Sample Question Paper 15

(Detailed Solutions)

1. (b) Configuration of Fe 2+ is 3d 6, while Fe 3+ is 3d 5. Since, 9. (c) For a first order reaction half-life is independent of
Fe 3+ contains half-filled d-orbital. Hence, it is more initial concentration.
stable than Fe 2+ .
t½ = 10 min
2. (b) KMnO 4 in acidic medium cannot be used to oxidise In 100 minuites there are 10 half lives.
primary alcohols to aldehydes because it convert
100
primary alcohols into carboxylic acid. The direct Reactant left after 10 half lives = 10
oxidation of primary alcohols to carboxylic acids can be 2
carried out using KMnO 4. 100
=
3. (a) Phenol reacts with neutral ferric chloride solution to 1024
give violet colouration, whereas alcohols do not react. = 0.097
4. (a) O O Reactant used or reaction complete = 100 − 0.097
—

COOH C—Cl C—NH2 NH3 = 99.9%

—
—

SOCl2 NHl3
Br2 10. (c) The IUPAC name of CH 3COCH(CH 3 )2 is
KOH 3-methyl-2-butanone.
Benzoic Benzoyl Benzamide
Aniline
(Z )
11. (a) Λ°HCl = 425 S cm 2/mol
acid chloride (Y)
(X) Λ°NaCl = 150 S cm 2/mol
5. (c) For the reaction : R → P for a second order reaction,
Λ°CH 3COOH = 350 S cm 2/mol
rate= k[R ]2. If conc. of R is increased by four times,
rate = k[4R ] 2 = 16k[R ]2. Hence, the rate of formation of P Now, Λ°CH 3COONa = Λ°CH 3COOH + Λ°NaCl − Λ°HCl
increases by 16 times. = 350 + 150 − 425
6. (b) Co-ordination number of Ni in [Ni(C 2O 4 )3 ]4− is 6. This
= 75 S cm 2/mol
is because C 2O 2– 4 (oxalate) is a

O O 2– 12. (d) p-dichlorobenzene being symmetrical has zero

C—C
dipole moment. Toluene due to + I effect of the  CH 3
O O group has a small and finite dipole moment. The two
dipoles are 60° apart in o-dichlorobenzene. So,
Bidentate ligand and thus,each coordinated with the o-dichlorobenzene has the highest dipole moment
central atom at two sites.
followed by toluene and then p-dichlorobenzene.
7. (b) The correct match is A-(4), B-(3), C-(1), D-(2). Hence, B < A < C is the correct order of increasing
H
3 dipole moment.
1
2
A.
Cinnamaldehyde
O 13. (a) Both (A) and (R) are true and (R) is the correct
explanation of (A).
3-phenyl prop-2-enal
14. (a) Both (A) and (R) are true and (R) is the correct
O explanation of (A).
C Acetanilide is less basic than aniline because electron
Acetophenone 1 CH3
B. 2 density on nitrogen is lowered by acetyl group.
1-phenyl ethanone 15. (b) Lucas reagent is an equimolar mixture of anhyd.
O ZnCl 2 and conc. HCI. In Lucas test, tertiary alcohols
Valeraldehyde react immediately because of the formation of the more
C. 5
4
3
2
1 H stable tertiary carbocations. Thus, both (A) and (R) are
Pentanal true, but (R) is not the correct explanation of (A).
Acrolein 1 H 16. (a) At isoelectric point, the amino group does not
D. O C 2 3 H
migrate under the influence of electric field because at
C C
H H isoelectric point, amino acid exists as a Zwitter ion.
Prop-2-enal
17. (a) Maltose is a disaccharide as it consists of two
8. (a) According to Werner theory for coordination α-D-glucose units. Starch is polysaccharide, while
compounds primary valencies are ionisable. glucose and fructose are monosaccharide. (1)
 (b) (b) Geometrical isomerism This type of isomerism
Fibrous proteins Globular proteins arises in heteroleptic complexes due to different
Usually insoluble in water. Usually soluble in water. possible geometric arrangements of the ligands.
They are structural They are functional proteins. Cl NH3 Cl NH3
proteins.
Pt Pt
(1)
Cl NH3 NH3 Cl
Or cis trans (1)
(a) Pernicious anaemia (1)
CHO 21. (a) Increasing the concentration of one or more
 reactants will often increase the rate of reaction.
HI
(b) (i) ( C HOH )4 → This occurs because a higher concentration of a
 ∆ reactant will lead to more collisions of that
CH 2OH reactant in a specific time period. (1)
CH 3 CH 2 CH 2 CH 2 CH 2 CH 3 (b) Rate of reaction depends upon the number of
n-hexane molecules possessing a minimum energy which
CHO COOH undergo effective collisions. The energy of
 HNO 3
 molecules depend upon temperature because
(ii) ( C HOH )4    → (C HOH )4 kinetic energy is directly proportional to
  temperature, therefore , rate of reaction depends
CH 2OH COOH
Saccharic acid (1) upon temperature. (1)
So, as the temperature is increased rate of
18. At anode The oxidation of zinc metal takes place and reaction also increases upto a certain point.
–
the zinc ions react with the OH ions from the electrolyte
to form zinc hydroxide. (1) 22. (a) [Co(NH 3 )4Cl 2 ]
− − It will show geometrical isomerism.
Zn(s)+2OH → ZnO+H 2O + 2e
Cl Cl
Zn 2+ + 2OH − → Zn(OH)2
NH3 NH3 NH3 Cl
At cathode The reduction of mercuric oxide to mercury Co Co
metal takes place. NH3 NH3 NH3 NH3
− −
HgO(s)+ H 2O + 2e → Hg(l ) + 2OH (1)
Cl NH3
trans-isomer cis-isomer (1)
The overall reaction is
3−
Zn(s)+ HgO(s) → Zn(OH)2 + Hg(l ) (b) [Co(C 2O 4 )3 ]

19. (a) KCN is ionic so they can attach through C or N but 3d6 4s 4p
3+ 6
C—C bond is stronger than C—N bond. So, alkyl Co =3d
cyanide is the major product but AgCN is covalent
3d6 4s 4p
so more electronegative N can attach to C and
form isocyanides. (1) Co3+= ×× ×× ×× ×× ×× ××

(b) Due to more electronegative nature of halide atom

in haloalkanes, carbon atom becomes slightly
positive and is easily attacked by nucleophilic 3 (C2O42–)
reagents. While in haloarenes due to resonance, Hybridisation d 2sp3, inner orbital complex, low
carbon atom becomes slightly negative and is spin.
attacked by electrophilic reagents. (1) Magnetic character Diamagnetic (1)
20. (a) Stereoisomer (Optical isomer)
Common One can make mistake by considering
3+ 3+ as a weak field ligand. Due to this one
en en Mistake
can write the hybridisation ‘ sp3d2 ’
en Co Co en (high spin complex) instead of d2 sp3
(low spin complex).
en en
(c) [Cr(NH 3 )3Cl 3 ]
d-tris-(ethane-1, 2-diamine) l-tris-(ethane-1, 2-diamine)
cobalt (III) cobalt (III) IUPAC name Triamminetrichloridochromium (III) (1)
(1)
23. (a) p-isomers are comparatively more symmetrical and fit Mechanism
closely in the crystal lattice, thus require more heat to ˜ Protonation

break these strong forces of attraction. Therefore,

H
they have higher melting point than o-and m-isomers. CH3CH2—O—H + H+ CH3CH2—O
Cl Cl Cl H (1)
Cl ˜ Nucleophilic attack
H
Cl CH3CH2—O—H + CH3CH2—O
H
Cl
(Most symmetric) CH2CH3
(2) CH3CH2—O +H2O
(b) The given reaction is represented as, H
C2H5 C2H5 ˜
CH2CH3
CH3CH2—O + H—O—CH2CH3
+ HI I H
(1) H
CH3CH2—O—CH2CH3 + CH3CH2—O
Or H (1)
(a) Chlorobenzene has lower dipole moment than (c) Ethanol reacts with Cu at 573 K to give ethanal.
cyclohexyl chloride due to lower magnitude of − ve
The reaction involved is as follows
charge on the Cl atom and shorter C Cl distance.
Cu / 573K
Due to greater s-character, a sp2-hybrid carbon is CH 3CH 2OH → CH 3CHO
3 Ethanol Ethanal (1)
more electronegative than a sp -hybrid carbon.
2
Therefore, the sp -hybrid carbon of C Cl bond in 25. Given : Tf = 272.4 K
chlorobenzene has less tendency to release electrons
Tf = 273 K
to Cl than a sp3 hybrid carbon of cyclohexyl chloride.
. K kg mol −1
K f = 186
sp2—H Hybrid carbon
K b = 0.512 K kg mol −1
δ–
—Cl Less negative charge Vapour pressure of water at 298 K = 23756
. mm Hg
δ+
∆Tf = K f × m
sp3—H Hybrid carbon
0.6 = 186
. ×m
δ– 0.6
—Cl More negative charge m= = 0.323 molal
δ+ 186
. (1½)
(2)
∆Tf 186
.
(b) Alkyl halides and polar molecules are held together by We know, =
∆Tb 0.512
dipole-dipole interaction. The molecules of H 2O are
held together by H- bonds. Since, the new forces of 0.6 186
.
=
attraction between water and alkyl halide molecules ∆Tb 0.512
are weaker than the forces of attraction already
∆Tf = 0.17 K
existing between alkyl halide-alkyl halide molecules
and water-water molecules, therefore 0.17 = Tb − 273
alkyl halides are immiscible (not soluble) with water.(1) (Boiling point)Tf = 27317
. K (1½)
24. (a) The phenol reacts with (aq )Br2 to give 26.(a) The process of ammonolysis yield a mixture of
2, 4, 6-tribromophenol. The reaction involved is as primary, secondary, tertiary amines and quaternary
follows salts. The separation of amines is very complicated
OH OH process and difficult. (1)
—

Br — — Br Hence, ammonolysis of alkyl halide is not a good

Br2(aq)
method to prepare pure primary amines.
(b) Aniline forms salt with Lewis acid catalyst, i.e. AlCl 3
—

Phenol
Br which is used in Friedel-Crafts reaction. Nitrogen of
2,4,6-tribromophenol (1) aniline acquires positive charge and hence acts as
H+ strong deactivating group for further reaction. (1)
(b) 2CH 3CH 2OH  → CH 3CH 2OCH 2CH 3
413 K
 (c) Nitration is usually carried out with a mixture of conc.
HNO 3 and conc. H 2SO 4. So, in the presence of these
acids, aniline gets protonated to form anilinium ion.
Therefore, the reaction mixture consists of aniline and
anilinium ion. NH 2 group in aniline is o, p-directing
and activating whereas the NH 3 group in anilinium is
m-directing and deactivating. Now, nitration of aniline
mainly gives p-nitroaniline due to steric hindrance at
o-position and the nitration of anilinium ion gives
m-nitroaniline.
NH2 NH2 NH2
—
28. It is given that compound C having the molecular
formula, C 6H7N is formed by heating compound B with
Br2 and KOH. This is a Hofmann Bromamide
degradation reaction. Therefore compound B is amide
and C is an amine. The only amine having the
molecular formula C 6H7N is aniline. Therefore B must
be benzamide (C 6H 5CONH 2), which is formed by
heating compound A with aqueous ammonia.
Therefore, compound A must be benzoic acid. (1)
COOH CONH2 NH2

— NO2 NH3, ∆ Br2/KOH

Conc. HNO3, Hofmann Bromamide
+ degradation reaction
Conc. H2SO4
Benzoic acid Benzamide Aniline
—

Aniline o-nitroaniline (A ) (B) (C)

NO2 (2%)
(2)
p-nitroaniline
(51%) 29. The relation of partial pressure of a gas and it’s mole
+ +
fraction is given by
NH3 NH3 NH2 (a) p = KH . χ (1)
—

+NO2
+
NH4OH (b) On same temperature, value of KH is different for
–H+ — — different gases. (1)
NO2
Anilinium NO2 m-nitroaniline (c) The limitation of Henry’s law is as follows
ion (47%)
(1) It is applicable only when
27. Let the rate law in terms of rate of formation of D be l the pressure of the gas is not too high and
d [D ] temperature is not too low.
= k [ A]a [ B]b l the gas should not undergo any chemical
dt (1)
changes.
1. 6.0 × 10 −3 = k (0.1)a (0.1)b … (i) l the gas should not undergo association or
−3 a b
2. 7.2 × 10 = k (0.3) (0.2) … (ii) dissociation in the solution. (2)
−2 a b
3. 2.88 × 10 = k(0.3) (0.4) … (iii) Or
−2 a b (c) (i) Aquatic species are more comfortable in cold
4. 2.40 × 10 = k(0.4) (0.1) … (iv) (1)
water due to the presence of more oxygen.
Divide Eq. (iv) by Eq. (i), we get Solubility of oxygen in water increases with
4 = (4)a decrease in temperature as solubility of a gas
∴ a=1 in given liquid decreases with increase in
temperature. (1)
Divide Eq. (iii) by Eq. (ii), we get
(ii) At high altitudes, the partial pressure of oxygen is
4 = (2)b
less than at the ground level. This leads to low
2 2 = (2)b concentration of oxygen in the blood and tissues
∴ b=2 of people living at high altitude or climbers.
Consequently they feel weak both physically and
Order with respect to A = 1
mentally. These are the symptoms of a medical
Order with respect to B = 2 (1) condition known as anoxia. (1)
d [D ]
Rate law = = k [ A][B]2 30.(a) Lactose is the disaccharide which on hydrolysis
dt gives glucose and galactose. (1)
On putting the value of ‘A’ and ‘B’ in any equation, say (i)
Or
6.0 × 10 −3 M min −1 = k (0.1 M) (0.1 M)2 Albumin is a globular protein. (1)
∴ k = 6 M−2 min −1 (1) (b) Guanine is complimentary base of cytosine in one
strand of DNA to that in another strand of DNA. (1)
To get maximum marks in these type of
questions following value point must be (c) Phosphodiester is the linkage by which nucleotides
Value Point included answer. Do not skip the steps are joined together between 5′ and 3′ atoms of
involved and write the unit. pentose sugar. Sucrose is a non-reducing sugar. (2)
31. Aldehyde a gives β-hydroxy aldehyde on reaction O

with an alkali. It is an aldol reaction. The aldehyde CH 3  C ONa + CHI3 (yellow ppt.)
formed is but-2-enal.
(b) (i) Butanone < Propanone < Propanal < Ethanol
OH
(ii) Acetophenone < p-tolualdehyde < benzaldehyde
H < p-nitrobenzaldehyde (2)
But-2-enal
It’s β-hydroxy substituted compound will be
OH O
32. (a) In the given equation, n = 2,
H F = 96500 C mol −1
So, starting aldehyde will be CH 3CHO and reaction ° ° °
Ecell = Ecathode − Eanode
will be
°
OH O Ecell = − 0.14 V − (− 0.76)
2CH3CHO + Dil. NaOH = − 0.14 V + 0.76 = 0.62 V
CH3 H °
∆G ° = − nFEcell
So, A = CH 3CHO.
= − 2 × 96500 × 0.62 = − 124
. × 96500
B undergoes disproportionation on treating with
conc. NaOH. Hence, it is an aldehyde with no α-H. = − 119660 = − 119.66 kJ/mol (3)
Since, C is an aryl alcohol it indicates an arylic (b) (i) From standard oxidation potential it is clear that
aldehyde as B. oxygen gas should be liberated at anode, but its
Aldehyde B is benzaldehyde which on reaction with rate of production is very low.
conc. NaOH undergoes Cannizzaro reaction and In order to increase that we increase the voltage
gives alcohol and an acid. Reactions are of external battery. Because of which chloride
H ions get oxidised easily and Cl 2 gas is liberated
H O HO O H OH at anode. (1)
(ii) Conductivity of solution is conductance of ions
Conc.
NaOH
+ present in unit volume of solution. On dilution
number of CH 3COOH ions per unit volume
(B) (C) (D)
decreases. Hence, conductivity decreases. (1)
When B reacts with Zn/HCl, toluene is formed. this
reaction is called Clemmensen reduction. (5) Or

Or (a) Conductivity Conductivity of a solution is equal to the

conductance of a solution of 1 cm length and cross
(a) (i) Due to stronger (− I ) effect, inductive effect of F
section area of 1 square cm. It may also be defined as
over Cl, the FCH 2COO − ion is much more stable
the conductance of one centimeter cube of one
than ClCH 2COO − ion. Hence, FCH 2COOH is conductor. It is represented by the symbol kappa (κ ).
stronger acid than ClCH 2COOH. (1) 1
κ=
Hence, pK a value of F CH 2COOH is lower than ρ
that of Cl CH 2COOH. ρ is resistivity. The unit of κ is ohm −1 cm −1 or S cm −1.
(1) DIBAL -H
(ii) CH 3 CH == CH CH 2CN    → The conductivity, κ, of an electrolytic solution depends
(2) H 2O
on the concentration of the electrolyte, nature of
CH 3CH == CH CH 2CHO (1) solvent and temperature.
O Molar conductivity Molar conductivity of a solution at
 a given concentration is the conductance of volume V
(iii) CH 3CH 2CHO and CH 3  C CH 3 can be of the solution containing one mole of electrolyte kept
Propanal Propanone
between two electrodes with area of cross section A
distinguished by using iodoform test. (1)
and distance of unit length. Therefore, distance is
CH 3CH 2CHO + NaOI → no reaction as there is unity. So,
no methyl group attached to carbonyl group. l =1
O
Volume = area of base × length

whereas, CH 3  C CH 3 + NaOI → So, V = A × l = A
k
Λm = × volume
mole
 K (b) Cr 2+ is a strong reducing agent because
Λm = × A ×1
1 Cr 2+ → Cr 3+ + e − results in change from d 4 to
Λm = K × V (2) more stable d 3(t 23g ). (1)
2 −1
Its unit is S cm mol . 2+
(c) Cu has 1 unpaired electron which get excited and
(b) Advantages of fuel cells. when come back to ground state, it emits radiation
l Because of the continuous supply of fuels, these which lies in visible region. Hence, coloured
cells never become dead. These cells are usually whereas, Zn 2+ has completely filled d-orbital (d 10 )
operated at a temperature of 70-140°C and gives a configuration. Hence, no unpaired electron.
potential of about 0.9 V. Therefore, Zn 2+ salts are white. (1)
l Fuel cells do not cause any pollution unlike thermal ∆
plant which burn fossil fuels like coal gas, oil etc. (d) 2MnO 2 + 4KOH + O 2 → 2K 2MnO 4 +2H 2O (1)
(11 2) (e) It is because V in the lower oxidation state is less
°
(c) Ecell = + 0.80 V − 0.77 V = + 0.03 V stable than Cr which in turn is less stable than Mn.
° Thus, MnO −4 has a great tendency to get reduced
∆ rG ° = − nFEcell
and hence, behave as a good oxidising agent.
= − 1(mol ) × (96500 C mol −1) × (0.03 V ) Similarly, VO +2 has the least oxidising power. (1)
⇒ − 2895 CV mol −1 = − 2895 J mol −1 (f) Both O 2 and F2 stabilise high oxidation states but the
∆ rG° = − 2.303 RT log KC ability of oxygen to stabilise these higher oxidation
= − 2895 = − 2.303 × 8.314 × 298 × log KC states exceeds that of fluorine due to ability of
log KC = 0.5074 oxygen to form multiple bonds with the metal atoms.
e.g. Mn form the highest fluoride as MnF4 whereas,
KC = Antilog (0.5074)
the highest oxide is Mn 2O7 . This is due to the
KC = 322
. (11 2) tendency of oxygen to form multiple bonds. (1)
33.(a) Manganese (Mn) shows highest oxidation state of + 7 (g) Transition metals are good catalyst because of their
ability to adopt multiple oxidation states and to form
with oxygen but with fluorine, it shows the highest of
complexes. Transition metals because of their
+ 4 because oxygen has the ability to form multiple
variable valencies and vacant d-orbitals form
bonds with manganese. Hence, oxidation state can
unstable intermediate compounds and provide a
be extended to + 7. (1)
new path with lower activation energy for the
reaction. (1)