eac h .
25th March
(v ) Q . n o . 23 i s av al u e b as ed q u es t i o n an d c ar r i es 4m ar k s .
(v i) Q . n o . 24 t o 26 ar e l o n g an s w er q u es t i o n s an d c ar r y 5 m ar k s eac h .
(v ii) U s e l o g t ab l es i f n ec es s ar y , u s e o f c al c u l at o r s i s n o t al l o w ed .

1. What is an adsorption isotherm? 10. How will you distinguish between (CH3)2NH and
2. Write down the electronic configuration of gadolinium (CH3)3N?
(Gd). (At. number : Gd = 64) 11. Answer the following :
3. Write the structure of the compound : (i) In a cubic close-packed structure of a mixed oxide one-
4-tert-butyl-3-iodoheptane eighth of tetrahedral voids are occupied by divalent ions, X2+
4. What happens when ferrimagnetic Fe3O4 is heated at while one half of the octahedral voids are occupied by trivalent
850 K and why? ions, Y3+. What is the formula of the compound?
(ii) Ferric oxide crystallises in a hexagonal close packed
5. Write the equation involved in the acetylation of salicylic
array of oxide ions with two out of every three octahedral
acid.
holes occupied by ferric ions. Derive the formula of the ferric
6. [Fe(CN)6]4 and [Fe(H2O)6]2+ are of different colours in oxide.
dilute solutions. Why?
12. State the principle involved in refining of metals by each
OR of the following methods :
Discuss the nature of bonding in metal carbonyls.
(i) Zone refining (ii) Vapour phase refining
7. Knowing the electron gain enthalpy values for (iii) Electrolytic refining
O O and O O2 as 141 and 702 kJ mol1 respectively,
13. Answer the following :
how can you account for the formation of large number of
(i) In the ring test of NO3 ion, Fe2+ ion reduces nitrate
oxides having O2 species and not O?
ion to nitric oxide, which combines with Fe2+ (aq) ion to form
8. Calculate the mass of ascorbic acid (vitamin C, C6H8O6) brown complex. Write the reactions involved in the formation
to be dissolved in 75 g acetic acid to lower its freezing point of brown ring.
by 1.5C. (Kf = 3.9 K kg mol1) (ii) Write the structure of pyrophosphoric acid and
9. A first order reaction has a specific reaction rate of peroxomonophosphoric acid.
103 sec1. How much time will it take for 10 g of the reactant
14. NiCl2[P(C2H5)3]2 exhibits temperature dependent
to reduce to 2.5 g? (Given : log 2 = 0.301, log 4 = 0.6021,
magnetic behaviour (paramagnetic or diamagnetic). Predict
log 6 = 0.778)

CHEMISTRY TODAY | MARCH 17 77


the coordination geometries of Ni2+ in which the complex sucrose is 6.22 kJ mol1, while the activation energy is only
behave as paramagnetic and diamagnetic. 2.15 kJ mol1 when hydrolysis is catalysed by the enzyme
15. Answer the following : sucrase. Explain.
(i) Explain why 21. Answer the following :
(a) the dipole moment of chlorobenzene is lower than that of (i) The half-life for radioactive decay of 14C is
cyclohexyl chloride? 5730 years. An archaeological artifact containing wood had
(b) alkyl halides, though polar, are immiscible with water? only 80% of the 14C found in a living tree. Calculate the age
(ii) Draw the structure of major monohalo product in the of the sample.
following reaction : (ii) Why does the rate of a reaction not remain constant
Fe throughout the reaction process?
+ Cl2 Dark 22. Answer the following :
16. Explain the following : (i) Why does cis-polyisoprene possess elastic properties?
(i) How does a delta form at the meeting place of sea and (ii) Which factor imparts crystalline nature to a polymer like
river water? nylon?
(ii) What happens when dialysis is prolonged? (iii) Why should the monomers used in addition
(iii) How does the precipitation of colloidal smoke take place polymerisation through free radical pathway be very pure?
in Cottrell precipitator? 23. Sonam is a student of Class XII. Once her mother fell
17. The degree of dissociation of Ca(NO3)2 in a dilute down from stairs and her leg bruished with lot of pain. Sonam
aqueous solution containing 7.0 g of the salt per 100 g of water gave her mother a non-narcotic analgesic which was safe to
at 100C is 70 percent. If the vapour pressure of water at 100C use. Her mother questioned if there is some other type of
is 760 mm, calculate the vapour pressure of the solution. analgesic as well. Sonam replied affirmatively and told her
OR mother that narcotic analgesics should be taken only when
At some temperature, the vapour pressure of pure benzene one is in acute pain.
(C6H6) is 0.256 bar and that of pure toluene (C6H5CH3) is After reading the above passage, answer the following
0.0925 bar. If the mole fraction of toluene in solution is 0.6. questions :
Then, (i) What values are expressed by Sonam by her choice about
(i) what will be the total pressure of the solution? using narcotic and non-narcotic analgesics?
(ii) what will be the mole fraction of each component in (ii) Give some examples of narcotic and non-narcotic
vapour phase? analgesics.
(iii) Give one example of an antipyretic which also acts as an
18. Answer the following : analgesic. How does it work as an analgesic?
(i) What is a developer used in photography and how does it
work? 24. Answer the following :
(ii) How will you synthesise (i) In the button cells, widely used in watches and other
(a) 1-phenylethanol from a suitable alkene? devices, the following reaction takes place :
(b) cyclohexylmethanol using an alkyl halide by an SN2 Zn(s) + Ag2O(s) + H2O(l) Zn2+
(aq) + 2Ag(s) + 2OH(aq)
reaction? Determine E and G for the reaction.
(Given : EAg +/Ag = + 0.80 V, EZn
2+/Zn = 0.76 V)
19. Write the structures of A, B and C in the following :
Br2/aq. KOH NaNO2 +HCl KI (ii) What type of a battery is the lead storage battery? Write
(i) C6H5 CONH2 A B C the anode and the cathode reactions and the overall reaction
0-5C
KCN LiAlH4 CHCl3 + alc. KOH occurring in a lead storage battery when current is drawn
(ii) CH3 Cl A B C from it.

20. Account for the following : OR
(i) Why does compound (A) given below not form an Answer the following :
oxime? (i) The cell in which the following reaction occurs,
2Fe3+
(aq) + 2I(aq) 2Fe2+
(aq) + I2(s) has Ecell = 0.236 V at 298 K,
calculate the standard Gibbs energy and the equilibrium
constant of the cell reaction.
(ii) The chemistry of corrosion of iron is essentially an
electrochemical phenomenon. Explain the reactions
occurring during the corrosion of iron in the atmosphere.
25. Answer the following :
(i) A blackish brown coloured solid A when fused with
(ii) Why must vitamin C be supplied regularly in diet? alkali metal hydroxide in presence of air, produces a dark
(iii) Activation energy for the acid catalysed hydrolysis of green coloured compound B, which on electrolytic oxidation

78 CHEMISTRY TODAY | MARCH 17


in alkaline medium gives a dark purple coloured compound OH OCOCH3
C. Identify A, B and C and write the reactions involved. COOH COOH
(ii) What happens when an acidic solution of the green
5. + (CH3CO)2O + CH3COOH
compound (B) is allowed to stand for some time? Give the
equation involved. What is this type of reaction called? Aspirin
OR 6. In [Fe(CN)6]4, CN is a strong field ligand hence, pairing
Answer the following : of electrons takes place.
(i) Explain why mercury(I) ion exists as Hg22+ ion, while 3d 4s 4p
copper(I) exists as Cu+ ion.
(ii) Assign suitable reasons for the following :
(a) Mn2+ compounds are more stable than Fe2+ compounds In [Fe(H2O)6]2+, H2O is a weak field ligand hence, pairing
towards oxidation to their +3 oxidation state. does not take place.
3d 4s 4p 4d
(b) In the 3d series from Sc (Z = 21) to Zn (Z = 30), the
enthalpy of atomisation of Zn is the lowest.
(c) Sc3+ is colourless in aqueous solution whereas Ti3+ is Both ligands show different magnitude of crystal field
coloured. splitting energy due to different nature hence, absorb different
wavelengths and show different colours.
26. Identify compounds (A to D) in the following reactions
sequence : OR

CHC6H5
(i) O3 dil. NaOH
(ii) Zn/H2O
A+B aq. ethanol C + H2O
(i) O3 M C O
A+D (ii) Zn/H2O

H2/Pt
E
Synergic bonding
OR
Answer the following : The metal-carbon bond in metal carbonyls possess both
(i) A compound with molecular formula, C4H10O3 on and character. The M C bond is formed by the donation
of lone pair of electrons on the carbonyl carbon into a vacant
acetylation with acetic anhydride gives a compound with
orbital of the metal. The M C bond is formed by the
molecular weight 190. Find out the number of hydroxyl
donation of a pair of electrons from a filled d-orbital of metal
groups present in the compound.
into the vacant antibonding * orbital of carbon monoxide.
(ii) Identify A, B and C and give their structures. The metal to ligand bonding creates a synergic effect which
O
strengthens the bond between CO and the metal.
CH3 Br2
A+B 7. This can be explained with the help of electronic
COCH3 NaOH H+ configuration.
(I) C (C7H12O) 1s 2s 2p
O
SOLUTIONS
T = constant
O
1. Adsorption isotherm is the
variation of the amount of gas O2
adsorbed by the adsorbent with As O2 has most stable configuration amongst these. So,
pressure at constant temperature. x formation of O2 is much more easier. In solid state, large
m amount of energy (lattice enthalpy) is released when oxides
are formed with divalent O2 ions. It is greater lattice enthalpy
p
of the crystal lattice of oxide (O2) which compensates for the
Adsorption isotherm
high energy required to add the second electron.
2. The electronic configuration of gadolinium is
7 1 2 8. Lowering in freezing point ( Tf ) = 1.5C
64Gd = [Xe]54 4f 5d 6s Mass of solvent (CH3COOH ), w1 = 75 g
1 2 3 4 5 6 7 Mass of solute, w2 = ?
3. CH3 CH2 CH CH CH2CH2CH3 Molar mass of solute, C6H8O6, M2 = 72 + 8 + 96 = 176 g mol1
I C(CH3)3 w2 1000
Tf = K f
4-tert-butyl-3-iodoheptane M2 w1
4. When ferrimagnetic Fe3O4 is heated at 850 K, it loses M2 w1 T f 176 75 1.5
ferrimagnetism and becomes paramagnetic due to alignment or w2 = 5.08 g
of spins in one direction.
1000 K f 1000 3.9

CHEMISTRY TODAY | MARCH 17 79


9. We know that for a first order reaction, suitable electrolytic bath containing soluble salt of the same
2.303 a metal. The more basic metal remains in the solution and the
t log
k a x less basic ones go to the anode mud.
Here, initial concentration, a = 10 g and concentration left At anode : Zn Zn2+ + 2e
after time t sec. = 2.5 g, i.e., (a x) = 2.5 g At cathode : Zn + 2e
2+
Zn
Specific reaction constant, k = 103 sec1
13. (i) NO3 + 3Fe + 4H+2+
NO + 3Fe3+ + 2H2O
2+
Time required for the reactant to reduce to 2.5 g [Fe(H2O)6] + NO [Fe(H2O)5(NO)]2+ + H2O
2.303 10 2.303 2.303 Brown ring
log log 4 0.6021
3 1 2.5 3 3
10 s 10 10
1386.6 sec (ii)
10. These can be distinguished by Liebermanns nitrosoamine
reaction. (CH3)2NH (dimethylamine) on treatment with
HNO2 (generated in situ by the action of dil. HCl on NaNO2) O
gives yellow coloured oily N-nitrosodimethylamine.
(CH3)2NH + HO N O (CH3)2N N O + H2O
P
HO OOH
Dimethylamine N-Nitrosodimethylamine OH
N-Nitrosodimethylamine on warming with a crystal of Peroxomonophosphoric acid
phenol and conc. H2SO4 forms a green solution which when 14. In the given complex, NiCl2[P(C2H5)3]2, nickel is in +2
made alkaline with aqueous NaOH turns deep blue and then oxidation state and the ground state electronic configuration
red on dilution. of Ni2+ ion in free gaseous state is
3d 4s 4p
(CH3)3N (trimethylamine), on the other hand, being a 3
2+
amine does not give this test. Ni :
For the given four coordinated complex to be paramagnetic,
11. (i) Let the number of O2 ions in the crystal be N.
it must possess unpaired electrons in the valence shell. To
Number of tetrahedral voids = 2N satisfy this condition, lone pairs from the four ligands occupy
Number of octahedral voids = N the four sp3 hybrid orbitals as :
1 N 3 4s 4p
Number of X2+ ions = 2N
8 4
3+ 1 N sp 3
Number of Y ions = N
2 2 Therefore, geometry of paramagnetic complex must be
2+ 3+ 2 1 1 tetrahedral. On the other hand, for complex to be diamagnetic,
X : Y : O = : :1 = 1 : 2 : 4 there should not be any unpaired electrons in the valence
4 2 shell. This condition can be fulfilled by pairing electrons of
The formula of the compound is XY2O4.
(ii) There is one octahedral hole for each atom in hexagonal 3d-orbitals as
3d 4s 4p
closed packed arrangement. If the number of oxide ions (O2)
per unit cell is x, then

2 2x dsp 2
Number of Fe3+ ions = 2/3 octahedral holes x The above electronic arrangement gives dsp2 hybridisation
3 3
2x and therefore, square planar geometry.
Ratio of Fe3+ : O2 = :x =2:3
3 15. (i) (a) There are two reasons :
Thus, formula of compound is Fe2O3. 1. In case of chlorobenzene, carbon to which chlorine is
12. (i) Zone refining is based on the principle that the attached is sp2 hybridised and is more electronegative than
impurities are more soluble in the melt than in the solid state the corresponding carbon in cyclohexyl chloride which
of the metal. is sp3 hybridised. So, the net dipole moment is lower in
(ii) In vapour phase refining, the metal is converted into a chlorobenzene.
Cl sp2 Cl sp3
suitable volatile compound and then decomposed to give
pure metal. So, the two requirements are :
(a) The metal should form a volatile compound with a
suitable reagent.
Chlorobenzene Cyclohexyl chloride
(b) The volatile compound should be easily decomposable,
so that the recovery is easy. 2. In chlorobenzene C Cl bond has some double bond
(iii) Zinc is refined by electrolytic refining. In this method, character so, its bond length is smaller. Hence, dipole moment
the impure metal is made to act as anode. A strip of the same is smaller than cyclohexyl chloride which has a longer C Cl
metal in pure form is used as cathode. They are put in a single bond.

80 CHEMISTRY TODAY | MARCH 17


(b) Alkyl halides are polar but are insoluble in water because For benzene,
energy required to break the intermolecular H bonding pB = pB xB
among water molecules is much higher than energy released xB = 1 xT = 1 0.6 = 0.4
by waterhalide interaction. and pB = 0.256 bar
Cl Then, pB = 0.256 0.4 = 0.1024 bar
Fe Total vapour pressure of solution,
(ii) + Cl2 Dark Ptotal = pT + pB = 0.0555 + 0.1024 = 0.158 bar
Chlorobenzene (ii) Mole fraction of toluene in vapour phase,
16. (i) River water is a colloidal solution of clay and mud. pT 0.0555
Sea water contains many salts or electrolytes. When these yT 0.351
Ptotal 0.158
electrolytes come in contact with river water where river and
Mole fraction of benzene in vapour phase,
sea meet, coagulation of clay and mud takes place and delta is
pB 0.1024
formed. yB 0.648
(ii) When dialysis is prolonged, the traces of electrolytes Ptotal 0.158
are also removed. These electrolytes stabilise the colloid and 18. (i) Hydroquinone (or benzene-1,4-diol) is used
when removed completely, make the colloid unstable and the as a developer in photography because it reduces Ag+
colloid gets coagulated. ions present on the exposed film to metallic silver.
(iii) Smoke is a colloidal solution of carbon particles in air. In +
HO OH + 2Ag+ O O + 2H +
Cottrell precipitator, when smoke is allowed to pass through
Hydroquinone p-Benzoquinone 2Ag
a chamber having a number of metal plates attached to a
metal, will be connected to a source of high potential. The (ii) (a) Addition of H2O to ethenylbenzene (or styrene) in
charged particles of smoke get attracted by oppositely charged presence of dil. H2SO4 gives 1-phenylethanol.
electrode and get precipitated after losing their charges. CH CH2
+ dil. H2SO4
17. Calculated (normal) molecular mass of Ca(NO3)2 = 164. + H OH
Markovnikovs addition
Calculated (normal) lowering of vapour pressure will be given
Ethenylbenzene
by or Styrene CH CH3
p w2 /M2 OH
p w1 /M1 1-Phenylethanol
( p)cal 7/164
or ( p)cal = 5.84 mm (b) Hydrolysis of cyclohexylmethyl bromide by aqueous
760 100/18 NaOH gives cyclohexylmethanol.
As Ca(NO3)2 is 70% dissociated, degree of dissociation, CH2Br CH2OH
a = 0.70.
+ NaOH
Ca(NO3)2 Ca2+ + 2NO3 SN2, Hydrolysis
Initial moles 1 0 0 Cyclohexylmethyl Cyclohexylmethanol
Moles after dissociation 1a a 2a bromide
Total = 1 + 2a + NaBr
vant Hoff factor,
( p)obs 1 2a CONH2 NH2 N2+Cl
i 1 2a
( p)cal 1 Br2 NaNO2+ HCl
( p)obs 19. (i)
aq. KOH 05C
or 1 2 0.70
5.84 (A) I (B)
or ( p)obs = 14.0 mm KI
i.e., p ps = 14.0 mm
or ps = p 14.0 = 760 14.0 = 746.0 mm
OR (C)
(i) According to Raoults law, KCN
(ii) CH3 Cl CH3CN CH3CH2NH2
For toluene, pT = pT xT (A) (B)
pT = 0.0925 bar
and xT = 0.6
Then, pT = 0.0925 0.6 = 0.0555 bar

CHEMISTRY TODAY | MARCH 17 81


20. (i) Glucose pentaacetate (A) does not have a free OH synthesis of prostaglandins which stimulate inflammation in
at C-1 and so cannot be converted to the open chain form to the tissues and cause pain.
give CHO group hence, it does not form the oxime. 24. (i) Since, EAg +/Ag > EZn 2+/Zn, the zinc electrode is the
(ii) Vitamin C is water soluble hence it is readily excreted in anode. The half-cell reactions are as follows :
urine and cannot be stored in the body.
At anode : Zn Zn2+ + 2e
(iii) Enzymes are biocatalysts which reduce the magnitude
of activation energy by providing alternative path. In the At cathode : Ag + e
+
Ag
hydrolysis of sucrose, the enzyme sucrase reduces the Overall cell reaction is
activation energy from 6.22 kJ mol1 to 2.15 kJ mol1. Zn + 2Ag+ Zn2+ + 2Ag
Ecell = Ecathode Eanode = 0.80 V (0.76) V
0.693
21. (i) t1/2 (For first order reaction) = 0.80 V + (0.76) V = 1.56 V
k Number of electrons involved is 2. Therefore, G value is
0.693 0.693 given by the formula,
k yr 1
t1/2 5730 G = nFEcell = 2 96500 C mol1 1.56 V
We know that, = 301080 J mol1 = 301.08 kJ mol1
(ii) Lead storage battery is a secondary cell.
2.303 [R] 2.303 100
t log 0 log Cell reactions during operation are :
k [R] 0.693 80 At anode : Pb(s) + SO42(aq) PbSO4(s) + 2e
5730 At cathode :
2.303 5730 100 2.303 5730 PbO2(s) + SO42(aq) + 4H+(aq) + 2e PbSO4(s) + 2H2O(l)
log log 1.25
0.693 80 0.693 Overall reaction :
2.303 5730 Pb(s) + PbO2(s) + 2SO42(aq) + 4H+(aq) 2PbSO4(s) + 2H2O(l)
0.0969 1845 yr (approx.) OR
0.693
(i) Two half reactions for the given redox reaction may be
Therefore, the age of the given archaeological artifact
written as :
containing wood is 1845 years.
(ii) The rate of a reaction does not remain constant throughout 2Fe3+
(aq) + 2e

2Fe2+
(aq)
the reaction process because the rate of the reaction depends 2I I2 + 2e
upon concentration of reactants which keeps on decreasing. 2 moles of electrons are involved in the reaction, so n = 2
1
22. (i) The cis-polyisoprene molecule consists of various rG = nFEcell = (2 mol) (96500 C mol ) (0.236 V)
= 45548 J = 45.55 kJ
chains held together by weak van der Waals interactions and
G
has a coiled structure. Hence, it can be stretched like a spring log K c
2 303 RT
.
and exhibits elastic properties.
( 45.55 kJ)
(ii) Strong intermolecular forces like hydrogen bonding 7.983
lead to close packing of polymer chains and thus, impart 2.303 (8.314 10 3 kJ K 1) (298 K )
crystalline nature to nylon. Kc = antilog (7.983) = 9.616 107
(iii) Even the traces of impurities may act like inhibitors (ii) According to electrochemical theory of rusting, the
which stop the growth of the polymers and polymers with impure iron surface behaves like small electrochemical cell.
Moisture having dissolved CO2 or O2 acts as an electrolyte.
shorter chain length are formed. Hence, pure monomers are
The reactions are given below :
required for polymerisation through free radical pathway. At anode : Fe Fe2+ + 2e; EFe2+/Fe = 0.44 V
23. (i) Sonam expressed values about the safety in choosing 1
At cathode : 2 H O 2e H2O; EH+/O2/H2O = 1.23 V
analgesics and her awareness about drugs. Non-narcotic 2 2
analgesics are non-addictive and hence, are safe to use but
narcotic analgesics are addictive, i.e., habit forming and hence,
are not safe to use. Therefore, narcotic analgesics should be MPP CLASS XII ANSWER KEY
used only in severe pain such as post-operative pain, cardiac 1. (b) 2. (b) 3. (c) 4. (b) 5. (b)
pain, pains of terminal cancer and in child birth.
(ii) Examples of non-narcotic analgesics are : aspirin, 6. (d) 7. (a) 8. (a) 9. (a) 10. (c)
paracetamol, naproxen, ibuprofen and diclofenac sodium. 11. (c) 12. (b) 13. (a) 14. (a) 15. (b)
Examples of narcotic analgesics are : morphine, codeine and 16. (d) 17. (c) 18. (a) 19. (d) 20. (b,d)
heroin.
(iii) Aspirin acts both as an antipyretic as well as an analgesic. 21. (a,b,c) 22. (b,c) 23. (a,b,c) 24. (8) 25. (9)
Its analgesic action is due to the reason that it inhibits the 26. (6) 27. (b) 28. (a) 29. (c) 30. (b)

82 CHEMISTRY TODAY | MARCH 17


Overall reaction : CHC6H5
(i) O3
1 2+ 26. C6H5CHO
Fe 2 H O Fe + H2O; Ecell = 1.67 V (ii) Zn/H2O
2 2 Benzaldehyde (A)
The ferrous ions formed react with the dissolved oxygen +
or oxygen from the air to form ferric oxide with further O
production of H+ ions.
1
2 Fe2 O 2 H2O Fe2O3 4 H Cyclohexanone (B)
2 2 Now compound (B) has a-hydrogens but (A) does not,
Ferric oxide then undergoes hydration to form rust as follow : therefore, in presence of dil. NaOH, cross aldol condensation
Fe2O3 + xH2O Fe2O3 xH2O occurs between them to give (C).
(Rust) O
Fuse dil. NaOH
25. (i) MnO2 + 4KOH + 2O2 2K2MnO4 + 2H2O H + O CH C H
H 6 5 (Cross aldol condensation
Pyrolusite (A) Potassium
(Blackish brown) manganate (B) (B) ( )
O
(Green coloured)
Alkaline H2 O +
2K2MnO4 + H2O + [O] medium 2KMnO4 CHC6H5
(B) Potassium permanganate (C)
2-Benzylidenecyclohexanone
(Purple coloured)
(C)
+ 2KOH Reductive ozonolysis of (C) gives (D) and (A).
(ii) When acidic solution of green compound (B), i.e., O O
(i) O3
potassium manganate is allowed to stand for some time, it
disproportionates to give permanganate as follows : (ii) Zn/H2O
CHC6H5 O
3MnO42 + 4H+ 2MnO4 + MnO2 + 2H2O (C) Cyclohexane-1,2-dione
These type of reactions are called disproportionation reactions. (D)
+ C6H5CHO(A)
OR (D) on catalytic reduction gives cyclohexane-1, 2-diol (E).
(i) The electronic configuration of Hg(I) is [Xe]4f 14 5d106s1.
O OH
H2/Pt
It has one unpaired electron in the valence 6s-subshell. It is
paramagnetic but actually Hg(I) compounds are diamagnetic. O OH
(D) Cyclohexane-1,2-diol
This change can be explained by assuming that the singly filled (E)
6s-orbitals of two Hg+ ions overlap to form Hg Hg covalent
bond.
Therefore, Hg+ ion exists as dimeric species, i.e., Hg22+. On the
other hand, Cu(I) ion has electronic configuration [Ar]3d10. WEST BENGAL at
It has no unpaired electron to form dimeric Cu22+ species and
therefore, it exists as Cu+ ion.
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enthalpy is very high, i.e., 3rd electron cannot be lost easily. In Rukmani Agencies - Kolkata Ph: 033-24666173, 224839473; Mob: 9830037811
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(c) Only those ions are coloured which have partially filled
d-orbitals facilitating d-d transitions.
Electronic configuration of Sc3+ = [Ar]
Electronic configuration of Ti3+ = [Ar]3d1

CHEMISTRY TODAY | MARCH 17 83


OR O
(i) During acetylation, one H-atom (at. mass = 1 amu) of CH3 Br2/NaOH
the OH group is replaced by an acetyl group, i.e., CH3CO
CHBr3 +
COCH3 (Haloform reaction) (B)
(molecular mass = 43 amu).
OH + (CH3CO)2O O COCH3 + CH3COOH (I)
In other words, acetylation of each OH group increases mass O O
by (43 1 =) 42 amu. Now, the molecular mass of C4H10O3 CH3 CH3
(CO2) H+
= 106 amu while that of the acetylated product is 190 amu,
COOH COO
therefore, the number of OH groups in the compound (Decarboxylation)
190 106 (II) (A)
2 (A -keto acid)
42 O
(ii) The given compound (I) contains CH3CO group and CH3
hence, in presence of Br2/NaOH, it undergoes haloform reaction
to give sodium salt of carboxylic acid (A) and bromoform,
CHBr3(B). (A) on protonation gives the corresponding acid 2-Methylcyclohexanone (C),
(II). (II) being a b-keto acid readily undergoes decarboxylation M.F. = C7H12O
on heating to give 2-methylcyclohexanone (C).

84 CHEMISTRY TODAY | MARCH 17


Class XII

T his specially designed column enables students to self analyse their


extent of understanding of complete syllabus. Give yourself four
marks for correct answer and deduct one mark for wrong answer.
Self check table given at the end will help you to check your
readiness.

Total Marks : 120 Time Taken : 60 Min.

NEET / AIIMS 6. Which of the following reactions is an example of


Only One Option Correct Type calcination process?
1. The fraction of the total volume occupied by the (a) 2Ag + 2HCl + [O] 2AgCl + H2O
atoms present in a simple cube is (b) 2Zn + O2 2ZnO
(c) 2ZnS + 3O2 2ZnO + 2SO2
(a) (b) (c) (d) (d) MgCO3 MgO + CO2
4 6 3 2 4 2
2. 1.0 molar solution of the complex salt, CrCl3 . 6H2O, 7. The following acids have been arranged in the order
displays an osmotic pressure of 3RT. 0.5 L of the of decreasing acid strength. Identify the correct
same solution on treatment with excess of AgNO3 order.
solution will yield (assume a = 1) I. ClOH II. BrOH
(a) 0.5 mol of AgCl (b) 1.0 mol of AgCl III. IOH
(c) 1.5 mol of AgCl (d) 3.0 mol of AgCl. (a) I > II > III (b) II > I > III
3. A galvanic cell is set up from a zinc bar weighing (c) III > II > I (d) I > III > II
100 g and 1.0 litre of 1.0 M CuSO4 solution. How 8. What would happen when a solution of potassium
long would the cell run if it is assumed to deliver a chromate is treated with an excess of dilute nitric
steady current of 1.0 ampere? acid?
(Atomic mass of Zn = 65) (a) Cr2O72 and H2O are formed.
(a) 1.1 hr (b) 46 hr (c) 53.6 hr (d) 24 hr (b) CrO42 is reduced to Cr3+.
4. The rate constant of a zero order reaction is (c) CrO42 is oxidised to Cr7+.
0.2 mol dm3 hr1. If the concentration of the (d) Cr3+ and Cr2O72 are formed.
reactant after 30 minutes is 0.05 mol dm3, then its
initial concentration would be 9. Among the following, the species having square
(a) 0.01 mol dm3 (a) 0.15 mol dm3 planar geometry for central atom are
(c) 0.25 mol dm 3
(d) 4.00 mol dm3 (i) XeF4 (ii) SF4
(iii) [NiCl4]2 (iv) [PdCl4]2
5. Which of the following will show Tyndall effect? (a) (i) and (iv) (b) (i) and (ii)
(a) Aqueous solution of soap below critical micelle (c) (ii) and (iii) (d) (iii) and (iv)
concentration.
(b) Aqueous solution of soap above critical micelle
concentration. 10.
(c) Aqueous solution of sodium chloride.
(d) Aqueous solution of sugar.

CHEMISTRY TODAY | MARCH 17 85


Identify A and B. of the crystal lattice before and after applying high
(a) Both A and B are (CH3)3COCH2CH3. temperature will be
(b) Both A and B are (CH3)2C CH2. (a) 1 : 1 (b) 3 : 2
(c) A is (CH3)3COCH2CH3 and B is (c) 2: 3 (d) 2( 2 )3 : ( 3 )3
(CH3)2C CH2. 17. The ionic strength of a solution containing
(d) A is (CH3)2C CH2 and B is
0.1 mole/kg of KCl and 0.2 mole/kg of CuSO4 is
(CH3)3COCH2CH3.
(a) 0.3 (b) 0.6
11. An organic compound with molecular formula, (c) 0.9 (d) 0.2
C2H6O2 evolves H2 when treated with sodium metal
and gives two moles of formaldehyde on oxidation 18. Compound A (molecular formula C3H8O) is
with HIO4. The compound is treated with acidified potassium dichromate to
(a) acetic acid (b) methyl acetate form a product B (molecular formula C3H6O).
(c) ethylene glycol (d) ethyl alcohol. B forms a shining silver mirror on warming with
12. In the given reaction sequence, ammoniacal silver nitrate. B when treated with
Zn CH3Cl Alk. an aqueous solution of H2NCONHNH2.HCl and
Phenol dust X Anhyd. AlCl Y Z, the sodium acetate gives a product C. Identify the
3 KMnO4
product Z is structure of C.
(a) benzaldehyde (b) benzoic acid (a) CH3CH2CH NNHCONH2
(c) benzene (d) toluene. (b) CH3 C NNHCONH2
Assertion & Reason Type CH3
Directions : In the following questions, a statement of assertion (c) CH3 C NCONHNH2
is followed by a statement of reason. Mark the correct choice as :
CH3
(a) If both assertion and reason are true and reason is the
correct explanation of assertion. (d) CH3CH2CH NCONHNH2
(b) If both assertion and reason are true but reason is not the 19. A dark brown solid (X) reacts with NH3 to form a mild
correct explanation of assertion.
explosive which decomposes to give a violet coloured
(c) If assertion is true but reason is false.
(d) If both assertion and reason are false. gas. (X) also reacts with H2 to give an acid (Y). (Y) can
13. Assertion : Acylation of amines gives a also be prepared by heating its salt with H3PO4. X
monosubstituted product whereas alkylation of and Y are respectively
amines gives polysubstituted product. (a) Cl2, HCl (b) SO2, H2SO4
(c) Br2, HBr (d) I2, HI
Reason : Acyl group sterically hinders the approach
of further acyl group. More than One Options Correct Type
14. Assertion : a-amino acids exist as internal salt in 20. Aryl halides are less reactive towards nucleophilic
solution as they have amino and carboxylic acid substitution reactions as compared to alkyl halides
groups in near vicinity. due to
Reason : H+ ion given by carboxyl group (COOH) (a) longer carbon-halogen bond
is captured by amino group (NH2) having lone (b) resonance stabilisation
pair of electrons. (c) the inductive effect
15. Assertion : Detergents are preferred to soaps for (d) sp2-hybridised carbon attached to halogen.
washing purposes.
Reason : Detergents having branched hydrocarbon 21. Which of the following reactions will yield phenol?
Cl
chains are non-biodegradable.
(i) fusion with NaOH at 300 atm
JEE MAIN / JEE ADVANCED / PETs (a)
(ii) H2O/H+
Only One Option Correct Type
NH2
16. Element X crystallises in a 12 coordination fcc
lattice. On applying high temperature, it changes to (i) NaNO2/HCl
(b)
8 coordination bcc lattice. The ratio of the density (ii) H2O (Warming)

86 CHEMISTRY TODAY | MARCH 17


(i) Oleum having d1 to d9 electrons whereas the compounds
(c)
(ii) NaOH, (Heating) containing d0 and d10 configurations are intensely
(iii) H+ coloured due to charge transfer transitions.
Cl
27. Which of the following compounds is not coloured?
(i)NaOH(aq), 298 K/1 atm
(d) (a) Na2[CuCl4] (b) Na2[CdCl4]
(ii) HCl
(c) K4[Fe(CN)6] (d) K3[Fe(CN)6]
22. An aqueous pink solution of cobalt(II) chloride
changes to deep blue on addition of excess of HCl. 28. The purple colour of [Ti(H2O)6]3+ ion is due to
This is because (a) unpaired d-electron
(a) [Co(H2O)6]2+ is transformed into [CoCl6]4 (b) transfer of an electron
(b) [Co(H2O)6]2+ is transformed into [CoCl4]2 (c) intermolecular vibrations
(c) tetrahedral complexes have smaller crystal field (d) presence of water molecules.
splitting than octahedral complexes SOLUTIONS OF FEBRUARY 2017 CROSSWORD
(d) tetrahedral complexes have larger crystal field 1
D I A S T A S
2
E
splitting than octahedral complexes. 3
T O L U
4
I D I N E
5 6
U R E A R
23. Arenium ion involved in the bromination of aniline 7
T
8
S L R E
9
V
is 10
A I T W
11
U D
12
C A R B E N E
+ L T I U E S
13
O R D E R
NH2 NH2 E R B R N E D
H H
14
X A N T H A T E S
15
B I
16
C
Br Br A N I Z 17
P U G
18
S A
(a) (b) N T T
19 20 21
+ 22
W O L F R A M I T E T
D E S O L D E R F I D E R A
+
NH2
23 24
NH2 25
E P E S I L O P A L
26
R O A S T I N G H R A T N H Y A
F I B I A O S M
+ 27
(c) (d)
28
L E I N S T E I N A N T A T O
H E E T G O N R
29 30
M E N D E L E E V I E N T R O P Y
Br
H Br I C S I H
N N O
U
Integer Answer Type G O
D S

24. The total number of a and b particles emitted in the E

nuclear reaction, 238


92U
214
82Pb is Winners of February 2017 Crossword
25. An organic compound undergoes first order Aditya Sharma, Punjab
decomposition. The time taken for its Garima Gupta, Indore
decomposition to 1/8 and 1/10 of its initial
Winners of January 2017 Crossword
concentration are t1/8 and t1/10 respectively. What is
Aman Diwakar, Agra
[t ]
the value of 1/8 10 ? (take log10 2 = 0.3) Devjit Acharjee, West Bengal
[t1/10 ]
Solution Senders of Chemistry Musing
26. Amongst the following the total number of
compounds soluble in sodium bicarbonate is Set - 43
Roshan Sahu, Uttar Pradesh
2, 4, 6-trinitrophenol, benzoic acid, salicylic acid,
Abhishek Kumar, Madhya Pradesh
acetyl chloride, acetic anhydride, trifluoroethanol,
acetamide, benzenesulphonic acid Set - 42
Mijan Ahamed Khan, West Bengal
Comprehension Type Chanakya Das, Assam
Transition metal compounds are coloured due to Parmar Prabhatsinh Rupsinh, Gujrat
d-d transition and charge transfer. Colour due to d-d Khandaker Abdul Majid, West Bengal
transition is shown by transition metal compounds Adithya, Kerala

CHEMISTRY TODAY | MARCH 17 87


Matrix Match Type 30. Match the chemical conversions in column I with
the appropriate reagents in column II.
29. All the compounds listed in column I react with
Column I Column II
water. Match the result of the respective reactions
with the appropriate options listed in column II. (A) Cl (P) (i) Hg(OAc)2
Column I Column II (ii) NaBH4
(A) (CH3)2SiCl2 (P) Hydrogen halide ONa OEt (Q) NaOEt
formation (B)
(B) XeF4 (Q) Redox reaction OH
(C) Cl2 (R) Reacts with glass (C) (R) Et Br
(D) VCl5 (S) Polymerisation
(T) O2 formation
(D) (S) (i) BH3
A B C D (ii) H2O2/
OH
(a) P, Q P P, Q, R, T P, S NaOH
(b) P, S P, Q, R, T P P, Q A B C D
(a) P Q R S
(c) P, S P, Q, R, T P, Q P (b) Q R P S
(d) P, S P, Q P, Q, R, T P (c) Q R S P
(d) S P Q R
Keys are published in this issue. Search now!

Check your score! If your score is


> 90% EXCELLENT WORK ! You are well prepared to take the challenge of final exam.

No. of questions attempted 90-75% GOOD WORK ! You can score good in the final exam.
No. of questions correct 74-60% SATISFACTORY ! You need to score more next time.
Marks scored in percentage < 60% NOT SATISFACTORY! Revise thoroughly and strengthen your concepts.

88 CHEMISTRY TODAY | MARCH 17


Readers can send their responses at editor@mtg.in or post us with complete address by 25th of every month to win exciting prizes.
Winners' name with their valuable feedback will be published in next issue.
ACROSS
Cut Here
1. The region in an infrared spectrum below 1500 wave 2 1 3 4
numbers. (11) 6
5 7
5. The sum of oxidation numbers of lead in litharge and 8
manganese in permanganate ion. (4)
9
6. The major constituent of the oil from orange peel. (8) 10
8. The trivial name given to a, b-unsaturated ketones 11 12 13
obtained by condensing an aromatic aldehyde with an
14 15
aryl methyl ketone in presence of a base. (9)
16
9. A chemical used as a weapon with devastating and
horrific effect in the 1914-18 war. (8)
17
10. A molecular structure or state which has the
characteristics of two or more other structures. (6) 19 18 20

11. A poisonous protein of the lectin class produced from


the seeds of the castor bean. (5) 22 21 23 24

14. Chemicals used to break and remove snow or ice. (7) 25

26 27
16. He is credited with coining the term, catalysis. (9)
17. Determination of molecular weight of a substance by
observing the elevation in boiling point of solution. (12) 28

18. Process of applying a protective zinc coating to prevent


rusting. (13) 29

21. An element named for the Greek word for hidden. (7) 30

26. Colloidal sols containing non-spherical particles which


are capable of orientating themselves in a streaming potential. 12. A high explosive made from a gel of nitroglycerine and
(9) nitrocellulose in a base of wood pulp and sodium or potassium
27. Methane is called as ________ gas. (5) nitrate. (9)

28. The oxide of this metalloid is toxic and has been used as a 13. It is estimated that the amount of this element in the earths
vermin poison. (7) crust at any particular time is less than 30 grams. (8)
29. ________ process is an industrial method for preparation of 15. Graph of free energy change with temperature is called
hydrogen by water gas. (5) _________ diagram. (9)
30. A device which measures the relative density of two liquids. (10) 19. A primary alcohol which is a constituent of geranium oil. (8)
DOWN 20. A mesoionic heterocyclic aromatic chemical compound. (7)
2. A method by which hydrophobic particles of an ore are
22. The nucleus and all inner shell electrons in an atom except the
separated from hydrophilic particles in a metallurgical
process. (10) valence electrons. (6)
3. A non metal, which has layers of hexagonally arranged carbon 23. The isomorphous salt, M2ISO4M IISO4 6H2O where, M I is an
atoms. (8) alkali metal and M II is a dipositive transition metal. (6)
4. It is slippery, corrosion resistant plastic. (6) 24. ________ is a mixture of copper sulphate and slaked lime and
7. A type of isomerism shown by substances which contain used as a fungicide. (8)
several asymmetric centres but differ in the configuration 25. ________ process is used for making sulphur (VI) oxide. (7)
around one asymmetric carbon. (9)

CHEMISTRY TODAY | MARCH 17 89


90 CHEMISTRY TODAY | MARCH 17

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