1. (b) Metal electrodes are commonly used as cathodes 11.

(d) A is a secondary alcohol, B is a tertiary alcohol and

because reduction occurs on cathode. In a galvanic C is a primary alcohol. Boiling point of alcohols is
cell, the cathode is the positive electrode, while in an determined by extent of H-bonding among the alcohol
electrolytic cell, it is the negative electrode. The cathode molecules. Tertiary alcohols being highly hindered will
attracts electrons. have least H-bonding and thus low boiling point as
compared to less hindered secondary alcohol.
2. (b) When benzyl alcohol is oxidised with KMnO 4,
Therefore, the order of boiling point is primary
benzoic acid is the product. alcohol>secondary alcohol > tertiary alcohol,
KMnO
C 6H 5CH 2OH + [O] →
4
C 6H 5COOH + H 2O i.e. C > A > B.

3. (c) Chlorophyll is a coordination molecule of magnesium 12. (b) Across lanthanide series, due to lanthanoid
that is found in plants and is important for contraction, size of cations decreases, which results in
increase in covalent character and decrease in ionic
photosynthesis.
character. So, the basicity of hydroxides decreases.
4. (a) Propanone can be prepared from ethyne by passing
a mixture of ethyne and steam over a catalyst, 13. (a) The cleavage of C  O bond in ethers takes place
magnesium at 420°C. under drastic conditions with excess of hydrogen
420°C
halides.
2CH ≡≡ CH + 3H 2O  
→ CH 3COCH 3 + CO 2 + 2H 2 Alkyl aryl ethers are cleaved at the alkyl oxygen
Mg
Ethyne Propanone
bond due to more stable aryl-oxygen bond. The
5. (a) The carbon atoms are concurrently attached to the reaction will give phenol and alkyl halide as
entering nucleophile and the existing group in the products.
transition state of SN 2 processes, and are thus Anisole with HI gives phenol and methyl iodide
connected to five atoms at the same time. It is
OCH3 OH
impossible to isolate such a geometry since, it is
unstable.
+ HI + CH3I
6. (a) The correct match is (i)-(q), (ii)-(r), (iii)-(s). Methyl
Anisole Phenol iodide
7. (c) From the given figure,
The activation energy of the forward reaction is A. Mechanism
The activation energy of the backward reaction is B. (i) Protonation of anisole
And, as we know ∆H = EB − Ef –
—OCH3 + H —I —O—CH3 +I
∆H = B − A
H
∆H = C
8. (b) The Hinsberg reaction is a test for primary, (ii) Is will combine with smaller group to avoid steric
secondary and tertiary amine detection. The amine is hindrance.
thoroughly shaken with Hinsberg reagent in the
presence of aqueous alkali in this test (either KOH or —O—CH3 +I —OH+CH 3I
NaOH). H
A substrate is treated with a reagent containing an
14. (b) Benzoic acid does not undergo Friedel-Crafts
aqueous sodium hydroxide solution and benzene
reaction because the carbonyl group is
sulphonyl chloride.
deactivating and the catalyst aluminium chloride
9. (c) Strong oxidisers, such as acidified potassium (Lewis acid) gets bonded to the carbonyl group.
permanganate or acidified potassium dichromate,
15. (d) On doubling the concentration, the emf will remain
convert alcohol to carboxylic acid immediately. Using
unchanged because [Zn 2+ ]/ [Cu 2+ ] will remain same.
CrO 3 as the oxidising agent in an anhydrous media,
however, only aldehyde can be produced. 16. (d) Vitamin A, D, E, K are fat-soluble. Vitamin D is
10. (b) For the first order reaction, the rate constant stored in the body’s Adipose tissue (fat). Hence, (A) is
increases on increasing temperature. But for the false.
half-life of a first-order reaction, the rate constant is Product of vitamin D metabolism are excreted through
inversely proportional to half-life; thus, on increasing the bile into the faeces and very little is eliminated
temperature, half-life decreases. through the urine. Hence, (R) is also false.
17. Complex so formed is occurs. Likewise, hydrogen bonding is also shown
CoCl 3 ⋅ 6 NH 3 + AgNO 3 → [Co(NH 3 )6 ]Cl 3 by alcohols but they have low molecular mass,
while, in aldehydes, no hydrogen bonding is
IUPAC name of complex is hexaamminecobalt (III)
chloride. (2) present.
1 2 So, the increasing order of their boiling point is
18. r = k [ A] [B]
CH 3CHO < CH 3CH 2OH < CH 3COOH (1)
(a) When concentration of B increases to 3 times, the
rate of reaction becomes 9 times;
r = kA[3B]2 = 9kAB 2 = 9 times (1)
(b) r = k[2 A][2 B]2
r = 8kAB 2 = 8 times (1) (b) Phenol and benzoic acid can be distinguished by
ferric chloride test. Phenol reacts with neutral FeCI3
19. (a) Ethyl iodide undergoes SN2 reaction faster than to form ferric phenoxide complex giving violet
ethyl bromide because I− ion is a better leaving colouration.
group than Br − ion. (1)
6C 6H 5OH + FeCl 3 → [Fe(OC 6H 5 )6 ]3− + 6H +
Phenol Iron -phenol complex
(b) Cl— —NO2 is more reactive because of the (Violet colour)

presence of electron withdrawing NO 2 and Cl + 3Cl – (1/2)

groups. (1) But benzoic acid reacts with neutral FeCl 3 to give a
buff coloured precipitate of ferric benzoate.
3C 6H 5COOH + FeCl 3 → (C 6H 5COO)3Fe +3HCl
Benzoic acid Ferric benzoate
(Buff coloured ppt.) (1/2)
21. (a) D-glucose reacts with acetic anhlydride to given
20. (a) Hell-Volhard-Zelinsky (HVZ) Reaction Carboxylic pentaacetate.
CHO CHO
acids having α-hydrogen atom are halogenated at
 
the α-position on treatment with chlorine or ( C HOH )4 + 5 (CH 3CO)2 O → (C HO C CH 3 )4
bromine in the presence of small amount of red  Acetic  
anhydride O
phosphorus to give α-halocarboxylic acids. The CH 2OH
Glucose CH 2 O C CH 3
reaction is known as Hell-Volhard-Zelinsky reaction. 
(i) X2, Red phosphorus O
R CH 2 COOH → Pentaacetate (1)
(ii) H 2O
R — CH —COOH (b) Change occurs in the nature of egg protein on
 boiling because the egg comes in contact with a
X solution of higher osmotic pressure, the egg will
α-halocarboxylic acid
( X = Cl, Br) (1) shrink due to moving out of water. This shrinking of
egg is called plasmolysis. (1)
(b) Decarboxylation refers to the reaction in which
carboxylic acids lose carbon dioxide to form 22. (a) N 2(g ) + 3 H 2(g ) → 2 NH 3(g )
hydrocarbons when their sodium salt are heated − d [N 2 ] 1 d [H 2 ] 1 d [NH 3 ]
Rate = =− =+
with sodalime. (1/2) dt 3 dt 2 dt (1)
e.g. Sodalime (mixture of (b) (i) It is the second order reaction because unit of
NaOH and CaO in
– + 3 : 1 ratio) rate constant for second order reaction is
CH 3COO Na → CH 4 + Na 2CO 3 L mol −1s −1.
∆ (1)
Sodium Methane
ethanoate 12 (ii) Units of k indicates that is first order reaction. (1)
Or
Given, T1 = 20 ° C = 293 K
k1 = 4.5 × 10 3s −1
Ea = 60 kJ mol −1
Or
= 60 × 10 3 J mol −1
(a) In carboxylic acid, the stronger intermolecular
hydrogen bonding is present and association k2 = 1.5 × 10 4s −1 (1)
 We know that, 25. ‘A’ is carboxylic acid (R COOH), ‘B’ is an alcohol
k Ea  T2 − T1 (R CH 2OH) and ‘C’ is an ester (RCH 2 COOR ).
log 2 =  
k1 2.303 R  T1T2  R CH 2OH  
Oxidation (KMnO )
→ R COOH
4

( B) ( A)
1.5 × 10 4  T − 293
log = 60 × 10 3 J mol −1  2  LiAlH 4 , reduction
4.5 × 10 3  293 T2  Alcohol (B) ← Carboxylic acid ( A)
O
 T − 293
0.523 = 3133.63  2   H 2SO 4
 293 T2  R  C OH + H  OH 2 C  R →
(Esterification)
T2 − 293 O
= 1.67 × 10 −4
293 T2 
R  C  O  H 2C  R + H 2O
T2 − 293 = 489.31(T2 ) × 10 −4 Ester (C)
(Fruity smell) (3)
−4
T2 − 489.31 × 10 T2 = 293
26. (a) Adenine and guanine are two purine bases present
T2 (1 − 489.31 × 10 −4 ) = 293 in DNA. Structure as follows
T2(0.951) = 293
NH2 O
T2 = 308 K = 35°C (2) N H N
N N
itE 1 × 10 × 60 × 3175. H H
23. (a) W = = = 0.2 g H N N H 2N N N
96500 96500
Mass of silver will be different because the Adenine H Guanine H (1)
equivalent mass of Ag is different. (1) (b) (c) Backbone of DNA is made up of alternate sugar
(b) Electrolyte ‘B’ will be strong electrolyte because it is and phosphate groups, joined together in regular
completely ionised and on dilution the molar 3′, 5′ phosphodiester linkages. (1)
conductance will increase to the small extent due (c) Thymine is present in DNA and uracil is present in
to increase in speed of ions only. (1) RNA. (1/2)
(c) The given cell is Cu(s)|Cu 2+ ||Cl − ||Cl 2(Pt)
27. —Cl+2Na+Cl—
Ether
Cu(s) → Cu 2+ + 2e −
—
At anode,
At cathode, Cl 2(g )+ 2e − → 2Cl − (1) Diphenyl
Reagents required to carry out the reaction are
24. (a) 1-iodobutane from 1-chlorobutane As iodine can sodium in presence of ether. (2)
replace chlorine from alkyl halide (due to more
Allyl chloride shows high reactivity because the
reactive nature), it gives 1-iodobutane from
carbocation formed by hydrolysis is stabilised by
1-chlorobutane via Finkelstein reaction.
resonance, while no such stabilisation of
Acetone
CH 3 (CH 2 )2 CH 2 Cl + NaI → carbocation exists in the case of n-propyl chloride.
reflux
(1)
CH 3 (CH 2 )2 CH 2 I + NaCl (1)
(b) As all the given species have same number of 28. Depression in freezing point is given by the formula,
carbon atoms, the 3° carbocation is most stable, 1000 × K f × w  1000 × w 
∆Tf = K f × m = Q m=
thus has most reactive halide molecule. M ×W  M × W 
CH 3 Firstly, molar mass of benzoic acid is calculated, then
 van’t Hoff factor and degree of association is
Therefore, CH 3 — CH 2 — C — CH 3
calculated.

Br Given that, mass of benzoic acid, w = 2g; mass of
(2-bromo-2-methylbutane) is most reactive. (1) benzene, W = 25 g
CH 3 K f = 4.9 K mol −1 kg; depression in freezing point,
1 2 3 4 5 ∆Tf = 162
. K
(c) C H 3 — CH ==CH —C — CH 3
 Molar mass of benzoic acid,
Br 1000 × 4.9 × 2
M= = 242 g mol −1
IUPAC name 4-bromo-4-methylpent-2-ene (1) . × 25
162
 The normal mass of benzoic acid = 122 g mol −1 (ii) Calculation of composition in the vapour phase,
Normal molar mass p A = χ A × p°A = 0.40 × 450 mm of Hg
van’t Hoff factor, i =
Observed molar mass = 180 mm of Hg
122 g / mol pB = χ B × pB° = 0.60 × 700 mm of Hg
⇒ i= = 0.504
242 g / mol
= 420 mm of Hg
i −1
Degree of association (α ) = Mole fraction of A in the vapour phase
1
−1 pA 180
n = = = 0.30
p A + pB 180 + 420
0.504 − 1
α= = 0.496 × 2 = 0.992 Mole fraction of B in the vapour phase
1
−1
2 = 1 − 0.30 = 0.70 (2)
[Here, n = 2 as it forms dimer] 30. (a) The best reagent to reduce nitriles is
Percentage association of acid sodium/alcohol or LiAlH 4 and the product of this
= 100 × α = 100 × 0.992 = 992
. %. reduction is primary amine. (1)
29. (a) Graph (B) represents the mixture of chloroform and Or
−
acetone, that means it shows negative deviation NaCN OH
CH 3CH 2I → CH 3CH 2CN →
from Raoult’s law. (1) Ethyl cyanide Partial hydrolysis
Ethyl iodide
(b) The positive and negative deviations from Raoult’s NaOH + Br2
law are based on interactions between the CH 3CH 2CONH 2 → CH 3CH 2NH 2
component of the mixture. In case of positive Propionamide Ethylamine (1)
deviation, the solute and solvent interactions are (b) The geometry of amines is pyramidal and
weaker than those of solute-solute or N-orbitals in amines are sp3-hybridised.
solvent-solvent interactions, while in case of
Due to the presence of one unshared pair of
negative deviation the interactions of solute-solvent
electrons, the angle C N C is less than 109.5°.
are stronger than those of solute-solute or
solvent-solvent. (1)
(c) Phenol and aniline mixture would also show N
negative deviation from Raoult’s law because H 107° H
phenol-aniline interactions are stronger than those H
Structure of amine (1)
of aniline-aniline and phenol-phenol interactions. (2)
Or (c) Complete conversion can be performed as
(c) (i) Given, Vapour pressure pure ethanal ( p°A ) = 450 O
mm of Hg NH2 Br2/KOH
NH2 CHCl /KOH
3

Vapour pressure of pure acetone ( pB° ) = 700 mm Hofmann Carbylamine

-bromamide reaction
of Hg Cyclohexyl reaction Cyclohexyl
amide amine
pTotal = 600 mm of Hg χ A × pºA
+ –
According to Raoult’s law, N ≡≡ C NH  CH3
H2/Pd
p A = χ A × p°A
pB = χ B × pB° = (1 − χ A )pB° Cyclohexyl Cyclohexyl
isocyanide methylamine (2)
pTotal = p A + pB = χ A × p°A + (1 − χ A )pB°
31. (a) (i) In [Fe(CN)6 ]3− complex, Fe is present as Fe 3+ .
= pB° + ( p°A − pB° )χ A
Configuration of Fe = [Ar] 3d 6 4s2 4 p0
On substituting the given values into the above
equation, we get Outer configuration of Fe 3+ = 3 d 5
600 = 700 + (450 − 700 )χ A 3d5 4s0 4p0
100 = 250 χ A
100
⇒ χA = = 0.40 CN − being strong field ligand, pair up the
250
unpaired d-electrons. Thus, two 3d-orbitals are
Thus, the composition of the liquid mixture will be now available for CN − ions.
χ A = 0.40 and χ B = 1 − 0.40 = 0.60
 3d5 [Fe(H2O)6 ]2+
[Fe(CN)6]3–
Outer configuration of 26Fe atom = [Ar] 3d 6 4s2
CN– CN– CN–CN– CN– CN–

d 2sp3-hybridisation 3d 6 4s 2 4p 0
Since, one electron remains unpaired, the Fe =
complex is paramagnetic. (1) Fe 2+ ion = [Ar] 3 d 6 4s0
(ii) The complex, [Pt(en)2Cl 2 ]2+ contains two 3d 6 4s 0 4p 0
symmetrical bidentate ligands, ethylenediamine Fe2+
(en) and exists in two geometrical isomers, cis
(H 2O being weak field ligands, they do not cause
and trans. Trans isomer being symmetrical does
electron pairing).
not show optical isomerism and hence, this
isomer is optically inactive, while cis being [Fe(H2O)6 ]2+
unsymmetrical shows optical isomerism. 3d 6 4d
Cl
2+
H2 O H2 O H2 O H2 O H2 O H2 O

en Pt en sp 3d 2-hybridisation
(octahedral geometry)

Cl The complex is paramagnetic in nature, as it has

trans-isomer four unpaired electrons. (2)
Cl Cl
Cl
2+
Cl
2+
[Ni(CN)4 ]2−

en Pt Pt en Outer configuration of 28Ni atom = [Ar] 3d 8 4s2

3d 8 4s 2 4p 0
en en Ni =
Mirror
cis-isomer
(Non-superimposable form) Ni 2+ ion = [Ar]3d 8 4s0
3d 8 4s 4p
Hence, the structure of geometrical isomer (i.e. 2+
Ni =
trans-isomer) of the complex [Pt(en )2Cl 2 ]2+,
which is optically inactive is as follows (CN − being strong field ligand pair up the
Cl Cl d-electrons of metal atom.)
2+ 2+
[Ni(CN)4 ]2− ion =
en Pt en en Pt en 3d 8 4p

Mirror CN – CN – CN – CN –
Cl Cl
trans-[Pt(en)2Cl2]2+ isomer optically inactive dsp 2-hybridisation
square planar structure
(Superimposable mirror images) (1)
The complex is diamagnetic in nature, as it has no
(iii) Hexaamminecobalt(III) sulphate
unpaired electrons. (2)
[Co(NH 3 )6 ]2(SO 4 )3 (1)
The IUPAC name of [Fe(H 2O)6 ]2+ and [Ni(CN)4 ]2−
(b) (i) In case of Ni , electronic configuration of
Ni = 3d 8 4s2 and when it forms Ni 2 + ion its are hexa aqua iron (II) ion and tetracyanido-
nickelate (II) ion respectively.
electronic configuration becomes 3d 8 4s0.
For low spin complexes, electrons gets pair up. 32. (a) Cu | Cu 2+ (aq, 1M) || Ag + (aq, 1M) |Ag (1/2)
Thus, will produce only one empty d-orbital. 2+ −
At anode, Cu (s) → Cu (aq) + 2e
Hence, d 2sp3-hybridisation is not possible in Ni
At cathode, 2Ag + (aq) + 2e − → 2Ag (s) (1/2)
to form octahedral complexes. (1)
(ii) The IUPAC name of the complex is diaqua silver Net reaction,
(I) dicyanidoargentate (I). (1) Cu (s) + 2Ag + (aq) → Cu 2+(aq) + 2Ag (s) (1/2)
(b) At anode, Sn (s) → Sn 2+(aq) + 2e − (1/2) number of CH 3COOH ions per unit volume
decreases. Hence, conductivity decreases. (2)
At cathode, 2H + (aq) + 2e − → H 2(g ) (1/2)
33. (a) E ° values of Mn 2+ and Zn 2+ are negative because
Net reaction,
of stabilities of half-filled (3 d 5 : Mn 2+ ) and fully-filled
Sn(s) + 2H + (aq) → Sn 2+(aq) + H 2(g ) (1/2)
(3 d 10 : Zn 2+ ) configuration respectively. Mn 2+ ion
2+ has higher E° value because of highest negative
° – 0.0591 log [Sn ]
Ecell = E cell enthalpy of hydrogen. (1)
2 [H + ]2
(b) The high melting points of transition metals are due
0.0591 0.04
= (E °H + /H − E Sn
° 2 + /Sn ) − log to strong metallic bonds between the atoms of
2 2 (0.02 )2 these elements. This is because of involvement of
0.0591 4 100 100 greater number of electrons in the interatomic
= [0 V −(−0 . 14 V )] − log × ×
2 100 2 2 metallic bonding from (n − 1)d orbitals in addition
= + 0.14 V − 0.0591 V = 0.0809 V (2) to ns electrons. (1)
(c) The electronic configuration of fluorine is
Or
2+ + 1s22 s22 p5. Thus, it can form only one bond as it
(a) Sn(s) | Sn (0.004 M) || H (0.020 M)
has only one unpaired electron. Electronic
| H 2(g ) ( 1 bar) | Pt (s) configuration of oxygen is 1 s22 s22 p4. It can form
Cell reaction is multiple founds with the metal atoms. Thus, oxygen
Sn + 2H + (0.020 M) → Sn 2 + (0.004 M) + H 2(1 bar) has greater bond formation capacity. In other
° words, it has greater ability to stabilise higher
Ecell = E° + 1
°
− ESn 2 +
H , H2 /Sn oxidation states in transition metals. (1)
2
(d) It is because in the beginning when 5f-orbitals
= 0 − (− 0.14 V) = 0 + 0.14 V = 0.14 V begin to be occupied, they penetrate less into inner
For calculation of emf, apply Nernst equation; core electrons. Thus, 5f-electrons are more
2+
° 0.0591 [Sn ] × pH 2 effectively shielded from the nuclear charge than
Ecell = Ecell − log 4f-electrons in the lanthanide series. Therefore,
n [H + ]2
outer electrons are less firmly held and thus these
0.0591 [0.004] × 1
= 0.14 − log electrons are available for bonding in actinoids and
2 [0.020] 2 their removal is much easier. On account of this,
0.0591 0.004 the ionisation enthalpies of Th, Pa and U are
= 0.14 − log
2 0.0004 comparatively lower than Ce, Pr and Nd. (1)
0.0591 (e) As the oxidation state of the element increases, its
= 0.14 − log 10
2 charge increases. According to Fajans’ rule, as the
0.0591 charge of the metal ion increases covalent
= 0.14 − = 0.110 V character increases because the positively charged
2 (3)
cation attracts the electron cloud on the anion
(b) From standard oxidation potential, it is clear that
towards itself. (1)
oxygen gas should be liberated at anode, but its
rate of production is very low. (f) Misch metal, a well known alloy, consists of
lanthanoid metal (~95%), iron (5%) and traces of S,
In order to increase that we increase the voltage of
C, Ca and Al. It is used to produce bullets shell and
external battery, due to which chloride ions get
lighter flint. (1)
oxidised easily and Cl 2 gas is liberated at anode.
(c) Conductivity of solution is conductance of ions (g) 2MnO −4 + 5NO −2 + 6H + → 2Mn 2+ + 5NO −3 + 3H 2O
present in unit volume of solution. On dilution (1)